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AutoLab PGstat 302N Manual - The Molecular Materials Research

1. Hide Links Figure 2 26 Unchecking the Enabled option will disable the command A disabled command will be displayed in grey in the procedure editor see Figure 2 27 Commands Parameters Chrono amperometry At gt 1 ms H E E E Remarks End status Autolab signal sampler Options Instrument Instrument description Autolab control set potential set cell Viait time 3 Record signals gt 1 ms set potential Record signals gt 1 ms set potential Record signals gt 1 ms set cell lt gt Figure 2 27 Disabled commands are displayed in grey Chrono amperometry At gt 1 ms Time WE Potential WE Current 1 Options 0 000 On 5 0 01 0 500 5 0 01 0 500 5 0 01 Of Links If you start the experiment you should only see two potential steps the first step having a duration of 5 seconds and the second step having a duration of 10 seconds 5 seconds 5 extra seconds from the third potential step as Record signals gt 1 ms command used to record the third step has not been disabled in Figure 2 27 74 Page NOVA User manual Figure 2 28 shows a comparison of the recorded WE 1 Potential values during the original Chrono amperometry procedure and the procedure in which the third Set potential command has been disabled Set potential 0 5 W E Set potential Ov i c_ oo A mi Set potential 0 5 W US a4 set potential 0 5 v
2. Peak height Figure 4 229 Defining the plot settings for the custom plot Figure 4 230 shows the resulting plot after changing the plot settings to a Point plot using a size 8 diamond as a marker As expected the points align on a Straight line The show origin option is used in the plot 308 Page NOVA User manual 0 0012 0 001 0 0008 0 0006 Feak height 0 0004 0 0002 1 an J OUr U7 Ula O82 Uar he square root scan rate V s ii Figure 4 230 The completed reversibility plot 4 12 The windower The windower is an additional tool that can be used for data analysis The role of the windower is to extract a cross section of the data grid It is designed to work in the same way as the signal builder it creates a new set of data based on measured or calculated signals The windower can be used to select a scan from a Series of cyclic voltammograms or select a potential step from a chrono amperometry experiment or select only the data points with positive current values This section will describe the use of the windower using an example from the demo database The Demo 06 Galvanostatic CV entry of the demo database contains three galvanostatic staircase cyclic voltammograms for lead deposition recorded using a polycrystalline gold electrode in 0 1 M HCIO solution Pb 0 01 M The reference electrode was a Ag AgCl KCI saturated and the counter electrode was a platinum sheet The
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4. 0 2 04 06 2 0 4 1 6 Potential applied V Potential applied V Figure 4 93 Slide zoom expanding the Y axis left and contracting it right using the sliding zoom function 4 7 13 2D Plots Moving Dragging mode The 2D plot can be moved around using the wheel mouse button if available This option is particularly useful to move hidden parts of the plot into view after zooming in on the plot To use this feature click and hold the wheel mouse button and drag the hidden part of the plot into view While the wheel mouse button is pressed the mouse pointer changes from an arrow to a cross like pointer Figure 4 94 illustrates this option 0 0012 urrent A urrent A VE 1 C VE 1 C 1 0 2 0 3 0 4 0 5 0 6 pan 0 3 0 2 0 1 0 0 Potential applied V Potential applied V 0 Figure 4 94 Using the moving feature 220 NOVA User manual Using the keyboard it is possible to move the plot relative up down left and right by using the corresponding keys In combination with the CTRL key and the SHIFT key the movement can be accelerated 4 7 14 3D Zooming Scrolling mode The zooming functionalities for a 3D plot are limited to scrolling in and out using the mouse wheel Depending on the location of the mouse pointer the zooming function will affect the whole plot or a specific axis If the mouse pointer is located anywhere on the plot except on one
5. NOVA User manual 0 0016 0 0014 0 0012 0 001 0 0008 0 0006 0 0004 WELTI Current 4 0 0002 0 0002 0 0004 U a 0 Standard CY Demonstration data 0 2 0 4 0 6 Fotential applied W Legend Position Border Style None 4 Edit Text Font E Line EditTextColor Shadow X z1 Hide 0 8 Figure 4 76 The legend sub menu for position border style and font edition Show Title 2D amp 3D plots this option will display a title for the data set s plotted in the 2D graph As with the legend the format of the title and of the subtitle can be edited using the right click menu Their position can be chosen from three predefined settings both for the 2D and for the 3D plots although the settings are independent for each type of plot Figure 4 77 shows the default title for the 2D plot and the right click menu used for editing text font and position of the title and the subtitle 0 0016 0 0014 0 0012 0 001 0 0008 0 0006 0 0004 0 0002 WE 1 Current A 0 0002 0 0004 Title T a titi i gt 0 2 0 4 Title Edit Sub Title Edit Text Font Edit Text Color Position Top Left Hicle E Top Center N Top Right 0 6 0 8 Potential applied V Figure 4 77 Displaying the title and the subtitle and using the right click menu 206 Page for editing NOVA User manual It is also possible to edit the title and the subtitle by double click
6. ccccceccececeeeeeeeeeeeeeeaeeeeeeeeeeneeeeens 239 4 8 1 4 Peak SQAIrCN ccccssecccneecceeseeseeeeceseeecaserseescesseseccesenseesenseeeeees 240 4 8 1 4 1 Automatic peak search weccincisiesteccuntesielanmedoliaaaciedsinee iain apatite id 243 4 8 1 4 2 Manual peak search ccccccccesceceeceseesensceeesceeeseeseecseseetes 245 BM cP SOEs SION g sctrerttos A A E nine eietoe saan E A 255 Pe dr DOT UI E sence E A PET N E E A 261 AGAS SNE E s e E E A 264 AS ko T PAY eer E E E E 267 aNs a Po EOE oE C E A E EE EE sseteuen ashe dare 271 4 8 1 9 1 Corrosion rate Tafel SlOp ssnnssnnusninserneerirsrrenrrrsrresnn 272 A 8 1 9 2 Corrosion rate Fit cecececceeececeeeeeeesaeeeeeeeeaeeeeeeaeeneees 276 4 8 2 Data set analysis tools ceciscriesinensatacdnwsiinds aws aveleasietawentetuansteelvnencdecdeces 280 NOVA User manual 4 8 2 1 IR ArOP COLPECtION ccceececececeseeceeecceeceeescsecesessueesseeenees 281 4 8 2 2 Hydrodynamic i VS W cc ccsceosveccne sas lt cusedsunannddadentneneradvedauedddvesecnedees 283 4 8 2 3 Calculate charge iccetetosnsccdacncsaseicnsseseasessioaspeterseose Selevescadseuenadets 287 ANS WSO e E EEE EE EE 289 4 10 The Calculate signal tool c ccccsscecscececcsseesseeesesseescsercsesersceseesnees 291 Be The BUNCH SIG IVA TON sere caetesces sesso trinctreanecacwtte sirens anaE aia RA a 298 4 11 1 The signal builder WINGOW ccccscccc
7. Figure 2 94 Opening the Sampler for the whole procedure The sampler editor will be displayed For illustration purposes the WE 1 Charge signal will be added to the sampler see Figure 2 95 Pi Edit Sampler 0O Signal sample Optimized Sampler configuration WE 1 Current Sampler WE 1 Potential E Segment Optimized WE 1 Power C H WWE 1 Current WET Resistance C kal Calculated signals WEC Charge m WEC Charge External 1 External 1 TA E Time Integrator 1 Charge Integrator l Integrated Current Time Sample alternating Figure 2 95 Adding the WE 1 Charge to the Sampler Click the button to close the Sampler window The Preview changes window will be displayed allowing you to choose for which measurement commands in the procedure this sampler should be used see Figure 2 96 127 Page NOVA User manual Preview changes Sampler Apply sampler settings to Optimize current ranqe C staircase C staircase galvanastatic Select all Select none Invert selection JK Cancel Figure 2 96 The Preview changes window 2 7 My commands The final section of this chapter describes the My commands framework This feature allows you to create new commands A specific database is available to store your own commands The location of this database can be defined using the database manager see Figure 2 97 Database management Procedures My pr
8. HIE E E E E E EE E ses Save in My comm ands Delete Col x Ctrl C Figure 2 22 Pasting the copied commands in the procedure The copied commands will be added to the procedure below the selected command see Figure 2 23 Commands Parameters Links Chrono amperometry At gt 1 ms Remarks Chrono amperometry At gt 1 ms m End status Autolab m oignal sampler Time WE 1 Potential vwE 1 Current al Options 1 Options m Instrument LALIT 0530 Instrument description Autolab contral Pr set potential 0 000 set cell On m ait time s p Record signals 1 ms 5 0 01 set potential 0 500 Record signals 1 ms E Z set potential 0 500 Record signals 1 ms E teanih E Set potential 0 500 e Record signals 1 ms 5 0 01 Set cell Ott lt gt Figure 2 23 The copied commands are added to the procedure 71 Page NOVA User manual 2 4 5 Favorite commands A dedicated command group called Favorite commands is available in the Command browser This group initially empty will fill up when commands are dragged and dropped in the procedure editor as explained in Section 2 4 3 This group will automatically keep track of the ten most used commands In Section 2 4 3 two commands have been dragged into the procedure editor Set potential and Record signals gt 1 ms Since these commands have been manually added to the procedure they are now listed in the Favorite commands group see Fig
9. Hinh sneer all fic Demo 01 Coppe Y E ind m T ox B C staircase 0 0015 Signal e ere G ivs E i LA X Potenti Add analysis Plot area Potential applied Ag Y WE 1 Current Scan Ae Z Time L 9001 WE 1 Current E Time Data explorer frame 2 WE 1 Potential O 0 0005 Index Li lt gt 0 Analysis frame 0 0005 0 0 5 1 Potential applied V User log message Time Date Command A WD Autolab USB connected AUT40034 5 24 11 PM 2 4 2013 p Start ihiialalnaiiialianiimiiiaaaah ALT70530 9 11 06 AM 2 5 2013 Sta rt Stop button 3AUT 70530 9 20 13 AM 2 5 2013 User log AUT40034 10 38 17 2 5 2013 vV Hardware based Basic User defined Figure 4 2 Overview of the Analysis View The Start Stop button toolbar and the User Log are both common to all views of NOVA Other noteworthy areas of the Analysis View are e Database displays the list of available data sets that can be used in the data analysis view Each entry of the database has a name a time stamp and a remarks field e Data explorer displays the data set s currently selected for data analysis e Plot area displays the selected data points in a 2D or 3D plot e Analysis frame displays the control parameters and the results of data analysis tools 4 1 Introduction This chapter of the user manual explores the Analysis view and provides in depth information about this essential part of the softw
10. NOVA User manual A new item called iR drop correction will be added to the data set below the CV Staircase item A new signal called Corrected potential will be added to the dataset This new signal can be used to create or change a plot and use the Corrected potential see Figure 4 192 Demo 13 Cyclic voltammetry Fee Fes 5 C staircase iws E oY X Potential applied 0 004 oof Y WE 1 Current P 0 0005 E R drop correction 5 livs E Corrected Ay X Corrected potential HA Y WEC Current S WEED Current 4 U 001 0 2 0 Oe 0 4 0 6 Potential applied W Figure 4 192 Using the corrected potential scale overlay of source data and corrected data It is possible to change the value of the uncompensated resistance by clicking the iR drop correction item in the data explorer The input field for the Uncompensated resistance will be displayed on the right hand side of the plot see Figure 4 193 E_T x Demo 19 Cyclic voltammetry Fe2 Fe3 C staircase F ivs E Ay X Potential applied 0 001 Ay Y WE 1 Current Ay Z Time signal Expression Unit lt 0 0005 iR drop correction B ivs E Corrected Uncompensated resistance Q 20 Ay X Corrected potential 0 Ag Y WE 1 Current A Ay Z Scan hae 0 0005 0 001 0 2 0 0 2 0 4 0 6 Potential applied V Figure 4 193 The uncompensated resistance can be adju
11. The CTRL X for Cut CTRL C for Copy and CTRL V for Paste keyboard shortcuts also work 69 NOVA User manual Commands Parameters Links Chrono amperometry At gt 1 ms Remarks Chrono amperometry At gt 1 ms m End status Autolab m oignal sampler Time WWE Potential WEOQ Current ma Options 1 Options m Instrument Instrument description Autolab control set potential 0 000 set cell On ma Viait time s s Record signals 1 ms 5 0 01 set potential Record signals 1 ms Set potential Record signale c1 oet cell Ea X Enabled Save in My commands Delete a Cut Col x Figure 2 21 Select the copy option from the right click menu To paste the copied or cut commands right click the command below which the commands need to be pasted and select the Paste option from the context menu see Figure 2 22 Note Paste commands are always added below the selected command 70 Page NOVA User manual Commands Parameters Links Chrono amperometry At gt 1 ms Remarks Chrono amperometry At gt 1 ms m End status Autolak m oignal sampler Time WWE 1 Potential vWwE1 Current ma Options 1 Options m Instrument LALIT 0530 Instrument description Autolak control set potential 0 000 set cell On m Viait time s Record signals gt 1 ms set potential Record signals gt 1 ms set potential Record signals gt 1 ms set cell
12. The highlighted symbol located on the right hand side of the Procedure Name column header triangle pointing up symbol indicates that the data sets are currently sorted by name ascending Clicking on the Procedure Name column header will switch the name sorting to descending see Figure 4 6 The displayed symbol will change to triangle pointing down Procedure name Demo 20 Iron screw in seawater Demo 19 Cyclic voltammetry Fe2 Fe3 Demo 18 Aniline electropolymerization Demo 1 Imported FRA data Demo 16 FRA impedance Demo 15 UME LSW Demo 14 FC CH2 2 FC in ACN CH2CI2 Demo 13 Imported pcPt GPES data Demo 12 Imported pcPt GPES data Demo 11 Hydrodynamic FRA with OCP determin Demo 10 Differential pulse measurement Demo 09 Chrono methods ADC1 64 with wariabl Demo 08 Chrono methods ADC164 20 steps Demo 0 High speed chrono methods Fast ADC Demo 06 Galvanostatic CY Demo 05 Fe ll Fe lll on poPt Demo 04 Hydrodynamic linear sweep voltammetr Demo 03 Bipotentiostat measurement Pt Pt Rin Demo 02 Lead deposition EQCM Demo 01 Copper deposition Xo Figure 4 6 Sorting the data sets by name descending Time stamp 4 5 2009 3 42 46 PM 3 17 2009 5 35 06 PM 5 5 2009 11 57 13 AM 6 10 2008 8 27 23 PM 4 9 2010 4 54 02 PM 6 10 2008 8 30 23 PM 6 10 2008 8 09 37 PM 6 10 2008 7 53 08 PM 6 10 2008 7 50 38 PM 4 6 2010 12 23 00 PM 5 25 2009 12 14 00 2 20 2007 9 37 06 AM 2 20 2007 8 40 08
13. 294 Page NOVA User manual E Mame Expression Full _ CY staircase S Cotential applied E Calculate signal Potential ve SHE Single value rit E 0 197 Parameters signals Functions JK Cancel Figure 4 210 Selecting the values of the Potential applied signal for the parameter E Click the OK button to finish the calculation of the new signal After the new signal has been created its values will be displayed in a new column in the data grid The corresponding formula will appear under the data grid toolbar on the right hand side of the screen see Figure 4 211 Potential applied V WE 1 Potential V WE 1 Current A Time s Scan Index oe gt 0 299988 0 300781 6 32935E 7 azo ho h 0 302429 0 303375 1 02966E 6 8 72889 1 J2 0 499429 0 304871 0 304962 2 14844E 6 8 75323 1 a losm87 0 307312 0 306824 2 87384E 6 8 77769 1 J4 lo504312 0 309753 0 311951 3 14392E 6 8 802093 1 fs 10 506753 0 312195 0 312744 13 15582E 6 laszea9 1 le osons 0 314636 0 313985 3 61328E 6 8 85083 ji fz os511636 0 317078 0 317535 4 19312E 6 8 875293 f1 fe 0 514078 A Ts x Signal Expression Unit Potential applied Vv Scan WE 1 Current A Time S WE 1 Potential Y Index Potential vs SHE E 0 197 Vv Figure 4 211 The newly created signal values shown in the data grid The matching e
14. 323 68 600 0 0015 800 0 001 1000 0000s 1200 Ef 1 Current 4 1400 EQCMi 1 AFreguency Hz 0 0005 1600 0 004 1500 0 0015 2000 0 8 0 6 0 4 0 2 0 J 0 4 0 6 0 8 Potential applied W Figure 4 81 Showing the pointer coordinates for a dual Y axis overlay plot Show Positioning lines 2D plots only this option will display the two lines following the position of the mouse pointer and helping in locating the position of the pointer on the screen Figure 4 82 WET Current 41 Tie ae 0 0 2 0 4 0 6 0 8 1 Fotential applied W Figure 4 82 Showing the positioning lines 210 Pa ge NOVA User manual 4 7 4 Stepping through data Most of the additions that were described in the previous part of this section are general additions which can be added to any plot regardless of the plotted data In some cases more data specific additions could be required NOVA has a convenient labeling function that can help you achieve this Right click anywhere on the plot and choose the Steo through Data option see Figure 4 83 The Steo through data option deactivates the Enable Zooming Moving option 0 0016 j 0 0014 ii Original Dimensions F4 0 0014 ky Zoom Back Shift F4 ooo Enable Zooming Moving a Step through Data 0 0005 Select Dataset R a 0 0006 E Grid 0 004 Background Show b 0 0002 La Print Preview 0 g Print EZ Copy to Clipboard 0 0002 Fe A a ean
15. Current m Options 1 Options a Instrument LALIT 0530 Instrument description Autolab contral zj set potential 0 000 set cell On m wWalttime s h Optimize current range z CY staircase U 000 1 000 1 000 0 000 2 0 1000000 set cell Ott m lt gt Figure 1 18 Clicking the button in the quick access toolbar opens the Edit options window The Edit Options window will be displayed see Figure 1 19 In this window the Automatic current ranging settings can be defined for each working electrode on the Automatic current ranging tab Additionally the Cutoff tab can be used to define cutoff conditions for the measured signals and the Autolab control tab can be used to define special actions for the Autolab instrument If an analog integrator is available the Automatic integration time option can be specified in the final tab 14 For example create a new drop on a Hg electrode in a polarographic measurements 25 Page NOVA User manual F Edit Options 0 Automatic Current Ranging Cutoff Autolab control Automatic Integration Time Highest current range 1 mA Lowest current range Lowest current range select the lowest current range for automatic current ranging JK Cancel Figure 1 19 The Edit Options window If the Automatic current ranging option is used the current range will be adjusted if necessary at the end of the sampling step
16. Hydrodynamic i vs Yw H Levich plot 0 0025 HH Regression through origin i TE 02 O4 06 08 Potential applied Y 0 001 0 0005 VVE 1 Current 0 0005 0 001 Figure 4 149 The data from the Demo 04 data file This demo file also includes an additional item located at the end of the file in the data explorer frame called Hydrodynamic i vs Vw This analysis item is designed to perform a simple Levich analysis on data recorded using forced convection This item automatically generates a Levich plot and performs two linear regressions on the plotted data using the inear and the inear no offset regression methods see Figure 4 150 Demo 04 Aydrodynamic Lo with increasing rotation rate i Control Autolab RDE H S 1 Value 500 H al 2 Value 0831 92 H al 3 Value 1247 9 H 4 Value 1747 9 H Wl 5 Value 2331 9 H 6 Value 3000 a Hydro dyn amicivs yi y H Levich plot X GH Regression through origin H Regression Figure 4 150 The Hydrodynamic i vs w analysis tool automatically adds two regression lines to the Levich plot Click the Regression item in the data explorer The Levich plot will be displayed in the plot area along with the linear regression line see Figure 4 151 257 Page NOVA User manual Demo 04 Aydrodynamic Lov with increasing rotation rate E Control Autolab ROE 0 003 g 1 Value 500 H a 2 Val
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18. Oo 1 2 LL 1 0 8 20 40 60 80 Time 5 Figure 4 248 Specifying several ranges in the windower 4 12 6 Direct windowing through X axis scaling It is also possible to window the data immediately using the X axis scaling as a selection criterion This alternative uses the data plotted on the plot area as the data to be windowed Starting from the E vs t plot obtained from the data provided in the Demo 06 set one of the different zooming or scale adjustment methods described in this chapter can be used to focus on a particular area of the plot see Figure 4 249 3 Please refer to Section 4 7 9 for more information 318 Page NOVA User manual WE 1 Potential V gt 40 45 50 55 60 65 Time s Figure 4 249 Adjusting the X axis scale in order to graphically select the second scan With the X axis adjusted right click the E vs t plot and select the Create Windower from X axis option from the context menu see Figure 4 250 Demo 06 Galvanostatic CY Demonstration data e CY staircase galvanostatic H E vst Plot Options Properties Create Windower from X axis N Add Analysis N Copy Visible Plot s to Show All Plots Hide All Plots Save in My commands A Delete Remove all from View Figure 4 250 Select the Create Windower from X axis to create a windowed set of data With the X axis adjusted right click the
19. a 0 0004 4 Value 0 1 3 LSY staircase 0 0002 divs E Peak search 0 0 0002 0 nsi 0 2 0 3 0 4 0 5 Potential applied W Figure 4 217 Select the whole data set and click the T button in data grid toolbar to use the signal builder This will open the Filter and Select Signals window see Figure 4 219 It is also possible to open the Calculate signal tool by clicking the CV staircase item in the data explorer frame and clicking the button in the quick access toolbar see Figure 4 218 300 Page NOVA User manual a Demo 05 Feil Fe j Build signal nonstration data OCP determinatio ok OCP value 0 243 1 Value 0 01 il LS staircase H ives E mm Feak search 2 VWalue 0 02 E Lo staircase H ivs E Peak search 3 VWalue 0 05 a LS staircase H ives E eimi Feak search a 4 Value 01 LSY staircase H ivs E m Feak search I m E Figure 4 218 The build signal tool is also available from the quick access toolbar Note Since the new signals use values of all the measurements in the data set clicking the header is required Y Build signal Analysis general Name Index Control Gy Measurement cyclic and linear sweep voltammetry G Measurement general E Untyped filter Search from 1 level s up Sort by order of 1st array high to low _ Sort by order of 1st array low to high canga F
20. ia Fi Autolab display F10 FRA manual control MDE manual control MUX manual control External manual control Profile Hardware based Basic Intermediate Advanced Corrosion Education Electroanalysis Energy Interfacial electrochemistry Semiconductors Reset user profile Import user profile Export user profile Hide Ctl H Unhicle Ctl Shift H Show all 12 Ctrl P Alt F4 File menu shows all the instructions related to creating saving and printing a procedure Multi Autolab related items are also found in this menu Some of the instructions have a corresponding button that can be present in the toolbar and a convenient keyboard shortcut View menu shows all the view related commands It also provides access to the control of some of the accessories Some of the instructions are highlighted indicating an active Status Profile menu shows all the available profile schemes in NOVA The profiles are arranged in three groups Hardware based Level based basic intermediate and advanced and Application based More information on the use of profiles is provided in Section 1 6 1 Some of the profiles are highlighted indicating an active Status NOVA User manual Run Run menu shows the Start Pause Skip and i Stop instructions The pause skip and stop pm instructions are only active during the Stop measurement Tools HRUNS Tools menu gives access to the options the Q Database Manage
21. 0 3 p 5 0 6 Ei io 0 4 t 30 9795 02 Figure 2 51 Illustration of the timing difference in NOVA The time between timed commands will always be very accurately determined by the internal clock of the Autolab The time delay introduced by untimed commands will be affected by the background activity of the host computer and will therefore be less predictable 2 5 2 Building advanced procedures The final section of this chapter describes how to use the procedure editor to create an advanced procedure from scratch Click the A button to clear the procedure editor frame The editor will display an almost empty procedure editor frame see Figure 2 52 95 P NOVA User manual Lommands Parameters Links New procedure Remarks End status Autolab signal sampler Time WE Current potions Mo Options Instrument ALITT 40006 Instrument description os Figure 2 52 The empty procedure editor frame The seven lines displayed in the procedure editor frame are the default components of each procedure i The default Signal sampler includes the Time and WE 1 Current optimized Signals The default Options are set to No Options Please refer to Sections 1 3 3 and 1 3 4 for more information on the Signal Sampler and the Options respectively In this section the step by step construction of an advanced procedure will be illustrated The intention is to create a procedure that performs a Linear sweep voltam
22. 1000 0 Amplitude D 0 1 SO000 IES Po ee Frequency Hz Figure 4 173 The raw impedance data after transformation from the time domain into the frequency domain The transformed data shows a single peak at 10 kHz consistent with the applied frequency The rest of transformed data shows the contributions from environmental or instrumental noise The transformed data is displayed in logarithmic scale on the Y axis The data is shown in arbitrary units 270 Page NOVA User manual 4 8 1 9 Corrosion rate The corrosion rate analysis tool can be used to convert the exchange current density in amount of material corroded per year The corrosion rate analysis tool is typically used on a linear polarization experiments and allows the determination of the polarization resistance the Tafel slopes and the exchange current density Double click on the demo file Demo 20 Iron screw in seawater entry of the demo database to load it into the data explorer frame This file contains data points of a linear sweep voltammetry experiment recorded with an iron screw in sea water Click the i vs E plot in the data explorer frame to display the data points from this demo file see Figure 4 174 a Dero 20 ilron screw in seawater Import GPES data JESS H i ws E X 2 E 225 SIB 5 iE gt A SIE 6 Current _ 5E 6 B SIE 5 2 E5 0 5 0 4 0 3 0 2 Potential W Figure 4 174
23. 1E 7 J fa 0 v Lower vertex potential V 0 400 lt gt 1 5E 7 q PET Stop potential V 0 000 Search mode 4 Number of stop crossings 2 2E 7 F q PoE Base line mode Step potential V 0 00244 E 2 BEY Minimum peak height Scan rate V s 0 1000000 l 1 1 1 1 1 1 1 i i i 0 8 0 6 04 0 2 0 0 2 0 4 0 6 0 8 0 5 0 0 5 viipe Potential V Potential V L LN Ria aa Stop gt Start E Measurement Analysis Display measured data Analysis results View data in 2D or 3D Perform calculations Display real time information about the electrochemical reaction Build new plots Export data Manage the database Figure 1 4 The four views of NOVA 14 Page NOVA User manual The Setup view provides a framework for procedure editing It is used to create procedures setup the way the data points are gathered and to manage user defined procedures through the use of a custom made database This part of NOVA is described in more detail in Chapter 2 of this user manual The Measurement view displays real time data points during an ongoing measurement It also provides an overview of the progress of the procedure Chapter 3 describes the Measurement view The Analysis view is used to perform data analysis on previously recorded measurements It lets the users plot experimental data in a 2D plot or in a 3D plot This view is also used to generate new plots and to perform calculations on the measured data using
24. 2 Value 0 0e LSY staircase H ivs E _ Peak search 3 Value 0 05 LSY staircase Hm ivs E mm Feak search l a 4 Value 0 1 LSY staircase H ivs E Peak search Figure 4 215 The four LSV curves of the Demo 05 data set The Demo 05 data set was obtained using the Repeat for each value command with four values used in procedure for the scan rate using in the LSV staircase measurement The first LSV was obtained with a scan rate of 0 01 V s the next LSV was recorded with a scan rate of 0 02 V s and so on The overlay plot of all four LSV curves is provided below see Figure 4 216 298 NOVA User manual 0 0012 0 001 0 0008 0 0006 WET Current tA 0 0004 0 0002 O 0002 J TA 0 2 ORs 0 4 05 Potential applied W Figure 4 216 The four LSV curves obtained using four different scan rates As the scan rate increases the anodic current increases For a reversible system like the Fe CN 6 Fe CN e system the peak current i is proportional to the Square root of the scan rate 3 1 1 iy 2 69 10 An2C D2yv2 where A is the area of the electrode n is the number of electrons F is Faraday s constant C is the bulk concentration of the electroactive species D is the diffusion coefficient and v is the scan rate A plot of the peak current vs the square root of the scan rate should yield a Straight line The procedure used to measure the data points of the Demo 05 exam
25. 216 Axis scale type 215 Axis scaling 177 Axis settings 172 B Baseline correction 233 239 Baseline mode 225 243 Begin value 107 BMP 217 Build procedure 95 Build signal 298 Bulk concentration 299 Butler Volmer equation 276 C Calculate charge 264 287 Calculate signal 291 293 294 305 Cathodic branch 273 Cathodic charge 153 CELL ON label 150 NOVA User manual Cell switch 150 Change plot settings 170 Charge determination 287 Check procedure 121 Chrono amperometry 60 65 Chrono load unload 90 Clear button 106 255 Clear measurement plot 11 Clipboard 217 Collapse one level 11 Command list 222 Command parameters 57 Commands 56 64 Commands browser 64 Commands database 29 Commands tab 64 Comment 56 120 Compatibility with previous versions 166 Control parameters 273 Conversion tool 166 Coordinates 203 Copy to Clipboard 217 Corrosion potential 271 Corrosion rate 271 279 Corrosion rate fit 276 Corrosion rate Tafel slope 272 Create new commands 128 Create new plot 179 Create new plots 178 Creating commands 136 Creating links 84 Current 20 Current density 271 Current overload 47 Current range 150 Custom plot 179 Customize Nova 42 Cutoff 24 56 110 CV Staircase 57 59 Cyclic voltammetry 54 D Data analysis 155 222 225 242 273 277 Data analysis frame 156 Data analysis toolbar 183 Data backup 161 Data conversion 166
26. Advanced Corrosion Education Electroanalysis Energy Interfacial electrochemistry Semiconductors Reset user profile Import user profile N Export user profile Hide Ctrl H Unhicle Ctil Shift H Show all Figure 1 38 Importing and exporting user profiles This means that any number of profiles can be created and used at any time using this method It is possible to reset the user defined profiles to default by using the Reset user profile option from the Profile menu see Figure 1 38 A confirm message will be displayed when the user profile is reset see Figure 1 39 Please confirm Ea amp All manual profile adjustments will be removed Are you sure T ERY Figure 1 39 A confirmation message is displayed with the user settings are reset 41 Page NOVA User manual 1 6 4 Software options It is possible to customize the behavior of NOVA through the Options window which can be accessed through Tools menu see Figure 1 40 File View Profile Run Tools Help Database Manager Check Procedure Alt F1 Hardware Setup pH Calibration Figure 1 40 Customization of NOVA can be done through the Options Selecting the Options displays the NOVA options window see Figure 1 41 Three different groups are shown in the left hand side panel of the window e Graphics e Autolab display e Advanced settings Nova options m Graphics Autolab display Advanced set
27. Autolab control Measurement general A WE 1 Mode Potentiostatic 4 Measurement cyclic and linear sweep valtammetry E WE 1 Current range 1mA 4 Measurement voltammetric analysis l i WE 1 Bandwidth High stability Measurement chrono methods rb Set potential 0 000 4 Measurement impedance ce Set cell On a H Data handling na 1 Optimize current range 5 H Analysis general 4 Analysis baseline correction 1 A H Analysis corrosion A 44 Analysis impedance Figure 2 62 Adding the Repeat for each value command to the procedure The Repeat for each value command creates a repeat loop for which the number of repetitions is equal to the number of pre defined values of the command Add the LSV staircase command from the Measurement Cyclic and linear sweep voltammetry group to the Repeat for each value command Next add an additional Set potentia command to the sequence as shown in Figure 2 63 102 P NOVA User manual Finish the sequence by adding a Wait time s command at the end of the repeat loop Commands New procedure Remarks End status Autolab signal sampler Options Instrument Instrument description Autolab control set potential set cell Optimize current range E Repeat for each value Number of repetitions Parameter link El LSY staircase star potential v stop potential v step potential v ocan rate y s Estimated number of points Inte
28. Customize Columns Demo 08 Chrono methods ADC164 20 steps 2 20 2007 8 40 08 AM Factory standard procedure AUT83072 Demonstration data Demo 09 Chrono methods ADC164 with variabl 2 20 2007 9 37 06 AM Combination of steps and levels AUTS83072 Demonstration data Demo 10 Differential pulse measurement 5 25 2009 12 14 00 Example forbaseline correction peak sea AUTS83072 Demonstration data Demo 11 Hydrodynamic FRA with OCP determin 4 8 2010 12 23 00 PM With Autolab RDE at 1000 RPM AUT83072 Demonstration data Demo 12 Imported pcPt GPES data 6 10 2008 7 50 38 PM Polycrystalline platinum in HCIO4 0 1 M Imported demonstration data Demo 13 Imported pcPt GPES data 6 10 2008 7 53 08 PM EtOH oxidation on polycrystalline Pt in HC Imported demonstration data Demo 14 FC CH2 2 FC in ACN CH2Cl2 6 10 2008 8 09 37 PM Ferrocene in Acetonitrile Chloroform Imported demonstration data Demo 15 UME LSY 6 10 2008 8 30 23 PM Use the smooth function Imported demonstration data Demo 16 FRA impedance 4 9 2010 4 54 02 PM Dummy cell c L3AUT 0530 Demonstration data Demo 1 Imported FRA data 6 10 2008 8 27 23 PM frademo cfr Imported demonstration data Demo 18 Aniline electropolymerization 5 5 2009 11 57 13 AM ESPR measurement Au disk y3SAUT 70530 Demonstration data Demo 19 Cyclic voltammetry Fe2 Fe3 3 17 2009 5 35 06 PM Cyclic voltammetry potentiostatic no extr p3MUT70530 Demonstration data Demo 20 lron screw in seawater 4 5 2009 3 42 46 PM Co
29. Data database 29 Data explorer frame 156 Data format 215 Data grid 168 244 289 Data information 211 Data location 211 Data point marker 236 Data point selection 235 Data presentation 139 Data repository 161 Data set analysis tools 222 280 Database 28 156 Database manager 28 321 NOVA User manual Database query 159 Delete commands 62 Delete data 167 Demonstration database 158 Derivative 261 Differential pulse voltammetry 233 Diffusion coefficient 299 DIO 98 Direction 259 Disable commands 73 Drag and drop 67 E Edit Axis 216 Edit Axis Color 216 Edit Label Color 216 Edit Label Font 216 Edit options 25 Edit procedure 53 Edit sampler 20 Edit Tick Text Font 216 Edit title 206 Electrochemical methods 119 Electrochemical signals 18 56 199 Enable commands 73 Enable zooming option 217 End key 213 End status Autolab 52 56 End value 107 EQCM 188 EQCM 1 Afrequency 189 Exchange current 271 Expand one level 11 Export data 164 Export to ASCII 289 290 Export to Excel 289 290 Expression builder 291 293 External signals 18 20 F F10 key 149 Factory standard procedures 119 Fast Fourier Transform 227 267 FFT 227 267 FFT filter type 229 FFT Smoothing 227 267 File menu 12 119 Filter and select signals 298 300 Filter data 298 Filter database 159 Filter scan rate 303 Find data 166 First derivative 262 Fix
30. Gir ivs E ivsE i Be ivs E H Logi ws E ivst A Logi vs E o B Custom Log i vs E gt EPET Logi vs Lag t vo Ay E VS i Fn Pye fa Evst E vs Laq i E vs Log t Figure 4 39 Creating a new plot for the data set The newly created Custom plot does not have any signals assigned for X Y and Z and therefore does not plot anything until these are defined by the user Change the signals in order to plot the measured current relative to the time X Time Y WE 1 Current Change the plot settings to a red Combi plot using a black pyramid upside down as a symbol size 10 plotting 1 point out of 40 and using a size 2 line Figure 4 40 Plot Options Data Axes Plot Analysis items Flot Flot style Combi plat we axis placement Left C Right Faint Point style Y Pyramid upside down a Point color Point size 10 Draw point every 40 datapointis Line Lnecoor __ Line size Advanced Reset values Apply OK X Cancel Figure 4 40 Setting the options for the newly added plot This new plot should like the one displayed in Figure 4 41 181 NOVA User manual Demo 01 Copper deposition CY staircase Bio i Ea i vate fee Time 2 a Y Potential applied oes B y 2 Time O 0012 E LogfijvsE oe X Potential applied bec ooo Y WE 1 Current ee Z Time 000p 5 Custom fe X Time a 0 0006 eof Y WE 1 Current o i Z Potential applied z 0 0004 9000
31. LSY staircase em ivsE Peak search 2 Value 0 02 5 LSY staircase ivs E L Peak search E 3 Value 0 05 LSY staircase Hh ivs E am Peak search ay 4 Value 0 1 x LS staircase i ivs E x Lm Peak search Plot Options Propertes Refresh Add VWincdower Generate index Add Plot Custom l Add Analysis N Show All Plots Hide All Plots Save the data in database Remove from View Remove all from View Figure 4 228 Adding a Custom plot to the data set A new custom plot will be added to the data explorer frame Set the X axis signal to Square root scan rate and the Y axis signal to Peak height Rename the plot to Reversibility plot Only three signals are defined for the whole data set Scan rate Square root scan rate and peak height Therefore only these three signals can be used for the plot see Figure 4 229 307 Page NOVA User manual Demo 05 Fell Fe ll on pct 6 S OCP determination oe OCP value 0 243 1 Value 0 01 E LSV staircase em ives E 3 im Peak search 5 2 Value 0 0e ad LSY staircase H v5 E L Peak search a 3 value 0 05 S LS staircase Gem ive E im Peak search 5 4 Value 0 1 e Lo starcase jys E 7 Feak search lea e Reversibility plot m Square root scan rate Ay Y Peak height sop Z Square root scan rate Scan rate V s
32. NOVA provides the users with a number of basic Objects corresponding to the low level functions of the electrochemical instrument These objects can be used as building blocks and can be combined with one another according to the requirements of the user in order to create a complete experimental method In essence the scientist uses NOVA as a programming language for electrochemistry building simple or complex procedures out of individual commands The instructions can be combined in any way the user sees fit Rather than providing specific electrochemical methods to the user NOVA uses a generic approach in which in principle any method or any task can be constructed using the available commands Figure 1 2 shows the NOVA strategy schematically 8 NOVA User manual JL CIL Library of individual objects Amplitude orale acl User defined Amplitude DC potential Automatic current ranging Figure 1 2 Schematic overview of the object based design of NOVA Impedance The NOVA approach allows the user to program an electrochemical method in the same anguage used by the instrument This new object based design philosophy has led to the current version of NOVA As any task can be solved generically the software is slightly less intuitive than a method based application Depending on the complexity of the experiments the learning curve can be more or less long For this reason we advise you to study carefully this
33. Placing the markers to define the baseline The number of markers required to drawn a polynomial baseline is equal to the polynomial order 1 The calculated baseline is not yet suitable for this experimental data and it requires additional fine tuning This is possible in two different ways e By adding extra marker points e By moving existing marker points 4 8 1 3 1 Adding extra marker points The first way to fine tune the baseline calculation is to add new markers to the plotted data Figure 4 121 shows the same plot as in Figure 4 120 but with an extra marker located close to the positive end of the potential scan When the new marker is placed the baseline is recalculated and replotted in the 2D plot area 236 P NOVA User manual Ee ass han i ae Et 1 6 Current Ay 156 7 1 2 1 0 8 0 6 0 4 0 2 J Potential applied W Figure 4 121 Adding extra markers to the baseline allows to fine tune the calculation The new marker allows for a better definition of the baseline at the positive end of the potential scan compared to Figure 4 120 It is possible to keep adding markers to the baseline in order to improve the fit if required Adding extra markers to a specific area of the curve increases the relative importance of that specific area of the plot in the baseline fit 4 8 1 3 2 Moving marker points A second option that can be used to fine tune the calculated baseline is to move m
34. The maximum number of points in real time view If the total number of points shown in one of the four plot areas in the measurement view exceeds the value defined for the Maximum number of points setting data points from finished commands will be removed in chronological order A Important A smaller number of points will increase the update rate of the plots during a measurement and reduce the memory usage of the computer A larger number of points will decrease the refresh rate and increase memory usage This setting is overruled by the Use maximum number of points in real time view see Figure 1 48 46 NOVA User manual Nova options e Graphics 4 General 2 Autolab display bo Overall graphical settings Advanced settings show serial in legend Yes 4 Measurement Yiew Maximum number of points 30000 Lise maximum number of points Apply OK Cancel Figure 1 48 It is possible to overrule the Maximum number of points setting When the Use maximum number of points property is set to No the software will try to display all the measured data points in each plot area up to a limit of 10000 data points for each individual plot 1 6 4 2 Autolab display In this category the colors used in the Autolab display can be defined see Figure 1 49 Nova options 4 LED colors 2 Autolab display Active LED color MB ControlText Advanced settings Alarm LED color MS Red Inactive LED color P ButtonSh
35. This frame is therefore helpful when running long procedures or procedures involving a number of repetitions e The modifiable parameters this frame displays a list of modifiable parameters for the running command as well as the current values used for these parameters Using this frame it is possible to change one or more of these parameters while the command is being executed Only the parameters of the running command can be moditied in real time Only specific parameters can be modified in real time For a complete list of commands and parameters please refer to the Command list document available from the Help menu The other items of the measurement view are the same as the other views User log start stop button toolbar 3 1 The procedure progress frame During the measurement an additional frame is provided in the measurement view This frame the procedure queue frame displays a condensed version of the procedure It shows the commands while the parameters are hidden from the view The command of the procedure that is currently executed is highlighted As an example the procedure progress of the standard Autolab linear polarization is shown in Figure 3 4 File View Profile Run Tools Help lee ee Ea Mt e SS eo eS oe e Ca Qe Linear polarization 2 Autolab control OCP determination 0 000 W gt oet reference potential 2 set potential Set cell Wait time 3 Optimize current ran
36. WE 1 Bandwidth High stability set potential 0 000 Set cell Ott m A Optimize current range 5 lt gt Figure 2 58 Adding the Set potential Set Cell Wait time and Optimize current range commands A warning symbol A will be visible in the procedure editor next to the Optimize current range command see Figure 2 58 This warning symbol only appears after adding the Optimize current range command to the sequence A toolip is available for each warning in the procedure editor see Figure 2 59 Commands Parameters Links New procedure Remarks ial End status Autolab m oignal sampler Time WE 11 Current ma potions Mo Options m Instrument LALIT 0530 Instrument description ee WE Mode Fotentiastatic WE Current range 1 mA WE Bandwidth High stability E Set potential 0 000 Set cell Ott m Optimize current range z A Figure 2 59 A tooltip is available for each warning in the procedure editor Note To provide help in the procedure building process validation of the procedure is performed in the background in real time Whenever a problem is detected NOVA will display a warning symbol A next to the command s afftected by this problem Whenever an error is detected NOVA will display an error symbol next to the command s affected by this error 100 NOVA User manual The default parameter of the Set ce command is Off Since this command must be used to switch the cell On the command ha
37. Wait time 10 s All these commands are timed commands and they will be executed without interruption To provide a visual indication a green line is shown on the left hand side of the procedure editor see Figure 2 46 E E EE Autolab control set potential Set cell Wait time 3 0 000 Orn Figure 2 46 The four commands in section A are all timed commands 91 P NOVA User manual The second section B which is the measurement itself contains two different levels see Figure 2 47 e The first level is a Repeat n times command e The second level is a series of measurement commands Repeatntmes 10 eee Number of repetitions 10 set potential 1 200 Record signals gt 1ms 2 5 0 01 set potential U 000 Record signals 1ms 2 5 0 01 lt gt Figure 2 47 The second part of the procedure contains the repeat loop and the measurement sequence The Repeat n times command creates a repeat loop Since this command is not a timed command it creates a break in the green timing guide indicating that there will be an interruption at each repetition Commands that are placed inside the Repeat n times command will be repeated 7 times when the procedure is executed However this is only true for those commands that are located on the second level under the Repeat n times command All the commands that are located under the Repeat n times command will be repeated The four commands located inside th
38. based on the last recorded value of the current If the Cutoff option is used for a sampled signal the last recorded value of this signal is tested against the threshold value defined in the cutoff Specific actions can be triggered by the Cutoff Stop command Stop complete procedure etc 1 4 Global and local sampler options The signal sampler and options detailed in the previous sections see Sections 1 3 3 and 1 3 4 can be defined for the complete procedure and for each measurement command that supports the use of the signal sampler and or options in the procedure When the sampler or options are defined for the whole procedure these will be referred to as global properties All the measurement commands included in the procedure will use the global sampler or global options When the sampler or options are defined for a single command in the procedure these will be referred to as local properties Only this single command in the procedure will use these properties and these will overrule the settings specified in the global sampler and options 1 gt The current range is set one range higher when the measured current is gt than 3 times the active current range The current range is set one range lower when the measured current is lt than 0 3 times the active current range 26 Page NOVA User manual Figure 1 20 shows an example of global and local options for the cyclic voltammetry potentiostatic procedure The CV
39. define the scan rate signal on top of the list as the y parameter by double clicking the scan rate signal Click the OK button to create the new signal see Figure 4 226 Calculate signal 0 Hi Name Square root of scan rate Single value Unit Expression SORT wsy05 o v Parameters Functions COMPLEXO ARG COMPLE DIY_IMAG COMPLEXO MOCI Signals Trigonometric functions Full _ Demo 05 Fe ll Fe lll on pcPt Peak height H OCP determinatio H LsS staircase S Scan rate y s vl H LSY staircase H LSY staircase LS staircase Clear Figure 4 226 Creating the square root of the angular frequency signal Three signals should now be available in the data grid see Figure 4 227 scan rate vis Feak height square root scan rate vrsi 1 2 0 00999998 0 000335539 0 020000 O 00048846 0 141422 0 050000 O O007 7 fa 0 225607 Figure 4 227 The signals required to build the plot 306 Page 4 11 5 Building the plot NOVA User manual With all the required signals available a plot to test the reversibility of the electron transfer can be added to the data set First click the 2D plot button and then right click the header of the data set in the data explorer frame and select the Add Plot Custom option from the menu see Figure 4 228 E a 05 Fell Fe lll on port B OCP determination ke OCP value 0 243 1 Value 0 01
40. 0 0002 0 0004 0 4 J 0 2 0 4 J G 0 8 Potential applied V4 Figure 4 86 Edited label and the edit menu 213 NOVA User manual Similarly to the other additions to the plots these labels are independently placed for each type of plot Saving the changes to the data set will also save the added labels 4 7 5 Axes and labels The final part of the customization of the plot will focus on the axes and the labels Some of the options are common to both types of plots while other options are only available for a specific type These options can be accessed by right clicking one of the axes of the plot see Figure 4 87 A description of these options is given below 214 0 0016 g 0014 Y AXIS O00 Scale type U0 Format z E gog Scaling mode Axes Coupling 0 00 y Show Label 0 00 ae LL 0 0002 0 0 0002 0 0004 Ua 0 0 2 NOVA User manual 0 4 0 6 0 8 1 Potential applied W 0 0015 MOP Eia 0 0005 i arpe i AXIS Scale type Format Scaling mode Origin Axes Location Show Label Edit Axis Toggle TextLocation Figure 4 87 Accessing the axes options in a 2D plot top and a 3D plot bottom 4 7 6 Common options e Scale Type choose from linear logarithmic absolute values square root 7 multiples and Time The direction of the axis can also be reversed e Format choose number formatting from general engineering scientific decimal expon
41. 0 150 5 Figure 3 18 The FRA manual control panel can be used to control the FRA2 module through the Autolab display This panel also displays measured impedance values during a frequency scan 3 4 3 Collapsible panels At any time it is possible to click on the button located in the top left corner of an Autolab display panel to collapse the contents of this panel in order to hide the information see Figure 3 19 3 More information can be found in the Impedance spectroscopy tutorial available from the Help Tutorials menu 152 NOVA User manual Autolab display Es v Autolab manual control u3AUT 0530 A FRA manual control frequency Hz amplitude HH k Lt ILI Mode Internal Wave type Sine Integration time s Minimum number of cycles to integrate Elapsed integration time s 1 0 7 EIEE ee ELA iy KOCI A KACI A HE i 601 9 p 9 099 m 5 0054 47 65 p 46 4a Freq Hz Z fd Phase f eee LH O20 k 101 4 10 79 99 57 18 98 Figure 3 19 Collapsing the Autolab control panel 3 4 4 Information during measurements During a measurement the Autolab view displays values of several relevant electrochemical signals These values are displayed at the bottom of the display The displayed information depends on the type of measurement Figure 3 19 shows the additional information displayed during a FRA measurement while Figure 3 16 displays information about the anodic and cathod
42. 000 Number of stop crossings Z step potential 0 00244 ocan rate fis 0 1000000 Estimated number of points 1650 Interval time s 0 024400 signal sampler Options Fotential applied Time WWE 1 Fotential WE Current Time WE 1 Current WE 1 1 mA 100 nA Scan lt array gt WE Potential array v Index Array iws E m Set cell Cit xxi F 4 3 Figure 2 89 The Cyclic voltammetry procedure added to the procedure editor Select the Cyclic voltammetry galvanostatic procedure and drop it into the procedure editor after the cyclic voltammetry procedure When the mouse button is released a message will be displayed see Figure 2 90 Choose Options and Sampler to use Ez Do you want to keep the Options and Sampler defined tn the procedure Cyclic voltammetry galvanostatic Press No to apply the Options and Sampler defined tn current active procedure a Figure 2 90 Choosing the Options and Sampler settings to use for the Cyclic voltammetry galvanostatic procedure 124 Page NOVA User manual Click s to continue The entire Cyclic voltammetry galvanostatic will be added into the procedure editor just after the Cyclic voltammetry potentiostatic procedure see Figure 2 91 The Options and Sampler defined in the Cyclic voltammetry galvanostatic procedure will be used Commands Farameters Links New procedure Remarks axl End status Autolab Pr oignal sampler Time WE
43. 08 PM 6 10 2008 8 09 37 PM 6 10 2008 8 30 23 PM 4 9 2010 4 54 02 PM 6 10 2008 8 27 23 PM 5 5 2009 11 57 13 AM 3 17 2009 5 35 06 PM 4 5 2009 3 42 46 PM Remarks CuS04 0 01 M H2504 0 1 M Ag AgCl R Pb Clo4j2 0 01 M HCIO4 0 1 M 0 RPM HCIO4 0 1 M Fe2 Fe3 NaQH 0 2 M Fe2 Fe3 Reversibility Test LS with in Lead deposition on gold galvanostatic Dummy cell c Factory standard procedure Combination of steps and levels Example forbaseline correction peak sea With Autolab RDE at 1000 RPM Polycrystalline platinum in HCIO4 0 1 M EtOH oxidation on polycrystalline Pt in HC Ferrocene in Acetonitrile Chloroform Use the smooth function Dummy cell c frademo cfr ESPR measurement Au disk Cyclic voltammetry potentiostatic no extr Corrosion rate analysis demo data NOVA User manual Instrument AUT63072 AUT63072 AUT63072 AUTS83072 AUT63072 AUT63072 AUT63072 AUT63072 AUT 63072 AUT63072 AUT63072 LIAUT 70530 W3IAUT 70530 WIAUT 70530 Instrument description Demonstration data Demonstration data Demonstration data Demonstration data Demonstration data Demonstration data Demonstration data Demonstration data Demonstration data Demonstration data Demonstration data Imported demonstration data Imported demonstration data Imported demonstration data Imported demonstration data Demonstration data Imported demonstration data Demonstration data Demonstration data Imported demonstration data
44. 1 Potential WE 1 Current Time and Index and the X Y and Z of the i vs E command Using a link it is possible to plot any combination of the available electrochemical Signals in the measurement view It is also possible to create more than one plot in the measurement view Click the LSV staircase command This triggers the quick access toolbar to appear see Figure 2 78 Autolab contral mm E Set potential 0 000 Fotential v 0 000 set cell On m Optimize current range z E Repestfor each value 00E 01A80E 0 Taane NE _ Number of repetitions G a nl Parameter link monn LSV staircase 0 000 1 000 Custom Start potential Cy 0 000 IvsE stop potential 0 1 000 ivet step potential v 0 00244 l Scan rate v s 0 050000 Log i vs E Estimated number of points qaz Logi vs Logt Interval time s 0 046600 E vsi oignal sampler Time WE Options 1 Options Evst N ES Fotential applied lt array Cy E vs Logi Time lt arrary gt E E vs Log t WE Current lt array gt Ap WE Potential array Cv Index Array B ivs E aaa ks Fotential applied 0 ve WEC Current 4 Z Time 5 show during measurement es m Measurement plot number 1 m set potential 0 000 Viait time 3 5 lt gt l Sat cell oti lt gt Figure 2 78 The quick access toolbar can be used to add plots to the measurement command il Note The list of plots shown in the quick access toolbar depends
45. 8 1 2 FFT Smoothing The FFT smoothing technique can be used to remove a specific frequency or frequency range from a data set in order to attenuate the influence of the selected frequency or frequency range and improve the signal to noise ratio In order to identify the different frequency components present in a given data set the FFT smooth function first transposes the source data from the time domain into the frequency domain by Fourier transformation The FFT smooth method can be used with four different filtering strategies e Low pass all the contributions from frequencies higher than the user selected cutoff frequency are rejected This method can be used to remove high frequency noise from a measurement e High pass all the contributions from frequencies lower than the user selected cutoff frequency are rejected This method can be used to remove low frequency noise from a measurement 227 NOVA User manual e Band pass only the contributions from frequencies within a user defined frequency range are kept All frequencies that fall outside of the user defined range are rejected e Band stop all the contributions from frequencies within a user defined frequency range are rejected Only the frequencies that fall outside of the user defined range are kept The type of FFT smoothing used depends on the noise characteristics in the measurement Double click on the demo file Demo 15 UME LSV entry of the demo data
46. A new plot showing the current vs time recorded during this experiment will be added to the data set Click this new plot to display the plot in the analysis view see Figure 4 159 Demo 19 Cyclic voltammetry Fe2 Fe3 0 0012 Cv staircase H ivsE 0 001 H ji vst N 0 0008 0 0006 0 0004 0 0002 0 0002 WE 1 Current A 0 0004 0 0006 0 0008 0 001 10 20 30 40 50 60 Time 5 Figure 4 159 The i vs t plot added to the data set To calculate the derivative of current vs time right click the i vs t item in the data explorer and select the Derivative tool from the Add Analysis menu see Figure 4 160 262 Page Demo 13 Cyclic voltammetry Fee Fes C staircase H ivs E l Plot Options Properties Copy Visible Plot s to Shaw All Plots Hide All Plots F Add Analysis NOVA User manual Smooth Baseline Correction Peak search Regression Save in My commands Delete Derivative X Integrate FFT Analysis Corrosion Rate Remove all from View Figure 4 160 Adding the Derivative tool to the i vs t plot A new item called Derivative will be added to the data set in the data explorer frame below the vs t plot see Figure 4 161 An additional plot called Derivative plot is automatically added to the Derivative analysis item ai Demo 149 Cyclic voltammetry Fee Fest a C staircase Ae ivs E Iw s t a Derivate H Derivat
47. AFrequency Control Autolab RDE Switch Autolab RDE off Figure 2 18 Inserting a Set potential command in the procedure Pay attention to the mouse pointer when the command is dragged on the procedure editor Depending on the type of command and the location in the procedure editor the mouse pointer can have three different shapes c gt Add command the command can be added at the pointer location Insert command the command can be inserted at the pointer P location All commands located below this position will be shifted downwards co 4 D Error the pointer location is not valid for the selected command 19 Smallest possible value 1 33 ms 67 NOVA User manual Note The drag amp drop action described in the last paragraph is a important part of the procedure editing process While the final sections of this chapter will cover this topic in more detail it is important to understand that the drag amp drop action is the most common user interaction in the procedure editor environment Special attention has been given to building an nte igent drag amp drop interface Nova will only allow to drop commands in places where these commands can in fact be dropped Repeat the drag and drop movement to add a Record signals gt 1 ms command under the newly added Set potentia command see Figure 2 19 File View Profile Run Tools Help Dag SS ie eo eG Eh Te ca Commands Co
48. Data Merge Data AFA S Ae ss Ld Set Active Procedure Propertes Store in Repository Show in Windows Explorer Figure 4 19 Right click anywhere to import a data file To import a data file right click anywhere in the database frame and select the Import data option from the context menu see Figure 4 20 arg Import data S Shared DataBases Demo Database 9 SearchDemo Database Organize New folder TF gt k Favorites i Name Date modified Type S Demo 01 C opper deposition 31 1 2013 09 54 NOX File gt I Libraries Demo 02 Lead deposition EQCM 31 1 2013 09 54 NOX File Demo 03 Bipotentiostat measurement 31 1 2015 09 54 NOX File b amp Hom egroup Demo 04 Hydrodynamic linear sweep 31 1 2013 09 54 NOX File me Demo 05 Fe ll Fe ll on pePt 31 1 2013 09 54 MOX File y File name NOX Files NOVA 1 3 or late Figure 4 20 The dialog shown during the importing of data files 165 Page NOVA User manual It is possible to import multiple files at the same time although an individual name and location must be specified for each file f Warning NOVA 1 10 is compatible with data measured with previous versions of NOVA Data and procedures from previous versions can be directly imported in the current version of NOVA A conversion tool which can be used to convert data from the previous versions to the 1 10 format is available Refer
49. Demo 03 Bipotentiostat measure 2 20 2007 3 37 48 PM 0 RPM HCIO4 0 1 M D b f Demo 04 Hydrodynamic linear sw 3 4 2009 11 21 58 AM Fe2 Fe3 NaQH0 2M atabase frame Demo 05 Fe ll Fe ll on pcPt 6 10 2008 1 27 46 PM Fe2 Fe3 Reversibility Test LSY with increasing Demo 06 Galvanostatic CV 3 26 2007 3 32 01 PM Lead deposition on gold galvanostatic Dema N7 Hinh sneed chrann met 54262009 4 36 33 Phd Dumra call io y S Demo 01 Copper deposition toem AY i x a a CY staircase i i vsE 0 0015 ainal Expressi Ae X Potential applied Potential applied Ag Y WE 1 Current scan Ag Z Time L 0001 WE 1 Current Ec Time WE 1 Potential O 0 0005 Index z lt gt 0 0 0005 0 0 5 1 Potential applied W User log message Time Date Command A i Autolab USB connected AUT40034 5 24 11 PM 2 4 2013 p Start i Autolab initialization finished u3AUT70530 9 11 06 AM 2 5 2013 Autolab initialization finished U3AUT 70530 9 20 13 AM 2 5 2013 amp Autolab USB connection lost AUT 40034 10 38 17 9 2 5 2013 v Hardware based Basic User defined _ Figure 4 4 The contents of the database are displayed in the database frame in the analysis view The demonstration database contains 20 data sets logged by Procedure Name Time stamp Remarks Instrument serial number and Instrument description The displayed date corresponds to the time stamp of the experiment The data sets can be sorted ascendi
50. E AC vs t i AC vs t and Lissajous see Figure 4 170 268 Page NOVA User manual 100 gt B S Demo 16 FRA impedance E FRA measurement potentiostatic a FRA frequency scan 80 pa 1 FRA frequency scan 10 0 kHz 5 FRA single frequency 60 H E AC vst H i AC vs t N _ Lissajous 2 FRA frequency scan 7 91 kHz 3 FRA frequency scan 6 25 kHz B 4 FRA frequency scan 4 94 kHz 5 FRA frequency scan 3 91 kHz z 6 FRA frequency scan 3 09 kHz FRA frequency scan 2 44 kHz B 6 FRA frequency scan 1 93 kHz 9 FRA frequency scan 1 53 kHz S 10 FRA frequency scan 1 21 kHz 11 FRA frequency scan 954 Hz B 12 FRA frequency scan 754 Hz 8 13 FRA frequency scan 596 Hz B 14 FRA frequency scan 471 Hz B 15 FRA frequency scan 373 Hz 8 16 FRA frequency scan 295 Hz 100 fs pa N 0 0 0005 0 001 0 0015 0 002 0 0025 0 003 requency scan z B 19 FRA frequency scan 146 Hz ad Mies clelniteI ES W 40 AAi NIAYA A A I ho M fs Potential resolution oO am I oO E P P P 0 0 0 0 0 0 E BH Figure 4 170 The raw recorded values are available for each individual frequency To use the FFT Analysis tool right click the E AC vs t plot in the data explorer frame and from the context menu select the FFT Analysis tool see Figure 4 171 Demo 16 FRA impedance a FRA measurement po
51. E vs t plot and select the Create Windower from X axis option from the context menu see Figure 4 250 A windower will be added to the dataset see Figure 4 251 This windower automatically uses the signal plotted on the X axis as the Source and the minimum and maximum of the X axis scale as the beginning and end of the windower respectively 319 Page NOVA User manual B Demo 06 Galvanostatic CV B Cy staircase galvanostatic Gro Evst Ne X Time We Ay Y WE 1 Potential ioe Z Current ba fah acre lE gt ae eee E E 1 4 G L A W s 1 0 8 Signal Expression Current applied A Index Scan Time S WE 1 Potential Figure 4 251 A new windower is added to the data 320 Page Index 2 2D plot 168 3 3D plot 184 185 3D plot rotation 185 A Abort measurement 1 1 Add commands 76 Add link 81 84 Add plot 179 Adding commands 64 Advanced procedure editing 90 122 Analog to digital conversion 21 Analysis view 10 15 155 Anodic branch 273 Anodic charge 153 Anodic stripping 234 Apply to selected 199 Autolab control 97 Autolab Control 97 Autolab Control Tabs 98 Autolab Display 47 149 Autolab procedures 53 119 Automatic current ranging 24 56 110 111 Automatic integration time 24 Automatic peak search 194 240 243 244 Automatic scaling 216 Auxiliary signal 127 Averaging 19 Axes Coupling 216 Axis labels 169 214 Axis location
52. File View Profile Run Tools Help he Shs St pn PIT S eo ee Gh co ow Commands Procedures Commands Parameters Links Autolab 3 z Remarks aa EEs OY clic voltammetry potentiostatic h Cyclic voltammetry galvanostatic Snc Daue AUNAN Zz yg i signal sampler Time WE 1 Current a t Cyclic voltammetry current integration Bar Options No Options ca e Linear sweep voltammetry potentiostatic NEWER ALT 40008 i Linear sweep voltammetry galvanostatic mr ee Pod fogs Instrument description gt Linear polarization eye m Chrono amperometry At gt 1 ms F Hydrodynamic linear sweep A E T i Chrono potentiometry At gt 1 ms Figure 2 87 Dragging and dropping the Autolab Cyclic voltammetry potentiostatic procedure into the procedure editor 122 Page NOVA User manual When the mouse button is released a message will be displayed prompting you to choose which Options and Sampler settings to use in the new procedure see Figure 2 88 Choose Options and Sampler to use Do you want to keep the Options and Sampler defined tn the procedure Cyclic voltammetry potentostatic Press No to apply the Options and Sampler defined in current active procedure Yes Na Cancel Figure 2 88 Choosing the Options and Sampler settings to use for the Cyclic voltammetry potentiostatic The following choices are available e Yes the Cyclic voltammetry potentiostati
53. The data provided in the Demo 20 data file To use the corrosion rate analysis tool on this data set right click the i vs E item in the data explorer frame and select the Corrosion Rate from the Add analysis context menu see Figure 4 175 34 This data set is an imported GPES file 271 NOVA User manual 1 a Demo 20 iron screw in seawater a Import GPES data H ws E Plot Options Properties Add Analysis Smooth Copy Visible Plot s to gt Baseline Correction gt Show All Plots Peak search Hide All Plots Regression Save in My commands Derivative Delete Integrate F FFT Analysis Remove all from View aa Corrosion Rate Corrosion rate tafel slope X Corrosion rate fit Figure 4 175 The Corrosion Rate analysis tool can be added to the data through the right click menu Two different corrosion rate tools are available from the context menu e Corrosion rate Tafel slope this tool is used to calculate the Tafel slope and the determination of the exchange current density e Corrosion rate fit this tool can be used to perform a calculation similar to that of the Tafel slope tool Additionally the data is fitted using the Butler Volmer equation 2 303 corr 2 303 corr a Cc l Icorr e Where ior IS the corrosion current Ecorr is the corrosion potential b and b are the anodic and cathodic Tafel constants respectively 4 8 1 9 1 Corrosion rate Tafel slope When the Tafel slo
54. The first one is labeled Potential applied while the other is labeled WE 1 Potential The Potential applied signal contains the values of the potential set by the software during the measurement while the WE 1 Potential signal shows the values of the potential recorded during the experiment Using the data grid it is possible to export the measured data points to other software packages for data analysis Excel Origin SigmaPlot This can be done by right clicking the data grid and by choosing the Export to ASCII file see Figure 4 205 290 Page Potentialapplied WE 1 Potential 0 300781 32935E 7 8 70449 0 302429 amp 0 30487 0 307312 0 30975 Copy Export ASCII data i o Po Form at Cell auto sizing NOVA User manual N WEG Current A Sean Time s Inder h Ctrl C oe ere ermen i ers emes p erm a Taams p eme o 0 514636 0 313965 t ASCII dat x 0 317078 0 317535 apa iii 0 319514 0 319946 EE 0 32196 0 322906 0 324407 0 375017 Column delimiter semicolon ty 0 326043 0 327118 Decimal separator w peace Bee File mode Overwrite w 0 331726 0 334167 0 336604 0 331515 T l 0 335205 Write column headers Hut 0 336334 5 lse Excel setings a Figure 4 205 Exporting the data to ASCII 4 10 The Calculate signal tool The analysis view comes with a Calculate signal tool that can be used to ca
55. User manual as well as the Getting started Because of the large number of possibilities provided by this application it is not possible to include the information required to solve each individual use case A number of typical situations are explained using stand alone tutorials refer to the Help menu Tutorials These tutorials provide practical examples In case of missing information do not hesitate to contact Metrohm Autolab at the dedicated nova metrohm autolab com email address 9 Page NOVA User manual 1 2 Working with NOVA This section briefly describes some features of the NOVA user interface More details will be provided in the next chapters on procedure setup data measurement and data analysis 1 2 1 The toolbar buttons Clicking a specific button in the toolbar can perform most of the NOVA operations Figure 1 3 shows an overview of the NOVA toolbar and its buttons be Ss Se ai e e 2B oo Figure 1 3 The NOVA toolbar The toolbar shows a number of buttons some of which might be grayed out in which case the attached instruction cannot be performed or highlighted which indicates a persistent state of NOVA This section provides an overview of the toolbar buttons New Procedure clears the procedure editor frame 4 Save Procedure saves the currently edited procedure in the database Print Procedure prints the currently edited procedure on the default printer Setup view switc
56. already be started at this point it is important to consider the options to be used during the experiment For this measurement the Automatic current ranging option will be used Click the button located on the Options line of the procedure editor to open the Automatic current ranging window see Figure 2 71 110 NOVA User manual Commands Farameters Links New procedure Remarks zaj End status Autolab wal signal sampler Time WE Current ma Mo Options Instrument UJAL T0530 Lae amp Edit Options 0 Automatic Current Ranging Cutoff Autolab control Automatic Integration Time Highest current range 10 mA Lowest current range Lowest current range select the lowest current range for automatic current ranging JK Cancel Figure 2 71 Accessing the Automatic current ranging options Check the WE 1 checkbox to activate the automatic current ranging option for the working electrode and set the highest and lowest current ranges to 10 mA and 1 pA respectively see Figure 2 71 Click the button to close the Automatic current ranging window You will be prompted to define for which measurement commands in this procedure you want to use this option through the Preview changes window There are two commands in this procedure that can use the automatic current ranging options see Figure 2 72 Since these options are intended to be used in
57. bar of NOVA in the lower right corner of the screen Figure 1 26 shows that the Intermediate profile and the Hardware based profiles are currently active User log message Time Date Command i Autolab USB connected AUT 72527 8 42 10 AM 2 1 2012 gt Start Ready Hardware based Intermediate Figure 1 26 The active profile or combination of profiles is indicated in the status bar of NOVA 1 6 1 1 Level based All the commands and the procedures in NOVA have been tagged with three levels basic intermediate and advanced When the basic profile is active only a few simple commands are shown when the advance profile is active all the commands are shown see Figure 1 27 32 Favorite commands Control F Measurement general Timed procedure Autolab control Set potential Get current Set cell Wait tire 3 Optimize current range OCP determination set reference potential Control Autolab RDE Switch Autolab RDE off NOVA User manual Favorite commands G Contra H Metrohm devices H External devices Si Measurement general Timed procedure Autolab control Set potential Set current Set cell Wait tire 3 e Optimize current range OCP determination e set reference potential e Interrupt measurement Hnterrupt measurement high speed Set BIPOT ARRAY potential Set pH measurement temperature Reset EQCM AFrequency Control Autolab RDE
58. corr Obs the observed experimental corrosion potential in Volts 3 See A J Bard and L R Faulkner Electrochemical Methods Fundamentals and Application 2 Edition Wiley NY Chapter 3 R Baboian Electrochemical Techniques for Corrosion Engineering NACE C H A Brett and A M O Brett Electrochemistry Principles Methods and Applications Oxford Science Publications D C Silverman Practical Corrosion Prediction Using Electrochemical Techniques Uhlig s Corrosion Handbook 2 Edition 279 NOVA User manual e jcorr and icorr the exchange current density and exchange current calculated from fitting of the Butler Volmer equation to the experimental data in A cm and A respectively e Corrosion rate the estimated corrosion rate of the material calculated from the intercept on the Tafel plot in mm year e Polarization resistance the estimated value of the polarization resistance calculated from fitting algorithm e E Begin E End the voltage limits corresponding to the measurement e 7 the squared sum of the difference between the data points of the fit and the experimental data points e Iterations the number of iteration used during the fitting of the data The results of both the Tafel slope analysis and the corrosion rate analysis are stored in the data grid 4 8 2 Data set analysis tools The data set analysis tools can be added to a complete data set in the analysis view using the right click men
59. demo database contains four linear sweep voltammograms in which four different scan rates were used This measurement is a typical reversible K Fe CN s K3Fe CN s reaction recorded using a polycrystalline platinum electrode in 0 2 M NaOH solution Fe Fe 0 05 M The reference electrode was a Ag AgCl KCI Sat d and the counter electrode was a platinum rod Load the Demo 05 data set into the data explorer frame You will notice that the data set contains four different entries see Figure 4 60 Demo 05 Fell Fe lll on port OCP determination ok OCP value 0 243 E 1 Value 0 01 LS staircase H IVSE i Peak search 2 Value 0 02 e LSY staircase H ivsE ie e Peak search 3 Value 0 05 BS LSY staircase d ivsE i Peak search 4 Value 0 1 H LSY staircase ivs E ia e Peak search Figure 4 60 The Demo 05 data set This data set was obtained using the Repeat for each value command with four values used in procedure for the scan rate of the LSV staircase The first LSV was obtained with a scan rate of 0 01 V s the next LSV was recorded with a scan rate of 0 020 V s and so on 193 NOVA User manual The procedure used to measure the experimental data contains an automatic peak search command Therefore each entry of the data set has a peak search analysis item Hold the CTRL key on the keyboard and click each individual entry of the data set to create an
60. four peaks are visible in the data set The last peak located around O V does not have a linear baseline The baseline fit tool can therefore be used to correct the data for this non linearity To correct the data using a polynomial baseline fit right click the i vs E plot in the data explorer frame and from the context menu select the Add analysis Baseline correction Polynomial fixed order see Figure 4 117 Demo 10 Differential pulse measurement Differential pulse H bi vs E Plot Options Properties Add Analysis j Smooth gt My comm ands Baseline Correction Polynomial fixed order Copy Visible Plot s to Peak search Polynomial maximum order N Show All Plots Regression Exponential Hide All Plots Derivative Save in My commands Integrate Delete FFT Analysis Corrosion Rate xo Remove all from View Figure 4 117 Adding a baseline correction to the data 234 Pa ge NOVA User manual A new item called Polynomial fixed order will be added to the data set in the data explorer frame below the vs E plot see Figure 4 118 Demo 10 Differential pulse measurement Differential pulse Hai vs E H Polynomial fixed order Figure 4 118 The newly added Polynomial fit fixed order analysis item Click the Polynomial fixed order analysis item The mouse pointer will change to a cross and a new area will be displayed on the right hand side of the plot see Figure 4 11
61. frame As an example a dedicated command to set the Autolab to galvanostic mode and set the current range to 10 mA will be created All instrumental settings are defined using the Auto ab contro command Using the drag and drop method add a Autolab contro command to the empty procedure see Figure 2 99 Commands Parameters Links New procedure Remarks End status Autolab oignal sampler Time WWE 1 Current Options No Options Instrument ALT 40034 Instrument description Autolab control m Figure 2 99 Adding a Autolab control command Dan DanA 1 CGA Ww ku oy i NOVA User manual Click the button to open the Autolab control editor window as shown in Figure 2 99 In the Autolab control window adjust the settings on the main potentiostat galvanostat section see Figure 2 100 Rave Autolab control Oo PGSTAT101 A Basic nis cell loft Integrator Mode Galvanostatic v a Summary Current range 1mA v Bandwidth IR compensation v Advanced Figure 2 100 Adjust the settings in the Auto ab contro command Click the button to close the editor The specified settings will be displayed in the procedure editor see Figure 2 101 Commands Farameters Links New procedure Remarks aaa End status Autolat E oignal sampler Time WWE 1 Current ma potions Mo Options m Instrument ALJ T40034 Instrument description Autolab control WE Mode halvanostatic WE Current range 1
62. intervention either when the experiment is finished or if the measurement is interrupted Using a database for data storage offers four major advantages compared to a file based storage system Everything is stored in a single structured folder Making backups of experimental data becomes very easy Filters allow fast recovery of experimental data The database provides a repository for easy data restoration ae i A database manager is provided in NOVA and it can be accessed by clicking on the Tools menu and clicking the Database Manager option see Figure 1 21 File View Profile Run Tools Help DD kee S a ee p Options E E co ca J Database Manager E1 Check Procedure Alt Fl R Hardware Setup pH Calibration Figure 1 21 Accessing the Database Manager The database management window will appear displaying the path for four different pre defined databases see Figure 1 22 Each database is located in a folder on the computer 28 Procedures My procedures Standards Measured data Data analysis Commands My Commands Circuits Circuits NOVA User manual Database management CAUsers UserDocuments My Documents My Procedures 1 10 Pracedures CAUsers UserDocuments My Documents My Procedures 1 10 standard CAUsers UserDocuments My Documents My Procedures 1 10 Novea LAUsers UserDocuments My DocumentsiMy Procedures 1 10 Commands CAUsers UserDocuments My DocumentsihMy Procedures 1 10
63. key on your keyboard to rotate the 3D plot around the Y axis slowly bringing the time axis in plane with your computer screen see Figure 4 50 You can use the CTRL key in combination with the arrow key to rotate the plot faster Press the Page Up and Page Down keys to spin the plot in the X Y plane 185 NOVA User manual UUTIS 0 001 0 0005 U Potentia i E gt Perah ia we 30 pme S Figure 4 50 Rotating the 3D view along the Y axis Alternatively click anywhere on the 3D plot and move the mouse in any direction while holding the mouse button to spin the plot in the direction of your choice see Figure 4 51 Figure 4 51 Moving the 3D plot with the help of the mouse pointer 186 Page NOVA User manual Note Pressing the F4 function or the Home key will restore the plot to its original size and orientation NOVA offers two types of 3D projections to visualize the data By default the perspective projection is selected An alternative orthogonal projection is available see Figure 4 52 Dimensions gt Enable Rotation RE Step through Data Select Dataset fe Grid Background gt Projection gt Orthogonal N Show gt b Perspective Print Preview Data projection on axes Print Copy to Clipboard Copy Data to Clipboard Save Image File Save Image File Custom size Figure 4 52 Plotting the data using the orthogonal projection 187 Pag
64. located after the peak The baseline is defined by clicking on the plot area and While holding the mouse button pressed dragging the mouse across the plot area drawing a straight line The software automatically connects the baseline to the curve at the data point for which the first derivative Is the closest to the slope of drawn baseline see Figure 4 143 251 NOVA User manual AE 7 ae AEN lest Current 4 1E 7 22ER 0 5 J Oe Potential W Figure 4 143 Using the Linear rear tangent baseline search method The base points used to specify the tangent baseline are indicated by the small vertical lines on the plot see Figure 4 143 Use the manual peak search function in combination with the Show coordinated option available from the right click menu see section 4 7 3 This will display the X and Y coordinates of the mouse pointer while the baseline is defined making it easier to fine tune the position of the peak see Figure 4 144 252 Page NOVA User manual AE T 3E 7 2E 7 lest Current 4 N C8 6075E 3 3 2220E 8 1E 7 22ER 0 5 J Oe Potential W Figure 4 144 Fine tuning the markers of the base line using the Show coordinates option in combination with the manual peak search tool It is important to be able to fine tune the base line used in the manual peak search after the search has been performed It is possible to redefine the position of the left and ri
65. mA lt gt Figure 2 101 Settings defined in the Autolab control command are shown in the procedure editor To save the Autolab control command with all the defined settings in the My commands group right click on the Autolab control command and select the Save in My commands option from the context menu see Figure 2 102 130 Page NOVA User manual Commands Farameters Links New procedure Remarks inal End status Autolat zeal signal sampler Time WWE 1 Current m potions Mo Options al Instrument ALT 40034 Instrument description Autolab control WE Mode WE Current range lt gt Enabled save in My commands Delete Cut Copy Faste Hide Figure 2 102 Right click the Autolab control command and select the Save in My commands option Aternatively it is also possible to click the button in the quick access toolbar see Figure 2 103 Commands Parameters Links New procedure Remarks ail End status Autolab oignal sampler Time WEQ Current a Options Bloa Ciatiaeg Ez Instrument Instrument description Autolab control WE Mode WE Current range lt gt Figure 2 103 Click the amp icon in the quick access toolbar to save the Autolab control command A window will be displayed Herein a name for the My command can be specified and remarks can be added This is helpful for bookkeeping purposes in order to identity the command more easily For
66. managing several user defined procedures The tooltip also displays the location of the procedure file 120 Page NOVA User manual 2 5 10 Procedure validation When the procedure is finished the validation tool can be used to check for errors From the Tools menu select the Check Procedure options see Figure 2 84 Tools Options Database Manager Check Procedure Alt F1 Hardware Setup X pH Calibration Figure 2 84 The Check procedure tool is available in the Tools menu Alternatively the keyboard shortcut Alt F1 can also be used NOVA will check the procedure for errors If no errors are detected the No problems found Message will be displayed see Figure 2 85 Validation results 0 The following problems were encountered during validation Messaqe Command U3AUT 0330 OK Cancel Figure 2 85 The No problems found message is displayed when no errors are detected 2 5 11 Running the measurement Figure 2 86 shows the resulting linear sweep voltammograms obtained using this procedure The four curves were recorded on one after the other and are available as a single entry in the database Each curve was obtained for a different scan rate and as the scan rate increases the peak current also increases The curves correspond to the Fe CN Fe CN s gt 0 05 M 0 05 M in 0 2 M NaOH electron transfer on polycrystalline platinum The reference electrode was a Ag AgCl KCI satur
67. of the axes scrolling the mouse wheel up and down zooms in and out on the plot see Figure 4 95 VWE 1 Current A av Potential applied PD 0 02 04 06 03 Figure 4 95 Using the scroll function to zoom in on the 3D plot If the mouse scroll function is used while the mouse pointer is located on top of one of the 3 axes of the plot the axis will expand or contract depending on the scrolling direction see Figure 4 96 0 0015 0 001 O O Q QO na VVE 1 Current A WE 1 Current A Crappie Figure 4 96 Expanding the X axis using the mouse scroll function 221 NOVA User manual Since 3D plots can be displayed in many different ways it might be convenient to set one specific view of the plot as a User defined view To do this right click on the 3D plot and from the Dimensions menu choose the Set as User Dimensions option or use the Shift F12 shortcut After defining the user dimensions you can return to this view at any time by pressing the F12 key Hitting the F4 key will return the 3D plot to the original dimensions 4 8 Data analysis The Analysis view is where the data analysis takes place So far this chapter has illustrated the mechanics of plotting measured data in the data analysis view however no data analysis tools have been explored as of yet This section will cover the available data analysis tools A detailed list of avail
68. on the signals defined in the signal sampler If the WE 1 Potential signal is not sampled the E vs t and the E vs log t plots will not be available see Figure 2 79 116 Page NOVA User manual kha IA AS Custom Custom IVSE TVSE Ivst Ivst Log i vs E Log i vs Logt Evsi Log i vs E Log i vs Log t E vsi Evst E vs Log i E vs Log t E vs Log i Figure 2 79 The list of plots shown in the drop down list depends on the signal sampler settings left WE 1 Potential sampled right WE 1 Potential not sampled Click the button in this toolbar to display a list of available plots in a drop down list and select the E vs t plot to add it to the LSV staircase command The vs t will be added to the LSV staircase command and the X and Y inputs of the plot will linked automatically to the signals provided by the command see Figure 2 80 Autolab control zz Set potential 0 000 set cell On m Optimize current range a fl Repeatfor each value 0 05 0 14005 0 29505 0 5 Number of repetitions 4 Parameter link 0 05 E LSY staircase 0 000 1 000 0 0500000 start potential v 0 000 stop potential v4 1 000 Step potential w 0 00244 ocan rate v s U 0500000 Estimated number of points die Interval time 3 0 040000 Signal sampler Time WE Potential WECQ Current a Options 1 Options ma Fotential applied lt aray gt 0 Time lt array gt 5 WEN Current lt arra
69. optimized Click the button located on the Signal sampler line of the procedure editor to open the Sampler editor window Click the WE 1 Potential check box to add the potential to the signal sampler see Figure 2 74 Commands Parameters Links New procedure Remarks End status Autolab Time WWE 1 Current EJ Options 1 Options d Instrument LALIT 0530 Instrument description i Fa Edit Sampler Signal sample Optimized Sampler configuration d WE 1 Current Sampler L WE 1 Potential aN Segment WE 1 Power i WET Potential WE Resistance C E segment Optimized WE 1 Charge E WE Current External 1 External 1 Hf dig Integrator 1 Charge 4 Integrator l Integrated Current Time Sample alternating Figure 2 74 Adding the WE 1 Potential to the sampler Click the button to close the Sampler editor window Again NOVA will prompt you to choose for which measurement commands you want to use this sampler through the Preview changes window Figure 2 75 Select all the measurement command and press the button 2 Please refer to Chapter 1 of this User Manual for more information on the different sampling Strategies in Nova 113 NOVA User manual Preview changes Sampler Apply sampler settings to Optimize current ranqe LS staircase Select all Select none Invert selection a Figure 2 75 Choosing the measurement commands f
70. order of a polynomial regression this parameter is only available when using the polynomial regression e Number of significant digits Defines the number of significant digits used in the Analysis results frame e Direction from All Forward and Reverse All will apply the regression calculation to the whole data set in the case of a cyclic voltammogram both the positive going sweep and the negative going sweep will be fitted Forward will only apply the calculation to the points from the positive going scan while Reverse will apply the fit only to the points from the negative going scan The linear regression confirms the linear relationship between the square root of the angular frequency V l dnd the anodic limiting current The details of the linear regression are displayed in the data explorer frame see Figure 4 153 Demo 04 Aydrodynamic Lov with increasing rotation Control Autolab RDE il 2 Value 831 92 l 39 Value 1247 9 a 4 Yealue 1 479 H i 5 Value 2331 9 H Sl 6 Value 3000 8 S Hydrodynamic i vs ft H Levich plot A Regression through origin Function 4 7106E 05 0 00015606x ven Correlation coefficient 0 99995 2 van a 4 1106E 5 _ b 0 0001 56064 Figure 4 153 The results of the linear regression are displayed in the data explorer The automatic regression tool does not extend the calculated curve beyond the experimental data points For plotting purposes it might howeve
71. potential 6 stop potential v step potential v Parameters Time VWWE 1 Current Mo Options SALUT Z70530 U 000 1 000 0 1000000 0 000 1 000 0 00244 0 1 000000 Estimated number of points 422 Interval time s signal sampler potions Potential applied Time WE Current Index Ive E E Set potential Potential tv ait time 3 lt gt 2 0 024400 Time WWE 1 Current Mo Options lt array Cv lt array gt 5 lt array 4 array gt 0 000 Links mua mua mua o Figure 2 64 Modifying the LSV staircase parameters and creating the link with the preconditioning potential The Repeat for each value command has three default pre defined values 1 2 and 3 To change these values click the button located on Values parameter line see Figure 2 65 104 Page Commands New procedure Remarks End status Autolab signal sampler Options Instrument Instrument description Autolab control set potential Fotential v set cell Optimize current range Repeat for each value Number of repetitions Farameter link E LS staircase start potential v stop potential v step potential 0v scan rate v s Estimated number of points Interval time s signal sampler potions Fotential applied Time WE Current Index Ive E E Set potential Potential v Wattne s 4 gt oe Parameters Time
72. potential value and change it to 0 2 V Press the enter key to confirm the change This will not only change the value of the Stop potential but also of the Start potential and the Set potential value see Figure 2 35 80 NOVA User manual Commands Parameters Links Cyclic voltammetry potentiostatic Remarks Cyclic voltammetry potentiostatic ma End status Autolab m oignal sampler Time WWE 1 Potential vWwE 1 Current m potions 1 Options a Instrument Instrument description Autolab control set potential 0 200 Potential tv set cell On Viait time s 5 Optimize current range LY staircase Start potential 4 Upper vertex potential v Lower vertex potential 6 Stop potential 0 Number of stop crossings p step potential v 0 00244 ocan rate vis 0 1000000 Estimated number of points 1650 Interval time s 0 024400 oignal sampler Time WE 1 Potential vWwE1 Current m Options 1 Options m Fotential applied lt aray Cv Time lt array gt 5 WE Current lt aray 4 ocan lt array gt WEN Potential array Cv Index Array iws E inal set cell Ott m lt gt Figure 2 35 Changing the value of one parameter changes the values of all the other parameters it is linked to Note The link connecting the three potential parameters changes from grey to black This happens whenever one or more parameters or signals that are linked are selected making it easy to ide
73. s Signal sampler Options Potential applied Time WE 1 Current Scan WE 1 Potential Index i ivs E H Set cell te c dl Fh t cw oy Parameters Links Cyclic voltammetry potentiostatic Time YWWE 1 Potential WE 1 Current 1 Options 0 000 0 000 5 1 000 1 000 0 200 2 0 00244 0 1000000 1732 0 024400 Time WWE 1 Potential WE 1 Current a 1 Options lt array gt VY lt array gt s lt array gt A lt array gt lt array gt VY lt array gt Off Figure 2 39 Restoring the link to the stop potential Note Removing an existing link requires only one selected parameter Creating a link on the other hand requires at least two selected parameters Links can also be created using the right click menu or using the CTRL L keyboard shortcut see Figure 2 40 85 Page NOVA User manual Commands Parameters Links Cyclic voltammetry potentiastatic Remarks Cyclic voltammetry potentiastatic End status Autolab oignal sampler Time WE Fotential WET Current m Options 1 Options Instrument Instrument description Autolab control E Set potential 0 000 Fotential v 0 000 set cell On Vat time 3 5 Optimize current range 5 E CY staircase 0 000 1 000 1 000 0 200 2 01000000 O o Start potential 0 0 000 Wpper vertex potential w 1 000 Lower vertex potential x 1 000 Stop potential v 0 200 Number of stop cros
74. settings can be changed e Auto save measured data Yes No this setting defines if the data is saved automatically at the end of a measurement default yes When this option is set to No the user is prompted to specify the Name and the 48 NOVA User manual Remarks for the measurement The option to discard the data is also provided see Figure 1 52 Save measured data Procedure name fe easel te ten lca late a0m 10 a Remarks Cyclic voltammetry potentiostatic NJ Figure 1 52 The Save measured data dialog e Clear measurement plot before start Yes No this setting defines if the measurement must be cleared before each measurement default yes e Hidden warning this option can be used to reset hidden warnings Click the button to reset all hidden warning in the validation dialog see Figure 1 53 Nova options e Graphics 4 Basic 2 Autolab display Auto save measured data No Advanced settings Clear measurement plot before start Yes Hidden warnings Reset Switch to measurement view when stat measuremer Yes Time outin seconds forthe validation dialog 30 e Expert Figure 1 53 Click the _ button to reset the hidden warnings Warnings can be hidden in the validation screen by using the right click menu see Figure 1 54 49 Page NOVA User manual Validation results The following problems were encountered during validation Message Command MACSB000 4 Cell is
75. staircase command has been edited and the WE 2 Current signal has been added to its local sampler Commands Cyclic voltammetry potentiostatic Ee Ee i Remarks End status Autolab signal sampler Options Instrument Instrument description Autolab control set potential set cell Viait time 3 Optimize current range LY staircase start potential v Upper vertex potential v4 Lower vertex potential 6 stop potential v Number of stop crossings step potential v ocan rate v s Estimated number of points Interval time s Parameters Links Cyclic voltammetry potentiostatic Time WE Potential WE Current 1 Options 0 000 Cn p p O 000 1 000 1 000 0 000 2 01000000 0 000 1 000 1 000 0 000 2 0 00244 0 1000000 1650 0 024400 signal sampler Options Potential applied Time WE Current Scan WE Potential WE Current Index Ive E set cell lt gt Time WE Potential WE Current WWwE 1 Current 1 Options array Cv arrary gt 5 array A arrery gt array gt gv array 4 arrayy gt AN A A NA Ott Figure 1 20 The Cyclic voltammetry potentiostatic procedure local sampler defined for the CV staircase command 27 Page NOVA User manual 1 5 Data management Data storage in NOVA is done by means of a user defined database In practice this means that all the measurements are stored in a single folder without user
76. steps Nova has been developed according to the Windows guidelines This means that the user interface of the software works as any other Windows application Selection of multiple items while holding the CTRL key drag amp drop dragging while holding the CTRL key context sensitive menus through the right mouse button and using the mouse wheel are all standard Windows actions which are present in Nova Cl i J Cc YF La NOVA User manual 2 4 2 Removing commands To remove potential steps from this procedure both the set potential and the record signals command have to be removed Hold the CTRL key on the keyboard and click the two commands for the third potential step and press the delete key It is also possible to use the right click button and choose the Delete option from the context menu This will remove both commands from the procedure see Figure 2 12 and Figure 2 13 Commands Parameters Links Chrono amperometry At gt 1 ms Remarks Chrono amperometry At gt 1 ms m End status Autolab m oignal sampler Time WE 1 Potential vWwE1 Current ma Options 1 Options m Instrument LALIT 0530 Instrument description Autolab control set potential 0 000 Set cell On wWalttime s A Record signals gt 1 ms 5 0 07 z set potential Record signals 1 ms a Set potential Record signals 1 ms Set cell lt gt e El Figure 2 12 Removing the third potential step from the proce
77. the contents displayed in NOVA according to one or more profiles The software comes with a number of factory default Profiles but it is possible to create additional user defined profiles More information is provided in Section 1 6 1 e Software options this is used to define more advanced software options like the default plot options the Autolab display and the saving mode of the data files More information is provided in Section 1 6 4 1 6 1 Profiles A profiling scheme is available in NOVA Using this tool it is possible to hide some commands in order to simplify the user interface Depending on the active profile some commands or procedures are hidden from view in order to filter out the most relevant information The profiles can be adjusted using the dedicated Profile menu see Figure 1 25 31 P NOVA User manual File View Profile Run Tools Help Dee S Harchvare basecl v Basic X Intermediate Advanced Corrosion Education Electroanalysis Energy Interfacial electrochemistry Semiconductors Reset user profile Import user profile Export user profile Hicle Ctrl H Unhicle Ctl Shitt H Show all Figure 1 25 The profile menu can be used to set the user profile The profiles are grouped in three sections e Level based mandatory set to Intermediate by default e Hardware based optional e Application based optional The active profile or combination of profiles is indicated in the status
78. the layout of the plot rather than to the data itself The data sets from examples 1 and 2 will be used for illustration purposes 4 7 1 The grid For plotting convenience a gray background grid is displayed on the plot making it easier to find a specific point Using the right click menu the grid can be set to fine coarse or can be turned off see Figure 4 70 Using a fine grid horizontal and vertical lines will be plotted for each major and minor tick on the axes A coarse grid will only plot these lines for the major ticks 0 0016 A Jriainal Di 0001A Original Dimensions F4 foom Back Shitt F4 Esl Enable Zooming Moving Z 0 004 Step through Data ooo0g Select Dataset Grid Fine J E oe Background Coarse Z O 0004 Show LU gt 0 0002 Print Preview Print U 8 Copy to Clipboard 0 0002 Copy Data to Clipboard Save Image File 0 0004 Save Image File Custom size jae 0 0 2 0 4 0 6 0 8 1 Patential applied W Figure 4 70 The grid settings can be adjusted using the right click menu 201 NOVA User manual To avoid overloading the computer a fine grid used in a 3D plot will temporarily be set to a coarse grid during free mouse rotation of the plot 4 7 2 The background All the plots in NOVA have a default background style default style horizontal center fade The background style can be changed by right clicking anywhere on the plot and choosing the required background style from the co
79. this example a name and remarks are provided as shown in Figure 2 104 131 Page NOVA User manual le Save command in My commands ac Ea Name My Galvanostatic Autolab control command Remarks sets the instrumentto GSTAT mode and sets the current range to 10 mA Figure 2 104 Defining a name and remarks for the My command Click the button to close the window This specific version of the Autolab control command will be added to the list of My commands see Figure 2 105 Commands Procedures Favorite commands Control H Metrohm devices g External devices H Measurement general H Measurement cyclic and linear sweep voltammetry H Measurement voltammetric analysis H Measurement chrono methods Data handling G Analysis general G Analysis baseline correction G Analysis corrosion Plots general E My commands ao hy Galvanostatic 4utolab control command PS ets the instrumentta GSTAT mode and sets the current range to 10 m Figure 2 105 The command is displayed in the My commands list Note The remarks are shown in the tooltip 2 7 2 Creating complex My commands The example shown in the previous section shows how to create a single My commana It is also possible to group commands together to create a complex set of commands as a single My command 132 Page NOVA User manual For this purpose a dedicated grouping command calle
80. time domain to frequency domain through the Fast Fourier Transform algorithm assumes that the data outside of the measured time segment Is either zero or that the data in this segment repeats periodically Double click on the demo file Demo 16 FRA impedance entry of the demo database to load it into the data explorer frame This file contains impedance Spectroscopy data points recorded on the Autolab dummy cell c Click the Nyquist Z vs Z plot in the data explorer frame to display the data points from this demo file see Figure 4 169 The data is presented as a Nyquist plot but it can also be plotted as a Bode plot Bode modulus and Bode phase plots are available 267 Page NOVA User manual Demo 16 FRA impedance El a FRA measurement potentiastatic 700 H a FRA frequency scan EE Nyquist 2 vs 2 H Bode modulus X anis i Bode phase 200 400 A n a Li 100 700 200 200 400 BOO S00 O00 Z c Figure 4 169 The data from the Demo 16 data file Detailed information on impedance spectroscopy measurement can be found in the Impedance spectroscopy tutorial available from the Help Tutorials menu Click the button next to the FRA frequency scan item in the data explorer This item will be expanded and the list of the individual frequencies used during the measurement will be displayed Expand the 7 FRA frequency scan 10 KHz group and the FRA single frequency group to reveal three plots
81. to a single value the first value of the calculated signal Figure 4 214 shows an example of a single value calculation The calculate signal tool is used to determine the maximum value of the current signal The Single value checkbox is checked forcing the calculate signal tool to return a single value H Calculate signal Mame Maximum current single value Unit A ia Expression MAS i Parameters Functions COMPLESSO ARG COMPLEXDIV_IMAG signals Full _ CY staircase Clear OK Cancel Figure 4 214 Using the Single value check box reduces the result of the calculate signal to a single value 297 Page NOVA User manual Single values are very convenient because they can be used as parameters in the procedure editor 4 11 The Build signal tool The calculate signal provided in the analysis view is a convenient tool for create any number of new signals However in some cases it might be necessary to extract measured values from other measurements as well as some of the procedure parameters and use them to create specific plots This can be done using the Build signal tool provided in the analysis view Load the Demo 05 data set into the data explorer frame You will notice that the data set contains four different entries see Figure 4 215 Dero 05 Feidh Fe lll on port B OCP determination hav OCP value 0 243 1 Value 0 01 e LSY staircase H ivs E mm Peak search al
82. tool is already added to the data For illustration purposes delete the Hydrodynamic i vs Vw analysis tool added to this data set by selecting this item in the data explorer frame and pressing the Delete key on the keyboard It is also possible to right click this item and select the delete option from the context menu see Figure 4 196 i 6 Value 3000 Control Autolab RDP LSY staircase H ivs E 5 Hydrodynamic i ws yw H Levich plot H Regression through E Regression Plot Options Properties Add Windower Generate index Adel Plot Show All Plots Hide All Plots Save in My commands bas Delete iy Remove all from View Figure 4 196 Right click the analysis item and select the Delete option from the context menu to remove the data analysis tool from the data set 285 Page NOVA User manual Once the item has been removed right click the data set header in the data explorer frame and select the Hydrodynamic i vs Vw analysis tool from the Add analysis context menu see Figure 4 197 Demo 04 Hydrodynamic LSW with increasing rotation rate E Control Autolab RDE Plot Options S 1 Value 500 ae Properties ee Control Autolab ROE a LSY staircase Refresh bm iveE l B a 2 Value B31 92 Add Plot gt mE Control Autolab RDE Add Analysis gt Hydrodynamic i vs v w ee Show All Plots Calculate charge R E a 3 Value 1247 9 Hide All Plots A
83. 0 0 000 2 0 100000 N start potential 0 U 000 Upper vertex potential i 1 000 Lower vertex potential w 1 000 stop potential v U 000 Number of stop crossings step potential v 0 00244 Scan rate v s 01000000 Estimated number of points 1660 Interval time fs 0 024400 Signal sampler Time WE Potential WWE Current Options 1 Options maj Fotential applied arras v Time array gt 3 WET Current aray gt A Scan lt arrery gt WE Q1 Potential array 2 0V Index lt aman a vs E m set cell tt mj gt Figure 2 6 Revealing the parameters of the cyclic voltammetry procedure and the general structure of a NOVA procedure The highlighted red lines correspond to the electrochemical signals sampled during the measurement 55 Page NOVA User manual A NOVA procedure has a number of components shown in Figure 2 6 56 Title this is the user defined title of the procedure which is located on top of the procedure editor Remarks this field is used to add a general comment to the procedure like experimental conditions reference electrode used temperature concen tration of the supporting electrolyte etc End status Autolab this instruction provides the settings of the instrument which are to be used when the measurement is finished or if the measurement is aborted by the user or by a cutoff condition Signal sampler this part of the procedure defines the electrochemical signals that are s
84. 0 000 1 000 1 000 0 000 2 0 1000000 start potential 0 000 Upper vertex potential v 1 000 Lower vertex potential 6 1 000 Stop potential v Number of stop crossings ee Unlink step potential 0 00244 Hide ocan rate v s 0 100000 Estimated number of points 1650 Interval time s 0 024400 oignal sampler Time WE 1 Potential vWwE1 Current m potions 1 Options m Fotential applied lt array Cv Time lt array 5 WE Current lt array 4 ocan lt arrary gt WE Potential lt array gt Cv Index Array gt iws E inal set cell Ott m lt gt Figure 2 38 Links can also be broken using the right click menu or using the CTRL U keyboard shortcut 2 4 8 3 Creating links To create a link at least two parameters must be selected To select multiple parameters press and hold the CTRL key on the keyboard and click the parameters that have to be linked in the procedure editor frame Note Links between parameters are not only working during the procedure setup but also during the measurement This means that using the links it is possible to setup dynamic procedures in which some parameters depend on experimental conditions encountered during the measurements 84 Page NOVA User manual Restoring the link between the Stop Start and Set potential values can be achieved by selecting the stop potential and either the start potent
85. 0 3 T pa set potential 0 5 Disabled 916 Set potential 0 V Z J ee A 0 1 L sa U 3 0 4 U 5 4 6 5 10 i 14 16 18 20 22 Time s Figure 2 28 The potential profile used during the measurement on the dummy cell a using the original Chrono amperometry procedure top and the modified procedure bottom 75 NOVA User manual As the third potential step in the procedure has been disabled NOVA does not execute it but instead moves to the next command in the procedure which is a Record signals gt 1 ms command The response of the cell is measured at a potential of 0 5 V for another five seconds If the third Set potentia command needs to be reactivated simply right click the command and set it back to Enabled see Figure 2 29 Commands Parameters Links Chrono amperometry At gt 1 ms Remarks Chrono amperometry At gt 1 ms m End status Autolab m oignal sampler Time WE 1 Potential vWE 1 Current ma Options 1 Options m Instrument Instrument description Autolab control set potential 0 000 set cell On m wWalttime s 5 Record signals gt 1 ms 5 0 01 Set potential Psd Enabledl a X me Set cell Save in My commands Sa A Delete A Cut Ctrl xX Copy Ctrl C E Paste Ctrl V Hide Figure 2 29 Right click a disable command to enable it again 2 4 7 Adding extra commands The previous examples focused on adding and remov
86. 003 Ef 1 Current 0 0005 0 001 0 US Potential applied v Figure 4 53 The i vs E plot for Example 2 To view the EQCM 1 AFrequency signal versus the applied potential right click the CV staircase line in the data explorer and choose the AFrequency vs E from the Add Plot context menu see Figure 4 54 Demo Ue Lead deposition ECM CV staircase H ivs E Plot Options Propertes Add Windower Generate index Add Plot an Custom Add Analysis IvsE Show All Plots Ivst Hide All Plots Log i vs E Save in My commands Log i vs Log t Delete E vsi Remove all from View Sedasi AFrequency vs E Figure 4 54 Adding the AFrequency vs E plot to the data set It is also possible to add the AFrequency vs E plot to the CV staircase using the quick access toolbar see Figure 4 55 189 Page NOVA User manual Tare Custom El Demo 02 Lead topos 5 CV staircase H ivs E ivs E Iivst Log i vs E Log i vs Log t E vsi E vs Log i AFrequency vs E N AT Figure 4 55 Adding the AFrequency vs E plot using the quick access toolbar You should have two completely different plots at your disposal shown in Figure 4 56 Demo 02 Lead deposition EQCM S CV staircase 0 0035 i Ae X gtential applied 0 003 Ag Y WE 1 Current oe Z WE 1 Current 0 0025 Ee AFrequency vs E sen As X Potential applied e 0 002 Ae Y EQCM 1 AF
87. 0035 0 A livs E wy X Potential applied 0 003 300 ee Y WE 1 Current hey Z WE 1 Current CICS 400 ee AFrequency vs E mAg X Potential applied a 600 E oo Y EQCM 1 AFrequency a wade 2 Scan fer OLIN 500 0 001 1000 amp D ie 0 0005 1200 lt I z 0 1400 S 0 0005 1600 0 001 1800 0 0015 aouu Potential applied Vv Figure 4 58 Overlaying both cyclic voltammograms In the data explorer frame both the AFrequency vs E and the i vs E plot lines are displayed in bold lettering indicating that both plots are shown in the data view frame However only the latter is ife ifelgess indicating that the i vs E plot is currently active Clicking the AFrequency vs E line will highlight it thus setting it to active 191 Page NOVA User manual To remove a plot from the overlay hold the CTRL key pressed and click the line in bold lettering in the data explorer corresponding to the plot you wish to remove 4 5 Overlays with the Measurement view It is possible to create an overlay of the data shown in the Analysis view and the data points recorded in the Measurement view at any time This feature allows a quick and convenient comparison between measurements Up to four different locations can be used to create the overlay in the Measurement view To add a plot from the Analysis view to any of the four available plots of the Measurement right click the plot in the data explorer fram
88. 013 09 54 Libraries Demo 02 Lead deposition EOCM 31 1 2013 09 4 NOX File Demo 03 Bipotentiostat measure 31 1 2013 09 4 NOX File ad Homegroup ie Demo 04 Hydrodynamic linear s 31 1 2013 09 54 MOX File ma Demo 05 Fe il Fe I on pePt 31 1 2013 09 54 MOX File iW Computer Demo 06 Galvanostatic CV 31 1 2013 09 44 NOX File Demo 07 High speed chrono me 31 1 2013 09 53 NOx File Network Demo 08 Chrono methods ADC 31 1 2013 09 54 NOX File 7 lt 149 items litem selected 566 KB Figure 4 22 The file is shown in Windows explorer 4 1 1 7 Deleting files To delete a data file from the database right click the corresponding database entry and select the Delete Data option from the context menu see Figure 4 23 Procedure name f Time stamp Remarks Demo 0l Cope meme US 04 O01 MM AesO4 0 1 MM Ag AgCl Ref KCI 5 Demo 02 Lead 2tActive Procedure Ph Clo4y 0 01 M HCIO4 OT M Demo 03 Bipo Propertes O RPM HCIO4 0 1 M Demo 04 Hydr mmm e Ulli ll eel Demo 05 Feil store in Repository Fe2 Fej Reversibility Test LSV with increasing Demo 06 Gala X1 Delete from Repository Lead deposition on gold galvanostatic Demo 07 High Dummy cell ic Restore from Repository Demo 06 Chro Factory standard procedure Demo 09 Chro Import Data Combination of steps and lewels Demo 10 Differ Example for baseline correction peak search Export Data Delete Data Merge Dat
89. 06 0 0004 WET Current tA 0 0002 0 0002 J 0 1 0 2 0 3 0 4 0 5 Potential applied W Figure 4 67 Resetting the plot options for the 0 1 V s plot 2 2 If the global options are changed again all the plots in the overlay will be displayed using these new options including the 0 1 V s plot 4 6 3 Changing the plot settings in an overlay plot The curves shown in Figure 4 67 are all displayed as the WE 1 Current vs the Potential applied This means that all the curves in the overlay are plotted using the same electrochemical signals If it is required to change the electrochemical signals used to display the curves in the overlay two options are available The first option is to change the electrochemical signals used to display each curve one after the other This is quite time consuming especially for overlays with a large number of plots The second option is to change the electrochemical signals of all of the plots of the overlay by using the Apply to selected option see Figure 4 68 This option can be accessed by right clicking the signal to change and click the small arrow next of the new electrochemical signal to use 199 NOVA User manual g a Demo 05 Felli Fe ill on poPt a OCP determination be OCP value 0 243 1 Value 0 01 LSY staircase EFmivse some Peak search 2 Value 0 02 LSY staircase Grmivse w Peak search 3 Value 0 05 LSY staircas
90. 1 IVSE l i Peak search Figure 4 62 Opening the plot options window for the whole data set Set the plot style to a size 2 red Line plot Click the OK button to confirm the change The four LSV curves will now be displayed using the new plot options see Figure 4 63 0 0012 0 001 0 0008 0 0006 0 0004 WET Current tA ORTO 0 0002 J 0 1 0 2 0 3 0 4 Oke Potential applied W Figure 4 63 The four LSV plots displayed using the new plot options Changing the plot settings of an individual plot is still possible Right click the last LSV staircase of the data set 0 1 V s in the data explorer frame to access the plot options of that particular plot Change the settings to a size 2 blue Combi plot using a size 10 star marker symbol and plotting 1 point out of 40 The overlaid plot should now look like the one displayed in Figure 4 64 195 Page NOVA User manual 0 0012 0 001 0 0008 0 0006 0 0004 WET Current tA 0 0002 0 0002 J 0 1 0 2 0 3 0 4 0 5 Potential applied W Figure 4 64 Changing the plot options for the linear sweep voltammetry recorded at 0 1 V s 4 6 2 Global options vs Local options Changing the Plot options for the whole data set defines the plot s global options The local options are defined as the plot options for a specific entry of the data set In the example shown in Figure 4 64 the global and local settings are e Global options Red Line p
91. 182 Adding the corrosion rate fit analysis tool to the data set A new item called Corrosion rate fit will be added to the data set in the data explorer frame see Figure 4 183 E S Demo 20 lron screw in seawater Import GPES data ivs E Corrosion rate fit Figure 4 183 The corrosion rate fit is added to the data set Click the corrosion rate data analysis item to display the data from the data set in logarithmic scaling see Figure 4 184 276 Demo 20 Iron screw in seawater Import GPES data H ivs E 1E 5 Corrosion rate fit Current A 0 5 0 4 0 3 Potential Y 0 2 NOVA User manual ALIX Signal Expression Unit Density g cm 7 86 Equivalent weight g mol 27 925 Surface area cm 1 Number of significant digits 5 Reset ooo Figure 4 184 The corrosion rate fit analysis tool automatically displays the experimental data in logarithmic scaling Additionally the control parameters of the corrosion rate fit analysis tool will be displayed on the right hand side of the plot This part of the view allows the definition of parameter for the corrosion rate analysis similarly to the Tafel slope analysis item see Figure 4 185 Density g cm Equivalent weight g mol SUTace area cr Number of significant digits Reset Figure 4 185 The parameters for the corrosion rate fit analysis tool The following parameters are avail
92. 2 O 0002 0 0004 10 Vs 20 25 20 Time s Figure 4 41 Plotting the current vs time in a new graph Each plot ca n be renamed To change the name of a plot from Custom to something else right click the Custom line you want to edit and select the Properties option A small window will be displayed which allows you to edit the name of the plot see Figure 4 42 Demo 01 Copper deposition B CY staircase H A ivs E Ag X Time amp Y Potential applied Ag Z Time B Logi ws E Enter new name amp y X Potential applied Ag Y WE 1 Current Ag Z Time H Custom Ag X Tit Plot Options _ livs NeW Properties bii a OK Cancel Create Windower from X axis s a Add Analysis r Copy Visible Plot s to t Show AIl Plots Hide AIl Plots Save in My commands X Delete X Remove all from View 2 Undo Insert Custom Ctl Z Figure 4 42 Editing the names of the plots Rename the first plot vs tand the third plot to vs t see Figure 4 43 182 Page NOVA User manual Demo 01 Copper deposition CY staircase Bte Ewst Logi vs E efe Potential applied mda Y WE 1 Current Figure 4 43 The edited plot names for Example 1 4 2 9 Saving the changes The changes that have been made to the plots of Example 1 can be saved in the database To save these changes the entry of the database corresponding to the edited data set must be update
93. 2 0 0 2 0 4 0 6 Potential applied W Figure 4 163 The Demo 19 data file Right click the CV staircase item in the data explorer frame and select the i vs t plot from the plot context menu see Figure 4 164 264 Page NOVA User manual S S Demo 19 Cyclic voltammetry Fe2 Fes El A aes ieee Plot Options H ivs E Propertes Add Windower Generate index Add Analysis ivs E Show All Plots Hide All Plots Logi vs E Save in My commands Logli vs Log t Delete E vs E vs Log i Remove all from View Figure 4 164 Adding the i vs t plot to the data set A new plot showing the current vs time recorded during this experiment will be added to the data set Click this new plot to display the plot in the analysis view see Figure 4 165 Demo 19 Cyclic voltammetry Fe2 Fe3 0 0012 Cv staircase H ivsE 0 001 H ji vst N 0 0008 0 0006 0 0004 0 0002 0 0002 WE 1 Current A 0 0004 0 0006 0 0008 0 001 10 20 30 40 50 60 Time 5 Figure 4 165 The i vs t plot added to the data set To calculated the integral of current vs time right click the i vs t item in the data explorer and select the Integrate tool from the Add Analysis menu see Figure 4 166 265 Page NOVA User manual Demo 19 Cyclic voltammetry Fee Fes E CY staircase a iVeE st Plot Options Properties Add Analysts z Smooth Copy Visib
94. 2009 12 14 00 Example forbaseline correction peak sea AUTS3072 Demonstration data Demo 11 Hydrodynamic FRA with OCP determin 4 6 2010 12 23 00 PM With Autolab RDE at 1000 RPM AUT63072 Demonstration data Figure 4 8 The filtered demonstration database The eleven data sets displayed in the filtered database have being obtained with the same instrument as the one used for the Demo 01 Copper deposition entry of the database AUT83072 By using the filtering option described above only the data sets for which the serial numbers are the same are displayed To remove the filter right click the database header and select the Show all option from the context menu see Figure 4 9 This will restore the database to its original content displaying all the data sets Procedure name f Time stamp ooo Damearke Inctument Instrument description Demo 01 Copper deposition 3 15 2007 6 25 27 PM Cu Filter selected dropped on row Demonstration data Demo 02 Lead deposition EQCM 2 4 2009 11 04 15 AM Pb Show all Demonstration data Demo 03 Bipotentiostat measurement PYPt Rin 2 20 2007 3 37 48 PM OF w Demonstration data Demo 04 Hydrodynamic linear sweep voltammetr 3 4 2009 11 21 56 AM Fel Best fit Demonstration data Demo 05 Feil Fe ll on poPt 6 10 2008 1 27 46 PM Fel Best fit all Demonstration data Demo 06 Galvanostatic CY 3 26 2007 3 32 01 PM Lee Finnie Cole Demonstration data Demo 0 High speed chr
95. 219 221 Moving markers 237 Multi Autolab view 10 Multiple plots 140 My commands 128 My commands database 128 My procedures 119 N New database 30 New procedure 10 52 53 Noise filtering 224 Noise reduction 224 Nova strategy 7 Nr of values 107 Number of points in search window 226 243 244 Number of potential steps 61 Number of scans 59 Number of significant digits 243 244 259 273 277 Number of stop crossings 59 O OCP determination 142 147 Open circuit potential 147 Optimize current range 58 101 Optimized 110 113 Optimized signal 20 21 22 Options 53 56 110 113 Origin 203 Origin Axes 216 Original Dimensions 218 Orthogonal projection 187 Overlay 188 191 194 Overlay in measurement view 192 Overload 47 Overrule global plot options 196 P Paste to powerpoint 201 Pause measurement 10 Peak current 194 Peak height 304 Peak search 223 240 NOVA User manual Peak search baseline 245 Peak type 243 Perspective projection 187 Plot background 202 Plot color 172 Plot options 172 Plot overlay 188 Plot properties 182 Plot settings 42 115 194 199 Plot style 172 Plot subtitle 207 Plot title 207 Plotting data 168 PNG 217 Point markers 172 Point plot 169 Polarization resistance 271 Polynomial baseline 235 Polynomial order 259 Polynomial regression 255 Positioning lines 203 Post measurement 109 Post treatment
96. 4 2 7 PIVEN SIS tems taD sensn aE EE ENS Era 176 aP E aE E E E E E V E 178 4 2 9 Saving the CHANGES is aiicnncinsunonceesunseasnscunndetmesenseaosaientdipenaheunpncntanceants 183 4 3 Plotting the data in 3D asicersssenisciccnnssamrsinntratigatsbtinnassinwevabedemcapiebtieanssestanenglenes 184 4 4 Advanced plotting and over layS ccccccccssseecseseeceeeecseeecseseeseeseesnees 188 4 5 Overlays with the Measurement VIQW ccccecceeeeeeeeeeeseeeeeseeeeeneeeeneeees 192 4 6 Data Sets with multiple entries c c ccceccssesecsssseeesseesnseeceeseeseeeesceses 193 4 6 1 Changing the DIOTSSMINGS we dcedessicetodeonresetiedaaenndensndedaaensdamesdaccensenendes 194 4 6 2 Global options vs Local options s nssnneennsninsnnrernnnirnrrsrrrsrrsrrene 196 4 6 3 Changing the plot settings in an overlay plot cece eeeeee ees 199 BT PCE OO CCUG as gates rac nenest cae baeenane sear annateneoassaconsiat oases talus suaectan oeoeeaeouaes 201 AD Me TNS QIN e E A E EE 201 4 7 2 The background sieasssiiworeanssatiedcandoenre sssntnaesnedenceniienccmuaworebnesvenneadoeerssues 202 4 7 3 Adding objects to the plot ascarastsanoimtenazangceoseaiatatwaiaeendbatenasatecdadeptens 202 4 7 4 Stepping through data cccccccessececsseeecseeeesseeesseeeseaseesseserenees 211 A Tom AXES ANAA 8 2 ee eee E EE ee 214 A ONO O O o a e E E ERA 215 4 7 7 2D Specific Options penaevacatscacetomas
97. 7E 08 3 3985E 08 3 6045E 08 1 3144E 08 NOVA User manual The table at the bottom right of the screen displays information for each peak The peak position peak height peak area are listed among other results These results are also available in the data grid see Figure 4 132 Peak Peak Peak Base Base Peak width Peak Peak sum of He position height area start end half height 12 derivatives P 0 037079 1 2413E 7 1 3067E 86 0 13962 0 089874 0 10276 0 045033 3 5521E 6 2 0 16265 1 5951E 7 3 3985E 8 0 06546 0 70012 0 16615 0 050395 3 3002E 6 3 0 10056 1 7930E 7 3 6045E6 65 0 76462 0 011749 0 15401 0 051147 3 85E 6 4 0 11817 1 47 14E 7 1 5144E 8 0 0028982 0 22171 0 10098 0 044652 3 7511E 6 Figure 4 132 The results of the peak search analysis are displayed in the data grid The following results are calculated by the peak search tool Index this is a unique label used to identify the peak in the curve Peak position X axis position of the maximum Y value with respect to the baseline in X units Peak height maximum Y value with respect to the baseline in Y units Peak area the geometric area located between the identified peak and the baseline in units of X Y Base start X axis position of the beginning of the baseline used to locate the peak in X units Base end X axis position of the end of the baseline used to locate the peak in X units Peak width half height the width of the peak in
98. 9 T x JE signal Expression Unit 4 5E 7 Fitted x Corrected Y 4E f Fitted Y 3 5E 7 a b 3E 7 2 5E T 2E 7 1 5E 7 1E 7 l Data selection method Snap to data 5E 8 C Free selection Reset _ VVE 1 6 Current A Polynomial order 1 12 1 0 8 0 6 04 0 2 0 Potential applied V Figure 4 119 Activating the baseline correction tool The area located on the right of the 2D plot is used to set the parameters of the baseline fit Set the Polynomial order to 4 for this example The point selection style field should be set to Snap to data When the Snap to data option is used the software automatically positions the marker on the closets data point on the plot Use the Free selection option to define points not on the curve Using the left mouse button click a total of 5 measured data points in the 2D plot area These points are used to define the points through which the baseline should pass Since a baseline of 4 polynomial order is used a minimum of 5 points are required although more than 5 can be defined Figure 4 120 shows an example of marker location used to calculate the polynomial baseline When the fifth marker is placed the baseline will be calculated and plotted in the 2D plot area see Figure 4 120 235 Page NOVA User manual Ee ass han i ae Et 1 6 Current Ay 156 7 SE 8 1 2 1 0 8 0 6 0 4 0 2 J Potential applied W Figure 4 120
99. 90 109 Potential 20 Potential overload 47 Potential vs SHE 293 296 Potentiostat mode 150 Power supply frequency 21 Pre treatment 60 90 Preview changes 111 113 127 Print plot 217 Print procedure 10 Procedure 56 Procedure browser 52 Procedure editor 52 Procedure parameters 55 57 Procedure progress 141 Procedure sequence 122 Procedure setup 51 Procedure validation 50 121 Procedures 64 Procedures databases 29 Procedures tab 64 Profile menu 12 Project mode 122 PSTAT label 150 Q QCM thickness 188 R Range builder 105 106 Range generator 106 Real time information 139 149 Record signals 60 61 65 67 68 Regression 255 Regression type 258 Remarks 52 56 118 119 120 158 183 Remove background 202 Remove commands 62 Remove link 81 323 NOVA User manual Repeat for each value 102 106 298 302 Repeat loop 92 Repeat n times 92 Rescale plot 218 Reset plot options 197 Residual plot 240 Restore data 161 Reverse 259 Reverse button 149 Reverse scan 149 Reversibility plot 307 Reversible electron transfer 299 Run menu 13 S Sampler 19 20 Sampler editor 113 Sampling rate 67 Sampling time 23 Save Image File 217 Save in My commands 136 Save plot settings 183 Save procedure 10 119 Save to database 183 Save to database button 183 Scaling mode 216 Scan rate 193 302 Scan selector 314 Search mode 258 Second si
100. A User manual To unhide a hidden item right click the item and select the unhide option from the context menu as shown in Figure 1 33 Note It is also possible to hide items using the CTRL H keyboard shortcut and to unhide items using the CTRL SHIFT H keyboard shortcut In the commands browser it is possible to hide single commands from a given group using the same method It is however also possible to completely hide a command group from the browser see Figure 1 34 Commands Procedures H Favorite commands E Control E Metrohm devices External devices External device initialize External device send z External device receive be External device clase External device specia H Measurement general Hide E Measurement cyclic and linear sweep vigammetr B Measurement voltammetric analysis H Measurement chrono methods H Measurement impedance Data handling Analysis general Analysis baseline correction d Analysis corrosion Analysis impedance ai Flots general Flots impedance g My commands H Favorite commands H Control H Metrohm devices B External devices External d Hide all i External d Extemald 4 Sort ascending External Z4 Sort descending o ie External d F Measuremer Original order E Measurement cyclic and linear sweep voltammetry H Measurement woltammetric analysis H Measurement chrono methods H Measurement I
101. AM 5 25 2009 4 36 33 PM 3 26 2007 3 32 01 PM 6 10 2008 1 27 46 PM 3 4 2009 11 21 58 AM 2 20 2007 3 37 48 PM 2 4 2009 11 04 15 AM 3 15 2007 6 25 27 PM Remarks Corrosion rate analysis demo data Cyclic voltammetry potentiostatic no extr ESPR measurement Au disk frademo cfr Dummy cell c Use the smooth function Ferrocene in Acetonitrile Chloroform EtOH oxidation on polycrystalline Pt in HC Polycrystalline platinum in HCIO4 0 1 M With Autolab RDE at 1000 RPM Example forbaseline correction peak sea Combination of steps and levels Factory standard procedure Dummy cell c Lead deposition on gold galvanostatic Fe2 Fe3 Reversibility Test LSW with in Fe2 Fe3 NaOH 0 2 M 0 RPM HCIO4 0 1 M Pb Clo4j2 0 01 M HCIO4 0 1 M CuS04 0 01 M H2504 0 1 M Ag AgCl R Instrument WIAUT 70530 ySAUT 70530 LIAUT 70530 AUT63072 AUT63072 AUT83072 AUT63072 AUT63072 AUTS3072 AUT63072 AUT63072 AUT63072 AUT63072 AUT63072 Instrument description Imported demonstration data Demonstration data Demonstration data Imported demonstration data Demonstration data Imported demonstration data Imported demonstration data Imported demonstration data Imported demonstration data Demonstration data Demonstration data Demonstration data Demonstration data Demonstration data Demonstration data Demonstration data Demonstration data Demonstration data Demonstration data Demonstration data The data can be so
102. Analysis general G Analysis baseline correction G Analysis corrosion Analysis impedance E Flots general E Flots impedance My commands Figure 2 25 It is possible to manually remove commands from the Favorite group using the right click menu 2 4 6 Enabling Disabling commands An alternative to removing commands from a procedure is disabling the commands This is convenient because it is possible to enable these commands again later if it is necessary without having to use the commands browser Reload the original Chrono amperometry procedure from the Autolab group This procedure has three potential steps but in this example the final potential step will be disabled To disable a command right click the command and deselect the Enabled option In this example disable the third Set potential command see Figure 2 26 730 NOVA User manual Commands Parameters Chrono amperometry At gt 1 ms ol E E E E E Remarks End status Autolab signal sampler Options Instrument Instrument description Autolab control set potential set cell Viait time s Record signals gt 1 ms set potential Set cell lt gt Record siqnals gt 1 ms Set potential Record signals 1 rs Delete A Cut Ctrl x Copy Ctrl C amp Paste Ctrl V Chrono amperometry At gt 1 ms Time WE Potential WE Current 1 Options Save in My commands
103. C1 Current ma Options Mo Options c Instrument ALJ TAQ0QE Instrument description El Cyclic voltammetry potentiostatic H Autolab contral ai Set potential 0 000 H Set cell On eel E at time s z Optimize current range z H CY staircase TORO LOO ICO e S H Set cell Cit lt gt El Cyclic voltammetry galvanastatic H Autolab control ami Set current 0 000E 00 Set cell On E alt time s 5 H CY staircase galvanostatic 0 000E 00 1 000E 03 1 000E 03 D H Set cell Cit lt gt lt gt Figure 2 91 The procedure editor with the two complete procedures Connect dummy cell c and press the start button When the measurement starts the procedure will first execute the complete Cyclic voltammetry potentiostatic procedure using Automatic current ranging When the first part of the measurement is finished the Cyclic voltammetry galvanostatic procedure starts The Autolab control command will switch the potentiostat to galvanostatic mode and set the current range to 1 mA before performing the current scan Figure 2 92 and Figure 2 93 show the measured data on the dummy cell c The first part of the measurement corresponds to the potentiostatic cyclic voltammetry The measurement stops after 47 seconds The second part of the measurement corresponds to the galvanostatic cyclic voltammetry which starts after 55 seconds The time difference between the two measurements stems from the preconditioni
104. Chrono amperometry At gt 1 ms Remarks Chrono amperometry At gt 1 ms m End status Autolak m oignal sampler Time WE 1 Potential vWE1 Current ma Options 1 Options m Instrument ALUT4000S Instrument description H Autolab control z E Set potential 0 000 set cell On m E at time s z Record signals gt 1 ms 5 0 01 Set potential 0 500 Record signals gt 1 ms a 0 01 set potential 0 000 El Record signals gt 1 ms En Duration s A Interval time s il a Estimated number of points z oignal sampler Time WE 1 Potential vwE1 Current ma Options 1 Options aa Corrected time lt array 5 Time lt array 5 WE Fotential lt aray gt Cv WE Current lt array 4 Index lt arrary gt v s t aaa Set cell Cit lt gt Figure 2 20 Editing the parameters for the two added commands In the Record signal gt 1 ms the duration must be longer than the interval time 2 4 4 Cut and Copy Paste commands It is also possible to use the well known cut copy and paste options to duplicate a command or a group of commands already present in the procedure For example to add an additional Set potentia command and an additional Record signals gt 7 ms command to the original Chrono amperometry At gt 1 ms procedure select the last two Set potential and Record signals gt 1 ms and right click the selected commands Select the Copy option from the context menu see Figure 2 21
105. Circuits Cancel Figure 1 22 The database management window with the four default databases The database management window displays the locations of two Procedures databases Standard and User a Measured data database Data a Commands anda Circuits database The User database is the database where all the user defined procedures are stored while the Data database is where all the measured data sets are recorded The Standard database is intended to be used as a second read only database If the path of this database points to a database containing some user defined procedures those procedures will appear under the standard group in the procedure browser frame but will have a read only status like the procedure displayed under the Autolab group in the procedure browser frame In practice any modification of a procedure from the Standard group can only be saved in the My Procedures group 1 The Commands database is used to store user defined NOVA commands Please refer to Chapter 2 of this User manual for more information 17 The Circuit database is used to store equivalent circuits used in the fitting and simulation of electrochemical impedance spectroscopy data Please refer to the impedance spectroscopy tutorial for more information 29 NOVA User manual Nova gives the user the possibility to create any number of databases A convenient way to manage your experiments is to create a new database eve
106. Demo 15 UME Lo ImportGPES data livs E H FFT Smooth H FFT smoothed plot Figure 4 108 The newly added FFT Smooth tool Click the FFT Smooth item A frequency domain plot will be shown On the X axis the frequency contributions are shown in Hz On the Y axis the intensity is shown in arbitrary units see Figure 4 109 BY st x Signal Expression Unit 1E 11 1E 12 D 1a z a 1E 13 Filter type Low pass h F 1E 14 requency 1 Frequency 2 1E 15 0 500 1000 1500 2000 Frequency Hz Figure 4 109 The frequency domain plot showing the amplitude vs frequency A new area will be displayed on the right hand side of the plot This part of the view allows the definition of settings used in the FFT Smooth tool see Figure 4 110 229 Page NOVA User manual Filter type Low pass A Frequency 1 Frequency 2 Figure 4 110 The FFT Smooth options 4 8 1 2 1 Low pass and high pass filtering Using the Filter tyoe drop down box one of the four filter types can be selected The default is the Low pass filter For the low and high pass filters a single cutoff frequency can be manually defined in the Frequency 1 field Alternatively the mouse pointer can be used to select the cutoff frequency in case of the high or low pass filter Click the frequency domain plot at the required frequency to specify the cutoff frequency A line will be drawn on the plot to indicate the position of the freque
107. E Copy Data to Clipboard 0 0004 Save Image File Save Image File Custom size s m 0 6 iR Potential applied V Figure 4 83 Selecting the stepping through data option This will change the mouse pointer to a hand Click anywhere on the displayed plot A tooltip label will appear together with an arrow locating the point you just clicked and displaying some information about the point index of the point in the data set X Y and Z coordinates of the plot see Figure 4 84 The information shown in the tooltip depends on the signals used for plotting the experimental data In the example shown in Figure 4 84 the X Y and Z signals are Potential applied WE 1 Current and Time respectively 211 NOVA User manual 0 0016 0 0014 O 0012 0 001 0 0008 0 0006 0 0004 WELT Current 41 0 0002 731 0 11932 2 6474E 5 26 516 U 0002 0 0004 0 2 0 0 2 0 4 0 6 0 8 Fotential applied W Figure 4 84 Displaying data information using the step through data option Clicking anywhere else on the plot will display the same information for the new point Holding the left and right arrow keys on the keyboard will walk through the whole data set in reverse and forward direction respectively It is also possible to scroll the mouse wheel up or down if available to walk through the data At any time you can press the insert key on the keyboard to add the label and the locating arrow to the plot see Fi
108. Figure 4 30 The axes settings tab NOVA User manual 4 2 6 Plot tab On this tab it is possible to define a title and a subtitle as well as their format It is also possible to define the grid settings and switch the legend on or off see Figure 4 31 Plot Options Data Axes Plot Analysis items Title Font x Arial 2pt stvle Reqular Title Title Sub title Sub title Chart Grid Coarse v _ Show legend Background Horizontal center fade w show origin Apply OK N Cancel Figure 4 31 The plot settings tab 175 NOVA User manual 4 2 7 Analysis items tab This tab defines the plot options used for the graphical data analysis tools All items added to a plot after data analysis like linear regression fit and simulation etc will be displayed using these settings Plot Options Data Axes Plot Analysis tems Analysis items Point style o w Color D Point size l Line size Reset values Apply OK N Cancel Figure 4 32 The analysis items tab The plot options window provides a convenient interface for changing all the available plot settings at the same time It is still possible to change specific plot options by right clicking the corresponding items on the plot directly For example right clicking on a plot axis will display a menu from which some of the options available in the Axes settings tab can be defined see Figure 4 33 176 NOVA User manual Axis S
109. I S Demo 02 Leai set Active Procedure Pb ClO4 2 0 01 M7 HCIO4 0 1 M Dermo 03 Bipa Properties 0 RPM HCIO4 0 1 M Demo 04 Hyd Fee Fea WaQH 0 2 Ml Demo 05 Fell Store in Repository Fe Fe3 Reversibility Test LSW with increasing Demo 06 GaN X1 Delete from Repository Lead deposition on gold galhvanostatic Seine ty yu Restore from Repository evening ee Import Data Export Data Delete Data Merge Data Show in Windows Explorer Figure 4 10 Select the Store in Repository option to create a backup of the database entry The store in repository option adds a copy of the original data set in the database using the backup creation time as the time stamp see Figure 4 11 Procedure name f Time stamp Remarks a Demo 01 Copper deposition lt lt lt PT a Behe PM E 001M eE aR p Demo 01 Copper deposition 0 18 2010 2 39 15 PR CusO4 0 01 M H2504 0 1 M AgfAgCl R Demo Ue Lead deposition EQCI effe009 11 04 15 AM PbCO 0 01 My ACO 0 1 ki Demo 03 Bipotentiostat measurement FYFt Rin 2fe0f200 3 37 48 PM 0 RPM HGIO4 0 1 Ml Demo 04 Hydrodynamic linear sweep voltammetr 3 42009 11 21 58 4h Fed Fes NaQH 0 2 M Demo 05 Feflh Fe lh on pct BAOf2008 1 27 46 PM Feet Fes Reversibility Test LSW with in Demo 0b Galvanostatic CY Jepi 3 32 01 PM Lead deposition on gold galvanostatic Demo 07 High speed chrono methods Fast ADG Sf25f2009 4 36 33 PM Dummy cell ic Demo 08 Chrono methods ADC164 20 st
110. M ACIO4 0 1 Ml Demo 01 Copper deposition Jepe 4 13 49 PM Cus04 0 01 M H2504 0 1 M AgfAgtl Refere Figure 4 16 The merged data is added to the dababase The new file will contain the data from the source data files 163 Page NOVA User manual Note Some Windows versions do not allow saving of data in the C Program Files folder 4 1 1 5 Import and Export data It is also possible to Import additional files into the database or to Export data files from the database as single files with a nox extension Importing and exporting of data Tiles is done through the right click menu To export a data file right click the corresponding entry in the database and select the Export data option from the context menu see Figure 4 17 Remarks _ Time stamp _ CuS04 0 01 Ma Heso4 0 1 M Ag AgCl Ref KCI S moi ieee Te ae ocedure Procedure name Demo 01 Copp J Set ctve Pr Demo 02 Lead Demo 03 Bipot Demo 04 Hyeri Demo 05 Fef Propertes Store in Repository Demo 06 Galia X1 Delete from Repository Demo High Restore from Repository Oemo 08 Chro i Demo 09 Chro Import Data Demo 10 Ditte Export Data xI Delete Data Merge Data Show in Windows Explorer PbiClo4 0 01 MsHCIO4 0 1 M 0 RPM HGO 0 1 M Fe Fea NWaQH 0 2 M Feet fFes Reversibility Test Lo with increasing Lead deposition on gold qalvan
111. My commands database 2 7 4 Using the My command Once a command has been added to the My commands database it can be dragged into the procedure editor as any other command Create a new procedure and drag the My Potentiostatic Preconditioning command into the procedure editor An exact copy of the original command will be added to the procedure see Figure 2 114 Commands Parameters New procedure Remarks End status Autolab signal sampler Time WEI Current Options No Options Instrument ALT 40006 Instrument description Links My Potentiostatic Preconditioning Autolak control set potential 1 200 set cell Or Wat time s S Optimize current range 5 lt gt ee Figure 2 114 Adding a My command into the procedure editor creates a copy of the original command 137 Page NOVA User manual Saving a complete Nested procedure instead of a single command allows you to very quickly group commands This simplifies the procedure building process especially for routine measurements 138 Page 3 The Measurement view NOVA User manual While the procedure is constructed within the setup view the measured data can be observed in real time using the Measurement view To switch this view click the corresponding button in the toolbar or select the measurement view option from the View menu Figure 3 1 File ans File J les 5 a gt a bg du I a Eja a al ee ee View Pr
112. NOVA User manual NOVA User manual Table of contents TOOU O 9 enema cee A E ee ee E ee eee ee 7 Le The philosophy of NOVA cece cite ducs oncececmsuiec dene enee are ENEE EEE 7 1 2 Working with INOV Ay 2s cscs ccecisseanscancbuexntadarensdneeceaiewssainiee eoecespanresandbaexnnseace 10 1 2 1 The toolbar buttons ercaretecrceeee car eseeeteestestseacle erdeeabstacaveiaenceveintacaxecGixes 10 1 2 2 The toolbar MENUS sa sexceronacgasesceacascosdessndacttanserimeanstaaesaccicuseceacmseensdess 12 123 Views and Mames eers E E 13 LO NOVA WON e E A ee 16 Tola TH COM N e E E EE 16 1 3 2 The measurement sequence c0cccscccseeesseeeecceeesceseeseseecceseecseeees 17 Loco TINS Signal sampler esr E E Ee EEEE 18 AST OO E E E E 24 1 4 Global and local sampler optionS s nennnennnsnnnnnnnnnnsnnsnnnnrrsrnrsrrsrrrerrenn 26 e ewe Data Manage MENE ee EE EEEn 28 RO CU OPIN NOVA sapne ENEE EAT E A EEE 31 Ee A E a E E E EE OE EE E E 31 Lo LIT La paS cic EE E E E EE ee EE 32 1 6 1 2 Hardware ased ri acroioosancsesadsacmnesGodenonesteeuekamuasictadwstueretetaesaawsik 33 1 6 1 3 Application based 20 eecccceccccteeeeeeeeeeeeeeeeeeeeaeeeesaeeeeeeeeeeaeeeeegs 34 1 6 1 4 Hide Show option ccccccecccsseeeceseesseseceeeeessesenseeereceeeecnseenens 35 1 6 1 5 Hidden commands warning cccceeeeeseeeeseeeeceeeecceseesseeeeess 39 1 6 2 Sorting function for the commands DrOWSE L
113. NOVA User manual av Autolab control wAutolab III lt Basic a cell ort Integrator Mode Potentiostatic Summary Current range 1mA Bandwidth w Advanced Figure 2 56 Using the Autolab control command to set the instrument to Potentiostatic mode and in the 1 mA current range Click the OK button to close the Autolab control window The settings specified Figure 2 56 will now be displayed in the procedure editor below the Autolab control command see Figure 2 57 Commands Parameters New procedure Remarks End status Autolab oignal sampler Time WWE 1 Current Options Mo Options Instrument LALIT 0530 Instrument description e Autolab control AS WE Mode Fotentiastatic WE Current range 1 mA WE 1 Bandwidth High stability lt gt Links Figure 2 57 The Autolab control settings are displayed in the procedure editor Next locate the Set potential Set cell Wait time and Optimize current range commands and drag them into the procedure editor under the Auto ab contro command see Figure 2 58 4 For more information please refer to the Command list document available from the Help menu 99 Page NOVA User manual Commands Parameters Links New procedure Remarks x End status Autolab m oignal sampler Time WwE 1 Current m Options Mo Options m Instrument LALIT 0530 Instrument description I oo WE Mode Fotentiastatic WE Current range 1 mA
114. NOVA User manual P Edit Sampler 0 Signal sample Optimized Sampler configuration WE Current Sampler WE1 Potential Segment WEH Power WE 1 Potential WE 1 Resistance E E Segment Optimized WE 1 Charge E dee ala WWE 2 Current ir aie oe Fe WEST Current WE 2 Charge X _Time Time Sample alternating Figure 1 12 Adding the WE 2 Current signal to the sample If more than one signal is optimized the total available time has to be shared Figure 1 13 shows a schematic representation of this situation The maximum number of signals can be measured optimized is six Last segment Time WE 1 Potential WE 2 Current WE 1 Current 1 sample 1 sample Optimized sample Optimized sample Figure 1 13 Sampling an extra external signal The WE 1 Current signal is always sampled in the last sampling step Figure 1 14 shows a practical example of sampling an electrochemical signal using a single A D conversion for each data point or the optimized sampling method The measured signal is the pH provided by the pX module for the Autolab PGSTAT Using the sample optimization reduces the noise pickup during the measurement 22 Page NOVA User manual pH signal optimized pH signal unoptimized Corrected time 5 Figure 1 14 A practical example showing the benefits of sampling a signal Optimized If the WE 2 Current signal must be recorded in the same sampling
115. Restore from repository removes any modification of the current data set and restores the data set to the backed up status 4 1 1 4 Merging data The database also allows the merging of two or more files When database entries are merged a new file containing the procedures and the data from the merged files will be copied to the new file This can be used to involve the data from two or more different measurements in a calculation or other data handling steps described in this chapter To merge two or more data files in the database select the files by clicking them while holding the CTRL key pressed The selected files will be highlighted in the database frame see Figure 4 13 File View Profile Run Tools Help Oe Se a EP SS eo ed cw Procedure name f Time stamp Remarks Demo 01 Copper deposition af bfell e 413 49 PM CusO04 0 01 M H2504 0 1 M Ag AgCl Refere JEE BB bes Demo 02 Lead deposition EQCH Hebfell 414 26 PM PoiClO4ie 0 01 M HGO 0 1 M Figure 4 13 Selecting multiple database entries Right click the selected database entries and select the Merge data option from the context menu see Figure 4 14 162 Page NOVA User manual Procedure name f Time stamp Remarks Demo 01 Copper deposition 15 2007 6 25 27 PM CusO4 0 01 M H2504 0 1 M Ag AgCl Ret KCI 5 es Demo 03 Bipot Set Active Procedure ORPM HCIO4 0 1 M Demo 04 Aydre Fe2 Fes NaQH 0 2 Ml Demo 05 Feil Fee Fes Reversib
116. Switch Autolab RDE off z Create new drop e Determine integrator drift e Muli 4utolab software synchronization e Muli 4utolab hardware synchronization Bet ECD current offset r Set DAC Figure 1 27 Difference between the basic left and the advanced right profile Note The intermediate profile is the default level based profile selected upon installation of Nova Important The selected level based profile is always on 1 6 1 2 Hardware based All the commands and the procedures in NOVA have been tagged with a hardware requirement marker When the hardware based profile is active only the procedures and commands that can be executed with the connected instrument are shown In Figure 1 28 the Autolab procedures are shown without and with the hardware based profile active for a uAutolablll Since the yAutolablll is not fitted with the required hardware several procedures are hidden 33 NOVA User manual Commands Procedures Sb Autolab Cyclic voltammetry potentiastatic Cyclic voltammetry qalvanostatic Cyclic voltammetry current integration Cyclic voltammetry linear scan Cyclic voltammetry linear scan high speed Linear sweep voltammetry potentiostatic Linear sweep voltammetry galvanostatic Linear polarization Hydrodynamic linear sweep Differential pulse voltammetry square wave voltammetry sampled OC polarography Chrono amperometry At gt 1 ms Chrono potentiometry At gt 1 ms Ch
117. WWE 1 Current Mo Options SALUT 205350 0 000 0 000 O 000 1 000 0 1 000000 0 000 1 000 0 00244 0 1 000000 dee 0 024400 Time VWWE 1 Current Mo Options lt aray Cv lt array gt 5 lt array 4 array gt 0 000 0 000 5 NOVA User manual E Figure 2 65 Adjusting the Repeat for each value command Links This will open a Range builder window that can be used to construct a sequence of values to be linked to the scan rate of the LSV staircase command see Figure 2 66 105 Page NOVA User manual Range builder Values ae Add value 3 Add range Clear N Mr of significants 5 OF OK Cancel Figure 2 66 Opening the Range builder window The Range builder is a useful tool that can be used to edit the sequence of the Repeat for each value command There are two ways to add values to the range e The first option is to type each individual value in the Value field on the top of the window and click the s button e The second option is to use the Range generator which is selected by pressing the button This option is suitable for adding a large number of values to the range The Range builder provides a button to remove any previously added values and a sort button which can be used to sort the values of the range Click the button to remove the default values from the range and click the Aid verge button to display the Range generator wi
118. X axis units at half the value of the peak height Peak 1 2 the difference between peak position and the peak position at half height in X axis units Peak sum of derivatives the sum of the absolute values of the maximum and the minimum in the derivative of the Y signal with respect to the X signal in Y X units Whenever one of the search criteria is updated in the software the calculation is automatically updated using the new user defined settings Changing the Minimum peak height to 1 5E 7 automatically updates the peak search results as more peaks are found see Figure 4 133 244 4E 7 3E 7 2E 7 1E f Current A 1E 2E 0 Potential NOVA User manual MEE x Search mode Automatic Manual Base line mode Minimum peak height 1 5E 07 Minimum peak width 0 015 Nr of points in search window 6 Number of significant digits 5 Reset Peak Type Forward C Reverse Index Peak Peak Peak area position height gt 0 18265 15951E 07 3 3985E 08 2 0 10056 1 7938E 0 3 6045E 08 Figure 4 133 Changing the peak search conditions automatically updates the results 4 8 1 4 2 Manual peak search Manual peak search allows for fine tuning of the search criteria and results To perform manual peak search switch to Manual search mode see Figure 4 134 i Note Switching search modes removes all the previously found peaks from the list search mode Base lin
119. a Show in Windows Explorer Figure 4 23 Deleting data from the database Note It is possible to delete multiple files at the same time Deleted data files are automatically moved to the Recycle bin 167 Page NOVA User manual 4 2 Plotting the data in 2D The basic display of measured data sets in NOVA is a 2D plot The way the data is rendered in the 2D plot depends on the available signals Assuming that a given data set consists of three different signals Current Potential and Time the data set can be displayed in six different 2D plots e Current vs Potential or Potential vs Current e Current vs Time or Time vs Current e Potential vs Time or Time vs Potential The data analysis view also includes a data grid which is a spreadsheet like advanced calculator that includes an expression builder that can be used to construct new signals based on existing signals This means that the plotting possibilities of NOVA are almost infinite the use of the data grid will be detailed in section 4 9 of this chapter 4 2 1 Loading and viewing data sets from the database The first step required to view the measured data from a given data set of the database is to load this data set in the Data explorer frame To do this double click the corresponding entry of the database This will copy the data set in the explorer frame see Figure 4 24 File View Profile Run Tools Help Db Se D Rea D Je E Se dE E o j
120. a built in spreadsheet The Analysis view also provides an overview of all the performed measurements and the user defined results database This view of the software is described in extensive detail in Chapter 4 of this manual The Multi Autolab view is used to configure multiple instruments connected to the same computer or Multi Autolab instruments fitted with multiple channels and to program the measurements to be performed on these devices The use of the Multi Autolab view falls outside of the scope of this User manual and more information can be found in the Multi Autolab tutorial available from the Help menu The Multi Autolab view is only used to configure multiple instruments connected to the same computer Procedure setup experiment monitoring and data analysis is still carried out in the respective views of the software Since the different parts of an experiment are performed in different views of the software Nova lets users perform data analysis in the Analysis view while a measurement is running in the Measurement view Analyzing data does not interfere with the measurement itself 15 NOVA User manual 1 3 NOVA workflow This section provides some details about basic concepts related to the way NOVA works More information is provided in the rest of this document and in the NOVA Getting started manual 1 3 1 The commands NOVA works with individual commands Each command can be used to perform a specific act
121. a cag e ka Demo 01 Copper deposition 15 fe UF b257 PM Cus04 0 01 M H2504 0 1 M Ag AgCl R Demo 02 Lead deposition EAC eff2009 11 04 15 AM Pepclodi 0 01 Ms HEGOA 0 1 bl Demo 03 Bipotentiostat measurement PPE An 2f20 200 23445 PM ORPM HCIO40 1 M Demo U4 Hydrodynamic linear sweep voltammetr 3 4 2009 11 21 56 AM Fed Fea NaQH 0 2 ti Demo 05 Feili Fe ih on pct O BADDE 1 27 46 PM Fez Fe3 Reversibility Test LSW with in Demo 0b Galvanastatic CY Webf200 3 32 01 Pe Lead deposition on gold galvanastatic Demo 07 High speed chrono methods FastyaDC 5 25 2009 4 36 33 PM Dummy cell c Demo 08 Chrono methods 400164 2l steps efeUfeOO 8 40 08 AM Factory standard procedure Demo 01 Copper deposition CY staircase H iws E Figure 4 24 Loading a data set from the database into the data explorer i Note The Demo 01 Copper deposition entry of the demo database contains a cyclic voltammogram for copper deposition on platinum recorded in 0 1 M CuSO in 0 1 M H SO solution The reference electrode was a Ag AgCl KCI sat d and the counter electrode was a platinum wire 168 Page NOVA User manual Once a data set has been added to the data explorer frame it can be plotted in a 2D plot By default a cyclic voltammogram experiment is displayed by plotting the applied potential on the X axis and the measured current on the Y axis To view the measured data using this setting click the blue i
122. able e Density specifies the density of the sample in g cm e Equivalent weight defines the equivalent weight of the sample in g mol of exchanged electrons e Surface area defines the area of the sample in cm e Number of significant digits Defines the number of significant digits used in the Analysis results frame When the corrosion rate fit analysis tool is selected the mouse pointer changes to a cross Using the mouse pointer click two points in the plot to specify the linear part of the anodic branch see Figure 4 186 Once the second point is clicked a line will be drawn on the plot 277 NOVA User manual JE 5 1E 6 Current Ay 1E 8 0 55 0 5 0 45 0 4 0 35 0 3 0 25 0 2 0 15 Potential gW Figure 4 186 The corrosion rate fit analysis tools requires the specification of the linear segments of the Tafel plot 1 2 The same must be repeated for the cathodic branch of the plot Once both linear segments have been defined the intercept is determined and indicated in the plot see Figure 4 187 TESS 0 302416 5 0154E 06 lE g 0 55 0 5 0 45 0 4 0 35 0 3 0 25 0 2 0 15 Potential gW Figure 4 187 The corrosion rate fit analysis tools requires the specification of the linear segments of the Tafel plot 2 2 278 NOVA User manual Select the anodic branch of the plot first and then the cathodic branch of the plot The intercept on the Tafel plot provides an esti
123. able analysis tools is provided in the Command list Help menu Tutorials Command list Two type of analysis tools can be added to data sets in NOVA e X Y analysis tools these are analysis tools that can be directly added to a plot in the analysis view These tools use the plotted X and Y values for data analysis The result of these analysis tools depend on the input X and Y displayed in the plot e Data set analysis tools these are analysis tools that can be added to one or more data sets All the values of the data set s are used in the analysis 222 NOVA User manual 4 8 1 X Y analysis tools The X Y analysis tools can be added to any plot in the analysis view using the right click menu see Figure 4 97 This section provides an overview of the available analysis commands in this category Cyclic voltammetry potentiostatic El il C staircase oe Ivs E Plot Options Properties Add Analysis z Smooth Copy Visible Plot s to i Baseline Correction Show All Plots Peak search Hide All Plots Regression X Save in My commands Derivative Delete Integrate ki F a a j FF A nals SIS wem ov all from View Figure 4 97 X Y analysis tools can be added directly to a plot in the analysis view It is also possible to add this type of analysis by clicking the plot directly and selecting the required analysis tool using the quick access toolbar see Figure 4 98 S Cyclic volta
124. adow Graphics Figure 1 49 The colors used in the Autolab display can be changed Three different colors are used in the Autolab display The Active LED color is used to highlight active settings of the instrument and indicate the noise levels for potential and current signals in the Autolab display The Inactive LED is used to show the inactive settings and the Alarm LED color is used to display warnings see Figure 1 50 47 Page NOVA User manual Autolab display x a Autolab manual control Warning LED Noise gauge Active LED CELL ON Se Inactive LED gt status current range SSS Figure 1 50 The colors used in the Autolab display are defined in the NOVA options 1 6 4 3 Advanced settings In this category advanced settings used in the software can be defined see Figure 1 51 Nova options r Graphics a Basic 2 Autolab display Auto save measured data Yes Ss Advanced settings Clear measurement plot before start Yes Hidden warnings Reset Switch to measurement view when stat measurement Yes Time outin seconds forthe validation dialog 30 C Expert Figure 1 51 The advanced settings of NOVA The settings are grouped into two categories Basic and Expert The Expert settings are used for debugging purposes and these settings should not be changed Detailed information on these settings falls outside of the scope of this manual The following Basic
125. aff ma lt 3 Figure 2 10 Changing the upper vertex potential has an effect on the Estimated number of points The procedure can now be started using the new experimental parameters 2 4 Advanced editing The previous section described a very straightforward use of the NOVA procedure editor loading a procedure editing some parameters and running the experiment This section will cover a more advanced use of the procedure editor It is the most important part of this chapter Special attention will be given to concepts like timing and linking 2 4 1 Adding Removing commands Section 2 3 described the use of ready made Autolab procedures While these procedures can be used without modifying their structure it might be necessary to change them to fit a specific need A typical example is the standard Chrono amperometry procedure Load the Chrono amperometry At gt 1 ms procedure into the procedure editor This procedure has a pre treatment step just like in the case of the cyclic voltammetry procedure During this procedure the potential of each step is set using the Set potentia command and the response of the cell is measured using the Record signals gt 1 ms command 60 Page NOVA User manual In the standard Autolab Chrono amperometry At gt 1 ms procedure three potential steps are applied using the Set potential command and the response of the cell is recorded for each step using the R
126. aircase O 000 1 000 1 000 0 000 2 0 1000000 set cell Ott m lt gt Figure 2 42 Modifying the Input box parameters To instruct the software to use the value typed into an Input box a link must be created between the Value parameter of the Input box and the parameter in the procedure it is supposed to replace in this case the scan rate Creating this link can be done in the same way as in the previous section Hold the CTRL key select the Value parameter of the Input box and the Scan rate parameter of the CV Staircase command and press the Link selected parameters button in the toolbar see Figure 2 43 88 Page Commands Cyclic voltammetry potentiostatic Remarks NOVA User manual Parameters Cyclic voltammetry potentiostatic Links End status Autolab aa signal sampler Time WE 1 Potential vwE 1 Current ma Options 1 Options aa Instrument LALIT 0530 Instrument description fl Input box Title of box SALUT 205350 Message Enter the value ofthe scan rate in V s 0 05 Time limit s a lse time limit No Autolab control set potential 0 000 set cell On Viait time 3 z Optimize current range z B CY staircase U 000 1 000 1 000 0 000 2 0 0500000 start potential v 0 000 Upper vertex potential v4 1 000 Lower vertex potential 6 1 000 stop potential v 0 000 Number of stop crossings 2 step potential v 0 00244 Scan rate v s O 0500000 Estimated number of points 1650 rf Interval
127. ample the current during a given amount of time and using an interval time larger than 1 ms Click the Set potentia command and while holding the left mouse button drag the command over to the procedure editor frame Place the command on a convenient insertion point a yellow arrow will appear indicating the insertion point of the added command and release the mouse button to confirm the insertion of the Set potential command see Figure 2 18 File View Profile Run Tools Help Ne Sh ah PN 28 go LE oo oo Commands Procedures Commands Parameters Links Chrono amperometry At gt 1 ms Favorite commands To Set potential Remarks Chrono amperometry At gt 1 ms E H Control End status Autolab al an l signal sampler Time WE Potential WET Current ca Metrohm devices External devices Spans Lopian 1 Instrument ALIT40008 H Measurement general aE Instrument description H Autolab control EE H Autolab control maj g oat potentia E H Set potential 0 000 i Set current W H Set cell On ail Get cell i pe z aut time is 5 H WAteut time 5 ine Record signals gt 1 ms E 0 01 H Optimize current range N S i Set potential 0 500 m OCF determination NG r x Record signals 1 ms 5 0 01 H Set reference potential 3 Set cel Of io zau i Elnterrupt measurement AS ste s Interrupt measurement high speed Set BIPOT ARRAY potential Reset EQCM
128. ampled during the measurement as well as the timing of the sampling of these signals in the course of the experiment A more detailed description of the signal sampler is provided in Section 1 3 3 of this manual The Autolab cyclic voltammetry potentiostatic procedure has the following signals defined in its sampler Potential applied Time WE 1 Current Scan WE 1 Potential Index O O O O OO Option s this field contains optional instructions to be used during the measurement More information on the options can be found in Section 1 3 4 of this manual In the case of the Autolab Cyclic voltammetry potentiostatic procedure the defined option s field authorizes the Autolab to use the automatic current ranging 1 mA to 100 nA Instrument this field is automatically filled by the software displaying the identifying serial number of the active instrument Instrument description this field can be used to assign a small description to the active instrument Procedure consists of a series of Commands listed under the Commands column and a series of Parameters listed under the Parameters column Timing guide this is a visual indicator of the timing accuracy of the sequence of commands The timing is displayed using a green line on the left hand side of the procedure editor Interruptions in the green line indicate that the timing of the sequence will be interrupted Link the lines drawn on the right hand side of the procedure editor f
129. applied lt array gt 4 Time lt array gt s WE 1 Current lt array gt A Scan lt arrary gt Index lt array gt ivs E Ley Figure 1 5 Comparison of the Set potential command left and the CV staircase command right i Note The command parameters for the CV staircase command are shown in different colors More information on this color scheme is provided in Chapter 2 of this manual 16 NOVA User manual 1 3 2 The measurement sequence A measurement in NOVA occurs according to a sequence of commands specified by the user in the Procedure When the measurement starts the procedure is always verified by the validation tool If no errors are detected in the procedure validation tool the measurement starts During the measurement the following basic steps are repeated e Set Autolab property the instrument state is changed according to the parameters defined by the user in the procedure Set potential Set cell apply next potential step etc e Sample signals a change in the instrument state can trigger a reaction of the electrochemical cell In order to monitor this reaction the electrochemical signals are sampled using the Signal sampler The measured data can be displayed on a plot e Options after the signals have been sampled a user defined set of options is used Automatic current ranging Cutoff condition etc These basic steps are repeated for each command in th
130. arch window Number of significant digits 5 E X Feak Type Forward C Reverse Figure 4 147 Pressing the Reset button removes previous results from the analysis results frame The results of the Peak search are stored in the data grid 4 8 1 5 Regression The regression analysis tool can be used to perform different regression calculations on measured data points A wide range of functions can be used in this type of calculation Linear no offset performs a linear regression using the y ax equation Linear performs a linear regression using the y ax b equation Polynomial fixed order this calculation uses a nt order polynomial function in the regression calculation The value of n is defined by the user Polynomial maximum order this calculation uses all the polynomial functions up to a maximum of n defined by the user The regression providing the smallest y Chi squared is automatically selected by the software 255 NOVA User manual e Exponential no offset this regression calculation is performed using the equation y be e Exponential this regression calculation is performed using the equation y a be e Circle this regression calculation is performed using the equation of a circle The regression tool can be added to a measurement using the right click menu and by selecting the Add analysis Regression item from the context menu see Figure 4 148 Cyclic voltammet
131. are Some examples are provided in this chapter and the corresponding data sets are available in the Demo database folder which is created during the installation of NOVA 1 10 This database contains all the examples used in this chapter 4 1 1 The database To use the database click the button on the right of the area displaying the path of the Measured data database Change the path to the Demo Database NOVA User manual located in the Program Files Metrohm Autolab NOVA 1 10 Shared DataBases folder see Figure 4 3 Click the button to confirm the change in the path of the database and click the button in the database management window to close it _Datahase mananement Browse For Folder Standards ce a Metrohm Autolab a Nova 1 10 d config d Metrohm 4 Shared DataBases ad Demo Database mir Module test gt Tutorials Cult Make New Fokder Bea d Cancel Figure 4 3 Loading the Demo database by setting as the Data database The demonstration database has been set as a Data database Its contents are displayed in the database frame of the Analysis view see Figure 4 4 157 Page NOVA User manual eed NOVA File View Profile Run Tools Help SN oi mt PT coc oe ge Procedure name f Time stamp Remarks Instrument Instrument descri a Demo 02 Lead deposition EQCM 2 4 2009 11 04 15 AM Pb ClO4 2 0 01 M HCIO4 0 1 M
132. are added to the Nested procedure sequence see Figure 2 109 e Autolab control e Set potential 1 2 V e Set cell On e Wait time s 5 e Optimize current range 134 Page NOVA User manual Commands Parameters Links New procedure Remarks z End status Autolab am oignal sampler Time WE 1 Current potions No Options z Instrument ALT 40006 Instrument description Nested procedure Autolab control ma set potential 1 200 Set cell Or ai Wart time s z Optimize current range 5 lt gt gt Figure 2 109 Adding the commands to the procedure editor Make sure that the commands are added to the Nested procedure sequence Use the Autolab contro command to set the instrument to High stability select the 1 mA current range and set the Autolab to potentiostatic mode see Figure 2 110 PGSTAT101 Basic slat cell off Integrator Autolab control Summary Mode Potentiastatic w r Current range 1mA v m Bandwidth IR compensation Advanced Figure 2 110 Set the initial Autolab conditions using the Autolab control interface 135 Page NOVA User manual 2 7 3 Saving My Commands Right click the Nested procedure command and select the Save in My commands option from the context menu or use the quick access shortcut icon see Figure 2 111 Lommands Parameters Links New procedure Remarks az End status Autolab Signa
133. arkers that are already placed on the plot In order to do this right click on an existing marker point and select the Move option from the menu see Figure 4 122 The same menu can be used to remove an existing marker point from the plot 237 NOVA User manual 5E 7 4 5E 7 4E 7 H al an rt 3E 7 2 5E 7 H 2E 7 fE 1 6 Current A WV cn mm 1E 7 5E 8 f Selected point Move selected point X Xi Remove Figure 4 122 Right clicking an existing marker point allows you to move or remove the marker After choosing the move option a label showing the X and Y coordinates of the point will be displayed below the selected marker Using the right and left key on the keyboard it is possible to move the selected marker along the plot see Figure 4 123 7 0 72159 0 72 159 1 2 1 0 8 0 6 0 4 0 2 J Potential applied W Figure 4 123 Choosing the move option allows you to relocate the marker 238 Page NOVA User manual When a suitable new position for the marker is located press the Enter key on the keyboard to validate the new position Click the plot to redefine the position of the marker for the baseline calculation The baseline will be recalculated and replotted using the new set of markers see Figure 4 124 1 2 1 0 8 0 6 0 4 0 2 J Potential applied W Figure 4 124 The recalculated baseline 4 8 1 3 3 Plotting the residual When the basel
134. ase 150 NOVA User manual 3 4 2 Additional control panels Additional control panels can be added to the Autolab display window by selecting the corresponding option from the view menu For example if a FRA2 or FRA32M module is available the FRA manual control option can be selected to display the manual control of this module see Figure 3 17 File View Profile Run Tools Help TL 3 aa eo 2 1 eo ot e i il Advanced procedure view B Setup View Multi Autolab View Measurement View la Analysis View fel User log F11 Ea Autolab display F10 FRA manual control MDE manual control MUX manual control External manual control Figure 3 17 Adding the FRA manual control to the Autolab display The FRA manual control panel can be used to control the FRA2 or FRA32M module and to perform impedance measurements see Figure 3 18 151 Page NOVA User manual Autolab display E a Autolab manual control p3AUT 70530 Current HSTAB CELL ON J status current range a FRA manual control frequency Hz amplitude a E Bint Mode Internal Wave type Sine maa ON Integration time s S Minimum number of cycles to integrate Elapsed time 3 eee ELA iy KOCI A KACI A HE i 506 0 p 10 14m 1 802 p 5216p 50 64 Freg Hz Z0 Phase h Z 0 a 1 000 k 194 4 50 73 123
135. astatic Dummy cell c Factory standard procedure Combination of steps and levels Example for baseline correction peak search Figure 4 17 Exporting a data file A name and a location for the file can be specified see Figure 4 18 era Export data Ea G T hared DataBases Demo Database Search Demo Database File name PEMA EAE E Save as type Procedure files nox Browse Folders Cancel Figure 4 18 Specifying a name and location for the exported file 164 Page NOVA User manual Note It is possible to export multiple files at the same time although an individual name and location must be specified for each file To import a data file right click anywhere in the database frame and select the Import data option from the context menu see Figure 4 19 Procedure name f Time stamp Remarks Demo 01 Coppi E _ gg CUSO4 0 01 M H2804 0 1 M Ag AgCl Ref KCI S Demo 02 Lead PbiClO4i2 0 01 M HEO 0 1 M Demo 03 Bipot 0 RPM HEIDA 0 1 M Demo 04 Hydri Fe Fea NaQH 0 2 M Demo QS Fe ll Fe Fea Reversibility Test LSW with increasing Demo 06 Gali WI Delete from Repository Lead deposition on gold galvanostatic SONE p Restore from Repository SU Ce te Demo 08 Chro Factory standard procedure Demo 09 Chro Import Data X Combination of steps and lewels Demo 10 Diffe Export Data Example for baseline correction peak search xI Delete
136. ated and the counter electrode was a platinum sheet 121 NOVA User manual 0 0012 0 5 0 001 L gt 0 4 0 0008 D E 03 5 0 0006 5 O A 02 0 0004 LU W 0 1 0 0002 0 0 0 0002 0 1 0 0 2 0 4 50 100 150 200 250 Potential applied V Time S Figure 2 86 The LSV curves obtained using the procedure described in this section left plot 1 i vs E right plot 2 E vs t 2 6 Dragging and dropping procedures This section of this chapter provides details on procedure constructions using pre defined procedures as building blocks The difference with the previous part of this chapter is that using this editing mode instead of dragging and dropping commands from the commands browser into the procedure editor entire procedures will be dragged from the procedure browser into the procedure editor This advanced mode of procedure editing allows for even more flexibility Create a new procedure by clicking the new procedure button in the toolbar to clear the editor frame Once the procedure editor has been cleared it Is possible to start building a procedure out of existing procedure As an example a procedure containing the pre defined Autolab cyclic voltammetry potentiostatic procedure and the Autolab cyclic voltammetry galvanostatic will be constructed Using the drag and drop method select the Cyclic voltammetry procedure and drop it into the procedure editor see Figure 2 87
137. ats by clicking the Advanced button in the Plot options window 172 P NOVA User manual Plot Options Data Axes Plot Analysis items Flot Flot style Faint plot Ww y axis placement Lett C Right Point Point style Cat i rincoor _ ss Point size 3 Draw point ever 1 datapointis Line E oma F 140 L Apply Cancel Figure 4 29 The plot options window The plot options window has four different tabs which can be used to define different aspects of the plot 4 2 4 Data tab The items located on this tab are related to the plot appearance It is possible to choose from different plot style to change the plot color and size and define a point style It is also possible to change the position of the Y axis see Figure 4 29 173 Page NOVA User manual 4 2 5 Axes tab This tab allows changing of the axes related options like type of scaling and formatting axes coupling axes labels It is also possible to define specific axes labels that will overwrite the defaults signal names in the plots see Figure 4 30 174 Plot Options Axes Plot Analysis items AXES z 7 3 scale style Linear w Linear w Linear w Color D Font Formatting General e General a General If Direction Reversed Reversed Reversed Axes coupling Independent C Isometric C Isotropic Label x lt Signal gt Label r lt Signal gt Label Z lt Signal gt Apply OK N Cancel
138. avorite commands Message box Set potential Record signals gt 1 ms H Control H Metrohm devices H External devices H Measurement general H Measurement Cyclic and linear sweep voltammetry mag Measurement voltammetric analysis H Measurement chrono methods H Measurement impedance H Data handling H Analysis general G Analysis baseline correction H Analysis corrosion Analysis impedance EH Flots general Plots impedance 3 My Commands Figure 2 33 The Message box command is added to the Favorite commands group when dragged into the procedure editor 2 4 8 Linking commands 2 4 8 1 Understanding links Linking commands is a very important part of procedure editing in NOVA A link can be defined as a relationship between two or more parameters in a procedure Reload the Autolab Cyclic voltammetry potentiostatic procedure In the toolbar click the Show all links button to expand the procedure and reveal the existing links see Figure 2 34 The Autolab Cyclic voltammetry potentiostatic procedure has a total of three links 79 NOVA User manual Commands Parameters Links Cyclic voltammetry potentiostatic Remarks Cyclic voltammetry potentiostatic ma End status Autolak m oignal sampler Time WWE 1 Potential vwE1 Current m Options 1 Options m Instrument Instrument description H Autalab control a E Set potential 0 000 Fotential v 0 000 Set cell On E veut time s 5 Op
139. b control command click the button located on the right hand side of the procedure editor window see Figure 2 54 2 It is a good habit to set the instrument to the correct settings at the beginning of a procedure 97 P NOVA User manual Lommands New procedure Remarks End status 4Autolab signal sampler potions Instrument Instrument description Autolab control Parameters Links Time WET Current ma Mo Options a ALT 40005 Figure 2 54 Opening the Autolab control settings A new window called Autolab control will be displayed see Figure 2 55 This window displays the settings currently defined on the connected instrument and can be used to change any of the instrument settings at any time during a procedure In Figure 2 55 the basic settings for the main potentiostat galvanostat can be defined wAutolab Ill lt Basic DIO Integrator Summary Bandwidth High stability Autolab control 0 cell Jof Mode Potentiostatic w Current range 1 mA i wi Advanced Cancel Figure 2 55 The Autolab control window For this procedure the Autolab control command will be used to set the instrument to potentiostatic mode and in the 1 mA current range Using the drop down menus set the Mode and the Current range settings to Potentiostatic and 1 mA respectively see Figure 2 56 3 The available Autolab settings depend on the hardware configuration 98 Page
140. bar Adding the windower tool triggers the Windower editor window to appear see Figure 4 234 P Windower 0 Source simple s Cancel Figure 4 234 The Windower editor window The following items need to be specified for the Windower tool to work properly e Source this is the source signal used to window the data The source signal is one of the available signals available in the data set Time Scan number WE 1 Potential Only one source signal can be selected e Simple checkbox this specifies if the simple editor is used selected by default e Values this defines the values of the selected source signal to use in the windower 311 Page NOVA User manual 4 12 2 Selecting the source of the windower The source is one of the available electrochemical signals and will be used to create the cross section of the data set The data set from Demo 06 has the following signals e Current applied A e Index e Scan e Time s e WE 1 Potential V To select the source for the windower select the Scan signal from the drop down list in the editor see Figure 4 235 c Windower Source Current applied can Time b WEN Fotentia Figure 4 235 Selecting the Scan signal as the windower source As soon as the source is defined the Windower editor displays a list of available values for the selected signal in the frame in the middle see Figure 4 236 Since this data s
141. base to load it into the data explorer frame This file contains data points recorded in NaOH 0 2 M in the presence of 0 05 M Fe CN using a Pt ultra micro electrode 5 um Click the i vs E plot in the data explorer frame to display the data points from this demo file see Figure 4 106 As frequently seen with this type of measurement the current levels are very small and affected by a significant amount of high frequency noise 1 8E 10 1 6E 10 1 4E 10 1 2E 10 1E 10 SE 11 BE 11 4E 11 26 11 J Current 2 za ex 4E 11 J 0 2 0 4 0 6 0 8 Potential W Figure 4 106 The data from the Demo 15 data file To use the FFT Smooth tool right click the i vs E plot in the data explorer frame and from the context menu select the FFT Smooth tool see Figure 4 107 NOVA User manual El a Demo 15 UME LSW Import GPES data lives E Plot Options Properties Add Analysis Sm ooth Copy Visible Plot s to Baseline Correction Show All Plots Peak search SG Smooth FFT Smooth N Ae Hicle All Plots Regression Save in My commands Derivative Delete Integrate amon cities a FFT Analysis Remove all from View i E Corrosion Rate Figure 4 107 Adding the FFT Smooth tool to the data A new item called FFT Smooth will be added to the data set in the data explorer frame below the i vs E plot see Figure 4 108 a
142. baselines can be defined in the software The baseline fit analysis tool can be added to any plot using the right click menu This section provides details on how to use the Baseline correction tool Three different baseline corrections are possible e Polynomial fixed order defines a polynomial baseline function of fixed order n The number of markers required is n 7 e Polynomial maximum order defines a polynomial baseline function The maximum polynomial order n is defined by the user The polynomial order of the baseline curve is determined by the software by minimization of the standard deviation values The number of markers required is N 7 e Exponential defines an exponential baseline function The equation used to determine the baseline curve can be modified using an optional offset value The number of markers required is 4 Double click on the demo file Demo 70 Differential pulse measurement entry of the demo database to load it into the data explorer frame This file contains data points recorded during a differential pulse voltammetry measurement Zn Cd Pb and Cu in acetate buffer Click the i vs E plot in the data explorer frame to display the data points from this demo file see Figure 4 116 233 NOVA User manual 5E 7 4 5E 7 AE 7 isla oo h i ake n 1 2 1 0 8 0 6 0 4 0 2 J Potential applied W Figure 4 116 The data points from Demo 10 Starting at a potential of 1 2 V
143. c procedure will be added to the current procedure in the editor frame The Options and Sampler settings defined in the Cyclic voltammetry potentiostatic procedure will be used during the measurement Automatic current ranging from 1 mA to 100 nA Sampler WE 1 Current and Time e No the Cyclic voltammetry potentiostatic procedure will be added to the current procedure in the editor frame The Options and Sampler currently defined in the procedure editor will be used No automatic current ranging Sampler WE 1 Current and Time The specific Options and Sampler defined in the Cyclic voltammetry potentiostatic procedure will be overridden e Cancel the procedure is not added to the procedure editor Press the s button to add the complete procedure to the procedure editor see Figure 2 89 The Options and Sampler settings defined in the Cyclic voltammetry potentiostatic procedure will be kept 123 NOVA User manual Commands Parameters Links New procedure Remarks aa End status Autolat E oignal sampler Time WWE Current ma Options Mo Options m Instrument ALJ TAQ0QE Instrument description E Cyclic voltammetry potentiostatic Autolab contral z set potential 0 000 set cell On ma iat time s z Optimize current range 5 B CY staircase O 000 1 000 1 000 0 000 2 0 10000 start potential v 0 000 Upper vertex potential ly 1 000 Lower vertex potential 63 1 000 stop potential v 0
144. cale type ii Linear Format Logarithmic Absolute values X scaling mode gt Square root Absolute values Axes Coupling Pi multiples Show Label Time Edit Axis Reversed Figure 4 33 Right clicking a plot axis displays a context menu Contrary to the setting defined in the Plot Options window the settings defined using the context menu are only valid for the related item in the active plot Changing the Y axis settings in a 2D plot does not affect the appearance of the corresponding 3D plot As an example select the i vs E plot from Example 1 data set and using the Plot Options window change the plot settings to a red Combi plot using a size 10 pyramid as a symbol plotting 1 point out of 40 and using a size 2 line see Figure 4 34 Plot Options Data Axes Plot Analysis items Flot Plot style C50 i aaa ae iv axis placement Left C Right Faint Point style A Pyramid F Pointcoior i __ Point size 10 Draw point every 40 datapoint s Line Line style m Lnecoor __ Line size Advanced Reset values Apply OK X Cancel Figure 4 34 The modified plot options for Example 1 177 NOVA User manual The cyclic voltammetry saw tooth profile should now be displayed as in Figure 4 35 Demo 01 Copper deposition El Cy staircase Potential applied Vv 10 les 20 23 30 35 Time 5 Figure 4 35 New plot settings for Example 1 The i vs E has changed
145. color and is preceded by a red pyramid symbol i vs E This feature makes it easier to identify a specific plot in an overlay see Section 4 4 4 2 8 Creating new plots It is often convenient to plot experimental data in different ways NOVA offers this possibility directly from the analysis view Using the right click menu it is possible to add any number of new plots to a data set Two different types of plots can be created a command specific predefined plot or a generic Custom plot In this section both options will be illustrated NOVA provides a number of predefined plots for every measurement command The experimental data from Example 1 was measured using the CV staircase command for which a total of nine predefined plots are available To add any of these plots to the data set right click the CV staircase line in the data explorer and select the Add Plot option from the context menu 178 NOVA User manual Nine plots will be provided in an additional sub menu see Figure 4 36 e Custom e ivseE e ivst e Log i vs E e Log i vs Log t e Evsi e Evst e Evs Log i e Evs Log t E Demo 01 Copper deposition H gl CY staircase Etr ives E Plot Options Propertes Add Windower Generate index Add Plot i Custom Add Analysis IVSE Show All Plots ivst Hide All Plots Logi vs E X Save in My commands Log i vs Logt Delete E vsi XT Remove all from View ai E vs Lo
146. cutive linear sweep voltammetry measurements will be performed using four pre defined scan rates For this part of the procedure the following steps are required 1 Start a linear sweep voltammetry measurement using the first defined scan rate 2 Repeat the previous measurement for the three other scan rates To perform this measurement it is possible to use a procedure in which four LSV staircase commands are used one after the other This is however quite cumbersome as the parameters of each command would have to be edited individually On the other hand the same results could be obtained by inserting a pre defined LSV staircase command into a repeat loop and by changing the scan rate after each repetition The Repeat for each value command from the Control group has been designed specifically for this task In this example it will be used in combination with the LSV staircase command Select the Repeat for each value command from the browser and drag it in the procedure editor frame under the preconditioning stage see Figure 2 62 File View Profile Run Tools Help BW Tee Sigal ae eee es en ee Commands Procedures Commands Parameters Links New procedure H Favorite commands 5 Control Remarks T 4 auba End status Autolab z Message box Signal sampler Time WE 1 Current ass LR Options No Options za H Repeat n times a ae Instrument UW3IAUT 70530 Repeat for each value Instrument description Nested procedure P B
147. d To save the changes click the Save button on the data analysis toolbar see Figure 4 44 This will save the changes of all the open data sets without changing the time stamp and the remarks File View Profile Run Tools Help i ah LT 5g 22 Cae Ms jE EB les Save all open data in database Figure 4 44 Updating the database i Note If the ongoing session of Nova is closed or if the data set is removed from the data explorer frame before the changes have been saved a warning message will be displayed prompting the user to choose whether or not to update the database Clicking the button will update the database in the same way as the Save button Choosing No will discard all the changes A Ysea y nowa button is also available for all the open data sets see Figure 4 45 Demo 01 Copper deposition Data changed Do you want to save the changes Figure 4 45 Dataset changed warning message ae Data changed 183 NOVA User manual It is also possible to save the changes to a data set by right clicking the data set in the data explorer frame and selecting the Save the data in database option see Figure 4 46 E Demo 01 Copper go gt B a CY staircase pia Evst Logi ws E bo oy X Potent x mati m m Plot Options Propertes Refresh Add Plot Add Analysis Show All Plots Hide All Plots Save the data in database Remove from View X Remov
148. d Nested procedure is used The Nested procedure command can be found in the Control group of commands see Figure 2 106 Commands Procedures Favorite commands 5 Control Input box Message box Send e mail Repeat n times e Repeat for each value e Repeat for multiple values S Nested procedure Metrohm devices A H Measurement gener commands into one command and sawe itin My commands H Measurement cyclic and linear sweep voltammetry EH Measurement voltammetric analysis H Measurement chrono methods H Data handling H Analysis general G Analysis baseline correction Analysis corrosion EH Flots general ial My commands m My Galvanostatic Autolab control command Figure 2 106 The Nested procedure command can be used to group commands Using a Nested procedure command it is possible to group commands together and save them into the My commands group Create a new procedure by clicking the new procedure button A in the toolbar to clear the editor frame As an example a pre conditioning command that sets the Autolab applies 1 2 V switches the cell ON waits during 5 seconds and selects the best possible current range will be constructed To start locate the Nested command in the Control group of commands and add it to the procedure editor see Figure 2 107 133 Page NOVA User manual File View Profile Run Tools Help LD Eee eee T oll 5 a 222 del ET
149. d editing tools More attention is given to Timed commands procedure structure and links 2 5 1 Advanced procedures structure Load the Autolab Chrono charge discharge procedure into the editor frame This is a more complex procedure than the procedures illustrated in the previous sections The procedure uses a Repeat n times command to create a repetition loop Careful inspection of the procedure reveals that the commands are grouped into three consecutive timed segments indicated by the green timing guide see Figure 2 45 e Segment A is the pre treatment of the cell e Segment B is the bulk of the Chrono charge discharge procedure e Segment C is the post treatment of the cell 90 C Commands Chrono charge discharge D E co Remarks End status Autolak signal sampler potions Instrument Instrument description Autolab control set potential set cell Vat time 5 Repeat n times Number of repetitions set potential Record signals gt 1 ms set potential Record signals gt 1 ms lt gt set cell lt gt ee Parameters Chrono charge discharge Time WE Potential WE Current 1 Options ALT 40006 0 000 n 10 10 10 1 200 eS 0 07 0 000 2 50 01 Cit NOVA User manual Links Figure 2 45 The chrono charge discharge procedure The first segment A the pretreatment consists of four separate commands Autolab control Set potential 0 V Set cell On
150. d plot options will be saved 3 3 Clearing the measurement view and zooming During the measurement the clear measurement plot button can be clicked at any time to clear all the plots in the measurement view The plotting of the data points will resume after the plot has been cleared The measured data points are however kept in memory The clear plot button can be extended by clicking the arrow button located next to the clear plot button This will show a context menu with which any one of the four plots can be cleared see Figure 3 13 File View Run Tools Help ERETTE IREAL MW mea le aaa a l G Measurement Plot 1 Measurement Plot 2 Measurement Plot 3 y Measurement Plot4 Figure 3 13 It is possible to clear a specific plot in the measurement view by extending the Clear plot button 147 NOVA User manual It is also possible to zoom in and out in the measurement view By default NOVA always tries to automatically adjust the X and Y scaling in order to plot all the data points However it is sometimes convenient to be able to zoom in on a particular zone of the plot in order to observe fine details of the curve It is only possible to zoom in and out on the data if the Enable zooming moving option is enabled To enable this option right click the plot area and select the Enable Zooming Moving option from the menu see Figure 3 14 Zooming in on the data can be done by dragging a box around
151. d to hide the Chrono coulometry fast procedure from the procedures browser 35 P lt NOVA User manual Commands Procedures Autolars fe Cyclic voltammetry potentiostatic a Cyclic voltammetry gqalvanastatic be Cyclic voltammetry current integration z Cyclic voltammetry linear scan Cyclic voltammetry linear scan high speed os Linear sweep voltammetry potentiastatic e Linear sweep voltammetry galvanastatic Linear polarization Hydrodynamic linear sweep e Diferential pulse voltammetry e square wawe voltammetry sampled DC polarography e Chrono amperometry At gt 1 ms e Chrono potentiometry t gt 1 ms e Chrono amperometry tast e Chrono potentiometry fast S Chrono coulometry fi z Chrono amperometr Hide gt e Chrono potentiometry high speed e Chrono charge discharge Hnterrupt Hnterrupt high speed Positive feedback e FRA impedance potentiostatic e FRA impedance qalvanastatic FRA potential scan Standards i My procedures Commands Procedures Autolaks Cyclic voltammetry potentiostatic a Cyclic voltammetry qalvanastatic bas Cyclic voltammetry current integration z Cyclic voltammetry linear scan e Cyclic voltammetry linear scan high speed e Linear sweep voltammetry potentiostatic e Linear sweep voltammetry galvanastatic Linear polarization Hydrodynamic linear sweep e Diferential pulse voltammetry e square wave voltammetry sampled DC polarography e Chrono amperomet
152. dded to the Potential applied signal In the expression builder window click the Name field and enter Potential vs SHE as a name Select the V unit from the Unit list Click the expression field and type the following expression E 0 197 Where E is the only parameter in the expression The parameter E corresponds to the Potential applied signal Click the parameters field to update the list of parameters Since there is only one parameter the field will only display E see Figure 4 209 293 NOVA User manual fi Calculate signal 0 Name Potential vs SHE Single value Unit v Expression E 0 197 Parameters Functions a RE signals Full CY staircase Clear OK Cancel Figure 4 209 Creating a new signal by adding 197 mV to the applied potential signal The final step required to calculate a new signal is to select which signals should be used for each parameter Click the E parameter from the list and click the button next to CV staircase group in the Signals list This will display all the available electrochemical signals provided by the CV staircase measurement command Double click the Potential applied signal to assign the values of this Signal to the parameters E see Figure 4 210 i Note Once the values of a signal have been assigned to a parameter of the expression builder the name of the parameter will be displayed next to the signal in between brackets see Figure 4 210
153. de etc This information will be stored alongside the measured data When the remarks field has been edited the procedure can be saved into the My procedures database To do this change the name of the procedure from New procedure to User manual example in the procedure editor and go to the File menu in the toolbar and select the Save procedure as new option This will add the currently edited procedure to the My procedures database The procedure Is logged in this database by name time and date and if the mouse pointer is moved over it it will display a tooltip showing the remarks for this procedure as well see Figure 2 83 119 NOVA User manual Commands Procedures mj Autolab je Cyclic voltammetry potentiostatic Cyclic voltammetry galvanostatic H Cyclic voltammetry current integration Linear sweep voltammetry potentiastatic Linear sweep voltammetry qalvanastatic Linear polarization Hydrodynamic linear sweep Chrono amperometry At gt 1 ms Chrono potentiometry At gt 1 msj Chrono amperometry fast Chrono potentiometry fast Chrono coulometry fast Chrono charge discharge Interrupt Positive feedback Standards El My procedures S User manual example 12 13 2012 3 24 12 PM Figure 2 83 The procedure is added to the My procedures database The remarks field can contain several lines of comment All the added lines will be displayed in the tooltip which is very convenient for
154. deeceesaceiatcindenceduiccesasersivcedoapeusedseseestore 149 3 4 2 Additional control DANES op cese onc dewinsica tered oeenciendsucaneedcosdaddasnetee dev dewndsest 151 34 3 COMA SIO IO DO aMGlS sssrinin enra D NA EEEE EEEE 152 3 4 4 Information during MEASUFEMENMS ccceeececeeeeeeeeeeeeeeeeeeeeesaeeeees 153 3 4 5 Information while NOt MEASULING cccceececeseeeeeeeeeeeeeaeeeeeeaeeeens 153 A Analys VIEW ogur rann AEE an EEE a crasictssonemoeseeacuaekenpinetacierie 155 A T Modu CUON snoeren E a E E EEEE ENERE EEEE 156 4 1 1 The datapase issena nearen antrad taian 156 Bie Vode Sorting Qalasan con S EEEE 159 4 11 2 Data Miter eseistas 159 Atl Ne data POD OS MOONY secioni Oai 161 ATAM da eee E EE T REE 162 4 1 1 5 Import and Export Cd dheccns nce cisateneaucedencextiandoeciasattieagslgeraneiauenteles 164 AkO L ON Ol E E a sd ates cemavocsiesauseneaseasciate 166 411 7 Deleting MeS rs ES a 167 4 2 Plotting the data in 2D c ccccsececeseceneseccsaecsssecscaseeseescesceeecaseeessesees 168 4 2 1 Loading and viewing data sets from the database 168 4 2 2 Changing the data set display settings cecceceecceseeeeeeeeeeeeeeeenees 169 4 2 3 Changing the plot options c ccccceececsseeecseseeeeseeseserseeseeeceserenees 172 Ae eek C E E T O E ne ee ee 173 4 NOVA User manual BZD PCS TAD saecce guste susetaiaser A E EE E 174 A2 O 918 A 0 ee ne ee ee ee ee 175
155. ds e Name each signal created using the expression builder must have a unique name e Unit the unit of the calculated signal The unit can be selected from a drop down list or can be entered manually e Expression this field is used to build the new signal using mathematical functions and trigonometric functions as well as parameters e Parameters this field displays the parameters of the expression e Functions this field proposes a list of typical mathematical operators that can be used to perform calculations on the data points of a given signal e Trigonometric functions a list of trigonometric operators is proposed in this field to be used in the same way as the mathematical operators e Signals this field displays the list of available signals that can be used in the signal creation process If the data set contains more than one measurement command it is possible to click the Full checkbox in order to display all the available electrochemical signals The available signals for the cyclic voltammogram from example 1 are Potential applied WE 1 Current Time WE 1 Potential scan and Index For plotting purposes it might be useful to express the applied potential relative to the Standard Hydrogen Electrode SHE The cyclic voltammogram was recorded using an Ag AgCl KCI saturated reference electrode which has a potential of 0 197 V relative to the SHE at 25 C In order to change the potential scale 197 mV has to be a
156. dure 1 2 Commands Parameters Links Chrono amperometry At gt 1 ms Remarks Chrono amperometry At gt 1 ms m End status Autolab ma oignal sampler Time WE 1 Potential vwE 1 Current m Options 1 Options m Instrument LALIT 0530 Instrument description Autolab contral am set potential 0 000 set cell On ma Viait time 3 z Record signals 1 ms 5 0 07 set potential 0 500 Record signals gt 1 ms E 0 07 Set cell lt 3 t Figure 2 13 Removing the third potential step from the procedure 2 2 62 Page NOVA User manual It is possible to undo an action at any time by clicking the button in the toolbar or using the CTRL Z keyboard shortcut It is also possible to right click the procedure editor and select the undo option from the context menu see Figure 2 14 Commands Parameters Links Chrono amperometry At gt 1 ms Remarks Chrono amperometry At gt 1 ms m End status Autolab ma oignal sampler Time WE 1 Potential vWE 1 Current ma Options 1 Options m Instrument LALIT 0530 Instrument description Autolab contral zz set potential 0 000 set cell On m Viait time s A Record signals 1 ms 5 0 07 set potential 0 500 Record signals 1 ms 5 0 01 7 Set cell rie Enabled Save in My commands Delete A Cut Ctl xX Ea Copy Ctrl C Hide Undo Delete 2 rows Ctl z Figure 2 14 The Undo opt
157. dvanced selection mode by unchecking the Simple checkbox The selection of the windowed points can then be performed by specifying a value range begin to end see Figure 4 245 316 Page NOVA User manual Source simple Figure 4 245 Switching the windower to advanced mode In Figure 4 245 the selection begins at 2 and ends at 3 which is the same selection as specified in Figure 4 243 This selection mode is useful when the number of available values for the selected signal is very high When the number of values for the selected source signal exceeds 300 Nova will automatically switch from simple to advanced Switch the source signal from Scan to Time using the dropdown list see Figure 4 246 Source Time ka Current applied PERAI Begin End can l Time 2 3 WEN Fotential D a Figure 4 246 Setting the source signal to Time Using the advanced selection mode and the Time signal as a source it is possible to select for example all the points measured from 20 s to 40 s see Figure 4 247 317 Page NOVA User manual Source Figure 4 247 Specifying a range of values Furthermore in Advanced selection mode it is possible to specify several value ranges Figure 4 248 shows an example in which a second data range has been added to the Windower from 60 to 80 seconds asx Signal Expression Unit Current applied A 1 8 Index Scan gt 1 6 Time S WE 1 Potential Vv E14
158. e NOVA User manual 4 4 Advanced plotting and overlays NOVA offers a large number of options that can be used to further customize the data plots and create overlays of different plots This section explores these options using a new example data set The Demo 02 Lead deposition EQCM entry of the demo database contains three cyclic voltammograms recorded using a gold TiO2 polished 6 MHz crystal in 0 01 M Pb ClO 2 0 1 M HClO solution The reference electrode was a solid Ag AgCl KCI Sat d and the counter electrode was a platinum rod Load Demo 02 Lead deposition EQCM in the data explorer frame The signals available for this data set are e Potential applied e WE 1 Current e WE 1 Potential e EQCM 1 AFrequency e EQCM 1 Temperature e EQCM 1 Driving force e Index e Scan e Time EQCM 1 AFrequency is the signal containing the values of the EQCM frequency change recorded using the Autolab EQCM during the measurement Both WE 1 Current and EQCM 1 AFrequency are potential dependent In order to plot both relative to the potential it is necessary to create two different plots using the same approach as the one illustrated in the previous section A plot i vs E is already attached to the CV staircase see Figure 4 53 188 NOVA User manual Demo Ue Lead deposition EQCM CY staircase 0 0035 H ivs E X 0 003 0 0025 0 002 A CLUS 0 001 0 0
159. e o GemivsE w Peak search S 4 Value 0 1 LSY staircase H ivs E me Peak search ood Y WE 1 Current Ag x Potential applier Potential applied Time Apply to selected X WE 1 C Apply to procedure Index WE 1 Potental Figure 4 68 Using the Apply to selected option to change the plot setting of all the plots in the overlay If this option is used to change the electrochemical signal used on the X axis for the overlay to the time signal the resulting plot will look like the one displayed in Figure 4 69 0 0012 0 001 0 0008 0 0006 0 0004 WET Current tA 0 0002 0 0002 S0 250 100 T20 Time 5 200 Figure 4 69 Changing the plot settings for all the plots in the overlay using the apply to 200 Page selected option NOVA User manual The plot shows the four linear sweep voltammetry curves obtained with increasing scan rate The time displayed on the X axis is the total experiment time The current increases with each new scan The electrochemical signal used on the X axis has been changed to Time for all the plots in the overlay 4 7 Plot objects Using the 2D 3D plotting feature of NOVA is not limited to just plotting the data It is also designed to enable NOVA users to prepare high resolution graphs that can be pasted directly into a manuscript or a presentation This section of the user manual will explore most of the plotting options related to
160. e Linear sweep voltammetry galvanostatic ai i oi 2 Set potential 0 000 b Linear polarization ni Set cell On z ie Hydrodynamic linear sweep F aig i ot on Wait time s 5 Differential pulse voltammetry ee _ Square wave voltammetry Optimize current range 5 q i CV staircase 0 000 1 000 1 000 0 000 2 0 1000000 Sampled DC polarography oo Of Chrono amperometry At gt 1 ms z Chrono potentiometry At gt 1 ms Chrono amperometry fast Chrono potentiometry fast Procedure editor frame Chrono amperometry high speed j Chrono potentiometry high speed Chrono charge discharge i Interrupt interrupt high speed e Positive feedback j FRA impedance potentiostatic e FRA impedance galvanostatic i FRA potential scan Pee Procedure amp Command browser User log message Time Date Command i Autolab USB connected AUT40008 9 56 19 AM 1 15 2013 gt Start User log Start Stop button Ready Intermediate _ Figure 2 2 Overview of the Setup view Note The User log and the Toolbar are elements common to all the views of the Nova software The Start button is visible in all the views except the Multi Autolab view The two most important parts of the Setup view are the procedure editor frame which provides a visual workspace for creating editing procedures and the procedure and command browser frame on the le
161. e Repeat n times command are all timed commands and they will be executed without interruption This is again indicated by the green timing guide located on the left hand side of the procedure editor see Figure 2 47 During the measurement the two potential steps Set potentia command and the two chrono measurements Record signals gt 1 ms command will be executed without timing interference from background Windows activity The final segment of this procedure consists of a single command that turns the cell off when the measurement is finished see Figure 2 48 Since this is again a timed command the timing guide will be shown on the left hand side Setcell Ott lt 2 Figure 2 48 The final segment of the procedure is used to switch the cell off at the end of the measurement The timing of the full procedure is interrupted at two locations as indicated by the timing guide on the left hand side of the procedure editor see Figure 2 49 NOVA User manual Commands Parameters Links Chrono charge discharge Remarks Chrono charge discharge End status Autolab xij signal sampler Time WE 1 Potental WE Current c Options 1 Options c Instrument ALIT 40006 Instrument description Autolab contral 4 i Set potential U 000 H Set cell On am Warttime s 10 G Repesatn times iu Number of repetitions 10 H Set potential 1 200 H Record signals ms 2 5 0 01 Set potential 0 000 Record signals lms
162. e all from View Figure 4 46 Using the Save the data in the database option to update the whole data set 4 3 Plotting the data in 3D NOVA introduces a powerful 3D graphic engine that allows the use of three signals to plot the data The plotting options and settings are common to those of the 2D plots which means that any change of these settings will affect both types of plots Load the data set from Example 1 back into the data explorer if necessary Create a new plot called Standard CV using a green Line plot using a size 2 line refer to the previous sections if required Set the Potential applied on the X axis WE 1 Current on the Y axis and Time on the Z axis see Figure 4 47 Demo 01 Copper deposition CY staircase H t E wst Logi ws E G jyst H Standard C Ng X Potentid spplied ae mae WE 1 Current Time Figure 4 47 Creating the Standard CV plot To view this new plot in 3D click the 3D view button amp in the Data Analysis Toolbar see Figure 4 48 184 F NOVA User manual File View Profile Run Tools Help Be Tee eee UN ee PC ene eee Renee yl Poe gt et Show 3D plot Figure 4 48 Switching from 2D to 3D When the 3D button is clicked NOVA will display the data from example 1 in a perspective 3D plot see Figure 4 49 WELT Current 4 Figure 4 49 The data from Example 1 in 3D Press and hold the right arrow
163. e and select the location of the plot in the Measurement view from the Copy Visible Plot s to context menu see Figure 4 59 Demo 01 Copper deposition a C staircase He E vs t H Logi vs E H ive t A Stapa Plot Options Properties Add Analysis Copy Visible Plot s to gt Measurement Plot 1 X Show All Plots Measurement Plot 2 Hide All Plots Measurement Plot 3 Save in My commands Measurement Plot 4 Al Delete Remove all from View Figure 4 59 Creating an overlay on the Measurement view using data plotted in the Analysis view The data shown in the analysis view will be copied as it is displayed to the location specified in the measurement view If more than one plot is shown in analysis view all the visible plots will be sent to the measurement view The overlay is only shown if the plot is visible in the measurement view Click the l or ss button in the toolbar to display more than one plot in the measurement view A Warning Overlays created this way must have the same signal on the X axis 192 NOVA User manual 4 6 Data sets with multiple entries Some data sets can contain several measurements if the measurements where performed using a repeat loop for example While these data sets are managed in the same way as regular data sets there are some particular features that will be explained in this section The Demo 05 Fe Fe l on pcPt entry of the
164. e data A new item called Peak search will be added to the data set in the data explorer frame below the i vs E plot see Figure 4 129 Demo 14 FACHA FC in ACNYCHECl2 Import GPES data Ali vs E Peak search Figure 4 129 The newly added Peak search analysis tool Click the Peak search analysis item A new area will be displayed on the right hand side of the plot This part of the view allows the definition of the selection criteria for the peak search tool see Figure 4 130 Search mode Automatic C Manual Base line mode Minimum peak height 1E 07 Minimum peak width 0 015 Mr of points in search window b Number of significant digits 5 Reset Feak Type Forward 0 Reverse Figure 4 130 The peak search selection criteria 242 Page NOVA User manual The following selection criteria for the peak search tool are available Search mode automatic or manual Baseline mode defines the type of baseline used to determine the base of the peak The linear tangent baseline is used when performing an automatic peak search Other types of baselines are available in manual peak search Minimum peak height defines the minimum height of the peak in Y axis units 0 means that this selection criterion is not used Minimum peak width defines the minimum width of the peak at half height in X axis units 0 means that this selection criterion is not used Nr of points in search window this parameter defi
165. e dedicated button in the toolbar see Figure 3 15 File View Profile Run Tools Help EET Advanced procedure view EJAJ e 2 AE ce aA Setup View Mult Autolab View Measurement View User log F11 ji ji ia Analysis View we i Autolab display F10 FRA manual contri MUX manual control External manual control File View Profile Run Tools Help F lig Sy a gt A I en ax a ali am c cs dr la e cu g j Show hide Autolab display Figure 3 15 Choose the Autolab display option from the view menu or use the dedicated button in the toolbar to open the Autolab display window 3 4 1 Manual control The manual control of the Autolab is built into the lower part of the Autolab display A series of labels are displayed in this section of the view see Figure 3 16 These labels can be clicked to change the settings of the instrument 27 The colors used in the Autolab display can be set using the Tools Options menu 149 Page NOVA User manual Collapse Expand button Saral number Autolab displ EJ Q Autolab manual control u3AUT70530 Current Potential f i i nic g E NIE AL _ Manual settings mm A po Active current range status current range Experimental control gt Peverse N qt x 9 170 mc 9 154 mc time Experiment data 77 76 01 s Measuring scan 2 Measurement progres
166. e detail in Figure 2 7 8 C staircase F000 1 000 1 000 0 000 2 0 1 090000 start potential w U 000 Upper vertex potential v 1 000 CV staircase Lower vertex potential y 1 000 Start potential V 0 000 stop potential Vv 0 000 Upper vertex potential V 1 000 Number of stop crossings 2 Lower vertex potential V 1 000 Step potential Cw 0 00244 k Stop potential v 2 0 000 Scan rate v s 0 1000000 iit Tarai tibial Saeed l yep Number of stop crossings 2 Estimated number of points 1650 z j 0 00244 Interval time s 0 024400 SPPA el amin Signal sampler Time WEC1 Potential WE 1 Curre 7 Scan rate V s 0 1000000 Options 1 Options Estimated number of points 1650 Potential applied array Vv Interval time s 0 024400 Time lt array gt 3 Sampler WE Current lt aray A Time ocan lt ANE Segment Ous WE Potential lt array gt Cv WE 1 Potential SENENG Segment 35900ys Set cell Or WE 1 Current gt Options WE 1 1 mA 100 nA Figure 2 7 A detailed view of the cyclic voltammetry potentiostatic procedure and its default parameters note the detailed tooltip Each command shown in the expanded view of the procedure has a number of parameters that can be edited These parameters are indicated in black Start potential Scan rate etc Some values are indicated in light grey This means that they cannot be edited by the user but that they are depend
167. e mode Minimum peak height Minimum peak width Mr of points in search window Number of significant digits Reset Feak Type 0 Automatic Manual Linear Curve Cursor Exponential cero base Pohkynomial Linear Curve Cursor Linear Free Cursor Linear Front Linear Rear Linear Front Tangent Linear Rear Tangent Figure 4 134 In Manual search mode the base line can be defined In this case the base line mode selection will become available see Figure 4 134 The peak area is calculated only when the Linear Curve Cursor or the Polynomial methods are used 245 Page NOVA User manual To perform manual peak search set the required search criteria and choose the base line mode from the drop down list A total of nine different baseline types are available in NOVA see Figure 4 134 e Exponential this option uses an exponential baseline in the determination of the peaks To define the baseline click on the plot area The software automatically connects the initial point to the nearest data point While holding the mouse button pressed drag the mouse across the plot area to define the baseline When the mouse button is released the final X position of the mouse pointer is used to define the X position of the final point of the baseline on the curve see Figure 4 135 a Current 4 05 0 Potential iV Figure 4 135 Defining an exponential baseline for the peak left location of the fir
168. e mouse button pressed drag the mouse across the plot area to define the baseline When the mouse button is released the final X position of the mouse pointer is used to define the X position of the final point of the baseline on the curve The tangent is then extended backwards and the peak is located see Figure 4 141 249 NOVA User manual AE 7 ae AEN lest Current 4 1E 7 22ER 0 5 J Oe Potential W Figure 4 141 Using the Linear rear baseline search method The base points used to specify the tangent baseline are indicated by the small vertical lines on the plot see Figure 4 141 e Linear Front Tangent this option finds peaks by extending the baseline located in front of the peak The baseline is defined by clicking on the plot area and While holding the mouse button pressed dragging the mouse across the plot area drawing a straight line The software automatically connects the baseline to the curve at the data point for which the first derivative is the closest to the slope of drawn baseline see Figure 4 142 250 P NOVA User manual AE T 3E 7 2E 7 lest Current 4 1E 7 22ER 0 5 J Oe Potential W Figure 4 142 Using the Linear front tangent baseline search method The base points used to specify the tangent baseline are indicated by the small vertical lines on the plot see Figure 4 142 Linear Rear Tangent this option finds peaks by extending the baseline
169. e of Expand one level Ei Expand one levelt used to expand the displayed procedure into a more detailed view opposite of Collapse one level Show all links expands the currently edited procedure in order to show all existing links 7 Undo cancels the last performed action if possible ca Redo repeats the last cancelled action if possible Clear measurement plot clears the contents of all plots in the measurement view or a specific plot 1 to 4 3 The Autolab display can also be shown by pressing the F10 key 4 Only active in the Setup view This button is greyed out in the two other views gt The following actions can be undone redone delete command move command insert command link unlink command parameter Only active in the Measurement view This button is grayed out in the two other views 11 NOVA User manual 1 2 2 The toolbar menus Some NOVA operations require the use of instructions located in the drop down menus of the toolbar A short overview of the menus is given below File _ New Procedure Wi Save Procedure Save Procedure as New Ctrl M Ctl 5 New Mult Autolab Configuration Open Mult Autolab Configuration Save Mult Autolab Configuration Page Setup L Print Preview ca Print Procedure Ey Import Procedure bl Export Procedure Exit View Advanced procedure view Setup View Mult Autolab View Measurement View Dei Analysis View User log F11
170. e procedure until the procedure ends or the user interrupts the measurement or a Cutoff condition is encountered When the measurement stops the measured data points can be stored into a user defined database Figure 1 6 shows a schematic overview of the basic steps involved in a NOVA procedure 17 NOVA User manual Start measurement Set Autolab property Procedure validation Display data Sample signals Options Stop measurement Store data points Figure 1 6 The basic steps in a NOVA procedure 1 3 3 The Signal sampler The Signal sampler is a fundamental component of NOVA The sampler defines what information electrochemical signals the Autolab instrument must gather during the course of an experiment Typically the Autolab will be used to measure both potential and current but other signals can be acquired during a measurement i e pH time temperature QCM etc The sampler also defines how these signals must be measured see Figure 1 7 18 Page NOVA User manual Current Time Y L Auxiliary Potential QCM T om pH Figure 1 7 The sampler is used to measure the electrochemical response of the cell Every measurement command has a user defined sampler This means that individual measurement steps can be designed in order to gather data points from the relevant sources The sampler is defined as a series of segments during each of which one or more electrochemical signa
171. e tool integrates the Y signal versus the X signal regardless of the type of signal plotted The calculate charge analysis tool calculates the charge in coulombs by integrating the current versus the time Double click on the demo file Demo 19 Cyclic voltammetry Fe Fe entry of the demo database to load it into the data explorer frame This file contains data points of a cyclic voltammetry staircase experiment recorded in a 0 05 M Fe CN in 0 2 M NaOH solution The number of scans is three To add the Calculate charge analysis tool to this data set right click the CV Staircase item in the data explorer frame and select the Calculate charge analysis item from the context menu see Figure 4 199 Demo 19 Cyclic voltammetry Fee Fes H a CY staircase em ivs E Plot Options Properties Add Windower Generate index Add Plot Add Analysis Calculate charge Show All Plots X Hide All Plots Save in My commands A Delete Remove all from View Figure 4 199 Select the Calculate charge analysis tool to add it to the data set A new item called Calculate charge will be added to the data set below the CV Staircase item Two plots Q vs E and Q vs t are automatically generated by this analysis tool see Figure 4 200 287 NOVA User manual Demo 149 Cyclic voltammetry Fed Fea A a CV staircase fem ive E 5 a Calculate charge H Cvs E N H Cyst Figure 4 200 The Calculate charge analys
172. ecord signals gt 1 ms command The duration is set to of 5 seconds and an interval time of 0 01 seconds is used The first step is at O V the pre treatment potential then at 0 5 V and finally at 0 5 V see Figure 2 11 Commands Parameters Links Chrono amperometry At gt 1 ms Remarks Chrono amperometry At gt 1 ms m End status Autolab m oignal sampler Time WWE 1 Potential vWwE1 Current ma Options 1 Options a Instrument LALIT 0530 Instrument description Autolab contral z set potential 0 000 Set cell On m wWalttime s 5 Record signals gt 1 ms Duration s a Interval time s 0 01 Estimated number of points 500 signal sampler Time WWE 1 Potential vwE 1 Current maa potions 1 Options m Corrected time lt array gt 5 Time lt array gt 5 WE Potential array Cv WE Current lt array A Index lt arrary gt h Ive t m set potential 0 500 Record signals gt 1 ms 50 01 set potential EDN Record signals 1 ms 5 0 01 Set cell Ct lt gt Figure 2 11 The default Autolab Chrono amperometry At gt 1 ms procedure the Record signal gt 1 ms command is expanded to show the details of the command The potential used for each step can be edited in the same way as the previous example However editing a chrono amperometry measurement is not only done by changing the duration of the potential steps and the interval time but also by changing the number of potential
173. ed in order to display the potential applied as a function of time Demo 01 Copper deposition Demo 01 Copper deposition B Cv staircase C staircase o eee ivsE N 2 Ay X Potential applied Ae X Potential applic HA Y WE 1 Current Ae Y WE 1 Current Potential applied ioe Z Time As 2 Time Scan s VWE 1 Current Time WE lgpotental A B Index ime Demo 01 Copper deposition Demo 01 Copper deposition a C staircase CY staircase a ivsE e ivsE oy X Time Ag x Time Aa Y WES11 Current As Y Potential applied ged E Potential applied Ay Z Time Scan WE 1 C u Potential applied Time VWE 1 Potental C Index D Figure 4 26 Changing the display settings to WE 1 Potential applied Y axis vs Time X axis A Expanding the signals list B Changing the signal displayed on the X axis C Changing the signal displayed on the Y axis D The new 2D plot for the data from example 1 Changing the display settings in order to plot the potential in function of time as described in the picture above will change the display of the data set and a familiar saw tooth potential profile of a cyclic voltammogram will be plotted see Figure 4 27 170 Page NOVA User manual Demo 01 Copper deposition EI CY staircase El iws E Potential applied W 10 15 20 nas al aa Time S Figure 4 27 The saw tooth profile of the cyc
174. ed minimum size scaling 216 Fixed scaling 216 Forward 259 FRA measurement 153 Functions 293 322 G GIF 217 Global plot options 196 GPES 57 Grid 201 Grid coarse 201 Grid fine 201 H Help menu 13 High resolution plots 201 High stability 150 Highest current range 111 150 Home key 213 HSTAB label 150 Import data 164 Individual plot 195 Input box 87 Insert commands 67 76 Insert label 212 Insert procedure 122 Integrate 264 Integrate plot 266 Interrupt 78 J JPG 217 L Legend 203 Legend font 205 Legend position 205 Legend style 205 Levich plot 257 281 283 Line frequency 21 Linear distribution 107 Linear regression 255 Linear sweep voltammetry 96 102 Link 56 Link Input box 87 Link parameters 11 Linking 60 81 Linking commands 79 Linking parameters 79 Links 79 Load data 168 Load database 156 Local plot options 196 Logarithmic distribution 107 Lowest current range 111 LSV staircase 102 Major tick 201 Manual control 149 Manual peak search 240 Mathematical expression 293 Mathematical operators 293 Measured data database 29 Measurement process 17 Measurement progress 140 141 Measurement view 10 15 139 Measurement view plots 144 Measurement view settings 115 Merge data 162 Message box 77 Minimum and Maximum 203 Minimum peak height 226 243 Minimum peak width 226 243 Minor tick 201 Mouse wheel
175. ed to calculate the first derivative of a plot This tool can be added to any Y vs X plot in the data analysis view Double click on the demo file Demo 19 Cyclic voltammetry Fe Fe entry of the demo database to load it into the data explorer frame This file contains data points of a cyclic voltammetry staircase experiment recorded in a 0 05 M Fe CN 6 in 0 2 M NaOH solution The number of scans is three Click the i vs E plot in the data explorer frame to display the data points from this demo file see Figure 4 157 A typical reversible electron transfer behavior is recognizable in the cyclic voltammogram Demo 19 Cyclic voltammetry Fe2 Fe3 0 0012 B a C staircase li vs Y 0 001 0 0008 0 0006 0 0004 0 0002 0 0 0002 0 0004 VVE 1 Current 0 0006 0 0008 0 001 0 2 0 0 2 0 4 0 6 Potential applied W Figure 4 157 The Demo 19 data file Right click the CV staircase item in the data explorer frame and select the i vs t plot from the plot context menu see Figure 4 158 261 Page NOVA User manual S S Demo 19 Cyclic voltammetry Fe2 Fes El A aes ieee Plot Options H ivs E Propertes Add Windower Generate index Add Analysis ivs E Show All Plots Hide All Plots Logi vs E Save in My commands Logli vs Log t Delete E vs E vs Log i Remove all from View Figure 4 158 Adding the i vs t plot to the data set
176. eeeecceeeeceeeeseeeeseeeeessaeees 300 4 11 2 Selecting the values of the scan rate cece ee ceeeeeeeeeeeeeneeeeeaes 302 4 11 3 Selecting the values of the peak height cc ceceeeeeeeeeeeeeeees 304 4 11 4 Calculating the square root of the scan rate eceeeceeeeeeeee ees 305 4 11 5 Building the Plot c ccccccsseecneseestecesseeeseseeeccedersseesecseeessueeesesses 307 A t2 TE WMO WY CP eiserne pear n n doe dese adaware aereo t 309 4121 Adding a WIN OW EE sesiis aa a inis 310 4 12 2 Selecting the source of the WINdOWET ssnnnssnnnssnrnesnrnesrrnesnrees 312 4 12 3 Plotting the Selected data c cccccccecssseceueecectveccsseesteeeseeseesseeees 314 4 12 4 Changing the selected data ccccseccceeeeceeeeesseeesceeeesesensseeees 315 4 12 5 Advanced SeIOCTION 2 cc csccccsseceseeeecsesecceseecseseesseeeseeseessesersnens 316 4 12 6 Direct windowing through X axis SCAlING cceceeeeeseeeeeeeeeeeneees 318 ON goss oaec ee seine EE A E E E EE 321 6 NOVA User manual 1 Introduction NOVA is designed to control all the Autolab potentiostat galvanostat instruments with a USB connection It is the successor of the GPES FRA software and integrates two decades of user experience and the latest NET software technology NOVA brings more power and more flexibility to the Autolab instrument without any hardware upgrade NOVA is designed to ans
177. eline mode left specification of the waypoints for the polynomial baseline right pressing Enter validates the polynomial baseline The polynomial search method locates the peaks in the curve segment closest to the first point defining the polynomial baseline Linear Curve Cursor this option uses a linear baseline in the determination of the peaks To define the baseline click on the plot area The software automatically connects the initial point to the nearest data point While holding the mouse button pressed drag the mouse across the plot area to define the baseline When the mouse button is released the final X position of the mouse pointer is used to define the X position of the final point of the baseline on the curve see Figure 4 138 247 NOVA User manual 4E 7 4E 7 3E 7 3E 7 2E 7 2E 7 1E 7 416 7 D a 0 6 0 1E 1E 7 2E 7 2E 7 0 5 0 0 5 0 5 0 0 5 Potential V Potential V Figure 4 138 Using the Linear curve cursor method to specify the baseline left location of the first point right location of the second point and drawing of the baseline e Linear Free Cursor this option uses a linear baseline in the determination of the peaks To define the baseline click on the plot area and while holding the mouse button pressed drag the mouse across the plot area When the mouse button is released the final X Y position of the mouse pointer is used to define the final point of the base
178. ent on the other user defined parameters Figure 2 7 shows that the CV staircase command has seven parameters that can be edited by the user as well as a signal sampler and options 57 Page NOVA User manual The six lines shown in red are the electrochemical signals that are sampled during the measurement Each command shows a summary of its parameters between brackets This is quite useful because it provides an overview of the parameters of the command even if it is displayed in its contracted form see Figure 2 8 Commands Parameters Links Cyclic voltammetry potentiastatic Remarks Cyclic voltammetry potentiastatic no extra modules required End status Autolab oignal sampler Time WEI Potential WWE Current al Options 1 Options m Instrument LSAT 70530 Instrument description Autolab control m set potential 0 000 Set cell On I Wart time 3 z Optimize current range z m CY staircase O 000 1 000 1 000 0 000 2 0 1 000000 set cell tt lt gt CV staircase Start potential V 0 000 Upper vertex potential V 1 000 Lower vertex potential V 1 000 Stop potential V 0 000 Number of stop crossings 2 Step potential V 0 00244 can rate V s 0 1000000 Estimated number of points 1650 Interval time 5 0 024400 Sampler Time Segment Ops WE 1 Potential Segment 5900us WE 1 Current Options WE 1 1 mA 100 nA Figure 2 8 A detailed view of the CV s
179. ential V Lower vertex potential V stop potential 0 Number of stop crossings 2 Wait time s step potential V 0 00244 Duration s 30 Scan rate V s 0 1000000 Figure 3 5 Overview of the command parameters that can be changed during a measurement left Wait time 5 command right CV staircase command 142 Page NOVA User manual To modify a parameter change the value of the parameter and press the button see Figure 3 6 Cyclic voltammetry potentiostatic Autolab control Set potential Set cell ge vait tire s 2 Optimize current range H V staircase Set cell Wait time s Duration s 60 Figure 3 6 Parameters can be changed by typing the new value and clicking the button Not all command parameters can be changed in real time For more information on the parameters that can be modified in the measurement view please consult the Command list document available from the Help menu in Nova 3 2 Measurement plots The measurement view is used to display the recorded data points during the experiment or the results of calculation or data handling instructions added to the procedure Up to four different plots can be used in the measurement view and it is possible to display one two or four plots at the same time The initial contents of these plots are defined in the procedure setup Each Plot command added to the procedure in the Setup view has two parameters that define the pl
180. ential vwE1 Current ma potions 1 Options m Instrument Instrument description Autolab control set potential 0 000 Potential tv set cell On Vat time s 5 Optimize current range z CY staircase U 000 1 000 1 000 0 200 2 0 1000000 Start potential v Upper vertex potential v4 1 000 Lower vertex potential 6 1 000 stop potential v 0 200 Number of stop crossings 2 step potential v 0 00244 ocan rate vis 0 1000000 Estimated number of points a Interval time s 0 024400 signal sampler Time WWE 1 Potential vWEM1 Current m Options 1 Options m Fotential applied lt aray Cv Time lt array gt 5 WE Current lt aray 4 ocan lt arrary gt WE Potential array Cv Index lt Array iws E ina set cell Ott m lt gt Figure 2 37 The Stop potential value is now independent Note Only one parameter can be unlinked at a time Links can also be broken using the right click menu or using the CTRL U keyboard shortcut see Figure 2 38 83 Page NOVA User manual Commands Parameters Links Cyclic voltammetry potentiostatic Remarks Cyclic voltammetry potentiostatic ail End status Autolab m oignal sampler Time WE 1 Potential vwE 1 Current m Options 1 Options a Instrument Instrument description Autolab control E Set potential 0 000 Fotential v 0 000 set cell On m Viait time fs z Optimize current range 5 E CY staircase
181. ential and squared values and set the required precision 215 Page NOVA User manual Scaling mode choose from automatic fixed only for 2D plots or fixed minimum size Automatic scaling will set the X and Y scaling to its optimal setting in order to display every data point Fixed scaling allows setting the scaling of an axis in such a way that only a specific part of the axis is displayed only for 2D plots Fixed minimum size scaling will plot the data using any scaling provided that displays all the data points on the screen If some data points are outside of the chart the scaling will be automatically adjusted Show Label toggle the labels on off Edit Axis displays the Edit Axis window through which the settings used for the axis can be modified see Figure 4 88 Edit Axis Label text Labelfont Arial 2pt stvle Reqular Label color Tick fort Arial bot style Reqular Tick color Tick angle 0 xis color JK gt Cancel Figure 4 88 The Edit Axis window can be used The Tick Angle setting is not available in 3D plots For 2D plots the tick angle can be set to any value between 0 to 90 degrees 4 7 7 2D Specific options Axes Coupling choose from independent iso metric or iso tropic 4 7 8 3D Specific options 216 Origin Axes overrides any axis position setting by moving the intersection of the axis at the origin of the plot point O O 0 Location set the p
182. ential array Cv Index lt Array gt Ive E m set cell Ott m lt gt Figure 1 35 Hiding and unhiding command parameters in the procedure editor 1 6 1 5 Hidden commands warning A warning is displayed in the status bar to inform the user when commands are hidden by the active profile in the procedure editor This message will blink a few times see Figure 1 36 User log message Time Date Command W Autolab USB connected W34UT 70530 11 56 36 3 26 2012 gt Start Ready Some commands or command parameters are hidden by the active profile Basic Figure 1 36 A warning is displayed when commands are hidden by the active profile To reveal the hidden commands select the Show all option from the Profile menu or adjust the active profile using the same menu 39 Page NOVA User manual 1 6 2 Sorting function for the commands browser The possibility to sort the commands in a group is now provided Right clicking a command group displays the different sorting options ascending or descending see Figure 1 37 It is always possible to return to the original order using the same strategy and using the Original order option provided in the context menu Commands H Favorite commands E Control E Metrohm devices H External devices H Measurement general H Measurement cyclic and linear sweep voltammetry H Measurement voltammetric analysis E Measurement chrono methods H Meas
183. epeat for each value Inst td inti Nested procedure nstrument description End status Autolab Autolab control H Measurement general Set potential 0 000 H Measurement cyclic and linear sweep voltammetry Set call O H Measurement voltammetric analysis ee i 1 Wait time s 5 4 Measurement chrono methods aiu H Measurement impedance SRS Saas 1 CY staircase 0 000 1 000 1 000 0 000 2 0 1000000 H Data handling Set cell Off z H Analysis general I lt gt Figure 2 30 Inserting a Message box to create a reminder Expand the inserted command A Message box has the following parameters e Title of box this is the title of the Message box By default the Title of box is automatically linked to the Serial number of the instrument Instrument parameter This link can be broken if necessary If no instrument is connected the Title of box will be unlinked e Message this is the message to display in the Message box e Time limit s this defines an optional count down for the Message box e Use time limit defines whether the time limit should be used When this parameter is set to No the Message box will be displayed indefinitely Type in the following strings for the Message parameter see Figure 2 31 Message Switch off the nitrogen purge 20 More information on links is provided in Section 2 4 8 77 NOVA User manual Commands Parameters Links Cyclic voltammetry poten
184. eps efeU 200 24006 AM Factory standard procedure Demo 09 Chrono methods 4000164 with variabl 2 20 2007 9 37 06 AM Combination of steps and levels Demo 10 Diferential pulse measurement Bf25 2009 12 14 00 Example forbaseline correction peak sea Figure 4 11 The repository backup creates a copy of the original data set Once a backup has been added to the repository it is possible to modify the original data set and restore it at any time by choosing the Restore from Repository see Figure 4 12 It is also possible to create more than one backup in the data repository 161 Page NOVA User manual Procedure name f Time stamp Remarks E Demo 01 Copper deposition 15 2007 6 25 27 PM CusO4 0 01 M H2504 0 1 M AgfAgCl Ref KCI amp CusO04 0 01 M H2504 0 1 M AgvAgCl Ref RCI S Demo O02 Lead PhiClo4ie 0 01 MHOGO 0 1 M Demo 03 Bipot Properties 0 RPM HCIO4 0 1 M4 Demo 04 Hydre eee gl SY et Fe MaGH 0 2 bl Demo 05 Fef Fed Fea Reversibility Test Lo with increasing Demo 06 Galve Delete from Repository Lead deposition on gold galvanastatic Demo 0 High Restore from Repository Dummy cell c Demo 06 Chro Factory standard procedure Demo 09 Chro Import Data Combination of steps and lewels Export Data Delete Data Set Active Procedure Store in Repository Merge Data Show in Windows Explorer Figure 4 12 Restoring the original data set from the repository backup Using the
185. equivalent weight of the sample in g mol of exchanged electrons e Surface area defines the area of the sample in cm e Number of significant digits Defines the number of significant digits used in the Analysis results frame For high cathodic or anodic over potentials the Butler Volmer equation can be reduced to the following linear expressions respectively E Ecorr 108 tcorr Da logli E Ecorr 108 torr De logli When the Tafel slope analysis tool is selected the mouse pointer changes to a cross Using the mouse pointer click two points in the plot to specify the linear part of the anodic branch see Figure 4 179 Once the second point is clicked a line will be drawn on the plot 273 NOVA User manual JE 5 1E 6 Current Ay TE 8 0 55 0 5 0 45 0 4 0 35 0 3 0 25 0 2 0 15 Potential gW Figure 4 179 The Tafel slope analysis tools requires the specification of the linear segments of the Tafel plot 1 2 The same must be repeated for the cathodic branch of the plot Once both linear segments have been defined the intercept is determined and indicated in the plot see Figure 4 180 1E em 0 30492 4 896E 06 2 1E 5 0 55 0 5 045 0 4 0 35 0 3 0 25 0 2 0 15 Potential gW Figure 4 180 The Tafel slope analysis tools requires the specification of the linear segments of the Tafel plot 2 2 274 NOVA User manual Select the anodic branch of the plot first and
186. es i Parameters Links Cyclic voltammetry potentiostatic Time YE Potential WWE Current 0 Options ALT 50004 0 000 0 000 0 300 On 5 Os Le sy ail 0 300 30 0 300 0 300 0 07 00000 0 300 0 300 0 00244 00 0100000 250 0 244141 Time WE Potential WET Current 0 Options Carrey Cv arrary gt 5 arrany gt A array fv array gt Cai D aa D aia S a Forward Ott Figure 4 220 Detailed view of the Repeat for each value linked to the Control external device command Expand the Measurement cyclic and linear sweep voltammetry group in the left frame and then expand the LSV staircase item Eight items will be displayed see Figure 4 221 302 Page NOVA User manual e Index e Potential applied e Scan rate V s e Start potential V e Stop potential V e Time e WE 1 Current e WE 1 Potential T Build signal O ES Analysis general Name Index H Control Measurement cyclic and linear sweep voltammetry LS staircase WE I Current WE 1 Potential H Measurement general H Untyped filter Search from 1 lewel si up _ Sort by order of 1st array high to low Sort by order of 1st array low to high OK Cancel Figure 4 221 Adding the value of the scan rate to the filter Double click the Scan rate V s located under the LSV staircase group to add it to the list in the frame o
187. eseaeees 73 2 4 7 Adding extra COMMANAS cccsscccceececceescsescessseecnesenssuetecseeesceders 76 2 4 8 Linking commands 23 ci0s0cniccaseaceiuvadpideneediaidecsieanvedaisessedadecdaasadease spices 79 ZAG VS Understanding NKS sesser rena unleaded vweaeede ENS 79 2A G2 REMON INKS aacracs geacereonecigcsoaeaaemccnanecedemeaaeasaactengaaceneraiaaeeainne 81 NOVA User manual 24 8 3 Creating INKS ase censecnerscncaieecscessacnvenoesanetesaschdiaderaadhasacaraadeeroster 84 2 4 8 4 Links the programming tools Of NOVA cccceeseeeeeeeeeeeeean ees 86 2 5 Advanced procedure CONTIG ba sonic ssitcinrerademanaatuedsmmcndnsaneldmanetenmeneaveeaieeawtens 90 2 5 1 Advanced procedures Structure cccccccccececeeeceeeeeteeeteeeeseeeaees 90 2 5 2 Building advanced procedures ccc cecceceeeeeeeeeeeeeeeeseeeeeaeeeeaeeeeeaeeees 95 2 5 3 Defining the preconditioning Stage ccccecccssseceeeseeeeeeeeeeeesneeeeeaes 97 2 5 4 Defining the measurement conditions ccceceecceeeeeeeeesaeeeeeae seen 102 2 5 5 Defining the post measureMment settings ccceccceseeeeeeeeeeeeeeneeees 109 2 56 TOC EC Live OPOS sensie EE 110 Z 57 Deining the Samplet snene nnee NEEE EEEE 113 2 5 8 Defining the plot settings ce cccccceseeeceeeeeeeeeeeeeeeseeeeeeaeeeeesaeeeees 115 2 5 9 Edit remarks and save procedure cccccececceseceeseceeeseueeseusensaes 118 2 5 10 P
188. ession Unit 1 9E 10 Result Smoothed 1E 10 a 5 5E 11 O Spike rejection 0 Smooth level Level 2 v Polynomial order 2 5E 11 Number of points left right 4 4 0 0 2 0 4 0 6 0 8 1 Reset Potential V Figure 4 103 The preview of the smoothed curve is displayed in black Changing on the SG Smooth tool settings will automatically trigger the recalculation of the smoothing on the original data set For example changing the Smooth level from Level 2 to Level 4 will immediately display the same curve with a heavier smoothing see Figure 4 104 MEE x Signal Expression Unit 1 5E 10 Result x Smoothed 1E 10 2 5 E 11 O Spike rejection 0 Smooth level Polynomial order 5E 11 Number of points left right 0 0 2 0 4 0 6 0 8 1 Reset Potential V Figure 4 104 A higher level results in heavier smoothing NOVA User manual The SG Smooth tool automatically generates an additional plot called SG smoothed plot corresponding to the result of the defined Savitzky Golay smoothing see Figure 4 105 Demo 15 UME LSV 1 6E 10 Import GPES data H ivs E 1 4E 10 SG Smooth SG smoothed plot 1 2E 10 1E 10 SE 11 6E 11 4E 11 Smoothed result Y 2E 11 0 2E 11 0 0 2 0 4 0 6 0 8 1 Result X Figure 4 105 The SG Smooth tool automatically generated a Smoothed plot Changing the settings of the SG Smooth tool automatically updates the Smoothed plot 4
189. et only contains three scans three checkboxes are provided one for each scan 312 Page NOVA User manual Source simple Figure 4 236 The contents of the Windower editor are updated as soon as the source signal is defined Select the checkbox corresponding to the second scan in the editor to select the second scan for the windower see Figure 4 237 Source Figure 4 237 Selecting scan number two in the editor Click the button to close the editor and add the specified windower to the data set see Figure 4 238 E Demo 0b Galvanastatic CY C staircase galvanostatic H E vs i Figure 4 238 The windower is added to the data set 313 Page NOVA User manual 4 12 3 Plotting the selected data Now that the windower has been completely defined a plot can be added to it The plot attached to the windower will display only the values in its data grid in the present example the recorded data points from scan number two To add a plot to the windower right click the signal windower in the data explorer and select the add plot E vs i option see Figure 4 239 a Demo U6 Galvanostatic CY CY staircase galvanostatic E vs i i i V indower Plot Options Properties Add Windovwer Generate index Add Plot t Custom Show All Plots ivs E Hide All Plots Log i vs E Save in My commands E vsi X Delete Evst E vs Loq i Remove all from View E vs Loq t Fi
190. etry z sampled OC polarography z Chrono amperometry At gt 1 ms z Chrono potentiometry At gt 1 ms z Chrono amperometry fast z Chrono potentiometry fast H Chrono coulometry fast z Chrono amperometry high speed z Chrono potentiometry high speed z Chrono charge discharge lnterrupt z Interrupt high speed Positive feedback z FRA impedance potentiostatic z FRA impedance galvanostatic FRA potential scan Standards ho My procedures Figure 2 3 The empty procedure editor frame and the factory standard procedures located in the Autolab group An empty procedure editor frame always displays the seven lines shown in Figure 2 3 and these can be edited during the procedure creation process New procedure is the default name for all new procedures The procedures displayed under the Autolab group in the procedure browser frame are factory standard procedures They are always available in NOVA and cannot be deleted To load a procedure into the editor frame right click an existing procedure in the procedure browser frame and select the Open for editing option from the menu see Figure 2 4 It is also possible to double click the procedure to load it in the procedure editor 53 NOVA User manual File View Profile Run Tools Help ee tee Bieter em EEE ee ome ET Commands Procedures Commands Parameters Links 5 Autolab New procedure ro Remarks as fe Cyclic voltammetry potentiostatic Hid
191. ey co Commands Commands Parameters l Mew procedure H Favorite commands E SE E i A End status Autolab Massage box Signal sampler Time WE 1 Current a eae Options Mo Options Instrument ALIT 40008 Repeat n times ms Repeat for each value z Repeat for multiple values 2 osteg proce dure Instrument description j y procedure gt lt gt 4 Metrohm devices H External devices H Measurement general H Measurement cyclic and linear sweep voltammetry H Measurement voltammetric analysis H Measurement chrono methods H Data handling H Analysis general H Analysis baseline correction H Analysis corrosion H Flots general i My commands My Galvanastatic Autalab control command Figure 2 107 Adding the Nested procedure command Links The Nested procedure command creates a subsequence in the procedure editor see Figure 2 108 Using the drag and drop method is it possible to add commands to the main sequence or the subsequence created by the Wexted procedure command Commands Parameters Links New procedure Remarks End status Autolab a oignal sampler Time WEQ Current a Lotions Mo Options m Instrument ALIT 40006 Instrument description oe Nested procedure Figure 2 108 The Nested procedure command creates a subsequence in the procedure editor From the command browser add the following commands into the procedure editor ensuring that they
192. ft of the screen which displays a list of available procedures and commands The toolbar also features some procedure editing related buttons that will be described in this chapter 2 2 The procedure editor and the structure of procedures The procedure editor provides a framework for editing procedures An existing procedure can be loaded into this frame from the procedure browser and can then be edited to fit your needs When NOVA is started for the first time the procedure editor frame is empty Seven lines are displayed New procedure Remarks End status Autolab Signal 52 Page NOVA User manual sampler Options Instrument and Instrument description and the procedure browser frame only lists procedures under the Autolab group see Figure 2 3 File View Profile Run Tools Help ee Te eet ee eae ee ee J Commands Procedures Commands Farameters Links New procedure 4utolab P Cyclic voltammetry potentiostatic PENGUINS a Cyclic voltammetry qalvanostatic SUE Statice Yg Signal sampler Time WEH Current m H Cyclic voltammetry current integration Options No Options ie H Cyclic valtammetry linear scan Instrument ALT 40008 H Cyclic voltammetry linear scan high speed o ae l l Instrument description H Linear sweep voltammetry potentiostatic AR i Linear sweep voltammetry galvanostatic H Linear polarization z Hydrodynamic linear sweep z Differential pulse voltammetry z square wave voltamm
193. g i E vs Log t Figure 4 36 Adding a standard plot to the data set The number of available plots depends on the signals available in the data set It is also possible to add a plot to the measurement by using the quick access toolbar Clicking the button displays the list of available plots see Figure 4 37 179 Page NOVA User manual a a C staircase Custom Ae ives E IvsE Ivst Log i vs E X Log i vs Log t E vsi Evst E vs Log i E vs Log Figure 4 37 Using the quick access toolbar to add a plot to the data set Select the Log i vs E plot This will add a predefined plot to the data set displaying the WE 1 Current on the Y axis in logarithmic scaling and the Potential applied on the X axis The plot will be displayed using the default plot settings see Figure 4 38 a Demo 0l Copper deposition Fl CY staircase o oo E e ivs E H Logfijvs E 0 0001 E35 WEC curent 8 Tee IE 0 2 0 fl 0 4 0 6 0 8 Potential applied w Figure 4 38 Adding a pre defined plot to the data set It is also possible to add a generic new plot to the data set simply called Custom which does not have any predefined settings To do this right click the CV Staircase line in the data explorer frame and select the Add Plot option see Figure 4 39 180 Page NOVA User manual A T TE A Demo 01 Copper Demo 01 Copper deposition B CY staircase Custom 5 B a CY staircase
194. g the button in the quick access toolbar opens the Edit sampler window The Edit Sampler window will be displayed In this window the available electrochemical signals displayed see Figure 1 10 A checkbox is provided for each signal rd Edit Sampler Oo Signal sample Optimized Sampler configuration WEI Current Sampler WE 1 Potential Segment WE 1 Power C o WE 1 Potential WE 1 Resistance O E Segment Optimized WEH Charge C A YEI Current WE 2 Current rl Ho 7 Time WER Charge Time Sample alternating Figure 1 10 The Sampler edit window Figure 1 10 shows a sampler setup to measure time Time potential WE 1 Potential and current WE 1 Current during the measurement Other signals are available but are not sampled during the measurement WE 1 Power WE 1 Resistance WE 2 Current and WE 2 Charge The WE 1 Current signal is also checked as Optimized in the sampler shown in Figure 1 10 whereas the Time and the WE 1 Potential signals are only checked once in the Sample column An important difference exists between a sampled signal and a sampled and optimized signal 20 Page NOVA User manual When a signal is sampled the instrument performs a single Analog to Digital A D conversion for that signal However when a signal is also optimized the measured value of a signal is an average value obtained from a large number of A D conversions Optimizing a signal improves the sig
195. galvanostatic CV from Demo 06 Is displayed in Figure 4 231 309 NOVA User manual 1 9 1 8 lee ge ka 1 4 Ia b i WEL Potential W 1 1 0 9 0 8 0 000 J 0 0005 0 001 0 0015 0 002 0 0025 0 003 Current applied A Figure 4 231 Galvanostatic CV measurement A total of three scans were recorded in this experiment The windower will be used in this section to extract the data points from the second scan 4 12 1 Adding a windower To use the windower which will be used to extract a cross section from the data grid right click the CV staircase galvanostatic and select the Add Windower option from the context menu see Figure 4 232 This will add a new item called Windower to the data set Demo 06 Galvanostatic CY a C staircase galvanostatic le E vs i Plot Options Propertes Add Windower Generate index X Add Plot Show All Plots Hide All Plots Save in My commands A Delete Remove all from View Figure 4 232 Adding a windower to the CV staircase galvanostatic 310 Page NOVA User manual It is also possible to open the Windower tool by clicking the CV staircase item in the data explorer frame and clicking the F button in the quick access toolbar see Figure 4 233 crr T Rn TE Demo U6 Galvanost uccs scorer slg mand staircase 1 ge alvanostatic Se Figure 4 233 The windower tool is also available from the quick access tool
196. ge EELS staircase nw Set cell Figure 3 4 The procedure progress frame during the standard Autolab linear polarization procedure the LSV staircase command is highlighted indicating that NOVA is currently running that command 141 NOVA User manual The 0 000 V value displayed next the OCP determination command in the progress frame is updated once the value has been determined experimentally during the measurement i Note Working with views offers the possibility of performing other tasks while a measurement is running The Autolab view is conveniently placed in an independent window and is always available to provide an overview of the measured data points and to provide the user with an interactive manual control of the instrument 3 1 1 Modification of command parameters in real time The measurement progress frame displays a series of editable command parameters for the running command if applicable The displayed command parameters can be modified while the command is running The parameters that can be modified are displayed in the dedicated frame see Figure 3 5 Cyclic voltammetry potentiostatic Cyclic voltammetry potentiostatic Autolab control Autolab control Set potential Set potential Bet cell Set cell S Waittime s Wait time 8 2 Optimize current range Optimize current range H O staircase a Cy staircase Set cell Set cell CY staircase Upper vertex pot
197. ge is that it is not possible to deviate from the methods provided in the software Moreover it is not possible to integrate all the possible electrochemical methods since new experimental protocols are developed on a daily basis This means that this type of software will require periodical updates and will necessitate significant maintenance efforts Figure 1 1 shows a typical overview of a classic method based application for electrochemistry 7 NOVA User manual Method 1 Method 2 Method 3 Method 4 Method n CV staircase S SEIS CV linear LSV staircase with pH scan Frequency range Amplitude Method 5 Impedance Automatic current ranging Potentiostat Set E DC oe Wait ON Apply Set cell frequency Raeren OFF Repeat for each frequency DC potential Figure 1 1 Schematic overview of a method based software In a method based application the user chooses one of the 7 available methods and defines the available parameters for the method When the measurement Starts the whole method is uploaded to the instrument where it is decomposed into individual low level instructions These are then executed sequentially until the measurement is finished If the method required by the user is not available the user will have to wait until the method is implemented in a future release NOVA has been designed with a completely different philosophy Rather than implementing well defined methods in the software
198. ght markers defining the base line To do this right click the peak label and select either the Move left base point or the Move right base point to redefine the left and right markers respectively see Figure 4 145 253 NOVA User manual AE 7 i H 1E Current A lear Peak Move left base point 2E 7 l Move right base point y AT Remove 0 5 J TS Potential W Figure 4 145 Choosing the Move left base point option allows you to move the base line marker A label will display the coordinates of the base point on the plot Figure 4 146 4E 7 SE gest 1E 7 o Lf AEF safest 0 5 J Hee Potential W Figure 4 146 The selected base point can be moved using the left and right key NOVA User manual Using the left and right arrow key on the keyboard it is possible to move the marker point to the left and to the right The base line used in the peak determination will be updated in real time while the marker is moved When a convenient position has been found press the Enter key on the keyboard to redefine the peak The results of the peak search calculation will be updated using the new base line To clear the Analysis results frame of previous data click the button located in the analysis frame see Figure 4 147 Search mode D Automatic Manual Base line mode Linear Curve Cursor w Minimum peak height 1E 07 Minimum peak width Mr of points in se
199. ging e Cutoff e Autolab control e Automatic Integration Time The Options can be defined for each measurement command To edit the options click the options button in the procedure editor see Figure 1 17 11 For more information on the Cutoff option please refer to the Cutoff tutorial available from the Help menu 12 For more information on the Autolab control option please refer to the Autolab control tutorial available from the Help menu 13 For more information on the Automatic Integration Time option please refer to the FI20 Filter and Integrator tutorial available from the Help menu 24 Page NOVA User manual Commands Farameters Links Cyclic voltammetry potentiostatic Remarks Cyclic voltammetry potentiostatic End status Autolat oignal sampler Time WE Potential WE Current potions I Options Instrument Instrument description Autolab control set potential 0 000 set cell On m wWalttime 3 z Optimize current range 3 CY staircase O 000 1 000 1 000 0 000 2 0 1000000 set cell Ott m lt gt Figure 1 17 Modifying the options for the cyclic voltammetry experiment The options can also be opened by clicking the button in the quick access toolbar when this button is shown see Figure 1 18 RAT Commands iors Links Cyclic voltammetry potentiostatic i Remarks Cyclic voltam Sse eas tic no extra modules required End status Autolab m oignal sampler Time vWE Potential WET
200. gnal 18 127 188 Segments 19 Sequence of procedures 123 Set cell 58 Set potential 58 60 67 Setup view 10 15 51 SG Smooth 223 SHE 293 Show all links 11 79 Show Coordinates 208 Show global maximum and minimum 207 Show Label 216 Show Legend 204 Show local maximum and minimum 207 Show Origin 203 Show Positioning lines 210 Show Title 206 Signal averaging 19 Signal builder 300 Signal sampler 18 53 56 113 Signal to noise ratio 22 223 Signals 293 Smoothing 223 Sort database 159 Square root distribution 107 Standard database 29 Standard Hydrogen Electrode 293 324 Start button 52 Start measurement 10 Start stop button 141 Step through data 213 Step through Data 211 Step type 107 T Tafel slope analysis 271 Tick Text Angle 216 TIF 217 Time 20 Time stamp 158 183 Timed procedure 54 60 Title 56 203 Toggle Text Location 217 Toolbar 10 Tools menu 13 Tooltip 58 Trigonometric operators 293 Tutorials 9 13 222 U Unlink parameters 11 Unlinking 81 Upgrade from previous versions 166 Use My Commands 137 Use procedure options 123 Use procedure sampler 123 User database 29 User log 52 141 User defined view 222 View menu 12 Wait time 58 WE 1 Potential 113 Windower 309 Windower source 310 WMF 217 X X Y analysis tools 222 Z Zooming 148 217 03 2013 Kanaalweg 29 G 3526 KM Utrecht The Netherlands
201. gure 4 239 Adding a E vs i plot to the signal windower Switch to a 2D plot and select the E vs i plot added to the Windower and change the plot options to a size 3 red line plot The data points from scan number two will be displayed see Figure 4 240 a Dero 06 Galvanostatic CY CY staircase galvanostatic 1 9 i E vs E a Windower 1 8 a F wsi a As X arent applied a Ay Y WE 1 Potential 16 R Pye Y Time aie T nm 1S a To 1 1 1 0 9 0 8 0 0005 0 COMO CLI WOU CIO IONICS OL Cs Current applied A Figure 4 240 Plotting the data points from scan two 314 P NOVA User manual Overlay both E vs i plots using the CTRL select method and set the time signal on the X axis for both plots The resulting overlay plot should look like the one displayed in Figure 4 241 after changing the X axis to Time ta T e Ie 1 6 la 1 4 ka T Pe WELT Potential W 0 9 0 8 10 20 aU At oO 60 TO ot zii Time s Figure 4 241 The original data set WE 1 Potential vs time blue curve and scan number 2 selected using the windower red curve Click the added windower item in the data explorer to reveal the control parameters defined in the editor on the right hand side of the 2D plot see Figure 4 242 Demo 06 Galvanostatic CV el Fa b d mj Xx j r Eit a k il 18 Signal Expression Unit Windower i Current applied A H IE vs i Index N Scan 0 gt T
202. gure 4 85 0 0016 0 0014 0 0012 0 001 0 0008 0 0006 0 0004 WELT Current Ay 0 0002 902 0 67841 4 4647E 6 20 929 0 00GA T3171 11932 2 6474 E 5 26 516 0 0004 0 2 0 0 2 0 4 UG J E Potential applied W Figure 4 85 Walking through the data using the keyboard arrows or the mouse wheel 212 P NOVA User manual You can add as many labels as you want to the plot using the insert key Pressing the home key automatically moves the marker to the first point of the data set and pressing the end key will move to the last point of the set Pressing the page up and page down keys moves the next or the previous data set in an overlay Holding the CTRL key while walking through the data will advance the arrow pointer using a 10 step Holding both the CTRL and the SHIFT key will advance the arrow pointer using a 100 step To stop walking through the data points click the Steo through Data option again from the right click menu You can further edit the labels that were added to the plot by right clicking them You can change the label text font and direction or remove a label or move it to a more convenient location Figure 4 86 shows an example of an inserted and edited label positioned on the maximum current OLO016 0 0014 Aaximurm current Data Label 0 0012 Move Move Text 3 0 001 Rem ove 0 0008 Edit Text N 0 0006 Edit Direction a Edit Text Font 0 OOo Edit Text Color O00
203. h Show data grid Figure 4 203 Clicking the Show data grid button in the toolbar will display the data grid instead of a 2D or 3D plot The data grid is shown instead of a 2D or a 3D plot and appears as a series of columns containing the measured values of each signal In the case of the cyclic voltammogram of example 1 the displayed values correspond to WE 1 Potential applied WE 1 Current Time and WE 1 Potential Index Scan see Figure 4 204 289 Page NOVA User manual Demo 01 Copper deposition Potential applied v WE 1 Potential v WE 1 Current A Time s Scan Index iat Ow staircase A 0 299988 0 300781 6 32935E 7 8 70449 1 1 E vs t H Log i vs E 0 302429 0 303375 1 02966E 6 8 72889 1 2 H ivst 0 304871 0 304962 2 14844E 6 8 75329 1 3 a Standard CV 0 307312 0 306824 2 87384E 6 8 77769 1 4 0 309753 0 311951 3 14392E 6 8 80209 1 5 0 312195 0 312744 3 15582E 6 8 82649 1 6 Figure 4 204 Displaying the data grid of the data set from example 1 You can scroll down to inspect every value of these signals For each value of WE 1 Potential applied a corresponding value of WE 1 Current Time WE 1 Potential index and scan is displayed The data grid shows the values tor the whole data set which means that the highlighted plot has no influence on the displayed Each plot uses the same set of data points The data grid shown in Figure 4 204 displays two columns containing values of the potential
204. he View menu see Figure 4 1 File View Profile Run Tools Help be Advanced procedure view a iHe Se ee jo Setup VI ei Mult Autolab View Measurement View Analysis View N User log F1 De u Aii Autolab display F10 FRA manual control MDE manual control MUX manual control File View Profile Run Tools Help E a EEEE en Ko Ca E l z ga E Analysis View Figure 4 1 Switching to the Analysis view This view like the other views of the NOVA software has a specific layout with several areas of interest An overview of the analysis view is given in Figure 4 2 i Note Like all the frames in Nova the frames in the data analysis view can be resized Moreover the user log can be toggled off using the view menu This allows you to maximize the size of the Data analysis frame for a better overview of the data 155 Page NOVA User manual Reed NOVA OCR File View Profile Run Tools Help Toolbar BE Bai rth DTT Bo EE oT Procedure name f Time stamp Remarks Instrument Instrument descri a Demo 02 Lead deposition EQCM 2 4 2009 11 04 15 AM Pb ClO4j2 0 01 M HCIO40 1M Demo 03 Bipotentiostat measure 2 20 2007 3 37 48 PM ORPM HCIO40 1M Demo 04 Hydrodynamic linear sw 3 4 2009 11 21 58 AM Fe2 Fe3 NaOH 0 2 M Data base frame Demo 05 Fe ll Fe ill Reversibility Test LSV with increasing Demo 06 Galvanostatic Quick access tool ba f sition on gold galvanostatic o Demo N7
205. hes to the Setup view highlighted button i e active Status Multi Autolab view switches to the Multi Autolab view Measurement view switches to the Measurement view a Analysis view switches to the Analysis view Start measurement starts the measurement by executing the currently d edited procedure j Pause measurement pauses the measurement click the start button again to continue j Skip command interrupts the current command and jumps to the next command in the procedure 1 This button is inactive during the measurement This button is active during the measurement 10 NOVA User manual a Abort measurement stops the measurement Show Hide Autolab display shows or hides the Autolab display 7 Show single plot during measurement is used to display a single plot in the measurement view JF Show two plots vertically tiled during measurement is used to display two plots vertically tiled in the measurement view Show two plots vertically tiled during measurement is used to display i 1 two plots horizontally tiled in the measurement view aa Show four plots during measurement is used to display four plots in the a 4 measurement view Link parameters is used to link two different parameters oy Unlink parameters is used to break an existing link between two different parameters E Collapse one levelt used to contract the displayed procedure into a more compact view opposit
206. ial WE 11 Current al Options 1 Options a Instrument UWSALIT YO530 Instrument description Autolab contral ail set potential 0 000 set cell On m wat time s g Optimize current range z CY staircase O 000 1 000 1 000 0 000 z 0 1000000 H Set cell Cit z lt Figure 2 5 The procedure editor frame with the loaded cyclic voltammetry potentiostatic procedure The cyclic voltammetry potentiostatic procedure is now displayed in the procedure editor frame The measurement sequence in this procedure contains a series of commands The sequence of commands defines the sequence of event that need to take place during the electrochemical measurement The commands are executed sequentially 54 Page NOVA User manual Click the button to expand the details of the CV staircase command as shown in Figure 2 6 It is possible to repeat this for all the commands in the measurement It is possible to click the Show all levels button in the toolbar to expand the displayed procedure in order to reveal all the details of the procedure parameters Lommands Parameters Links Cyclic voltammetry potentiostatic Remarks Cyclic voltammetry potentiostatic c End status Autolak mj signal sampler Time WWE Fotential WET Current a otions 1 Options maj Instrument ALITT 40006 Instrument description Autolab control an set potential 0 000 set cell On mj Wait time 3 A Optimize current range z CY staircase 0 000 1 000 1 00
207. ial or the value of the set potential or both Clicking the Link selected parameters button in the toolbar will restore the link see Figure 2 39 File View Profile Run Tools Help Hew Te Seca ee B Commands Procedures Autolab j Cyclic voltammetry potentiostatic peee Cyclic voltammetry galvanostatic ie Cyclic voltammetry current integration be Cyclic voltammetry linear scan Cyclic voltammetry linear scan high speed a Linear sweep voltammetry potentiostatic j Linear sweep voltammetry galvanostatic Linear polarization Hydrodynamic linear sweep a Differential pulse voltammetry Square wave voltammetry j Sampled DC polarography z Chrono amperometry At gt 1 ms z Chrono potentiometry At gt 1 ms z Chrono amperometry fast z Chrono potentiometry fast Chrono coulometry fast j Chrono amperometry high speed Chrono potentiometry high speed z Chrono charge discharge FRA impedance potentiostatic be FRA impedance galvanostatic H Standards i My procedures Commands o Link selected parameters F End status Autolab Signal sampler Options Instrument Instrument description Autolab control E Set potential Potential Vv H Set cell H YVait time s Optimize current range B CY staircase Star potential Vv Upper vertex potential 0 Lower vertex potential V Stop potential Vv Number of stop crossings Step potential v Scan rate s Estimated number of points Interval time
208. ic charge during a cyclic voltammetry measurement 3 4 5 Information while not measuring When no measurements are performed the Autolab display shows the real time values of the measured current and potential as well as the noise levels associated with both signals The noise is represented by the noise gauges present below the numerical values of current and potential see Figure 3 20 Autolab display H a Autolab manual control AUT40034 Potential oo ae Current LULILILI LILI I it _ Current noise gauge Potential noise gauge HSTAB 100 nA status current range Figure 3 20 The noise gauges are indicating the noise levels qualitatively 153 NOVA User manual The noise gauges provide real time information concerning the quality of the signals reported in the Autolab display The noise is represented by a horizontal bar graph It represents the standard deviation of the signals measured during one full measurement cycle 20 ms for systems working at 50 Hz and 16 67 ms for systems working at 60 Hz The noisier a signal the larger the standard deviation will be and the noisier the signal will be 154 NOVA User manual 4 Analysis view Data analysis is performed in the Analysis view The Analysis view can be accessed at any time even during an ongoing measurement by clicking the corresponding button amp in the toolbar or selecting the Analysis view from t
209. ic step Square root step 0 05 0 5 Value 4 Values Add value 0 05 0 14805061 4670408 nel 46 0409 Add ranqe Clear Mr of siqnificants E Clear a builder window Range builder Values sl Cancel a Figure 2 68 Closing the Range generator window will update the contents of the Range It is possible to sort the list in ascending or descending order by clicking the button located in the Range builder window Click the OK button to return to the procedure editor The Repeat for each value command will be updated see Figure 2 69 To complete the setup of the repeat loop the values of the command have to be linked to the Scan rate parameter of the LSV staircase command see Figure 2 69 NOVA User manual Commands Parameters Links New procedure Remarks z End status Autolab ma oignal sampler Time WE 11 Current ma Options Mo Options rr Instrument LALIT 0530 Instrument description Autolab contral mm E Set potential 0 000 Fotential v 0 000 set cell On ma Optimize current range z E Repesttor each value 0 05 0 14605 0 29605 0 5 ma Number of repetitions Parameter link El LSY staircase O 000 1 000 0 0500000 start potential v 0 000 stop potential v 1 000 step potential v 0 00244 Scan rate v s O 0500000 Estimated number of points 422 Interval time s 0 048600 oignal sampler Time WWE 1 Current ma potions Mo Options
210. ight Point Paint style Pat bd Point color Point size a 1 datapointis 1 Advanced Reset values Cancel Figure 1 44 The default plot options can be defined Four tabs are available e Data these settings define the overall aspect of the plots point plot line plot etc e Axes these settings define the type of axis to use in the plots linear logarithmic etc e Plot these settings are used to define the title the background style grid format etc e Analysis items these settings define the way data analysis items should be displayed on the plots More information on plot settings can be found in Chapter 4 of this user manual see section 4 2 2 1 6 4 1 2 Plot Legend settings NOVA User manual By default the Autolab serial number is displayed in the legend of any plot to facilitate the identification of the instrument in an overlay plot It is possible to deactivate this option through the NOVA options see Figure 1 45 Nova options 4 General m Graphics Autolab display Advanced settings bo Overall graphical settings show serial in legend Measurement View Maximum number of points Use maximum number of points Yes Apply JK Cancel Figure 1 45 The NOVA options allow the serial number to be activated or deactivated in the legend Figure 1 46 shows an example of plot legends with and w
211. ignal sampler for the CV staircase command It is therefore possible to add the i WE2 vs E plot to the measurement on plot 2 To remove a plot right click on the plots shown below the command and select the Delete option from the context menu see Figure 3 11 Cyclic voltammetry potentiostatic Autolab control Set potential Set cell Wait tire 3 e Optimize current range CY staircase Plot Options gt Delete N Figure 3 11 Deleting a plot from the measurement view This will remove the plot from the measurement view The data is saved at the end of the measurement using the plots existing at the end of the experiment If plots are removed during the experiment these will not be saved If plots are added these will be saved 146 Page NOVA User manual 3 2 2 Modification of plot options in real time It is possible to modify the plot options during the measurement Right clicking a plot in the measurement view displays a context menu see Figure 3 12 Select the Plot Options to change the settings of the selected plot Cyclic voltammetry potentiostatic Autolab control Wait time s e Optimize current range C staircase Plot Options X Delete Figure 3 12 Modifying the plot options during a measurement The data is saved at the end of the measurement using the plots existing at the end of the experiment If plot options are changed during the experiment the last use
212. igure 4 219 The filter and select signals window The Filter and select signals window has two frames The frame on the left contains five groups Each group contains the individual commands used in the procedure along with the electrochemical signals and the parameters The frame NOVA User manual on the right is empty It has two columns Name and Index A sorting option and a search depth are available at the bottom of the window The signal builder can be used to build new signals by filtering and selecting measured data points or procedure parameters using user defined criteria 4 11 2 Selecting the values of the scan rate The scan rate values used in the experiment were defined using the Repeat for each value command linking the values of this command to the scan rate value of the LSV staircase command see Figure 4 220 Commands Demo 05 Feili Fe dlh on port Remarks End status Autolab signal sampler Options Instrument Instrument description Autolab control OCP determination set reference potential set potential set cell Viait time s Repeat for each value Number of repetitions Parameter link Autolab contral set potential Viait time 3 El LSY staircase start potential v stop potential 0 step potential v Scan rate V s Estimated number of points Interval time s signal sampler Options Potential applied Time WE Current WE Potential Index Ive E Feak search lt gt set cell lt gt
213. ility Test LS with increasing Demo Ob Galve Lead deposition on gold galvanostatic Demo 07 High Dummy cell ic Demo 06 Chro Factory standard procedure Demo 09 Chro Combination of steps and lewels Demo 10 Differ Example for baseline correction peak search Properties Store in Repository Delete from Repository Restore from Repository Import Data Export Data xI Delete Data Merge Data 1 Show in Windows Explorer Figure 4 14 Right click the selected entries and select the Merge Data option A popup window will be displayed see Figure 4 15 Properties _ O ES Mame MERGED Demo 01 Copper deposition Enter the strings in the collection one per line Demo 0 Copper deposition Cus04 0 01 M H2504 0 1 M AgfAgCl Ref RCI Sat d Pt polycrystalline vvE Demo U2 Lead deposition EACH PafClo4ie 0 01 My ACIO4 0 1 bl Figure 4 15 A popup dialog is displayed when the files are merged Using the window a new database filename can be specified and the remarks field for the merged file can be edited Pressing the button and closes the editor adding a file to the database see Figure 4 16 File View Profile Run Tools Help Alagala EE E Procedure name Time stamp k Remarks MERGED Merged data afeff2012 3 15 45 Pe Demo 01 Copper deposition Demo Ue Lead deposition ECM Jepet 4 14 26 PM PefClodi2 0 01
214. ime S WE 1 Potential Vv lt ha Source WE 1 Potential W ma Simple _ ee 0 0 001 0 002 0 003 Current applied A Figure 4 242 The control parameters of the windower are displayed on the right hand side of the plot 4 12 4 Changing the selected data With the windower selected it is possible to select more than one value from the list in the control interface For example select the third scan by click the 315 NOVA User manual corresponding check box The plot will be immediately updated displaying the second and third scan in red see Figure 4 243 2 1 8 gt Le 514 T Le 1 2 LU 1 0 8 20 40 60 80 Time 5 Figure 4 243 Adding items to the windower will automatically update the selected data Note It is possible to use the right click menu on the list displayed in the control interface to quickly select or deselect all the available check boxes It is also possible to easily invert the selection see Figure 4 244 Source simple Select all Deselect all Inverse selection N Figure 4 244 The right click menu allows you to quickly select or deselect the available check boxes 4 12 5 Advanced selection When the Simple checkbox is selected the Windower will always list the possible values for the selected source signal as a list of checkboxes It is possible to switch to an a
215. ine has been defined it is possible to plot the original data corrected for the baseline To do this expand the Polynomial fixed order item in the data explorer frame and select the available Residual plot see Figure 4 125 Demo 10 Differential pulse measurement B Differential pulse El dives E E Polynomial fixed order Residual plot a 1 82668E 8 b 1 46617E 7 c 3 65641 E F 2 d 4 05652E 7 huas e 1 47975E 7 Figure 4 125 Selecting the Residual plot generated by the baseline correction tool 239 NOVA User manual The coefficients listed below the Residual plot item correspond to the coefficients used in the polynomial regression of the baseline In this example a fourth order polynomial fit was used resulting in five coefficients y a bx ex The data will be displayed in the 2D plot see Figure 4 126 Em 4 3E AF Does DE Ms 2E En leat SE 8 Corrected Y er a aiio U 6 0 4 U2 0 Fitted Figure 4 126 The data point from Demo 10 after baseline correction The fitted Y values corresponding to the baseline and the corrected Y values corresponding to the corrected data are available in the data grid 4 8 1 4 Peak search The peak search analysis tool can be used to locate and characterize peaks in an experimental curve The peak search tool searches for peaks that fit the user defined search criteria and displays information about the pea
216. ing existing commands to or from a procedure The commands browser however displays a large number of commands that can be inserted in a procedure using the same darag and drop mechanism described previously This will be explained in more detail in the next part of this chapter This section provides a very simple example for the Autolab cyclic voltammetry potentiostatic procedure Reload the procedure into the editor frame and switch the browser frame to commands browser It is common practice to purge the solutions with nitrogen before each measurement in order to get rid of dissolved electroactive gases Sometimes measurements are started while the solution is still being purged An easy way to 76 Page NOVA User manual avoid this is to insert a reminder in the procedure In the commands list there is a command that does precisely that Locate the Message box command under the Control list in the browser frame Drag and drop the Message box command at the very beginning of the procedure before the Auto ab control command see Figure 2 30 File View Profile Run Tools Help BW te ike ee ee RCC ok eee me ied Commands Procedures Commands Parameters Links Favorite commands Cyclic voltammetry potentiostatic 1 Remarks Cyclic voltammetry potentiostatic Control Input box signal sampler Time VWE 1 Potential WWE 1 Current SMessage box i a Options 1 Options Repeatn times a peer ae Instrument LW3SAUT 70530 R
217. ing it Show Global minimum and maximum 2D plots only this option displays the points of the plot corresponding to the absolute lowest and the highest value of the signal plotted on the Y axis Figure 4 78 shows the location of the Global minimum and maximum for the cyclic voltammogram of example 1 The labels can be removed by selecting this option once again 0 0016 i 0 0014 0 0012 0001 T 0 0008 T a 0 0006 0 0004 LI 0 0002 ol 0 0002 0 0004 WV 02 0 0 2 0 4 0 6 08 1 Potential applied V Figure 4 78 Showing the position of the Global minimum and maximum In the case of an overlay plot using two different Y axes the maximum and minimum for both axes are displayed Show Local minimum and maximum 2D plots only this option displays the points of the plot corresponding to the relative lowest and the highest value of the signal shown on the Y axis When the automatic scaling option is used for the Y axis the Local minimum and maximum correspond to the Global minimum and maximum Figure 4 79 shows the location of the Local minimum and maximum for a specific portion of the cyclic voltammogram of example 1 The labels can be removed by selecting this option once again 207 NOVA User manual O O0015 i 0 0001 T 5 SES z i 0 5E 5 0 0001 0 16 URTI 0 16 0 19 Ja 0 24 O22 eas Potential applied W Figure 4 79 Showing the position of the Local minimum and maximum It is n
218. ion is also available from the right click menu Clicking the redo button button in the toolbar or using the CTRL Y keyboard shortcut will redo the last undone action It is also possible to right click the procedure editor and select the redo option from the context menu see Figure 2 15 63 Page NOVA User manual Commands Parameters Links Chrono amperometry At gt 1 ms Remarks Chrono amperometry At gt 1 ms m End status Autolab m oignal sampler Time WWE 1 Potential vWwE1 Current ma Options 1 Options m Instrument LALIT 0530 Instrument description Autolab control set potential 0 000 set cell On m Viait time s A Record signals 1 ms 5 0 07 z set potential Record signals 1 ms Set potential 0 500 Record signals 1 ms 5 0 01 Enabled Save in My commands Delete me m Cut Ctl x Copy Ctrl C Hide Redo Delete 2 rows Ctl Y A Figure 2 15 The Redo option is also available from the right click menu 2 4 3 Adding commands The procedures browser frame also has a Commands browser On top of the frame two tabs are located These tabs are called Commands and Procedures respectively The default tab is the Procedures tab While this tab is selected the browser frame displays the available procedures If you click the Commands tab you will switch the content of that frame to a list of commands see Figure 2 16 Detailed information on all available command
219. ion like defining a potential value or performing a cyclic voltammetry measurement The following nomenclature is used to describe commands in NOVA e Command this is the name of the command by which it is identified in the software The name of the command also indicates the role of the command in the procedure e Command parameter this is a parameter of a given command A single command can have one or more command parameters Each command parameter specifies a value required for the Command to work as expected Figure 1 5 shows a comparison of the Set potentia command and the CV staircase command The Set potential command has a single command parameter Potential V which defines the behavior of the whole command The CV staircase command has a total of seven editable command parameters two non editable command parameters Additionally the CV staircase command also has a local sampler options The editable command parameters must all be specified for the command to work w CY staircase 0 000 1 000 1 000 0 000 2 0 1000000 amp CY staircase 0 000 1 000 1 000 0 000 2 0 1000000 lt gt Start potential v 0 000 Upper vertex potential V 1 000 Lower vertex potential V 1 000 Stop potential v 0 000 Number of stop crossings 2 Step potential Vv 0 00244 Scan rate v s 0 1000000 Estimated number of points 1650 Interval time s 0 024400 Signal sampler Time WWE 1 Current c Options No Options en Potential
220. is item automatically generates the Q vs E and the Q vs t plots Click the Q vs t plot to display the plot The plot should be similar to the plot obtained with the same data set in combination with the integrate analysis tool see Figure 4 201 and Figure 4 168 0 0035 0S 0 0025 0 002 O 0015 Charge CC 0 001 0 0005 O 0003 10 30 30 40 50 60 Time s Figure 4 201 The Q vs t plot generated by the calculate charge analysis tool Click the Q vs E plot to display the same information plotted versus the applied potential The plot should look like the one shown in Figure 4 202 288 Page NOVA User manual 0 0035 0 003 0 0025 0 002 C O 0015 Charge 0 001 0 0005 0 0005 0 2 J 0 2 0 4 J E Potential applied W Figure 4 202 The Q vs E plot generated by the calculate charge analysis tool The data provided by the Calculate charge command Is stored in the data grid 4 9 The data grid The data grid works as a spreadsheet that can be used to perform calculations on measured signals to create new signals to filter experimental data points or procedure parameters and to export the data to Excel or ASCII New signals created in the grid can then be used to plot the measured data in a different way To access the data grid click the corresponding button in the data analysis toolbar see Figure 4 203 File View Profile Run Tools Help Bee ee Ie eee E T SS we eee EPS e
221. ithout the serial number of the instrument displayed jvs E AUTS1 425 0 0003 0 0002 0 0001 WEC Current WEC Current 4 0 0001 0 000A 0 4 0 0 2 0 6 Potential applied W 0 2 0 0003 0 0002 0 0001 0 4 0 0 2 0 6 Potential applied W 2 Figure 1 46 Plot legend with left and without right the serial number of the instrument displayed 45 Page NOVA User manual 1 6 4 1 3 Maximum number of points in real time view Individual plots shown in the measurement view are limited to a fixed value 10000 points A circular plotting buffer is used to plot data points which means that when more than 10000 points are plotted in real time a running buffer of 10000 points will be shown When a measurement command is finished the last 10000 points collected by this command will remain displayed in the plot area and the next measurement command will start adding points to the plot if applicable The Maximum number of points setting can be used to define the maximum number of points to show in the real time view during a measurement for each of the four plots areas The default value is 30000 see Figure 1 47 Nova options m Graphics 4 General 2 Autolab display bo Overall graphical settings H Advanced settings show serial in legend Yes 4 Measurement iew Maximum number of points 30000 Use maximum number of points Yes Apply OK X Cancel Figure 1 47
222. ive plot Figure 4 161 The newly added Derivative analysis tool Click the Derivative plot to display the first derivative of the current see Figure 4 162 Demo 19 Cyclic voltammetry Fe2 Fe3 0 0035 CV staircase Aa 0 003 Lt ivs t Derivative H Derivative plot N 0 0025 0 002 gt 0 0015 gt D 0 001 0 0005 D O 0 0 0005 0 001 0 0015 10 20 30 40 50 60 Derivative X Ss Figure 4 162 The derivative of the i vs t plot 263 Page NOVA User manual The results of the Derivative are stored in the data grid 4 8 1 7 Integrate The integrate analysis tools can be used to calculate the integral of a plot This tool can be added to any Y vs X plot in the data analysis view Double click on the demo file Demo 19 Cyclic voltammetry Fe Fe entry of the demo database to load it into the data explorer frame This file contains data points of a cyclic voltammetry staircase experiment recorded in a 0 05 M Fe CN 6 in 0 2 M NaOH solution The number of scans is three Click the i vs E plot in the data explorer frame to display the data points from this demo file see Figure 4 163 A typical reversible electron transfer behavior is recognizable in the cyclic voltammogram Demo 19 Cyclic voltammetry Fe2 Fe3 0 0012 B a C staircase i vs Y 0 001 0 0008 0 0006 0 0004 0 0002 0 0 0002 0 0004 VVE 1 Current 0 0006 0 0008 0 001 0
223. ks in the Analysis view NOVA offers two types of peak search modes Automatic or Manual 240 P NOVA User manual Double click on the demo file Demo 14 FC CH2 2 FC in ACNW CH2C 2 entry of the demo database to load it into the data explorer frame This file contains data points of a cyclic voltammetry staircase experiment recorded in aceto nitrile chloroform in the presence of 1 2 Diferrocenylethane with TBu4PF as supporting electrolyte Click the i vs E plot in the data explorer frame to display the data points from this demo file see Figure 4 127 Two anodic and two cathodic peaks are visible in the cyclic voltammogram AE 7 3E 7 2E 7 le Current Ay l Es7 SAE 0 8 0 6 04 02 J J2 0 4 0 6 0 8 Potential W Figure 4 127 The data from the Demo 14 data file To use the peak search analysis tool right click the i vs E plot in the data explorer frame and from the context menu select the Peak search tool see Figure 4 128 32 This data set is an imported GPES file 241 NOVA User manual El Demo 14 FC CH2 2 FC in ACN CH2Cle Import GPES data H vs E Plot Options Properties Add Analysis Smooth Copy Visible Plot s to i Baseline Correction Show All Plots Peak search X Hide All Plots Regression Save in My commands Derivative l Delete Integrate FFT Analysis Remove all from View Corrosion Rate Figure 4 128 Adding the peak search analysis tool to th
224. l sampler Time WWE Curent Options Ke Custans a Instrument T LH is Instrument description e Nested procedure Autolab control set potential 1 200 Set cell On ma Wart time 3 3 Optimize current range a gt gt Figure 2 111 Select the Save in My commands option from the right click menu You will be prompted to specify a name and remarks for the command see Figure 2 112 Name Save command in My commands My Potentiastatic Preconditioning Remarks Complete preconditioning example Cancel Figure 2 112 Specify a name and remarks for the command In the example shown here the whole Nested procedure will be saved in the My commands database as My Potentiostatic Preconditioning Once the button is clicked the whole Nested procedure will be saved in the My commands database see Figure 2 113 136 Page NOVA User manual Commands Procedures Favorite commands H Control H Metrohm devices H External devices H Measurement general H Measurement cyclic and linear sweep voltammetry H Measurement Voltammetric analysis H Measurement chrono methods H Data handling H Analysis general H Analysis baseline correction H Analysis corrosion H Flots general i My commands z My Galvanastatic Autolab control command mt y Potentiastatic Preconditioning a omplete preconditioning example Figure 2 113 The command is added to the
225. lculate new signals using the values of the available signals This can be done through the dedicated Ca culate signal window available in the Analysis view Clicking the calculator button located in the toolbar on the right hand side of the data grid opens the Calculate signal interface see Figure 4 206 m T st x ag Expression J Calculate signal WENI Current Time WE Fotential Index Figure 4 206 Clicking the button allows to calculate new signals Note It is also possible to open the Calculate signal tool by clicking the CV staircase item in the data explorer frame and clicking the button in the quick access toolbar see Figure 4 207 291 Page NOVA User manual __ awy p ai Demo 01 Lop crucpoucnoni ilo y a CV staircase H t Evst Calculate signal H Logi vs E ia 7 ivs t H Standard CY Figure 4 207 The calculate signal tool is also available from the quick access toolbar Clicking the button will display the calculate signal window which can be used to define a new signal and the required expression to calculate it see Figure 4 208 Fal Calculate signal Oo Name Single vate Unt v Expression L Parameters Functions signals Full amp C staircase Clear Cancel k Figure 4 208 The calculate signal window 292 Page NOVA User manual The calculate signal window contains several fiel
226. le Plot s to i Baseline Correction gt Show All Plots Peak search Hicle All Plots Regression Save in My comm ands Derivative XI Delete Integrate N FFT Analysis AT Remove all from View ei Corrosion Rate Figure 4 166 Adding the Integrate tool to the i vs t plot A new item called Integrate will be added to the data set in the data explorer frame below the i vs t plot see Figure 4 161 An additional plot called Integrate plot is automatically added to the Integrate analysis item B Demo 14 Cyclic voltammetry Fee Fea CY staircase H ivs E Is t ee Integrate H Integrate plot Figure 4 167 The newly added Integrate analysis tool Click the Integrate plot to display the integral of the current vs time see Figure 4 168 D a IN QD 266 Pa ge NOVA User manual Demo 19 Cyclic voltammetry Fe2 Fe3 A CY staircase H j v5 E 0 0035 H j yS t B Integrate 0 003 H Integrate aay 0 0025 gt 0 002 Ww 0 0015 2 3 0 001 0 0005 0 0 0005 10 20 30 40 50 60 Integration result X Figure 4 168 The integral of the i vs t plot The results of the Integral are stored in the data grid 4 8 1 8 FFT Analysis The FFT Analysis tool can be used to transform experimental data from the time domain into the frequency domain in order to identify the different frequency components present in a given data set The transformation from
227. lic voltammogram of Example 1 Changing the signals used to display the data points from example 1 also changes the labels displayed on the axes of the plot A Warning The time signal is the total elapsed time since the beginning of the measurement It includes the preconditioning time used during the experiment If required it is possible to use the calculate signal tool to correct the time scale see section 4 10 171 NOVA User manual 4 2 3 Changing the plot options Although NOVA uses default settings for all the plots it is possible to customize the appearance of each individual plot This can be done by right clicking a plot in the data explorer frame and selecting the Plot Options item from the context menu see Figure 4 28 Demo 01 Copper deposition CY staircase El ivs E oo X Plot Options 2 i Propertes X Lae Fs Add Analysis Copy Visible Plot s to Show All Plots Hide All Plots Save in My commands A Delete Remove all from View Figure 4 28 Changing the plot options The Plot Options window will be displayed Through this window it is possible to customize every aspect of the selected plot see Figure 4 29 It is possible to change the plot color the plot style the point markers axes configuration etc The settings defined in the Plot options window are used for both 2D and 3D plots It is possible to define specific settings for both data presentation form
228. line see Figure 4 139 4E 7 4E 7 3E 7 3E 7 2E 7 2E L 1E 7 L 1E 7 E g 0 6 0 1E 1E 7 2E 7 2E 7 0 5 0 0 5 0 5 0 0 5 Potential V Potential V Figure 4 139 Using the Linear free cursor method to specify the baseline left location of the first point right location of the second point and drawing of the baseline e Linear Front this option finds peaks by extending a tangent baseline located in front of the peak To define the baseline click on the plot area The software automatically connects the initial point to the nearest data point While holding the mouse button pressed drag the mouse across the plot area to define the baseline When the mouse button is released the final X position of the mouse pointer is used to define the X position of the final point of the baseline on the curve The tangent is then extended frontwards and the peak is located see Figure 4 140 248 Paqge NOVA User manual AE 7 oer Ze 1E Current A 1E 7 ACET 0 5 J 0 5 Potential W Figure 4 140 Using the Linear front baseline search method The base points used to specify the tangent baseline are indicated by the small vertical lines on the plot see Figure 4 140 Linear Rear this option finds peaks by extending the baseline located after the peak To define the baseline click on the plot area The software automatically connects the initial point to the nearest data point While holding th
229. lot size 2 e Local options 0 1 V s Blue Combi plot size 2 Star marker size 10 1 point out of 40 By design local options always overrule global options Right click the Demo 05 line to change the global options of the overlay plot Set the plot to a black size 2 Line plot The resulting plot is displayed in Figure 4 65 196 NOVA User manual 0 0012 0 001 0 0008 0 0006 0 0004 WET Current tA 0 0002 0 0002 J 0 1 0 2 0 3 0 4 0 5 Potential applied W Figure 4 65 Modifying the global settings of the overlay plot Changing the plot options for the whole data set only modifies the options for the plots which do not have user defined local options in this case the plot corresponding to a scan rate of 0 1 V s is not affected To remove the user defined local options open the Plot options window for the 0 1 V s plot use the right click procedure and press the button see Figure 4 66 197 NOVA User manual Plot Options Analysis items Plot Flot style Combi plot Ww Y axis placement Lett C Right Point Point size Draw point every datapoint s Line incor i Ts Line size Pressing the Figure 4 66 Resetting the plot options for the 0 1 V s plot 1 2 Fesewaues button will remove the local options of the plot and the global options will be used instead see Figure 4 67 198 Page NOVA User manual 0 0012 0 001 0 0008 0 00
230. lp File View Profile Run Tools Help Th ee ee ERC EEE oe oe Se E MERTE e hk P Se eo 2S fel oo 9 bow Wj Select instument E Cyclic voltammetry potentiostatic 4E 7 pr T T T T T T T Procedure name Timestamp Remarks Instrument Instrument descri A Import GPES data 4 Autolab control 3 5E 7 F FRA impedance tutorial 1 2 1 2013 11 1433AM FRA impedance potentiostatic requires FRA module 13AUT70530 Set potential FRA impedance tutorial 6 2 1 2013 10 40 23 AM FRA impedance potentiostatic requires FRA module 3AUT70530 Set cell 3E 7 FRA impedance tutorial 5 2 1 2013 10 38 42 AM FRA impedance potentiostatic requires FRA module p3AUT70530 Weittime s FRA impedance tutorial 4 2 1 2013 10 36 56 AM FRA impedance potentiostatic requires FRA module p3AUT 70530 Optimize current range 2 5E f i y FRA impedance tutorial 3 2 1 2013 10 34 52 AM FRA impedance potentiostatic requires FRA module p3AUT 70530 CY staircase FRA impedance tutorial 2 2 1 2013 10 32 23AM_ FRA impedance potentiostatic requires FRA module p3AUT 70530 S Setcell 2E 7 EDA inmadance tutorial 1 2119012 10 21 18 AM EDA imnadancanotontinctati rcuime FRA modulo UIALTINEAN Cyclic voltammetry potentiostatic 4E 7 T T T Ty i x 1 5E 7 5 ba m J 71 z a Se Signal Expre A T 1E 7 F 4 Lo Peak search 3E 7 1 Index g Peak position 2 5E 8 27 Peak height J Peak area 2 0 E a Base start O ET Base end paal Peak width half height 5 Peak 1 2 Upper vertex potential V 0 600
231. ls are recorded The user can decide if a specific electrochemical signal can be sampled only one time during a segment or if an averaged value of several measurements is required The sampler can be edited by clicking the sampler button in the procedure editor see Figure 1 8 Commands Parameters Links Cyclic voltammetry potentiostatic Remarks Cyclic voltammetry potentiostatic ail End status Autolab m Signal sampler Time WE 1 Potential WE 1 Current Options 1 Options JA Instrument Instrument description Autolab contral j set potential 0 000 set cell On m wWattime s z Optimize current range p CY staircase O 000 1 000 1 000 0 000 z 0 1000000 set cell Ott m lt gt Figure 1 8 Modifying the signal sampler for the cyclic voltammetry experiment The signal sampler can also be opened by clicking the button in the quick access toolbar when this button is shown see Figure 1 9 Dana ra Qe aw NOVA User manual AX TB Commands ORA S Links G Cyclic voltammetry potentiostatic N Remarks Cyclic voltammy Edit sampler no extra modules required End status Autolab m oignal sampler Time vWE Potential WE Current al potions 1 Options aa Instrument LALIT 0530 Instrument description Autolab contral zz set potential 0 000 set cell On m Wattne s p Optimize current range p CY staircase U 000 1 000 1 000 0 000 2 0 1000000 Set cell Cit m gt Figure 1 9 Clickin
232. lt aray 4 WEN Fotential array Cv Index Array gt H iws E z B E wst awl ks Time s r WE Fotential 6 Z Index show during measurement es m z H Set potential 1 E Waittime 8 2 lt gt g amp Setcell 4 lt gt Figure 2 81 Defining the location of the E vs t plot 2 5 9 Edit remarks and save procedure Before running this procedure it is convenient to use the Remarks line at the top of the screen to enter a comment This will prove useful in the data analysis view and it will help sort the experimental data To edit the remarks click the remarks line and click the button displayed right of the Remarks line in the procedure NOVA User manual editor This will open a new window in which you can enter a series of comments see Figure 2 82 Commands Parameters Links New procedure End status Autolab oignal sampler Time WE 1 Potential vWwE1 Current potions Instrum Edit remarks 0 Instrum Autolak Enter the strings in the collection one per line set pot eT Pa User manual Chapter 2 complete example using a Repeat for set cell each value loop Gptimiz E Repeal z Murr ee Fari 7 LEV z set OK Cancel Wei px lt gt cet cell Cit lt gt Figure 2 82 Changing the remarks for the Cyclic voltammetry potentiostatic procedure The remarks can be used to add information on the cell setup electrolyte working electrode reference electro
233. m Fotential applied lt array gt iv Time lt array gt 5 WE Current lt array A Index lt arrary gt ivs E aa E Set potential 0 000 Potential v 0 000 Wattne s 5 lt gt lt gt Figure 2 69 The updated Repeat for each value loop the values are linked to the Scan rate parameter of the LSV staircase command 2 5 5 Defining the post measurement settings The final part of this procedure is to switch the cell off after the last linear sweep voltammetry For this part of the procedure a single step is required 1 Switch the cell off A Set cell command must be added to the procedure The default parameter setting of the Set cell command is off which means that the command does not have to be edited Figure 2 70 shows the complete procedure after addition of the final two commands 109 Page NOVA User manual Commands Parameters Links New procedure Remarks xi End status Autolab m oignal sampler Time WE 11 Current m Options Mo Options m Instrument LALIT 0530 Instrument description Autolab contral z E Set potential 0 000 set cell On m Optimize current range 5 E Repeat for each value 0 05 0 14605 0 29605 0 5 ma Number of repetitions d Farameter link 0 05 7 H LSW staircase O 000 1 000 0 0500000 set potential 0 000 4 Vat time s z lt gt set cell Ott ma lt gt Figure 2 70 The completed procedure 2 5 6 Defining the Options Although this procedure could
234. mation of the corrosion current and the corrosion potential These values are used as initial conditions for the fitting algorithm After convergence has been achieved the complete details of the calculation are summarized in the data explorer frame see Figure 4 188 Demo 20 liron screw in seawater Import GPES data H ivs E Corrosion rate fit 2 ba tvidec 670 420 m dec be fdec 314 760 mdec ve Ecorr Calc 303 160 mi ve Ecorr Obs 0J 318 740 my eo jeorr Afcm 9 57870 pAycrn 2 ve corr 4 9 57070 A oe Corrosion rate mmea 0 1113 oe Polarization resistance 02 9 71170 ka 2 E Begin 529 170 mi ve E End fv 157 470 m ve 1 3903E 11 Iterations 8 Figure 4 188 The results of the Tafel slope analysis are shown in the data explorer frame The reliability of the fitting results greatly depends on the data provided as input for the fitting algorithm A number of conditions must be verified for the data points to be valid Particular care must be taken when defining the linear section of the Tafel plot at large overpotentials As a rule of thumb the linearity of the Tafel plot should extend over at least one decade of current The following information is provided in the data explorer frame e b amp b the anodic and cathodic Tafel coefficient in V decade e corr Calc the corrosion potential calculated from the intercept on the Tafel plot in Volts e
235. metry measurement at four different pre defined scan rates This procedure will be designed with a preconditioning stage 96 NOVA User manual 2 5 3 Defining the preconditioning stage The preconditioning of the working electrode for this example involves four consecutive steps 1 ae Setting the instrument to potentiostatic mode and selecting the initial current range Setting the potential to the preconditioning value 0 V Switching the cell On Waiting for 5 seconds Finding the most suitable current range The commands required to perform these actions are all located in the Measu rement general group of the commands browser 1 Autolab control 2 Set potential 3 Set cell 4 Wait time 5 Optimize current range Select the Autolab control command and drag it into the procedure editor see Figure 2 53 File View Profile Run Tools Help Be TW NES a ee LJ ip E E ee Cx Commands Procedures Commands Parameters Links g New procedure Favorite commands Remarks or Control End status Autolab er Metrohm devices signal sampler Time YE 1 Current en External devices Options No Options Measurement general Instrument AUT40008 Autolab control a Instrument description Set potential gt es Set current N Set cell A Wait time s Optimize current range Figure 2 53 Adding the Autolab control command To set the parameters of the Autola
236. ming Moving Step through Data Select Dataset ee Grid gt Background Show h Print Preview g Print EJ Copy to Clipboard E Copy Data to Clipboard ei Save Image File amp bal Save Image File Custom size 9 2 9 4 NOVA User manual Origin X Legend Title Global minimum and maximum Local minimum and maximum Coordinates Positioning Lines 0 6 0 8 1 Potential applied W Figure 4 72 The right click menu and the show sub menu From the Show sub menu you can select some additions for the plot e Show Origin 2D e Show Legend 2D 3D e Show Title 2D 3D e Show Global minimum and maximum 2D e Show Local minimum and maximum 2D e Show Coordinates 2D e Show Positioning Lines 2D All these additions can be toggled on and off at any time and the changes can be saved in the database using the save button Show Origin 2D plots only this option will display the origin of the plot 0 0 on the 2D graph two orange lines are shown The scaling of the plot is adapted if required Figure 4 73 below shows the same cyclic voltammogram plot with its origin 203 Page NOVA User manual WET Current tA 0 2 J 0 2 0 4 0 6 J E Fotential applied W Figure 4 73 Showing the origin of the plot Show Legend 2D amp 3D plots this option will display a legend for the data set s plotted in the 2D graph using the color and markers as well as the name of the plot s Fig
237. mmands Parameters Links Chrono amperometry At gt 1 ms El Favorite commands YE eet potential Remarks Chrono amperometry At gt 1 ms ail Record signals gt 1 ms Sul shields cb Contral signal sampler Time WE 1 Potential YWE Current a 1 Options 1 Options m Metrohm d robe a N n eae Instrument ALT 40008 l H External devices I 1 Instrument description H Measurement general a H Autolab control m H Measurement cyclic and linear sweep voltarr 1 H Set potential 0 000 Measurement voltammetric analysis L Set cell On Measurement chrono methods Sa Measurement template potentiostatic ETS E nee ee 3 Record signals p1 msi 5 0 01 3 a a a W l H Chrono methods Ma za R ott Sih Record signals gt 1 msi 5 0 01 Measurement template galvanostatic A i i H Set potential 0 000 hs Record signals 71 ms galvanostatic Chrono methods galvanastatic H Data handling H Analysis general G Analysis baseline correction H Analysis corrosion HA Flots general 2 My commands b Set cell Ort me Figure 2 19 Inserting a Record signals gt 1 ms command in the procedure Having added the two commands their parameters can be edited in order to set the potential to the required level and sample the current for the required amount of time with a convenient sampling rate see Figure 2 20 68 NOVA User manual Commands Parameters Links
238. mpedance Eai Data handling H Analysis general H Analysis aseline correction H Analysis corrosion H Analysis impedance mag Flots general azi Flots impedance eat My commands Figure 1 34 Hiding a command left and a command group right When a command group is hidden the whole group will become invisible Finally in the procedure editor it is possible to hide or unhide command parameters using the same method see Figure 1 35 For example if the interval time is not important it can be hidden from view This can be used to further simplify the user interface NOVA User manual Commands Parameters Links Cyclic voltammetry potentiostatic Remarks Cyclic voltammetry potentiostatic ma End status Autolab m oignal sampler Time WE 1 Potential vWwE1 Current m Options 1 Options m Instrument Instrument description Autolab contral z set potential 0 000 set cell On m ait time s s Optimize current range A B CY staircase O 000 1 000 1 000 0 000 z 0 1000000 start potential v 0 000 Upper vertex potential v 1 000 Lower vertex potential 6 1 000 stop potential v 0 000 Mumber of stop crossings 2 step potential v 0 00244 ocan rate v s 0 1000000 Estimated number of points Interval time s signal sampler L z Options 1 Options m Fotential applied array Cv Time lt array gt 5 WE Current lt aray A ocan lt array gt WE Pot
239. n f be T S g S C stairce a Smooth Baseline Correction Peak search Regression R Derivative Integrate FFT Analysis Corrosion Rate Figure 4 98 X Y analysis tools can be added directly to a plot using the quick access toolbar The analysis tools in this group use the X and Y values of the plot they are added to 4 8 1 1 SG Smooth The Savitzky Golay SG smoothing tool can be used to remove noise from measurements in order to enhance the signal to noise ratio of experimental data The SG Smooth method is described in Anal Chem 36 1627 1964 It involves a polynomial fit through the experimental data This method is also called weighted 223 NOVA User manual moving averaging Before the smooth routine of Savitzky and Golay is applied to the data set spikes in the set of data can be removed The SG smooth method can be used with different levels of smoothing High levels lead to heavy filtering In NOVA the following levels can be used e Level 1 5 point weighed moving average e Level 2 9 point weighed moving average e Level 3 15 point weighed moving average e Level 4 23 point weighed moving average e User defined this setting can be used to customize the smoothing The applicable smooth level depends on the number of points of the data set The more data points the higher the smooth level can be without modifying the curve too much Double click on the demo file Demo 15 UME LSV ent
240. n the right hand side Figure 4 222 303 Page NOVA User manual T Build signal ES Analysis general Name Index l H Control l G Measurement cyclic and linear sweep voltammetry oo LS staircase Lov staircase ee Scan rate v s o Potential applied Scan rate v s Start potential Stop potential WE 1 Current WET Potential H Measurement general H Untyped filter Search from 1 level s up Sort by order of 1st array high to low OK Cancel _ Sort by order of 1st array low to high Figure 4 222 Double click the scan rate item to add it to the filter and select list Clicking the OK button generates a new signal called Scan rate V s in the data grid This signal contains four values see Figure 4 223 scan rate vis 0 050000 0 1 Figure 4 223 The Scan rate signal The signal obtained using the signal builder contains all the scan rate values used in the LSV staircase command 4 11 3 Selecting the values of the peak height The second signal which is required for the plot is a signal containing the values of the peak height For this example a filter designed to extract the values of the peak height for curve will be constructed Click the Build signal button T to open the Filter and select signals window In the Analysis general locate the Peak height in the Peak search list Double click the Peak heigh
241. nal to noise ratio It is only possible to optimize a signal if it is sampled The Time signal cannot be optimized because of its discrete nature WE 1 Power WE 1 Resistance and WE X Charge are calculated values and cannot be optimized In the case of the sampler shown in Figure 1 10 the Time and WE 1 Potential are only sampled once at the beginning of the segment and then the WE 1 Current Signal is sampled and optimized for a longer period of time yielding an averaged value at the end of the segment see Figure 1 11 Last segment Time WE 1 Potential WE 1 Current 1 sample 1 sample Optimized sample Figure 1 11 A schematic view of the sampling process The total time spent sampling Time and WE 1 Potential is roughly 40 us while the time spent sampling the WE 1 Current signal is about 20 ms or 16 67 ms depending on the line frequency defined in the Hardware setup 50 or 60 Hz If an extra signal has to be sampled for example the WE 2 Current provided by the BA module it must be selected in the sampler window This extra signal can then be sampled once just like Time and WE 1 Potential or for a longer time in which case it will be measured several times and averaged Figure 1 12 shows the Edit Sampler window corresponding to this situation This is the approximate duration of a single A D conversion 10 Or the maximum available time when the interval time is smaller than 20 ms or 16 67 ms 21 P
242. ncy in the plot see Figure 4 111 This frequency value will also be shown in the FFT Smooth options ieee 1E 8 1E 9 Amplitude TE 10 1E 11 J S00 1000 1500 2000 Frequency Hz Figure 4 111 Specifying the cutoff frequency for a low pass or high pass FFT filter 230 Page E NOVA User manual 4 8 1 2 2 Band pass and band stop filtering For band pass or band stop filtering two frequencies need to be specified in the FFT Smooth options panel Frequency 1 and Frequency 2 as shown in Figure 4 112 Filter type Band pass ty Frequency 1 205 631 Frequency 2 1917 01 Figure 4 112 Two frequencies need to be specified in the FFT Smooth options panel for band pass or band stop filtering Note Frequency 1 must be smaller than Frequency 2 Alternatively the mouse pointer can be used to select an area of the plot defining the frequency band for the band pass or band stop filter Click the frequency domain plot at one of the required frequency limits and while holding the mouse button drag an area across the plot Release the mouse button at the other frequency limit to define the frequency band to be used in the FFT Smooth filter see Figure 4 113 a E E S O S E E E N S Amplitude Amplitude 1E 10 1E 10 1E 11 1E 11 0 500 1000 1500 2000 0 500 1000 1500 2000 Frequency Hz Frequency Hz Figure 4 113 The frequency band can be defined graphically by dragging an area across the plo
243. ndow see Figure 2 67 106 NOVA User manual Range generator Range builder Begin value Value End value 1 Mr of values d Values al Values Add value i Linear step _ Add range N Logarithmic step C Square root step Sere Mr of significants Aiai Clear 5 OK Cancel JK Cancel Figure 2 67 Pressing the button displays the Range generator window The Range generator is used to create a list of values using the following parameters Begin value the first value of the list End value the final value of the list Nr of values the total number of values in the list Step type the distribution of the values in the list linear logarithmic or Square root If a list of identical values needs to be created the End value checkbox can be unchecked When this is done only the Begin value will be used to create the list For this example we are going to use a total of four values ranging from 0 050 V s to 0 5 V s with a square root distribution Type these parameters in the range generator window and press the button to generate the list of values click the button to close the generator window and return to the Range builder window The generated list of values will be displayed in the Values field of the Range builder window see Figure 2 68 107 NOVA User manual Range generator Begin value End value Mr of values C Linear step CD Logarithm
244. nes the number of points that must be located above and below a zero crossing of the first derivative of the signal in order to qualify as a peak This setting is useful to discriminate between noise and real peaks Number of significant digits defines the number of significant digits used in the Analysis results frame Peak type forward or reverse Using the forward setting NOVA will search for regular peaks anodic peak during the positive going scan or cathodic peak in the opposite direction The reverse setting allows NOVA to search for peaks in the opposite direction 4 8 1 4 1 Automatic peak search When the peak search analysis tool is added to the data as described in the previous section see Figure 4 128 the calculation should be performed automatically using the default settings A total of four peaks should be detected as shown in Figure 4 131 Automatic 4E 7 mT Si x Search mode 3E 7 Base line mode Minimum peak height 2E 7 5 5 Minimum peak width a 1E 7 Nr of points in search window G i sree nes Number of significant digits 3 O 0 Reset Peak Type Peak position 0 16265 1E 7 Index 2E 2 3 0 10056 4 0 1191 0 Potential V Figure 4 131 The results of the automatic peak search 33 This parameter is inactive in Manual search mode Forward C Peak height 1 2413E 0 1 5951E 0 1 7938E 07 1 27 14E 07 243 Manua Reverse Peak area 1 306
245. ng or descending using one of the five columns Figure 4 5 shows a detailed picture of the database 31 This is the serial number used by the software to identify the instrument For measurements performed on an Autolab with an external USB interface the serial number of the USB interface will be used to identify the device 158 Page Procedure name f Demo 01 Copper deposition Demo 02 Lead deposition EQCM Demo 03 Bipotentiostat measurement PtPt Rin Demo 04 Hydrodynamic linear sweep voltammetr Demo 05 Fe ll Fe lll on poPt Demo 06 Galvanostatic CV Demo 0 High speed chrono methods Fast ADC Demo 08 Chrono methods ADC164 20 steps Demo 09 Chrono methods ADC164 with variabl Demo 10 Differential pulse measurement Demo 11 Hydrodynamic FRA with OCP determin Demo 12 Imported pcPt GPES data Demo 13 Imported pcPt GPES data Demo 14 FC CH2 2 FC in ACN CH2Cl2 Demo 15 UMELSY Demo 16 FRA impedance Demo 1 Imported FRA data Demo 16 Aniline electropolymerization Demo 19 Cyclic voltammetry Fe2 Fe3 Demo 20 Iron screw in seawater Figure 4 5 Detailed view of the demonstration database 4 1 1 1 Sorting data Time stamp 3 15 2007 6 25 27 PM 2 4 2009 11 04 15 AM 2 20 2007 3 37 48 PM 3 4 2009 11 21 58 AM 6 10 2008 1 27 46 PM 3 26 2007 3 32 01 PM 5 25 2009 4 36 33 PM 2 20 2007 8 40 08 AM 2 20 2007 9 37 06 AM 5 25 2009 12 14 00 4 6 2010 12 23 00 PM 6 10 2008 7 50 38 PM 6 10 2008 7 53
246. ng stage at the beginning of the cyclic voltammetry galvanostatic measurement 125 NOVA User manual 0 001 0 0008 0 0006 0 0004 0 0002 0 0002 Et 1i current 4 Wi l _ _ _ E U udg 0 0005 sog D 10 15 20 AD 30 25 At AS Time sS Figure 2 92 The first part of the measurement Cyclic voltammetry potentiostatic measured current vs time WWE 1 Potential W DD 60 69 TU fis S50 oo zii Time s Figure 2 93 The second part of the measurement Cyclic voltammetry galvanostatic measured potential vs time The Options and Sampler can be modified for the whole procedure or for each individual procedure in the procedure editor Click the button located next the Sampler in the procedure editor or use the quick access toolbar see Figure 2 94 126 NOVA User manual IAA TY eB Commands TORSE New procedure Edi F Remarks eer End status Autolab m oignal sampler Time WWE Current ma Options Mo Options a Instrument ALT 40008 Instrument description El Cyclic voltammetry potentia static Autolab contral Err set potential 0 000 set cell On m Viait time s z Optimize current range A CY staircase TORO e a LO TOO OO set cell Cit m lt gt El Cyclic voltammetry galvanastatic Autolab contral z set current O 000E 00 Set cell On ai Viait time s a CY staircase galvanastatic M oE s OVO 0E a OO Oe OE Ie set cell Cit m lt gt lt gt
247. nted using the Print command in the right click menu a print preview is also available 4 7 9 Zooming in and out Zooming in on some specific areas of the plot is a convenient way to get more insight on the measured data NOVA allows users to zoom in and out in several ways using the mouse buttons and if available the mouse wheel The zoom functions are available if the Enable Zooming Moving option is active right click Enable Zooming Moving 4 7 10 2D plots Zooming Box mode Zooming in on specific area of a 2D plot can simply be done by dragging a box around the area of interest Left click on a spot of the plot and while holding the left mouse button pressed move the mouse in a direction to draw a box around the area of interest see Figure 4 89 Release the mouse button to complete the operation 217 NOVA User manual 0 0 0 0 0 0 WEE 11 Current A 0 0 0 0004 It is possible to return to the original plot settings by choosing the Original Dimensions instruction from the right click menu or by pressing the shortcut F4 the keyboard If several boxes have been drawn it is possible to return step by step to the initial plot by choosing the Zoom Back option from the same key on 0016 0014 0012 0 001 008 O06 ODA 002 A002 O 2 J 0 2 0 4 0 6 0 8 Potential applied W Figure 4 89 Zooming in by dragging a box around the area of interest menu or by using the shortcu
248. ntext menu see Figure 4 71 0 0016 m Original Dimensions F4 00014 Zoom Back Shift F4 0 0012 Enable Zooming Moving 0 0G 1 Step through Data Select Dataset 0000s ee Grid O 0 0006 Background Solid 0 0004 Show Horizontal Print Preview Vertical 9 0002 Print Horizontal center fade J Copy to Clipboard Vertical center fade 00002 Copy Data u Clipboard Forward diagonal Save Image File Backward diagonal 0 0004 il Save Image File Custom size None 0 2 0 0 2 G4 056 O08 ih Potential applied W Figure 4 71 The background style of NOVA can be changed using the dedicated right click menu item 4 7 3 Adding objects to the plot Typical additions to a plot consist of a legend a title or subtitle clear axes labels and some markers to indicate the position of relevant points in the plot NOVA can add these features at any time by using the right click menu Load the data set from example 1 into the data explorer and plot the third plot called Standard CV plot restore the Y axis to its original position This plot should appear as a green Line plot To insert some of the above mentioned additions to the plot right click anywhere on the plot This will display the menu shown in Figure 4 72 202 Page 0 0016 0 0014 O 0012 0 001 0 0008 0 0006 0 0004 WELT Current Ay 0 0002 U 0002 0 0004 lt Original Dimensions F4 Shift F4 wil Zoom Back amp Enable Zoo
249. ntify the relationship in the procedure Existing links can be removed or modified and new links can be created 2 4 8 2 Removing links In the previous example all three potentials are linked If the Stop potential should differ from the Start potential and the Set potential value then the link to the other parameters has to be removed Click the Stop potential parameter to select it and click the Un ink selected parameter button in the toolbar to remove the link see Figure 2 36 81 Page NOVA User manual File View Profile Run Tools Help 5D he Ss St el a e Sa EX Commands Procedures G Autolab Cyclic valtammetry potentiostatic ie Cyclic valtammetry galvanostatic fon Cyclic voltammetry current integration fe Cyclic voltammetry linear scan Cyclic voltammetry linear scan high speed z Linear sweep voltammetry potentiostatic z Linear sweep voltammetry galvanostatic Linear polarization Hydrodynamic linear sweep j Differential pulse voltammetry Square wave voltammetry os Sampled DC polarography Chrono amperometry At gt 1 ms z Chrono potentiometry At gt 1 ms j Chrono amperometry fast Chrono potentiometry fast Chrono coulometry fast a Chrono amperometry high speed z Chrono potentiometry high speed Chrono charge discharge z FRA impedance potentiostatic b FRA impedance galvanostatic H Standards i My procedures ce E Commands Parameters Link
250. o Save the data in database Ee LW staircase Hive E B Wl 4 Value 1747 9 x ieg Control Autolab RDE 3 El Lov staircase em ivs E 5 Control Autolab RDE E Ao Remove from View Remove all fram View Figure 4 197 Adding the Hydrodynamic i vs V analysis tool can be done through the right click menu The Hydrodynamic i vs Vw analysis tool will be added again to the data set providing a Levich plot as well as two different linear regression lines see Figure 4 198 Demo 04 Hydrodynamic LSY with increasing rotation rate Control Autolab RDE 0 003 H 1 Value 500 2 Value 831 92 4 3 Value 1247 9 0 0025 4 Value 1747 9 5 Value 2331 9 4 6 Value 3000 0 002 3 Hydrodynamic i vs Yu H Levich yp S T H Regression gpugh origin ae H x Regression D 0 0015 O 0 001 0 0005 kk _ ER 0 5 10 iS vw Figure 4 198 The Hydrodynamic i vs V analysis tool generates the Levich plot automatically D a IN QD 286 Pa ge NOVA User manual The Levich plot is always built using the first measured data point for each rotation rate 4 8 2 3 Calculate charge This data analysis tool can be used to calculate the charge involved in an electrochemical measurement This analysis tool can be added to a data set using the right click menu The result of this analysis tool is different from the result of the Integrate data analysis tool shown in Section 4 8 1 7 The integrat
251. ocedures CAUsers UserDocuments My Documents My Procedures 1 10 Fracedures standards CAUsers UserDocumentsiMy Documents My Procedures 1 1 0 Standard Measured data Data analysis CAUsers UserDocuments My Documents My Procedures 1 10 Novea Commands My Commands LAUsers UserDocuments My DocumentsiMy Procedures 1 10 Commands Circuits Circuits CAUsers UserDocuments My DocumentsihMy Procedures 1 10 Circuits Cancel Figure 2 97 The database manager can be used to define a Commands database 128 NOVA User manual Commands defined using the My commands framework will be stored in the defined database and will be available for procedure building in the commands browser see Figure 2 98 H Favorite commands H Control E Metrohm devices External devices H Measurement general E Measurement cyclic and linear sweep voltammetry Gy Measurement voltammetric analysis H Measurement chrono methods H Measurement impedance H Data handling Analysis general G Analysis baseline correction H Analysis corrosion H Analysis impedance E Flots general E Flots impedance mh Y commands Figure 2 98 The My commands group is located in the commands browser 2 7 1 Creating simple My commands This section illustrates the use of the My commands framework in NOVA to create a dedicated single My command Create a new procedure by clicking the new procedure button A in the toolbar to clear the editor
252. ofile Run Tools Advanced procedure view Setup View Mult Autolab View Measurement View Analysis View User log 3 hl e 00 Autolab display FRA manual control MDE manual control MUX manual control F11 F10 External manual control View Profile Run Tools Measurement View Help Tee Help Figure 3 1 Selecting the Measurement view Real time information on the measured data and the procedure is shown and updated as the data is collected Figure 3 2 provides an overview of the Measurement view i Note By default Nova switches to the Measurement view automatically when the Start button is pressed Refer to Section 1 6 4 3 for more information 139 Page NOVA User manual avd NOVA x File View Profile Run Tools Help Toolbar Oe gg eee The Sere ee eae CR ce eR ind E Cyclic voltammetry potentiostatic AE 7 j Autolab control Set potential 3 5E 7 Measurement frame Set cell Wait time s 3E 7 Optimize current range ECV staircase 2 5E 7 i Set cell 2E 7 1 5E 7 Procedure progress _ 1E 7 5E 8 O Upper vertex potential vV 0 600 Lower vertex potential V 0 400 Stop potential V 0 000 Number of stop crossings 2 Step potential V Scan rate V s 0 6 0 4 0 2 0 Potential W 0 2 0 4 0 6 0 8 User log message Time Date Command j Autolab USB connected W3AUT 70530 5 18 39 PM 2 4 2013 a S
253. ol requires a value of the uncompensated resistance to be specified in Ohm This value is used to calculate a new potential scale according to Ecatcutatea t Ru where i is the measured current WE 1 Current and R is the specified uncompensated resistance Double click on the demo file Demo 79 Cyclic voltammetry Fe Fe entry of the demo database to load it into the data explorer frame This file contains data points of a cyclic voltammetry staircase experiment recorded in a 0 05 M Fe CN 6 2 in 0 2 M NaOH solution The number of scans is three To add the iR drop correction analysis tool to this data set right click the CV Staircase item in the data explorer frame and select the iR drop correction analysis item from the context menu see Figure 4 190 Demo 19 Cyclic voltammetry Fed Fes wees Plot Options oo Properties oN Add Windower Generate index Add Plot Add Analysis Calculate charge Show All Plots IR drop correction Hide All Plots X Save in My commands A1 Delete Al Remove all from View Figure 4 190 Select the iR drop correction analysis tool to add it to the data set A popup window will be displayed The uncompensated resistance can be specified in the window in Ohm see Figure 4 191 are iR drop correction Uncompensated resistance 22 UI OK N caia Figure 4 191 The uncompensated resistance value can be specified in a popup window 281
254. ono methods FastADC 5 25 2009 4 36 33 PM Du Demonstration data Demo 08 Chrono methods ADC164 20 steps 2 20 2007 8 40 08 AM Factory standard procedure AUT63072 Demonstration data Demo 09 Chrono methods ADC164 with variabl 2 20 2007 9 37 06 AM Combination of steps and levels AUT863072 Demonstration data Demo 10 Differential pulse measurement 5 25 2009 12 14 00 Example forbaseline correction peak sea AUTS3072 Demonstration data Demo 11 Hydrodynamic FRA with OCP determin 4 6 2010 12 23 00 PM With Autolab RDE at 1000 RPM AUT83072 Demonstration data Figure 4 9 Select the Show all option to view the entire contents of the database Note Use the Best fit and Best fit all to automatically adjust the width of the columns in the database 160 Page NOVA User manual 4 1 1 3 The data repository An additional feature of the database storage system is the data repository With the repository it is possible to create one or more internal backups of a database entry This makes it possible to recover the original data and it can also be used as audit trail To store data in the repository right click the corresponding entry in the database and choose the Store in Repository option from the context menu see Figure 4 10 Procedure name Timestamp Remarks oo Demo 01 Copia a wee CE0 001 M H2504 0 1 M Ag AgCl Ref KC
255. oothed plot Figure 4 101 The newly added SG Smooth tool Click the SG Smooth item A new area will be displayed on the right hand side of the plot This part of the view allows the definition of settings used in the SG Smooth tool see Figure 4 102 Spike rejection smooth level Level 2 W Polynomial order E Number of points left right 4 d Reset Figure 4 102 The SG Smooth options The following settings for the SG Smooth tool are available e Spike rejection yes no e Smooth level defines the number of points in the weighted moving average function The higher the level the heavier the smoothing default Level 2 225 NOVA User manual e Polynomial order defines the order of the polynomial function fitted through the data Small order leads to heavy smoothing default 2 e Minimum peak width defines the minimum width of the peak at half height in X axis units 0 means that this selection criterion is not used e Number of points left right this parameter defines the number of data points in the weighted moving average Both values are fixed for the pre defined Smooth levels When the User defined level of Smoothing is used the number of points left right can be defined The larger the values the heavier the smoothing These two values should always be identical Clicking the SG Smooth item displays a preview of the smoothed data in the analysis view see Figure 4 103 y x Signal Expr
256. or which to use the sampler Note It is also possible to open the Sampler by clicking the button in the quick access toolbar which appears when the procedure header is selected see Figure 2 76 Commands New procedure dit sampler Remarks waa End status Autolab m oignal sampler Time WE 1 Potential vWwE 1 Current m Options 1 Options ro Instrument LALIT 0530 Instrument description Autolab contral Pre set potential 0 000 set cell On m Optimize current range z E Repesattor each value 0 05 0 14605 0 29605 0 5 m Number of repetitions d Farameter link 0 05 7 LS staircase O 000 1 000 0 0500000 set potential 0 000 alt time 3 a lt gt set cell Ott m lt gt Figure 2 76 Opening the Sampler editor can also be done by clicking the button in the quick access toolbar 114 Page 2 5 8 Defining the plot settings NOVA User manual The procedure setup allows the definition of the plot settings to be used in the measurement view Each measurement command like LSV staircase has a signal sampler which provides a number of signals These signals can be linked to a P ot command which is attached to the measurement command By default the LSV staircase command has a pre defined P ot command called i vs E see Figure 2 77 Plot commands like the i vs E plot used in this procedure have two parameters e Show during measurement Yes No defines whether the plot should be displayed du
257. osition of the axis relative to the scale of the other axes The default setting uses the minimum of each axis to locate the origin of the 3D plot Choose maximum to locate the axis at the highest value of the first available axis Choose maximum alternate to locate the axis at the NOVA User manual highest value of the other axis example choosing the maximum location for the X axis will move the axis to the highest value of the Y scale while choosing the maximum alternate location for the X axis will move the axis to the highest value of the Z axis The same options for the Y axis will move the axis to the highest value of the X axis and the Z axis respectively e Toggle Text Location changes the position of the axis labels and tick labels relative to the axis Using these advanced features a given data set can be plotted in a very clear way and the plot can then be pasted into a document When editing is finished the plot can be exported to another application either directly through the clipboard or to an image Tile on the hard drive From the right click menu choose the Copy to Clipboard to copy the whole plot 2D or 3D or select the Save Image File option to save the plot as a picture on the hard drive A number of file types are available BMP TIF WMF PNG GIF JPG The Portable Network Graphics PNG which offers a lossless compression of the image is the default file format used in NOVA Alternatively the plots can be pri
258. ot possible to show the Global and the Local minima and maxima Selecting one of the two options automatically deselects the other one Show coordinates 2D plots only this option displays the coordinates of the mouse cursor in the 2D as a tooltip The coordinates shown depend on the scaling and the types of axes chosen for the plot The coordinates are refreshed when the mouse pointer is moved Figure 4 80 shows the results of this option on the 2D plot 208 P NOVA User manual 0 0016 0 0014 O 0012 0 001 0 0008 0 0006 0 0004 WELT Current 41 0 0002 OUTA 0 0004 0 2 0 0 2 0 4 0 6 0 8 Potential applied W Figure 4 80 Showing the coordinates of the mouse pointer on the plot The displayed coordinates correspond to the position of the mouse pointer expressed in terms of the signals chosen to plot the data In the example shown in Figure 4 80 the X coordinate corresponds to the applied potential and the Y coordinate corresponds to the measured current In the case of an overlay of two or more plots using two different Y axes see Section 4 4 the Show coordinates option will display two different sets of coordinates The first set corresponds to the coordinates relative to the left default Y axis The second set corresponds to the coordinates relative to the right Y axis see Figure 4 81 209 NOVA User manual 0 0085 0 008 300 0 0025 A0 6 4008E 2 2 6388E 3 0 002 6 4008E 2
259. otential WE 1 Current Cyclic voltammetry current integration s Li 4 Options 1 Options inear sweep voltammetry potentiostatic P _ a Instrument p3AUT 70530 Linear sweep voltammetry galvanostatic inet td ii Linear polarization A AREE era Instrument 1 Hydrodynamic linear sweep i LSAS Cono Description Procedure h amp Set potential 0 000 p rono amperometry At gt 1 ms y jit V Use active procedure Plot Options Setcell On Chrono potentiometry At gt 1 ms T h Waittime s 5 Instrument Output tano amperomety fast Optimize current range 5 3AUT70530 v Browse v Store in database hrono potentiometry fast B CV staircase 0 000 0 600 0 400 0 000 2 0 100000 L Chrono coulometry fast E Set cell Off Chrono charge discharge ar H Standards v Instrument 2 is My procedures Description Procedure v Use active procedure Plot Options Instrument Output AUT40034 v Bros v Store in database SelectAll Add G AAN gt Start Selected Stop Selected ere eee configuration Select None Remove User log mg User log message LaAutol j Autolab USB connected 3AUT70530 ver verload occurre gt Start amp o A Overload occurred Overl A Overload occurred 4 Autolab USB connected AUT 40034 ry bese becca Multi utolab Create the procedure M Itipl S tup the Sampler and Autolab devi the Options Set d f M th Itiple inst t d Start t t t NOVA 2 NOVA 0 File View Profile Run Tools He
260. otting settings in the Measurement view see Figure 3 7 143 Page NOVA User manual GE ivs E m Fotential applied v a WEI Current 4 Z lt empty gt show during measurement Bs m i re d 4 Figure 3 7 The i vs E plot command used in the Autolab cyclic voltammetry potentiostatic procedure The following parameters can be specified in the Setup view for each plot e Show during measurement Yes No defines if the plot should be displayed in the measurement view during the experiment When this parameter is set to No then the plot is not shown during the measurement The plot is however added to the data set and is available for plotting in the Analysis view e Measurement plot number 1 2 3 or 4 defines the location of the plot in the Measurement view Up to four plots can be shown in the measurement view see Figure 3 8 Plot 1 Plot 2 Plot 3 Plot 4 Figure 3 8 The location of the four plots available in the Measurement view 144 NOVA User manual Click the 11 or 3 button in the toolbar to display more than one plot in the measurement view Figure 3 9 shows an example of four plots displayed in the measurement view during an impedance spectroscopy measurement Plot 1 corresponds to the Nyquist plot plot 2 is the Bode plot both modulus and phase plot 3 is the Lissajous plot and plot 4 shows the resolution for both channels plotted versus time s00 400 300 N se
261. overlay of the four cyclic voltammograms Since the Fe II Fe III electron transfer reaction is reversible the peak position is independent of the scan rate used in the experiment The peak current however increases with increasing scan rate Figure 4 61 shows the overlay plot 0 0012 0 001 0 0008 0 0006 0 0004 WET Current tA 0 0002 0 0002 J J 1 0 2 Os 0 4 tes Potential applied W Figure 4 61 The overlay plot of the four linear sweep voltammetry curves 4 6 1 Changing the plot settings To change the plot settings of the overlay displayed in Figure 4 61 the plot settings of each individual plot can be modified as it was shown in the previous sections It is also possible to change the plot settings of the whole data set To modify the whole data set right click the Demo 05 header line in the data explorer window and select the Plot Options for the whole data set see Figure 4 62 194 NOVA User manual Demo 05 Feil Fe lll on pcr 7 S OCP determination Plot Options aus OCP value 0 243 Properties X 1 Yalue 0 01 LSY staircase Refresh Hs ivs E Add Plot in e Peak search Saad 5 2 Value 0 02 Add Analysis BS LSY staircase Show All Plots H tvs E Hide All Plots i e Peak search i 3 Value 0 05 ka Save the data in database pap rev aE Remove from View Hl IWS E i e Peak search XI Remove all from View S 4 Value 0 1 LSY staircase
262. parameter This link can be broken if necessary If no instrument is connected the Title of box will be unlinked e Message this is the message to display in the nout box e Value this is the default value for the input value of the nput box e Time limit s this defines an optional count down for the nput box e Use time limit defines whether the time limit should be used When this parameter is set to No the nout box will be displayed indefinitely In this example the nout box command will prompt the user to enter the requested scan rate for the cyclic voltammogram The preset value for this procedure is 100 mV s but this value will be overruled by the user once the procedure is started Type in the following parameters see Figure 2 42 e Message Enter the value of the scan rate in V s e Value 0 050 e Time limit s 30 e Use time limit no 21 More information on links is provided in Section 2 4 8 87 NOVA User manual Commands Parameters Links Cyclic voltammetry potentiostatic Remarks Cyclic voltammetry potentiostatic ma End status Autolak m oignal sampler Time WWE 1 Potential vWwE1 Current m potions 1 Options m Instrument LALIT 0530 Instrument description G Input box Title of box SALUT Z70530 Message Enter the value ofthe scan rate in V s 0 050 Time limit 5 30 se time limit No m Autolab contral z set potential 0 000 set cell On m wWalttime s z Optimize current range z CY st
263. pe analysis tool is added to the data as described in the previous section see Figure 4 175 a new item is added to the data explorer frame Demo 20 iron screw in seawater 5 Import GPES data Gives E H Corrosion rate tafel Sopen Figure 4 176 The corrosion rate Tafel slope is added to the data set Click the corrosion rate data analysis item to display the data from the data set in logarithmic scaling see Figure 4 177 272 NOVA User manual Demo 20 Iron screw in seawater Fl T m Import GPES data Hee vs E 1E 5 Corrosion rate tafel slope N Signal Expression Unit Density g cm 7 86 Equivalent weight g mol 27 925 Current A Surface area cm 1 Number of significant digits 5 Reset 0 5 0 4 0 3 0 2 Potential Y Figure 4 177 The Tafel slope analysis tool automatically displays the experimental data in logarithmic scaling Additionally the control parameters of the Tafel slope analysis tool will be displayed on the right hand side of the plot This part of the view allows the definition of parameter for the Tafel slope analysis see Figure 4 178 Density g cm rob Equivalent weight g mol er 925 SUMTaACe area cre 1 Number of significant digits a Reset Figure 4 178 The parameters for the Tafel slope analysis The following parameters are available e Density specifies the density of the sample in g cm e Equivalent weight defines the
264. ple included an automatic peak search command Therefore the peak height and peak position is available for each individual curve in the data set The data grid provides a tool called the Build signal which is designed to create such a plot by filtering and selecting information coming from the available Signals and the procedure parameters 299 NOVA User manual To create the plot the following information must be extracted from the measured data and the procedure 1 The scan rate used for each curve 2 The peak height of each peak Furthermore it will be necessary to determine the square root of the scan rate The use of the signal builder will be illustrated for the construction of the first two items The third item can be created using the Calculate signal tool described in the previous section 4 11 1 The signal builder window Click the Demo 05 data set in the data explorer to select the whole data set To create a new signal using procedure parameters or a specific set of values of an electrochemical signal click the build signal button Ti in the data grid toolbar Figure 4 217 Demo 05 Feil Fe Ill on pePt OCP determination ej E init OCP value 0 243 Ig presso Naj 1 Value 0 01 0 0012 LSV staircase 0 001 Peak search 2 Value 0 02 pen LSY staircase lt 0 0008 ivs E Fa me Peak search 7 5 3 Value 0 05 5 0 0006 amp LSV staircase i
265. qeasmeancensncentmanccestxceanstneactagenuczana 216 4 7 8 3D Specific Options ssicasasacancencnenadnidstenecedeeeyneshnedurdetandauiacsadexabencaraanin 216 479 ZOOM MING Nand OUT secre E E AEE EEEE ES 217 4 7 10 2D plots Zooming Box mode ssnnesnnsnnnsnneernsnirerrsrrrrrrernnne 217 4 7 11 2D Plots Zooming Scroll mode anneennennnsnnesnnsnnesrrsnrrsrrsnnnn 219 4 7 12 2D Plots Zooming Sliding mode ccccceeeceeeeseeeeseeeseeeeees 220 4 7 13 2D Plots Moving Dragging MOde ccecceceeeeeeeeeeeeeeeeeeenees 220 4 7 14 3D ZOOMING Scrolling mode coiccsniecccscvsssiersvcncasescseardeetessweceande 22 1 A feed B 18 fro 82 AV en no eee 222 48 1 XPV analysis TOONS wcdcccccdoicewceddasdnsais Mbesueddondeiexwsedeitessadedeaesdesasencedec 223 Ae Ve Woes GE SIMO CIN esd tease eadse este tccad N EEEE 223 he 2 EP SMO OU MING sac rnsanretenarasiaccncnianan tyes armen E S 227 4 8 1 2 1 Low pass and high pass filtering ccccceeeeeeeeeeeeeeeeae eens 230 4 8 1 2 2 Band pass and band stop filtering ccccecccceeeeeeeeeeeees 231 4 8 1 3 Baseline COM COTO corse sesccsiuasecewachacantonacrcaucieehostouedysdneseedntadewesks 233 4 8 1 3 1 Adding extra marker points cccccceeceeeneeeeeeeeeeaeeeeaeeeeens 236 4 8 1 3 2 MOVING Marker points 0 0 cece cece eeeeeeeeeeeeeeeaeeeeeneeeeeeeeeens 237 4 8 1 3 3 Plotting the residual
266. r aaa database manager the procedure check and the Hardware Setup hardwa re setup pH Calibration Help Tutorials gt Help menu used to access the Tutorials About 1 2 3 Views and frames The NOVA user interface uses four different views Three of these are dedicated to a specific part of the experiment A fourth view is dedicated to the control of multiple Autolab instruments Procedure setup measurement and data analysis are performed sequentially Each part of the experiment is carried out in a specific view of NOVA see Figure 1 4 The tutorials require Acrobat Reader to be installed 8 More information on the use of the Multi Autolab view can be found in the Multi Autolab tutorial available from the Help Tutorials menu 13 NOVA User manual NOVA ona NOVA 0 File View Profile Run Tools Help File View Profile Run Tools Help HAGA T Ea a MI RE SS ata RE SG Dalai E a i D T Se 0 aali Selectinstrument p3AUT70530 Commands Procedures Commands Parameters Links Configurationiname Autolab Cyclic voltammetry potentiostatic f Cyclic voltammetry potentiostatic Remarks Cyclic voltammetry potentiostatic ea Remarks Cyclic voltammetry galvanostatic End etal z a F Signal sampler Time WE 1 P
267. r be useful to extend the regression line through the origin of the plot To do this switch to Manual search mode see Figure 4 154 Search mode C Automatic tem Regression type Linear v Folynomial order Number of significant digits z Direction All Ww Reset Figure 4 154 Using the manual regression search mode 259 NOVA User manual Switching from Automatic to Manual search mode removes the results of the previous linear regression While holding the left mouse button drag the mouse pointer across the 2D plot to define the region to use for the regression calculation see Figure 4 155 0 003 0 003 0 0015 0 0015 Current 4 Current LA 0 001 0 001 gt AncnC E G AAAA Figure 4 155 Defining the region to use in the manual regression Once the search region has been defined the calculation is performed automatically using the settings defined in the control interface Using this approach the regression line can be extended through the origin of the plot as shown in Figure 4 155 If the shift key is pressed while the search window is defined it is possible to fine tune the search window see Figure 4 156 0 003 0 002 0 0015 Current 4 0 001 0 0005 Figure 4 156 The shift key allows to fine tune the search window 260 NOVA User manual The results of the Regression are stored in the data grid 4 8 1 6 Derivative The derivative analysis tools can be us
268. rame are an optional links between two or more parameters listed under the Links column In the case of the Autolab cyclic voltammetry potentiostatic procedure for example a link is used to link the Set potentia command with the Start potential and the Stop potential from the CV staircase command Links are a critical part of the NOVA procedures and they are discussed in much more detail in Section 2 4 8 of this Chapter NOVA User manual e Validation symbols the parameters and commands are validated in real time When errors or warning situations are identified a suitable symbol is provided on the left hand side of the procedure editor to provide a visual indicator about an error or a warning 2 3 Simple editing The easiest form of procedure editing in NOVA consists of loading a pre defined procedure into the procedure editor modifying some of the parameters of the procedure and running the experiment This very simple mode of operation will be explored in this section of the manual The next sections will describe advanced procedure editing The default Autolab cyclic voltammetry potentiostatic procedure is designed to run one staircase cyclic voltammogram starting from a potential of O V going up to a potential of 1 V then back to 1 V and finally stopping again at O V The scan rate is 100 mV s and the step potential is 2 44 mV These experimental parameters can be found in the expanded view of the procedure shown in mor
269. rates A 3 mm platinum disc was used as working electrode This example was already used in Section 4 8 1 5 Figure 4 194 shows an overlay of the linear sweep voltammogram recorded at different rotation rates 283 NOVA User manual 0 003 0 002 0 001 WET Current t inii 0 002 0 4 0 2 J 0 2 0 4 0 6 J E Potential applied W Figure 4 194 The linear sweep voltammograms recorded at different rotation rates This data set was recorded using the default Autolab Hydrodynamic linear sweep procedure This procedure automatically adds the Hydrodynamic i vs Vw analysis tool to the data at the end of the experiment This tool is therefore already added to the data see Figure 4 195 NOVA User manual E Demo 04 Hydrodynamic LSW with increasing rotation rate 5 Control Autolab RDE a 1 Value 500 n LSV staircase Gives E S 2 Value 831 92 n al LS staircase ivs E 5 3 Value 1247 9 n LSY staircase Gives E 4 Value 1747 9 E LS staircase H vs E a 5 Value 2331 9 n LSV staircase Gives E 5 6 Value 3000 E LSY staircase Be ivs E Hydrodynamic iws yu H Levich plot E Control Autolab RODE li Control Autolab RDE i Control Autolab RDE li Control Autolab RDE li Control Autolab RDE i Control Autolab RDE i Regression through origin H Regression Figure 4 195 The Hydrodynamic i vs J analysis
270. requency a As Z Scan 0 0015 D 5 0 001 O 0 0005 LU 0 0 0005 0 001 0 0015 0 5 0 05 Potential applied Y Demo 02 Lead deposition EQCM S CY staircase TES 0 Ere ivsE fy X Potential applied 200 Age Y WE 1 Current A Z WE 1 Current 400 5 AFrequency vs E y Ae X Potential aplaged Tama as mAg Y EQCM 1 AFrequency gt indy Z Scan 800 5 1000 D Le 1200 a 1400 i 1600 1800 2000 0 8 0 6 04 0 2 0 02 04 O06 O08 Potential applied W Figure 4 56 The two plots for the data set from example 2 the measured current relative to the applied potential top and the EQCM frequency change relative to the applied potential bottom 190 Page NOVA User manual The data explorer frame should now look like the one shown in Figure 4 57 Demo O02 Lead deposition EOCM Ee C staircase A ive E Age X Potential applied ae Y WE 1 Current Lie Ae 2 WEI Current AFrequency vs E oof Potential applied oof Y EQCM 1 AFrequency Figure 4 57 Available plots in the data explorer frame Presently only the AFrequency vs E is being plotted in the 2D plot indicated by the bold lettering To overlay this plot with the i vs E plot hold the CTRL key pressed on the keyboard and click the vs E plot The new 2D plot should now look like the one displayed in Figure 4 58 E S Demo 02 Lead deposition EOCM CY staircase 0
271. ring the measurement or not e Measurement plot number 1 2 3 or 4 defines the location of the plot in the measurement view Up to four plots can be shown real time in the measurement view Commands New procedure Remarks End status Autolab signal sampler Options Instrument Instrument description Autolab control set potential set cell Optimize current range E Repeat for each value Number of repetitions Parameter link El LSY staircase start potential v stop potential v step potential x ocan rate y s Estimated number of points Interval time s signal sampler Options Potential applied Time WE Current WE Potential Index eo show during measurement Measurement plot number set potential Viait time 3 lt gt set cell lt gt Parameters Time YE Potential WE Current 1 Options USAT Y0530 0 000 On A 0 05 0 14605 0 29605 0 5 d 0 05 O 000 1 000 0 0500000 0 000 1 000 0 00244 0 050000 dee 0 048600 Time YE Potential WE Current 1 Options array Cv arrary gt 3 Jarreay gt 4 array fv Array WET Current 4 Time 5 Yes 1 0 000 z Ott Links Figure 2 77 The vs E Plot used in combination the LSV staircase command 115 Page NOVA User manual The plot settings are defined using links The links are located between the electrochemical signals provided by the LSV staircase command Potential applied WE
272. rocedure validation sressszssecsnddccuseesancovadanss venus ted dubaedaeescnouaeduenences 121 2 5 11 Running the measurement cece eee eeeeteeeeeeeeeeeeeeesaeeeeseeeeeaeeeens 121 2 6 Dragging and dropping procedures cccecccceeeceseeeeeeeeeeeeeeeeeeeeeneeeeeas 122 DoF IVC OW INOS eE A E E A ORE 128 2 7 1 Creating simple My COMMANAS cccceeeeeeeneeeeeeeeeeeeeeeseeeeeaeeeeeas 129 2 7 2 Creating complex My COMMANAS ccceceeeeeeeeeeeeeeeeeeeeeeeeeeeeeens 132 ZT 3 SON MAG WAY COMMANA ect oy einarrewsiaarsae saved E a 136 2 7 4 Using the My command ccecccceeeeeeeeeeeeeeeeeeeeeaeeeesaeeeeaeeeeeaeeeeens 137 3 TNE Measurement VIEW 200 0ccccseeceseseecesecesseecesesesedseesseseteneeeseeseesseseesceeeess 139 3 1 The procedure progress frame ccccccsccccseseecceeseecceesscceegeeeseuseessaeeeess 141 3 1 1 Modification of command parameters in real time 00cceee 142 3 2 Measurement plots cccccccsecccseeceececeeecee cece ceseueeseeeesseeseasessusenseeeas 143 3 2 1 Adding and removing plots in real time cccececeeeeeeeeeeeeeeeeeeeees 145 3 2 2 Modification of plot Options in real tiMe ccceccceeeeeeeeeeeeeeeneeees 147 3 3 Clearing the measurement VIEW and ZOOMING cceceeeeeeeeeeeeeeeneeeees 147 Aa The PU ON a AiSPlay eirinen putes camteat eevee tats EEEE SEENE 149 ie NAM ACO MF Ol sen steno secs ioevsa
273. rono amperometry fast Chrono potentiometry fast Chrono coulometry fast Chrono amperometry high speed Chrono potentiometry high speed Chrono charge discharge Interrupt e interrupt high speed Positive feedback FRA impedance potentiastatic FRA impedance qalvanastatic FRA potential scan Commands Procedures mi Autolak Cyclic voltammetry potentiostatic Cyclic voltammetry qalvanostatic Cyclic voltammetry current integration Linear sweep voltammetry potentiostatic Linear sweep voltammetry galvanostatic Linear polarization Hydrodynamic linear sweep Chrono amperometry At gt 1 ms Chrono potentiometry At gt 1 ms Chrono amperometry fast Chrono potentiometry fast Chrono coulometry fast Chrono charge discharge Figure 1 28 Overview of the Autolab procedures with a pAutolablll left hardware based profile not active and right hardware based profile active 1 6 1 3 Application based All the commands and the procedures in NOVA have been tagged with an application marker corrosion energy electroanalysis etc When a given application profile is active only the commands and procedures relevant for this application are shown see Figure 1 29 Commands Frocedures Autolab Cyclic voltammetry potentiastatic Linear sweep voltammetry potentiostatic Linear polarization e Hydrodynamic linear sweep e Chrono amperometry At gt 1 ms Chrono potentiometry At gt 1 ms PRA impedance po
274. rrosion rate analysis demo data Imported demonstration data Figure 4 7 Filtering the database using the Instrument column The contents of the database will be updated displaying only the database entries obtained with the instrument with serial number AUT83072 see Figure 4 8 Procedure name f Time stamp Remarks Instrument Instrument description Demo 01 Copper deposition 3 15 2007 6 25 27 PM CuSO4 0 01 M H2504 0 1 M Ag AgCl R AUTS63072 Demonstration data Demo 02 Lead deposition EQCM 2 4 2009 11 04 15AM Pbi ClO4j2 0 01 M HCIO4 0 1 M AUT63072 Demonstration data Demo 03 Bipotentiostat measurement PYPt Rin 2 20 2007 3 37 46 PM ORPM HCIO4 0 1 M AUTS83072 Demonstration data Demo 04 Hydrodynamic linear sweep voltammetr 3 4 2009 11 21 58 AM Fe2 Fe3 NaOH 0 2 M AUT83072 Demonstration data Demo 05 Fe ll Fe ll on pcFPt 6 10 2008 1 27 46 PM Fe2 Fe3 Reversibility Test LSY with in AUT83072 Demonstration data Demo 06 Galvanostatic CY 3 26 2007 3 32 01 PM Lead deposition on gold galvanostatic AUT83072 Demonstration data Demo 07 High speed chrono methods Fast ADC 5 25 2009 4 36 33 PM Dummy cell c AUT83072 Demonstration data Demo 08 Chrono methods ADC164 20 steps 2 20 2007 8 40 08 AM Factory standard procedure AUT63072 Demonstration data Demo 09 Chrono methods ADC164 with variabl 2 20 2007 9 37 06 AM Combination of steps and levels AUT863072 Demonstration data Demo 10 Differential pulse measurement 5 25
275. rted on Procedure name Time stanp Remarks Instrument serial number and Instrument description 4 1 1 2 Data filtering The database also provides a filtering option that can be useful when exploring a database with a lot of entries By using the filter option it is possible for example to select all measurements that have been obtained using a specific instrument Click the Demo 01 Copper deposition entry of the database and right click on the Instrument header Select Filter with selected dropped on row using a Like option see Figure 4 7 159 Page NOVA User manual Procedure name t Time stamp Remarks Instrument Instrument description Demo 01 Copper deposition 3 15 2007 6 25 27 PM CuS0O4 0 01 M H2504 0 1 M Ag AgCl R AUT83072 Filter selected dropped on row gt Like Demo 02 Lead deposition EQCM 2 4 2009 11 04 15 AM Pb Clo4j2 0 01 M HCIO40 1M AUT83072 Show all Greater N Demo 03 Bipotentiostat measurement PYPt Rin 2 20 2007 3 37 48 PM 0 RPM HCIO4 0 1 M AUT83072 Demo 04 Hydrodynamic linear sweep voltammetr 3 4 2009 11 21 58 AM Fe2 Fe3 NaOH 0 2 M AUT83072 Best fit l Smaller Demo 05 Fe ll Fe lll on pcPt 6 10 2008 1 27 46 PM Fe2 Fe3 Reversibility Test LS with in AUT63072 Best fit all Demo 06 Galvanostatic CY 3 26 2007 3 32 01 PM Lead deposition on gold galvanostatic AUTS83072 f Demo 07 High speed chrono methods FastADC 5 25 2009 4 36 33 PM Dummy cell c AUT83072
276. rval time s signal sampler Options Fotential applied Time WE Current Index Ive E set potential m Wait time s E E E Parameters Time VWwE 1 Current Mo Options LWSAUT 205350 0 000 On 5 Meia 3 O 000 1 000 0 1 000000 0 000 1 000 0 00244 0 7 000000 dee 0 024400 Time WE 11 Current Mo Options lt aray gt Cv lt array gt 5 lt aray 4 array gt 0 000 Links Figure 2 63 Adding the LSV staircase Set potential and Wait time commands to the procedure For this example the Start potential of the LSV staircase command will be 0 06 V and the Stop potential will be set to 0 55 V The start potential value will also be used as the preconditioning potential 103 Page NOVA User manual Create a link between the Potential parameter of the Set potential command used in the preconditioning stage and in the repeat loop and the Start potential parameter of the LSV Staircase command see Figure 2 64 Change the values of the Start potential and the Stop potential of the LSV staircase command to 0 06 V and 0 55 V respectively see Figure 2 64 Commands New procedure Remarks End status Autolab signal sampler Options Instrument Instrument description Autolab control set potential Potential Vv set cell Optimize current range Repeat for each value Number of repetitions Parameter link E LSY staircase ocan rate v s Start
277. ry At gt 1 ms e Chrono potentiometry t gt 1 ms e Chrono amperometry tast e Chrono potentiometry fast e Chrono amperometry high speed Chrono potentiametry high speed e Chrono charge discharge Hnterrupt Hnterrupt high speed Positive feedback ee FRA impedance potentiostatic FRA impedance qalvanastatic FRA potential scan Standards i My procedures Figure 1 31 Hiding a procedure from the procedure browser Once an item has been hidden from view it will not be shown until it is unhidden To unhide hidden commands procedures or command parameters select the Show all option from the Profiles menu see Figure 1 32 36 NOVA User manual File View Profile Run Tools Help ERTE NE Hardware based Basic Interm eciate Advanced Corrosion Education Electroanalysis Energy Interfacial electrochemistry Semiconductors Reset user profile Import user profile Export user profile Hicle Ctrl H Unhicle Ctl Shitt H Show all Figure 1 32 Select the Show all option from the Profile menu to display all hidden items Hidden items are shown in green see Figure 1 33 Commands Procedures Commands Procedures m Autolak z Cyclic voltammetry potentiastatic e Cyclic voltammetry qalvanostatic ee Cyclic voltammetry galvanastatic Cyclic voltammetry current integration z Cyclic voltammetry current integration Cyclic voltammetry linear scan Cyclic voltammetr
278. ry week or create a specific database for each type of experiment The database can also be located on a mobile storage device like a USB stick an external hard drive or on a network drive To change a database click the L button on the right of area displaying the path of the currently used database This will open a browser interface which can be used to select another database folder Browse For Folder Data analysis 4 User 4 My Documents a My Procedures 1 10 Circuits Comm ands Nova _ Procedures _ Standard Make New Folder OK Cancel Figure 1 23 A file browser window is used to change the location of the database folder The database browser window can be used to create a new database by clicking the enwrier button This will create a new folder which can be renamed and used as a new database see Figure 1 24 30 NOVA User manual Browse For Folder Data analysis 4 User J My Docum ents J My Procedures 1 10 Circuits bh Comm ancls i Nova h Procedures d Standard Make Bley sain OK Cancel Figure 1 24 Creating a new database It is possible to rename existing database folder by right clicking the folder and selecting the Rename option from the context menu The same menu can be used to delete a folder 1 6 Customizing NOVA Two different customization options are provided in NOVA e Profiles this option is used to filter
279. ry of the demo database to load it into the data explorer frame This file contains data points recorded in NaOH 0 2 M in the presence of 0 05 M Fe CN using a Pt ultra micro electrode 5 um Click the i vs E plot in the data explorer frame to display the data points from this demo file see Figure 4 99 As frequently seen with this type of measurement the current levels are very small and affected by a significant amount of noise 1 3E 10 1 6E 10 1 4E 10 1 2E 10 1E 10 SE 11 BE 11 4E 11 2E 11 J Current Ay ZE 11 4E 11 J T 0 4 0 6 0 8 Potential W Figure 4 99 The data from the Demo 15 data file NOVA User manual To use the SG Smooth tool right click the vs E plot in the data explorer frame and from the context menu select the SG Smooth tool see Figure 4 100 i Demo 15 UME LSW Import GPES data H ivs E Plot Options Propertes Add Analysis Smooth z SG Smooth X Copy Visible Plot s to Baseline Correcton gt FFT Smooth Show All Plots Peak search Hide All Plots Regression Save in My commands Derivative Delete Integrate FFT Analysis xo Remove all from View i Corrosion Rate Figure 4 100 Adding the SG Smooth tool to the data A new item called SG Smooth will be added to the data set in the data explorer frame below the i vs E plot see Figure 4 101 a Demo 15 UME LSW Import GPES data H li vs E oG Smooth SG sm
280. ry potentiostatic 5 C staircase a l Y Plot Optons Propertes Add Analysis Copy Visible Plot s to Show All Plots Hide All Plots Save in My commands xo Delete Remove all from View Smooth Baseline Carrecton Peak search Regression X Derivative Integrate FFT Analysis Corrosion Rate Figure 4 148 The regression tool can be added to a plot using the right click menu Double click on the demo file Demo 04 Hydrodynamic LSV with increasing rotation rate entry of the demo database to load it into the data explorer frame This file contains data points recorded at different rotation rates with the Autolab RDE in a 0 05 M Fe CN in 0 2 M NaOH solution The data file contains a total of six linear sweep voltammograms see Figure 4 149 256 NOVA User manual a Demo 04 Hydrodynamic LS with increasing rotation rate Control Autolab RDE 1 Value 500 0 0035 ll Control Autolab RDE 0 003 amp LSY staircase 2 H ivs E 0 0025 5 li 2 Value 831 92 Control Autolab RDE 0 002 amp LSY staircase co iets 0 0015 S a 3 Value 1247 9 i Control Autolab RDE LSV staircase H ivs E 5 a 4 Value 1747 9 i Control Autolab RDE LSY staircase o BeivsE 5 a 5 Value 2331 9 li Control Autolab RDE 5 8 LSV staircase H ivs E 5 6 Value 3000 e Control Autolab RDE 0 0015 LSV staircase amp eivsE 0 002
281. s Cyclid Unlink selected parameters Rertrearr Cyclic valtammetry potentiostatic End status Autolab Signal sampler Options Instrument Instrument description Autolab control amp Set potential Potential Vv Set cell Wait time s Optimize current range B C staircase Start potential v Upper vertex potential Vv Lower vertex potential V Stop potential V Number of stop crossings Step potential v Scan rate V s Estimated number of points Interval time s Signal sampler Options Potential applied Time WE 1 Current Scan WE 1 Potential Index H ivs E Set cell lt gt Time YWWE 1 Potential WE 1 Current 1 Options 0 200 0 200 On z3 5 5 0 200 1 000 1 000 0 200 2 0 1000000 0 200 1 000 1 000 2 0 00244 0 1000000 1650 0 024400 Time YWWE 1 Potential WE 1 Current 1 Options lt array gt VY array gt s array gt A aray gt aray gt 0v array gt A A A A Off Figure 2 36 Unlinking the Stop potential If the Start potential is now set back to O V only the value of the Set potential will be set to the same value The Stop potential value will remain equal to 0 2 V since it is no longer linked to the two other parameters see Figure 2 37 82 Page NOVA User manual Commands Parameters Links Cyclic voltammetry potentiostatic Remarks Cyclic voltammetry potentiostatic ma End status Autolab m oignal sampler Time WWE 1 Pot
282. s Figure 3 16 An overview of the Autolab display during a CV measurement uAutolab III The available current ranges are displayed on the right hand side of the Autolab display The highest and lowest possible current range depend on the hardware settings in the case of Figure 3 16 the instrument is a UAutolab Ill therefore the highest current range is 10 mA The serial number of the instrument is located in the header of the Autolab display window The selected current range is highlighted The Pees button located in the Autolab display can be used to reverse the scan direction The active settings are highlighted It the case of Figure 3 16 the settings are e Potentiostat mode PSTAT label e Current range 1 mA 1 mA label e High stability on HSTAB label e Cell on CELL ON label Most of the labels of the manual control are interactive A setting of the Autolab potentiostat can be changed by clicking the corresponding label Clicking the labels of the manual control will also update the settings displayed on the front panel of the instrument The information displayed at the bottom of the Autolab display window depends on the experimental method 8 This is the indentifying serial number of the instrument When the Autolab is used in combination with an external USB interface the serial number of the USB interface is shown This option is only available for cyclic voltammetry and linear sweep voltammetry stairc
283. s can be found in the Command list document available from the Help menu 64 Page NOVA User manual Commands Procedures Control Metrohm devices External devices Measurement general Measurement cyclic and linear sweep voltammetry Measurement voltammetric analysis Measurement chrono methods Measurement impedance Data handling Analysis general Analysis baseline correction Analysis corrosion Analysis impedance Plots general Plots impedance n Why Commands _ P H H H H 0 0 0 0 0 H A Figure 2 16 Switching to commands browser by clicking the commands tab The commands are grouped into sixteen categories Figure 2 17 highlights the two commands used in the chrono amperometry procedure The Set potential command is located in the Measurement general group This group contains general purpose commands like Set cell Wait time etc On the other hand the Record signals gt 1 ms command is located in the Measurement chrono methods group This group contains all the commands specifically related to the time resolved measurements More information on chrono measurements can be found in the Chrono methods and the Chrono methods high speed tutorials available from the Help menu 18 Please refer to the Command list description available from the Help Tutorial
284. s menu for more information on each command 65 P NOVA User manual Commands Favorite commands g Control H Metrohm devices H External devices Measurement qeneral b Autolab control Set potential set current e Wait time 5 reference electrode in volts x Optimize current range OCP determination set reference potential Interrupt measurement Control Autolab RDE Switch Autolab RDE off Create new drop Determine integrator drift H Measurement cyclic and linear sweep voltammetry H Measurement voltammetric analysis Measurement chrono methods Measurement template potentiostatic Record signals gt 1 ms Chrono methods initiates a measurement of current and other signals Measurement template during a given amount of time in s Can be used with Interval Record signals 1 ms times gt Irs During the measurement the data is shown in the plot o Chrono methods galva With Interval times lt 1ms use the Chrono methods commands H Data handling H Analysis general H Analysis baseline correction H Analysis corrosion Plots general E My commands Figure 2 17 The Set potential and Record signals gt 1 ms commands used in the Chrono amperometry procedure 66 Page NOVA User manual The Set potential command is used to set a specific potential on the electrochemical cell The Record signals gt 1 ms command is used to s
285. s to be expanded and the parameter changed from Off to On see Figure 2 60 Commands Parameters Links New procedure Remarks zj End status Autolab m oignal sampler Time WWE 1 Current ma Options Mo Options m Instrument LALIT 0530 Instrument description El Autolab control m WE Mode Fotentiostatic WE Current range 1 mA WE Bandwidth High stabilit set potential 0 000 On 4 Optimize current range Orff Figure 2 60 Changing the settings of the Cell status parameter Note As soon as the cell is set to On status in the procedure editor the warning symbol AX next to Optimize current range command is cleared since the warning is no longer valid see Figure 2 61 Commands Parameters Links New procedure Remarks aa End status Autolab ma oignal sampler Time WWE 1 Current maa Options Mo Options m Instrument LALIT 0530 Instrument description E Autolab control WE Mode Fotentiastatic WE Current range 1 mA WE 1 Bandwidth High stability Setpotental CS O e Setcell Optimize current range a lt gt Figure 2 61 The warning is removed when the Cell status is switched to On in the procedure editor The value of the preconditioning potential is not yet defined It will be linked to the start potential of the linear sweep voltammetry command which means that its value is not relevant at this time 101 Page NOVA User manual 2 5 4 Defining the measurement conditions For this example four conse
286. segment as the WE 1 current the Sample a ternating option can be used see Figure 1 15 Using this option the WE 1 Current and the WE 2 Current signals will be sampled at the same time in an alternating way ff Edit Sampler 0 Signal sample Optimized Sampler configuration WE Current Sampler WE 1 Potential Segment WE 1 Power C o WE 1 Potential WE 1 Resistance C E Segment Optimized WEH Charge C 7 WELZ Current WE 2 Current ae WE 2 Charge Time Mane alternating Figure 1 15 The Sample alternating option can be used to sample signals in the same segment The equivalent sampling time will still be the same as in the previous case but using this option both signals will be collected at the same time see Figure 1 16 AE NOVA User manual Last segment WE 2 Current Optimized sample Time 1 sample WE 1 Potential 1 sample Current Optimized sample Figure 1 16 Sampling an external signal using the sample alternating option Using the sampler lets the user define exactly which electrochemical signal to record during a measurement and when these signal have to be recorded 1 3 4 The Options The options can be used at the very end of each sampling step to evaluate the measured data and change the data acquisition settings test a cutoff condition or trigger a special action The following actions are part of the options e Automatic current ran
287. set cell Ott m X When the scan rate is changed the line shown between brackets next to the CV Staircase command is updated from 0 000 1 000 1 000 0 000 2 0 10000 to 0 000 1 000 1 000 0 000 2 0 20000 Figure 2 9 Modifying the scan rate Changing the scan rate of the cyclic voltammetry procedure has an effect on some of the grey parameters The interval time originally was 24 4 ms and now is 12 2 ms because the scan rate has been doubled If the upper vertex potential is changed to 0 8 V the Estimated number of points will also change see Figure 2 10 59 Page NOVA User manual Autolas control z set potential 0 000 Set cell On rm E E E E Wart time 3 p Optimize current range z El CY staircase O 000 0 600 1 000 0 000 2 02000000 start potential 7 0 000 Upper vertex potential v4 Lower vertex potential 0 Stop potential fv Upper vertex potential in V Number of stop crossings step potential 6 Scan rate vis Upper vertex potential gt Lower vertex potential To reverse the scan direction specify a negative Step potential Estimated number of points Job Interval time 3 0 012200 Signal sampler Time WE 1 Potential WWE Current m Hotions 1 Options m Fotential applied lt array gt fv Time lt array gt s WEI Current lt array A See lt array gt WE 1 Potential lt array v Index lt _array gt Ives E z Set cell
288. sings Step potential 4 0 00244 Scan rate vss O 1 000000 Estimated number of points 1732 Undo Unlink Stop potential v Ctl Z Interval time s O024400 a a a a signal sampler Time WWE 1 Potential WW E 1 Current Options 1 Options ma Fotential applied lt aray Vv Time lt arrary gt 3 WE Current lt aray gt 4 Scan array gt WE 1 Potential array Vv Index Array ivs E oet cell Off 3 Figure 2 40 It is possible to create links and remove links using the right click menu Note The Undo Unlink option is also provided in the right click menu see Figure 2 40 The Undo and Redo options can be used to restore broken links or break restored links 2 4 8 4 Links the programming tools of NOVA Links can be used to program in NOVA Using links procedure parameters can be linked with one another Results of data handling steps can be used for plotting or as new parameters for the rest of the experiments Using links it is possible to program just about any measurement sequence Links can be used to create interactive or dynamic procedures which allows a change to a procedure parameter While the experiment is running depending on parameter values provided by the user or calculated by the software during the experiment 86 Page NOVA User manual A very convenient command called Input box is available in the commands browser under the Control section The nout box
289. sistance calculated from the intercept and the Tafel slopes according to 1 2 303 gt J om iror R e E Begin E End the voltage limits corresponding to the measurement 275 NOVA User manual 4 8 1 9 2 Corrosion rate Fit The Tafel slope analysis tool provides an estimation of the polarization resistance and the exchange current density Accurate determination of these parameters can be done by fitting the Butler Volmer equation to the experimental data set taking into account that the corrosion current is related to the polarization resistance and the Tafel slopes according to R 2 303 l lcorr d ba be This expression can be used in combination with the Butler Volmer equation in order to perform a non linear fit of the equation to the data set In order to do this in NOVA the Corrosion rate fit analysis tool can be used To add this analysis tool to a data set right click the i vs E plot and select the Corrosion rate fit analysis tool from the Add Analysis menu see Figure 4 182 El a Demo 20 Iron screw in seawater Import GPES data 4 livs E Plot Options Properties Add Analysis Smooth Copy Visible Plot s to Baseline Correction gt Show All Plots Peak search Hide All Plots Regression Save in My commands Derivative Delete Integrate FFT Analysis XI Remove all from View ao Corrosion Rate Corrosion rate tafel slope Corrosion rate fit X Figure 4
290. st point T r r Current A 4E 7 eq aaas 0 5 0 0 5 Potential W right location of the second point and drawing of the baseline e Zero Base no baseline is used in the determination of the peak Click anywhere on the plot and while holding the mouse button drag the mouse across the plot area to define the search window on the X axis Using this baseline mode the data point on Y axis with the highest absolute value located within the range defined on the X axis is used as a peak see Figure 4 136 AEF uence Current A 0 5 0 Potential iV Current A 4AE 7 eee ose 0 5 0 O45 Potential W Figure 4 136 Using the zero base method to specify the base line 246 P NOVA User manual The zero base search method locates the absolute maximum value of the curve in the curve segment closest to the first point defining the search window Current A Polynomial this baseline uses a polynomial function in the determination of the peaks The polynomial baseline is constructed by clicking two or more points on the plot These waypoints do not have to be on the curve itself When the last point has been defined press the Enter key on the keyboard to perform the analysis with the defined baseline see Figure 4 137 4E 7 4E 7 3E 7 3E 7 2E 7 2E 1E 7 L 1E 7 0 N a o 1E X 1E 2E 7 2E 7 0 5 0 0 5 0 5 0 0 5 Potential V Potential V Figure 4 137 Using the polynomial bas
291. sted at any time by clicking the iR drop correction item in the data explorer 282 Page NOVA User manual 4 8 2 2 Hydrodynamic i vs Vw This data analysis tool can be used to create a Levich plot using the limiting current values recorded in an experiment using forced convection by means of the Autolab rotating disc electrode Typically in this type of experiment a potential scan is performed at different rotation rates As the rotation rate increases the convective drag from the electrode also increases and the diffusion layer decreases in thickness As a result the current values in the mass transport controlled region increase Under these experimental conditions the limiting current values i are related to the rotation rate of the working electrode according to 2 1 i 0 62 AnFD3v 6C Vw Where A is the geometric area of the working electrode n is the number of electrons involved in the electrochemical reaction F is the Faraday constant D is the diffusion coefficient v is the kinematic viscosity C is the bulk concentration of the electroactive species and is the angular frequency of the working electrode Double click on the demo file Demo 04 Hydrodynamic LSV with increasing rotation rate entry of the demo database to load it into the data explorer frame This file contains data points of six linear sweep voltammetry experiment recorded in a Fe CN 0 05 M in 0 2 M NaOH solution at different rotation
292. switched off l LY staircase qalvanostatic E Hide warning N A OK Cancel Figure 1 54 Hiding a warning in the validation screen e Switch to measurement view when start measurement Yes No this setting defines if NOVA should switch to the measurement view when a measurement starts default yes e Time out in seconds for validation dialog this value is the time out used when a Warning message is displayed during procedure validation see Figure 1 55 The default value is 30 seconds Validation results The following problems were encountered during validation Message Command USAUT 0530 A Cell is switched off Optimize current range A Cell is switched off LY staircase Time remaining 30 seconds Cancel Figure 1 55 A time out is used when a Warning is displayed in the Procedure validation 50 Page NOVA User manual 2 The Setup view Procedure setup is usually the first and most important step in an electrochemical measurement This critical part of the experiment must be carefully prepared because mishaps during the measurement of the experimental data can have unpleasant consequences More often than not these problems can be attributed to poor experiment design This chapter will focus on procedure editing and will cover all the aspects of designing an electrochemical experiment using NOVA Some examples will be provided along the way 2 1 The workspace Set
293. t Two lines will be drawn on the plot to indicate the positions of the frequencies in the plot see Figure 4 113 These values will also be shown in the FFT Smooth options Tip use the Show coordinates option to help define the frequency or frequency range in the FFT Smooth analysis tool see Figure 4 114 231 Page NOVA User manual 1E 208 11 7 1881E 8 1E 8 IE Amplitude TE 1E 11 J SOO 1000 1500 2000 Frequency Hz Figure 4 114 Use the Show coordinates options to easily define the frequency or frequency range in the FFT Smooth analysis tool The smoothed data will be automatically generated using the filtering conditions specified through the FFT Smooth options panel or graphically see Figure 4 115 1 6E 10 1 4E 10 1 2E 10 TE 10 SE 11 BE 11 4E 11 smoothed result 2E 0 i 0 2 ga 0 6 0 8 Result x Figure 4 115 The Smoothed data plot generated by the FFT Smooth tool 232 Page NOVA User manual If required a new frequency or frequency range can be selected by clicking the frequency domain plot again or by specifying a new frequency or frequency range in the FFT Smooth options panel The data will be automatically re filtered using the new settings 4 8 1 3 Baseline correction The baseline correction can be used to fit a user defined curve through measured data points to define a baseline and to automatically correct the data for it Different forms of
294. t Shift F4 key combination see Figure 4 90 WE TD Current 4 218 P 0 0016 0 0014 Original Dimensions F4 Zoom Back Shitt F4 0 0012 Enable Zooming Moving Step through Data Select Dataset 0 0008 Grid Background 0 0 0 0 Bi Show Print Preview Print 0 001 0 0004 Copy to Clipboard 0 0002 Copy Data to Clipboard 0 jl Save Image File Save Image File Custom size 0 0002 b 0 1 0 0 1 0 2 0 3 0 4 0 5 0 6 Potential applied W Figure 4 90 Enabling zooming and zooming back using the right click menu U NOVA User manual It is only possible to zoom on the data if the Enable Zooming Moving option is selected The orange background and the check mark in the right click menu will indicate which option is currently active see Figure 4 91 Original Dimensions F4 Shift F4 mesma Zoom Back Enable Zooming Moving eG Step through Data X Select Dataset Grid Background Show Print Preview Print Copy to Clipboard Copy Data to Clipboard Save Image File E t T p Save Image File Custom size Original Dimensions F4 Shift F4 Ky Zoom Back Enable Zooming Moving X S Step through Data Select Dataset Grid Background Show Print Preview Print Copy to Clipboard Copy Data to Clipboard Save Image File E t T Io Save Image File Custom size Figure 4 91 Switching from Step through data to Enable
295. t item to add it to the filter see Figure 4 224 304 Page NOVA User manual Y Build signal 0 Analysis general Name Index Feak search W Peak search 2 2 Base end Base start L Peak width half height H Control H Measurement cyclic and linear sweep voltammetry H Measurement general H Untyped filter Search from 1 level s up Sort by order of 1st array high to low _ Sort by order of 1st array low to high OK Cancel Figure 4 224 Adding the Peak height from the Peak search group to the filter Click the OK button to validate the filter A new signal will be created in the data grid containing the values of the peak height for each LSV Staircase curve of the data set see Figure 4 225 ocan rate Wis Feak height P o oo239998 0 00033539 O 0200001 O O0048646 0 050000 1 O O00 7 6 0 1 0 001 114 Figure 4 225 The data grid and the two filtered signals 4 11 4 Calculating the square root of the scan rate For the construction of the plot a final signal is required containing the square root of the scan rate In order to create this signal click the button located in the toolbar to use the Calculate signal tool In the Calculate signal window create a Square root scan rate signal using the following expression SQRT v It is possible to copy and paste the expression displayed above into the expression builder Dana rdQe NOVA User manual In the signal list
296. taircase command in the contracted form Note Positioning the mouse pointer on the CV staircase command will display a tooltip which provides an overview of the parameters see Figure 2 7 and Figure 2 8 The five commands preceding the CV staircase command in this procedure Autolab control Set potential Set cell Wait time and Optimize current range are used as a pre treatment 58 Page NOVA User manual To change a parameter expand the CV staircase command and click the parameter you want to edit Type in the new value of the parameter and press the enter key to confirm the change Figure 2 9 shows a modification of the scan rate of the CV staircase command from 0 1 V s to 0 2 V s A tooltip reminding you to enter the scan rate in V s is displayed Autolab control aml Set potential O 000 cet cell On Wart time s s Gptimize current range LY staircase start potential 6 Upper vertex potential tv 1 000 m Lower vertex potential 0 1 000 stop potential 6 0 000 Number of stop crossings 2 step potential fv 0 00244 Scan rate v s 0 2000000 Estimated number of points Scan rate in V s Interval time s 0 012200 Signal sampler Time WWE Potential WWE 1 Current ma Lotions 1 Options ma Fotential applied array fv Time lt array gt 3 WEJ Current lt array A Scan lt arreay gt WEN Potential array fv Index lt array gt iws E
297. tentiostatic FRA frequency scan i 1 FRA frequency scan 10 0 kHz S FRA single frequency E AC vet Plot Options Lissajous Properties g EA T FRA frequency SC ma 3 FRA frequency sc Add Analysis Smooth H al 4 FRA frequency sc Copy Visible Plot s to Baseline Correction H 5 FRA frequency sc H lal 6 FRA frequency sc show All Plots Peak search H a 7 FRA frequency sc Hide All Plots Regression H al 0 FRA frequency sc ave in ands Derivatve H B 9 FRA frequency sc Save in My commands H a 10 FRA frequency s Integrate ee FFT Analysis a 11 FRA frequency 3 hai Remove all from View id 1 FRA frequency s Corrosion Rate Figure 4 171 Adding the FFT Analysis tool to the data A new item called FFT Analysis will be added to the data set in the data explorer frame for the 10 kHz frequency see Figure 4 172 269 Page NOVA User manual a Demo 16 FRA impedance il FRA measurement potentiostatic El FRA frequency scan i A FRA frequency scan 10 0 kHz 2 Gg FRA single frequency He E AC vs t AL vs t H Lissajous E FFT Analysis H FFT plot E 2 FRA frequency saan 7 91 kHz 5 3 FRA frequency scan b 25 kHz 5 41 FRA frequency scan 4 94 kHz Figure 4 172 The newly added FFT Analysis tool Click the FFT plot generated by the FFT Analysis tool to display the transformed data see Figure 4 173
298. tentiostatic standards My procedures Commands Frocedures Autolaks z Cyclic voltammetry potentiastatic Linear sweep voltammetry potentiostatic e Hydrodynamic linear sweep w Differential pulse voltammetry e square wave voltammetry Sampled DC polarography i Chrono amperometry At gt 1 ms standards My procedures Figure 1 29 Difference between the corrosion left and the electroanalytical right profile 34 NOVA User manual It is possible to combine all the profile schemes at the same time For example it is possible to set the profile to show hardware based and intermediate commands and procedures for the energy application see Figure 1 30 File View d F ir a7 we we Profile Run Tools Help Harchvare based Basic Interm ecdiate Advanced Corrosion Education Electroanalysis Energy Interfacial electrochem ay Semiconductors Reset user profile Import user profile Export user profile Hicle LInhicle Ctrl H Ctl Shift H Show all Figure 1 30 It is possible to combine several profiles at the same time intermediate hardware based and energy related 1 6 1 4 Hide Show option To further customize the appearance of the user interface the option to hide and show procedures commands and command parameters has been added To hide an item in NOVA simply right click menu In Figure 1 31 this option the item and select the hide option from the is use
299. the whole procedure click the Select all button to check all the available measurement command and then press the button to validate the options for these commands 111 Page NOVA User manual Preview changes Options Apply options to Optimize current range LS staircase Select all Select none T Invert selection Cancel Figure 2 72 Choosing the measurement commands for which to use the options Note It is also possible to open the Options by clicking the button in the quick access toolbar which appears when the procedure header is selected see Figure 2 73 New procedure Commands X Qa Ta Remarks asl End status Autolab m oignal sampler Time WWE 1 Current m potions 1 Options m Instrument LALIT 0530 Instrument description Autolab contral zj set potential 0 000 set cell On m Optimize current range z E Repesttor each value 0 05 0 14605 0 29605 0 5 ma Number of repetitions d Farameter link 0 05 7 LS staircase O 000 1 000 0 0500000 set potential 0 000 Viait time 3 z lt gt Set cell Cit lt gt Figure 2 73 Opening the Options editor can also be done by clicking the button in the quick access toolbar 112 Page NOVA User manual 2 5 7 Defining the Sampler It is also important to consider the data acquisition settings Signal sampler properly For this measurement the potential current and time will be sampled The current will be
300. the zone of interested or by scrolling the wheel mouse Changing the scaling during the measurement disables the automatic rescaling To resume this function press the F4 key on the keyboard AE 3 9E f Original Dimensions F4 2E 7 KW Zoom Back Shift F4 355 7 e Enable Zooming Moving X ET Step through Data j Select Dataset 1 5E Grid T 1E F Background ic Lar T E Show Print Preview U Print 5E 8 Copy to Clipboard AES i Copy Data to Clipboard Save Image File 5E See Save Image File Custom size SADE 0 8 0 6 0 4 0 2 0 Ua 0 4 0 6 0 8 Potential Figure 3 14 Right click the plot to select the Enable Zooming Moving option Additional options are available in the context menus in the measurement view More information is provided in Chapter 4 Section 4 7 3 to 4 7 13 If a wheel mouse is not available it is possible to use the and keys on the keyboard to achieve the same results 148 P NOVA User manual 3 4 The Autolab display The Autolab display is an extra window which can be displayed in each of the four views Setup Multi Autolab Measurement and Analysis It has two purposes the first is the manual control of the instrument and the second function is the display of real time information about measured data during an experiment The Autolab display can be opened by selecting the Autolab display option from the View menu by using the F10 key or by clicking th
301. then the cathodic branch of the plot The intercept on the Tafel plot provides an estimation of the corrosion current and the corrosion potential These values are labeled on the plot The complete details of the calculation are summarized in the data explorer frame see Figure 4 181 Demo 20 liron screw in seawater i Import GPES data H ivs E a Corrosion rate tafel slope se ba videc 202 130 m dec be videc 396 000 mdec Ecorr Calc 0i 304 920 m Ecorr Obs Wj 316 740 mY eo jcorr Avcrn 4 89600 p rm icorr 4 4 09600 pA Corrosion rate mmAear 0 056591 oe Polarization resistance 0 11 8710 ki E Begin 0 527 040 mi E End fv 156 540 mi Figure 4 181 The results of the Tafel slope analysis are shown in the data explorer frame The following information is provided in the data explorer frame e b amp b the anodic and cathodic Tafel coefficient in V decade e corr Calc the corrosion potential calculated from the intercept on the Tafel plot in Volts e corr Obs the observed experimental corrosion potential in Volts e jcorr and icorr the exchange current density and exchange current calculated from the intercept on the Tafel plot in A cm and A respectively e Corrosion rate the estimated corrosion rate of the material calculated from the intercept on the Tafel plot in mm year e Polarization resistance the estimated value of the polarization re
302. time s 0 048600 oignal sampler Time WWE 1 Potential vwE1 Current m Options 1 Options m Fotential applied lt aray gt Cv Time lt array gt 5 WE Current lt aray A Sean lt arraty gt WE 1 Potential Carrey Cv Index lt arraty gt Ive E m set cell Ott m lt gt Figure 2 43 Linking the Input box value to the scan rate When the link is created a new black line appears on the right side of the procedure editor frame linking the value of the Input box to the scan rate The scan rate also changes from 0 1 V s to 0 050 V s when the link is created thus Substituting the preset value with the default value of the nput box Note Using nput box commands and links allows the creation of interactive procedures This can simplify research when a procedure has to be repeated a number of times but with different parameters It also provides a very useful educational tool 89 Page NOVA User manual Press the Start button Instead of starting right away NOVA will display a window prompting the user to type the required scan rate Figure 2 44 The default value of 0 05 V s can be validated by clicking the button If another value should be used a new value can be typed in the Input box H3AUT 70530 Enter the value ofthe scan rate in Wis OK N Cancel Figure 2 44 The scan rate value Input box window 2 5 Advanced procedure editing This section provides details on advance
303. timize current range z E CY staircase O 000 1 000 1 000 0 000 2 0 1000000 start potential v 0 000 Upper vertex potential v 1 000 Lower vertex potential 6 1 000 stop potential v 0 000 Number of stop crossings 2 step potential v 0 00244 ocan rate vis 0 1000000 Estimated number of points 1650 Interval time s 0 024400 signal sampler Time WE 1 Potential WE 11 Current m potions 1 Options Fotential applied array Cv Time lt array gt 5 WE Current lt aray 4 ocan lt array gt WE Potential array Cv Index lt array gt a i ws E a Fotential applied v a WE Current 4 Z Scan show during measurement es Measurement plot number 1 m H Set cell Cit lt gt Figure 2 34 The links used in the Cyclic voltammetry potentiostatic procedure Links are shown as grey lines on the right hand side of the procedure editor frame under the Links column In the example shown in Figure 2 34 a link is used between Potential parameter of the initial Set potential command and the Start and Stop potential parameters of the CV staircase command Two extra links are used to link the WE 1 Current and the Potential applied signals to the Y and X axis of the i vs E plot respectively The Z axis is linked to the Index signal The three potential values Set potential Start potential and Stop potential are linked Editing one of them will immediately change all of them to the new value Click the Stop
304. ting up a procedure is done using the setup view This view can be selected by clicking the corresponding button in the toolbar or by selecting the Setup View from the View menu see Figure 2 1 File View Profile Run Tools Help Be Advanced procedure view 88 eo o Em eo cu s Setup View Mult Autolab View X Measurement View Analysis View User log F11 hl 2 e ot Autolab display F10 FRA manual control MDE manual control MUX manual control External manual control File View Profile Run Tools Help Re te Siete eee Cee ee ed Figure 2 1 Selecting the Setup view from the toolbar or the View menu The setup view which is the default startup view of NOVA has several important features shown in Figure 2 2 51 P NOVA User manual NOVA p x Toolbar Quick access toolbar mea File z tun Tools Help ORT Ve E e eae EE RECE 2 YB Commands Procedures Commands A E Autolab n i i n o Remarks Cyclic voltammetry pote sets er ES Cyclic voltammetry potentiostatic i Cyclic voltammetry galvanostatic End status Aulolab al o ap a Signal sampler Time WE 1 Potential WE 1 Current aa e Cyclic voltammetry current integration a i Pf i f Options 1 Options i Cyclic voltammetry linear scan n i oi Instrument AUT40008 i Cyclic voltammetry linear scan high speed _ Pod A j Instrument description ie Linear sweep voltammetry potentiostatic i i j Autolab control i
305. tings Apply Cancel Figure 1 41 The NOVA options window 42 Page NOVA User manual 1 6 4 1 Graphics In this category the settings are grouped in two sections see Figure 1 42 e General settings related to the plotting of the data e Measurement view settings related to the number of points displayed in the measurement view during a measurement Nova options g sraphics 4 General 2 Autolab display bo Overall graphical settings Advanced settings show serial in legend Yes 4 Measurement Yiew Maximum number of points 30000 Use maximum number of points Yes Apply Cancel Figure 1 42 The options listed in the Graphics section 1 6 4 1 1 Default graphical settings The default graphical settings can be defined by clicking the button next to the overall graphical settings to open the plot options window see Figure 1 43 Nova options s Graphics 4 General Autolab display Overall graphical settings Advanced settings show serial in legend Yes N 4 Measurement Yiew Maximum number of points 30000 Use maximum number of points Yes Figure 1 43 The default plot options can be defined in the NOVA options NOVA User manual The Plot Options window will be displayed see Figure 1 44 This window can be used to define the default settings used for all the plots in the software Plot Options Data Axes Plot Analysis items Plot Flot style Faint plot w Y axis placement Lett C R
306. tiostatic Remarks Cyclic voltammetry potentiostatic ma End status Autolab m oignal sampler Time WE 1 Potential vWE 1 Current ma Options 1 Options m Instrument LALIT 0530 Instrument description E Message box Tithe of box USALIT 70530 Switch off the nitrogen purge ll E Time limit 5 30 se time limit No ail Autolab contral set potential 0 000 Set cell Gn Ea Viait time s A Optimize current range z CY staircase 0 000 1 000 1 000 0 000 2 0 1000000 Set cell Cit Ea lt gt Figure 2 31 Editing the reminder message When the measurement start before the cell is switched on NOVA will display a window displaying the reminder message see Figure 2 32 u3AUT70530 u3AUT70530 Switch of the nitrogen purge Switch of the nitrogen purge OK X Time remaining 30 seconds Figure 2 32 The reminder generated by the Message box command left Use time limit off right Use time limit on il Note If the Use time limit parameter is set to No the procedure will not continue until the OK button is clicked The Message box command can therefore be used as an interrupt command It holds the procedure until the user clicks the OK button Messages box commands can be placed anywhere in the procedure As explained in Section 2 4 5 the Message box command will be added to the Favorite commands group when dragged into the procedure see Figure 2 33 78 NOVA User manual Commands ep F
307. to the Upgrading files from previous version tutorial available from the Help menu for more information 4 1 1 6 Location of files The location of a single file of the database can be quickly determined by right clicking the entry in the database frame and selecting the Show in Windows explorer option from the context menu see Figure 4 21 Procedure name f Time stam Remarks ae eames 0504 0 01 M H2504 0 1 M Ag AgCl Ref KCI S Demo 02 Lead set Active Procedure PhiClogy20 01M HCIO401M a Demo 03 Bipot Propertes O RPM HCIO4 0 1 M Demo 04 Aydr l l Fe2 Fes NaQH 0 2 Ml Demo 05 Feil store in Repository Fe Fe3 Reversibility Test LSW with increasing Demo 06 Gala X1 Delete from Repository Lead deposition on gold galvanostatic ee ile Restore from Repository EA ea Demo 08 Chro i Factory standard procedure Demo 09 Chro Import Data Combination of steps and lewels Demo 10 Differ Export Data Example for baseline correction peak search Delete Data Merge Data Show in Windows Explorer X Figure 4 21 The Show in Windows explorer option provides a shortcut to the location of a database entry A Windows explorer window will open showing the location of the selected file see Figure 4 22 166 Page NOVA User manual File Home Share View ww Gy toL My Procedures 1 10 Nova v Search Nova F K Pavers Name Date modified Type i Demo 01 Copper deposition _ 31 1 2
308. tolab Cyclic voltammetry galvanostatic ide _ ae Siri ican egal er Time WE 1 Current a Cyclic voltammetry current integr Open for editing No Options mm H Cyclic voltammetry linear scan eens een Export procedure AUT 40008 Cyclic voltammetry linear scan hi Linear sweep voltammetry potent X Delete procecure s Load the selected procedure in the procedure setup z Linear sweep voltammetry galvar Linear polarization z Hydrodynamic linear sweep z Differential pulse voltammetry z Square wave voltammetry z Sampled DC polarography z Chrono amperometry At gt 1 ms i Chrono potentiometry At gt 1 ms H Chrono amperometry fast z Chrono potentiometry fast H Chrono coulometry fast z Chrono amperometry high speed z Chrono potentiometry high speed z Chrono charge discharge Interrupt i i Interrupt high speed Positive feedback z FRA impedance potentiostatic z FRA impedance galvanostatic FRA potential scan Standards i My procedures Show in Windows Explorer Figure 2 4 Loading the cyclic voltammetry potentiostatic procedure into the procedure editor frame When the cyclic voltammetry potentiostatic procedure is loaded into the procedure editor the contents of the procedure are displayed see Figure 2 5 Commands Parameters Links Cyclic voltammetry potentiostatic Remarks Cyclic voltammetry potentiostatic no extra modules required End status Autolab ma oignal sampler Time WE 1 Potent
309. top A Overload occurred 5 19 24 PM 2 4 2013 CY staircase A Overload occurred 5 21 46 Phi 2 4 2013 C staircase AUT 40034 5 24 11 PM 2 4 2013 Start Stop button Measuring ome commands or command param eters are hidden by the active profile Hardware based Basic User defined _ Figure 3 2 An overview of the Measurement view There are several highlighted areas in this view e Measurement frame this is where the measured data points are plotted in real time The last measured point plotted in this frame is located by the cross marker see the top right corner of the frame in Figure 3 2 A total of four plots are available in the Measurement frame Dedicated toolbar buttons can be used to switch the Measurement frame to different plot arrangements see Figure 3 3 File View Profile Run Tools Help Eee te See ee ee es Sa eck ee Show four plots during measurement Figure 3 3 Up to four different plots can be displayed in the measurement frame Note The contents of the plots are defined in the procedure setup see next Section 140 Page NOVA User manual e The procedure progress this frame displays a condensed version of the procedure that is currently running Only the names of the commands are displayed During the procedure the progress frame can be updated displaying information collected during the measurement
310. u see Figure 4 189 These analysis tools differ from those that fall into the X Y analysis tools category because they require more information that a set of X and Y values Therefore these tools are added to a complete data set and not to a plot This section provides an overview of the available analysis commands in this category a Demo 04 Hydrodynamic Low with increasing rotation rate i Control Autolab RDE Plot Options H al 1 Walue 500 voll Properties H a 2 Yalue 031 92 Gy ll 3 Value 1247 9 Refresh Gy 4 Value 1747 9 il 5 Value 2331 9 Add Plot a a Add Analysis b Hydrodynamic i vs vw T EEA an Show All Plots Calculate charge R i Regression through origit Hide All Plots T WE i H Regression W Save the data in database x Remove from View Remove all from View Figure 4 189 Data set analysis tools can be added directly to a plot in the analysis view The example shown in Figure 4 189 corresponds to the Hydrodynamic i vs Vw analysis tool This tool is used to create a Levich plot using the limiting current values recorded at different rotation rates Two linear regressions are automatically included 280 NOVA User manual 4 8 2 1 iR drop correction This data analysis tool can be used to correct the measured data for the voltage drop introduced by the uncompensated resistance This tool is used to correct the measured for ohmic drop This to
311. ue b31 92 H 3 Value 1247 9 0 0025 H a 4 Value 1747 9 H a 5 Value 2331 9 H 5 6 Value 3000 EB Hydrodynamic iws fu H Levich plot iH Regression through origin H Regression X 0 001 0 0003 0 002 0 0015 Current 4 Figure 4 151 Clicking the Regression item in the explorer view displays the Levich plot and the regression line Clicking this regression item also displays the parameters of the regression analysis tool on the right hand side of the plot see Figure 4 152 i YT i x 0 003 Signal Expression Unit a b 0 0025 0 002 e Search mode Automatic Manual 2 0 0015 Regression type Linear v z Polynomial order 1 0 001 Number of significant digits 5 Direction All vV 0 0005 Reset 0 3 10 1S gt 7 236 0 0011 704 17 725 0 0028073 vu lt Figure 4 152 The parameters of the Regression analysis tool are located on the right hand side of the plot The regression tool has a number of parameters that can be defined in the control interface e Search mode Automatic or Manual When the Automatic mode is used the whole data set is used in the regression Using the manual search mode lets the user define a window in which to use the regression calculation The window is determined by clicking and holding the left mouse button while moving the mouse left or right e Regression type Defines the type of regression 258 Page NOVA User manual e Polynomial order Defines the
312. ure 2 24 E Favorite commands Set potential b Record signals gt 1 ms Control H Metrohm devices a External devices Measurement general Measurement cyclic and linear sweep voltammetry Measurement voltammetric analysis Measurement chrono methods Measurement impedance Data handling Analysis general Analysis baseline correction Analysis corrosion Analysis impedance j Flots general Plots impedance My Commands H H E H H H E Figure 2 24 The Favorite commands group automatically ranks the ten most used commands The list of commands shown in the Favorite commands group is automatically updated each time a new command is manually added to the procedure All these commands are ranked by popularity and the ten most often used commands are listed in the group at any given time It is however possible to manually remove a command from the Favorite group by right clicking the command and choosing the Remove from Favorite commands option see Figure 2 25 72 NOVA User manual Commands Favorite commands Set potential S Record signals gt 1 msi E Control Remove from Favorite comm ands X E Metrohm devices TER H External devices H Measurement general H Measurement Cyclic and linear sweep voltammetry i Measurement woltammetric analysis H Measurement chrono methods H Measurement impedance H Data handling H
313. ure 4 74 shows a typical example WET Current 4 204 Standard CY Demonstration data 0 0016 0 0014 00u12 0 001 0 0008 0 0006 0 0004 0 0002 O 0002 0 0004 0 2 J 0 2 0 4 0 6 J E Potential applied W Figure 4 74 Showing the legend of the plot NOVA User manual The legend displays the serial number or the instrument description from the data set between brackets see Figure 4 74 This provides a convenient way of identifying points trom different data sets If the nstrument description field is filled in the dataset this will be indicated between brackets in the legend Please refer to Section 4 1 1 for more information If no nstrument description is provided the serial number is indicated instead see Figure 4 75 0 0016 Standard CY AUTS 4123 0 0014 augi 0 001 0 0008 0 0006 0 0004 WET Current tA 0 0002 0 0002 0 0004 0 2 J 0 2 0 4 0 6 0 8 Potential applied Vv Figure 4 75 The serial number of the instrument is provided in between brackets when no instrument description is provided The position the font and the style of the legend can be edited using a specific right click menu A total of eight positions are available for a 2D plot and four positions for a 3D plot as well as three different border styles The legend can also be hidden from view using this menu see Figure 4 76 The legend settings are set independently for each type of plot 205
314. urement Impedance Scan sel Hide all e Sort ascending N Calculate f Sort descending Import Gl Import FF Import ASCII data Export ASCII data Exportto 2view L Generate index H Analysis general G Analysis baseline correction c Analysis corrosion Analysis impedance H Flots general EH Plots impedance I My commands Original order Commands H Favorite commands EH Control H Metrohm devices H External devices H Measurement qeneral Gy Measurement cyclic and linear sweep voltammetry H Measurement voltammetric analysis H Measurement chrono methods H Measurement impedance Hide all Build signe Calculate sa Export Asd F Exportto Z Z Sort descending sort ascending E Generate il port AS Crs Import FRA data Import GPES data Scan selector o h Windower HH Analysis general H Analysis baseline correction H Analysis corrosion H Analysis impedance g Flots general E Plots impedance i Why commands Original order Figure 1 37 Sorting the commands in a group in the commands browser 1 6 3 Import Export profiles It is possible to hide any number of items in NOVA and to create a new profile for this customized view Using the Profile menu it is possible to import and export user profiles see Figure 1 38 NOVA User manual File View Profile Run Tools Help PETTE Hardware based Basic Interm ediate
315. vs E line This will plot the experimental data from the data set as a blue Point plot shown in Figure 4 25 Nova assigns default axis labels based on the signals used to plot the measured data Demo 01 Copper deposition E pi Cv staircase 0 0016 H i s E 0 0014 0 0012 0 001 0 0008 0 0006 0 0004 WE TD Current 4 0 0002 A 0 0004 0 2 J 0 2 0 4 0 6 O16 Potential applied C Figure 4 25 Plotting example 1 in a 2D plot Clicking the i vs E line will change it to bold lettering and it will be highlighted e The bold lettering indicates that the data set is currently plotted in the data analysis frame e The Aelel status indicates that the data set plotted in the data analysis frame is currently also the active plot in the case of an overlay of several plots only one can be active 4 2 2 Changing the data set display settings The way the data is displayed is controlled by the signals used for the plot The data from example 1 shown in Figure 4 25 is displayed using the Potential 169 NOVA User manual applied signal for the X axis the WE 1 Current signal for the Y axis and the Time signal for the Z axis although the latter in not shown in the 2D plot To change these display settings expand the signals list by clicking the symbol right click on any of the signal and select the desired signal from the list In the example shown in Figure 4 26 the plot settings are chang
316. wer the demands of both experienced electrochemists and newcomers alike Setting up an experiment measuring data and performing data analysis to produce publication ready graphs can be done in a few mouse clicks NOVA is different from other electrochemical software packages As all electrochemical experiments are different and unique NOVA provides an innovative and dynamic working environment capable of adapting itself to fit your experimental requirements The design of NOVA is based on the latest object oriented software architecture NOVA is designed to give the user total control of the experimental procedure and a complete flexibility in the setup of the experiment This user manual provides in depth details about the functionality of NOVA It explains the most important features of the software using many practical examples The user manual has four chapters e Chapter 1 provides an overview of NOVA e Chapter 2 describes the procedure building process e Chapter 3 describes the measurements with NOVA e Chapter 4 provides information regarding the data analysis 1 1 The philosophy of NOVA NOVA differs from most software packages for electrochemistry The classic approach used in existing electrochemical applications is to code a number of so called Use cases or Electrochemical methods in the software The advantage of this approach is that it provides a specific solution for well defined experimental conditions The disadvanta
317. works in the same way as the Message Dox Reload the Autolab cyclic voltammetry potentiostatic procedure into the procedure editor and select the Input box command from the command browser Drag and drop it into the procedure placing it at the very beginning of the procedure see Figure 2 41 File View Profile Run Tools Help OR Tee Bika Se eee eC Oe ee eS Commands Procedures Commands Parameters Links Favona commends Cyclic voltammetry potentiostatic L Control Remarks Cyclic voltammetry potentiostatic ca End status Autolab aay Message box Signal sampler Time WE 1 Potential WE 1 Current y Options 1 Options Repeatn times Repeat for each value Nested procedure Instrument Instrument description Autolab control a Measurement general i rf Set potential 0 000 Measurement cyclic and linear sweep voltammetry L Sat call O Measurement voltammetric analysis Hi i l 4 Wait time s 5 Measurement chrono methods 4 Measurement impedance PIRES Are nena i L H CY staircase 0 000 1 000 1 000 0 000 2 0 1000000 Data handling n Set cell Off ay Analysis general lt gt Figure 2 41 Inserting an Input box in the procedure Expand the inserted command An nput box has the following parameters e Title of box this is the title of the nout box By default the Title of box is automatically linked to the Serial number of the instrument Instrument
318. xpression is shown on the right hand side 295 Page NOVA User manual Having created a new signal for the experimental data from example 1 the Standard CV plot settings can be edited Right clicking the settings for the X axis of the Standard CV plot change the plot settings from Potential applied to the newly created Potential vs SHE see Figure 4 212 Demo 01 Copper deposition CY staircase Eb tir E vst H Logi SE H eet El Standard CY A K Potential applied oof Y WE 1 Current Potential applied Lede Z Time Scan WE D Current Time WE 1 Potental Index Potential vs SHE ile Potential vs SHE Figure 4 212 Creating a new plot using the modified potential scale The new 2D plot should now look like the one displayed in Figure 4 213 0 0016 0 0014 0 0012 0 001 0 0008 0 0006 0 0004 WET Current 4 0 0002 0 0002 0 0004 J 0 2 0 4 0 6 0 8 1 2 Potential vs SHE Figure 4 213 Plotting the data from example 1 using the corrected potential scale 296 Page NOVA User manual The number of values in the calculated signal is always equal to the number of values in the signal used as expression parameter If more than one signal is used in the calculation the signals used in the mathematical expression should all have the same length If the Single value checkbox is checked in the Calculate signal window the result of the calculation will be reduced
319. y 4 WEN Potential lt array v Index lt array iws E oa Be Evst m ks Time s ea WEI Potential x Z Index show during measurement ves Measurement plot number 1 a set potential 0 000 Wait time 3 z lt gt Set call Ott 2 Figure 2 80 The vs t plot command is automatically linked to the signals provided by the LSV staircase command 117 Page NOVA User manual Plots are automatically linked to the required signals if these signals are specified in the signal sampler In this case the WE 1 Potential and the Time signal are both specified in the signal sampler of the LSV staircase command and the vs t plot can therefore automatically link its X and Y axis to these signals when the plot is added to the measurement command Change the location of the vs t plot command to plot 2 using the drop down list provided for the Measurement plot number parameter see Figure 2 81 Autolab contral mm set potential 0 000 set cell On ma Optimize current range A E Repeat for each value 0 05 0 14605 0 29605 0 5 ma Number of repetitions d Farameter link 0 05 E LS staircase O 000 1 000 0 0500000 start potential v 0 000 stop potential 0 1 000 step potential 0 00244 ocan rate y s 0 050000 Estimated number of points q z Interval time s 0 046600 signal sampler Time YWE 1 Potential WE Current c Options 1 Options a Potential applied array Cv Time lt array 5 WE Current
320. y linear scan Cyclic voltammetry linear scan high speed Cyclic voltammetry linear scan high speed Linear sweep voltammetry potentiostatic ee Linear sweep voltammetry potentiostatic Linear sweep voltammetry galvanastatic z Linear sweep voltammetry galvanastatic z Linear polarization z Linear polarization Hydrodynamic linear sweep Hydrodynamic linear sweep Differential pulse voltammetry Differential pulse voltammetry e square wave voltammetry e oquare wave voltammetry he sampled DC polarography z sampled DOC polarography Chrono amperometry At gt 1 ms Chrono amperometry At gt 1 ms Chrono potentiometry At gt 1 ms Chrono potentiometry At gt 1 ms e Chrono amperometry fast z Chrono amperometry fast Chrono potentiometry fast e Chrono potentiometry fast Chrono coulometry fast Chrono coulometry fast e Chrono amperometry high speed Chrono amperometry H Unhice Chrono potentiometry high speed Chrono potentiometry high spee Chrono charge discharge ee Chrono charge discharge Hnterrupt Hmterrupt Interrupt high speed p Hnterrupt high speed Positive feedback e Positive feedback FRA impedance potentiastatic z FRA impedance potentiostatic z FRA impedance qalvanastatic i PRA impedance qalvanastatic m FRA potential scan h FRA potential scan m Standards z standards H My procedures H My procedures Figure 1 33 Right click hidden items to unhide them NOV
321. y md 100 OF 100 200 400 600 1000 10000 7 Q Frequency Hz 100 100 2E 5 3 50 50 gt Z 165 E 0 mS 0 z T Q a N if E z J 50 50 ales u 2E 5 100 100 0 0 05 0 1 0 01 0 0 01 Time domain s Potential AC V Figure 3 9 Example of four plots shown in the measurement view during an impedance spectroscopy measurement i The contents of each plot are removed whenever the type of signal used on the X axis changes during a measurement 3 2 1 Adding and removing plots in real time While the measurement is running it is possible to add or remove plots from the measurement view To add a plot right click a measurement command in the procedure progress frame and use the context sensitive menu to add a new plot to the measurement as shown in Figure 3 10 145 Page NOVA User manual Cyclic voltammetry potentiostatic Autolab control Set potential Set cell Wait time 8 e Optimize current range ma i Set cell Add Plot to Measurement Flot 1 Add Plot to Measurement Flot 2 ivs E Add Plot to Measurement Flot 3 ivst Add Plot to Measurement Plot4 Log i vs E WE vs E X E vsi Evst Figure 3 10 The right click menu can be used to add a new plot to the measurement The list of available plots shown in the context menu depends on the signals Sampled during the measurement In Figure 3 10 the WE 2 Current recorded through the Bipotentiostat module is present in the s
322. z2 5 0 01 gt lt gt Setcell Off a gt Figure 2 49 The timing of the procedure is interrupted at the beginning and at the end of the Repeat n times command The interruptions are located before and after the Repeat n times command Since the Repeat n times command is not a timed command it creates a small interruption in the measurement timing This interruption will be observed at each repetition Depending on the activity of the host computer the interruption can be in the range of a few seconds Figure 2 50 shows the potential profile used in the standard chrono charge discharge procedure A sequence of steps is repeated ten times during the measurement The potential changes from 0 V to 1 2 V 93 NOVA User manual Initial potential 1 2 W 0 8 0 6 oO J WELT Potential W 0 2 J 10 20 30 AQ D0 60 T Time sS Figure 2 50 The potential profile used in the standard chrono charge discharge procedure Detailed inspection of the data shown in Figure 2 50 shows that the time delay between two recorded steps within the same repeat loop is 0 012 s 30 979 s 30 967 s whereas the time delay between two consecutive steps located in two different repetitions is 0 6 s 17 385 s 16 773 This illustrates the timing difference and the time delay introduced by untimed commands like a Repeat n times command see Figure 2 51 94 NOVA User manual t 17 385 5 1 _ t 30 967 5 gt
323. zooming moving 4 7 11 2D Plots Zooming Scroll mode As an alternative to dragging a box around the area of interest of the plot the mouse wheel can be scrolled forwards and backwards to zoom in and out on the plot This option will always keep the centre of the plot in the same position as the wheel is scrolled in either direction see Figure 4 92 0 0025 oO No 0 0015 ra urrent A 0 0005 WE 1 C 0 0005 0 001 0 5 0 0 5 1 Potential applied V YVE 1 Current A 0 0016 0 0014 0 0012 0 0002 0 1 0 0 1 0 2 0 3 0 4 0 5 0 6 Potential applied V Figure 4 92 Scroll zoom Scrolling in left and scrolling out right Dane 219 Page ef NOVA User manual It is possible to zoom in and out by using the and keys respectively Using the CTRL key in combination with the and keys it is possible to zoom in and out faster by a factor 10 Using both the SHIFT and the CTRL key the rate increases by a factor 100 4 7 12 2D Plots Zooming Sliding mode A third way of zooming on the data Is available by clicking and sliding the mouse left right for the X axis and up down for the Y axis to expand or contract the scaling of the axes The clicked position on the axis will stay in the same position while sliding the axis see Figure 4 93 0 0025 rrent rrent VWE 1 Curre A rv Ta 0 0002

AutoLab PGstat 302N Manual - The Molecular Materials Research

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