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Gas Sorption System Operating Manual

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1. NOTE Do not place the dewar with coolant under the sample cells until the Start L button is clicked Placing the dewar under the cells too early will pre cool the cells affecting the initial measurements NOTE The Start button is only active when there are no errors listed at the L bottom of the window The error list appears at the bottom of the window to indicate erroneous settings and invalid parameters Double click on an item from the error list to highlight offending fields related to this item P N 05079 Rev Page 45 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION 3 Sample Analysis Setup To perform an analysis of one or more samples up to four with a given adsorbate attach sample cells with the outgassed samples to the NOVA instrument The dewar of coolant should not be placed on the lift drive base until ready to start the experiment NOTE Do not place the dewar with coolant under the sample cells until the Start L button is clicked Placing the dewar under the cells too early will pre cool the cells affecting the initial measurements L NOTE All cell calibrations as well as analyses have to be performed with an appropriate filler rod Sample analysis using the NOVA instrument requires proper setting of several parameters These parameters describe methods and conditions for the measurements Po determination data point selection and equilibrium conditions After the Operation Mode Helium or
2. Argon Carbon dioxide HM Butane Argan Figure F 15Selecting adsorbate for analysis the NOVA Operation Manual regarding the use of different adsorbates before proceeding Only non corrosive gases compatible with materials of construction may be used with NOVA If in doubt call Quantachrome Instruments or your local authorized dealer for more information A CAUTION Some adsorbates may be incompatible with the instrument Refer to 3 3 2 Set P Options for Adsorbates After selecting the adsorbate the user must select appropriate Po options Please note that for different adsorbates including adsorbates measured at different bath temperatures there are various Po options available 3 3 2 1 Nitrogen at 77 K and Argon at 87 K For adsorbates that are used at their boiling point temperature such as Nitrogen at 77 K LN gt 2 temperature and Argon at 87 K LAr temperature all Po options are available Adsorbate Gas Nitrogen Adsorbate Gas Argon PO options PU options PO mode PO mode PU Station PO Station Continuous Continuous Figure F 16 Selecting Po options for nitrogen at 77K and argon at 87K P N 05079 Rev Page 49 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION Measure This selection will result in the measurement of P during the analysis by condensing the adsorbate N 77K or Ar 87K on the sample in the sample cell during a run This method is least recommended and is to b
3. DFT method k Monte Carlo j Monte Carlo method Fractal Dimension Methods Area Volume Summary d Total Pore Volume b Graphs Average Pore Size Tables Fractal Dimension Methods Reports a demo isotherm View Audit Trail ee EA demo total pore volume Data Reduction Parameters ee o a Analysis Data wi een demo t plot method Graph Properties demo bjh Overlay m Curves k foom To Unzoeom Figure G 6 Floating menus for Graphs Tables and Reports Da To edit the header information of the data file open the file right click on the graph and select Analysis Data This opens the Analysis Data window 6 Editing Analysis Data Information P N 05079 Rev Page 71 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN Analysis Data Instrument HOYA Instrument version 0 00 Station A Date 2009 10 27 DAT File N94 amp 2701 D4T Cell ID 0 Software Yersion 2 11 Operator Jonathon Salsbury Cell Wol n a Sample ID BMS 650032 Description Lot 9439920 weight ia JIB0 g Volume 0 00000 cc Density 0 00000 g cc Comments Analysis Duration 7609 minutes Adsorbate gas Nitragen Bath temperature 77 39 K Ambient temperature 298 10 K e Mus ee hours Po 74202 mmHg Outgas temperature 25 00 C Adsorption Desorption Thermal delay 180 Sec Pressure tolerance 0 100 0 700 Equilibration time B B Equilibrium timeout 240 240 x Cancel Help Figure G 7 Editing the analysi
4. Nova Mode is set in Operation gt gt Instrument Settings model 26 and above only next you need to setup the analysis parameters In the NovaWin program go to Operation menu and click Start Analysis This will activate the Start Analysis window In this window depending on the current operation mode Helium or Nova mode there are slight differences in the set up options model 26 and above The dialog window is divided into tabbed segments to specify parameters that are common to the instrument and ones that are specific to each station Click on the tabs at the top of the Start Analysis window to view and set parameters for all stations Common or for each specific station Stations L NOTE Depending on the operation mode Helium or Nova mode the Start Analysis window contains slightly different setup options 3 1 Common Setup Helium Mode Only model 26 and above In the Helium Mode the Common window is shown below P N 05079 Rev Page 46 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION Click here to select change the adsorbate Start Analysis Common Stations Operator IL icthibaul Adsorbate Gas Nitrogen Click here to l set common TARON ee ee Select the Po options 1 P mode Entered appropriate for a options for all Thermal delay 180 1200 4 PP P Stations given adsorbate 1 a0 ZEC PO value 8 760 00 mmHg Evacuation Cross over
5. mol DR method Affinity Coetficient Beta 0 330000 Figure G 15 Editing parameters for BJH DH and DA methods The BJH and DH methods can be used to calculate pore size distribution curves and tables for the adsorption and or desorption branches of the isotherm Tag the appropriate adsorption and or desorption data points with the P tag This calculation uses the statistical thickness of the adsorbed layer of the adsorbate on the surface of the sample so you must choose a t method calculation method de Boer Carbon Black Halsey or Generalized Halsey that you wish to use in the BJH and or DH calculations The Moving point average determines number of points averaged in a sliding window average Set this value to 1 in order to include all of the P tagged data points in the calculation without averaging Check Ignore P tags below 0 35 P Po to ignore these points in the calculation To set interpolation ranges for the BJH DH method calculations click the BJH Interpolation Settings button to access the Interpolation Parameters window P N 05079 Rev Page 79 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN Interpolation Parameters Interpolation ranges Radius 7A Start End Interval 00 allow overlapping W use for Adsorption Figure G 16 Setting the interpolation parameters for the BJH and DH methods Fill in the desired ranges in the fields provided Check the box for adsorption and or desor
6. uantachrome INSTRUMENTS Characterizing Porous Materials and Powders NOV A e Series Models 25 and 26 Nova Win NovaWin CFR GAS SORPTION SYSTEM OPERATING MANUAL Versions 11 01 and 11 02 P N 05079 Rev N 2008 2012 Quantachrome Instruments Nova e NovaWin Operating Manual CONTACT INFORMATION Quantachrome Instruments 1900 Corporate Drive Boynton Beach Florida 33426 USA Tel 1 561 731 4999 Fax 1 561 732 9888 E mail qc service quantachrome com qc support quantachrome comail www quantachrome com P N 05079 Rev Page 2 of 133 Nova e NovaWin Operating Manual QUANTACHROME WARRANTY POLICY Quantachrome Instruments warrants its instruments to be free from defects in material and workmanship for a period of one year from date of shipment under normal use and conditions For the period commencing with the date of shipment and ending one year later Quantachrome will at its option either repair or replace any part within an instrument that is found by us to be defective in material or workmanship without charge to the customer at our facility or at a customer s facility if the instrument purchased is backed by Quantachrome s on site warranty as evidenced by the sales contract The customer is responsible for all transportation charges to our factory Damages during the warranty period resulting from unstable utilities operator error or unauthorized repairs will not be covered by this warranty Par
7. D SOFTWARE CONFIGURATION o Figure D 8 Example of system log window 2 Edit Parameters Ls 0 NOTE When using NovaWin CFR users at the operator level may view these parameters but they may not modify them Edit Adsorbate Parameters To view or modify the adsorbate model parameters click Manage Materials gt gt Adsorbates on the Configure menu This will open the Adsorbate Parameters window P N 05079 Rev Page 26 of 133 Nova e NovaWin Operating Manual D SOFTWARE CONFIGURATION Adsorbate Parameters Hame Nitrogen b TAE Argon 7 Basic Advanced go Carbon dioxide Adsorbate temperature 77 350 K Butane Molecular weight sma g mol Argon Cross sectional area fezo A mol Liquid density jos gcc Non ideality factor E 5600e 05 torr Surface tension 3 650 erg cne Contact angle 0 000 degrees co New ny Copy Figure D 9 Editing adsorbate parameters Click the Name button h and select the adsorbate from the dropdown list The current values for selected adsorbate model parameters will be displayed Parameters for several most often used adsorbates are predefined in the NovaWin software and these parameters cannot be changed their entry fields are grayed out To modify the model parameters for the predefined adsorbate click Copy and give a new name to the adsorbate model Enter Value Enter name of new adsorbate aS LE Cancel
8. The size of the screen display and margins may also be set Tabular View Properties Use font Arial Size 8 Tabular view screen sizes pixel A Select Font Page width 300 Margin 0 Font style Regular A T GB atang Italic i Lancel FP mB atangChe Bold Bold Italic F GulinChe Sample AaB ye Script western Figure H 7 Selecting font for tables 1 4 Creating Overlay Plots The NovaWin software allows you to construct overlay plots containing different data files An overlay plot can be made for any of the plots available in the software Right click on the plot for which you want to overlay additional data files This will activate the Floating Menu Clicking Overlay on this menu will create the root overlay plot lt unnamed gt where you may add additional plots to overlay over the original data set Right clicking on this root plot will display anew Floating Menu P N 05079 Rev Page 94 of 133 Nova e NovaWin Operating Manual H DATA PRESENTATION Graphs Manage Reload all Graph Properties Curves Zoom To Unzoom Figure H 8 Overlay plot floating menu Click Manage on this menu to access the Overlay Manager window Overlay Manager CANO CdataphysisorbOeeah PLE gps root ce Add Synch Figure H 9 Managing overlay plots Click Add and select the appropriate file from the list in the Open window then click Open Enter Value Enter display label for new inst
9. measurement has completed 3 4 2 3 Editing Data Points Once data points are selected tags can be added removed points can be deleted and point sets P N 05079 Rev Page 58 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION can be saved for future use Setting Removing tags First highlight the data point s that you wish to modify Next click the On or Off box s next to the tag s you wish to set or clear The tags will be modified accordingly in the list Deleting data points First highlight the data point s that you wish to delete Next click the Delete button The selected data points will no longer appear in the list Saving loading data points If you wish to save a specific set of data points for use at a future time click the Save Points button and assign a file name The file is saved in the NovaWinCfg folder see Sections D 3 and D 4 with a npr extension Click the Load Points button and select the file from the folder to load the desired points NOTE It is not necessary to save individual files for different stations when using L the same data points For example if a data point selection file was saved for Station A you may use this same file for the point selection for Stations B C and or D 3 4 3 Equilibrium Tab Once the points have been selected for the stations click the Equilibrium tab to choose the equilibrium conditions for the measurements Start Analysis C
10. specifies the minimum amount of time between raising the dewar and measuring the first data point This option is used to assure the thermal equilibrium of the sample after it is immersed in the coolant bath before the actual collection of the first valid data point The length of the thermal delay depends on the size mass surface area of the sample and its thermal conductivity Thermal delay 180 1 200 180 ZEC Figure F 24 Entering the thermal delay NOTE It is recommended to use a shorter Thermal Delay time for standard L bulbless cells and longer for large bulb cells Additional time may be necessary for large masses of low surface area material NOTE Various times thermal delay before the measurement might be required to L uniformly cool down samples with different thermal conductivities as materials with low thermal conductivity will require more time to achieve a stable uniform temperature 3 3 4 Evacuation Cross over Pressure Enter the pressure at which the Nova will switch from fine to coarse vacuum when evacuating a sample For fine powders a pressure of 30Torr is usually appropriate For granules or pellets a pressure of 77Torr is recommended P N 05079 Rev Page 53 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION Evacuation Cross over Pressure 39 mmHg Figure F 25 Setting evacuation crossover pressure 3 4 Stations Setup The Stations panel consists of four sub tabs Sample Points Equi
11. was taken to be equivalent to the adsorbent area measurable with a yardstick of a size proportional to a at any given P Po Accordingly a plot of log Sig vs log ac should also yield a straight line within the multilayer region of the isotherm from which the fractal dimension D can be readily calculated P N 05079 Rev Page 129 of 133 Nova e NovaWin Operating Manual J TROUBLESHOOTING GUIDE J TROUBLESHOOTING GUIDE Table J 1 Guide to typical problems and their solutions Symptom Open isotherm adsorption If isotherm is unexpectedly open desorption loop does not Under equilibrated conditions extend the desorption equilibration close i e desorption branch time Microporous materials often always lies above adsorption need longer desorption equilibration branch even at low relative times ressure are p Extend outgassing time and or Incomplete outgassing increase out gassing temperature Crossed isotherm Check integrity of o ring on sample cell Make sure o ring is lightly greased Make sure that the bulkhead is free from other O rings Choose proper cell calibration file Incorrect cell geometry defined Sample measurement conditions must during calibration be identical temperature use of filler rod to the cell calibration conditions System contamination Pump down unit overnight Dewar goes up but analysis Upper limit switch not hit Check for obstruction to dewar travel hangs Unit fails vacuum integrit
12. Cancel Figure H 21 Customizing the display and report header P N 05079 Rev Page 101 of 133 Nova e NovaWin Operating Manual H DATA PRESENTATION Enter the header in the Header Text field 3 lines max add a custom logo if desired and click OK when finished Figure H 22 shows an example of a custom header When the new text is added Quantachrome NovaWin 1994 2012 Quantachrome Instruments v11 02 will remain in this portion of the Header To restore the default text for this portion of the Header open the Report Header Properties window and delete the text Click on the button to remove the custom logo Click OK to save your changes Cusp We l Y Lee Kaiotee Manager Quantach e ne Quantachrome NovaWin 1994 2012 Quantachrome Instruments v11 02 ai adalat a Figure H 22 Example of a custom header with custom logo P N 05079 Rev Page 102 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION I THEORY AND DISCUSSION This section contains an overview of the theories on which the Nova e is based It is intended to give the reader a basic understanding of adsorption chemistry and how it is used to characterize powders and porous materials It is not intended to be a comprehensive treatise on the subject For a more in depth treatment of the subject the reader is referred to Characterization of Porous Solids and Powders Surface Area Pore Size and Density 1 Surface Area The Brunauer Emmet
13. Figure D 10 Naming a new adsorbate Click OK and the new window with active parameters fields will appear P N 05079 Rev Page 27 of 133 Nova e NovaWin Operating Manual D SOFTWARE CONFIGURATION Adsorbate Parameters Adsorbate Parameters Name N2 Hame N2 Basic Advanced oe Basic Advanced Adsorbate temperature 77 35 K Average diameter 0 300 ne Molecular weight 28 01 34 g mol Polarizability 1 AE eemol e24 Cross sectional area 1 6 20 AZ mol Magnetic 20 2 00 cc mol x 12 29 susceptibility Liquid density 0 808 fl ye Molecular density 6 70 mol cre x 1e 14 NO ea aoe 6 5800e 05 Jette Critical temperature 126 2 K Surface tension 8 95 erg cr eE 35 atrn Contact angle g 0 00 degrees Supercritical Ads no Const K 1 00 cA Hew amp Delete Help cA Hew Delete Help 3 H Fl Close ny Copy ff Close Figure D 11 Defining the parameters for an adsorbate model Click on the Advanced tab to view more parameters Modify the parameters values as you wish and click Save to store the new model parameters assigned to the new adsorbate name in the appropriate model database To create a new model click New and follow the steps described above The Adsorbate Parameters window will have all fields filled with zeros which you will need to replace with appropriate values To delete an existing model select it from the list and then click Delete Note that predefined models cannot be de
14. Figure F 37 Instrument status window P N 05079 Rev Page 63 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION 4 3 Uploading Data Points Data points are automatically displayed on the PC as they are acquired during the analysis If the program was closed when the last data point was acquired you may upload the data using the Operation gt gt Upload Data function or press F9 L NOTE The measurement must be initiated using the NovaWin software in order to access the Upload Data function The Upload Data command initiates a query toward the instrument and when the response is received displays a list of all available stations their status and the points available Select the appropriate station s from which to upload The resulting data file will be named according to the name specified in the File Name Template with the qps extension NOTE In the event that the instrument loses power or if another measurement is L started the Upload Data feature will not retrieve the data from the last run The upload must be requested prior to starting another measurement P N 05079 Rev Page 64 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN G DATA ANALYSIS USING NOVAWIN In addition to providing PC control over the measurements NovaWin is also a comprehensive program for enhanced data analysis While NovaWin provides features such as graphical plots alternative theoretical models external dat
15. P N 05079 Rev Page 20 of 133 Nova e NovaWin Operating Manual D SOFTWARE CONFIGURATION D SOFTWARE CONFIGURATION 1 Configuration of NovaWin CFR security features 1 1 Initial Security Configuration When NovaWin CFR is opened for the first time the following screen will appear Contigure Security Security Level 15 mir C Custom 30 deus m days after pwd expired v E passwords Min Id amp password length E a characters Warming IFAccount Expire option is enabled all superuser accounts are also subject to thig limitation Itis the system manager s responsibility to ensure that at least one superuser account i kept active at all times Failure to do so may result in complete system lockout whose resolution requires re installing the software and re creating all user accounts 2 ts Figure D 1 Selecting security level in NovaWin CFR Select Full Security Level to enable all of the security features of NovaWin CFR including required login full audit trail for any changes to data files the ability to print audits and software timeout due to user inactivity L NOTE You must select Full Security Level for the software to operate within the guidelines of 21 CFR Part 11 Selecting Custom Security Level will allow you to choose which security features you wish to incorporate Check the boxes next to the security action you wish to have enabled Selecting None for Security Level will disable all
16. Pressure Si 3 ag Ta ecm ere em mee ee ee ee eK He KH KH Ke Yo Backfill Blue area E r Select a gas to backfill sample points out He PumpDown 0 60 cell s after the run options 0 mh specific for poe Helium Mode Active stations AA Load Preset Pee i Aw B Cancel Hel ha SE EEPE p als ft Save Preset x z p Figure F 12 Setting parameters common to all stations 3 1 1 Backfill model 26 only In the Helium Mode you can select which gas the adsorbate or helium will be used to backfill the sample cell after the run is complete Backill Backill Adsorbate C He C Adsorbate He He PumpO own 0 60 He PumpO own 0 60 0 mir 0 mir Figure F 13 Select backfill gas This choice option is not available in the Nova Mode or Nova 10 0 Model 25 The instrument will backfill with adsorbate by default 3 2 Common Setup Nova Mode Only In the Nova Mode the Common window is slightly different than in Helium Mode P N 05079 Rev Page 47 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION i In the Nova Mode chose to calculate or to 7 Start Analysis measure Sample s Volume ee ee ay Common Stations Operator ID cthibautt i abate Gas Nitrogen Sample Volume PO options Calculate Measure D PO mode Entered Thermal delay 180 1 200 i 190 sec SED value 760 00 mmHg Evacuat
17. activated carbons lt 2nm and a cylindrical model for pore widths gt 2 nm NLDFT N silica equilibrium 0 35 nm 100 nm Siliceous materials e g some transition kernel at 77 K based on a types of silica gels porous cylindrical pore model glasses MCM 41 SBA 15 MCM 48 and other adsorbents which show type H1 sorption hysteresis NLDFT N silica adsorption 0 35 nm 40 nm Novel siliceous materials with branch kernel at 77 K based on a hierarchically ordered pore cylindrical pore model for pores of structure SBA 16 silica some diameter lt 5 nm and spherical types of porous glasses and pores model for pores of diameter some types of silica gels gt 5Snm P N 05079 Rev Page 124 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION NLDFT GCMC Monte Applicable Pore Examples Carlo Kernel File Width Range NLDFT N2 silica adsorption 0 35 nm 100 nm Siliceous materials such as branch kernel at 77 K based on a controlled pore glasses MCM cylindrical pore model 41 SBA 15 MCM 48 and others Allows obtaining an accurate pore size distribution even in case of type H2 sorption hysteresis NLDFT Ar zeolite silica 0 35 nm 100 nm Zeolites with cylindrical pore equilibrium transition kernel at channels such as ZSMS 87 K based on a cylindrical pore Mordenite and mesoporous model siliceous materials e g MCM 41 SBA 15 MCM 48 some porous glasses e g CPG and silica gels
18. applicable pore size ranges Adjust the minimum and maximum relative pressure range in the Range relative pressure box It is recommended to use the entire relative pressure range over which the model was calculated 10 1 L NOTE Please refer to Table I 2 on page 124 for a comprehensive description of Quantachrome s offering of DFT and GCMC methods P N 05079 Rev Page 76 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN Click the Interpolation Settings button on the DFT or Monte Carlo page to open the Interpolation Parameters window where you can set the appropriate diameter ranges and intervals for the interpolation Interpolation Parameters Interpolation ranges A adius A Stark End Interval allow overlapping use Interpolation x Cancel Figure G 13 Setting the interpolation parameters for DFT or Monte Carlo methods Check the Use Interpolation box for interpolation to be applied in the calculation Click the Save button Y when you finished Assign a name to the settings and the software will save the file name with the extension qip This file can be recalled at a later date by pressing the Load button A L NOTE For most applications it is not recommended to use the interpolation function uncheck use Interpolation box 8 2 Review of the Data Analysis Methods 8 2 1 HK Horvath Kawazoe Method SF Saito Foley Method Tags None Click the HK SF tab
19. course a difficulty to the pore size analysis of the porous materials and the decision whether the adsorption or desorption branch should be taken for calculation of the pore size distribution curve depends very much on the reason s which caused the hysteresis 3 1 Total Pore Volume and Average Pore Radius The total pore volume is derived from the amount of vapor adsorbed at a relative pressure close to unity by assuming that the pores are then filled with liquid adsorbate For a discussion of the relationship between pore size and relative pressure see Section 1 3 2 If the solid contains no macropores the isotherm will remain nearly horizontal over a range of P Po approaching unity and the pore volume is well defined However in the presence of macropores the isotherm rises rapidly near P Po and in the limit of large macropores may exhibit an essentially vertical rise In this case the limiting adsorption can be identified reliably with the total pore volume assuming careful temperature control of the sample The volume of nitrogen adsorbed Vaas can be converted to the volume of liquid nitrogen Vjj contained in the pores using equation 1 14 That is Pa V aas Vm 1 14 V liq RT in which P and T are ambient pressure and temperature respectively and Vm is the molar volume of the liquid adsorbate 34 7 cm mol for nitrogen Since pores which would not be filled below a relative pressure of 1 have a negligible contr
20. editing adsorbate parameters 2 3 Edit Data Reduction Parameters DRP Click Physi Data Reduction Parameters on the Configure menu to view and modify the data reduction parameters DRP This DRP method allows the user to manage create or modify pre defined DRP sets Modifying the DRP set does not affect the data reduction of the current data file or the parameters used in the next acquisition These DRP sets can be loaded in when setting up the parameters for a data acquisition or when processing an existing data set To modify the DRP parameters used when a new file is created save the DRP set as default drp Once a default DRP file is created it is automatically loaded when a new file is created e g importing data from non native formats To change the DRP set of an existing data file access this dialog from the Floating Menu of any graphical or tabular view of the data file After you edit a DRP set you can save it as a new file for later use DRP sets are saved in the program s Config folder 3 Set Data Folders To set default folders for the data file types that NovaWin recognizes click Set Data Folders on the Configure menu This will open the System Folders window P N 05079 Rev Page 29 of 133 Nova e NovaWin Operating Manual D SOFTWARE CONFIGURATION System Folders Click the Select Path button s Lluadra in Contig Files LO Cdata Quadra inchg to change 2 directory folder s Quantachrome Ph
21. gas leaving the cell when evacuation begins and thus it is less likely to entrain powder particles and transport them upwards and out of the cell The presence of a filler rod significantly increases gas velocity because of the narrowing of the internal dimensions and can exacerbate elutriation In problematical cases the filler rod may be dispensed with during analysis but some loss of resolution and or sensitivity may result The most dramatic elutriation problems are encountered during degassing of damp light powders As the sample heats from ambient the pressure over the sample decreases due to the action of the vacuum At some point the water flashes into steam This rapid expansion of gas volume drives powder out of the bulb and up the stem of the cell This condition can be reduced or eliminated by 1 pre drying the samples in a conventional drying oven and outgassing under just vacuum or 11 raising the temperature of the heating mantle in 20 degree steps It is recommended that the temperature be paused at 60 C for 30 60 minutes under vacuum to allow for a milder removal of moisture before increasing the temperature to 80 C then 100 C and finally maximum degas temperature P N 05079 Rev Page 34 of 133 Nova e NovaWin Operating Manual E SAMPLE PREPARATION A further flow restriction in the form of a tight fitting glass fiber filter cartridge called a Non Elutriating plug which can be inserted into the stem
22. list a number of procedures you may select such as view user manual download Adobe Reader visit QC Web etc To install the program select the appropriate link 3 The Install Wizard will start Follow the prompts to specify 1 Program root folder C Program Files Quantachrome Instruments NovaWin 2 Data root folder C QCdata 3 Start menu folder Quantachrome Instruments 4 Installation type full upgrade or Security Reset a Full installs program files sample data and CONFIG FILES Also resets security and all configurations materials reports etc b Upgrade installs program files only Leaves all configurations intact c Security Reset does not install any files just resets security information On next start of the program security must be configured and user account recreated 4 Continue following Installer prompts Reboot if necessary 5 After installation is complete the start launcher can be closed or other links explored 1 2 NOVA P Instruments The NOVA P instruments are specifically designed to be used with the NovaWin CFR software The following tasks must be performed when installing NovaWin CFR with the NOVA P instrument 1 Installation of the NOVA P vacuum pump dewar flask gas connection keypad keyboard configuration Refer to the NOVA Operation Manual for details 2 Enabling lockouts on System Manager on the NOVA The NovaWin CFR software provides the means to operate the NOVA in a secure
23. of the operation mode at the top of the Stations tab click the Sample sub tab see Figure F 27 Select one active station you will repeat all the steps individually for each active station For the analysis on a given station enter and verify a file name enter attributes of the sample ID Weight Description Comments Station Selection button Multi station NOVA users should first select the appropriate station for which the sample information parameters will be entered Make sure that the sample information entered into this window corresponds to the correct sample and cell on that station Sample information point P N 05079 Rev Page 54 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION selection and equilibrium conditions are entered separately for each of the stations being used for the analysis File Name Enter the name of the data file here The file will be uploaded and stored in the Physisorption Files folder automatically created by the NovaWin software installation see Section D 3 at the completion of the run with the extension qps You may use any valid Windows accepted characters in the filename with the exception of quotation marks periods equal signs colons and slashes both forward and back NOTE The software will automatically upload the data for each of the stations as VA the data points are taken At the completion of the measurement the dat file will be converted to a qps file w
24. oie Sae Abort Analysis Tile Exit Ed Tile Horizontal Upload data Tile Vertical Instrument Status Fe Edit Instrument Settings Firmware Upgrade Help Show Instrument Message Cri 1 Contents Fi Search Database About About instrument Figure C 2 Menus in NovaWin L NOTE When any data file is open the Floating Menu is also accessible 1 4 Instrument PC Connection To begin using NovaWin make sure that the following steps are performed 1 NOVA instrument installation is completed for details see NOVA Operation Manual P N 05069 P N 05079 Rev Page 17 of 133 Nova e NovaWin Operating Manual C NovaWin SOFTWARE INSTALLATION 2 NovaWin software installation is completed 3 Connect the serial cable P N 26057 from a communication port COM port on the PC to the RS 232 port on the back of the NOVA see NOVA manual for location of RS 232 port 4 Power on the NOVA Allow the instrument to run through the initialization sequence When this sequence is finished the Main Menu will be on the NOVA display NOTE If the instrument needs to establish a safe status due to aborted analysis it L will perform this automatically and will ring after the routine is complete This may take up 20 minutes depending upon the amount of gas remaining in the sample cell 5 Start the NovaWin program on the PC The PC will display the following Startup Screen Qi Quantachrome NovaWin File Edit Configure Operation Window Hel
25. on the Data Reduction Parameters window to access parameters for these methods P N 05079 Rev Page 77 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN Data Reduction Parameters Urita Display General Adsorbate Adsorbent t MF alpha s BJH DH DA DA HK SF DFT Monte Carlo A V Summary HE method Tabulated data interval il SF method Tabulated data interval 1 Figure G 14 Setting the Parameters for the Horvath Kawazoe and Saito Foley methods The Tabulated data interval is the number of data points that will be displayed on the data tables For example if you wish to tabulate every other data point a value of 2 should be entered for the Tabulated data interval 8 2 2 DA Dubinin Astakhov Method Tags None 8 2 3 BJH Barrett Joyner amp Halenda Method DH Dollimore Heal Method Tags P 8 2 4 DR Dubinin Radushkevich Method Tags R Click the BJH DH DA DR tab on the Data Reduction Parameters window to access parameters for these methods P N 05079 Rev Page 78 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN Data Reduction Parameters Urita Display General Adsorbate Adsorbent t MF alpha s BJH OH DA OA HK SF DFT Monte Carlo AM Summary BJH DH pore size distribution Moving point average size 1 BJH Interpolation Settings DA method Increment E 500 000000 Increment n oO o0000 Interaction constant K 2 960000 kl nnf
26. pore may now be expressed as iai 1 21 rgi At 2 V pl v When the relative pressure is again lowered to P Po 3 the volume of liquid desorbed includes not only the condensate from the next larger size pores but also the volume from a second thinning of the physically adsorbed layer left behind in the pores of the largest size The volume V desorbed from pores of the smaller size is given by 2 z Fp f 1 22 V p2 te he z v Van An expression for V at 1s Van At Aci Ue where Ac is the area exposed by the previously emptied pores from which the physically adsorbed gas is desorbed Equation 1 23 can be generalized to represent any step of a stepwise desorption by writing it in the form n l Var At z AC 1 24 j l The summation in equation 1 24 is the sum of the average area in unfilled pores down to but not including the pore that was emptied in the desorption Substituting the general value for V at into equation 1 22 results in an exact expression for calculating pore volumes at various relative pressures Z n F pn 1 25 oy te i 2 3 jel Since the area Ac for any one size empty pore is not a constant but varies with each decrement of P Po this term must be evaluated The area of each pore A is a constant and can be calculated from the pore volume assuming cylindrical pore geometry That is P N 05079 Rev Page 111 of 133 Nova e NovaWin Operating Manual I THEORY AND DIS
27. pore size distribution 4 6 Horvath Kawazoe HK Method The HK method enables the calculation of pore size distribution of micropores from the low relative pressure region of the adsorption isotherm Many pore size distribution methods are derived from the Kelvin equation which describes the phenomenon of capillary condensation Some have questioned the reliability of the capillary condensation approach in the small confines of micropores The HK method is derived independent of the Kelvin equation The HK method expresses the adsorption potential function within slit like micropores as a function of the effective pore width DT eT AT P N 05079 Rev Page 120 of 133 P 4 4 10 4 10 ar m E x Mast Mads aje o oo Po Nova e NovaWin Operating Manual I THEORY AND DISCUSSION The parameters A and A can be calculated using the following equations 2 Omc Qs QA As 1 52 As QA ee LE Xs X A 3mc aa Xa 1 53 a as where m mass of an electron c speed of light a polarizability of adsorbent aa polarizability of adsorptive x Magnetic susceptibility of adsorbent X magnetic susceptibility of adsorptive and d effective pore width d d da d diameter of adsorbent molecule da diameter of adsorbate molecule distance between two layers of adsorbent o 0 858d 2 K Avogadro s number Ns number of atoms per unit area of adsorbent Na number of molecule
28. referred to as fractal because their magnitude is proportional to X where D is a fractional exponent that generally assumes values between D 2 for smooth surfaces and D 3 for surfaces so rough that they essentially occupy all available volume The fractal P N 05079 Rev Page 127 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION dimension D can thus be used to quantify the roughness of real surfaces in terms of a single parameter Among the various approaches proposed in the literature to evaluate D two in particular have gained popularity because they make use of single gas sorption isotherms for their calculations These are the Frenkel Halsey Hill FHH method and the Neimark Kiselev NK method 7 14 Frenkel Halsey Hill FHH Method By noting that in the multilayer adsorption region the influence of surface forces tends to be smoothed out several independent authors derived an isotherm expression of the general form Po _ B log 1 62 eae 1 62 where B is a parameter related to adsorbate adsorbent and adsorbate adsorbate interactions V is the amount of adsorbed material and the exponent s is a constant characteristic of a given adsorbent Equation 1 62 came to be known as the Frenkel Halsey Hill or FHH equation Pfeifer et al postulated that the FHH exponent s is related to the fractal dimension D of the adsorbent through the expression D 3 1 s 1 63 In deriving eq
29. required click the Adsorbate button and choose from the drop down list A particular cell calibration must be done using the same adsorbate that will be used for the sample measurement in this cell if you plan to measure nitrogen adsorption in given cell n calibrate it with nitrogen P N 05079 Rev Page 40 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION 2 3 Adsorbate Gas Calibration Parameters The Adsorbate Gas part of the Calibrate Cell s window is used to define the parameters related to the adsorbate used for the calibration on all active stations Click the Adsorbate Gas drop down list button V and select the adsorbate gas from the dropdown list containing model adsorbates currently defined in the program database Calibrate Cell s Adsorbate Gas Nitrogen Carbon dioside Figure F 6 Selecting the adsorbate gas for calibration 2 3 1 Cell Calibration with Nitrogen Nitrogen is displayed as a default in the Adsorbate Gas field nitrogen adsorption at bath temperature of 77 K when the adsorbate gas is nitrogen and the coolant in the dewar is LN32 There are two Pp modes drop down list to evaluate Po during cell calibration with nitrogen 1 Calculate or 11 Enter Calibrate Cell s Calibrate Cell s Adsorbate Las Adsarbate Gas Nitrogen Nitrogen o o l POU options PO options POmode REE PO mode PO Value 760 0 mmHg It is recommended to ch
30. span by clicking the Between checkbox and selecting the date range The currently selected range may be printed by clicking the Print button A new file may be started by clicking the Start New button The old file will be archived and can be accessed by selecting Configure gt gt Security gt gt View Archived Log P N 05079 Rev Page 25 of 133 Nova e NovaWin Operating Manual System Log ft Start Hew i 4 2 1 eat n ih i iat iy eat Ay cae h i ih iat iat iy S 2009 10705 08 39 00 2009 10 05 16 51 40 2010 01728 12 41 29 2010701728 12 47 49 2010701728 12 41 57 2010701728 12 42 55 2010701728 14 43 03 2010701728 12 43 04 2010 06 13 17 20 05 2010 08 13 17 20 27 2010 06 13 17 20 34 2010 08 13 17 20 40 2010708713 17 20 4 2010708713 17 20 50 201070813 17 21 04 2010708713 17 21 16 Ca A oa Ken SS eS aS SO New system log created user system Invalid login attempt Invalid login attempt Invalid login attempt Invalid login attempt Invalid login attempt Invalid login attempt cthibault lab cthibault cthibault cthibault cthibault User account disabled cthibautt Invalid login attempt Invalid login attempt Invalid login attempt Invalid login attempt Invalid login attempt Invalid login attempt Invalid login attempt Invalid login attempt MM anager MM anager mmanager manager manager cthigault cthigault cthibault Tr Print Ir Between 1o 5 2009 1 18 2011
31. step by summing the expressions je 2 V cf Eq 1 26 P Fp and L Ap 1 30 2H Fp respectively P N 05079 Rev Page 112 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION 3 3 Surface Area of Microporous Samples by Langmuir Method In the absence of meso and or macropores a sample containing micropores will exhibit a Type I or Langmuir isotherm see Section 3 The Langmuir equation 1 31 is a limiting case of the BET equation 1 1 for the adsorption of a single molecular layer of adsorbate W __ CLPT Pe 1 31 W 1 C P P W and Wn are the weight of adsorbate at some P Po and the weight in a monolayer respectively C is a constant associated with the energy of adsorption Equation 1 31 rewritten in the form of a straight line W CW m W m allows the determination of the slope 1 W m from a plot of P Po W versus P Po The weight of a monolayer Wm may then be used to calculate the total surface area of the sample from equation 1 5 This method is not applicable to composite materials containing micropores and meso and or macropores 4 Micropore Analysis Several different approaches to micropore analysis are available using NovaWin While no single treatment is applicable to all situations enough flexibility is provided for the user to select the analysis most suitable for a given situation or material 4 1 V t Method The NovaWin software uses the t method of Halsey the generally p
32. used Pre Exponential term a C Carbon black 6 053300 S bea Exponential term b f generalized Halsey 3 000000 MP method Thickness interval 0 500000 A alpha method Standard isotherm tile _ACARB PePo 0 400000 Figure G 22 Setting parameters for t MP and alpha s methods For the t plot method calculations T tags must be set for the desired data points Select and check one option from de Boer Carbon Black Halsey or Generalized Halsey for t method used Note that the Carbon Black t method calculation corresponds to ASTM D5816 The MP method does not require data tags Enter the value for the Thickness interval in its field For the alpha s method calculation you must first assign T tags to the appropriate data points Select a Standard Isotherm File from the pull down list Table G 4 lists the Standard Isotherm Files available in the software Finally select the desired P Po value for the calculation P N 05079 Rev Page 84 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN Table G 4 Standard Isotherm Files for alpha s Method alpha s Standard Isotherm File Material Experimental Conditions pasar _asilar 8 2 8 FHH Frenkel Halsey Hill Method NK Neimark Kiselev Method Tags R These two methods constitute the Fractal Dimension calculations for the NovaWin software Both of these methods can be used for the adsorption and or desorption branches of the isotherm Assign R t
33. 9 Rev Page 81 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN the quantity of C must be positive i e any negative intercept on the ordinate of the BET plot is an indication that one is working outside the valid range of the BET equation and 2 the application of the BET equation is limited to the pressure range where the term n Po P or alternatively n 1 P Po continuously increases with P Po n is the adsorbed amount This procedure has been suggested in ISO standard ISO FDIS 9277 2010 Figure G 18 shows the plot of n Po P vs P Po for the argon adsorption isotherm at 87 3 K ona faujasite zeolite It is clearly visible that based on the second criterion above only data points below a relative pressure of 0 053 can be used for application of the BET calculation The resulting BET plot is shown in Figure G 19 i e the BET equation is applied for relative pressures below about 0 053 down to 0 01 and a linear plot with positive C constant is obtained Range of points to use for BET calculations OO ir H15 24 E ji Ft Figure G 18 Plot of the term n Po P vs P Po Fit of data in the traditional range of BET equation has a negative intercept z Lpu E Fy Fit of data using the low pressure points as described in the text has a positive intercept 0 hi H12 O15 2 iE gji rit Figure G 19 BET plot for argon on a faujasite zeolite at 87K 8 2 5 2
34. 994 K S W Sing Surface Area Determination D H Everett and R H Ottewill Eds Butterworths London 1970 p 25 R S Mikhail S Brunauer and E E Bodor J Colloid Interface Sci 26 45 1968 M Polanyi Verh Dtsch Phys Ges 16 1012 1914 M M Dubinin and L V Radushkevich Dokl Akad Nauk SSSR 55 331 1947 M M Dubinin Chemistry and Physics of Carbon Vol 2 pp 51 118 P L Walker Ed Marcel Dekker New York 1966 M M Dubinin and H F Stoeckli J Colloid Interface Sci 75 34 1980 M G Kaganer Zh Fiz Khim 32 2209 1959 M M Dubinin Chem Rev 60 235 1960 H Marsh and B Rand J Colloid Interface Sci 33 101 1970 H F Stoeckli Microporous Carbons and Their Characterization the Present State of the Art Carbon Vol 28 No 1 pp 1 6 1990 M J G Janssen and C W M van Oorschot The Characterization of Zeolites by Gas Adsorption in Zeolites Facts Figures Future 1989 P A Jacobs and R A van Santen Eds Elsevier P N 05079 Rev Page 131 of 133 Nova e NovaWin Operating Manual REFERENCES 23 24 25 26 27 28 29 30 31 32 o gt 34 35 36 37 38 39 40 41 42 43 G Horvath and K Kawazoe Method for the Calculation of Effective Pore Size Distribu tion in Molecular Sieve Carbon J Chem Eng Japan Vol 16 No 5 1983 pp 470 475 A Saito and H C Foley AIChE Journal 37 429 1991 R Evans U M
35. ATION Every sample should be outgassed by flow or vacuum before analysis For the detailed degassing procedure refer to Section V 5 3 in the NOVA Operation Manual P N 05069 1 Selecting a Sample Cell There are two factors to consider when selecting a sample cell stem diameter and sample amount bulb size Stem diameter Choose the narrowest diameter cell that will comfortably admit the sample For example a fine powder should be analyzed in a 6 mm outer diameter 0 d 4 mm 1 d stem cell Use the 12 mm o d stem cells for large pieces that cannot be reduced in size Larger particles such as granules and small pellets might require a 9 mm o d 7 mm 1 d diameter stem Of course cohesive powders may be analyzed in 9 or 12 mm stem cells to facilitate addition removal and cleaning Sample amount Bulb size Always use the smallest bulb that will accommodate the optimal amount of surface area Larger total surface areas can certainly be analyzed but they may lengthen the analysis For surface area determinations only sample amounts from at least 1 m to 5 m can be analyzed using nitrogen but careful consideration should be given to proper degassing and equilibrium criteria Full adsorption and desorption isotherms should have at least 15 20 m in the cell Wider stems and larger bulbs can be beneficial in reducing elutriation 2 Methods of Sample Preparation NOTE Access to the degasser must be performed using the NOVA L keypad
36. B Marconi and P Tarzona J Chem Soc Faraday Trans II 82 1763 1986 P I Ravikovitch G L Haller A V Neimark Advances in Colloid and Interface Science 76 77 203 1998 K E Gubbins In Physical Adsorption Experiment Theory and Application J Fraissard ED Kluwer Dordrecht 1997 L D Gelb K E Gubbins R Radhakrsihnan and M Sliwinska Bartowiak Rep Prog Phys 62 1573 1999 N A Seaton J P R B Walton and N Quirke Carbon 27 853 1989 A Vishnyakov P Ravikovitch and A V Neimark Langmuir 16 2311 2000 A V Neimark P I Ravikovitch M Gruen F Schueth and K K Unger J Colloid Interface Sci 207 159 1998 P I Ravikovitch D Wie W T Church G L Haller and A V Neimark H Phys Chem B 101 3671 1997 S Dushman Scientific Foundations of Vacuum Technique p 65 J Wiley amp Sons New York 1989 S C Liang J Phys Chem 57 910 1953 K F Poulter et al Vacuum Vol 33 No 6 pp 311 316 1983 D Avnir Ed The Fractal Approach to Heterogeneous Chemistry J Wiley amp Sons New York 1989 P Pfeifer Y J Wu M W Cole and J Krim Phys Rev Lett 62 1997 1989 A V Neimark Ads Sci Tech 7 210 1991 P Pfiefer J Kennter and M W Cole Fundamentals of Adsorption Edited by A B Mersmann and S E Sholl Engineering Foundation New York p 689 1991 S Lowell J E Shields M A Thomas amp M Thommes Characterization of Poro
37. CUSSION ZV 1 26 Fp Then the pore areas can be cumulatively summed so that for any step in the desorption process Ap is known The BJH method offers a means of computing gt Ac from A for each relative pressure decrement as follows It is assumed that all pores emptied of their condensate during a relative pressure decrement have an average radius r calculated from the Kelvin equation 1 16 radii at the upper and lower values of P Po in the desorption step The average capillary core radius is expressed as 1 27 a rp r where f_ is the thickness of the adsorbed layer at the average radius in the interval in the current pressure decrement and is calculated from equation 1 19 The term c in equation 1 24 then is given by reo _ Vp tr 1 28 Equation 1 25 now can be used in conjunction with equation 1 28 as an exact expression for the computation of pore size distributions 9 2 2 DH Method A computationally simpler approach to evaluating mesopore size distributions was developed by Dollimore and Heal The DH approach differs from the BJH method in that the term Y in equation 1 24 is calculated from Vor AnA AseZ2 7 412 Ls 1 29 where the summations XA and XL represent the areas and lengths respectively of all the pores emptied of condensate in previous desorption steps Assuming cylindrical pore geometry the cumulative pore areas and lengths can be estimated for each desorption
38. E E E T A E E E T 25 1 4 DVS a T a E e E E E E E E E E 25 2 E eP AE E S E ON A E A OEA 26 ZA Edit AadsGtp ate Paracel earl itl lela le lated altel elt idles 26 Ze Edit Adsorbent Parane hers 5 65 Gatch Sisal fons a uiieh ancl Aantal a e Mendieta ite 28 2 3 Edit Data Reduction Parameters TIR Pharrr nena nn una enn neuen ean 29 3 oA 2 M ET a E ce E E E A E E A eT ee 29 4 Serec Daa Folde ecareeae ean E E O E OAN O O A E 30 E SAMPLE PREPARATION aa i ier ie oe A eee 32 1 De SCH aA Sample Ce U ssssacsssacasevaratesacatesatanesctassadsandedespasatenannnacsioatatetueaniadesesctensvassnannaeesdtes 32 2 Methodsof Sample PreparalOiircic estaresdacactameatssualsesantadsesanasdacsustaaecenatecoentesnaeraadranendivs 32 3 Choice of Outeassine Temperature arid TIME taicise ceicies dancenensdeaeevbineumnscsdeocotinasecasbeucues 33 4 Elutriation and Its PREY SOR m srsesseiserssererereseriirrcserssersserisrer anriecssersvesi senisest endinsa 34 5 Unl adine the IDC oasser ainra os a ON se iene aria OTAVAN 35 F INSTRUMENT OPERA TION seee EEEE E ESS 36 1 Manifold Volunre C abraio inersia ein eTEN RE E OEE 36 2 Sample Cell Void Volume DetetminA hoM ircciccnts taste datecteades dees E A RES 36 2 1 Helium Void Volume Mode model 26 only ccc essssseseseecceeeeseeeeeeeeeceaeseeeeaeeeeaeseeeeaeeeeees 37 ZD Cell Calibration ING ya MO denrea a hes cha dade ceen Sadatna eels Sethe odie edaeee eats 37 25 Adsorbate Gas Calibration Parametets cscccccsc
39. Kaganer to evaluate micropore surface area from the plot intercept log Vo by applying equation 1 5 Other modifications of the DR method include a Allowing the DR exponent n to differ from n 2 in order to provide a better data fit for non Gaussian pore size distributions see next section and b Introduction of a supercritical adsorption constant K into equation 1 45 P N 05079 Rev Page 118 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION 2 log W log W m og x Pe LaS where W weight adsorbed at P W total weight adsorbed m slope of straight line K BE P critical pressure of adsorbate mm Hg Po saturated vapor pressure of adsorbate mm Hg T adsorption temperature K Te critical temperature of adsorbate K Equation 1 48 has been proposed as a valid correlation for adsorption data at temperatures exceeding the critical temperature of the adsorbate 4 5 Dubinin Astakhov DA Method For a large number of microporous materials the adsorption isotherm can be well characterized by the Dubinin Radushkevich equation However for those microporous materials with heterogeneous distributions or strongly activated carbons the Dubinin Radushkevich equation fails to linearize the adsorption data To describe adsorption on wider range of microporous materials the Dubinin Astakhov equation was proposed RT n P Pe 1 49 w weer where W weight ads
40. Kr adsorption isotherms P N 05079 Rev Page 86 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN graph Kr 87K Thin film PS method dV log d Thin Film_Demo_ordered_silica qps Kr 87K Thin film PS method d log d m 3 92e 01 9 30e 01 3 60e 01 j 3 54e D1 3 20e 01 f 7 59e 01 2 80e0 esseni 2 00e 01 D OOOO Fula aad OO EE 4 74e 01 1 60e 01 i io 3 80e 01 Ss amp Pu 2 g 2 8 2 E Oo 1 20e 01 p 2 85e 01 8 00e 02 1 90e 01 4 00e 02 i 9 49e 02 0 00e 00 aia 0 00e 00 3 000 Pore Diameter nm Figure G 24 Pore size distribution from Kr87 method NOTE A moving point average smoothing using the Moving point average size L from the BJH DH DA DR tab of the Data Reduction Parameters dialog is applied to the pore size distribution data 8 3 Adsorption Volume Summary Selecting Tables gt gt Area Volume Summary gt gt Area Volume Summary from the floating menu of physisorption data will generate a summary consisting of the data header information and areas and volumes calculated from the selected models To select the models you want to include in the Area Volume Summary open the Data Reduction Parameters dialog and click on the A V Summary tab Check the boxes of the calculation models you want to include on the summary and uncheck the ones you don t Be sure to set all the required parameters for the selected methods P N 05079 Rev Page 87
41. LECTRICAL NOMS Co aag Coa aaeinec O E 110 120V PECGQUCHCY on E 50 60 Hz Power 10 Glass Deieren a a 108W Quarz ADEC ean ienn 125W ENVIRONMENTAL Temperi areca E a 15 C 40 C Max Relative Humidity eee 80 non condensing P N 05079 Rev Page 11 of 133 Nova e NovaWin Operating Manual B SAFETY B SAFETY 1 Symbols Used in this Manual AN HOT This sign denotes a possible hazard to the operator due to high temperatures CAUTION This sign denotes a hazard that could result in damage to the instrument L NOTE This sign denotes an important detail TOOLS REQUIRED This signifies that tools are required for the described action These symbols refer to the 21CFRPart11 compliant version where S Superuser M manager and O operator A cross through the symbol denotes that that security level does not have the capability described in that section 2 Safety Instructions for the NOVA e This instrument has been designed for laboratory use only e The NOVA requires a trained operator to use the instrument e This instrument must not be used for any application other than that for which it was designed e Because the dewar flask can shatter unexpectedly a protective shield safety glasses and gloves should be worn when filling the flasks P N 05079 Page 12 of 133 Nova e NovaWin Operating Manual B SAFETY e When using a gas other than N gt or Ar at its boiling point do
42. NLDFT and GCMC Methods For The Non Linear Density Functional Theory NLDFT and Grand Canonical Monte Carlo GCMC methods no tags are required To access pages with parameters for these methods click the DFT Monte Carlo tab on the Data Reduction Parameters window and then click the DFT or Monte Carlo tab Data Reduction Parameters Data Reduction Parameters Units Display General Adsorbate Adsorbernt t MP alpha s Units Display General Adsorbate Adsorbent t MF alpha s BJH DH DA DR Hk sF DFT Monte Cario aay Summary OFT Monte Carla DFT Monte Carla Calculation model Calculation model N2 at 77 E on carbon slit pore NLOFT equilibrium model coz at 273 K on carbon MC model v Range relative pressure Range relative pressure Miri 11 000000e 07 Max 1 000000 Miri 11 000000e 07 Max 1 000000 Histogram Histogram Scale Scale C Log e f Log g Lin Binpore width 0 500000 Lin Binpore width 0 500000 A Interpolation Settings Moving point avg E Interpolation Settings Moving point ava E Treat adsorbate as Nitrogen m FFE Treat adsorbate as Nitrogen m rE T Treat adsorbent as Carbon Treat adsorbent as Carbon r Figure G 12 Parameters for DFT and Monte Carlo data reduction methods Select the appropriate DFT Monte Carlo Kernel from the Calculation model pull down list Table I 2 on page 124 lists the various Kernel Files along with their
43. Points Equiibrium Reporting Tagg FrPo Tags on off reset Al Adsorption 3 DB Desorption Spread points Ml Multi BET S SingeBET TI Thickness Crit Pore volume L Langmuir P Pore size R DR amp Fractal 3 Add point Station A Taj H ads 0 des T Eh Load Points L Load Station Appia selected Save Station Active stations H morea le B fw E E X Cancel Help je Save Preset z z Figure F 30 Selecting the points for analysis The selection of the data points is closely associated with the type of measurement that is desired Common measurements for the NOVA include e Surface Area Langmuir and Multi point Single point BET methods e Surface area and pore volume by t plot de Boer Halsey Carbon Black Generalized P N 05079 Rev Page 56 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION Halsey alpha s MP methods e Mesopore Characterization Pore size distribution total pore volume and average pore size by BJH DH and DFT methods e Micropore Characterization volume and area Statistical thickness t plot alpha s MP and DR methods pore size distribution using NLDFT To select data P Po points it is recommended that you use the Spread Points feature that will provide even spacing between the data points The minimum spacing between points is 0 0025 P Po Use the Add feature for additional poi
44. SSION NLDFT GCMC Monte Applicable Pore Examples Carlo Kernel File Width Range NLDFT Ar carbon equilibrium transition kernel at 87 K based on a slit pore model NLDFT CO carbon equilibrium transition kernel at 273 K based on a slit pore model GCMC CO carbon equilibrium transition kernel at 273 K based on a slit pore model QSDFT N2 carbon equilibrium transition kernel at 77 4 K based on 0 35 nm 1 5 nm 0 35 nm 1 5 nm 0 35 nm 40 nm Activated carbons activated carbon fibers novel micro mesoporous carbons of type CMK 1 and others Ultramicroporous activated carbons activated carbon fibers Ultramicroporous activated carbons activated carbon fibers Disordered Micro Mesoporous carbons with heterogeneous a slit pore model surface chemistry e g activated carbons activated carbon fibers NOTE In the case of GCMC CO carbon kernel a three center potential function has been developed with interactions between the sites of different molecules modeled as a sum of Lennard Jones and electrostatic contributions Hence the GCMC model may serve as a benchmark for L quantitative estimates The CO NLDFT kernel is based on a common one center Lennard Jones model this kernel is also important in case a comparison with appropriate DFT results in the literature is needed For details about the application of CO2 NLDFT GCMC kernels please contact QC
45. Support Quantachrome com for Quantachrome s Powder Tech Note 35 NOTE Contrary to regular NLDFT the QSDFT method Quenched Solid Density Functional Theory for details see Quantachrome s Powder Tech Note 40 which can be found by contacting QC Support Quantachrome com takes into account the effects of surface roughness and heterogeneity explicitly Hence Quantachrome s library of DFT GCMC methods offers L the possibility to perform pore size analysis of carbons with different degrees of surface heterogeneity This also allows one to assess the reliability of the pore size analysis of unknown carbon samples Methods based on NLDFT are more accurate for ordered carbon materials whereas the QSDFT method is advantageous for the textural analysis of geometrically and chemically disordered carbons P N 05079 Rev Page 126 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION 6 Thermal Transpiration At the low pressures commonly employed for nitrogen and argon micropore characterization the ati 33s 34 35 eee phenomenon of thermal transpiration can result in significant pressure measurement errors if not compensated Thermal transpiration results in a pressure gradient between the sample at temperature T and pressure P and the pressure transducer at temperature Tz and pressure P gt if the inner diameter of the tubing between the two parts of the system is very small compared with the mean free path of the gas The r
46. The BET Assistant A feature has been added to the software to facilitate the implementation of this method of selecting points within the linear range of the BET equation When in the Edit data points dialog by selecting Edit Data Tags from the floating menu click on the BET Assistant button This will open the Micropore BET Assistant window shown in Figure G 20 A plot of V 1 P Po vs P Po is displayed and the recommended range for the BET equation is highlighted The normal left click and drag zoom function works the same as with other plots Clicking Unzoom on the User Actions menu or Floating menu reverts to the unzoomed display P N 05079 Rev Page 82 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN Micropore BET Assistant The sliders may be used to override the automatically selected range VEL PFP oy oc Upper limit is at maximum point 5 8304e 04 User Actions Figure G 20 Selecting points for BET analysis using the BET Assistant The software automatically selects the range of pressures to use but it is possible to override the automatic selection by dragging the sliders below the graph to move the boundaries of the BET region The boundaries can also be entered by selecting Enter Low Limit or Enter High Limit from the User Actions menu and entering the limits Selecting Set Range Low or Set Range High from the Floating menu will set the respective limit to the position of the cursor when t
47. UPAC classification of sorption isotherms Type V isotherms show pore condensation and hysteresis However in contrast to Type IV the initial part of this sorption isotherm is related to adsorption isotherms of Type III indicating relatively weak attractive interactions between the adsorbent and the adsorbate P N 05079 Rev Page 107 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION The type VI isotherm is a special case which represents stepwise multilayer adsorption on a uniform non porous surface particularly by spherically symmetrical non polar adsorptives The sharpness of the steps depends on the homogeneity of the adsorbent surface the adsorptive and the temperature gt Amount Adsorbed Relative pressure gt Figure I 3 IUPAC classifications of hysteresis loops It is widely accepted that there is a correlation between the shape of the hysteresis loop and the texture e g pore size distribution pore geometry connectivity of a mesoporous adsorbent An empirical classification of hysteresis loops was given by the IUPAC which is based on an earlier classification by de Boer The IUPAC classification is shown in Figure 1 3 According to the IUPAC classification type H1 is often associated with porous materials consisting of well defined cylindrical like pore channels or agglomerates of compacts of approximately uniform spheres It was found that materials that give rise to H2
48. a a a T a 103 1 LL Ea cr EN EEE N A E E E I E ENE E E A E E TE 103 1 1 Mal pont BET MARO daina a a E OA ONO O OO OOOO OO 103 1 2 Stele Point BET MeMod stisctesctscateucasgedecscstediacostsdatenstedeteastedeacostsdatoutedetsestedeteontssateonteStserteases 104 1 3 Maltipoint Single Point ComMpatison s ssssssssessessessessessessessesesstsstsessessessessesseosesseeseesesseeseeses 105 Ze POOS DY GISAN Neorama aa a A 106 3 ES aal E E aa EE E EE PEE PA E AE E A eaeena eee 106 3 1 Total Pore Volume and Average Pore RAdiUS sooie iene ET ETERN 109 3 2 Pore Size Distributions Meso DOr arin anaa E EET EEO ECEE 109 ral BIPM Hodie a p a ap a o a eE 110 rA DEEN Kas go fa eee ee eee arn eC oa eo oP 112 3 3 Surface Area of Microporous Samples by Langmuir Method ssssssesssesesesrseeresrsrsresesressseses 113 Ae Micropore Analys IS an oaa RE A EE 113 4 1 Stl a T T TI T ETO PE ETE ETE 113 e AT CONN O n uN ETON OT Tey or yy even errr 116 4 3 VIP TAO o sess ea Sak ss aa este hs se So aa Soa ta as dss nd ah tn hata Maths Meee a ta eins 116 4 4 Dubinin Radushkevich DR Viethod c4acccucacnancuandaadincdtinadsoutiausawae 118 4 5 D ubninsAstak hoy DA Mhod aese E E EET CETTE 119 4 6 EL OL VAL OIA A ZOG HK Methodersssssssrsrorononroran ana nananana anana nanawan 120 4 7 SaO FoR Or MCHHOG sais cctrsiarottptare aaneen e n a a eia anea 122 5 Density Functional Theory and Monte Carlo Simulation Methods ssssessssesssesssese 129 5 1 Library of DFT an
49. a archiving and editing capabilities NovaWin CFR users have the additional option to operate the software within full compliance of 21 CFR Part 11 guidelines To this end a full audit trail is enabled when utilizing the full security features of NovaWin CFR 1 NovaWin Audit Trail Full Compliance Within 21 CFR Part 11 Guidelines If the audit option is enabled see Section D 1 1 each change to any data file will be tracked and stored The audit entry for each change includes the full name of the user making the change the date and time of the change a description of the change including the old and new values of the changed item and the reason for the change as entered by the user This allows re creation of earlier states of the data if desired Entries in the audit trail are grouped by the user and time of changes Each entry under a main node marked by the memm icon is marked for severity The following icons mean the following severity levels h C Critical change this operation may have invalidated the whole data set iy W Warning changes in this case are severe but do not necessary invalidate the data Ay I Information changes were made to certain parameters but these changes are usually part of the daily use of the system 7 Reason displays the reason for the changes in the group The print audit sub option will cause the audit trail to be printed on every report printed by the system The system features al
50. able and select Analysis Data see Section G 6 for details Enter the sample preparation information in the spaces provided 4 Start and Monitor Analysis Once all of the required fields have been entered correctly and the Missing Incorrect Parameters box disappears the Start button will be enabled Click the Start button on the Start Analysis window This will open a confirmation window to start the analysis Click the Yes button to begin the measurement At this time the dewar of coolant should be filled and placed on the lift drive P N 05079 Rev Page 61 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION NOTE Do not place the dewar with coolant under the sample cells until the Start L button is clicked Placing the dewar under the cells too early will pre cool the cells affecting the initial measurements Start Analysis Common Stations Sample Points E quiibrium Reporting Station File Hame Jetty lt STN gt h e H Sample ID test Description Weight o o000 q Volume Calculation Density 3 00 g mL Sample cell Comment P HL Load Station Save Station Active station A Load Preset M Br cr of Start af OK x Cancel Help E Save Preset z Hovawin Connected to HOYA 4200 Confirmation c Ready to start analysis 2 Place Cell and Rod Sets Containing Degassed Samples in the Analysis Stations Check Dewar s Level of coolant Cli
51. ad data Calibrate Tell Instrument Status Instrument Settings Firmware Upgrade Figure F 3 Selecting Calibrate Cell from Operation menu Nova mode of operation reduces analysis times by eliminating the helium void volume measurement steps L NOTE It is strongly recommended that all cell calibrations as well as analyses are performed with an appropriate filler rod The cell calibration is a blank measurement used to account for the amount of adsorbate gas occupying the cell void volume during the adsorption measurement It follows that a cell which will be used in an analysis at a given temperature with a given adsorbate must be calibrated at the same temperature and with the same adsorbate P N 05079 Rev Page 38 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION NOTE A calibrated cell may be used repeatedly for the same type of analysis for which it was calibrated For most users all standard bulbless cells can be considered equivalent for each diameter Therefore one cell calibration L will suffice for all cells of the same diameter Nevertheless for the most accurate results especially for low surface area materials it is recommended to use in the analysis the same cell rod combination that was actually calibrated for that analysis To perform a calibration with a given adsorbate attach one or more cells to the available stations up to four depending on NOVA model and place the dewar containing appropria
52. ags to the desired data points 8 2 9 Total Pore Volume Tags V The Total Pore Volume calculation can be found in the Tabular Data portion of the software Assign the V tag to the desired data point usually the last adsorption data point in the isotherm or a point on the plateau region of the isotherm 8 2 10 Average Pore Size Tags V M The Average Pore Size calculation can be found in the Tabular Data portion of the software For the Average Pore Size calculation requires the calculation of the Multi point BET surface area M tags in addition to the V tag 8 2 11 Kr 87 Thin Film Pore Size Method Tags P This is a novel method for the pore size analysis of thin porous siliceous oxidic films by krypton adsorption at 87 K according to the method suggested by Thommes et al analysis see Powder Tech Note 39 available from your local Quantachrome representative or QC Support Quantachrome com A NOTE For additional information about using Krypton for thin film pore size In the core application range of this method 1 e the pore diameter range between ca 2 5 nm and 8 nm the obtained pore size data are traceable to NLDFT pore size data please see the mentioned references for more info on this The wider application range of this Kr 87 K thin film method extends from ca 0 7 nm to up to 8 nm P N 05079 Rev Page 85 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN In order to apply this data reduct
53. alve knob clockwise to reduce gas flow turn valve counterclockwise to increase gas flow Weigh an empty cell add sample Insert the body of the sample cell into the heating mantle Place the flow outgas tube into the sample cell Adjust the collar stop so that the end of the tube is approximately 0 5 cm above the sample with the collar stop resting on the rim of the cell stem Do not allow the tube to dip into a bed of powder Load degasser set the desired outgassing temperature and switch the heating mantle on After sufficient time for complete outgassing switch the mantle off Allow sample cell to cool Unload degasser when ready to analyze sample Remove cell reweigh to obtain dry outgassed sample weight FloVac Degasser Accessory Details on using the FloVac degasser can be found in the FloVac manual A sample can be considered ready for analysis when the sample passes a degas test of no more than 20 mTorr per minute at the outgassing temperature A sample that cannot pass the same criterion at room temperature may not analyze accurately Remember the NOVA must be able to pull and hold a vacuum in the sample cell in the presence of sample A contaminated FloVac degas station may give artificially high degassing rates during test You can establish the background pressure rise of a degas station by installing and testing a dowel pin or clean and empty sample cell A clean system should be able to pass a 20 mTorr per minute test Alway
54. ance of document Max 5 characters ovl carea Figure H 10 Enter the display label for the data set Finally when prompted enter the display label for the added data click OK and view the overlay graph P N 05079 Rev Page 95 of 133 Nova e NovaWin Operating Manual li epraph lsotherm Linear ovl H DATA PRESENTATION lsotherm Linear Fioat Ads Rodr BS ine Ads lines Des Sy apt cee th Ge agt yeh ey Mee a ede hehe gta gt ME On fe ests cg dete oot vy GM de itqg yer st hse ce aaa aaa sys 2 See a nid Ces anaes sae a ae ae tyne ee ce eee ell eee Se ee E 6 40 tee i ati aera eee ait E HEHEHE atts a eae et m a ee pes Jesss E e E Sa he S 5 0 poop ftp EEE foes E EE E EECA ete DEE ae ee es Ca ans unre ee a 1 1 1 1 o oe 4 80 Ta Aana a a a a a aaa ade ar Sa a eee nes a Ta AOIN u E E Sarena a a eel 5 3 20 i La p E a a ee ge E a P _ ae Peis ea pO E e e a es Fe E beh re ae aa a ae a a a Acc cee BR tee eg ee Kame k et a eee AN AR aaa R S T 1 SRS Ss ites i a ans asa eae lrg aan oa a a e a pe eS Be 1 60 AA en te E En AET en a aneian ar ppe ERATE T a ra 0 80 pS ne Da Poe 4 penne ne de ooo t te 7 acacia hata laeae ec DC ee ets pon Sean ee cain 0 00 O 20 o 40 0 60 0 80 1 00 1 09 Relative Pressure P Po Figure H 11 Sample overlay graph showing two data sets If you wish to change the graph properties right click on the graph an
55. anifold must be re calibrated when changing to a different adsorbate e g carbon dioxide butane NOTE For NOVA P NovaWin CFR users If the Security Level configuration is set at Full it is recommended that the superuser enable the lockout for Manifold Calibration in the System Manager on the NOVA after the manifold has been calibrated NOTE Manifold calibrations must be performed with the NOVA keypad keyboard St Se 2 Sample Cell Void Volume Determination Model 26 of NOVA 10 0 Instrument Series and newer allow two methods of sample cell void volume determination so called Helium and Nova modes see Sections F 2 1 and F 2 2 for details Therefore the appropriate Operation Mode needs to be selected using NOVA Model 26 keypad or NovaWin Software Instrument Settings as described earlier Model 25 of NOVA 10 0 Instrument Series is not capable of helium measurement and helium mode described in Section F 2 1 1s not applicable in this case P N 05079 Rev Page 36 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION NOTE Do not place the dewar with coolant under the sample cells until the Start L button is clicked Placing the dewar under the cells too early will pre cool the cells affecting the initial measurements 2 1 Helium Void Volume Mode model 26 only D lt Measuring the void volume of the sample cell immediately prior to sorption measurements in the presence of sample using non adsorbing hel
56. ate on nor in a heating mantle Do not expose the heating mantle to a corrosive atmosphere of any kind e Do not make any unauthorized modifications to any Quantachrome heating mantle Do not remove the serial number tag Removing the tag will void the warranty e Make sure that mantle clamps are correctly situated when the heating mantle is on the sample cell see examples on the next page P N 05079 Rev Page 14 of 133 Nova e NovaWin Operating Manual B SAFETY Figure B 1 Correctly assembled mantle clamp and cell Figure B 2 Incorrectly assembled mantle clamp and cell P N 05079 Rev Page 15 of 133 Nova e NovaWin Operating Manual C NovaWin SOFTWARE INSTALLATION C NovaWin SOFTWARE INSTALLATION To install the NOVA Instrument for the first time prior to use please refer to Section III of the NOVA Operation Manual P N 05069 1 1 NovaWin Program CD The installation CD contains the NovaWin software It can be installed on any Windows based PC Windows 2000 and up Ideally before proceeding with the installation make a backup copy of the Installation CD Store the installation CD and its backup copy in safe locations preferably not the same place Follow the installation steps below 1 Insert NovaWin installation CD in your CD ROM drive 1 if auto insert notification is enabled the startup menu will launch automatically 2 if not open the CD ROM drive in explorer and manually run START EXE 2 The launcher will
57. aw Files Documents volume pressure Po time ee al Documents Onl User Disk Documents P N 05079 Rev Page 67 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN Assigned Physisorption Overlay Deere OVp Overlays of plots a hoa Heats of Adsorption files Documents 2 2 Data Processing Warnings When opening a data file that has relative pressures greater than 1 0 or that has non monotonic points points that do not increase in volume with increasing pressure a warning like the one in Figure G 3 is displayed Data reduction is not prevented however some processing may not function properly on these data Data Reduction Problems e Data file is invalid for Data Reduction because w Point s with relative pressure gt 1 0 Do not show this warning any more Figure G 3 Warning about possible problems with data For data with relative pressures greater than one the Pp should be checked for validity For non monotonic data the offending points may be deleted and the data saved to a new file for processing Usually the non monotonic points are at very low pressures where little adsorption has taken place and the signals are in the noise range of the transducers Deleting these points does not affect the integrity of the data If non monotonic points occur at higher pressures gt 0 1 P Po the data should be questioned and rerun if possible These warnings may be suppressed by checking th
58. be calculated from the slopes and each successive interval calculation represents the area of all the micropores remaining unfilled The calculations are continued until no further decrease in slope is found in the V vs t plot indicating that all the micropores have been filled The surface area of pores in the range of thickness from 4 to 4 5 A for example is the difference between the values calculated from the first and second slopes The area of pores in the thickness range from 4 5 to 5 A is the difference between the values calculated from the second and third slopes and so on Pore volumes can similarly be calculated using the relation V 10 S S em g 1 41 Where S surface area calculated from slope 1 S2 surface area calculated from slope 2 t thickness at beginning of interval used for slope 2 t2 thickness at end of interval used for slope 2 Each succeeding group of pores is correspondingly treated and a distribution of pore volume is thus obtained While the exact pore shape is usually unknown cylindrical pores are generally assumed It has been shown that this pore volume relation is equally valid for cylindrical pores or parallel plates Viiq ml q 8 10 12 o 2 4 6 t A Figure I 7 Typical V vs t plot with internal slopes P N 05079 Rev Page 117 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION 4 4 Dubinin Radushkevich DR Method Based on the Polanyi pote
59. can then be obtained from the slope s and intercept i of the BET plot From equation 1 1 mca 1 2 WmC and TE 1 3 WnC Thus the weight of a monolayer Wm can be obtained by combining equations 1 2 and 1 3 1 W 1 4 S i The second step in the application of the BET method is the calculation of the surface area This requires knowledge of the molecular cross sectional area Acs of the adsorbate molecule The total surface area S of the sample can be expressed as Wh N As 1 5 S M where N is Avogadro s number 6 0221415 x 10 molecules mol and M is the molar mass molecular weight of the adsorbate Nitrogen is the most widely used gas for surface area determinations since it exhibits intermediate values for the C constant 50 250 on most solid surfaces precluding either localized adsorption or behavior as a two dimensional gas Since it has been established that the C constant influences the value of the cross sectional area of an adsorbate the acceptable range of C constants for nitrogen makes it possible to calculate its cross sectional area from its bulk liquid properties For the hexagonal close packed nitrogen monolayer at 77 K the cross sectional area Ass for nitrogen is 16 2 The specific surface area S of the solid can be calculated from the total surface area S and the sample weight w according to equation 1 6 S 5 w 1 6 1 2 Single Point BET Method For routine measurements of surface a
60. cell in instrument memory Up to 99 cell calibrations can be saved During a sample analysis the NOVA program refers to this file It 1s very important to use the correct cell calibrations with the cells that are actually used otherwise differences in volumes will result in erroneous data Instructions on calibrating sample cells using the NovaWin software can be found in Section F 2 2 of this manual To select the Nova Mode open Communication Setup window go to Operation Instrument Settings P N 05079 Rev Page 37 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION Unmark this box to Communication Setup select the Nova Mode you will need to calibrate your cells in advance cell void volume determination Select communication part LOM Instrument in He mode M Cancel Help Figure F 2 Selecting NOVA mode analysis NOTE For users of Nova Model 25 NOT helium capable make sure that the L Instrument in He mode box is always UNMARKED to avoid communication error The cell calibration is required while operating in NOVA MODE That is if the option Instrument in He mode is UNMARKED the Helium mode for the cell void volume determination during the analysis is NOT selected The Calibrate Cell option is available active in the Nova Mode only Qi Quantachrome NovaWin Fie Edit Configure Mems Window Help ce re i ei Stark Analysis Abort Analysis Uplo
61. ck ves when ready or ho to abort Figure F 35 Starting a data acquisition It is useful to be able to monitor the progress of an analysis once it has been started especially since surface area measurements particularly full isotherms may take an extended period of time to complete NovaWin offers the following features to accommodate this need e Communicator window e Instrument Status window e Automatic uploading of acquired data points 4 1 Communicator Window As soon as the measurement or cell calibration is started the Communicator window will appear only if the PopUp box is left checked This window displays the functions of the instrument such as the acquisition of data points throughout the course of the measurements Click the PopUp box button uncheck the box if you do not wish to have the NOVA Messages P N 05079 Rev Page 62 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION window automatically display on screen The Communicator window keeps a log of the instrument functions throughout the measurement even if the PopUp box is left unchecked Select Print if you would like a printout of the contents in the Communicator window printer must be connected to the PC To reopen the Communicator window go to Operation on the Main Menu Bar and select Show Instrument Message or press CTRL I keys Clicking OK will close the Communicator window The Communicator window will be continuously updated even fro
62. d GCMC Methods in Quantachrome s Data Reduction Software 124 6 Taraa TAN O E A O T TOOT 127 7 Facal ie SOs VOCS menner in dtoe cases Conbt eek aaseaaeteneneebaasebaatenemeusacnst 127 7 1 Frenkel Halsey bills PELE Methodes niesna a i 128 da Si sib uate cd el Serena ONY Om Faldo 0a lenpeemmnee emer er tcrnr eee ere N ne 128 Te TROUBLESHOOTING GUIDE crena a EEEE 130 P N 05079 Rev Page 8 of 133 Nova e NovaWin Operating Manual A INTRODUCTION A INTRODUCTION NovaWin is a Windows based comprehensive program that allows for the integration of the NOVA Series instruments to a remote PC The program serves the dual function of setting up measurement parameters and providing a platform for enhanced data analysis in the generation of reports including graphical plots and tables NovaWin also allows for the direct communication with the NOVA Series instruments and a PC with the automatic uploading of data points as they are acquired throughout the course of the measurement An enhanced version NovaWin CFR is also available with configurable security features that conform to 21 CFR Part 11 electronic records as mandated by the FDA for use in the pharmaceutical industry NOTE This operating manual is for both versions of the software NovaWin and NovaWin CFR NovaWin CFR contains all of the features of the standard L NovaWin software and any reference to NovaWin will be relevant to both versions of the software In cases where the instruction
63. d by P 30K Ns As Na Aa 1 ae a d 2 PIK NT eT Fie Ne 1 es ie Se SAD See 5 2 P G where 1 5 kY eee 1 56 a i s e E k a 1 57 and a bo 1 P N 05079 Rev Page 122 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION D d effective pore diameter All of the other parameters have been defined in the previous section HK method The numerical solution of the above equations is again analogous to that of the HK method and yields pore size distributions and cumulative pore volumes for cylindrical pores in the micropore range 5 Density Functional Theory and Monte Carlo Simulation Methods Classical macroscopic theories like for instance the Dubinin Radushkevich approach the BJH method and semi empirical treatments such as those of Horvath and Kawazoe HK and Saito and Foley do not give a realistic description of the filling of micropores and even narrow mesopores This leads to an underestimation of pore sizes In order to achieve a more realistic description microscopic theories which describe the sorption and phase behavior of fluids in narrow pores on a molecular level are necessary Treatments such as the Density Functional Theory DFT or methods of molecular simulation Monte Carlo simulation MC and Molecular Dynamics MD provide a much more accurate approach for pore size analysis Hence methods such as the DFT of inhomogeneous flui
64. d then click Graph Properties on the Floating Menu This will open the Configure Graph Properties window Locate Physi Overlay on the Tree and follow the procedure described in the previous section All graphs H E phys Overlay graphs Contigure Graph Properties 3 H Physi Overlay Raw Data Isotherm Lin ie AB ee ee ee Pe ee ee x Cancel 1 Ads 1 Des 2 408 2 Des 3Ads 3 Des 4 Ads 4 Des p Ads p Des b Ads Om Select the Line that you wish to configure the graph properties A total of 16 lines overlays are permitted s Help gt Figure H 12 Changing properties of overlay plot You can access and modify the Data Reduction Parameters for the overlay plot by clicking DRP on the Overlay Manager window Figure H 9 You can also synchronize Data Reduction Parameters for all overlay plots by clicking Synch on the Overlay Manager window To change P N 05079 Rev Page 96 of 133 Nova e NovaWin Operating Manual H DATA PRESENTATION the label or description of a file select the file from the list in the Overlay Manager window and click Label or Descr To remove a file from the graph select it on the list and click Remove To save the overlay graph click Save As in the File menu The graph will be saved under a new name in the Auxiliary Data folder An alternative method exists for overlaying isotherm data only To begin click New on the File menu and then click Phystsorp
65. d volume gives the micropore volume Vyp That is Viup i x0 001547 cm 1 38 The two linear regions of the t plot in Figure I 6 indicate the presence of micropores larger than 7 A and the actual pore width 2t can be estimated at the position where the two linear plots intersect The slope of the upper linear portion B of the t plot in Figure I 6 gives the mesopore surface area using equation 1 34 while the slope of the lower linear portion A represents the total surface area of all pores Point C indicates the presence of micropores of about 10A width 2t Sue Sper St 1 59 The linear BET region for microporous materials generally occurs at relative pressures less than 0 1 The linear t plot range will be found at higher relative pressures and is dependent on the size distribution of micropores The micropore surface area Smp then is the difference between the BET surface area and the external surface area from the t plot 4 2 Alpha s Method An empirical analogue to the t method was proposed by Sing who pointed out that comparing a given isotherm to a standard curve does not require invoking the concept of a statistical thickness t which in turn depends on the BET surface area of nonporous reference materials see equation 1 36 Instead similar trends and conclusions to those derivable from t plot figures can be reached by replacing the BET area as a normalization factor by the amount adsorbed at some arbi
66. ds and Monte Carlo simulations bridge the gap between the molecular level and macroscopic approaches The Non Local Density Functional Theory NLDFT and the Grand Canonical Monte Carlo simulation GCMC methods correctly describe the local fluid structure near curved solid walls adsorption isotherms in model pores are determined based on the intermolecular potentials of the fluid fluid and solid fluid interactions The relation between isotherms determined by these microscopic approaches and the experimental isotherm on a porous solid can be interpreted in terms of a Generalized Adsorption Isotherm GATI equation Wmax N P P N P1P W f W aw 1 58 Wun where N P Po experimental adsorption isotherm data W pore width N P Po W isotherm on a single pore of width W f W pore size distribution function The GAI equation reflects the assumption that the total isotherm consists of a number of individual single pore isotherms multiplied by their relative distribution f W over a range of pore sizes The set of N P Po W isotherms kernel for a given system adsorbate adsorbent can be obtained as indicated above by either Density Functional Theory or by Monte Carlo computer simulation The pore size distribution is then derived by solving the GAI equation numerically via a fast non negative least square algorithm The DFT and the Monte Carlo simulation method have largely been applied to the characterization of mic
67. e John Frances 0 Comment Pe Access Level Username and password must be 6 characters or longer ool 2 Hen Figure D 2 Setting user properties for superuser Enter a User ID and a Password both are case sensitive and must have the minimum length specified on the Configure Security window Re type the Password in the Confirm Password box Finally enter the full name of the user in the space provided An entry in the Comment box is optional If all of the required fields in the User Properties box have been filled in correctly the OK button will be active Click the OK button when you are finished After you have created the superuser account the System Login window will appear P N 05079 Rev Page 22 of 133 Nova e NovaWin Operating Manual D SOFTWARE CONFIGURATION NovaWin system login User ID A Tor we gE MS M a a a E r E wit Figure D 3 System login window Enter your Used ID and Password in the spaces provided and click the Login button NOTE You have three chances to enter a correct User ID and Password combination The software will automatically disable the User ID s account L if the NovaWin System Login is failed three times in succession If a superuser s account is disabled and this is the only superuser account for the given installation the software must be uninstalled and then re installed 1 2 Assigning Access Level to New Users D lt Dx After login as the superuser cl
68. e that these sizes refer to the printout size of the whole page MINUS THE HEADER Figure H 18 Selecting the size of a report component The custom report can be assigned to a data file before the measurement by requesting the report to be automatically printed at the end of the analysis To assign the custom report to the open data file activate the Floating Menu click Reports on this menu and click the appropriate report on the submenu When a report is assigned to the data file all graphs tables and metadata data reduction parameters and calculation method summaries will be produced by the software The title of the window will appear as reprt report file name data file name i reprt demo isotherm novaDemo1 gps Click this button to scroll through the individual graphs and tables in the report T z iu E Relative Pressure PyYPo Figure H 19 Selecting graphs and tables available in a report P N 05079 Rev Page 100 of 133 Nova e NovaWin Operating Manual H DATA PRESENTATION NOTE Make sure that you have correctly assigned the necessary data reduction L tags for the models that will be contained in the report If this is not done prior to selecting the report an error message will appear prompting you to add the required data reduction tags 1 6 Saving Tables as Text Any table can be saved as text Right click on the table and then select Save as Text from the Floating Menu T
69. e the relative error decreases with increasing relative pressure Therefore a relative pressure as high as possible yet still in the linear region of the BET plot should be chosen for single point surface area determinations For all except microporous samples a P Po of about 0 3 is preferable For single point determinations on microporous samples a relative pressure as high as possible on the linear BET plot should be chosen C s i l 1 13 Table I 1 gives the relative error for various C values calculated from equation 1 13 using P Po of 0 3 When the C constant is 100 a 2 percent error is indicated P N 05079 Rev Page 105 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION Table I 1 Single Point BET Error Single Point Multipoint Comparison C Constant Relative Error Prior to using the single point method for the determination of surface area the C constant can be evaluated from a multipoint BET plot That is where s and i are the slope and y intercept respectively of the BET plot Subsequently the single point method can be used on materials having the same composition For greater accuracy if the C constant is known the single point result may be corrected using equation 1 12 2 Porosity by Gas Adsorption It is expedient to characterize pores according to their sizes a Pores with openings exceeding 500 A in diameter are called macropores b The term micropores describes pores with dia
70. e used for certain analyses only The station used to measure P is always Station A PU options P mode Measure PO Station Figure F 17 Selecting Measure Po mode Entered Enter the value of Po in the Po field Ambient pressure plus 10 Torr is a good approximation for the Po value For example if the ambient pressure is 750 mm Hg then enter a value of 760 mm Hg PU options PO mode Entered PU value 760 00 mmHg Figure F 18 Entering the Po value Daily The Daily Po option instructs the NOVA to use the last measured Daily Po value in memory The actual Daily Po measurement must be initiated on the NOVA keypad keyboard If this has not been done the defaulted Daily Po value of 770 Torr will be used Before the user can select a Daily Po option using NovaWin a prior Daily Po must be measured On the NOVA display under Measure Options in the Control Panel select Daily Po Insert a 9 mm bulbless cell do not include filler rod in Station A Upon starting the measurement the cell will be evacuated the dewar will rise and the cell will be filled with liquid nitrogen It will proceed to measure the Daily Po Once this is done a Po value resides in memory and is used each time Daily Po is selected for an analysis That value will not change until a new Daily Po is measured NOTE for NovaWin CFR users The superuser must first disable the lockout for L Measure Options in the Control Panel via the System Manager before
71. e Do not show this warning any more box To restore all warnings select Configure gt gt Reset all warnings 3 Locating Data Files During installation an optional database feature can be installed If this feature was installed a database of analyses can be created and maintained to facilitate organizing and locating data files In order to quickly locate specific analysis results the user can specify a number of criteria to select from analysis results stored in the database P N 05079 Rev Page 68 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN Qunatchrome Gas Sorption Data Manager Search Build samb ti sSOS S OOOOOOOO Sample Desc BCR 04 Operator FO Comment Use date range 12 21 2011 2 12 28 2011 Search J IBCR704_AR87_MK2H_ 10105 20100319 qpsc aCdata Physisorb C Thibault Sy i Operator Description BCR 704 Comment Testing Cryostat on ASIG vv filler rod BCRF04_St1_ 77 K_101_20100219 gpscC oCdata Physisorb Operator C Thibault Sample id BCR F04 ent BCR 704 Station 1 on ASi0104 BCR O04_ St1_ ff K_101_20100223 qpsc OCdata Physisorb C Thibault Sample id BCR Test St1 BCR 704 BCR 704 Station 1 on ASi0101 BCR704 St 77K 101 20100219 qpscAdoCdata Physisorb Sample id BCRFO4CryoTest Figure G 4 Searching the Quantachrome Gas Sorption database Enter values in the Sample ID Sample Desc Operator and Comment fields to list only tho
72. e adsorption L and desorption branches of the isotherm Please note that these parameters depend on details of the adsorbent adsorbate system That is the optimal values for a specific system may differ from the recommendations given above 3 4 4 Reporting Tab The Reporting Tab is where you can select an Auto report to automatically appear on screen at the end of the measurement consult Section O of this manual for information on creating custom reports Click the Auto print box if you would like the report to be automatically printed by the default printer connected to the PC at the end of the analysis You may select a different report for each station that will be used in the measurements Sample Points Equilibrium Reporting Auto report lt no autorepork gt Sample Preparation Information Qutgas tine joqg hours Outgas temperature 0 L Ambient temperature 0 0 k Auta report eno auborepork gt rio auboreoork gt Sample Pri demo isotherm demo bet Outgas tir derno total pore volume demo average pore size Outgas ten demo dft dema t plot method Ambient te demo bik Figure F 34 Setting post acquisition reporting parameters Enter the sample preparation information in the spaces provided You may enter sample preparation information at this time or at the end of the analysis If you choose to enter this information later click the right hand mouse button on any open graph or t
73. e data set you wish to show In this example the following selection was made v t Meth ads data data used in the calculation v All ads data all adsorption points Y Best fit best fit line P N 05079 Rev Page 91 of 133 Nova e NovaWin Operating Manual H DATA PRESENTATION This feature can be applied for various linear plots to visually inspect the region of linearity in comparison with all data points 1 2 Configuring Graph Properties You can modify features of the graphs using the Configure Graph Properties window Configure Graph Properties Liep Froperties Uncheck the auto box and you will be able to T modify both y axes _ TmT 0 100 BJH method iE Adsorption MrT mar 5 Desorption auta I S E dvin w Markerspacing 1 a dfr Line properties Global dr Marker Square Graph Colors E d log r Frame BkGrnd dSf log r ne Labels Grid E DH method af i ER Cony Line thickness zj screen inter H erer e TE Figure H 4 Customizing graph attributes You can access this window in two ways 1 Click Display Properties on the Configure menu and then click Graph Properties on the submenu 2 Click Graph Properties on the Floating Menu Graph properties can be set for every plot that is generated by the software Each plot may have different settings such as x and y axes values data point marker style gra
74. e having no micropores as evidenced by the ability to extrapolate the line to the origin since the slope represents the total surface area S of all the pores that is _Vuis 15 47 1 36 tA STP where V a 18 the volume of gas adsorbed corrected to standard conditions of temperature and pressure and the constant 15 47 represents the conversion of the gas volume to liquid volume STP VADS t A Figure I 4 t Plot of a mesoporous material P N 05079 Rev Page 114 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION STP VADS t A STP VADS Figure I 6 t Plot of a microporous material Using the slope s of the t plot as shown above equation 1 36 reduces to S m e sx 15 47 1 37 In the absence of micropores there is good agreement between the t area S and the surface area determined by the BET method P N 05079 Rev Page 115 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION When micropores are present the t plot will exhibit a positive intercept t Plots for two types of microporous materials are shown in Figure I 5 and Figure I 6 Figure I 5 is a t plot of a sample with pore openings smaller than 7 8 A in diameter Quantitative pore volume data from t plots cannot be obtained below t 3 5 A corresponding to pores smaller than 7 A wide since this t value represents the diameter of a nitrogen molecule The intercept I in the t plot when converted to a liqui
75. e narrow pore width and the high adsorption potential The limiting uptake is being governed by the accessible micropore volume rather than by the internal surface area Type II sorption isotherms are typically obtained in case of non porous or macroporous adsorbent where unrestricted monolayer multilayer adsorption can occur The inflection point or knee of the isotherm is called point B This point indicates the stage at which monolayer coverage is complete and multilayer adsorption begins to occur The reversible Type III isotherm is convex to the P Po axis over its entire range and therefore does not exhibit a point B This indicates that the attractive adsorbate adsorbent interactions are relatively weak and that the adsorbate adsorbate interactions play an important role Isotherms of this type are not common but an example is nitrogen adsorption on polyethylene or the adsorption of water vapor on the clean basal plane of graphite Type IV isotherms are typical for mesoporous materials The most characteristic feature of the Type IV isotherm is the hysteresis loop which is associated with the occurrence of pore condensation The limiting uptake over a range of high P Po results in a plateau of the isotherm which indicates complete pore filling The initial part of the type IV can be attributed to monolayer multilayer adsorption as in case of the type IT isotherm II II Amount adsorbed Relative pressure gt Figure I 2 I
76. ed into any part of the instrument or a computer supplied as part of a Quantachrome Instruments instrument are provided as is Quantachrome Instruments warrants the software will perform substantially in accordance with the accompanying materials for the period of this warranty All software is licensed and not sold Quantachrome Instruments retains all rights to all software You may not reverse engineer decompile or disassemble the software You may not distribute or copy the software except for the purpose of storing a back up copy The exclusive remedy for any software failing to perform substantially in accordance with the accompanying materials shall be at Quantachrome s option a repair or replacement of the software b return of the amount paid for the software You are not entitled to any damages including but not limited to incidental punitive indirect or consequential damages including but not limited to loss of profits business interruption personal injury and other pecuniary losses P N 05079 Rev Page 3 of 133 Nova e NovaWin Operating Manual QUANTACHROME INSTRUMENTS TERMS AND CONDITIONS OF SALE Terms Acceptance of this order is conditional on agreement by the Buyer to all terms herein Buyer s agreement is assumed unless we are notified to the contrary prior to our invoicing None of the provisions terms and conditions contained in this document may be added to modified superseded or otherwise changed e
77. ed this way NOTE NovaWin can be used to analyze the data for samples that were run without L the NovaWin software all NOVA files run on the instrument without using NovaWin have the extension dat see Table G 1 2 1 Selecting File Type The NovaWin software supports various file extensions Click the button for Files of type to display the documents that are supported P N 05079 Rev Page 66 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN Look m 4 Physisorb Ej 45 M5 Dema gps Ej novaDemol gps E novabemoz gps E Nova glass gps My Recent Documents Desktop My Documents as My Computer A S as i i Places Quantachrome Physisorption Data documents Cancel Quantachrome Physisorption Data documents Instr data NOVA HS St documents Novain 1 8 data documents Aubosorb AAW data documents Physisorption DAF data documents Physisorption Overlay documents Heats of Adsorption documents Figure G 2 Selecting type of file to open Files of type Below is a table describing file types that can be opened with the NovaWin software Table G 1 File types that NovaWin can open Assigned Quantachrome Physisorption Data Documents Autosorb RAW Data Autosorb physisorption files from AS1 Win 1 x _ Documents or ASWin 1 x Physisorption files generated by newer Quantachrome software Pastis DRED yg Autosorb physisorption Data R
78. ee 65 1 NovaWin Audit Trail Full Compliance Within 21 CFR Part 11 Guidelines 65 2 Openin DATGA O A srt 65 2 1 Seleena Tie Tpi sates secs oa ana A E AOO 66 2 Data PROCESSING WV ARINC raiar an a OTTO ETARA OORO 68 3 Locdune Dua Je eS icri a a E A EE 68 4 Rebuilding Physisorption Database ssssessssessesesesrsesesrsesesrsrsrsresesesetsrststsesrsrersreeeeeereeses 70 5 AE ETET EN E a E E ree ere wear A eer ener te E tee mene are EA E are anon E mere 71 5 1 Gaiph Tables and REPOT irran a AAA OOA TO OOOO OOT xl 6 Ediu ne Analysis Data Mato Manon seisssiisieeirieiiiee iieiaei eiei iieii 71 F Seino Data Reductor Tag Siinsioriiaeasmadig aidsiin oido piaia aaea aiaa 73 8 Bettina Data Red cuon PATAMelers tacacatsucrcssswscnsssdeoonataassoneitnatatarearaadiveresborinteinecsoonenanas 74 8 1 Parameters for NLDFT and GCMC Methods voce ceecsccccsssscccccssssccscesssesescesssesessosseeees 76 8 2 Review or the Data Analysis Methods lt cccceccadudacsnnenaneeaesaonaoeeenauas 77 8 2 1 HK Horvath Kawazoe Method SPF Saito Foley Method eeseseeseeeeneeeeeeeeeees ae O22 JAS Dab init Astakh ov MehnOG ses iendcentcidesecietdisineatdisn vetseanmuceanestedeeus ea e nean 78 8 2 3 BJH Barrett Joyner amp Halenda Method DH Dollimore Heal Method 78 O24 OR Dubin Radu shkevich Methodrasocsononononnnon t anaana NOn Ona nA 78 P N 05079 Rev Page 7 of 133 Nova e NovaWin Operating Manual TABLE OF CONTENTS S25 BEIT Bronauer Toomet amp Teler Meth
79. eeding 205 Torr will solidify argon in the sample cell other than N2 at 77 K or Ar at 87 K that is when using adsorbate that is not at its boiling point do not use the Calculate Po option Instead Enter the appropriate Pmax value A CAUTION When calibrating the empty cell and or during analysis with adsorbate As an example when using Ar at temperature of 77 K which is the boiling point of nitrogen and not of argon the boiling point of Ar being 87 K use the Enter Pg option and enter value of 205 Torr in this case the saturation pressure of argon corresponds to a solid phase and amounts to 205 Torr for an ambient pressure of 760 Torr The recommended Pmax value for argon adsorbate at 77 K is 205 mm Hg Calibrate Cell s Adsorbate Gas PU options Priax Value 205 0 mmHg Sample Temp 77 35 E Figure F 10 Po options for argon at 77K P N 05079 Rev Page 43 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION 2 3 2 4 User Defined Adsorbate Operators of the NOVA 1200 2200 3200 and 4200 4200 P instruments have the option of using adsorbates other than those that are set in the software If the desired adsorbate is not listed in the Adsorbate drop down list in the Calibrate Cell window you can create your own customized adsorbate To do that go to Configure menu and click Manage Materials gt gt Adsorbates Note that the entries for Nitrogen Argon87 and Carbon Dioxide in Adsorbate Parameter dialo
80. elationship between pressure and temperature can be expressed as follows for very low pressures P P2 X VTi T gt 1 59 At higher pressures the empirical model of Liang transpiration corrections for measured pressures P a Box t JT T Ps ag x 8 xti can be employed to calculate thermal 1 60 where x 0 133Pod P P gt are in Pascal d diameter of connecting tube m a 2 52 B 7 68 1 JT is the pressure shift factor that varies for gases relative to the value 1 00 for helium and can be calculated by for helurn 0 27 log log D 9 59 1 61 where D is the molecular diameter of the gas in meters 7 Fractal Dimension Methods Surface characterization methods based on fractal geometry describe the topography of real surfaces in terms of a roughness exponent known as fractal dimension D Ideal surfaces being relatively smooth can be modeled using simple geometric concepts e g 6L for cubes 4R for spheres etc For such surfaces D 2 because the surface area is proportional to X where X is some characteristic dimension of the adsorbent e g X L for squares R for circles etc In contrast real surfaces are generally rough because of atom packing arrangements and defects kinks and dislocations and pores themselves depending on the scale considered Many real surfaces present surface irregularities that appear to be similar at different scales These surfaces are
81. environment With the exception of accessing the degassing stations and aborting sample measurements all functions related to the instrument operation must be performed through the PC Using the System Manager enable all lockouts except Manifold Calibration Main Menu gt gt Calibration Menu gt gt 3 Manifold Calibration and Degas Stations Main Menu gt gt Control Panel gt gt 2 Degas Stations Refer to the NOVA Operation Manual for details on accessing the System Manager on the NOVA P N 05079 Rev Page 16 of 133 Nova e NovaWin Operating Manual C NovaWin SOFTWARE INSTALLATION 1 3 NovaWin Menu System The NovaWin program uses a standard Windows style interface consisting of menus buttons and various dialog windows The main menu bar contains six drop down menus providing access to operations and procedures of the program as well as help Some of the procedures can also be accessed using standard windows shortcut buttons and custom buttons as shown below E Novalin Connected to NOVA 4200 DER Fie Edit Configur Operation Window Help cat Figure C 1 NovaWin main menu bar File Physisorption Overlay Configure Mew Heats of Adsorption Edit Adsorbates Open Edit Adsorbents Reopen FL novaDemo gps Edit Data Reduction Parameters Clear Recent List Display ORAS Graph Properties Set Data Folders Table Properties Manage reports Report Header Properties Printer Setup Operation Window Start Analysis Cascade
82. esssseressssessssseesssssoercssseesssseesessseeees 53 3 4 SI OO Oe ole b v an a mer Parner r i r E errr My Cert E ere ero ree 54 DA ONPE MD eek wit et te aut A A eaten ase van oven ode bane wea eet yebaae tin 54 Br P T 2 eR meen COO UTED Ite CR ORT RE RT ETE EE EEE CRE MEET CE RTT CET ERECT RESET EEE Ura 56 3 4 2 1 Point Selection Surface Area Measurements sseeesseessseeesssssseeeessssssereeessessee si 3 4 2 2 Point Selection Mesopore Micropore Characterization cscs 58 342 5 Patino Daa POS n cca San sean tea Rvcas sacs AOE AONO O ONAA 58 DAD Egulbrum VA tasscsscasarssnciotsssrstoneronnsanesseenstwsaaraesnsatesacovaqescaeaensaaes sasenonsaeteaeniustesstbweneaesiastwaas 59 3 4 3 1 Pressure Tolerance Adsorption and Desorption ssssssessesssesrsrerereersrerrsesreres 60 3 4 3 2 Equilibration Time Adsorption and Desorption seessessssesreresrersrerrsreresreresres 60 3 4 3 3 Equilibration Timeout Adsorption and Desorption eesseseesreeerrrrrrreerrres 60 DAY REPORT AID aee a wie ca A I vial vou sae iat vould ink ube dela 61 4 Start and Monitor Analysis ossis n en ean wit eet nade 61 4 1 Comman eOr WC ON ieee ete tat thet et ih cil ti e 62 4 2 URravciat ce be oY cua tues Yau oim bT cl oh eee eerees em nen eet ene vee een UeERD tr IVER tne Ea ne veg TRE Wea EE 63 4 3 E e e AD r E a A E E E EE E A ma TrnU enya 64 G DATA ANALYSIS USING NOVAWIN n eeneeeseesosssoessossossoossosssosssossosesossssssoseso
83. ether with the Products to a transferee which has accepted this provision of Quantachrome s Terms and Conditions of Sale in writing Changes Orders accepted by the Seller cannot be changed or modified in whole or part except with the written consent of Seller Return Policy Prior approval must be obtained from an authorized Seller representative to return any Product Seller will assign a return authorization number and record the reason for return Seller will examine returned part to determine the actual cause if any leading to Buyer s return If Product has a manufacturing defect Seller will at its discretion repair or replace with like product Restocking charges Product purchased under the sole discretion of the Seller may be returned for a 20 restocking fee and must be returned within 90 days of date of delivery Product cannot be returned if used or modified Claims Claims for shortages or damage must be reported within 10 business days after receipt of shipment All claims for loss or damage in transit must be made against the carrier Warranty Quantachrome Instruments warrants all instruments that it manufactures for a period of twelve months from the date of delivery This warranty includes all parts and labor Quantachrome does not warrant any product against damage from corrosion contamination misapplication improper specification or wear and tear and operational conditions beyond the Seller s control This warra
84. formance which may result there from Taxes Buyer shall reimburse Seller for all taxes excises or other charges which seller may be required to pay to any government National State or Local upon the sale production or transportation of the commodities sold hereunder and amended from time to time Proprietary Information All specifications data drawings designs and software are proprietary information which are the sole and exclusive property of the Seller and purchaser agrees to retain any and all such proprietary information as Seller may disclose to him in confidence and not disclose it to other parties or use it except in inspection and evaluation purposes in connection with a contract with Seller P N 05079 Rev Page 4 of 133 Nova e NovaWin Operating Manual Software License Title to all software provided as separate modules or embedded in the Products Software shall remain the property of Quantachrome or Quantachrome s licensors Quantachrome grants to Buyer a non exclusive limited license to use the Software together with the Products Buyer shall not decompile disassemble or otherwise reverse engineer the Software and may create derivative works only to the extent permitted by Quantachrome Buyer shall not sublicense assign copy distribute or disclose any portion of the Software to a third party without the express written consent of Quantachrome Buyer may transfer or sell its license rights to use the Software only tog
85. g cannot be deleted You can amend the parameters of N butane and Argon77 adsorbates to suit customized applications or create customized User Defined Adsorbates Go to Configure gt gt Manage Materials gt gt Adsorbates click New enter the New Name and adjust the values in all the fields as required Click Save to finish Gf you do not save before closing the window you will be prompted to do so Once the new User Defined Adsorbate is created it will appear in Adsorbate drop down list after the Calibrate Cell window is open the NOVA Operation Manual regarding the use of different adsorbates before proceeding Only non corrosive gases compatible with materials of construction may be used with NOVA If in doubt call Quantachrome Instruments or your local authorized dealer for more information A CAUTION Some adsorbates may be incompatible with the instrument Refer to 2 4 Activate Stations and Run the Calibration 1 Check the Active stations boxes at the top right of the Calibrate Cell s window for the stations that you intend to use in the calibration run with the currently selected adsorbate P N 05079 Rev Page 44 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION 2 Click on the station tab at the top right of the window to define properties of the cell to be calibrated on this station Mark Unmark to Activate Deactivate available stations Active stations iw Ei Active stations Aw EB l
86. he right mouse button was clicked lt Drag sliders to setrange gt Logarithmic TOERE y OK XM Cancel Help Enter Low Limit Enter High Limit Reset to Recommended Reset to Tagged Figure G 21 User Actions menu on the BET Assistant window The display can be changed between linear and logarithmic by checking or unchecking the Logarithmic menu item When the BET Assistant is started it will be automatically set to Logarithmic display if the data span 3 or more decades Selecting Reset to Recommended will revert to the original recommended values and Reset to Tagged will revert to the range defined by the M tags set prior to entering the BET Assistant Once the desired range is selected click OK to set M tags to all adsorption points within the highlighted range or Cancel to return without making any changes P N 05079 Rev Page 83 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN 8 2 6 Langmuir Surface Area Tags L If you desire to calculate the Langmuir surface area for the sample set the appropriate data points with the L tag 8 2 7 t plot Statistical Thickness Method MP Method alpha s Method Tags T Click the t MP alpha s tab on the Data Reduction Parameters window to access parameters for these methods Data Reduction Parameters BJH DH 04 0R HK SF DFT Monte Carlo A V Summary Unita Display General Adzorbate Adsorbent MF alpha s method
87. his will open the standard Save as window with Exports as default folder These text files can be imported into spreadsheet and other programs for further display and analysis Alternatively Export to CSV can be selected This will open the standard Save as window with Exports as default folder These are text files with a list of data values separated by comas These files can easily be imported into spreadsheet and other programs for further display and analysis 1 7 Changing Header Information lt The following is an example of a report header and Reduction Quantachrome NovaWin Data Acquist lt for NOVA instruments 1994 2012 Quantachrome Instrum version 11 02 Ma Quantachrome INSTRUMENTS Pi If you wish to insert a company logo in the header it will appear here The logo will appear only on the printout not on screen This part of the Header may be changed Figure H 20 Sample report header To change the information at the top of the Header that is displayed on screen and on each printed page of the report click Display Properties on the Configure menu and then click Report Header Properties on the submenu This will activate the following window Report Header Properties Click here to remove the custom logo Click here to enter a graphics file for your company logo Header T ext Add your header text here Company Logo x
88. hysteresis are often disordered and the distribution of pore size and shape is not well defined Isotherms revealing Type H3 hysteresis do not exhibit any limiting adsorption at high P Po which is observed with non rigid aggregates of plate like particles giving rise to slit shaped pores The desorption branch for Type H3 hysteresis contains also a steep region associated with a forced closure of the hysteresis loop due to the so called tensile strength effect This phenomenon occurs for nitrogen at 77K in the relative pressure range from 0 4 0 45 Similarly Type H4 loops are also often associated with narrow slit pores but now including pores in the micropore region The dashed curves in the hysteresis loops shown in Figure I 3 reflect low pressure hysteresis which may be observable down to very low relative pressure Low pressure hysteresis may be associated with the change in volume of the adsorbent 1 e the swelling of non rigid pores or with the irreversible uptake of molecules in pores of about the same width as that of the P N 05079 Rev Page 108 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION adsorptive molecule In addition chemisorption will also lead to such open hysteresis loops An interpretation of sorption isotherms showing low pressure hysteresis is difficult and an accurate pore size analysis is not possible anymore But also the hysteresis loops usually associated with pore condensation imposes of
89. ibility to the features of the NovaWin CFR software Superuser level Operator level Manager level Symbols with an X marked through denote that the feature is not accessible for users at that security level Each user account is assigned a level of access at time of creation The Access Level can be changed by superuser level administrators through the User Manager window P N 05079 Rev Page 24 of 133 Nova e NovaWin Operating Manual D SOFTWARE CONFIGURATION 1 3 Change Password o Click Security on the Configure menu and then click Change Password This will open the system login window NovaWin system login User ID cthibault ags ods E ks Lon Se Se ee ee eS L UE E E A E E E E Ea a 7 E wit Figure D 6 System login window Enter your current password and click Login In the following window enter a new password and confirm The new password must be different from the last n passwords where n is the number of passwords remembered by the program User properties User ID cthibault i Password Iv Confirm password Expires 2012 01 18 Username and password must be 6 characters or longer Figure D 7 User properties window for changing password 1 4 Viewing the Security Log From the Configure menu select Security gt gt View System Log This will display the security messages in a window like the one in Figure D 8 The display may be narrowed down to a specific time
90. ibution to the total pore volume and the surface area of the sample the average pore size can be estimated from the pore volume For example assuming cylindrical pore geometry Type H1 hysteresis the average pore radius rp can be expressed as _ 2V tig 1 15 S Where Vj is obtained from equation 1 14 and S is the BET surface area For other pore geometries a knowledge of the shape of the hysteresis in the adsorption desorption isotherm is required F p 3 2 Pore Size Distributions Mesopore The distribution of pore volume with respect to pore size is called a pore size distribution It is generally accepted that the desorption isotherm is more appropriate than the adsorption isotherm for evaluating the pore size distribution of an adsorbent The desorption branch of the isotherm for the same volume of gas exhibits a lower relative pressure resulting in a lower free energy state Thus the desorption isotherm is closer to true thermodynamic stability In certain cases for example samples exhibiting Type H2 hysteresis the adsorption isotherm is recommended for pore size distribution determinations The NovaWin software offers the capability of using either branch of the isotherm for the calculation Since nitrogen has been used extensively in gas P N 05079 Rev Page 109 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION adsorption studies it has been well characterized and serves as the most common adsorbate for po
91. ick Security on the Configure menu and then click User Manager This will open the User Manager window User ma naver The Properties and Delete buttons are active un grayed only after a User ID is highlighted Figure D 4 User manager window Click New to open the User Properties window see Figure D 5 Enter the required information into the fields provided User ID Password Confirm Password Full Name P N 05079 Rev Page 23 of 133 Nova e NovaWin Operating Manual D SOFTWARE CONFIGURATION User properties User ID alchemist z Password pees Confirm password pee Expires APA Full name Alchemist Comment Pe Access Level operator operator Account disabled manager SLPEIUSer Username and password must be 6 characters or longer x Cancel Help Figure D 5 Setting user properties for new users NovaWin CFR has three Access Levels Superuser Manager and Operator Click on the Access Level button and select the level from the list Superuser users in this level have full control of the system including defining and managing user accounts Manager users in this level are allowed to change most of the configuration options but cannot change user assignments Operator users of this level are allowed to operate the software however they are forbidden to change most of the configuration options Throughout this manual the following symbols will be used to denote access
92. ion Cross over Pressure Gans AA S 0 0 rn This area points out options specific for the Nova Mode not present in Helium Mode a en EEEE Active stations fh Load Preset Load Preset Aly B Ok C Hel iv a a F S Save Preset Z x A Figure F 14 Selecting Pp method when running in Nova Mode 3 2 1 Sample Volume For the operation in the Nova Mode you will need to use pre calibrated sample cells as well as to select the option for determination of the volume of each sample in each cell choose Calculate or Measure in the Sample Volume box as shown in Figure F 14 Note that this selection will apply for all the stations Therefore if you choose to calculate the volume you will also need to provide the Density for each of your samples see Section F 3 4 1 This option is not necessary thus NOT available in the case of Helium Mode Model 26 3 3 Common Setup Helium and Nova Modes Select the Operator ID and the adsorbate gas as they must be the same for all stations L NOTE In secure mode in case Login Required is specified the operator ID cannot be changed L NOTE Depending on the analysis mode specified in the Analysis section some of these pages may not be available Note 3 3 1 Select Adsorbate Gas Click the Adsorbate Gas drop down list button V to select the adsorbate gas P N 05079 Rev Page 48 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION Adsorbate Gas Nitrogen
93. ion method on Kr 87 K adsorption isotherm data as measured i e the experimental saturation pressure corresponds to the sublimation pressure of krypton at 87 K the following steps need to be applied 9 Open the data file in the NovaWin software 10 Select as an adsorbate Krypton87 check that Krypton 87K is stated as Adsorbate otherwise check the box Override Analysis Gas Parameters under Data Reduction Parameters 11 Apply P tags to the adsorption data points you want to include in the pore size distribution please note that the method is not applicable to desorption data Please make sure not to include data from potential bulk sublimation transition indicated by a steep step in the isotherm close to or at the saturation pressure 12 Select Kr 87 Thin film PS method graph or table from the floating menu and then display the PSDd preferably as dv logd see Figure G 23 and Figure G 24 graph lsotherm Linear Thin Film_Demo_ordered_silica qps Isotherm Linear Tables b Isotherm Reports b BET t Plot method Langmuir DR method Alpha S method Graph Properties MP method Overlay BJH method Curves ay Kr 87K Thin Film PS method dvd Zoom To DH method dv log d Unzoom HK method ee SF method DA method DFT Monte Carlo Fractal Dimension Methods Edit data tags Data Reduction Parameters Analysis Data gt o 2 a wo E w 2 0 60 0 64 0 67 Relative Pressure P Po Figure G 23 Analyzing
94. is OK dh Insufficient persmissions to folder Contact your system administrator Ao Folder does not exist Modify entry Figure D 13 Selecting default folders for data Whenever a file of these types is being opened saved the file selector dialog starts in the specified folder The list entries on the top of the window display the current path setting for each folder recognized by the software To change the default location click on the Select Path button or double click on an item in the list and using the standard Windows type folder locator dialog navigate to the desired folder and then click on the Select button See your operating system documentation for a detailed explanation of file system security and access rights Clicking Cancel will close this window without saving the changes and OK will save them The OK button is grayed out when there is any problem in the list When this window is invoked automatically upon starting the software it indicates that the software found problems with some of the folder definitions In this case closing the window with the Cancel button will exit the software as well In case there are problems and the current user is under management level a message window pops up describing the problem and requesting that a higher level user be logged in to correct the indicated problems P N 05079 Rev Page 31 of 133 Nova e NovaWin Operating Manual E SAMPLE PREPARATION E SAMPLE PREPAR
95. ith the file name specified in File Name box of the Sample window Sample ID Enter the sample identification in this box Sample Weight Enter the weight of the sample in grams in this box Comments If desired enter any comments specific to the analysis into this space Note that this is not a required entry field to initiate the sample measurement s In the case of Nova Mode operation for each station also select correct Sample Cell Additionally if you prefer to Calculate the Sample Volume see Section F 3 2 1 for each sample enter value of Density Common Stations Sample Yolume Volume Calculation f Calculate Measure Density 1 00000 g mL Figure F 28 Entering Density when Calculate Sample Volume is selected Entering information about density of each sample is unnecessary option grayed out when for each of them Sample Volume is Measured Common Stations Sample Yolume Volume Calculation C Calculate Measure c gt Density g mL Figure F 29 Entering Density is unnecessary when Measure Sample Volume is selected Load Save Station buttons The Save Station feature allows you to save all of the information on the Sample Points and Equilibrium tabs If you choose to use this feature it is recommended to leave the Sample tab information blank and enter only the information for the Points and Equilibrium tabs prior to saving the setup Otherwise the information on the Sample tab will be sa
96. its boiling point the available Po options are limited n Butane Enter the bath temperature 273 15 K is recommended and the Po value Adsorbate Gas H Butane PU options PO value 760 00 mmHg Sample bath Temp 273 1 z E Figure F 20 Po setting for n Butane P N 05079 Rev Page 51 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION CQO Enter the bath temperature only 273 15 K is recommended Adzorbate Gas r PO options Sample bath Temp 273 15 E Figure F 21 Po settings for carbon dioxide Argon77 that is the argon adsorbate at temperature of LN the following Po options are available Adsobate Gas agon7 PO options PO mode PO Station Continuous Figure F 22 Po options for argon at 77K L NOTE For individual description of each Po option refer to Section F 3 3 2 1 NOTE If you chose to ENTER the Po for Argon77 Ar adsorbate using LN bath L at 77 35 K you must enter Pp 205 Torr In this case at 77 K the saturation pressure of argon corresponds to a solid phase and amounts to 205 Torr for an ambient pressure of 760 Torr Adsorbate Gas Argon PO options PO mode Entered PU value 205 00 mmHg Figure F 23 Entered Po value for argon at 77K NOVA 2000 Series users may choose either Station A or Station B to conduct the Continuous Po measurements during the run For NOVA 3000 and 4000 Series users the highest remaining Station letter available wil
97. ium is the classical method used in many non vapor gas sorption instruments See Analysis Parameters This method allows omitting a calibration of an empty cell in advance of a measurement but does require access to properly pressure regulated high purity helium at least 99 99 If you want to use the Helium Void Volume method please make sure that a Helium tank is connected to the NOVA Instrument To select the Helium Mode open Communication Setup window go to Operation gt gt Instrument Settings Mark this box to Communication Setup select the He Select communication port COMT Mode x Cancel Help Figure F 1 Selecting helium mode NOTE Cell calibrations are not required for the He measurement therefore L during operation in the helium mode the Calibrate Cell option is not available grayed out 2 2 Cell Calibration Nova Mode Ds An individual sample cell or cell type stem diameter amp bulb size must be calibrated prior to an analysis This needs to be conducted for each sample cell filler rod station combination and for each adsorbate coolant combination Once this is done there is no need for further calibration for that particular combination This calibration is essentially a 25 point blank analysis 1 e without sample All the characteristics of the empty cell or cell type are saved into a cell calibration file named ACURVE OXX where XX is the unique identifying number of the
98. k Copy to mark the currently selected item as the source select the target and click Paste to copy the properties of the source to the target Source and target must be the same type of node only graph to graph or line to line copies are allowed If there is no proper source selection made the paste button is grayed e For lines the color and marker selections are copied e For graphs all graph specific properties and a list of line properties are copied If the target has more lines than the source the lines that have no matching counterparts will be reset to default values black line with no marker If the source has more lines the excess line property data is ignored Click Save to store the current settings to permanent storage otherwise the changes made will be lost when the program is closed Click OK to return to the main window of the program and apply all changes made Ls Imb To change the appearance of tables displayed on the screen or printed select Configure gt gt Display Properties gt gt Table Properties from the main menu This will open the P N 05079 Rev Page 93 of 133 Click Cancel to discard all changes made in this window 1 3 Configuring Table Properties Nova e NovaWin Operating Manual H DATA PRESENTATION Table Properties window shown in Figure H 6 The font may be selected from the pull down list in the Use font field or click on Select Font to open a dialog to set the font and font properties
99. keyboard NOVA 4200 P superusers should keep the access to the degasser enabled do not lockout this function in the System Manager Vacuum Degas Weigh an empty cell add sample sufficient for 2 50 m total area place the sample cell in the pouch of the heating mantle set clamp in place insert cell into fitting and tighten fitting Load the degasser and pull vacuum on the sample for at least 10 minutes Next set the temperature select to the required degas temperature see below on choosing an outgassing temperature and switch the heating mantle on After sufficient time for complete outgassing switch the mantle off Allow sample cell to cool Unload degasser when ready to analyze sample Remove cell reweigh to obtain dry outgassed sample weight Flow Degas The apparatus shown in the Figure E 1 below must to be attached for flow degassing P N 05079 Rev Page 32 of 133 Nova e NovaWin Operating Manual E SAMPLE PREPARATION Needle valve flexible tubing flexible tubing Collar Stop ka Knurled metal insert Metal flow tube Figure E 1 Flow Degasser Assembly Use 6 mm O ring adapter sleeve to mount the metal insert into the fitting The gas flow rate can be set by placing the metal flow tube into a beaker of water and adjusting the needle valve to set a flow of 1 2 bubbles per second For fine powders the needle valve may have to be readjusted so sample particles are not carried out of the sample cells Turn the v
100. l be the dedicated station for the Continuous Po measurements As an example if you are using a NOVA 4000 and you wish to use Stations B and D as the analysis Stations Station C will be the station for the Continuous Pp measurements For NOVA 3000 Series users Station C is the default station for the Pp measurements using Continuous Po while for NOVA 4000 Series users Station D is the default station for the Continuous Po P N 05079 Rev Page 52 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION measurements Continuous Pp measurements should be made using an empty 9 mm bulbless cell without filler rod NOTE When using a gas other than N2 77 K or Ar 87 K i e an adsorbate which is not at its boiling point the Calculate Pp option in unavailable while calibrating the empty cell or during the physisorption run As an L example when using Ar Adsorbate at 77 K which is the boiling point of nitrogen the boiling point of Ar being 87 K use the Entered Po option in the analysis setup and enter a value of 205 Torr In this case at 77 K the saturation pressure of argon corresponds to a solid phase and amounts to 205 Torr for an ambient pressure of 760 Torr NOTE If you are using a coolant other than LN e g LAr you must be sure to L obtain and install the correct coolant level sensor see NOVA instrument manual 3 3 3 Thermal Delay Enter the length of Thermal Delay in the range 180 1200 seconds Thermal Delay
101. l button to highlight the data points clicking the M Multi BET flag and then click the Apply to selected button 3 4 2 2 Point Selection Mesopore Mictopore Characterization Mesopore characterization measurements require the measurement of the full isotherm that is from approximately P Po 0 025 to P Po 0 99 for the adsorption branch and 0 99 to 0 1 on the desorption branch It is recommended to measure both the adsorption and desorption branches of the isotherm Information such as the sample s specific surface area pore size distribution average pore size and total pore volume can be obtained from these data see Section G 7 In order to increase the resolution of the pore size analysis it 1s recommended to increase the number of selected data points for the upper regions of both the adsorption P Po of 0 60 0 99 and desorption branches of the isotherm P Po of 0 99 0 60 Selecting the data points for a full isotherm is similar to the point selection procedure discussed in the preceding section Points may be entered either individually Add point and or as an evenly spaced group Spread points Both adsorption and desorption points should be added Additional data reduction flags may be set by highlighting them using the normal windows multi select method and then clicking on the appropriate flags for each range and clicking the Apply to selected button L NOTE Adding and or removing data reduction flags can be done after the
102. leted the Delete button is disabled for these models L NOTE The delete operation is not reversible once a model is deleted it cannot be restored Click Close to leave the window and return to the main program If you have not saved changes at this time you will be prompted NOTE The Name of the adsorbate represents the model adsorbate defined by the set of model Adsorbate Parameters One adsorbate gas may have several L Names representing different sets of Adsorbate Parameters For example if an adsorbate is used at several temperatures some of its parameters will be different for different temperatures 2 2 Edit Adsorbent Parameters To view or modify the adsorbent model parameters click Manage Materials gt gt Adsorbent on the Configure menu This will open the Adsorbent Parameters window P N 05079 Rev Page 28 of 133 Nova e NovaWin Operating Manual D SOFTWARE CONFIGURATION Adsorbent Parameters Hame Carbon b Carbon Oxygen eolite Atom diameter 0 340 ami 7 Polarzability i O20 cc mol x 1e 24 Magnetic susceptibility 3 500 cc mol x 12 29 Surface atom density 38 450 moliem s 1e 14 Adsorbent density 2 246 ace DA exponent ri 2 000 qe New nfs Copy Figure D 12 Setting the Adsorbent model parameters There are two predefined adsorbent models in the NovaWin software Carbon and Oxygen Zeolite To modify or add new models follow the steps analogous to those described above for
103. librium and Reporting Here the user must enter specific information and setup parameters individually for each station active in a given physisorption run From the Stations tab Start Analysis Click Stations to set up individual K aea Sl options for each station sub tab to enter specific information for each active station Common Stations sample Points E quiibrium Reporting igure F 26 The four tabs on the Stations panel 3 4 1 Sample Tab Depending on the mode selected earlier Nova or Helium model 26 only the Sample sub tab may or may not model 26 only contain Sample Cell selection and Volume Calculation option Click here to select an active station Start Analysis Common Stations Sample Paints Eqgulibriurn Reporting Station A pacoeeecceecs Le Hame str lt STN gt ho hEds Very ss Pre calibrated ae a f Volume Calculation oe ae bees lt 2 setup option is only selection box is feseniption gt present in NOVA Mode only present in weight 0 10000 g p Wolume Calculation Pe Nova Mode A Density 1 00000 g mL Ns in cae ae ef oy eh oe earn cell Comment PE HL Load Station fe Save Station Active stations Load Preset r ames L m _ sat eee Preset 2 X Canos A _ 2 Heb Help Figure F 27 Sample tab showing sections only available in NOVA mode Regardless
104. low verification of multipage documents integrity as well via the unique report id and printing page number and total number of pages on each page To simplify printouts the icons are replaced by the printable characters listed above References to the audit trail feature for NovaWin CFR users will be made throughout this section of the manual where appropriate 2 Opening Data Files Ls I e To start using the NovaWin software for data analysis first open the desired data file To open a data file click the Open Folder Icon S on the Main menu bar or click Open on the File menu By default NovaWin stores the data files in the Physisorb folder see Section D 3 P N 05079 Rev Page 65 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN r My Recent E Carbonz gps Documents E Carbona E Hw 2006 02 09 01 0P5 E Hw 2006 02 13 _01 0P5 E nowaDemol gps E novabDemos gps E Sill gps E test gps Ej beste gps Places a Files of type Quantachrome Physisorption Data documents Cancel Figure G 1 Physisorb folder where data are stored Select one or more files and click Open Alternatively to reopen recently opened files click Reopen on the File menu or click the T Reopen Folder Icon on the Main menu bar Additionally NovaWin software allows opening any known data file by simply dragging and dropping one from Windows Explorer into the NovaWin main window Multiple files can also be open
105. m is to be measured click on the Equilibration Time box under the Desorption column and enter the desired value Longer equilibration times may be necessary for relatively large sample weights gt 1g and for samples with low thermal conductivities 3 4 3 3 Equilibration Timeout Adsorption and Desorption If the pressure tolerance is not met and the pressure does not fall below the lower pressure limit upper limit for desorption within the time specified by the Equilibration Timeout the data point will be taken The acceptable equilibration timeout range is from at least twice the equilibration time to 5400 seconds Click on the Equilibration Timeout box under the Adsorption column and enter the desired value If only a surface area measurement is required only the equilibrium conditions for the Adsorption portion of the isotherm need be specified If a full isotherm is to be measured click on the Equilibration Timeout box under the Desorption column and enter the desired value The recommended value is two times the equilibrium time P N 05079 Rev Page 60 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION Longer times may be necessary for relatively large sample weights gt 1g and for samples that exhibit low thermal conductivity high surface area and or large pore volume NOTE It is advisable to use the same equilibration parameters pressure tolerance equilibration time and equilibration timeout values for both th
106. m run to run until you click the Clear button This action will erase all messages from the display The log file whose name and path are displayed on the bottom of the Communicator window will continue to save the messages A new log file 1s created whenever NovaWin is started This log file contains valuable information that can be used in troubleshooting problems with the analysis Communicator Click this box Saved in C User Contig 043 for the Checking Integrity of Vacuum System Building Test Pressure Communicator Evacuating System window to Vacuum system Integrity Test PASSED appear automatically This file path shows where after the the messages have instrument automatically been saved performs a function Log CVO Cdata Noval inchgsh LOG 200701244 01 log Popup 4 Clear E Print Help Figure F 36 Instrument messages display 4 2 Instrument Status Window If the status of the instrument is desired at any point during a cell calibration or sample measurement go to Operation on the Main Menu Bar and select Instrument Status or simply press the F8 key This window will display the progress of the analysis for each of the stations that are being used and the number of points that have been acquired thus far in the measurements Click OK to exit the Instrument Status window A Running 0 B Running 0 C Running 0 D Running 0 Instrument status received
107. meters not exceeding 20 A c Pores of between 20 500 A are called mesopores Porosity of powders and other porous solids can be conveniently characterized by gas adsorption studies Two common techniques for describing porosity are the determination of total pore volume and pore size distribution For the evaluation of the porosity of most solid materials nitrogen at 77 K is the most suitable adsorptive 3 Isotherms Based upon an extensive literature survey performed by Brunauer Demming Demming and Teller BDDT the IUPAC published in 1985 a classification of six sorption isotherms The appropriate IUPAC classification is shown in Figure I 2 Each of these six isotherms and the conditions leading to its occurrence are now discussed according to Sing et al The reversible Type I isotherm is concave to the P Po axis and the adsorbed amount approaches a limiting value as P Po gt 1 Type I isotherms are obtained when adsorption is limited to at most only a few molecular layers This condition is encountered in chemisorption where the asymptotic approach to a limiting quantity indicates that all of the surface sites are occupied In the case of physical adsorption sorption isotherms obtained on microporous materials are often of Type I Micropore filling and therefore high uptakes are observed at relatively low pressures P N 05079 Rev Page 106 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION because of th
108. mperature would be that which lies in a plateau or weight stable region of the thermogram Ideally the thermal analysis should be conducted under vacuum In general too low a degassing temperature will cause lengthy preparation and may result in lower than expected surface areas and pore volumes Too high a temperature can cause irreversible damage to the sample which can result in a decrease in surface area due to sintering or an increase in surface area due to a thermally induced decomposition Time for complete degassing that is complete removal of unwanted vapors and gases adsorbed on the sample surface can only be properly determined by conducting a series of tests to determine those conditions of temperature and time which yield reproducible data As a general guideline however three hours at temperature should be considered a reasonable minimum IUPAC recommend no less than sixteen hours which can be conveniently achieved overnight Samples that require low temperatures generally require the longest outgas times However the USP recommended degassing period for magnesium stearate is just two hours at 40 C 4 Elutriation and Its Prevention Elutriation or loss of powder out of the sample cell is caused by too rapid a gas flow out of the cell It is most problematical for low density samples fumed silica for example Wider stems and larger bulbs can be beneficial in reducing elutriation Wider stems reduce the velocity of the
109. mple because of the extreme curvature of the ca 0 5 nm pore channels and the relatively large size of the probe molecule the BET analysis underestimates the true surface area Conversely in broader super micropores gt 0 7 nm a number of molecules those filling in the center of the pores do not touch the surface and this leads to an overestimation of the surface area Therefore the surface area obtained by applying the BET method on adsorption isotherms from microporous solids does not reflect the true internal surface area but should be considered as a kind of characteristic or equivalent BET area The application of the BET method is also problematic for estimating the surface area of mesoporous molecular sieves of pore widths less than ca 4 nm because pore condensation 1s observed at pressures very close to the pressure range where monolayer multilayer formation occurs on the pore walls This may again lead to a significant overestimation of the monolayer capacity hence surface area when using the BET method In any case the range of linearity for the BET plot over which the surface area is calculated must be reported with the surface area The question remains of how to find the linear range of the BET plot for microporous materials in a way that reduces any subjectivity in the assessment of the monolayer capacity This was addressed by Rouquerol et af who suggested a formal procedure based on the criteria that 1 P N 0507
110. n open plot or a table associated with this file to activate the Floating Menu see Section G 2 2 Click Edit data tags on this menu to open the Edit data points window see Section G 7 Add or remove appropriate tags in this window Click OK when you are finished This will automatically update all the open plots and tables related to the modified data To help you make appropriate modifications in the tag selection the software enables you to show or hide data points for a given plot For example Figure H 3 shows a t plot for novaDemol qps the demo data file found in the C QCdata physisorb folder upon installation of the software As a general guideline the linear region for the t method calculation is typically between 0 2 and 0 5 P Po However it may extend to higher or lower relative pressures graph t plot novaDemol gps All adsorption points marker open circles Tagged data points for the calculation marker filled circles Graphs Only the checked Tables data set sets will Reports ii appear in the plot View Audit Trail Edit data tags a Ti 5 mh e w ea a E Data Reduction Parameters Analysis Data Best fit line eco Overlay Curves w t Meth ads data Zoom To t Meth des data Unzoom ALL ads data Oooo M ALL des data v Bestfit Figure H 3 Sample t plot To select curves points for viewing right click on the plot then click Curves on the Floating Menu and on the submenu select check th
111. nd or the points clearly do not fall on a straight line the point range should be adjusted as described below P N 05079 Rev Page 80 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN HMult Point BET Plot 0 000e 00 B 000e 02 1 200e 01 1 600e 01 2 000e 01 2 400e 01 2 800e 01 3 300e 01 Relative Pressure PPa Figure G 17 Typical BET Plot 8 2 5 1 The BET Equation and Micropores The BET equation is certainly applicable to nonporous solids and materials consisting of pores of wide pore diameter But in a strict sense it is not applicable to microporous adsorbents Notwithstanding the problems arising from the chemical and geometrical heterogeneity of the surface the type of porosity 1 e macro meso or micropores therefore plays an important role in the applicability of the BET equation The problem is that it is difficult to separate the processes of mono multilayer adsorption from micropore filling usually completed at relative pressures P Po below 0 1 Another problem is associated with the size and shape of adsorptive molecule 1 e the effective yardstick used to assess the surface area In case of very narrow cylindrical micropores ultra micropores lt 0 7nm the area calculated by the BET analysis to be covered by the adsorptive is significantly smaller than the total geometric area Take ZSM 5 an aluminosilicate zeolite used as an isomerization catalyst in the petrochemical industry for exa
112. not use the Calculate Po option while calibrating the empty cell or during analysis AN HOT Never handle hot mantle cells or clamps with your bare hands e Operate this instrument only at the voltage specified on the nameplate on the rear of the instrument e Inform yourself regarding hazards associated with the sample under test e Inform yourself regarding hazards associated with the gas es used e This instrument must be disconnected from the mains for any cleaning maintenance or Service e Do not make any unauthorized modifications to this instrument e When attaching a plug to the power cord be sure to follow the color code shown below Brown live blue neutral green yellow earth ground 3 Safety Instructions for the Heating Mantle e Quantachrome heating mantles are designed for heating sample cells for the purpose of outgassing solid samples and only on Quantachrome instruments equipped for the same purpose Use only on instruments with properly functioning calibrated heating mantle stations e Insert the power plug of a heating mantle only into the socket provided for that purpose on a Quantachrome instrument Do not insert the power plug of a heating mantle into any mains supply socket Do not insert the plug of any other device into the heating mantle socket on the Quantachrome instrument e Insert the thermocouple plug of a heating mantle only into the socket provided for that purpose on a Quantachrome instrumen
113. ntial theory of adsorption Dubinin and Radushkevich postulated that the fraction of the adsorption volume V occupied by liquid adsorbate at various adsorption potentials can be expressed as a Gaussian function V V exp A 1 42 where A is the free energy of adsorption which in the early Dubinin s works was called adsorption potential A e RTIn P P 1 43 In equation 1 42 Vo represents micropore volume Eo is the so called characteristic energy of adsorption and is the affinity coefficient which can be approximated by a ratio of the liquid molar volumes v of a given adsorbate and benzene used as the reference liquid 7 B 1 44 Vc6H6 Equation 1 42 can be written in the following linear form 2 logo V log V 204 2T log By PY 0 1 45 which shows that micropore volume Vo and Eg parameter can be calculated from the linear fit of the isotherm data plotted as log V vs log Po P Intercept of the fitted straight line gives log Vo while its slope m can be used to calculate Eo p 2303 RT 1 46 ee as m p The linear range for these plots is usually found at relative pressures of less than 10 Based on empirical studies Dubinin and Stoeckli proposed that Ep can be related to the characteristic micropore width for a carbonaceous adsorbent by the following simple formula Pore Width 26 kJ nm mol Eo 1 47 The linear form of the DR equation was also used by
114. nts in the isotherm Tags Add point on off iz reset AL Adsorption l D Desorption Spread paints MT Multi BET Jo 5 Single BET Tl Thickness Crt m Pore volume L Langmuir P Pore size Ai DR amp Fractal Enter points individually in this space and click the Add button All data points must have at least an A ora D tag selected Enter the lower limit in the left box and upper limit of the P Po points in the right box Then enter the total number of points in the Cnt Count field Finally click the Add button HL Load Points Figure F 31 Setting points individually or setting a range of points NOTE Data point flags are used in the software to denote whether a point is an adsorption point a desorption point Thus any data point that is selected must have at least an A flag Adsorption or a D flag desorption set If L neither of these flags is present the Add buttons will be grayed out and thus will not function Data point flags are also used in tagging specific points for inclusion in the various data reduction calculations models offered in NovaWin These flags may be added after the experiment 3 4 2 1 Point Selection Surface Area Measurements If only a Single Point BET is required click the A Adsorption flag and the S Single BET flag then enter the desired P Po point usually at P Po 0 3 Finally click the Add button The data point selected
115. nty excludes all glassware and expendable items associated with each instrument Repairs made during the warranty period are guaranteed until the end of the warranty period or 90 days whichever is greater P N 05079 Rev Page 5 of 133 Nova e NovaWin Operating Manual TABLE OF CONTENTS TABLE OF CONTENTS As INTRODUC PION iit ei eis kA Re 9 1 SUNNA Ol F eA UTO 6 tice se octara iia racic esom asain oat etn seem eae memnatae 9 2 Fece e P E e a EA EEN NEA 10 BSAFE TI ea E ssa ata ein pete sons ene enone news 12 1 Sym boR W Sec tra Cia STA case Spe etn sd estes hutdea ade geen bude dcdpued ease sd cake Sab 12 2 wateby histuctions Tor Me NOVA gasses ticks scabs nai ea aaeain eai 12 3 Safety Instructions for the Heating Mantle sssssssesssssssrseseeesesererrersesrsresrsrserreerseseereersens 13 C NOVAWIN SOFTWARE INSTALLATION csccccccccccccccccccccccsscccsceees 16 ips Nova Wart Pros rant GD ssstckcscsecs trac nR I Aan EEA 16 1 2 NOVA P Instrume rr N R 16 1 3 Nova a Menu S yS e iena A a Le 1 4 Peas er ete G26 fille CLIO iss cast ta ss ccateuatanscocstsusaeusacasscostcunesascauketuaseabedaaasuneduatauteaseasaduascusenantuuss E D SOFLWARE CONFIGURATION sinea 21 l Configuration of NovaWin CFR security features essssessesesesesseeereeeresrersrsrseserrrserreeess 21 1 1 Kucalsccun t COnMOULAON eee i ae E E A E 21 t2 Asson ne ACeS evel tO New Usetsis sien isisontsmuntenunenuninienaninunientniniensines 23 1 3 Dae ASS E E E E E
116. ocess is complete the Close button can be used to leave the feature or selecting the Search tab will return the user to the Database Search function P N 05079 Rev Page 70 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN 5 Floating Menu The Floating Menu is the main navigating tool used to obtain tables plots and reports including raw data as well as results calculated using various methods To activate the Floating Menu right click on an open graph or a table associated with a given measurement data file The Floating Menu will give you an access to the results related to this file If you right click on a document associated to another data file you will gain access to the results from that file 5 1 Graphs Tables and Reports Graphs d Raw Data Graphs Tables r Isotherm Tables Isotherm Reports d BET Reports BET View Audit Trail Sie i View Audit Trail ic Edit data tags anmu Edit data tags ea i Data Reduction Parameters oe oenen Data Reduction Parameters a aa Analysis Data Alpha 5 method j Anya Daia Alpha 5 method MP method j MP method Sapi DopE BJH method SERRA EL BJH Pore Size Distribution Overlay Kr 87K Thin film PS method Overlay Kr 87K Thin film PS method gt agai DH method coe DH Pore Size Distribution Gri lE HK method aint HK method papal SF method fna SF method DA method j DA method DFT
117. od anonimionot n a n n n a n EAn 80 8 2 5 1 The BET Equation and MictopOt Siriei an aa OE 81 oz SDT ey O16 GAN se aces ae kre ns ta ate dae s eae ase tos ata Rae gs testes testes dad 82 O20 AAO SU ACEA cate sicstcsatntscsntatatoensstatcoteneansaaseiabotyntensainun tant iaoroenenasancenesanets 84 8 2 7 t plot Statistical Thickness Method MP Method alpha s Method eee 84 8 2 8 FHH Frenkel Halsey Hill Method NK Netmark Kiselev Method eee 85 O29 Oral Porte Viola Aie si t d cds tones Ata docs delete dete o dcndeta duty bie Aa A 85 lO a isos 18K em bg Od ona A caper ea eer RMSE a IPO RTT TaP OT A TERT Renae 85 Alk Kaen Thin Film Pore Size Methods ana anunn anan 85 O Adorp on Volanie SUNN A geerrmmrerreerrercrerrrerreer a a error renee Terre rer 87 9 Calculation of Isosteric Heats of Adsorption s sssessesssessrsesesesesesrsrereresesrsrsrseseseseneseseeeses 88 He DATA PRESEN TA TOW cu N T E E 90 1 1 Interactive Modification OF TAS S eleCHON ieciteestesstosigenrtatsaatarstonatetcnutenstertenscastensartensciasccds 91 12 Contiounne O taph Propor eS sorsra ssia naen aeae E E OTETO O E 92 1 3 Contiounlne Table POPE eS sts ciastssciesctaicesseceice iat saneriesnatetcadeatoeaattadataetta eis E AN 93 1 4 il OL A E SS 94 135 Gencraitino CUNE Ni DOR pre rr rer ere rey mente PERT r ren emer ocr ees a 97 1 6 Saving Aa ae Lex eet ee ens 101 1 7 Chae ae aO O a ty Sore reper ter Ror a here yn ar emery ar store 101 lL THEORY AND DISCUSSION raia Taoa a
118. of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN Data Reduction Parameters Urita Display General Adsorbate Adsorbent LMP alpha s Include in Area Yolume Summary table Single point BET Kdulti point BET Langmuir BJH method adsorption BJH method desorption DH method adsorption DH method desorption T method DR method DA method DFT Monte Carlo HE method SF method For each method selected additional paramerters andor data Tage may need be properly specified for the method s result be included in the 4reaYolume Summary table Figure G 25 Methods included in Area Volume Summary report Only results from the methods selected on the A V Summary tab of the Data Reduction Parameters dialog will be displayed 9 Calculation of Isosteric Heats of Adsorption Lsk In order to calculate the isosteric heat of adsorption on a sample it is necessary to measure at least two isotherms at different temperatures To perform the calculation click New on the File menu and then click Heats of Adsorption File Edit Configure Window Aubosorbid Help Physisorption Overlay Open Heats of Adsorption Reopen Figure G 26 Calculating Heats of Adsorption This will open the Heats of Adsorption window P N 05079 Rev Page 88 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN Heats of Adsorption iw Use desorption curve Figure G 27 Selecting files for heats of adsorpti
119. ommon Stations Sample Points Equilibrium Reporting Station A Adsorption Desorption Pressure tolerance O 05 2 0 i OU a1 O0 mmHg E guilibration time 1 2 1800 60 60 E quilibration timeout 2 equ 5400 240 240 Gt Load Station Save Station Active stations h Load Preset h Load Preset Preset Ah Bf CT or x Cancel Help a Save Preset i z Figure F 33 Setting equilibration parameters The following equilibration criteria are used during the measurement to determine if a given experimental point may be accepted as a valid point on the adsorption or desorption isotherm P N 05079 Rev Page 59 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION Pressure Tolerance is the range of pressure in Torr mmHg within which the pressure in the cell must remain for the defined equilibration time in order that the point may be accepted as a valid data point Equilibration Time is the user defined time during which the pressure in the cell must not change by more than the defined pressure tolerance in order that the point may be accepted as a valid data point Equilibration Timeout If the pressure tolerance is not met and the pressure does not fall below the lower pressure limit upper limit for desorption within the time specified by the Equilibration Timeout the data point will be taken This is to prevent the acquisition to hang on a single point due to instability of the
120. on calculation Click Add to open and add an isotherm file to the set of isotherms that you want to use to calculate the heats of adsorption It is recommended to add the lowest temperature isotherm first When you have opened at least two isotherms you can click OK to perform the calculations This will display the results An example of calculated heats of adsorption for hydrophobic carbon sample is shown below You can save the results under a new name using the File gt gt Save As command eraph Heats of Adsorption Heat of ads hoa Heats of Adsorption 51 200 40 000 0 000 Heats of Adsorption k Jimol 40 000 69 900 0 000 200 000 400 000 i O00 800 000 1030 000 seh frei i Figure G 28 Sample heats of adsorption plot P N 05079 Rev Page 89 of 133 Nova e NovaWin Operating Manual H DATA PRESENTATION H DATA PRESENTATION After opening the file setting the appropriate Tags for the data points and setting the necessary Data Reduction Parameters the NovaWin software can be used to construct graphical plots and tables for the data Tables and plots generated for a given data file can be accessed from the Floating Menu To view the list of available graphs or tables click Graphs or Tables on the Floating Menu This will open the respective submenu On this submenu click particular item which you wish to access In some cases this item is listed on a lower level submenu For example in the case of the iso
121. oose Calculate Po at run time mode Figure F 7 Selecting Po mode for nitrogen It is recommended to select the Calculate mode however if you wish to enter a desired value of Po select the other option 2 3 2 Cell Calibrations with Other Adsorbates Besides the default nitrogen at 77 K there are four other adsorbate options available in the NovaWin software e Argons7 e Carbon dioxide P N 05079 Rev Page 41 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION e N butane e Argon77 L NOTE If the required adsorbate is not on the database list you may add it to the list For instructions see Section D 1 4 2 3 2 1 Argon87 Chose this option for argon adsorption at bath temperature of 87 K that is when adsorbate gas is argon and the coolant in the dewar is liquid argon Similar to nitrogen Section F 2 3 1 there are two Po modes drop down list for argon adsorbate at 87 K to evaluate Po during cell calibration 4 Calculate or 41 Enter Calibrate Cell s Calibrate Cell s Adsorbate Gas Adsorbate Gas Angon8F o o PO options PO options PO mode Calculate PO mode PU Value 760 0 mmHg PU Value 760 0 mmHg Figure F 8 Selecting Po mode for argon at 87K It is strongly recommended to select the Calculate mode however if you wish to enter a desired value of Po select the other option 2 39 22 Carbon Dioxide and N butane Calibrate Cell s Calibrate Cell s Adsorbate Gas Ads
122. orbate Gas Larbon dioxside N E utkane PU options PU options Proax Value 760 0 mmHg PO Walue 760 0 mmHg Sample Temp 273 1 5 K Sample Temp 273 15 E Figure F 9 Selecting Po option for carbon dioxide and N Butane For cell calibration with Carbon Dioxide enter the sample cell temperature bath temperature and the Pmax Maximum Pressure for CO2 The calibration will be performed in the pressure P N 05079 Rev Page 42 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION range from 0 to Pmax This pressure range should include maximum pressure applied in the sample analysis The recommended values of Temperature and Pmax for CO are 273 15 K and 760 Torr respectively L NOTE Pmax should be smaller or equal the Po of the adsorbate at the bath temperature and it should not exceed 800 Torr For the cell calibration with N Butane enter the sample cell temperature and the corresponding Po saturation pressure for N butane at this temperature The recommended values of Temperature and Po for N butane are 273 15 K and 760 Torr respectively 2 3 2 3 Argon77 Chose this adsorbate option for argon adsorption at bath temperature of 77 K that is when adsorbate gas is argon and the coolant in the dewar is liquid nitrogen NOTE For argon at 77 K that 1s when adsorbate gas is argon and the coolant in L the dewar is LN2 enter Pmax 205 Torr which is the saturation pressure of argon vapor in equilibrium with solid phase Exc
123. orbed at P Po and T Wo total weight adsorbed E characteristic energy n non integer value typically between 1 and 3 is a generalized form of the Dubinin Radushkevich equation n 2 and has been found to fit adsorption data for heterogeneous micropores The Dubinin Astakhov equation requires the parameters n and E to be calculated re iteratively by non linear curve fitting to the adsorption isotherm in the low relative pressure micropore region The values of n and E obtained are then used in equation 1 50 d w w _ 3 dieg 5 sn 1 50 dr P N 05079 Rev Page 119 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION where r pore radius K interaction constant 2 96 kJ x nm x mol N gt 2 34 kJ x nm x mol Ar A plot of d w wo dr vs r yields the DA Method pore size distribution see Figure I 8 ba Hethod Dy fr m miee e e e me l l l a la B a E r i ill it ai al E tietOooO Pore Volume Lee Ly g ii i L L 4 p 1 1 i mml am i 1 i I mmja am i I i emjee i i if be I i I oe I F d d a F a E E E E ba a E d m ele mm es dees se eae ds ee be a a fl iF E E a C E a o l la al ee A llan mMm nm m i a a a am ia aaa aa aa 0 00 0 40 0 80 1 20 L 2 00 2 40 280 3 20 3 60 4 08 Pore Width A lLetOl Figure I 8 Plot of DA method
124. ou may unload the degasser during a sample measurement by pressing L the button on the NOVA keypad or the BACKSPACE button on the optional keyboard if connected The NOVA will display the Analysis Pause Menu which will allow you access to the degasser P N 05079 Rev Page 35 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION F INSTRUMENT OPERATION This section describes operation of NovaWin software in conjunction with NOVA instrument An essential part of the NovaWin NOVA system operation is the sample analysis To perform this main task accurately and effectively several additional operations such as cell and manifold calibrations or setting up various operational parameters need to be done 1 Manifold Volume Calibration The manifold is the volume from which the adsorbate is dosed onto the sample The accurate determination of the manifold volume 1s critical since all quantitative sorption measurements are made with respect to this volume The dosing manifold was calibrated using nitrogen as the adsorbate gas at the factory prior to shipment thus it needs to be checked only infrequently e g every 4 months or when service to the system may have affected this volume For detailed instructions on how to perform a manifold calibration consult the NOVA Operation Manual Section V 5 1 NOTE There is no need to perform a manifold calibration before every analysis NOTE For NOVA 1200 2200 3200 and 4200 users The m
125. p cet uantachrome INSTRUMENTS Indicates if the NOVA is connected to the PC or not Name of Currently Logged in User User Al Chemist Not connected Figure C 3 NovaWin Startup screen When communication is established between the PC and the instrument the software will display Connected 9600 at the lower right corner of the screen The NovaWin software also differentiates which NOVA model is connected NOTE If communication between the NOVA and the NovaWin software has not L been established the bottom right corner of the Startup Screen will display Not Connected If the Startup Screen displays Not Connected in the lower right corner check to make sure the following tasks are completed e Instrument is installed with Version 11 or later firmware e NovaWin is opened on the PC when the NOVA is displaying the Main Menu e Serial cable is properly attached to the instrument and or PC Serial port settings on the PC and the NovaWin software are set properly The NovaWin software allows for the P N 05079 Rev Page 18 of 133 Nova e NovaWin Operating Manual C NovaWin SOFTWARE INSTALLATION switching of COM ports by selecting the Operation submenu on the Main Menu Bar Select Instrument Settings and the following Communications Setup window will appear on the screen Q Quantachrome NovaWin fa 5 x File Edit Configure Operation window Help o Setup c T E j L j Start Analysi
126. performing the Daily Pp measurement Once the Daily Po measurement has been completed the superuser must re enable the lockout Calculate With this selection the ambient pressure is measured in the manifold and the Po value is calculated as ambient pressure plus 10 Torr This is one of the recommended methods in the determination of Po P N 05079 Rev Page 50 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION L NOTE The Calculate Po option is not available for adsorbates other than N2 77K or Argon 87K Continuous This option provides the analysis with a continuous update of Po throughout the entire run The Po value is updated every n points according to the number n entered in the Pt s Update field The actual saturation pressure Po is measured over the condensed nitrogen in a cell on a dedicated station The user must place a 6 mm Pp cell which is provided for this purpose in the analysis station assigned for this purpose By default Port A is used but it can be changed to any available station The station assigned to measure Pp in continuous mode cannot be used to measure a sample This option is only available on Nova 2000 3000 and 4000 series instruments PU options PO mode Continuous PO Update E ots update PO Station A Figure F 19 Selecting Continuous mode for Py measurement 3 3 2 2 Other Adsorbates When adsorbate gas other than Nz or Argon87 is selected that is an adsorbate that is not at
127. ph colors and line thickness To set these values for the individual plots locate the method in the Graph Properties Tree P N 05079 Rev Page 92 of 133 Nova e NovaWin Operating Manual H DATA PRESENTATION Configure Graph Properties All graphs As an example the V t plot H E phys can contain the following dE other data sets curves H BET A selected Adsorption points Click the sign to expand the list of plots for the method Click the A t Plot method D selected Desorption points sign to hide the list SAE t plot all A all Adsorption points w A all B all Desorption points a D BF best fit line for data set BF Langmuir 4 DR method 4 Alpha 5 method E MP method 4 BJH method E DH method wt LI aL Figure H 5 modifying properties for a specific plot type Select a graph or graph curve from the list on the left Graphs usually are grouped by the method by which they are generated Click on the sign to expand nodes or on the sign to collapse an open one The selected active item is highlighted That is the one for which you are setting the properties When a graph is selected graph line properties cannot be changed grayed out When a graph line is selected the graph properties of the graph the line belongs to can still be adjusted For quick copying of properties use the copy paste buttons Their effect depends on whether they are applied to graphs or lines Clic
128. pressure readings Care should be taken to ensure the time is long enough to allow equilibration otherwise under equilibrated data will be acquired 3 4 3 1 Pressure Tolerance Adsorption and Desorption The pressure tolerance is the range Torr within which the pressure in the cell must remain for the defined equilibration time in order that the point be accepted as a valid data point The acceptable range is 0 05 to 2 00 Torr Click on the Pressure Tolerance box under the Adsorption column and enter the desired value If only a surface area measurement is required only the equilibrium conditions for the Adsorption portion of the isotherm need be specified If a full isotherm is to be measured click on the Pressure Tolerance box under the Desorption column and enter the desired value Recommended values N2 and Ar isotherms for Pressure Tolerance are 0 1 Torr for both adsorption and desorption 3 4 3 2 Equilibration Time Adsorption and Desorption The equilibration time is the user defined time during which the pressure in the cell must not change by more than the defined pressure tolerance in order that the point be accepted as a valid data point The acceptable range is 18 to 1800 seconds Click on the Equilibration Time box under the Adsorption column and enter the desired value If only a surface area measurement is required only the equilibrium conditions for the Adsorption portion of the isotherm need be specified If a full isother
129. ps l Select the station for the calibration not applicable for NOVA 1000 Series users Users of the multi station NOVA instruments NOVA 2000 3000 and 4000 Series must make the distinction as to which cell is in each station Cells of different sizes may be calibrated together during a cell calibration run Choose a Po option see Section F 2 3 for details Enter a unique Cell Number to identify the particular sample cell Please note that a certain number between 1 and 99 can only be given once This number is associated with a certain sample cell type The cell calibrations are stored on the User Disk for the NOVA 4200 P they are stored on the DOC This calibrated sample cell can then be used in any of the stations for the analysis In the event that you choose a cell number that has already been used the NovaWin software will display a warning that the new cell calibration will overwrite the previous cell calibration file on the User Disk or the DOC Once the calibration is performed on a cell the operator has to enter the appropriate cell number at analysis time Select the Cell Size of the sample cell to be calibrated The drop down sub menu contains selections for the 6 9 12 mm diameter cells with rods as well as 6 and 9 mm without filler rods w o rod Choose the Adsorbate for cell calibration NOVA 1200 2200 3200 and 4200 4200 P users only Nitrogen is the default selection If an adsorbate other than nitrogen is
130. ption branch of the isotherm Finally save your selected interpolation ranges by clicking the Save button Click OK or Cancel to close the Interpolation Parameters window For the DA Method enter initial values for the E and n parameters and the appropriate Interaction constant K for the adsorbate used See Section 1 4 5 To use the DR method set R Tags for the desired P Po points in the measurement and enter the Affinity Coefficient B The value of the DR exponent n can be adjusted on Adsorbent page of the Data Reduction Parameters window See Section 1 4 4 8 2 5 BET Brunauer Emmett amp Teller Method Tags M Multi point S Single point If you want to calculate the Multi point BET surface area for the sample set the appropriate data points with the M tag Use the S tag usually at P Po 0 3 if you would like to calculate the value for the Single point BET The BET surface area calculation requires a linear plot of 1 W Po P 1 vs P Po which for most solids using nitrogen as the adsorbate is restricted to a limited region of the adsorption isotherm For nonporous materials this is usually in the P Po range of 0 05 to 0 35 however this linear region is shifted to lower relative pressures for microporous materials A typical BET plot is shown in Figure G 17 The standard multipoint BET procedure requires a minimum of three points preferably five in the appropriate relative pressure range If the Y intercept is negative a
131. rameters for calculations with different methods The parameters are grouped on the same pages according to their applications Use the tabs on the top of the window to navigate through different pages Click Save WY or Load A to store retrieve a full set of parameters The files are stored in the program s Config folder Click Cancel to close the window without saving changes Before referring to specific calculation methods click the Adsorbate and Adsorbent tabs to check 1f the correct adsorbate and adsorbent are selected for the analysis See Section D 1 4 NOTE When modifying Adsorbate parameters of an existing dataset via the Data L Reduction Parameters dialog the Override Analysis Gas Parameters checkbox must be checked or the values set at acquisition time will be used Table G 2 provides a general guide for the Tag selection based on the analysis type and gas sorption calculation methods Table G 3 gives a guide to the pressure ranges in which various calculation models are applicable A detailed discussion of the methods listed in these tables can be found in Section I THEORY AND DISCUSSION Table G 3 Gas Sorption Calculation Methods P P Range Calculation Model 0 0001 0 1 DR DA HK SF P N 05079 Rev Page 75 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN P P Range Calculation Model 0 05 0 3 t plot alpha s FHH DFT 5 0 35 BJH DH Fractal FHH NK 8 1 Parameters for
132. re convenient method for estimating t was proposed by de Boer in the form of equation 1 19 and is accessible for pore size distribution calculations in the NovaWin software 1 2 13 99 1 19 ee or cr nee oa Other expressions for t calculations available through the NovaWin software are presented in the Section 4 NovaWin computes the pore size distribution using the methods proposed by Barrett Joyner and Halenda BJH and by Dollimore and Heal DH as described in the following sections 3 2 1 BJH Method Assuming that the initial relative pressure P Po is close to unity all pores are filled with liquid P N 05079 Rev Page 110 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION The largest pore of radius rp has a physically adsorbed layer of nitrogen molecules of thickness t Inside this thickness is an inner capillary with radius rg from which evaporation takes place as P Po is lowered The relationship between the pore volume V and the inner capillary Kelvin volume Vx is given by Vp Vri r1 rki 1 20 When the relative pressure is lowered from P Po to P Po 2 a volume V will desorb from the surface This liquid volume V represents not only emptying of the largest pore of its condensate but also a reduction in the thickness of its physically adsorbed layer by an amount At Across this relative pressure decrement the average change in thickness is At 2 The pore volume of the largest
133. re size distribution measurements Therefore the following discussion will apply to the use of nitrogen as the adsorbate Mesopore size calculations are made assuming cylindrical pore geometry using the Kelvin equation 1 16 in the form ___ 7 27 Vn 1 16 RT n P P FK where y the surface tension of nitrogen at its boiling point 8 85 ergs cm at 77 K Vm the molar volume of liquid nitrogen 34 7 cm mol R gas constant 8 314x10 ergs deg mol T boiling point of nitrogen 77 K P Po relative pressure of nitrogen rg the Kelvin radius of the pore Using the appropriate constants for nitrogen equation 1 16 reduces to o 4 15 Me 1 17 rx log P P The Kelvin radius rx is the radius of the pore in which condensation occurs at a relative pressure of P Po Since prior to condensation some adsorption has taken place on the walls of the pore rg does not represent the actual pore radius Conversely during desorption an adsorbed layer remains on the walls when evaporation occurs The actual pore radius rp is given by ea eet 1 18 where t is the thickness of the adsorbed layer This statistical t can be considered as 3 54 Vaas Vm in Which 3 54 A is the thickness of one nitrogen molecular layer and Vaqgs Vm 1s the ratio of the volume of nitrogen adsorbed at a given relative pressure to the volume adsorbed at the completion of a monolayer for a nonporous solid of the same composition as the porous sample A mo
134. reas a simplified procedure may be applied using only a single point on the adsorption isotherm in the linear region of the BET plot For nitrogen the C value is usually sufficiently large to warrant the assumption that the intercept in the BET equation is zero Thus the BET equation 1 1 reduces to By measuring the amount of nitrogen adsorbed at one relative pressure preferably near P Po 0 3 the monolayer capacity Wm can be estimated using equation 1 7 and the ideal gas equation That is 1 7 P N 05079 Rev Page 104 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION PVM 1 8 E l P P RT o The total surface area then can be obtained from equation 1 5 That is g EYN Aa U P Po 9 RT 1 3 Multipoint Single Point Comparison The relative error introduced by the single point versus the multipoint method for determining surface area is a function of the BET C constant and the relative pressure used The magnitude of the error in the single point method can be determined from a comparison of the monolayer weight obtained from the BET equation I 1 and the single point equation 1 7 Solving equation I 1 for Wm gives Wa Ww 22 7 1 Cl P 1 10 P C C Po Rewriting the single point equation H7 gives W W p P 1 P Po 11 The relative error inherent in the single point method then 1s Wee Wiis 2 AT PO 1 12 W 1 P P C 1 Equation 1 12 indicates that for a given C valu
135. referred one of de Boer or the CB Carbon Black method for the determination of micropore volume in the presence of mesopores This technique involves the measurement of nitrogen adsorbed by the sample at various low pressure values The procedure is the same as that employed in the BET surface area measurement but it extends the pressure range to higher pressures to permit calculation of the matrix or external surface area that is the non microporous part of the material A t plot is a plot of the volume of gas adsorbed versus t the statistical thickness of an adsorbed film In the NovaWin software the t values are calculated as a function of the relative pressure using either the de Boer equation 13 99 1 2 cf 1 19 log Po P 0 034 A the Carbon Black equation t csl A 0 88 P P Y 6 45 P P 2 98 1 33 or the Halsey equation which for nitrogen adsorption at 77 K can be expressed as P N 05079 Rev Page 113 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION 1 3 t A 3 54 ee io 2 303 log P P or in a generalized form found useful for other adsorbates and or temperatures as I b t Er 1 35 In Py P Where the pre exponential term a and the exponential term b are 6 0533 and 3 0 for nitrogen adsorption at 77 K respectively Typical t plots are shown in Figure 1 4 Figure I 5 and Figure I 6 below representing various possible pore sizes First t plot of a sampl
136. ro and mesoporous carbons silica s and zeolites t Please P N 05079 Rev Page 123 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION contact QC Support Quantachrome com for Powder Tech Notes 27 31 and 36 for more details The NovaWin software includes a number of kernels consisting of individual P Po W isotherms derived for the systems nitrogen carbon argon carbon nitrogen silica and argon silica by the Non Local Density Functional Theory and Grand Canonical Monte Carlo computer simulation Please refer to a summary in Table I 2 of the kernels implemented in the NovaWin software and recommendations for the pore width ranges where these models work best 5 1 Library of DFT and GCMC Methods in Quantachrome s Data Reduction Software Table I 2 List of available kernels for DFT and GCMC methods Carlo Kernel File Width Range NLDFT N2 carbon equilibrium 0 35 nm 40 nm Activated carbons activated transition kernel at 77 K based on a carbon fibers novel slit pore model micro mesoporous carbons of type CMK 1 etc NLDFT N carbon equilibrium 0 35 nm 40 nm Novel micro mesoporous transition kernel at 77K based on a carbons e g CMK 3 carbon cylindrical pore model nanotubes carbon aerogels etc NLDFT N2 carbon equilibrium 0 35 nm 40 nm Novel micro mesoporous transition kernel at 77 K based ona carbons some CMK s certain slit pore model for pore widths
137. rogram Click on the Close button to exit this feature P N 05079 Rev Page 69 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN 4 Rebuilding Physisorption Database To allow inclusion of data files already existing on the user s computer the software provides the database rebuild function To access this feature select the Build tab from the Database manager window Here a list of locations can be entered The software will remember these selections and will reload them whenever the function is invoked Qunatchrome Gas Sorption Data Manager Search Build Folders to Search Ta All None Remove ga Add Empty before building Rebuild 7 Help A Close Figure G 5 Rebuilding the database Use the Add button to specify a folder to be included when searching for files to add to the database and the Remove button to remove the selected line from the list L NOTE Each folder entry will also include all of its subfolders Once the folder list is complete click on the Rebuild button to start the process If the Empty before building box is checked the current contents of the database will be discarded The build process can take several minutes depending on the number of analysis files contained in the selected folders The status bar at the bottom of the window will display the file currently being processed L NOTE Only gps data files are included in the rebuild function Once the pr
138. rt file by clicking New or Duplicate on this window New will create a blank report which can be edited to include the elements needed and Duplicate will create a copy of the selected report which can be modified as needed To remove unwanted report file highlight its name and click Delete L NOTE Deleting a report file is an irreversible action Once a report file has been deleted it cannot be retrieved Click New or Duplicate on the Report Manager window to generate a custom report A window will appear prompting you to enter a filename for the report that you wish to create Enter Value Name of new report M p repart OK Cancel Figure H 16 Creating a new report Enter the filename click OK The following Report Editor window will appear P N 05079 Rev Page 98 of 133 Nova e NovaWin Operating Manual H DATA PRESENTATION Properties of My report Applicable to W phys B Graphs 2 6 Tables BET Click the sign to Langmuir display the individual WY method graphs tables metadata DA method and or formatting options Alpha 3 method MP method BJH Pore Size Distribution ff Adsorption E Desorption ajo ee Figure H 17 Report editor Choose the desired combination of graphs tables metadata data reduction parameters and calculation method summaries and formatting options from the right hand window These report items are listed in a hierarchical view grouped as follow
139. s Abort Analysis Upload data F9 Calibrate Cell Instrument Status F Instrument Settings Firmware Upgrade User Frances Select Communication Port Figure C 4 Selection the COM port on the PC The Operation menu on the Main Menu Bar contains operation functions for the instrument To change communication settings and or the operation mode Nova vs Helium Mode click Instrument Settings on this menu This will open the Communication Setup window see Figure C 4 which allows selecting the appropriate Communication Port and Operation Mode Show Instrument Message Ctrl I Select Instrument s Operation Mode 1 Helium Mode Nova Model 26 and above Mark this box to select the He Mode Select communication port COMA Communication Setup x Cancel Help Figure C 5 Selecting helium mode in NovaWin 2 Nova Mode Model 25 and above P N 05079 Rev Page 19 of 133 Nova e NovaWin Operating Manual C NovaWin SOFTWARE INSTALLATION Ummak bocio Communication Setup select the Nova Mode you will need to calibrate Select communication part LOM your cells in Instrument in Ae mode advance cell void volume ok Cancel Hel determination x fier Figure C 6 Selecting NOVA mode in NovaWin NOTE For users of Nova Model 25 NOT helium capable make sure that the L Instrument in He mode box is always unmarked to avoid communication error
140. s Graph available graph items further grouped by the calculation methods Tables tabular data lists grouped by calculation method MetaData additional text data Including calculation result summaries data reduction parameters and analysis parameters Formatting items used to format the report Currently the only item available is the page break entry that forces a new page in the report printout Highlight your selection and click Add Your selections will appear in the left hand space To change the printing order for the report highlight the selection and click the or buttons Select the size of the printed selection by clicking the buttons next to the current size selection See Figure G 21 Available choices are Full Page 1 2 Page and 1 3 Page Note that these sizes refer to the printout size of the whole page minus the header Click Del to remove the selection from the report Use the OK button to accept the changes Cancel to discard them and return to the Report Manager P N 05079 Rev Page 99 of 133 Nova e NovaWin Operating Manual H DATA PRESENTATION Properties of My report Applicable to i phys 4S Graphs j Isotherm Linear Full Fage Tables 483 MetaData y Multi Point BET Flot Full Page ie Formatting Page Break DR method Del al af OK X Cancel Select the size of the printed selection here Available choices are full 1 2 and 1 3 page Not
141. s degas without a filler rod in the cell 3 Choice of Outgassing Temperature and Time Samples should be outgassed at the highest temperature that will not cause a structural change to the sample up to 350 C This will accelerate the degassing process For instance most carbon samples can also be degassed at 300 C as can calcium carbonate Many hydroxides must be degassed at a lower temperature Degassing organics must be performed with care since most have quite low softening or glass transition points For example magnesium stearate a common pharmaceutical formulating compound should be degassed at 40 C according to the USP P N 05079 Rev Page 33 of 133 Nova e NovaWin Operating Manual E SAMPLE PREPARATION Loosely bound water physisorbed water will be lost at relatively low temperatures under the influence of vacuum but strongly bound surface water might require high temperatures Many zeolites for example will retain significant quantities of water in their micropores up to 300 C Use technical reference literature such as the Handbook of Chemistry and Physics CRC Boca Raton Florida and standard methods such as those published by ASTM DIN ISO etc to guide your selection of an appropriate degassing temperature If you have access to thermal analysis equipment especially gravimetric an analysis should be conducted on a separate aliquot of material prior to degassing on the NOVA instrument A suitable degassing te
142. s differ a specific reference to the individual software program will be clearly noted NOTE This instruction manual refers to any NOVA 10 0 or higher Series L instruments Models 26 Helium Mode Capable and 25 not Helium Mode Capable 1 Summary of Features e Menu driven easy to use software allows user to collect display analyze and archive data e User configurable defaults simplify operations and offer flexibility in customizing reports and plots e Plots of data generated on screen for quick preview or printed for archival purposes e The PC is used as an intelligent terminal for control of most function of the NOVA e e Any or all data reports can be saved to disk enabling data archiving e During arun each data point can be acquired and saved to the data file so that in the event of an error condition data that has been acquired will not be lost e User defined analysis files enable flexible and easy operation of the NOVA e In summary the following actions are possible using a PC installed with NovaWin and NovaWin CFR Cell calibrations Surface area determinations Pore size distribution measurements Data archiving Report generation including graphical plots and tables NovaWin CFR incorporates the features above along with advanced security features which include P N 05079 Rev Page 9 of 133 Nova e NovaWin Operating Manual A INTRODUCTION Tamper evident data files Required system login with unique
143. s information for a data set The Analysis Data window contains the information that is displayed in the header of each page of the report If a parameter that is used for calculating reduced data is changed such as the sample weight the data will be recalculated when OK is selected Clicking Cancel will disregard any changes to this window NOTE for NovaWin CFR users Only the superuser security level will have the L option to change the information on this window Any changes to the Analysis Data window will prompt the superuser to state the reason for the change for documentation in the audit trail Please give the reasons for the changes outlined below changed sampleDens from 0 00000 to 2 00000 changed sample eight from 1 00000 to O 05000 Corrections of eroaneaus entries Figure G 8 Entering reason for change for audit trail P N 05079 Rev Page 72 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN NOTE Any changes to the Analysis Data window will be lost when the file is A closed unless the file is saved using Save or Save As from the File menu Ei If you attempt to close to the Analysis Data window without saving you will be prompted to make a decision Alternatively you may click the Save Icon on the Main Menu Bar C 0Cdatalphysisorb Ow1_041111_12 0Ps X Document has changed Do you want to sawe changes Figure G 9 Confirmation to avoid data loss 7 Setting Data Red
144. s of sample cells so long as they don t have hanging filler rods Non elutriating plugs are available for 6mm 9mm and 12mm sample cells Contact Quantachrome for more information In the most difficult cases and the aforementioned methods have not eliminated the problem it might be necessary to insert a small glass wool plug into the cell stem This can be held in place between two halves of a cut in two glass filler rod This is the only time that a filler rod should be used in the degasser 5 Unloading the Degasser Preferably the adsorbate should be used as backfill gas to prevent or minimize buoyancy errors A sample cell will weigh less when filled with helium than when filled with air or nitrogen The error introduced is approximately 1 mg per mL of cell volume This can be significant when using extremely small sample weights lt 50 mg Allow the mantle to cool below 100 C before unloading the degasser Remember heating mantle clamps may be very hot A sample cell which feels only warm to the touch whilst still under vacuum can be much hotter to the touch when backfilled with gas This is particularly true if you are degassing a large mass of metal sample Exercise caution A warm sample cell can also introduce weighing errors The sample cell should be allowed to cool to room temperature before weighing If sample throughput permits cool thoroughly while attached to the NOVA otherwise remove and transfer to a desiccator NOTE Y
145. s per unit area of monolayer of adsorbate Aa Kirkwood Mueller constant of adsorptive As Kirkwood Mueller constant of adsorbent By selecting effective pore widths in the micropore range equation 1 51 can be used to calculate the corresponding relative pressures From the adsorption isotherm the amount of adsorption at each of these relative pressures is determined Differentiation of weight or volume of gas adsorbed relative to the total uptake W Wo with respect to the effective pore width yields a pore size distribution in the micropore range see Figure below P N 05079 Rev Page 121 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION HE Method Dvir Nee ee ee ee Pore Volume ces g Ele o0 e o e Pore Width A letOL Figure I 9 HK method pore size distribution 4 7 Saito Foley SF Method Even though the HK method is adequate for materials with a predominance of slit like pores activated carbons layered clays certain solids e g zeolites are better represented assuming cylindrical pore geometry Hence the SF method was developed as an alternative to the slit like pore based HK method As with the HK method the SF method enables the calculation of pore size distributions of microporous materials independently from the Kelvin Equation The computational approach is analogous to that of the HK method except that cylindrical pore geometry is assumed Accordingly equation 1 51 is replace
146. se results whose corresponding fields match the pattern entered Each field can contain an asterisk character at the beginning and or at the end of the field value The asterisk will match zero or more characters in the data file s field value Example The field value of alpha will match any of the alpha alphabeta alpha999 values but will not match alph XXalpha XXalphabeta The field value of alpha will match any of the XXalpha alphabeta XXalpha999 values but will not match alph lpha If no asterisk is included the field must match exactly Fields left empty are excluded from the selection criteria In addition a date range can be specified Check the box Use data range and specify a starting and ending date utilizing the two calendar controls Note that the dates are inclusive for example specifying 3 2 2007 as a start date will include analyses performed on 3 2 2007 and later The search will omit files that are outside of the date range Once the criteria are specified click the Search button to initiate the search If the result contains more than 100 files a prompt will offer the choice to stop and revise the criteria Once the search is completed matching records are listed in the lower half of the window listing all relevant information of the entry Using the scrollbar on the right side of the list allows reviewing the matching results and double clicking on an entry will open the corresponding data file in the host p
147. security features The following security features can be selected at installation time Login required requires user identification before using the system P N 05079 Rev Page 21 of 133 Nova e NovaWin Operating Manual D SOFTWARE CONFIGURATION Audit changes print Audit Auto re login Password aging tracks changes made to the data prints change history with each document prevents unattended workstations to be used by unauthorized users enforces password changes in pre defined periods Password retention remembers a pre configured number of previous passwords and prevents re use The following security features are always active Report integrity check allows verification of report printout integrity System security log maintains a list of all relevant security events Minimum ID length forces user ID and password minimum length six by default 4 After you have co NOTE Once a given Security Level is selected it cannot be changed for a given installation If you wish to change the Security Level you must first uninstall and then re install the software nfigured the security level for the software you must create a superuser account Only a superuser has full control of the system including defining and managing user accounts After the security level has been configured the User Properties screen will appear User properties User ID Frances Password Iw Expires 190007 29 Full nam
148. selection state Shift click to select range from last clicked item or use the Select All or Select None buttons Then check a box in the same row as the tag you want to apply The box should be checked in the On column to add tags or OFF column to remove tags Unchecked tags will be left in their current state To apply changes click Apply to Selected Use the Clear button to deselect all tag checkboxes Click Delete to remove the points permanently This button is available only at the superuser level Click OK to return to the main program All related calculations will be re evaluated and the new results will appear in the open tables or graphs Click Cancel to discard the changes and return you to the main program L NOTE For NovaWin CFR all changes are tracked in the audit trail 8 Setting Data Reduction Parameters Ls m Ds After the points have been tagged for use in the calculations click Data Reduction Parameters on the Floating Menu This activates the following window P N 05079 Rev Page 74 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN Data Reduction Parameters Thermal transpiration Iw On Effective molecule diameter O 3 540000 Effective cell stem inner diameter d 4 000000 Fo overde Enable 760 00 torr Temperature Compensation 4utosorb Files J Enable Cell type Emm word G 11 General data reduction parameters Use this dialog window to set modify certain pa
149. ssccssesscsoccsessavncccusoecccescovecscteseseacccsseseuteceoesoues 41 2 iCelltGalibration witht Nit CSIs secaecditadatsnsestiesertsdatrsitsetorateditenstoiatenstedatonatettensteieteascelatens 41 23 2 Cell Calibrations with Other Ads rbates ecco niece ac nent cen eeseoea heats eee ar esa ea oes 41 22 4 PNT OOM AEE E EE asap EE E E E E E E E E E E 42 P N 05079 Rev Page 6 of 133 Nova e NovaWin Operating Manual TABLE OF CONTENTS 2 3 2 2 Carbon Dioxide and N butane 3323653 ce0ot ota a ae oueweuseee 42 pike We INGO G1 I aI E O OA AAAG 43 2 3 2 4 User Defined Adsorbate essssesesssessesssoesonsscessnsrossessrosssssreessssresesssrsssusssosossssesenssses 44 2 4 ANC ALE OLA OMS and Run the Calibra oi essnee a a a aR 44 3 SAM lea S15 OCD aana aa N 46 3 1 Common Setup Helium Mode Only model 26 and above ssesssseesseeressrssesisrsrerersreres 46 aE Packi model 20 Only iie a E S 47 Ja Lommonrocdip No Modena s Ant nck dest ode cotatetnaeaset detain 47 a DAPEN ONN a a ny aN ar ee nrer ny Ue Doron ee a sory OREN E 48 3 3 Commons etup elum and Nova M desyoisns ia A A 48 SS Glec Adiorbaie GAS pr a A N ee 48 Dow Set Po OpHons Tor AdS OrDate iaa T TT 49 95251 INitrOoem ats Rand Arconate l Koinn ana aA saat eat atetadesds 49 3 3 2 2 OE O D eu EAA E eeaserateeez 51 IIE Emal D yaer error errr rey Teer ere rrr err Perret verre ner ret serene tereeen 53 3 3 4 Evacuation Cross over Pressure eeeeessseosessseeesssses
150. t Do not insert the thermocouple plug of a heating mantle into any other socket Do not insert the plug of any other device into the thermocouple socket on the Quantachrome instrument e If the instrument has more than one heating mantle station always ensure that the power plug and thermocouple plug of one heating mantle are inserted into the sockets of the same heating mantle station Do not insert the power plug of a mantle into the power socket of one heating mantle station and the thermocouple plug of the same mantle into the thermocouple socket of a different heating mantle station P N 05079 Rev Page 13 of 133 Nova e NovaWin Operating Manual B SAFETY HOT The outer surfaces of the heating mantle may become hot during use Do not hold hot heating mantles without wearing protective gloves Never insert fingers inside the pocket to determine if the mantle is heating up Do not place a hot heating mantle on a surface which is not heat resistant Switch off when not in use e The outer surfaces of the heating mantle may become hot during use Do not hold hot heating mantles without wearing protective gloves Never insert fingers inside the pocket to determine if the mantle is heating up Do not place a hot heating mantle on a surface which is not heat resistant Switch off when not in use e Do not allow liquids to come into contact with the heating mantle and do not handle heating mantles with wet hands Do not allow dust to accumul
151. t Teller BET method is the most widely used procedure for the determination of the surface area of solid materials and involves the use of the BET equation 1 1 1 o dl C 1 1 1 N FS W Po P 1 Wn Wl Po where W is the weight of gas adsorbed at a relative pressure P Po and W is the weight of adsorbate constituting a monolayer of surface coverage The term C the BET C constant is related to the energy of adsorption in the first adsorbed layer and consequently its value is an indication of the magnitude of the adsorbent adsorbate interactions 1 1 Multipoint BET Method The BET equation 1 1 requires a linear plot of 1 W Po P 1 vs P Po which for most solids using nitrogen as the adsorbate is restricted to a limited region of the adsorption isotherm usually in the P Po range of 0 05 to 0 35 This linear region is shifted to lower relative pressures for microporous materials A typical BET plot is shown in Figure I 1 HMult Point BET Plot 46 0000 0 0000 0000 a 0000 E Oooo D000 0 0000 40 0000 0 0000 0 000e 00 B 000e 02 1 200e 01 1 600e 01 2 000e 01 2 400e 01 2 800e 01 3 300e 01 Relative Pressure PPa Figure I 1 Typical BET Plot P N 05079 Rev Page 103 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION The standard multipoint BET procedure requires a minimum of three points in the appropriate relative pressure range The weight of a monolayer of adsorbate W
152. te coolant on the lift drive base After selecting Nova Mode the Calibrate Cell option in the Operation menu is active Click on it to open the Calibrate Cell s window Click here for the Adsorbate Gas Calibrate Cell s Adsorbate Gas Active stations A Ww Bf a is Nitrogen PU options PO mode Minimum thermal delay is 180 seconds Cell number 4 Thremal delay 160 1200 sec 180 Cell Size 3mm Start button will be ungrayed only after all of the required fields have been entered correctly Figure F 4 Setting cell calibration parameters P N 05079 Rev Page 39 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION Click here to Calibrate Cellf activate stations Adsorbate Gas Hitrogen PU options Scroll between active Stations Active stations PO mode Calculate station A Valid cell numbers are 1 99 Cell number p If any of the fields are entered improperly the Incorrect Missing Parameters box will appear below displaying the error s Thremal delay 180 1200 sec 190 Cell Size 9mm x Cancel Station A is invalid because Invalid cell ID Figure F 5 Selecting remaining cell calibration parameters The Calibrate Cell s window is used to select the cell calibration parameters for the analysis Cell calibrations using NovaWin are performed by the following ste
153. therm plot you can select a linear or a logarithmic plot Graphs gt Raw Data Tables Isotherm Linear Reports BET Log Scale View Audit Trail t Plot method Absolute Pressure Edit data tags os j Data Reduction Parameters Enn peewee Da Alpha method MP method b Graph Properties BJH method p Sey Kr 87K Thin film PS method BLS i DH method CAL HK method munon SF method DA method DFT Monte Carlo Fractal Dimension Methods Figure H 1 Selecting desired graph to display If a plot or a table is selected and the Data Reduction Parameters and or the appropriate Tags for the calculation are not set properly the NovaWin software will display an error message For example if you wish to generate a t plot for a given set of data without tagging the desired points with T Tags for the calculation the following message will be displayed Quantachrome Novatin2 Error x Thickness calculation error Insufficient T tags selected Figure H 2 Error displayed when not enough points are selected for a calculation P N 05079 Rev Page 90 of 133 Nova e NovaWin Operating Manual H DATA PRESENTATION When you view a plot or a table with the results of calculations obtained by a given method you may wish to change the number of data points used for that calculation 1 1 Interactive Modification of Tag Selection To modify data tags for a given data file right click on a
154. tion Overlay Quantachrome OQuadraWin wie Edit Configure GS oncoml Window Physisorption Overlay Open Reopen Figure H 13 Creating an overlay file from main menu Open the first isotherm file as a root To add next isotherm plot click New and Physisorption Overlay again In the Open window click on the file you want to add and then in the following box Enter Value Enter display label for new instance of document Maz 5 characters 02 crea Figure H 14 Give each data set a unique recognizable name Enter the name label for the added plot 1 5 Generating Custom Reports To generate custom reports click Manage Reports on the Configure menu This activates the Report Manager window P N 05079 Rev Page 97 of 133 Nova e NovaWin Operating Manual H DATA PRESENTATION Report Manager fos Telos ital These demo report files a ny are automatically demo total pore volume installed with the demo average pore size demo cft software You may use E OS or edit these files for dema bih custom reports Edt New ny Duplicate Delete AT Close Help Figure H 15 Modifying and creating reports The files listed in this window were saved during the software installation The list includes seven sample report files titled demo X XX which you may use or edit To modify an existing report file highlight the file name and click Edit You may also create your own repo
155. trarily chosen relative pressure usually P Po 0 4 Therefore the Alpha s method in principle allows a more direct comparison between actual and nonporous reference isotherms In practice complications arise because the Alpha s method is found to depend on the exact nature of the material chosen as nonporous reference Nonetheless the Alpha s method by analogy with the t method has found use for the determination of micropore volumes by extrapolation of Alpha s curves to a 0 and for the determination of nonporous surface area contributions from the slopes of linear portions of Alpha s curves since the ratio of actual to reference BET surface areas is equal to the ratio of actual to reference slopes in these Alpha s plot regions by qualitative comparison of actual isotherms with judiciously selected reference isotherms 4 3 MP Method An extension of de Boer s t method for micropore analysis was proposed by Mikhail Brunauer and Bodor This MP method uses the fact that t can be calculated independently of the solid by 10 V t A S BET 1 40 P N 05079 Rev Page 116 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION A V vs t plot is constructed from t vs P Po data for a sample with a similar BET C value as shown in Figure I 7 below using linear slopes constructed for t value intervals from the origin to 4 A 4 to 4 5 A 4 5 to 5 A etc Using the equation above micropore surface areas can
156. ts purchases are warranted to be free of defects for 90 days from shipping date The following limits apply to our warranty Glassware including Dewar flasks is not covered under this warranty except if damaged during shipment Claims for damage during shipping must be made in writing within 10 days of receipt of the goods Expendable items are warranted for 90 days for other than glassware breakage Such items include but are not limited to sample tubes lamps fuses valve plungers seals O rings amp other seals hoses flexible tubing thermocouple vacuum tubes filters oils and other fluids Products sold by Quantachrome under their own brand name are not warranted by Quantachrome but our best effort will be made to secure repair or replacement if found to be defective Warranty is void in the event of modifications or repairs by persons other than Quantachrome s service personnel unless permission is given in writing for such repairs or modifications Warranty is also void in the event of exposure to corrosive atmospheres of any kind Prior authorization must be obtained before returning any item to Quantachrome Instruments Items must be decontaminated before return to Quantachrome Any and all computer program s software firmware code data acquisition and or data reduction methods computations graphical and or tabular data reporting or presentation methods collectively referred to as software provided with or in or load
157. uation 1 63 surface tension effects were neglected That is the assumption was made that the surface tension of the adsorbate at a molecular scale does not differ appreciably from its bulk liquid value If surface tension effects are accounted for the relationship between D and s 1s given by D 3 s 1 64 where D is the surface fractal dimension and s is a constant characteristic of a given adsorbent In either case for fractal surfaces a plot of log V vs log log Po P should yield a straight line with negative slope s within the multilayer region of the isotherm 7 2 Neimark Kiselev NK Method Combining thermodynamic and fractal arguments Neimark reasoned that above the onset of capillary condensation fractal surfaces should conform to the following equation 2 D Se K a 1 65 where D is the surface fractal dimension K is a constant a is the mean radius of curvature of the adsorbate vapor interface given by the Kelvin equation AF Vn ea A E 1 66 and S is the adsorbate vapor interface area given by the Kiselev equation P N 05079 Rev Page 128 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCUSSION RT F S 2a 1 67 GoD with R being the universal gas constant T the adsorption temperature y the adsorbate surface tension Vm the adsorbate molar volume and n and nmax the amounts of gas adsorbed at a given P Po and at saturation respectively In other words the cumulative area S
158. uction Tags Dx To select or modify data tags for a given data file right click on an open plot or a table associated with this file This activates the Floating Menu Click Edit data tags on this menu to open the following window Edit data points On _ Cea M Multi point BET Single point BET T Statistical thickness Pore volume HL Langmuir data fp Pore size distribution ml R DR and Fractal Ta Select All Select None Micropore BET Assistant ok x Cancel 7 Help Figure G 10 Setting and clearing data reduction tags The tags A D or AD shown on the list in the first column next to the volume values indicate that a given point belongs to the adsorption A desorption D or both AD branches of the isotherm The tags shown in the following columns indicate which data reduction method will be applied to the points marked by a given tag The following is the list of tags and their corresponding data reduction methods Table G 2 Physisorption Tags and their respective calculation methods Calculation Method P N 05079 Rev Page 73 of 133 Nova e NovaWin Operating Manual G DATA ANALYSIS USING NOVAWIN Lae EEA R Pore Size Distribution Dubinin Radushkevich and Fractal I 4 4 amp I 7 To make changes to the list of points follow the steps 1 Select points by using the Windows standard selection method click to select one point Ctrl click to toggle an item s
159. us Solids and Powders Surface Area Pore Size and Density Springer 2004 K S W Sing D H Everett R A W Haul L Moscou R A Pierotti J Roquerol and T Siemieniewska Pure Appl Chem 57 603 1985 T L Hill J Phys Chem 59 1065 1955 M Thommes et al Aspects of a novel method for the pore size analysis of thin silica films based on krypton adsorption at liquid argon temperature 87 3 K Studies in Surface Science and Catalysis 165 2007 551 P N 05079 Rev Page 132 of 133 Nova e NovaWin Operating Manual REFERENCES 44 Rouquerol J Llewellyn P and Rouquerol F Is the BET equation applicable to microporous adsorbents In Characterization of Porous Solids VII P Lewellyn F Rodriguez Reinoso J Rouquerol N Seaton Eds Studies in Surface Science and Catalysis 160 2007 pp 49 56 P N 05079 Rev Page 133 of 133
160. user name and password combination Fully detailed audit trail 3 access levels programmable by system administrator Programmable session time out auto logoff Unique report identification There are several functions that must be performed on the NOVA keypad keyboard and hence are not controlled by NovaWin including e Manifold calibration see Section 2 3 of NOVA Operation Manual for procedure e Operation of outgas stations refer to Section 3 2 of NOVA Operation Manual for procedure e Aborting sample measurements Section 5 1 of NOVA Operation Manual e Operation of Manual Mode see Section 3 8 of NOVA Operation Manual e Access to Control Panel Menu options refer to Section 3 0 of NOVA Operation Manual 2 Technical Specifications NOVA Instrument ELECTRICAL be Lech 1 e naurnce ee ee eerie eer am Unie a ee nee 100 120 220 240 V see nameplate on rear of unit PRCQUENICY errno aa E 50 60 Hz POWT MAR eara 140 W COMME CH ON eesriie Grounded single phase outlet PHYSICAL Here Mics a 79 cm 31 in DATE AE a AE NEA EE A ENEA 51 cm 20 in DEDU a rer neer error meer ter ern a 51 cm 20 in NY CLS T EE NA unseat 38 kg 83 Ibs Bench space allocation ccccceeeeeeees 104 cm 41 cm ENVIRONMENTAL Temperature saxo it a 15 C 40 C Max Relative Humidity 0 0 0 eee 80 Both doors open fully P N 05079 Rev Page 10 of 133 Nova e NovaWin Operating Manual A INTRODUCTION Heating Mantle E
161. ved as well The information on the Sample tab is specific to the particular sample and station i e Sample ID Sample Weight and File P N 05079 Rev Page 55 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION Name and subsequently will have to be erased each time that particular setup 1s chosen for an analysis Develop the setup and click on the Save Station button on the Start Analysis window This will open a window where a file name can be given for the setup The file is saved in the NovaWinCfg folder of the NovaWin program with a stn extension To load as go to the Station Selection box and choose the station for the analysis Click the Load Station button and select the appropriate setup file You may select any stn file for the station you wish to use Load Save Preset buttons A preset is the full content of the Analysis Start window including common parameters data for all stations and the selection of stations for activation NOTE for NovaWin CFR users Users at the Operator security level only have L access to the Load Preset button when analyzing samples Therefore the Superuser Manager security level users must create the desired analysis conditions and save them as a preset 3 4 2 Points Tab The Points tab Figure F 30 is where the data points for the measurements are selected for each of the stations in the Analysis Setup parameters Start Analysis Common Stations Sample
162. w i E Station A Station B Switch between Active Marked stations to assign cells for each of them Assign cell number to the cell being calibrated on selected station Cell number E Cell Size 3mm Select appropriate cell size and rod combination Cell number Cell Size 5mm Figure F 11 Selecting stations and cells for calibration 3 In the Cell number field enter a unique ID number between 1 and 99 identifying the particular sample cell The cell calibration data associated with their IDs are stored in the permanent storage so that they can be used for future analyses 4 If the entered cell number matches one from the list of existing cell IDs the Overwrite check box appears and the error box at the bottom of the window includes an error message Cell ID conflict To resolve the conflict you can 1 Check the Overwrite box 2 Change the cell number to an unused one 5 Click the Cell Size button V and from the drop down list select the size of the sample cell to be calibrated The drop down list contains selections for the 6 9 and 12 mm diameter cells with rods as well as 6 and 9 mm w o rod without rods Repeat steps 2 5 for all active stations selected in step 1 7 To close the window without starting calibration 1 Click OK to save the settings 2 Click Cancel to close the window without saving 8 Click Start to initiate the process A
163. which show type H1 sorption hysteresis NLDFT Ar zeolite silica 0 35 nm 100 nm Zeolites with cylindrical pore adsorption branch kernel at 87 K channels such as ZSM5 based on a cylindrical pore model Mordenite etc and mesoporous siliceous materials such as MCM 41 SBA 15 MCM 48 porous glasses and some silica gels etc Allows obtaining an accurate pore size distribution even in case of H2 sorption hysteresis NLDFT Ar zeolite silica 0 35 nm 100 nm Zeolites with cage like equilibrium transition kernel based structures such as Faujasite on a spherical pore model pore 13X etc diameter lt 2 nm and cylindrical pore model pore diameter gt 2 nm NLDFT Ar zeolite silica 0 35 nm 40 nm Zeolites with cage like adsorption branch kernel at 87 K structures such as Faujasite based on a spherical pore model 13X etc pore diameter lt 2 nm and cylindrical pore model pore diameter gt 2 nm NLDFT Ar carbon 0 35 nm 7 nm Novel micro mesoporous equilibrium transition kernel at carbons e g CMK 3 carbon 87 K based on a cylindrical pore nanotubes carbon aerogels model and others NLDFT Ar carbon 0 35 nm 40 nm Activated carbons activated equilibrium transition kernel at carbon fibers novel 77 K based on a slit pore model micro mesoporous carbons of type CMK 1 and others P N 05079 Rev Page 125 of 133 Nova e NovaWin Operating Manual I THEORY AND DISCU
164. will appear in the column on the left along with the select flags P N 05079 Rev Page 57 of 133 Nova e NovaWin Operating Manual F INSTRUMENT OPERATION Tags Add point P Po Tags on off S reset E Add OS00000 A 5 WAL Adsorption Bo n Desorption Spread points M Multi BET Ww S Single BET T Thickness Crt 10 Add Pore volume L Langmuir P Pore size Ai OR amp Fractal Selected data P Po points and flags will be listed here Highlight desired data points and click the any additional flags that you wish to set for the points Then click the Apply to selected button when finished Click the All button to highlight all of the data points in the column i EL Load Paints e Save Points Figure F 32 Point selection for surface area measurements Data points for Multi Point BET surface area measurements may be entered one at a time using the Add button and or as a group by clicking the Spread Points function Enter the lowest P Po point for the spread in the left space and the highest P Po data point in the right space Then select the total number of P Po points in the Cnt count space Typically the multi point BET surface area measurements incorporate five to seven points more may be acquired for greater resolution in a relative pressure range of 0 05 to 0 30 The A and the M tags should be set for these points either when adding them or afterwards by clicking the Al
165. xcept by a written instrument signed by the Seller s authorized representative regardless of any contrary or additional provisions contained in any purchase order or other form from the buyer FOB Point The FOB Point is Boynton Beach FL unless otherwise indicated on our Quotation or agreed to in writing by an authorized Seller representative Payment terms Terms are net 30 days from date of invoice for established accounts where Seller has received adequate financial information to warrant extending credit to Buyer Purchase orders from customers not meeting with Seller s financial approval are not accepted under credit terms Delivery Delivery dates are Seller s best estimate of the time products will be shipped from our factory and we assume no liability for loss damage or consequential damages due to delays No liability shall result from delay in performance or non performance of this agreement directly or indirectly caused by fire explosion accidents flood labor trouble or shortage war act of God or arising from contingencies happenings or causes beyond the control of the party affected Material Shortages In the event of inability for any reason to supply the total demands for the materials specified in this order Seller may allocate its available supply among any or all purchasers as well as departments and divisions of the Seller on such basis as it may deem fair and practical without liability for any failure or per
166. y Vacuum hose and or fittings Check hose and tighten fittings test on boot up leak Replace as necessary Sample elutriates during See E 4 Elutriation and Its Prevention outgassing P N 05079 Rev Page 130 of 133 Nova e NovaWin Operating Manual REFERENCES 10 11 12 13 14 15 16 17 18 19 20 pale 22 REFERENCES S Brunauer P Emmett and E Teller J Amer Chem Soc 60 309 1938 A V Kiselev and Y A Eltekov World Congress on Surface Activity Vol II p 228 Butterworths London 1957 S Lowell J Shields G Charalambous and J Manzione J Colloid Interface Sci 86 191 1982 S Brunauer L S Deming W S Deming and E Teller J Amer Chem Soc 62 1723 1940 J H de Boer The Structure and Properties of Porous Materials p 68 Butterworths London 1958 J H de Boer B C Lippens B G Lippens J C P Broekhoff A van den Heuvel and Th V Osinga J Colloid Interface Sci 21 405 1966 E P Barrett L G Joyner and P P Halenda J Amer Chem Soc 73 373 1951 D Dollimore and G R Heal J Appl Chem 14 109 1964 G D Halsey J Chem Phys 16 931 1948 J H de Boer B G Linsen Th van der Plas and G J Zondervan J Catalysis 4 649 1965 R W Magee Evaluation of the External Surface Area of Carbon Black by Nitrogen Adsorption Presented at the meeting of the Rubber Division of the American Chem Soc October 1
167. ysisorption fles C QCdata Physisorb or to create a new folder for s Duantachrome RAM fles CG Cdatat A aw ihe selected fle type w Instrument DAT files CAO Cdatas instrument Data Soran Dinor ments CAAC datas a wilian Data Legend w This entry is OF dh Insufficient persmissions to folder Contact your system administrator A Folder does not exist Modify entry Use this configuration window to specify the default location of the selected file type Whenever a file of these types is being opened saved the file selector dialog starts in the specified folder Select a file type from the list and see the current setting in the Path field To change the default location click on the Browse button Use the Select Folder window to navigate to the desired folder Click Select or Cancel on that window to return the System Folders window Click Cancel to close the window without saving the changes Click OK to close the window and save the changes 4 Select Data Folder Da The software allows predefined default folder settings for each data file type it recognizes Use this configuration window to specify the default location of the selected file type P N 05079 Rev Page 30 of 133 Nova e NovaWin Operating Manual D SOFTWARE CONFIGURATION D teste 4 dh HOV files D testFolder wf Ausihary Documents CAO Cdataaueiany Documents w laer Files CAR Catarina Select Path Legen w This entry

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