SML5 ソフトウエアの和文取扱説明書はこちらから
Contents
1. 43 General description of the new SML 5 software Mean Std Deviation Contact Medium OCTADECYL 1 18 0 126 Fal Migration concentration mg kg OL TADECYL 3 05 5 Dl tert BUTYL 4 HYDROXYPHENYL PR 1 SE 0 1 JE 1 1E 0 1 0E 0 UE DIE UE DIE 5 0E 1 4 0E 1 3 0E 1 2 OE 1 1 UE 0 0E 0 DU 5 10 15 20 25 30 35 40 45 50 55 B 65 70 75 80 85 J0 95 100 time days Fig 5 2 Quantification of the amount of variance that each input factor Xi all variables of the articles contributes with on the unconditional variance of the output V Y Sensitivity measures based on the MCS approach include regression based measures Standardized Regression Coefficients SRC Partial Correlation Coefficients PCC Standardized Rank Regression Coefficients SRRC Partial Rank Correlation Coefficients PRCC Some of them have been implemented in the present version2. The analysis methods available in SML software are SML5 e Monte Carlo e Fourier Amplitude Sensitivity Test FAST FAST e Sobol 42 General description of the new SML software 5 5 2 Monte Carlo Simulation MCS Monte Carlo Simulation MCS is a widely used method for uncertainty or sensitivity analysis It involves random sampling from the distribution of inputs and successive model runs until the desired accuracy of the outputs is reached Not only the means and variances but also the distributions of input parameters are required to run the MCS In the present version of SML only Gaussian normal distribution have been implemented for the different input parameters MCS
3. MCS SML5 Thickness um Gt n Le z A Thickness pm Density g cm3 CTN Density g cm3 NITROCELLULOSE een POLYPROPYLENE isotactig Standard Devi tion 2 Standard Deviation 87 5 NITROCELLULOSE S MOL CDRODLENE isotactic z UICE NEN v OK 3 Cancel POLYPROPYLENE otactic OK Cancel NLTROCELLULOSE POLYPROPYL NE isotactic ContactMedum NITROCELLULOSE POLYPROPYLENE isotactic M and milk based drinks m 350 5 87 5 500 5 50 Thickness um i OCTADECYL 3 3 OCTADECYL 3 3 0 Gim mg L of substance in current layer Concentration mg kg Falm 500 s 50 Mean Standard Deviation v OK Cancel OK Cancel Fig 5 1 Random sampling from the distribution of inputs Gaussian normal distribution
4. 26 General description of the new SML software 5 3 Predictions and temperature profiles When all properties of an article are filled it is possible to proceed with prediction calculations by clicking on the prediction button Run prediction Fig 0 1 The prediction button Different types of predictions are available e lsothermal e Non Isothermal e Stepwise e Modulated e Shock e Worldwide e SIANAG NATO SML e Customized 31 Isothermal In the isothermal conditions mode it is possible to set a number of isotherms and the temperature difference AT between each isotherm
5. Spearman RCC CC PRCC PCC Rank transformed statistics are more robust and provide a useful solution in the presence of long tailed input output distributions A rank transformed model is not only more linear it is also more additive Thus the relative weight of the first order terms is increased on the expense of higher order terms and interactions see for example 5 1 additive 1 5 expense FALET 47 General description of the new SML 5 software 5 3 Variance based methods for sensitivity analysis The main idea of the variance based methods is to quantify the amount of variance that each input factor Xi contributes with on
6. 32 General description of the new SML software 5 3 9 The c t chart a c t Pot Iso 5 C 100d Concentration mq kq ADIPIC ACID BIS 2 ETHYLHEXYL ESTER Contact Medium OCTADEC TL 3 3 5 Dl tert BUTYL 4 HYDROAY PHENYL PR Contact Medium 1 ZE 1 1E 0 1 OE 0 UE DIE r UE 6 OE 1 5 0E 1 4 0E 1 3 0E 1 0E 1 1 OE 1 0 0E 0 a 10 15 20 25 30 35 40 45 50 55 DU 65 FO 75 80 85 80 95 100 time days Fig 0 2 The c t chart 0 35 The c t chart shows the migration of the chemicals over time The chemicals and layers to be displayed can be selected by using the checkboxes in the results grid C t result grid check box 33 General description of the new SML 5 software 3 10 The c x t chart c x t Pot Iso 5 C 100d ADIPIC ACID Bls 2 ETHYLHEX Y L ESTER OCTADECYL 3 03 5 Dl tert BUI T L 43 H DRO YPHEN YL PR 1 1E 1 OE 4 BE 3 8 0E 3 i E 7 0E 3 5 EnE 3 S 5 DE 3 T 4 DEA 5 3 DE 3 2 DE43 OES 77 URL RR D DEA D 50 100 150 200 250 300 350 Layer Thickness um LI 400 days
7. 2 Layers Then enter the number of layers and fill the information for each of them 3 Chemicals Enter the number of chemicals and fill the information for each of them 4 Data First fill the concentration of each substance in each layer then the diffusion coefficients and finally the partition coefficient The package being fully created it is possible to start calculating predictions by clicking on the Run Prediction button Run Prediction Note the Wizard is optional Wizard General description of the new SML software 5 2 5 Article Properties The article grid AHI Y y F RAH Article Surface cm 2 33 Add layer s POLYVINYL Primer n contacted ll Thickness um 2 5 ADIPIC ACID 4E04 MELAMINE 0 Concentration Diffusion coefficient Partition co
8. Temperature 20 i AT 10 p Number ofisotherms 5 Final Temperature 60 a Fig 0 2 Isothermal conditions 2f General description of the new SML 5 software 32 Non lsothermal In the non isothermal conditions the starting temperature and different heating rates can be defined Starting temperature 20 K Heating rate C min 4 K min 8 K min Fig 0 3 Non Isothermal conditions 3 3 Stepwise The stepwise conditions are a combination between isothermal and non isothermal temperature modes A number of cycles can be also fixed Time unit min Time max 100 min Number of cydes 1 From Temp C To Temp C Heating rate C hour Time hour 20 ec 40 c 1 K min 20 mn X 40 ec 40 ec ln K min 10 mn X 40 C ep a 2 K min 10 mn X 60 C 60 c o K min D mn X Fig 0 4 Stepwise conditions 28 29 General description of the new SML software 5 3 4 Modulated In the modulated conditions it is possible to set an oscillat
9. c x t Pot Iso 5 C 100d ADIPIC ACID Bls 2 ETHYLHEX Y L ESTER OCTADECTL 3 03 5 Dl tert BUI T L 3 H DRO RS PHENYL PR B 5E 2 6 0E 2 5 5E 2 5 0E 2 D 4 5E 2 D E 40E 2 c 3 5E 2 30E2 E 2 5E 2 d 20E 2 B 15E 2 1 0E 2 5 nE 1 0 0E 0 0 20 40 DU 0 100 120 140 160 180 200 220 240 260 280 300 320 340 360 Layer Thickness Cum LI 100 days Zoomed Fig 0 3 The c x t chart The c x t chart shows the migration of the chemicals into the different layers the dotted line being the average concentration of a chemical inside a layer c x10 mcr M General description of the new SML software 5 3 11 Comparison Output The comparison output window allows comparing the calculation results of different outputs To add an output to the comparison drag and drop the output from the list on the left to the dedicated zone in the comparison output window Output Comparison T Drop outputs here To add them into the comparison Tid Iso 5 G 100d Pat ele 100d POLYVINYLBU Primer Aluminium HS Lacquer Contact Medium B Amt ACID
10. 3 1 33 34 3 6 3 8 31 General description of the new SML 5 software Outputs The output window shows the results of the prediction calculations The window is divided in three parts Output window window 3 e The results grid e The c t chart SE rtl e The c x t chart xt Moving the mouse pointer over the c t chart will update the results grid and the c x t chart based on the time pointed on the c t chart C 0 c 0 c x 0 Artide NITROCELLU d POLYPROPYL Mop NITRQCELLU POLYPROPYL Thickness 1m 350 v ADIPIC ACID ADIPIC ACID 7 881E 03 5 856E 4 02 NEM ccrapECC OCTADECYL 1 835E 02 4 545E 02 Concentration Diffusion coefficient Partition coefficient Fig 0 1 The result grid c t The grid shows the values of the concentration the diffusion coefficients and the partition coefficients for all substances in all layers
11. 1 2 2 Xi 2 A model without interactions is said to be additive for example a linear one The first order indices sums up to one in an additive model with orthogonal inputs For additive models the first order indices coincide with what can be obtained with regression methods For non additive models we would like to know information from all interactions as well as the first order effect For non linear models the sum of all first order indices can be very low 1 1 1 1 1 1 The sum of all the order effects that a factor accounts for is called th
12. a Substances 1 will be Irganox 1076 a 1 Irganox1076 General description of the new SML 5 software c mb Surface cm 2 600 Concentration Diffusion coefficient Partition coeffident ie Qc eg Chemical PHOSPHOROUS ACID TRIS 2 4 DI tert BUTYLPHENYL ESTER Set to user defined Set to user defined Molecular weight g mol 5536 94 b Substances 2 will be Irgafos 168 b 2 lrgafos168 4 Step Define initial concentration of migrants in the polymer layer 100 ppm for Irganox 1076 500 ppm for Irgafos 168 Irganox1076 100ppm Irgafos168 500ppm Surface cm 2 600 General description of the new SML software 5 4 Step Define the estimation procedure for the diffusion coefficient of the migrants in the polymer layer e g selected Piringer approach Piringer Example for 20 C on 2 s P 9 045E 11 General description of the new SML 5 software 5 Step Define the partition coefficient of the migrants between polymer layer and food simulant selected known K
13. PCCs 2 x y PCC CC PCC x y PCC 2 Fig 5 3 Correlation coefficients CC providing a measure of the strength of the linear relationship between two variables x variable parameters in the article and y migration 45 General description of the new SML 5 software Thickness of NITROCELLULOSE Concentration co CH 3 8 AN C Concentration O 00E 0 z 00E 0 4 00E 0 6 00E 0 8 00E 0 1 00E 1 0 00E 0 2 O0E 2 4 O0E 2 Variation Variation c 0 022 oc 40 051 pcc 40 0325636219942979 111822700743569 Concentration of OCTADECYL 3 3 5 Dl tert BUTYL KP Solu Known of OCTADECYL 3 3 5 DI tert BUTYL c e C oncentrat ca c c TI Concentration B DD EZ O O0E 0 1 00E 0 2 00E 0 S 0Q0E 0 4 00E d O0E 2 5 DOE variation Variation cc 0 956 cc 0 015 pec 0 958818312434365 pec 0 20946960
14. Software starts with definition of the packaging geometry in this example the EU cube EU cube surface 600 cm 1 Package Choose the package geometry and enter the number of all articles For all articles enter the number of layers and substances Contact surface cm 2 500 Width cm 10 12 Layers Volume of contact medium cm 3 1000 Height cm 10 Define all layers for all articles Mass of contact medium oi 1000 Length cm 10 3 Substances Define all migrants for all articles 4 Data Enter in all cells of the grid the concentration diffusion and partition coefficients of all substances in all layers O Use wizard for articles 2 Step Define the number of layers minimum two 2 for a monolayer plastic and the food simulant Add Layer 2 1 1 4 4 1 5 1 E dB Article1 Package 1 e Jm rm Al Article Surface cm 2 600
15. Y Y Sj 5 To estimate the value of Sj we require realizations of the input distributions and the associated model evaluations The ratio S was named first order sensitivity index by Sobol 6 The first order sensitivity index measures only the main effect contribution of each input parameter on the output variance It doesn t take into account the interactions between input factors Two factors are said to interact if their total effect on the output isn t the sum of their first order effects The effect of the interaction between two orthogonal factors Xi and Xj on the output Y can be computed see for more details 5 and is known as the second order effect Higher order effects can as well be computed see for example 5 Sj TOSI Sobol 6 1
16. MELAMINE SS E E E E alpha METHYLSTYR E F P CH E BA ocrapecun 3 3 5 E F F acce 1000 Eet 505 C 1000 NITROCELLU POLYPROPYL Contact Medium E ACIPIC ACID E A A oocTADECYL 7 EI 1 2E 0 c 1 1E n 1 0E D _ 80E 1 DI GIE II E 7 DE 1 S 60E 7 5 0E We lid E 406 1 lif Iso 5 C 100d 7 80DE al Pot 2 0E dli Iso S C 100d ET SUM Iso 5 C 100d LT Comparison 2 nnE n DU 5 10 15 20 25 20 35 40 45 50 55 60 B5 FO 75 80 85 S30 95 100 time days Fig 0 4 The comparison output window 35 General description of the new SML 5 software 3 12 Sum Output The sum output window allows adding the calculation results of outputs of same substances To add an output to the comparison drag and drop the output from the list on the left to the dedicated zone in the comparison output window sum output 1 comparison output ny ewe S ELS Surface selected Lid 33 cm 2 Pot 156 cm 2 ADIPIC ACID 0 lt 189 2 cm 2 MELAMIME 0 lt 189 2 cm 2 CH alpha METHYLSTYRENE 0 lt 189 2 cm 2 OCTADECYL 3 3 5 DI tert BUTYL 189 lt 189 2 m
17. Egypt Cairo T England London Fig 0 7 Worldwide conditions 3 7 STANAG STANAG 2895 is a NATO Standardisation Agreement describing the principal climatic factors which constitute the distinctive climatic environements found throughout the world Time m x 3 year Y L A1 diurnal seasonal storage A1 diurnal storage i a A2 diurnal seasonal storage F A2 diurnal seasonal A diurnal storage W A2 diurnal A3 diurnal seasonal storage A3 diurnal seasonal A3 diurnal storage F1 A3 diurnal B1 diurnal seasonal storage 3 Bi diurnal seasonal 40 B1 diurnal storage 15 7 L B1 diurnal j Fi B2 diurnal seasonal storage lime months B2 diurnal seasonal B2 diurnal storage temperature DEET EC ET Fig 0 8 STANAG conditions 30 General description of the new SML software 5 3 8 Customized The customized prediction mode allows loading a file with a custom temperature profile i e when using a datalogger Fi S Ty Be Ei Zeit 1 yi 1 1 J 2 3600 3 3 7200 4 4 10800 5 5 14400 D 6 18000 Temperature 3 19 378 19 335 19 351 19 333 19 318 19 273 Fig 0 9 Customized conditions d 39 6 W 39 8 r Time Column 2 Unt s Temperature Column 3 Unit DC d Repeating temperature profile Number of cycdes 1 Prediction AKTS
18. SML 5 Software General Description SML5 BLEND COFFEE CONTACT Schweizerische Fid senschaft e End nA 7 Ge MIDC Tec systems AKTS Canfederazione Svizzera d Confederaziun svizra AKTS AG MDCTec Systems GmbH TECHNOA Swiss is Gutenbergstrasse 5 3960 Sid Federal Office of Public Health D 82205 Gilching poe Food Safety Division Germany e E Schwarzenburgstrasse 165 Tel 49 0 173 6662097 us pe ee SCH e 3003 Bern Fax 49 0 3212 1029321 RE eT l p i Switzerland http www mdctec com info contact akts com Tel 41 0 31 322 9568 email info mdctec com i Fax 41 0 31 322 9574 http www bag admin ch General description of the new SML 5 software Table of contents Introduction 2012 5 16 General description of the new SML software 5 1 SML5 3 13 1 Step
19. d e C LI tme daz mg kg 11 General description of the new SML 5 software Regislation Confirmity 3 Migration SML mg kg of contact medium Specific Migration Limit QM mg kg of packaging Quantity Maximum OMA mg dm 2 of packaging Quantity Maximum per Area DL mg kg of contact medium Detection Limit Green Compliant Red Not compliant Substance 1 5 517E 01 mg kg European Union Regulatory EU No 10 2011 SML QM QMA DL Switzerland Regulatory SR 817 023 21 SML QM QMA DL European Union Regulatory 2002 72 EC SML QM QMA DL EU SML 6mg kg 0 5517mg kg Compliant non Compliant General description of the new SML software 5 1 Compliance certificate Packaging 120219 Package yogo new 5um Geometry Type Truncated cone Volume cm 3 198 4 Mass oi 198 4 Contact area cm 2 189 2 Article Mame Lid Number of substances 4 Contact medium Food contact material structure POLYVINYLBUTYRALS HS Lacquer Contact Medium 13 Prediction time Contact Medium Country 20 0
20. 1 for both migrants because of good solubility in vegetable oil Known 1 SML5 Kp Solubility Pow Kp 1 L t AOiffuson coeficert ey Add substances JC Layer Contact Medium Substance Substance 2 Partition coefficient Kp Known 1 Solubility Pow General description of the new SML software 5 6 Step Run prediction e g at 40 C for 10 days 40C 10 ec Predictions Temperature profiles Number of Runs 1 I Include Sobol Runs Fast distribution Ku AT Humber of isotherms 1 FnalTemperature 20 Results IO c NI Qutput Calculation a ajm yE k 0 Artide C Lavera d Contact Med i Thickness um 100 557704 BE subenne OCTADECYL 5255301 5 517E 01 BM subsane PHOSPHORD 233790 2 758E 400 Concenitraton Diffusion caeFfiaent Partition coefficient Temperature 40 C 1 Aride 1 Iso 40 C 10d Substance 1 Conisct Mecium Subeisnce J Contact Maclium E cn E 5 T B
21. ADIPIC ACID BIS 2 ETHYLHEXYL 0 lt 189 2 cm 2 RI T x UT E Md m A 3 Lid D ai r D v li Iso 5 C 100d E P F Ji Dot n C e b s hil Iso 5 C 100d lli SUM Iso 5 C 100d 0 10 20 30 40 50 BO ZU GU a 100 time days Fig 0 5 The sum output window 36 General description of the new SML software 5 4 Legislation and compliance In the last years migration modelling got more and more accepted and was introduced in legislation for plastic food contact materials and articles allowing for compliance assessment with applicable specific migration limits stipulated by legislation 2011 SML PEIFU Legislation conformity check Compliance evaluation for substances with specific migration limit SML listed in the Plastics Regulation EU No 10 2011 and generation of compliance certificates EU NO 10 2011 SML 37 38 Compliance certificate JackKaa i
22. D Halt Fig 0 12 Contact medium database Reset layer Realistic A 0 4 B 0 Worst Case A 0 4 B 0 4 Fig 0 13 Additional properties for contact medium type layer 21 General description of the new SML 5 software Set to user defined allows customizing the properties of the polymer When the polymer is set to user defined it is possible to enter the properties of the polymer Otherwise if the polymer is loaded from the database its properties are filled automatically Reset layer allows setting the default values Reset layer 2 6 Substances properties OS lave 473 Substance MELAMINE Le JL JL Copy from Substance abbreviation MELAMINE E Database Chemical MELAMINE d Set to user defined Molecular weight g mol Substance details Pow Melting point CH 133 08 Density g cm 3 Electronegativity 10 Fig 0 14 Substance properties The sub
23. 10 Additional properties for polymer type layer 20 General description of the new SML software 5 Database allows browsing for a known polymer 4024048 ig Selecting polymer s Browse polymer database Reference number CAS number POLYMER CAS number o009004 34 6 14500 43280 0009004 57 3 16325 53280 0009004 70 0 22450 43330 0009003 17 2 23515 00090 16 00 6 23547 76721 0009002 89 5 23680 81280 0063148 65 2 23710 o009006 04 6 24250 84560 ACRYLIC ACID METHYL METHACRYLATE COPOLY 0025322 25 2 31545 ACRYLONITRILE BUTADIENE COPOLYMER 4 mt Fig 0 11 Polymer database Contact medium m E Type Polymer 8 Contact medium Thickness um 50115 Density gfem3 1 Layer abbreviation Contact Medium FE ETF it up 7 Milk A Milk and milk based drinks whole partly dried and skimmed ges Milk B Milk powder including infant formula based on whole milk pc Fermented milk such as yoghurt buttermilk and similar products Fi Cream and sour cream Rahm und Sauerrahm Cheeses A Whole with not edible rind Kase A Ganz mit nicht Cheeses B Natural cheese without rind or with edible rind gouda LA Cheese C Processed cheese soft cheese cottage cheese and sir Cheese D Preserved cheese L In an oily medium Kase
24. Artide li Number of layer s to add 2 Concentration Diffusion coefficient Partition coefficient g e substances ok Annuler General description of the new SML 5 software a Layer 1 will be of type Polymer POLYETHYLENE LOW DENSITY from Database a 1 type Polymer Database POLYETHYLENE LOW DENSITY Selecting Polymer i Selecting polymer s Browse polymer database Reference number Mame CAS number Type Total chemicals Found 248 number OO09004 34 6 OO039004 57 3 oo0039004 70 0 oo039003 17 2 0009016 00 6 ooo9002 89 5 0063148 65 2 OO039006 04 6 ETHYLCELLLILOSE NITROCELLULOSE POLVYBLITADIENE POLYDIMETHYLSILORANE Ma 68500 POLYVINYTLALCOHOLS POLYVINYLBLUITYRALS RUBBER MATLUR AL Molecular weight Reference number 14500 43280 16925 53260 22450 43330 23515 east fore 236850 81280 23710 24250 64560 Mol 448 aay 31545 31605 HN te O009003 15 3 ACRYLIC AcCID METHYL METHACRYLATE COPOLY ACRYLONITRILE BUTADIEME COPOLYMER Il x polymer lt 8 Article 1 Package 1 ole c N Artide E3 Surface cm 2 600 WPye 2 Ji LA POLYETHYLE Not defined Artide Thickness um 100 100 Concentration Diffusion coefficient Partition coe
25. Height cm 7 Diameter D cm 6 5 Diameter d cm 5 5 Surface hy article Total surface of all artides cm 2 189 Fig 0 6 The package panel The package panel allows changing the geometry and the size of the package The surface of each article can be defined in the grid General description of the new SML 5 software 2 4 The Wizard When creating an article many information and properties have to be filled The role of the Article Creation Wizard is to help filling all this information step by step Article Creation Wizard Wizard Close Wizard A Article Creation Wizard 2 Layers 3 Chemicals 5 Run prediction lt Previous Step ext Step b Your article is fully customized You can now run a prediction on it Fig 0 7 The wizard interface 1 Surface The surface of the article has to be entered first
26. of SML and are described below MCS SML5 SRC PCC SRCC PRCC 44 General description of the new SML software 5 Correlation coefficient CC and partial correlation coefficients PCC CC PCC The correlation coefficients CC usually known as Pearson s product moment correlation coefficients provide a measure of the strength of the linear relationship between two variables x and y and is denoted by corr x y see for example 5 for more information on the definition of CC CC Pearson product moment correlation coefficient 2 X Y x y corr x y CC example 5 The correlation coefficient measures the extent to which y can be approximated by a linear function of x
27. of contact medium cm 3 198 4 Mass of contact medium oi 198 4 New article O Use wizard for articles E Height cm 7 Diameter D cm 6 5 Diameter d cm 5 5 Surfaces Total 189 1 Package Choose the package geometry and enter the number of all articles For all articles enter the number of layers and substances 2 Layers Define all layers for all articles 3 Substances Define all migrants for all articles 4 Data Enter in all cells of the grid the concentration diffusion and partition coefficients of all substances in all layers Fig 0 5 The package panel for packaging and article creation Fig 4 5 1 Package 2 Layers 3 4 16 General description of the new SML software 5 T 120219 Package yogo new Geometry A Truncated cone Contact surface cm 2 Volume of contact medium cm 3 Mass of contact medium oi
28. process See the Predictions chapter for more information Run Prediction Prediction General description of the new SML 5 software Contact medium Thickness um Density a cm3 Copy from Layer abbreviation POLYVINYLBUTYRALS Material POLYVINYLBUTYRALS di 5et to user defined Reset layer Upper limit A p 2 21 lo A p 2 21 Realistic case Ap 13 1 1577 Ap 7 721 Layer details Fig 0 9 Layer properties The layer properties panel allows defining the properties of the current selected layer Type of layer defines if the layer is a contact medium typically food or a polymer Upper limit A n 2 21 Tau 0 Am 2 21 Realistic case Ap 13 1 Tau 1577 Ap 7 721 zl Layer details Molecular weight g mol 1000000 Glass transition temperature C 63 Electronegativity 10 Fig 0
29. the bottle itself 1 2 Article 1 cap Article 2 bottle Fig 0 2 A package can be composed of multiple articles An article is composed of one or more layers of different sizes and properties 1 1 j i Contact ANN Layers medium Chemicals Fig 0 3 An article is composed of multiple Fig 0 4 Chemicals can be found in all layers layers Chemicals can be found in one or more layers 1 ariticles ORE General description of the new SML 5 software 2 3 Creating packages and articles Package Geometry Fo Truncated cone Contact surface cm 2 189 2 Volume
30. 0 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 time days Fig 5 5 Quantification based on FAST analysis of the amount of variance that each input factor Xi all variables of the articles contributes with on the unconditional variance of the output V Y concentration mak g 50 General description of the new SML software 5 CELLULOSE DE 1 22 Thickness of POLY PROPYLENE Ds 74 Concentration of OCTADECYL EE 0 9 KP Solu Known of QCTADECYI CO 23536 Unexplained OCTADECYL 3 3 5 DI tert BUTYL 4 HYDROXYPHENYL PR FAST em Sensibility 1 100 g5 au B3 Bs T5 ZU B3 BO 55 Sus 4555 40 3555 AU 25 20 15 10 395 Oo 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 50 85 90 95 100 time day Fig 5 6 FAST analysis results Sensitivity S v of each variable influence of each examined variable on the migration results 5 5 Sobol s indices via Winding Stairs Chan Saltelli and Tarantola 11 proposed the use of a new sampling scheme to compute both first and total order sensitivity indices in only N x k model evaluations The sampling method used to measure the main effect was called Winding Stairs developed by Jansen Rossing and Deemen in 1994 12 A first set of variables simply comes from the Gaussian distribution Then a lot of other set of input of variables are generated from the first set and will be used in complex mathematics analysis afterward For example if one ent
31. 00E 04 cm 2 s Known MELAMINE Propertes Density g om 3 1 Molecular weight g mol 126 12 POW 1 37 Initial concentration Partition coefficient POLYVINYLBUTYRALS Primer 5 854E 05 Solubility based Primer Aluminium 0 5 Solubility based Aluminium H5 Lacquer 0 000115 Solubility based H5 Lacquer Contact Medium 0 5 Solubility based Diffusion coefficient POLYVINYLBUTYRALS 1 453E 12 cm 2 s Piringer based Primer 1 504E 12 cm 2 s Brandsch equation based Aluminium 3 336E 20 cm 2 s Piringer based HS Lacquer 1 131E 08 cm 2 s Piringer based Contact Medium 1 000E 04 cm 2 s Known 39 General description of the new SML 5 software alpha METHYLSTYRENE Properties Density g cm 3 1 Molecular weight g mol 118 18 POW 3 48 Initial concentration H5 Lacquer 10mg kg Partition coefficient POLYVINYLBUTYRALS Primer 0 0002587 Solubility based Primer Aluminium 0 5 Solubility based Aluminium HS Lacquer 0 00039319 Solubility based H5 Lacquer Contact Medium 1 Solubility based Diffusion coefficient POLYVINYLBUTYRALS 1 639E 12 cm 2 s Piringer based Primer 1 798E 13 cm 2 s Piringer based Aluminium 3 762E 20 cm 2 s Piringer based HS Lacquer 1 276E 08 cm 2 s Piringer based Contact Medium 1 000E 04 cm 2 s Known OCTADECYL 3 3 5 DI tert BUTYL A HYDROXYPHENYL PR Properties Density g cm 3 1 Molecular weight g mol 530 88 POW 13 41 Initial
32. 2 2012 Prediction temperature temp 100 day s I Switzerland Gi European Union Thickness um 2 5 Density g cm 3 1 POLYVINYLBUTYRALS Thickness um 1 Density g cm 3 1 FORMALDEHYDE 2 4 6 TRIAMINO 1 3 5 TR Thickness uim 37 Density g cm 3 2 7 Aluminium Thickness um 100 Density g cm 3 1 BUTADIENE STYRENE COPOLYMER Thickness um 6 011E04 Density g cm 3 1 User defined General description of the new SML 5 software 2 AKTS SML5 SMLS SML5 Help 2 1 Basics The use of AKTS SML software can be described in four steps AKTS SML 4 2 3 4 1 Defining 2 lemperature Package Prediction zs 4 Legislation 3 Calculated Confirmity Outputs Fig 0 1 Applications of SML Software from packaging definition to legislation conformity Define the package by creating the different articles of the package and filling their properties Predict the migration using different temperature profiles iso non iso worldwide climate etc Analyze the calculated outputs Check the co
33. 2339 789 Fig 5 4 Scatter plots illustrating relationships between the input factor Xi variable parameters in the article and the output Y migration WETA DF A plot of the points Xij Yj for j 1 2 N usually called a scatter plot can reveal nonlinear or other unexpected relationships between the input factor Xi and the output Y Scatter plots are undoubtedly the simplest sensitivity analysis technique and is a natural starting point in the analysis of a complex model It facilitates the understanding of model behavior and the planning of more sophisticated sensitivity analysis Du for j f Z N EHDA y 46 General description of the new SML software 5
34. 3 Cheese C Processed cheese soft cheese cottage cheese and sir Cheese D Reeg cheese I In an ily mci K se D Halt 7 General description of the new SML 5 software Add layer s Concentration Diffusion coefficient Partition coefficient Thickness um ee Density g cm3 1 Layer abbreviation Contact Medium d Layer 2 Contact medium thickness calculated from volume over area of packaging d 2 BAO RM BREE ABD SHR SENET 1000cm 600cm 1 6667cm dB Article 1 Package 1 Sollee Surface cm 2 600 Number of substance s to add 2 I oes 3 Step Define the number of migrants minimum one 1 1 2 General description of the new SML software 5 4B Selecting Polymer 26 Selecting substance s CAS number Reference number OCTADECYL 3 3 5 DI tert BUTYL 4 HYDROXYPHE 0002082 79 3 68320 Substances are qmm from the Bb an eg iones 1076 Assign to Layer lrganox1076 n Diffusion coefficient Partition coefficient ul
35. 5 4347 s 0 00023 0 0005174 5 1276 5 0 0003919 5 5 006 5 2 909 SD 1452 5 3 42 EE Layer Primer Partition coefficient O Known X Solubility mg L of substance in previous layer E Known 1 Based on temperature Example for 20 C g L 0 0005659 Pow Solubility mg L of substance in current layer Known i amp Based on temperature Example for 20 C g L 0 0002587 Calculated Kp X Y 2 187 Set all to default value Apply same mode to all layers and substances Fig 0 17 Determination of the partition coefficients The data properties shown are based on the current selected tab of the article grid The partition coefficient value can be entered manually when known In case of liquid contact media the solubility can be entered or the Pow Pow Note n Octanol Water LogPow LogPow
36. DE 000108 24 7 10150 1c ACETOGUANAMINE 000542 02 9 10155 12 12 1 ACETOPHENONE N00098 86 2 10157 alpha ACETOXYSTYRENE D02206 94 2 10160 beta ACETOXYSTYRENE 0010521 96 7 10162 1 p ACETYLAMINO BENZOIC ACID 0000556 08 1 10180 Lp 4 d t Fig 0 15 Substance database 23 General description of the new SML 5 software 2 7 Data concentration diffusion and partition coefficients The tab Data allows defining e the concentration e the diffusion coefficient e the partition coefficient Diffusion coefficient POLYVINYLB FORMALDEH Aluminium BUTADIENE Thickness um 2 5 1 37 100 ADIPIC ACID P 1 087E 12 P 1 192bE 13 P 2 496E 20 P 8 462E 09 0 0001 MELAMINE P 1 453E 12 P 3 338E 20 P 1 131E 08 0 0001 alpha METHY P 1 639E 17 P 1 798E 13 P 3 762E 20 P 1 276E 08 0 0001 m OCTADECYL P 2 09E 14 P 2 293E 15 P 4 799E 22 P 1 627E 10 0 0001 T Concentration Diffusion coefficien iPartition coefficient 1 Add substances JE Los Poet Substance MELAMINE Data diffusion coefficient Diffusion coefficent C Known or with Exdif Interpolation based on Tg Piringer 3 Customized equation 5 Brandsch equatio Example for 20 C cm 2 s BCL 504
37. E 12 EUER Apply same mode to all layers and substances Fig 0 16 Determination of the diffusion coefficients The data properties shown are based on the current selected tab of the article grid The diffusion coefficient values can be entered manually when known or it is possible to load a value from the database to use an Arrhenius Piringer or Brandsch calculation and even to enter a customized equation Pirin9er Brandsh Brandsh Piringer Brandsch 2 240 Version5 00 Brandsch 24 General description of the new SML software 5 25 General description of the new SML 5 software Partition coefficient 100 d 5 3 802 0 005539 5 88 85 5 0 01125 5 3 569 S 0 0001171
38. Gaussian m mean s standard deviation mg kg The main advantage of the MCS is its general applicability MCS suffers for its computational requirements since thousands of repetitive runs of a model are required to reach convergence High speed personal computers have minimized the computational challenges Another limitation of MCS is the need for user specified rules for determining the number of simulations required see 2 4 for more information and recommendation on the subject MCS MCS 1 1000 MCS user specified 2 4 e words jp MCS
39. Rank correlation coefficient RCC and partial rank correlation coefficients PRCC RCC PRCC Since the correlation coefficient and partial rank correlation coefficient methods are based on the assumption of linear relationships between the input output factors they will perform poorly if the relationships are nonlinear With SML Software rank transformation of the data is possible too This concept can be used to transform a nonlinear but monotonic relationship to a linear relationship When using rank transformation the data is replaced with their corresponding ranks The usual correlation procedures are then performed on the ranks instead of the original data values Spearman rank correlation coefficient RCC are corresponding CC calculated on ranks and partial rank correlation coefficients PRCC are PCC calculated on ranks SML5
40. and vice versa In particular if exactly y a bx then corr x y 1 if b 1 and corr x y 1 if b 7 CC only measures the linear relationship between two variables without considering the effect that other possible variables might have y x y a bx then corr x y 1 if b 1 and corr x y 1 ifb 1 CC 200 2 When more than one input factor is under consideration as it usually is the partial correlation coefficients PCCs can be used instead to provide a measure of the linear relationships between two variables when all linear effects of other variables are removed PCC between an individual variable xi and y can be written in terms of correlation coefficients see for example 5 It is denoted by pcc xi y PCC characterizes the strength of the linear relationship between two variables after a correction has been made for the linear effects of the other variables in the analyses 1
41. concentration HS Lacquer 350mg kg Partition coefficient POLYVINYLBUTYRALS Primer 1 455 Solubility based Primer Aluminium 0 5 Solubility based Aluminium HS Lacquer 3 42 Solubility based HS Lacquer Contact Medium 1 Solubility based Diffusion coefficient POLYVINYLBUTYRALS 2 090E 14 cm 2 s Piringer based Primer 2 293E 15 cm 2 s Piringer based Aluminium 4 739E 22 cm 2 s Piringer based HS Lacquer 1 627E 10 on 2 s Piringer based Contact Medium 1 000E 04 cm 2 s Known Time Temperature conditions Iso 5 C 100days Migration SML mg kg of contact medium Specific Migration Limit QM mg kg of packaging Quantity Maximum mg dm 2 of packaging Quantity Maximum per Area DL mg kg of contact medium Detection Limit Green Compliant Red Mot compliant Fig 4 1 Legislation and compliance report calculated migration values 40 General description of the new SML software 5 Fig 4 2 Legislation and compliance report migration limits 41 General description of the new SML 5 software 5 Sensitivity Analysis Methods 5 1 Introduction Sensitivity analysis studies how the uncertainties in the model inputs X1 X2 Xk affect the model s response Y which for simplicity we assume to be a scalar Y f X45Xo XQ where f describes the implemented model A sensitivity analysis attempts to provide a ranking of the model s input assumptions with resp
42. e total effect 7 So for an input Xi the total sensitivity index STi is defined as the sum of all indices relating to Xi first and higher order 1 X STi XX 48 General description of the new SML software 5 There are different techniques to obtain these sensitivity indices such as Sobol s indices Jansen s Winding Stairs technique Extended Fourier Amplitude Sensitivity Test E FAST Sobol Jansen Winding Stairs Fourier Amplitude Sensitivity Test FAST Fourier Amplitude Sensitivity Test In the present software two m
43. ect to their contribution to model output variability or uncertainty The difficulty of a sensitivity analysis increases when the underlying model is nonlinear nonmonotonic or when the input parameters range over several orders of magnitude Many measures of sensitivity have been proposed For example the partial rank correlation coefficient and standardized rank regression coefficient have been found to be useful Scatter plots of the output against each of the model inputs can be a very effective tool for identifying sensitivities especially when the relationships are nonlinear In a broader sense sensitivity can refer to how conclusions may change if models data or assessment assumptions are changed see 1 for more details on the subject
44. efficient 1 Add substance s Run prediction Fig 0 8 The article grid The article grid displays the layers which can include the contact medium and the substances In the grid it is possible to customize the concentration the diffusion coefficient and the partition coefficient for all chemicals and layers The button Add Layer adds a new layer represented as a column in the grid The button Add Chemical adds a new chemical represented as a row in the grid Add Layer column Add Chemical row See more about e The layer properties e The chemical properties e The data concentration and coefficients e e When all the properties of the article are filled click on Run Prediction to start a calculation
45. ependent multivariate sources Predictability and Nonlinear Modelling in Natural Sciences and Economics 334 343 1994 53
46. ers 10 runs and has 1 substance with 4 variables it will run the simulations 4 1 10 times 1 10 4 1 4 1 x10 Leos o1 General description of the new SML 5 software 8195 Concentration of OCTADECYL 2 O 18336 Unexplained M wu E fz i E D GI 0 5 10 15 20 25 30 35 40 45 50 55 B 65 FO 75 680 85 80 95 100 time days Fig 5 7 Sobol analysis results Total sensitivity St v of the variables influence of all variables on the migration results The above figures illustrate the total sensitivity St v of the variables influence of all variables on the migration results and the evolution of the total sensitivity as a function of time In some cases there are unexplained values This situation can happen when the percentage calculation doesn t reach 100 Two cases are possible e The number of runs chosen to perform the calculations is not sufficient e Not enough variables are chosen to apply the method correctly Comments about our example All methods clearly demonstrate for our examined article tha
47. ethods are implemented the FAST method and the Sobol s indices based on Jansen s Winding Stairs technique SML5 2 FAST Fourier Amplitude Sensitivity Test Jansen s Winding Stairs Sobol 49 General description of the new SML 5 software 5 4 Fourier Amplitude Sensitivity Test FAST The Fourier Amplitude Sensitivity Test FAST was proposed already in the 70 s 8 10 and was at the time successfully applied to two chemical reaction systems involving sets of coupled nonlinear rate equations The Fourier Amplitude Sensitivity Test FAST is a sensitivity analysis method which does not use a Gaussian distribution Rotating vectors are assigned to each variable and each has a unique frequency and an amplitude of the mean A lot of input sets are generated making the variables oscillating A Fourier analysis is then applied on the results The number of runs depends only on the number of variables but it is not linear Note that the graphs of the FAST method are the same than the graphs of Sobol except that FAST shows only the local sensitivity Mean Std Deviation Contact Medium MO OCTADECYL 1 19 0 12 Fa Migration OL TADECYL 3 3 5 Dltert BUTYL 4 HYDROX Y PHENYL PR 1 3E 0 1 2E 0 1 1E n 1 0E 0 3 DE 1 8 DE 1 7 DE 1 B nE 1 5 DE 1 4 DE 1 3 0E 1 2 DE 1 1 0E 1 O 0E 0 D 5 10 15 2
48. fficient Add substance s E j taver taveri d JL x Type Polymer Contact medium Thickness um 100 el Density g om3 2 925 m Copy from Layer abbreviation Layer 1 Material POLYETHYLENE LOW DENSITY b Layer 1 LDPE thickness e g 100 um b LL f v TILDPEIE27 277100 um LEF Salt 2 AI 2 amp B 6 IA 73x 3 General description of the new SML software 5 Concentration Diffusion coefficient Partition coefficient al LX Type Polymer Contact medium Thickness um Density g cm3 Layer abbreviation Contact Medium c Layer 2 will be of type Contact medium vegetable oil food simulant c 2 li Layer Contact Medium E2 Type Polymer amp Contact medium Thickness um Density gm3 1 Copy from Layer abbreviation Contact Medium Milk A Milk and milk based drinks whole partly dried and skimmed ges Milk B Milk powder including infant formula based on whole milk pc Fermented milk such as yoghurt buttermilk and similar products Fi Cream and sour cream Rahm und Sauerrahm Cheeses A Whole with not edible rind Kase A Ganz mit nicht Cheeses B Haira dines without rind or with edible rind gouda
49. nformity of the results with different legislations ad dm Tg 2 3 4 General description of the new SML software 5 2 2 Package Structure A package is a group of different articles each article having different layers properties For instance a bottle can be divided into two articles the bottle cap and
50. ory temperature mode i e a day night cycle Time max 1 year Underlying es Underlying temperature Amplitudes Frequency Units Heati Nbr of oscillations 30 0 ec 24 0 K min 0 Iso mode 30 EN ec 24 0 Kinn 3 7802 hour lt 0 Kmn Fig 0 5 Modulated conditions 3 5 Shock The shock temperature conditions simulate a rapid temperature raise The frequence of the temperature shocks can be also defined Sharpen 10 Time max 1 day b al Star tii 1C T shock Frequency Units Nbr of T shocks 20 C 200 a 24 hour 1 Fig 0 6 Shock conditions General description of the new SML 5 software 3 6 Worldwide The worldwide temperature mode allows calculating predictions with real atmospheric temperatures The temperatures can be chosen for different climates yearly temperature profiles with daily minimal and maximal fluctuations l Time max Units Australia Sydney Belgium Brussels Brazil Rio Janeiro Canada Alert Canada Calgary Canada Ottawa Canada Quebec E i rar S00 mono Ecuador Quito
51. r Volume cm 3 Mass dq Contact area cm 2 Article Mame Lid Number of substances A Contact medium Contact Medium Food contact material structure POLYVINYLBUTYRALS Contact Medium General description of the new SML 5 software 120219 Package yogo new Sum Truncated cone 198 4 198 4 189 2 20 02 2012 Report 7 6 5 H Prediction temperature temp Prediction time Country 100 day s Wl Switzerland European Union Thickness um 2 5 Density g cm 3 1 POLYVINYLBUTYRALS Thickness um 1 Density g cm 3 1 FORMALDEHYDE 2 4 6 TRIAMIMO 1 3 5 TR Thickness um 37 Density g cm 3 2 7 Aluminil H Im Thickness um 100 Density g cm 3 1 BUTADIENE STYRENE COPOLYMER Thickness um 6 011E04 Density a cm 3 1 User defined General description of the new SML software 5 Density g cm 3 1 Molecular weight g mol 146 14 POW 0 08 Initial concentration POLYVINYLBUTYRALS 4E04mg kg Partition coefficient POLYVINYLBUTYRALS Primer 0 002769 Solubility based Primer Aluminium 0 5 Solubility based Aluminium HS Lacquer 0 005627 Solubility based HS Lacquer Contact Medium 0 5 Solubility based Diffusion coefficient POLYVINYLBUTYRALS 1 087E 12 cm 2 s Piringer based Primer 1 192E 13 cm 2 s Piringer based Aluminium 2 496E 20 cm 2 s Piringer based HS Lacquer 8 462E 09 on 2 s Piringer based Contact Medium 1 0
52. stance properties panel allows defining the properties of the current selected substance When the substance is set to user defined it is possible to enter the properties of the substance Otherwise if the substance is loaded from the database its properties are filled automatically Subustance set to user defined Substance 22 General description of the new SML software 5 Database allows browsing for known substances 13 000 chemicals additive monomer photoinitiator pigment solvent etc 13 000 p Selecting substance s Browse polymer database Reference number CAS number Total chemicals found 13289 Name CAS number Rel PHOTOINITIATOR ABIETIC ACID 0000514 10 3 10 PIGMENT ACETALDEHYDE 0000075 07 0 100 SCCVENT ACETIC ACID 0000064 19 7 10090 30000 gC ACETIC ACID VINYL 000108 05 10120 BE ACETIC ANHYDRI
53. stem Safety 42 327 367 1993 4 http www epa gov reg3hwmd risk human info guide1 htm 5 P A Ektr om Eikos A simulation toolbox for sensitivity analysis degree project 2005 6 M Sobol Sensitivity analysis for nonlinear mathematical models Mathematical Modeling and Computational Experiment 1 407 414 1993 7 T Homma and A Saltelli Importance measure in global sensitivity analysis of nonlinear models Reliability Engineering and System Safety 52 1 7 1996 8 R I Cukier C M Fortuin Kurt E Shuler A G Petschek and J H Schaibly Study of the sensitivity of coupled reaction systems to uncertainties in rate coefficients theory The Journal of Chemical Physics 59 3873 3878 1973 9 J H Schaibly and Kurt E Shuler Study of the sensitivity of coupled reaction systems to uncertainties in rate coefficients Il applications The Journal of Chemical Physics 59 3879 3888 1973 10 R 1 Cukier J H Schaibly and Kurt E Shuler Study of the sensitivity of coupled reaction systems to uncertainties in rate coefficients Ill analysis of the approximations The Journal of Chemical Physics 63 1140 1149 1975 11 Karen Chan Andrea Saltelli and Stefano Tarantola Winding stairs A sampling tool to compute sensitivity indices Statistics and Computing 10 187 196 2000 12 M J W Jansen W A H Rossing and R A Daamen Monte Carlo estimation of uncertainty contributions from several ind
54. t the initial concentration of the migrant OCTADECYL 3 3 5 Dl tert BUTYL 4 HYDROXYPHENYL PROPIONATE plays the most important role concerning its migration from the article to the contact medium The other parameters such as the thickness of both layers and the solubility of migrant in the contact medium have in comparison a negligible influence on the migration OCTADECYL 3 3 5 DI tert BUTYL 4 HYDROXYPHENYL PROPIONATE MEE 52 General description of the new SML software 5 1 A Saltelli K Chan M Scott Eds Sensitivity Analysis Probability and Statistics Series John Wiley and Sons 2000 2 J C Helton F J Davis Sampling Based Methods Chapter 6 in Mathematical and Statistical Methods for Sensitivity Analysis of Model Output Edited by A Saltelli K Chan and M Scott John Wiley and Sons 2000 3 Helton J C Uncertainty and sensitivity analysis techniques for use in performance assessment for radioactive waste disposal Reliability Engineering and Sy
55. the unconditional variance of the output V Y Xi V Y We are considering the model function Y f X where Y is the output and X X1 X2 Xk are k independent input factors each one varying over its own probability density function The values of the input parameters are not exactly known We assume that this uncertainty can be handled by using random variables XJ j 1 k of known distributions Then the model output is also a random variable Y f X1 XK Y fO YIKTOWA SLCX X1 X2 X k 15 5 Y f X1 Xk OF The first order effect for the input factor is the fraction of the variance of the output Y which can be attributed to the input Xj and is denoted by Sj see for example 5 1
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