233 Journal homepage: www.fia.usv.ro/fiajournal Journal of Faculty of Food Engineering, Stefan cel Mare University of Suceava, Romania Volume XIV, Issue 2 – 2015, pag. 233 - 240 MATHEMATICAL MODELLING OF THE CONSTITUENTS’ CONCENTRATIONS OF AISI 304 STAINLESS STEEL SAMPLES THAT DIFFUSE INTO SIMULATED ACIDIC ENVIRONMENTS *Silviu-Gabriel STROE1 1Faculty of Food Engineering, Stefan cel Mare University of Suceava, 13 Universitatii Street, 720229, Suceava, Romania, silvius@fia.usv.ro *Corresponding author Received May 16th 2014, accepted June 7th 2014 Abstract: The purpose of this research was to study the mathematical modelling of dependence between testing parameters and some metallic elements diffused into simulated acidic environments. Diffusion processes occurring at the contact between AISI 304 stainless steel samples and simulated acidic environments were analyzed to fulfill this goal. In order to process the experimental data by statistical and mathematical methods, the following steps were taken: diffusion testing of Cr, Mn, 56Fe and Ni elements from AISI304 stainless steel samples into solutions with concentration of 3%, 6% and 9% acetic acid; chemical analysis of corrosive solutions using mass spectrometry and inductively coupled plasma method (ICP-MS); the results were processed using ANOVA method and thus resulting the mathematical models that describe the dependence between variables. A polynomial model with independent variables was used to obtain the mathematical models: temperature of acidic simulated solutions (X1), testing time (X2), stirring grade of environment (X3) and the dependent variables (response function): Y1 - concentration of chromium (Cr), Y2 - concentration of manganese (Mn), Y3 - concentration of iron (56Fe) and Y4 - concentration of nickel (Ni) found in corrosive environments. After having made the analysis of variance ANOVA, a model having the lowest P value (critical probability) for all variables was chosen. The regression coefficient was determined to verify the validity of each mathematical model. Keywords: stainless steel, simulated environments, diffusion, ANOVA method, mathematical model. 1. Introduction It is known that food raw materials have their own natural metal content. In case when there are additions to this natural content, the diffusion from metal surfaces coming into direct contact can cause serious health problems or a change unwanted organoleptic characteristics of the finished product. These metals are found in absolutely all foodstuffs in lower or higher concentrations, depending on various circumstances [1]. A mathematical model that describes the physical processes which occur at the contact of some material from the food processing chain is considered a very important tool that can replace, at least partially, the experimental investigations which are expensive and require longer time. The models thus obtained aimed at complying with the conformity assessment of specific regulations concerning migration limits and at describing the time variation of the http://www.fia.usv.ro/fiajournal mailto:silvius@fia.usv.ro Food and Environment Safety - Journal of Faculty of Food Engineering, Ştefan cel Mare University - SuceavaVolume XIV, Issue 2 – 2015 S i l v i u- G ab r ie l S T R OE , Mathematical modelling of the constituents’ concentrations of AISI 304 stainless steel samples that diffuse into simulated acidic environments, Fo od a nd E nvir o nme nt Sa f e t y, V o l u me X IV , Is s ue 2 – 20 1 5, p a g 2 3 3-2 4 0 234 values of parameters. Having in view the advantages of this tool, in recent years, numerous studies have been undertaken for this purpose [2-7]. The research described in the literature highlights a relatively limited approach of the diffusion systems consisting of materials intended to come into contact with foodstufs. Firstly, it is useful to present a schematic illustration of the mathematical formulation stages of this problem and the finding of adequate solutions is shown in Figure 1 [8]. Fig. 1. The problem formulating stages and finding solutions [8] The general mathematical model solutions thus obtained provide a quantitative and qualitative perspective on how the parameters affect the phenomenon; further research could be focused on the application of these basic equations [8]. The aim of this work was to study the mathematical modelling of dependence between the constituents’ concentrations of AISI 304 stainless steel samples that diffuse into simulated acidic solutions and the testing parameters. Similar researches have been conducted for advanced characterization behavior of AISI321 stainless steel samples in acidic environments [4]. 2. Matherials and methods 2.1. Metallic samples In this research metallic samples made of AISI304 stainless steel grade were used. The samples sizes were of 400.5 x 400.5 x 1 mm and they were established by the Ministerial Decree of 21.03.1973, which stipulates that the ratio of exposed surface of the stainless steel samples and solution volume should be between 0.5 ... 2 [9]. The chemical composition of metallic samples (according to the SR EN 10088- 2:2005 Romanian standard) is shown in Table 1. Table 1 Chemical composition of AISI304 stainless steel samples (wt %) Fe C Mn P S Si Cr Ni 67 0.07 1-2 0.045 0.03 0-1 17-19 8-10.5 A systeM μScan (manufactured by NanoFocus - Germany) was used to determine roughness of the metallic samples. Measurement and calculation of usual surface parameters were made according to DIN EN ISO 4287 and DIN EN ISO 4288 standards. The surface mean roughness of AISI304 stainless steel samples was = 0.5988750.0125 . 2.2. Corrosive environments All solutions were freshly prepared with quality analytical chemical reagents. Given the fact that acidic environments are one of the most aggressive environments in the food processing industry, within the experiment we used 3%, 6% and 9% CH3COOH in double distilled water (according to Italian D. M. of 21-03-1973) [9]. Glacial acetic acid (Sigma-Alorich, Germany) was used to prepare the experimental solutions. 2.3. Testing method To cover a domain as broad as that of using AISI304 stainless steel, three testing Solutions Solving Mathematizatio n Initial assumption s Problem formulation Identificatio n phenomenon Food and Environment Safety - Journal of Faculty of Food Engineering, Ştefan cel Mare University - SuceavaVolume XIV, Issue 2 – 2015 S i l v i u- G ab r ie l S T R OE , Mathematical modelling of the constituents’ concentrations of AISI 304 stainless steel samples that diffuse into simulated acidic environments, Fo od a nd E nvir o nme nt Sa f e t y, V o l u me X IV , Is s ue 2 – 20 1 5, p a g 2 3 3-2 4 0 235 parameters were chosen. To determine the variation levels of testing parameters, the usual values encountered in the processing industry were considered. The levels of the three parameters used in the experiment are shown in Table 2. Table 2 Variation levels of testing parameters Levels Parameters Minimum level Central level Maximum level Temperature solution, [°C] 22 28 32 Testing time, [min] 30 60 90 Stirring environment, [r/min] 0 125 250 The samples were kept in the oven to make the experiments in stationary environment and at temperatures different from the room temperature one (22°C). A magnetic heat stirrer Heidolph MR Hei-Tec (Heidolph, Germany) was used to make the experiments at the temperature of 28°C, 34°C respectively and in stirred environment. 2.4. Chemical analysis of corrosive environments Inductively coupled plasma mass spectrometry (ICP-MS) was used to analyze the chemical composition of corrosive environments, both before having used them in the corrosion tests, and after having made them, taking into consideration the adavantages of this method as compared to other analytical ones. 2.5. Mathematical modelling of the constituents’ concentrations ANOVA method, known as the variance analysis was appealed to in order to find a mathematical model as accurate as possible which describe the diffusion phenomena. This technique was chosen due to the fact that it is highly recommended when studying a larger number of levels of independent variables, providing higher accuracy of the effect that the independent variables have upon the dependent ones as well as of the their joint effect. Having in view that some practical values (minimum values) of responses are to be determined, it is necessary to establish some interdependences capable of describing both the nature and the extent of the influences taken into consideration (see also [4]). To develop the predictive-mathematical models the Design Expert software (trial version) was used. In order to obtain the mathematical models a polynomial model with independent variables was used: acidic simulated solutions temperature (X1), testing time (X2), stirring grade of environment (X3) and the dependent variables (response function): Y1 - concentration of chromium (Cr), Y2 - concentration of manganese (Mn), Y3 - concentration of iron (56Fe) and Y4 - concentration of nickel (Ni) found in corrosive environments. After having made the analysis of variance ANOVA, a model having the lowest P value (critical probability) for all variables was chosen. The regression coefficient was determined to verify the validity of each mathematical model. 3. Results and discussion The chemical analysis of corrosive environments was intended to determine the concentration of Cr, Mn, Fe and Ni elements migrated from AISI304 stainless steel samples. 3.1. Mathematical modelling of metallic constituent concentrations migrated into 3% CH3COOH solutions The statistical summary of mathematical models is shown in Table 3. Food and Environment Safety - Journal of Faculty of Food Engineering, Ştefan cel Mare University - SuceavaVolume XIV, Issue 2 – 2015 S i l v i u- G ab r ie l S T R OE , Mathematical modelling of the constituents’ concentrations of AISI 304 stainless steel samples that diffuse into simulated acidic environments, Fo od a nd E nvir o nme nt Sa f e t y, V o l u me X IV , Is s ue 2 – 20 1 5, p a g 2 3 3- 24 0 236 Table 3 Summary statistic of mathematical models proposed for the dependent variables Dependent variable P Model Standard deviation [σ] R-Squared [R2] Adjusted R-Squared [R2 adjusted] Y1 0.0070 Quintic 8.59 0.9967 0.9783 Y2 0.0190 Quintic 1.71 0.9964 0.9765 Y3 0.0490 Quintic 323.04 0.9910 0.9300 Y4 0.0099 Quintic 7.82 0.9964 0.9765 The mathematical model that defines the variation of chromium concentration (dependent variable) depending on the testing parameters (independent variables) is shown in Equation 1. = 7.96 + 3.83 ∙ X − 3.72 ∙ X − 1.28 ∙ X + 3.06 ∙ X + 6.06 ∙ X + 3.06 ∙ X + 17.75 ∙ X ∙ X − 45.25 ∙ X ∙ X − 0.25 ∙ X ∙ X + 25.08 ∙ X ∙ X + 48.92 ∙ X ∙ X + 15.25 ∙ X ∙ X + 9.58 ∙ X ∙ X − 9.50 ∙ X ∙ X ∙ X + 5.42 ∙ X ∙ X + 30.25 ∙ X ∙ X ∙ X + 43.42 ∙ X ∙ X + 21.00 ∙ X ∙ X ∙ X − 26.25 ∙ X ∙ X ∙ X − 9.58 ∙ X ∙ X (1) In order to check the validity of the mathematical model proposed, the experimental values vs model values were plotted (Figure 2). Fig. 2. Validity check of the Y1 (chromium concentration) mathematical model The mathematical model of the Y2 response function is shown in Equation 2. = 4.04 − 0.59 ∙ X − 0.35 ∙ X2 + 1.39 ∙ X + 0.38 ∙ X + 0.68 ∙ X2 + 0.18 ∙ X + 3.18 ∙ X ∙ X2 − 8.20 ∙ X ∙ X + 0.30 ∙ X2 ∙ X + 4.18 ∙ X ∙ X2 + 8.98 ∙ X ∙ X + 4.24 ∙ X ∙ X2 − 7.88 ∙ X ∙ X − 0.47 ∙ X2 ∙ X + 1.95 ∙ X2 ∙ X − 0.63 ∙ X ∙ X2 ∙ X + 0.83 ∙ X ∙ X2 + 4.02 ∙ X ∙ X2 ∙ X + 8.35 ∙ X ∙ X + 3.43 ∙ X ∙ X2 ∙ X − 2.73 ∙ X ∙ X2 ∙ X − 0.40 ∙ X2 ∙ X (2) The validity of the Y2 mathematical model proposed was plotted by experimental values vs model values (Figure 3). Fig.3. Validity check of the Y2 (manganese concentration) mathematical model The mathematical model of the Y3 response function is shown in Equation 3. = 394.07 − 88.33 ∙ X − 1.67 ∙ X2 + 116.67 ∙ X − 56.11 ∙ X + 123.89 ∙ X2 − 1.11 ∙ X + 437.50 ∙ X ∙ X2 − 887.50 ∙ X ∙ X + 0.002 ∙ X2 ∙ X + 372.50 ∙ X ∙ X2 + 1012.50 ∙ X ∙ X + 637.50 ∙ X ∙ X2 − 762.50 ∙ X ∙ X − 115 ∙ X2 ∙ X + 55 ∙ X2 ∙ X + 430 ∙ X ∙ X2 ∙ X + 194.17 ∙ X ∙ X2 + 305 ∙ X ∙ X2 ∙ X + 1019.17 ∙ X ∙ X + 772.5 ∙ X ∙ X2 ∙ X + 52.50 ∙ X ∙ X2 ∙ X − 253.3 ∙ X2 ∙ X (3) The validity of the Y3 mathematical model proposed was plotted by experimental values vs model values (Figure 4). R² = 0.9967 0.00 50.00 100.00 150.00 200.00 250.00 0.00 50.00 100.00 150.00 200.00 250.00M od el v al ue , C r [p pb ] Experimental value, Cr [ppb] R² = 0.996 0.00 10.00 20.00 30.00 40.00 50.00 0.00 10.00 20.00 30.00 40.00 50.00 M od el v al ue , M n [p pb ] Experimental value, Mn [ppb] Food and Environment Safety - Journal of Faculty of Food Engineering, Ştefan cel Mare University - SuceavaVolume XIV, Issue 2 – 2015 S i l v i u- G ab r ie l S T R OE , Mathematical modelling of the constituents’ concentrations of AISI 304 stainless steel samples that diffuse into simulated acidic environments, Fo od a nd E nvir o nme nt Sa f e t y, V o l u me X IV , Is s ue 2 – 20 1 5, p a g 2 3 3- 24 0 237 Fig. 4. Validity check of the Y3 (iron concentration) mathematical model The mathematical model of the Y4 response function is shown in Equation 4. = 20.44 ∙ X − 8.39 ∙ X2 + 2.00 ∙ X − 7.56 ∙ X − 0.86 ∙ X2 + 0.64 ∙ X + 15.25 ∙ X ∙ X2 − 24.75 ∙ X ∙ X − 2.25 ∙ X2 ∙ X + 26.83 ∙ X ∙ X2 + 37.50 ∙ X ∙ X + 8.60 ∙ X ∙ X2 − 37.40 ∙ X ∙ X + 9.00 ∙ X2 ∙ X + 10.83 ∙ X2 ∙ X − 13.63 ∙ X ∙ X2 ∙ X + 14.23 ∙ X ∙ X2 + 28.88 ∙ X ∙ X2 ∙ X + 34.23 ∙ X ∙ X + 2.63 ∙ X ∙ X2 ∙ X − 23.88 ∙ X ∙ X2 ∙ X + 4.03 ∙ X2 ∙ X (4) The validity of the Y4 mathematical model proposed was plotted by experimental values vs model values (Figure 5). Fig. 5. Validity check of the Y4 (nickel concentration) mathematical model 3.2. Mathematical modelling of metallic constituent concentrations migrated into 6% CH3COOH solutions Statistical summary of mathematical models to describe the found dependent variables Cr, Mn, 56Fe and Ni is shown in Table 4. Table 4 Summary statistic of mathematical models proposed for the dependent variables Dependent variable P Model Standard deviation [σ] R-Squared [R2] Adjusted R-Squared [R2 adjusted] Y1 0.0400 Cubic 2.67 0.9618 0.9006 Y2 0.0480 Quintic 0.19 0.9999 0.9978 Y3 0.0015 Quintic 17.25 0.9979 0.9866 Y4 0.0018 Quintic 27.76 0.9890 0.9553 The mathematical models that define the studied response functions (dependent variables) depending on testing parameters (independent variables) are presented in the following equations. = 19.67 + 2.50 ∙ X + 7,72 ∙ X + 4,28 ∙ X − 4.33 ∙ X + 2.00 ∙ X + 0.17 ∙ X + 0.083 ∙ X ∙ X 1.50 ∙ X ∙ X + 3.00 ∙ X ∙ X − 3.58 ∙ X ∙ X − 0.67 ∙ X ∙ X + 3.25 ∙ X ∙ X − 1.00 ∙ X ∙ X + 2.83 ∙ X ∙ X − 0.33 ∙ X ∙ X + 2.13 ∙ X ∙ X ∙ X (5) The validity of the Y1 mathematical model proposed was plotted by experimental values vs model values (Figure 6). Fig. 6. Validity check of the Y1 (chromium concentration) mathematical model The mathematical model of the Y2 (Mn concentration) response function is shown in Equation 6. R² = 0.9964 0.00 50.00 100.00 150.00 200.00 250.00 0.00 50.00 100.00 150.00 200.00 250.00 M od el v al ue , N i [ pp b] Experimental value, Ni [ppb] R² = 0.9965 0.00 10.00 20.00 30.00 40.00 0.00 10.00 20.00 30.00 40.00M od el v al ue , C r [p pb ] Experimental value, Cr [ppb] R² = 0.996 0.00 10.00 20.00 30.00 40.00 50.00 0.00 10.00 20.00 30.00 40.00 50.00 M od el v al ue , M n [p pb ] Experimental value, Mn [ppb] Food and Environment Safety - Journal of Faculty of Food Engineering, Ştefan cel Mare University - SuceavaVolume XIV, Issue 2 – 2015 S i l v i u- G ab r ie l S T R OE , Mathematical modelling of the constituents’ concentrations of AISI 304 stainless steel samples that diffuse into simulated acidic environments, Fo od a nd E nvir o nme nt Sa f e t y, V o l u me X IV , Is s ue 2 – 20 1 5, p a g 2 3 3- 24 0 238 = 3.87 − 1.60 ∙ X + 4.70 ∙ X + 0.75 ∙ X + 0.54 ∙ X + 3.04 ∙ X − 1.11 ∙ X + 0.30 ∙ X ∙ X + 3.05 ∙ X ∙ X + 1.92 ∙ X ∙ X − 4. 25 ∙ X ∙ X − 3.10 ∙ X ∙ X + 1.75 ∙ X ∙ X − 1.55 ∙ X ∙ X + 1. 72 ∙ X ∙ X − 1.73 ∙ X ∙ X + 1.83 ∙ X ∙ X ∙ X − 4.77 ∙ X ∙ X − 0.32 ∙ X ∙ X ∙ X + 2.83 ∙ X ∙ X − 1.42 ∙ X ∙ X ∙ X + 1.15 ∙ X ∙ X ∙ X − 0.49 ∙ X ∙ X + 2.68 ∙ X ∙ X ∙ X + 3.00 ∙ X ∙ X ∙ X + 2.85 ∙ X ∙ X ∙ X (6) The validity of the Y2 mathematical model proposed was plotted by experimental values vs model values (Figure 7). Fig. 7. Validity check of the Y2 (manganese concentration) mathematical model The mathematical model of the Y3 (56Fe concentration) response function is shown in Equation 7. = 167.41 − 16.11 ∙ X + 143.33 ∙ X + 80.00 ∙ X + 123.89 ∙ X + 128.89 ∙ X + 18.89 ∙ X − 70 ∙ X ∙ X − 72.50 ∙ X ∙ X − 12.50 ∙ X ∙ X − 90 ∙ X ∙ X + 57.50 ∙ X ∙ X + 31.67 ∙ X ∙ X − 0.83 ∙ X ∙ X − 2.50 ∙ X ∙ X − 22.50 ∙ X ∙ X + 0.002 ∙ X ∙ X ∙ X − 88.33 ∙ X ∙ X + 10 ∙ X ∙ X ∙ X − 5.83 ∙ X ∙ X + 152.50 ∙ X ∙ X ∙ X − 5.00 ∙ X ∙ X ∙ X − 5.83 ∙ X ∙ X (7) The validity of the Y3 mathematical model proposed was plotted by experimental values vs model values (Figure 8). Fig. 8. Validity check of the Y3 (iron concentration) mathematical model The mathematical model of the Y4 (Ni concentration) response function is shown in Equation 8. = 311.44 − 24.67 ∙ X − 181.50 ∙ X + 41.17 ∙ X + 7.50 ∙ X + 24.33 ∙ X − 8.83 ∙ X − 69.25 ∙ X ∙ X + 6.33 ∙ X ∙ X − 15.67 ∙ X ∙ X + 97.25 ∙ X ∙ X − 1.50 ∙ X ∙ X + 35.75 ∙ X ∙ X − 8.00 ∙ X ∙ X + 7.50 ∙ X ∙ X + 12.50 ∙ X ∙ X − 7.38 ∙ X ∙ X ∙ X (8) The validity of the Y4 mathematical model proposed was plotted by experimental values vs model values (Figure 9). Fig. 9. Validity check of the Y4 (nickel concentration) mathematical model 3.3. Mathematical modelling of metallic constituent concentrations migrated into 9% CH3COOH solutions Statistical summary of mathematical models to describe the found dependent variable Cr, Mn, 56Fe and Ni is shown in Table 5. R² = 0.9981 0.00 2.00 4.00 6.00 8.00 10.00 12.00 0.00 5.00 10.00M od el v al ue , M n [p pb ] Experimental value, Mn [ppb] R² = 0.9958 0.00 200.00 400.00 600.00 800.00 1000.00 1200.00 0 500 1000 1500M od el v al ue ,5 6 F e [p pb ] Experimental value, 56Fe [ppb] R² = 0.9623 0.00 5.00 10.00 15.00 20.00 2.00 7.00 12.00 17.00 M od el v al ue , N i [ pp b] Experimental value, Ni [ppb] Food and Environment Safety - Journal of Faculty of Food Engineering, Ştefan cel Mare University - SuceavaVolume XIV, Issue 2 – 2015 S i l v i u- G ab r ie l S T R OE , Mathematical modelling of the constituents’ concentrations of AISI 304 stainless steel samples that diffuse into simulated acidic environments, Fo od a nd E nvir o nme nt Sa f e t y, V o l u me X IV , Is s ue 2 – 20 1 5, p a g 2 3 3- 24 0 239 Table 5 Summary statistic of mathematical models proposed for the dependent variables Dependent variable P Model Standard deviation [σ] R-Squared [R2] Adjusted R-Squared [R2 adjusted] Y1 0.010 Quintic 1.06 0.9965 0.9771 Y2 0.020 Quintic 0.21 0.9981 0.9876 Y3 0.035 Quintic 41.82 0.9960 0.9730 Y4 0.040 Cubic 0.89 0.9823 0.9220 The mathematical models that define the studied response functions are presented in the following equations. = 8.67 + 0.33 ∙ X + 2.17 ∙ X + 0.17 ∙ X − 6.00 ∙ X − 2.50 ∙ X − 0.50 ∙ X + 2.00 ∙ X ∙ X + 0.25 ∙ X ∙ X + 1.50 ∙ X ∙ X + 1.00 ∙ X ∙ X + 1.25 ∙ X ∙ X + 4.00 ∙ X ∙ X + 0.75 ∙ X ∙ X + 3.00 ∙ X ∙ X + 6.00 ∙ X ∙ X + 3.00 ∙ X ∙ X ∙ X + 6.00 ∙ X ∙ X + 1.25 ∙ X ∙ X ∙ X + 0.75 ∙ X ∙ X + 3.50 ∙ X ∙ X ∙ X + 2.00 ∙ X ∙ X ∙ X + 1.50 ∙ X ∙ X (9) The validity of the Y1 mathematical model proposed was plotted by experimental values vs model values (Figure 10). Fig. 10. Validity check of the Y1 (chromium concentration) mathematical model The mathematical model of the Y2 (Mn concentration) response function is shown in Equation 10. = 1.46 − 0.00005 ∙ X + 1.21 ∙ X + 0.13 ∙ X − 0.22 ∙ X + 0.88 ∙ X − 0.12 ∙ X + 1.15 ∙ X ∙ X + 0.025 ∙ X ∙ X + 0.63 ∙ X ∙ X − 0.33 ∙ X ∙ X + 0.26 ∙ X ∙ X + 0.93 ∙ X ∙ X + 0.11 ∙ X ∙ X + 0.91 ∙ X ∙ X + 0.042 ∙ X ∙ X + 0.93 ∙ X ∙ X ∙ X + 0.25 ∙ X ∙ X + 0.20 ∙ X ∙ X ∙ X + 0.17 ∙ X ∙ X + 0.90 ∙ X ∙ X ∙ X + 0.10 ∙ X ∙ X ∙ X + 0.025 ∙ X ∙ X (10) The validity of the Y2 mathematical model proposed was plotted by experimental values vs model values (Figure 11). Fig. 11. Validity check of the Y2 (manganese concentration) mathematical model The mathematical model of the Y3 (56Fe concentration) response function is shown in Equation 11. = 147.78 − 18.89 ∙ X + 190.00 ∙ X + 57.78 ∙ X − 66.67 ∙ X + 83.33 ∙ X − 16.67 ∙ X + 157.50 ∙ X ∙ X − 47.50 ∙ X ∙ X + 100.00 ∙ X ∙ X − 42.50 ∙ X ∙ X + 40.83 ∙ X ∙ X + 180.83 ∙ X ∙ X − 9.17 ∙ X ∙ X + 53.33 ∙ X ∙ X − 15.00 ∙ X ∙ X + 105.00 ∙ X ∙ X ∙ X + 12.50 ∙ X ∙ X − 7.50 ∙ X ∙ X ∙ X + 77.50 ∙ X ∙ X + 162.50 ∙ X ∙ X ∙ X + 7.50 ∙ X ∙ X ∙ X − 20.00 ∙ X ∙ X (11) The validity of the Y3 mathematical model proposed was plotted by experimental values vs model values (Figure 12). R² = 0.9965 0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 0.00 10.00 20.00 30.00 40.00 M od el v al ue , C r [p pb ] Experimental value, Cr [ppb] R² = 0.9981 0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 0.00 2.00 4.00 6.00 8.00 10.00 M od el v al ue , M n [p pb ] Experimental value, Mn [ppb] Food and Environment Safety - Journal of Faculty of Food Engineering, Ştefan cel Mare University - SuceavaVolume XIV, Issue 2 – 2015 S i l v i u- G ab r ie l S T R OE , Mathematical modelling of the constituents’ concentrations of AISI 304 stainless steel samples that diffuse into simulated acidic environments, Fo od a nd E nvir o nme nt Sa f e t y, V o l u me X IV , Is s ue 2 – 20 1 5, p a g 2 3 3- 24 0 240 Fig. 12. Validity check of the Y3 (iron concentration) mathematical model The mathematical model of the Y4 (Ni concentration) response function is shown in Equation 12. = 8.44 + 1.09 ∙ X + 1.28 ∙ X + 1.74 ∙ X − 1.49 ∙ X − 0.23 ∙ X + 0.37 ∙ X + 1.07 ∙ X ∙ X + 0.59 ∙ X ∙ X + 0.76 ∙ X ∙ X − 0.47 ∙ X ∙ X − 0.21 ∙ X ∙ X + 0.0083 ∙ X ∙ X + 0.91 ∙ X ∙ X + 0.24 ∙ X ∙ X + 0.72 ∙ X ∙ X + 1.18 ∙ X ∙ X ∙ X (12) The validity of the Y4 mathematical model proposed was been plotted by experimental values vs model values (Figure 13). Fig. 13. Validity check of the Y4 (nickel concentration) mathematical model 4. Conclusions ICP-MS method and ANOVA method were used to establish the relationships between migration test parameter values and Cr, Mn, 56Fe and Ni concentrations found in solutions. Besides the fact that these instrumental analysis techniques provide the checking of mathematical models’ validity for each dependent variable, we can also draw the conclusion that they are highly performing and accurate instruments that can be used in estimating the values of objective function (see also [4]). 5. References [1]. BARNES, K. A., SINCLAIR, C. R., WATSON, D.H., Chemical migration and food contact materials, Woodhead Publishing Limited, ISBN-13: 978-1-84569-029-8, England, (2007); [2]. SANCHES SILVA A., CRUZ J. M., SENDOR GARCIA R., FRANZ R., PASEIRO LOSADA, P., Kinetic migration studies from packaging films into meat products, ScienceDirect, Meat Science 77, 238-245, (2007); [3]. SOOJIN J., IRUDAYARAJ J.M., Food Processing operations modeling - Design and Analysis, Second Edition, CRC Press- Taylor&Francis Group, 1-2, (2009); [4]. STROE S. G., GUTT G., Statistical study of the dependence between concentration of metallic elements migrated from stainless steel grade AISI321 and working parameters, Food and environment safety, Faculty of Food Engineering, Volume 12, Issue 2, (2013); [5]. TEHRANY E. A., DESOBRY S., Partition coefficient of migrants in food stimulants/polymers systems, ScienceDirect, Food Chemistry 101, 1714- 1718, (2007); [6]. AMANI S. ALTURIQI, LAMIA A. ALBEDAIR, The Egyptian Journal of Aquatic Research, ScienceDirect, Volume 38, Issue 1, 45– 49, (2012); [7]. KAMAL J. ELNABRIS, SHAREEF K. MUZYED, NIZAM M. EL-ASHGAR, Heavy metal concentrations in some commercially important fishes and their contribution to heavy metals exposure in Palestinian people of Gaza Strip (Palestine), Journal of the Assoc. of Arab Universities for Basic and Applied Sciences, Volume 13, Issue 1, April 2013, Pages 44–51, (2013); [8]. DATTA A. K., Biological and Bioenvironmentat Heat and Mass Transfer, Cornell University Ithaca, New York, Marcel Dekker Inc., ISBN: 0-8247-0775-3, 11-12, (2002); [9]. D.M. 21-03-1973, Italian law text, Decreto Ministeriale del 21/03/1973 - Disciplina igienica degli imballaggi, recipienti, utensili, destinati a venire in contatto con le sostanze alimentari o con sostanze d'uso personale, (1973); R² = 0.9958 0.00 500.00 1000.00 1500.00 0 500 1000 1500M od el v al ue ,5 6 F e [p pb ] Experimental value, 56Fe [ppb] R² = 0.9623 0.00 5.00 10.00 15.00 20.00 2.00 7.00 12.00 17.00M od el v al ue , N i[ pp b] Experimental value, Ni [ppb]