a b s t r a c tThe migration of components from paper into Tenax Ò was studied to determine the influence of molecular size and chemical character of the migrant and the influence of paper characteristics in the migration process. The Weibull model was applied because Fick's 2nd law of diffusion gave poor fits in some cases. The migration pattern depended on the migrants molecular size and was independent of temperature in the studied range. The migration rate decreased with the migrant molecular size. The influence of the migrants character (polarity and vapour pressure) on the migration behaviour was also studied: nonpolar migrants with high vapour pressure presented low relative migration values and polar migrants presented high values of relative migration. Results indicated that the apparent partition coefficient between paper and the simulant Tenax Ò increased with the migrant vapour pressure and with both the paper grammage and the recycled pulp content.
The mathematical modeling of migration of additives from plastics to food simulants was studied using experimental data published in the literature, following two routes: the conventional approach using the solution of Fick's 2nd law, and a kinetic model based on the Weibull distribution function. The objective of this comparison was to permit using a mathematically simpler model equally able to describe migration data, and that could have a generally wider applicability by describing situations more complex than those that simple diffusional phenomena can describe. The relationship between the parameters of the two models was analyzed by regression of data generated by Fick's law using the Weibull model. The results show that the time constant parameter is related to the diffusion coefficient and the material thickness. It depends on temperature and on the molecular weight of the migrant in a similar manner to the diffusion coefficient. The activation energy presented values from 72 to 125 kJ/mol. The shape parameter is a function of the contribution of the mass transfer resistance at the interface. It was independent of temperature and of the migrant, assuming a global constant value of 0.67, for the systems and conditions studied. The results indicate that the Weibull model can be used to describe and analyze the migration of additives from plastics to foods with a meaning of the parameters in terms of the underlying physical phenomena. PRACTICAL APPLICATIONS The Weibull model can be used to describe the migration from packaging to foods with the advantage of significant simplicity of calculation compared to Fick's 2nd law. The model can be applied in packaging systems with mass transfer processes more complex than those that simple diffusional phenomena can describe. In the migration of components from paper‐based materials (instead of plastics) into solid foods, mass transfer occurs in a heterogeneous medium of paper fibers and air. Migration curves commonly present an initial lag phase for heavier migrants. The sigmoidal‐shape of the migration curves are not adequately described by the established models based in Fick's 2nd law solutions, and the Weibull model is a good alternative. Additionally, this simple model can potentially be used in probabilistic approaches for exposure assessments of consumers to migrants originating from packaging materials.
This paper describes the second part of a project whose main objective was to develop the know-how to produce certified reference materials (CRMs) for specific migration testing. Certification parameters discussed are the diffusion coefficient, D(P), the respective polymer-specific coefficient, A(P), of the migrant polymer combinations and the partitioning coefficient, K(P,F), describing the partitioning of the migrant between the polymer and a food simulant. The parameters were determined for 16 preliminary candidate CRMs. Each parameter was determined by one laboratory. The six materials most suitable as reference materials were selected and the parameters then determined by four laboratories. The coefficients resulting from this small-scale interlaboratory comparison study can be regarded as the most reliable values available to date. These coefficients were applied for a comparison of experimental and predicted migration data. The experimental migration data arose from the same project and were determined by one laboratory for the first 16 materials and subsequently by four laboratories for the six materials selected in the second phase. Overall, experimental and predicted migration data fit together quite well. Roughly half of the predicted data were within +/-10%; almost all predicted data were within +/-40% compared with the experimental data.
The paper describes a project with the main objective of developing the know how to produce certified reference materials (CRMs) for specific migration testing. Certification parameters discussed are the initial concentration of the migrant in the polymer (C(P),0) and the specific migration into a food simulant under certain temperature/time conditions. Sixteen preliminary candidate CRMs were defined and produced. The most important polymers (low- and high-density polyethylene (LDPE and HDPE), polypropylene (PP), polystyrene (PS), polyethylene terephtalate (PET), plasticized polyvinyl chloride (PVC), rigid PVC, polyamides (PA)) and additives as well as monomers representing different physicochemical properties as target substances for migration were chosen. The stability and homogeneity of the migrants in the materials were tested and methods for the determination of the certification parameters were developed and validated. > From the 16 materials produced, the six most suitable CRM candidates (LDPE//Irganox 1076/Irgafos 168, LDPE//1,4-diphenyl-1,3-butadiene (DPBD), HDPE//Chimassorb 81/Uvitex OB, PP homo//Irganox 1076/Irgafos 168, HIPS, 1% mineral oil//styrene, PA 6//caprolactam) were selected. The feasibility of CRM production for the six candidate materials was demonstrated and a trial certification exercise was performed with participation of all four partner laboratories. All six materials showed suitable properties for future production as certified reference materials.
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