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- Badia, J. D., et al.
(författare)
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A statistical design of experiments for optimizing the MALDI-TOF-MS sample preparation of polymers. An application in the assessment of the thermo-mechanical degradation mechanisms of poly (ethylene terephthalate)
- 2011
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Ingår i: Analytica Chimica Acta. - : Elsevier BV. - 0003-2670 .- 1873-4324. ; 692:1-2, s. 85-95
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Tidskriftsartikel (refereegranskat)abstract
- The sample preparation procedure for MALDI-TOF MS of polymers is addressed in this study by the application of a statistical Design of Experiments (DoE). Industrial poly (ethylene terephthalate) (PET) was chosen as model polymer. Different experimental settings (levels) for matrixes, analyte/matrix proportions and concentrations of cationization agent were considered. The quality parameters used for the analysis were signal-to-noise ratio and resolution. A closer inspection of the statistical results provided the study not only with the best combination of factors for the MALDI sample preparation, but also with a better understanding of the influence of the different factors, individually or in combination, to the signal. The application of DoE for the improvement of the MALDI measure of PET stated that the best combination of factors and levels was the following: matrix (dithranol), proportion analyte/matrix/cationization agent (1/15/1, V/V/V), and concentration of cationization agent (2 g L-1). In a second part, multiple processing by means of successive injection cycles was used to simulate the thermo-mechanical degradation effects on the oligomeric distribution of PET under mechanical recycling. The application of MALDI-TOF-MS showed that thermo-mechanical degradation primarily affected initially predominant cyclic species. Several degradation mechanisms were proposed, remarking intramolecular transesterification and hydrolysis. The ether links of the glycol unit in PET were shown to act as potential reaction sites, driving the main reactions of degradation.
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| 2. |
- Badia, J. D., et al.
(författare)
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Assessing the MALDI-TOF MS sample preparation procedure to analyze the influence of thermo-oxidative ageing and thermo-mechanical degradation on poly (Lactide)
- 2011
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Ingår i: European Polymer Journal. - : Elsevier BV. - 0014-3057 .- 1873-1945. ; 47:7, s. 1416-1428
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Tidskriftsartikel (refereegranskat)abstract
- Multiple processing by means of successive injection cycles was used to simulate the thermo-mechanical degradation effects on the oligomeric distribution of PLA under mechanical recycling. Likewise, an accelerated thermal ageing over PLA glass transition was performed in order to simulate its service life. MALDI-TOF MS was used for the analysis and the sample preparation procedure was assessed by means of a statistical Design of Experiments (DoE). The quality effects in use for the analysis were signal-to-noise ratio and Resolution. Different matrixes, analyte/matrix proportions and the use of NaTFA as cationization agent were considered. A deep inspection of the statistical results provided a better understanding of the influence of the different factors, individually or in combination, to the signal. The application of DoE for the improvement of the MALDI measurement of PLA stated that the best combination of factors (levels) was the following: matrix (s-DHB), proportion analyte/matrix (1/5 V/V), and no use of cationization agent. Degradation primarily affected the initially predominant cyclic [LA(C)](n) and linear H-[LA(L)](n)-OH species, where LA stands for a PLA repeating unit. Intramolecular and intermolecular transesterifications as well as hydrolytic and homolytic reactions took place during the formation and disappearance of oligomeric species. In both degradation mechanisms induced by thermal ageing and thermo-mechanical degradation, the formation of H-[LA(L)](n)-O-CH(3) by intermolecular transesterifications was highlighted.
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