Thermoset materials characterization by thermal desorption or pyrolysis based gas chromatography-mass spectrometry methods

被引:8
作者
Campbell, C. Garrett [1 ]
Astorga, Dominik Jordon [1 ]
Duemichen, Erik [2 ]
Celina, Mathew [1 ]
机构
[1] Sandia Natl Labs, POB 5800,MS 1411,Dept 1853, Albuquerque, NM 87185 USA
[2] Bundesanstalt Mat Forsch & Prufung BAM, Unter Eichen 87, D-12205 Berlin, Germany
关键词
Polymer analysis/characterization; Thermal desorption mass spectrometry; Thermoset composition; Volatiles from thermosets; Degradation signatures; SOLID-PHASE MICROEXTRACTION; ENVIRONMENTAL-SAMPLES; OXIDATIVE-DEGRADATION; TESTING CONDITIONS; POLYMER MATERIALS; PERFORMANCE; EXTRACTION; DECOMPOSITION; TEMPERATURE; PRODUCTS;
D O I
10.1016/j.polymdegradstab.2019.109032
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Thermoset materials characterization is often limited to solid state analytical techniques such as IR, NMR, DSC, TGA and mechanical testing. Alternatively, their off-gassing behavior can also be evaluated using GC based techniques such as TD-GC-MS, allowing this method to be applied to thermoset materials analyses such as identification, aging characterization, and formulation optimization. As an overview, common thermoset materials were evaluated by analyzing their gaseous degradation products via TGA-based pyrolysis and subsequent TD-GC-MS for the identification of representative volatile signatures. It is thereby possible to distinguish different classes of phenolic materials or cured epoxy resins, as well as their amine or anhydride curatives. Additionally, this method enabled quantification of a volatile fragment (bisphenol A, BPA) which is associated with oxidation of epoxy/amine thermoset materials. The amount of evolved BPA increased linearly with aging time and this trend exhibits linear Arrhenius behavior over the temperature range (80-125 degrees C) studied, in agreement with oxidation sensitivies based on oxygen consumption data. Further, TD-GC-MS was used to explore how off-gassing of residual anhydride curative from an epoxy/anhydride material depends on formulation stoichiometry. Even in formulations that theoretically contained enough epoxy to consume all anhydride (1:1 stoichiometry), an imperfect final cure state resulted in residual anhydride which could evolve from the material. For such materials, a slightly epoxy-rich formulation is required to ensure that the material contains no residual unreacted anhydride. Analysis of volatiles generated by thermal exposure is an attractive characterization approach enabling compositional analysis as well as complementary diagnostics for materials degradation. (C) 2020 Elsevier Ltd. All rights reserved.
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页数:18
相关论文
共 64 条
[1]   Use of a respirometer to measure oxidation rates of polymeric materials at ambient temperatures [J].
Assink, RA ;
Celina, M ;
Skutnik, JM ;
Harris, DJ .
POLYMER, 2005, 46 (25) :11648-11654
[2]   A review on solid phase micro extraction-high performance liquid chromatography (SPME-HPLC) analysis of pesticides [J].
Aulakh, JS ;
Malik, AK ;
Kaur, V ;
Schmitt-Kopplin, P .
CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY, 2005, 35 (01) :71-85
[3]  
Bicchi C, 2000, HRC-J HIGH RES CHROM, V23, P539, DOI 10.1002/1521-4168(20000901)23:9<539::AID-JHRC539>3.0.CO
[4]  
2-3
[5]   Bond dissociation energies of organic molecules [J].
Blanksby, SJ ;
Ellison, GB .
ACCOUNTS OF CHEMICAL RESEARCH, 2003, 36 (04) :255-263
[6]   Oxygen diffusivity and permeation through polymers at elevated temperature [J].
Celin, Mathew C. ;
Quintana, Adam .
POLYMER, 2018, 150 :326-342
[7]   Oxidation profiles of thermally aged nitrile rubber [J].
Celina, M ;
Wise, J ;
Ottesen, DK ;
Gillen, KT ;
Clough, RL .
POLYMER DEGRADATION AND STABILITY, 1998, 60 (2-3) :493-504
[8]   Correlation of chemical and mechanical property changes during oxidative degradation of neoprene [J].
Celina, M ;
Wise, J ;
Ottesen, DK ;
Gillen, KT ;
Clough, RL .
POLYMER DEGRADATION AND STABILITY, 2000, 68 (02) :171-184
[9]   Review of polymer oxidation and its relationship with materials performance and lifetime prediction [J].
Celina, Mathew C. .
POLYMER DEGRADATION AND STABILITY, 2013, 98 (12) :2419-2429
[10]   A perspective on the inherent oxidation sensitivity of epoxy materials [J].
Celina, Mathew C. ;
Dayile, Angela R. ;
Quintana, Adam .
POLYMER, 2013, 54 (13) :3290-3296