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Volumn 42, Issue 10, 2009, Pages 3469-3482

Degradation of PEO in the solid state: A theoretical kinetic model

Author keywords

[No Author keywords available]

Indexed keywords

[CARBONYL; AB INITIO; DEGRADATION MECHANISM; DEGRADATION PROCESS; DRIVING FORCES; END-PRODUCTS; H-ABSTRACTION; HYDROPEROXIDE; HYDROPEROXIDE GROUP; HYDROXYL RADICALS; INDUCTION TIME; KEY REACTIONS; KINETIC MODELS; OXIDATIVE DEGRADATION; PEROXY RADICALS; PHOTO-INDUCED; POLYMER SYNTHESIS; POLYMER SYSTEMS; QUANTITATIVE KINETICS; SIMPLE STRUCTURES; TERMINATION REACTIONS; THEORETICAL RATES; THERMO-OXIDATIVE; UNIMOLECULAR;

EID: 66249127211     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma802469u     Document Type: Article
Times cited : (111)

References (85)
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    • Gaussian 03, Revision B.05, Frisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Montgomery, Jr, J. A, Vreven, T, Kudin, K. N, Burant, J. C, Millam, J. M, Iyengar, S. S, Tomasi, J, Barone, V, Mennucci, B, Cossi, M, Scalmani, G, Rega, N, Petersson, G. A, Nakatsuji, H, Hada, M, Ehara, M, Toyota, K, Fukuda, R, Hasegawa, J, Ishida, M, Nakajima, T, Honda, Y, Kitao, O, Nakai, H, Klene, M, Li, X, Knox, J. E, Hratchian, H. P, Cross, J. B, Bakken, V, Adamo, C, Jaramillo, J, Gomperts, R, Stratmann, R. E, Yazyev, O, Austin, A. J, Cammi, R, Pomelli, C, Ochterski, J. W, Ayala, P. Y, Morokuma, K, Voth, G. A, Salvador, P, Dannenberg, J. J, Zakrzewski, V. G, Dapprich, S, Daniels, A. D, Strain, M. C, Farkas, O, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Ortiz, J. V, Cui, Q, Baboul, A. G, Clifford, S, Cioslowski, J, Stefanov, B. B, Liu, G, Liashenko, A, Piskorz, P, Kom
    • Gaussian 03, Revision B.05, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian, Inc.: Wallingford CT, 2004.
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    • CTST rate constants were calculated with the Absolute Rate Theory program of Pr. W. L. Hase
    • CTST rate constants were calculated with the Absolute Rate Theory program of Pr. W. L. Hase.
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    • -1.
    • -1.
  • 68
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    • 0 = 2273 or 90909 in order to match experimental conditions.
    • 0 = 2273 or 90909 in order to match experimental conditions.
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    • The intermolecular H-abstraction reaction is included in the model for primary alkoxy radicals because the formate pathway is not available to this species. For in-chain alkoxy radicals, the rate constant of the β-scission mechanism is larger than that of intermolecular H-abstraction reactions
    • The intermolecular H-abstraction reaction is included in the model for primary alkoxy radicals because the formate pathway is not available to this species. For in-chain alkoxy radicals, the rate constant of the β-scission mechanism is larger than that of intermolecular H-abstraction reactions.
  • 75
    • 66249130301 scopus 로고    scopus 로고
    • -1, respectively. Italicized frequencies correspond to the rotational modes that are coupled.
    • -1, respectively. Italicized frequencies correspond to the rotational modes that are coupled.
  • 81
    • 66249103249 scopus 로고    scopus 로고
    • The Matlab package and the ode15s solver, a variable order solver based on the numerical differentiation formulas, was used to solve the set of differential equations listed in the Appendix.
    • The Matlab package and the ode15s solver, a variable order solver based on the numerical differentiation formulas, was used to solve the set of differential equations listed in the Appendix.
  • 82
    • 66249116571 scopus 로고    scopus 로고
    • [2-mer] in this expression is the concentration of a polymer unit that contains two 1-mer units.
    • [2-mer] in this expression is the concentration of a polymer unit that contains two 1-mer units.
  • 83
    • 66249116939 scopus 로고    scopus 로고
    • This reflects competition between the decrease of average chain length and the decay of peroxy radicals through the tetroxide pathway
    • This reflects competition between the decrease of average chain length and the decay of peroxy radicals through the tetroxide pathway.
  • 84
    • 66249127120 scopus 로고    scopus 로고
    • -γ is mainly driven by entropic factors.
    • -γ is mainly driven by entropic factors.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.