a. College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering of China, Sichuan University, Chengdu 610065, China
b. Performance Material Center, National Institute of Clean-and-low-carbon Energy (NICE), Beijing 102209, China
c. CAS Key Laboratory of Engineering Plastics, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
Yan-hua Niu(牛艳华),E-mail:yhniu@scu.edu.cn
收稿:2016-03-01,
修回:2016-3-23,
录用:2016-3-23,
纸质出版:2016-10-05
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Niu Yan-hua, Liang Wen-bin, Zhang Yin-ling, 等. Crosslinking Kinetics of Polyethylene with Small Amount of Peroxide and Its Influence on the Subsequent Crystallization Behaviors[J]. Chinese Journal of Polymer Science, 2016,34(9):1117-1128.
Niu Yan-hua, Liang Wen-bin, Zhang Yin-ling, et al. Crosslinking Kinetics of Polyethylene with Small Amount of Peroxide and Its Influence on the Subsequent Crystallization Behaviors[J]. Chinese Journal of Polymer Science, 2016, 34(9): 1117-1128.
Niu Yan-hua, Liang Wen-bin, Zhang Yin-ling, 等. Crosslinking Kinetics of Polyethylene with Small Amount of Peroxide and Its Influence on the Subsequent Crystallization Behaviors[J]. Chinese Journal of Polymer Science, 2016,34(9):1117-1128. DOI: 10.1007/s10118-016-1819-z.
Niu Yan-hua, Liang Wen-bin, Zhang Yin-ling, et al. Crosslinking Kinetics of Polyethylene with Small Amount of Peroxide and Its Influence on the Subsequent Crystallization Behaviors[J]. Chinese Journal of Polymer Science, 2016, 34(9): 1117-1128. DOI: 10.1007/s10118-016-1819-z.
Crosslinking reactions of high density polyethylene with low peroxide concentrations ranging from 0.1 wt% to 1.0 wt% at temperatures of 170
180 and 190℃ were monitored by rheological measurements. A critical gel forms at the peroxide concentration of 0.2 wt%
where the transition from long chain branching generation to crosslinking network formation could occur. Rheokinetics of crosslinking can be fitted well by Ding-Leonov’s model. The curing rate
k
2
at the earlier stage exhibits about 3 times acceleration per 10℃ with increasing temperature
while the equilibrium modulus
G
′at the fully cured stage is almost independent of temperature. Influences of crosslinking on the subsequent crystallization behaviors were detected by DSC measurements. Above the critical gel concentration
crystallization is largely retarded as evidenced by the lower crystallization temperature
T
c
and crystallinity
X
c
due to the network formation. The secondary crystallization valley located at the temperature near 80℃ can be observed above the critical concentration
which becomes more evident with the increasing peroxide concentration and curing temperature. This phenomenon provides another evidence of crystallization retardation by the crosslinking network.
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