预剪切对交联聚乙烯流变行为的影响.doc

预剪切对交联聚乙烯流变行为的影响 张小虎，，， 浙江大学高分子科学与工程学系 高分子合成与功能构造教育部重点实验室 杭州 310027 Email: yanghongmei@zju.edu.cn; s_yh0411@zju.edu.cn 使用过氧化二异丙苯（DCP）交联剂制得了不同交联程度的交联聚乙烯。采用流变仪对可交联聚乙烯在不同剪切速率下剪切10 min，然后进行热交联，考察了剪切速率对交联聚乙烯流变行为的影响。结果表明，在0.1 phr DCP时，剪切作用使交联聚乙烯弹性模量（G(）降低，损耗角正切（tanδ）增加，如Fig.1 (a) 图1a无力学损耗。另一方面，剪切作用使平台模量降低，松弛指数减小；剪切速率为2 s-1时，平台模量消失，时间无穷大松弛模量为零，如Fig.1 (b)所示。交联剂为0.5 phr DCP时，损耗角正切tanδ随频率增加而出现极大值，如Fig.1 (c)所示，说明聚乙烯发生液固转变，但所得交联聚乙烯凝胶含量约为70%，高于化学凝胶点。剪切速率增加，tanδ增加，但液-固转变所对应的频率不随剪切速率增加而改变。 关键词：交联聚乙烯，凝胶，稳态剪切，应力松弛 Fig.1 Influence of shear rate on dynamic rheological behaviors (a) and stress relaxation (b) of crosslinked LDPE using 0.1 phr DCP. Influence of shear rate on tanδ of crosslinked LDPE using 0.5 phr DCP (c). Influence of pre-shear on rheological behaviors of crosslinked polyethylene Xiaohu Zhang, Hongmei Yang*, Yihu Song*, Qiang Zheng Department of Polymer Science and Engineering, Key Laboratory of Macromolecular Synthesis and Functionalization, Ministry of Education, Zhejiang University, Hangzhou 310027, China Crosslinked polyethylene of different crosslinking degrees were prepared using dicumyl peroxide (DCP) as crosslinker. Crosslinkable polyethylene sheared at different shear rates for 10 min using rheometer was crosslinked and the influence of pre-shear rate on rheological behaviors of crosslinked polyethylene was studied. The results show that storage modulus (G() decreases and loss tangent (tanδ) increases with increasing shear rate (Fig.1(a)). On the other hand, the shear action decreases the low-frequency plateau modulus and relaxation exponent of crosslinked polyethylene; the plateau disappears at 2 s-1 of shear rate and the relaxation modulus at infinite time is zero (Fig.1(b)). At 0.5 phr DCP, the maximum tanδ occurs at a given frequency (Fig.1(c)), indicating the occurrence of liquid-solid transition. However, the gel fraction of corresponding sample is about 70 % far beyond the chemical gelation point. Though tanδ increases with increasing shear rate, the f