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Flow-induced crystallization of polybutene-1 and effect of molecular parameters

机译:流动诱导聚丁烯-1的结晶和分子参数的影响

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摘要

There are two main goals of this thesis: to investigate the flow-induced crystallization behaviour of Polybutene-1 (PB-1 samples, and to study the effects of molecular parameters on the crystallization behaviour While flow-induced crystallization is not a new area in polymer research, well-defined experimental methods that allow access to high flow rate range comparable to that encountered in real processing are still lacking. Two types of flow are considered: shear and uniaxial elongational. Regarding the second aim, several molecular parameters considered are: molecular weight, molecular weight distribution, isotacticity, presence of nucleating agents, and copolymer content. For this purpose an array of PB-1 samples were used. It is found that each of these parameters can have significant effect on the crystallization behaviour. Mainly rheological methods were utilized to conduct the flow-induced crystallization experiments. Crystallization onset time is defined from the change in viscosity or other related parameters. The experiments begin with low shear rate range, to ensure that the results are comparable with literature data. In this range we encounter the quasi-quiescent onset time at very small. shear rates, which draws an interesting comparison with another physical parameter, the gel time. Beyond a critical flow rate a decrease in the onset time is seen, and a plateau-and-slope trend is evident for a curve of onset time vs. shear rate. Using a combination of three experimental methods, shear rates ranging from Q0001 - 500 s-1 are successfully achieved, and a good agreement between these methods is observed. Furthermore, a normalization procedure is introduced, which yields temperature-invariant curves for the mentioned range of shear rate. For the uniaxial elongation flow, the Elongational Viscosity Fixture (EVF) is employed, with the strain rate ranging from 0.0001 - 10 s'. A greater reduction in onset time as compared to shear (at the same shear/strain rate) is observed, and the difference in the onset times for shear and elongation already reaches more than one decade for a flow rate of 10 5. This quantitative comparison is particularly important; since not so many data on elongation-induced crystallization are available in the literature. Finally, the thesis compares several flow induced crystallization models that can be useful as prediction tools and selects one of these models to be compared with the experimental data. A qualitative agreement is found, however, for better quantitative prediction the model still needs to be.
机译:本论文有两个主要目的:研究聚丁烯-1(PB-1样品)的流动诱导结晶行为,研究分子参数对结晶行为的影响,而流动诱导结晶不是硅的新领域。聚合物研究尚缺乏明确的实验方法,该方法允许获得与实际加工中可比较的高流速范围的流动,其中考虑了两种流动类型:剪切流动和单轴伸长;关于第二个目标,考虑的几个分子参数为:分子量,分子量分布,全同立构规整度,成核剂的存在和共聚物的含量,为此目的,使用了一系列PB-1样品,发现这些参数对结晶行为都有重要影响。用各种方法进行流致结晶实验,结晶的开始时间是根据结晶度的变化来确定的。粘度或其他相关参数。实验从低剪切速率范围开始,以确保结果与文献数据相当。在此范围内,我们遇到的准静态启动时间非常短。剪切速率,它与另一个物理参数(胶凝时间)进行了有趣的比较。除了临界流速,还可以看到起效时间减少,并且起效时间与剪切速率之间的关系曲线呈现出平稳和倾斜的趋势。结合使用三种实验方法,成功实现了Q0001-500 s-1的剪切速率,并且在这些方法之间观察到了很好的一致性。此外,引入归一化程序,其针对所述剪切速率范围产生温度不变曲线。对于单轴伸长率流动,使用伸长率粘度夹具(EVF),应变率范围为0.0001-10 s'。与剪切(在相同的剪切/应变速率下)相比,开始时间的减少更大,并且对于10 5的流量,剪切和伸长的开始时间的差异已经达到了十多年。特别重要;因为在文献中没有太多关于伸长引起的结晶的数据。最后,本文比较了几种可以用作预测工具的流致结晶模型,并选择了其中一种模型与实验数据进行比较。找到了定性的协议,但是,为了更好地进行定量预测,该模型仍然需要。

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    Hadinata C;

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  • 年度 2007
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