泡沫塑料动态成核机理的研究
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摘要
在塑料发泡成型过程中，气泡核的形成阶段对泡孔的密度和分布起着决定性的作用，是控制泡体质量的关键阶段。前人对泡沫塑料气泡成核过程的研究基本上都是以经典成核理论为基础进行的。经典成核理论假设气泡核的形成是在静态条件下发生的，它没有反映在口模流场中动态因素(拉伸、剪切等)对气泡成核的影响。近来的一些实验研究表明，剪切流动能对气泡成核产生显著的影响。但是目前还缺少深入合理的理论分析和专题研究，成核机理研究还未见有突破性进展。为了完善气泡成核理论，使它能更有效地指导实践，本文作了以下研究。
将高分子链取向、分子链间空穴大小的分布情况和气泡成核行为联系在一起，首次提出了拉伸和剪切等动态因素影响塑料发泡成核行为的微观机理。根据这一机理可以比较合理地解释Han CD和Lee等人观察到的一些剪切流动影响气泡成核行为的实验现象，概括如下：(1)塑料挤出发泡时，高分子链在剪切流场作用下发生分子取向。分子取向程度越高，分子链间空穴的大小差距越小，气泡成核需要的气体过饱和度越大，开始形成气泡核的时间越晚。由于在口模厚度方向上分子取向度的分布情况是流道中心处分子取向度最小，越靠近口模壁面分子取向度越大，所以在流道中心最先形成气泡核，越靠近口模壁面则开始形成气泡核的时间越晚。这可以解释Han JH和Han CD观察到的实验现象；(2)剪切速率越大则分子取向程度越高，分子链间空穴的尺寸大小差距越小，一旦开始形成气泡核，可以作为成核点的空穴数量越多，气泡成核速率越大。这可以解释Lee观察到的挤出发泡时制品泡孔密度随剪切速率增大而增大的实验现象；(3)口模平直流道中心线附近分子取向度始终近似为零，不随挤出流量的变化而变化，所以此处气泡开始成核时的熔体临界压力与挤出流量无关。这就是Han CD和Villamizar通过可视化实验测出的气泡开始成核临界压力与剪切速率无关的原因。
根据上述拉伸和剪切等动态因素影响塑料发泡成核行为的微观机理，首次提出分子取向有利于得到泡孔数量多而且分布均匀的优质泡体。进而提出了一个强化气泡成核效果的新方法：在塑料挤出发泡过程中，通过改进口模设计和优化挤
In the foam process of cellular plastics, bubble nucleation has decisive effect on cell density and cell distribution, so it is the crucial factor to control the foam quality. Almost all the former work on bubble nucleation of cellular plastics is based on classical nucleation theory. Because classical nucleation theory supposes that bubble formation is occurred under static state, it doesn't reflect the effects of dynamic factors on bubble nucleation, such as shear and elongation. Recently, some experimental results show that shear flow has significant influences on bubble nucleation. However, it is still lack of reasonable theoretical analysis on bubble nucleation, and bubble nucleation mechanism made no essential progress. In order to improve the bubble nucleation theory to instruct practical appliance; following researches are done in this paper.
By combining macromolecule orientation, size distribution of voids among molecule chains and bubble nucleation, the microcosmic mechanism of the effect of dynamic factors such as shear and elongation on bubble nucleation are put forward for the first time in this paper. Some experimental phenomena reflecting the effect of shear flow on bubble nucleation behavior, observed by Han or Lee, can be explained by the mechanism logically, as follow. (1) During the foam extrusion, macromolecules are oriented in the shear flow field. As the orientation degree increases, size difference of voids becomes smaller, so the gas supersaturates degree needing for bubble nucleation increases. Therefore, bubble nucleation is put off In the transaction direction of extrusion die, macromolecule orientation degree increases from the centerline to the die surface. Therefore, bubble formation occurred foremost at the centerline of the die, then gradually extend to the die surface. This can explain the experimental results observed by Han JH and Han CD. (2) As shear rate increases, molecule orientation degree increases while size difference of voids becomes smaller. Once the bubble nucleation begins, the number of voids acting as nucleating sites become larger. Therefore, bubble nucleation rate becomes larger. (3) At the centerline of straight die, molecule orientation is approximately omitted, so the critical pressure starting to nucleation is irrespective
将高分子链取向、分子链间空穴大小的分布情况和气泡成核行为联系在一起，首次提出了拉伸和剪切等动态因素影响塑料发泡成核行为的微观机理。根据这一机理可以比较合理地解释Han CD和Lee等人观察到的一些剪切流动影响气泡成核行为的实验现象，概括如下：(1)塑料挤出发泡时，高分子链在剪切流场作用下发生分子取向。分子取向程度越高，分子链间空穴的大小差距越小，气泡成核需要的气体过饱和度越大，开始形成气泡核的时间越晚。由于在口模厚度方向上分子取向度的分布情况是流道中心处分子取向度最小，越靠近口模壁面分子取向度越大，所以在流道中心最先形成气泡核，越靠近口模壁面则开始形成气泡核的时间越晚。这可以解释Han JH和Han CD观察到的实验现象；(2)剪切速率越大则分子取向程度越高，分子链间空穴的尺寸大小差距越小，一旦开始形成气泡核，可以作为成核点的空穴数量越多，气泡成核速率越大。这可以解释Lee观察到的挤出发泡时制品泡孔密度随剪切速率增大而增大的实验现象；(3)口模平直流道中心线附近分子取向度始终近似为零，不随挤出流量的变化而变化，所以此处气泡开始成核时的熔体临界压力与挤出流量无关。这就是Han CD和Villamizar通过可视化实验测出的气泡开始成核临界压力与剪切速率无关的原因。
根据上述拉伸和剪切等动态因素影响塑料发泡成核行为的微观机理，首次提出分子取向有利于得到泡孔数量多而且分布均匀的优质泡体。进而提出了一个强化气泡成核效果的新方法：在塑料挤出发泡过程中，通过改进口模设计和优化挤
In the foam process of cellular plastics, bubble nucleation has decisive effect on cell density and cell distribution, so it is the crucial factor to control the foam quality. Almost all the former work on bubble nucleation of cellular plastics is based on classical nucleation theory. Because classical nucleation theory supposes that bubble formation is occurred under static state, it doesn't reflect the effects of dynamic factors on bubble nucleation, such as shear and elongation. Recently, some experimental results show that shear flow has significant influences on bubble nucleation. However, it is still lack of reasonable theoretical analysis on bubble nucleation, and bubble nucleation mechanism made no essential progress. In order to improve the bubble nucleation theory to instruct practical appliance; following researches are done in this paper.
By combining macromolecule orientation, size distribution of voids among molecule chains and bubble nucleation, the microcosmic mechanism of the effect of dynamic factors such as shear and elongation on bubble nucleation are put forward for the first time in this paper. Some experimental phenomena reflecting the effect of shear flow on bubble nucleation behavior, observed by Han or Lee, can be explained by the mechanism logically, as follow. (1) During the foam extrusion, macromolecules are oriented in the shear flow field. As the orientation degree increases, size difference of voids becomes smaller, so the gas supersaturates degree needing for bubble nucleation increases. Therefore, bubble nucleation is put off In the transaction direction of extrusion die, macromolecule orientation degree increases from the centerline to the die surface. Therefore, bubble formation occurred foremost at the centerline of the die, then gradually extend to the die surface. This can explain the experimental results observed by Han JH and Han CD. (2) As shear rate increases, molecule orientation degree increases while size difference of voids becomes smaller. Once the bubble nucleation begins, the number of voids acting as nucleating sites become larger. Therefore, bubble nucleation rate becomes larger. (3) At the centerline of straight die, molecule orientation is approximately omitted, so the critical pressure starting to nucleation is irrespective
引文
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