聚乙烯醇水溶液二维定向凝固的微观组织演化

为了深入探究定向多孔聚合物材料的微观组织形成机理,利用定向凝固原位实时观察手段,研究不同浓度及不同分子量聚乙烯醇(PVA)水溶液在不同抽拉速度下的定向凝固形貌演化.PVA水溶液的定向凝固形态在低浓度(1 wt%,2.5 wt%)和小分子量(M_w=24000)情况下,一次枝晶间距随着抽拉速度的增加而减小.随着PVA浓度和分子量的增加,一次枝晶间距随抽拉速度变化不明显,枝晶主轴尺寸则随速度增加呈现减小的趋势.与传统凝固形态形成机理相比,PVA水溶液的凝固形态由PVA分子的扩散引起的凝固界面不稳定性机理和PVA高分子链交联引起的局部相分离机理竞争决定.

Microstructure evolution of polyvinyl alcohol aqueous solution solidated in two-dimensional direction

Porous polymers have received much attention in recent years because of their light quality,high strength,good permeability and easy-revisable.Various fabrication methods of porous polymers have been used in which ice templating is a process which can prepare porous materials with complex structures and fine microstructures.This method has been widely used to prepare porous polymers but it still has many problems,such as poor homogeneity of pore distribution and pore connectivity.To solve these problems,it is necessary to understand the morphology of ice crystal growth in the solidification process of polymer solution.In situ observation of directional solidification is adopted in this paper to study the morphology evolution during directional solidification of polyvinyl alcohol (PVA) aqueous solution with different concentrations and molecular weights under different pulling speeds.The experimental results show that the primary dendrite spacing of PVA aqueous solution decreases with the increase of pulling speed at low concentration (1 wt%,2.5 wt%).However,increasing PVA concentration does not result in significant change in primary dendrite spacing.The primary dendrite spacing varies with pulling speed whereas the dendritic primary arm tends to shrink with increasing velocity.The effects of PVA concentration and pulling speed on morphology are partly because of diffusion instability from the classical solidification theory.When the concentration of solution is 5 wt%,there is little change of primary dendrite spacing with the velocity,which is due to the suppressed diffusion instability by high concentration of the polymer solution and large viscosity.When the concentration of solution increases to 10 wt%,ice crystal morphology is seaweed-like,where the PVA molecules are enriched and crosslinked ahead the ice crystal,leading to the continuous bifurcation of the dendrites.For the solidification morphologies of the aqueous solutions with different PVA molecular weights,the primary dendrite spacing of PVA aqueous solution decreases with the increase of pulling speed at low molecular weight (M_w=24000).Increasing PVA molecular weight does not result in significant change in primary dendrite spacing.At the low PVA molecular weight,the interface shows cell morphology.With the increase of PVA molecular weight,the large chain length leads to the stronger interaction among them and suppressing their diffusion. The corresponding constitutional undercooling is strengthened,thereby promoting the interfacial instability and dendrite formation.From the classical solidification morphology formation mechanism it may be concluded that the solidification morphology of PVA aqueous solution is determined by the competition between the two different mechanisms,i.e., interface instability induced by diffusion of PVA molecule and the local phase separation from the crosslinking of PVA polymer chains.