Modification of the Crystallization Kinetics of a Mixed Bath of Alkanes in the Presence of Coil-Crystalline Block Copolymer Micelles

D. Buzza, T. McLeish
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引用次数: 3

Abstract

Recent Neutron Scattering experiments by Richter et al. [1] show that the presence of coil-crystalline block copolymer (PE-PEP) micelles in a mixed alkane bath suppresses the crystallization out of solution of the long alkane component at low temperatures. Motivated by these experiments, we study theoretically the thermodynamics and kinetics of lamellar coil-crystalline block copolymer micelles in a bimodal solvent to better understand the factors determining the anti-precipitation action of coil-crystalline block copolymers. We assume an Alexander-de Gennes brush model for the strongly stretched corona chains and explicitly account for the polydispersity of the solvent chains. For the thermodynamic distribution of solvent chains in the corona, we find a predominance of short solvent chains to long solvent chains in the corona phase compared to the solvent bath, both with and without nematic interactions in the corona phase. We also calculate the rate of crystallization of the long solvent chains onto the micellar crystal core and find that the rate is sensitive to both brush and core parameters. In particular, we predict that to maximize the rate, both E fold /kTN A and X n need to be made as small as possible, where E fold is the folding energy of the crystal core chains, N A the number of statistical segments of the solvated corona chains and X n parameterises the strength of nematic interactions in the micellar corona. This leads to the surprising result that for fixed E fold , the rate of crystallization is increased when we increase the molecular weight of the corona blocks.
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盘状嵌段共聚物胶束存在下烷烃混合浴结晶动力学的改变
最近Richter等人[1]进行的中子散射实验表明,在混合烷烃浴中,线圈结晶嵌段共聚物(PE-PEP)胶束的存在抑制了长烷烃组分在低温下的结晶出液。在这些实验的激励下,我们从理论上研究了双峰溶剂中层状盘状-结晶嵌段共聚物胶束的热力学和动力学,以更好地了解盘状-结晶嵌段共聚物抗沉淀作用的决定因素。我们假设了强拉伸电晕链的亚历山大-德热纳电刷模型,并明确地解释了溶剂链的多分散性。对于溶剂链在电晕中的热力学分布,我们发现与溶剂浴相比,在电晕相中存在或不存在向列相互作用的情况下,短溶剂链比长溶剂链更占优势。我们还计算了长溶剂链在胶束晶体核心上的结晶速率,发现该速率对电刷和核心参数都很敏感。特别是,我们预测,为了使速率最大化,E fold /kTN A和X n都需要尽可能小,其中E fold是晶体核心链的折叠能量,n A是溶剂化电晕链的统计段数,X n是胶束电晕中向列相互作用强度的参数。这导致了一个令人惊讶的结果,即对于固定的E折叠,当我们增加电晕块的分子量时,结晶速率会增加。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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