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聚合物共混物和二嵌段共聚物熔体中涨落的单圈理论的重整化。

Renormalization of the one-loop theory of fluctuations in polymer blends and diblock copolymer melts.

作者信息

Grzywacz Piotr, Qin Jian, Morse David C

机构信息

Department of Physics and Department of Chemical Engineering & Materials Science, University of Minnesota, 421 Washington Avenue S.E., Minneapolis, MN 55455, USA.

出版信息

Phys Rev E Stat Nonlin Soft Matter Phys. 2007 Dec;76(6 Pt 1):061802. doi: 10.1103/PhysRevE.76.061802. Epub 2007 Dec 14.

Abstract

Attempts to use coarse-grained molecular theories to calculate corrections to the random-phase approximation (RPA) for correlations in polymer mixtures have been plagued by an unwanted sensitivity to the value of an arbitrary cutoff length, i.e., by an ultraviolet (UV) divergence. We analyze the UV divergence of the inverse structure factor S(-1)(k) predicted by a "one-loop" approximation similar to that used in several previous studies. We consider both miscible homopolymer blends and disordered diblock copolymer melts. We show, in both cases, that all UV divergent contributions can be absorbed into a renormalization of the values of the phenomenological parameters of a generalized self-consistent field theory (SCFT). This observation allows the construction of an UV convergent theory of corrections to SCFT phenomenology. The UV-divergent one-loop contribution to S(-1)(k) is shown to be the sum of (i) a k -independent contribution that arises from a renormalization of the effective chi parameter, (ii) a k-dependent contribution that arises from a renormalization of monomer statistical segment lengths, (iii) a contribution proportional to k(2) that arises from a square-gradient contribution to the one-loop fluctuation free energy, and (iv) a k-dependent contribution that is inversely proportional to the degree of polymerization, which arises from local perturbations in fluid structure near chain ends and near junctions between blocks in block copolymers.

摘要

试图运用粗粒化分子理论来计算聚合物混合物中相关性的随机相位近似(RPA)修正值时,一直受到对任意截止长度值的不必要敏感性的困扰,即受到紫外(UV)发散的影响。我们分析了由类似于先前几项研究所使用的“单圈”近似预测的逆结构因子S(-1)(k)的UV发散情况。我们考虑了可混溶的均聚物共混物和无序的二嵌段共聚物熔体。我们表明,在这两种情况下,所有UV发散贡献都可以被吸收到广义自洽场理论(SCFT)现象学参数值的重整化中。这一观察结果使得能够构建一种对SCFT现象学修正的UV收敛理论。对S(-1)(k)的UV发散单圈贡献被证明是以下各项之和:(i)由有效χ参数重整化产生的与k无关的贡献;(ii)由单体统计链段长度重整化产生的与k有关的贡献;(iii)由对单圈涨落自由能的平方梯度贡献产生的与k(2)成比例的贡献;以及(iv)由链端附近和二嵌段共聚物中嵌段间连接点附近流体结构的局部扰动产生的与聚合度成反比的与k有关的贡献。

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