两嵌段共聚高分子链通过薄膜上纳米孑孔隙输运的研究

针对两嵌段高分子链的跨膜输运过程,分别给出与不同输运次序相对戍的高分子链的自由能,进而通过求解Fokker-Planck方程并在不同条件下对平均首次通过时间进行了数值计算.计算结果表明,当共聚高分子链由良溶剂区向不良溶剂区输运时,不能发生线团一链滴转变的链首先输运总是有利于整个高分子链的输运.而在给定输运次序的情况下,化学势、线团一链滴转变、共聚链的组成以及输运速率等因素对输运时间可产生显著影响.相关研究结果可为调控实际生物高分子链的输运时间提供可能的理论线索.     

A_a型Patchy胶体粒子的相态结构

根据热力学微扰理论研究了Aa型Patchy胶体的相态结构,考察了Patch之间的缔合强度及Patch数目对体系相态结构的调控机制.利用相平衡原理给出了Patchy胶体的流体、玻璃态固体和面心立方晶体之间转变及溶胶-凝胶转变的相图,讨论了玻璃态和晶态固相的成核机制、临界现象和相变问题.研究结果表明,Patchy胶体粒子之间的缔合作用和Patch数目可以显著地调控体系的三相点、临界温度和临界密度等特征.在高温条件下,Patchy胶体以一次成核方式结晶;而在低温条件下则以两步成核方式逐步成核结晶,中间经过非晶态的玻璃态固相作为过渡.说明Patchy粒子之间的缔合作用对其相态结构具有决定性影响,因而成为调控体系聚集态结构的重要因素.     

Influences of surface effects and large deformation on the resonant properties of ultrathin silicon nanocantilevers

The purpose of the present work is to quantify the influences of the discrete nature,the surface effects,and the large deformation on the bending resonant properties of long and ultrathin 100 silicon nanocantilevers.We accomplish this by using an analytical semi-continuum Keating model within the framework of nonlinear,finite deformation kinematics.The semi-continuum model shows that the elastic behaviors of the silicon nanocantilevers are size-dependent and surfacedependent,which agrees well with the molecular dynamics results.It also indicates that the dominant effect on the fundamental resonant frequency shift of the silicon nanocantilever is adsorption-induced surface stress,followed by the discrete nature and surface reconstruction,whereas surface relaxation has the least effect.In particular,it is found that a large deformation tends to increase the nonlinear fundamental frequency of the silicon nanocantilever,depending not only on its size but also on the surface effects.Finally,the resonant frequency shifts due to the adsorption-induced surface stress predicted by the current model are quantitatively compared with those obtained from the experimental measurement and the other existing approach.It is noticed that the length-to-thickness ratio is the key parameter that correlates the deviations in the resonant frequencies predicted from the current model and the empirical formula.     

三元非等活性自缩合乙烯基聚合体系的Z均回转半径

利用Monte Carlo模拟方法研究了由单体、引发单体和引发核组成的三元自缩合乙烯基聚合反应体系. 重点考察了两类活性基团反应活性的差异、引发单体分数、引发核的配比及活性基团数等因素对体系中无核和有核两类超支化高分子Z均回转半径的影响. 结果表明, 这些因素对超支化高分子的结构和尺度影响显著, 因而通过调节有关参数可以实现对超支化高分子结构和尺度的调控.     

Lennard-Jones流体中胶体粒子间耗尽势的密度泛函理论研究

基于Roth, Evans和Dietrich有关耗尽势的密度泛函理论研究了Lennard-Jones (L-J)流体中胶体粒子间的耗尽势. 通过计算胶体稀溶液中两个胶体粒子在不同条件下的耗尽势, 进一步分析了L-J流体的相关因素对耗尽势的影响. 结果表明, L-J流体分子的体积分数、胶体粒子与溶剂分子的尺寸比率、L-J流体分子间的相互作用以及胶体粒子与流体分子之间的弱相互作用等因素均可对胶体粒子间耗尽势产生显著影响. 研究结果可为实验上调控胶体粒子间的相互作用提供可能的线索.     

Influences of surface effects and large deformation on the resonant properties of ultrathin silicon nanocantilevers

The purpose of the present work is to quantify the influences of the discrete nature, the surface effects, and the large deformation on the bending resonant properties of long and ultrathin 〈100〉 silicon nanocantilevers. We accomplish this by using an analytical semi-continuum Keating model within the framework of nonlinear, finite deformation kinematics. The semi-continuum model shows that the elastic behaviors of the silicon nanocantilevers are size-dependent and surface-dependent, which agrees well with the molecular dynamics results. It also indicates that the dominant effect on the fundamental resonant frequency shift of the silicon nanocantilever is adsorption-induced surface stress, followed by the discrete nature and surface reconstruction, whereas surface relaxation has the least effect. In particular, it is found that a large deformation tends to increase the nonlinear fundamental frequency of the silicon nanocantilever, depending not only on its size but also on the surface effects. Finally, the resonant frequency shifts due to the adsorption-induced surface stress predicted by the current model are quantitatively compared with those obtained from the experimental measurement and the other existing approach. It is noticed that the length-to-thickness ratio is the key parameter that correlates the deviations in the resonant frequencies predicted from the current model and the empirical formula.     

Patchy胶体粒子的结晶、玻璃化和凝胶化问题

本文探讨了中性多缔合位点Patchy胶体粒子系统的相图及其相关问题. 在研究中,计入了分子间的硬芯Lennard-Jones势和缔合作用,进而阐明了系统的流体相(F),无规密积相(RCP)和面心立方相(FCC)之间转变的相态结构. 在体系丰富的相结构中,F-F,F-RCP及F-FCC相转变以及描述粒子间联结性的溶胶-凝胶转变相互影响,致使一些相态在不同相互作用强度时可以呈现亚稳态和稳态. 同时,本文重点阐述了缔合能量以及patch数目对体系的临界温度、临界密度、临界三相点以及溶胶-凝胶转变等的调控机制.     

二元自缩合乙烯基聚合反应体系的统计热力学

应用统计力学原理对二元自缩合乙烯基聚合反应体系(由单体和引发单体组成)的统计热力学特征予以研究.首先从两种不同的角度给出与聚合反应相应的配分函数,据此得到反应体系的平衡自由能、质量作用定律以及超支化高分子的数量分布函数,进而计算了体系的比热和等温压缩系数等热力学量.进一步研究了超支化高分子的空间尺度,给出反应体系k次均方回转半径的递推公式,计算了各种不同溶剂条件下的均方回转半径,指出引发单体分数、反应程度和溶剂效应对超支化高分子空间尺度的影响.     

存在初始分布时自缩合乙烯基聚合体系的统计理论

本文利用生成函数方法对存在初始分布的自缩合乙烯基聚合反应体系进行研究．首先在任意初始分布情形下,构造并通过反应体系的微分动力学方程导出对应的生成函数．进一步分别考察了均一初始分布和混合初始分布两种情形,利用生成函数获得反应体系的数均、重均和Z-均聚合度以及多分散指数等物理量．研究结果表明,利用生成函数方法不仅可以给出超支化高分子的数量分布函数,而且可以使平均高分子物理量的计算大为简化．同时发现,反应体系的统计特征与初始分布密切相关,相应的结果可为进一步研究分批投料、多组分及非等活性等更加复杂的自缩合乙烯基反应体系提供可能的基础．     

AaDd型氢键流体的统计理论（V）：球形微腔中的相平衡

利用密度泛函理论并结合改进的基本度量理论研究了球形微腔中AaDd型氢键流体的相态结构．首先,根据氢键流体在球腔中的吸附一脱附等温线以及相应的巨势等温线获得不同条件下氢键流体的相图．在此基础上,重点讨论了氢键作用、球腔尺寸以及腔壁与流体之间的相互作用等因素对氢键流体相平衡特征的影响．结果表明,流体层化转变和毛细凝聚的临界温度、临界密度和临界相区域等相态特征与这些因素密切相关．研究结果可为进一步揭示几何约束下氢键流体的相平衡及聚集态结构提供可能的理论线索．