磁性高分子链的磁性质和构象性质的Monte Carlo模拟

采用退火 (Annealing)MonteCarlo方法 ,从高温到低温顺序模拟了简立方格点上考虑最近邻Ising相互作用的磁性高分子链在不同温度的磁性质和构象性质 .磁性高分子链在低温下存在自发磁矩 ,无限长链的临界温度Tc=1 77± 0 0 5J kB.在临界温度附近 ,高分子链经历了从伸展的无规线团到紧缩球体的塌缩相变 .对链的尺寸、形状、近邻数及能量的分析表明 ,高分子链的构象性质从温度Tc=1 77开始发生较明显的变化 ,这表明高分子Ising链的相变是Ising相互作用和链节运动协同作用的结果 .     

端基附壁高分子模型链的塌缩转变

借MonteCarlo和模拟退火方法研究了端基附壁高分子尾形链在不同温度下的形态变化 ,链的模型采用有最近邻相互吸引作用的自避行走 .计算机实验结果表明 ,对于端基附壁的高分子尾形链 ,与自由链一样 ,当温度逐渐降低时高分子链会发生从松散的无规线团到紧密球体的塌缩转变 .计算机模拟得到了端基附壁链的均方末端距及其分量 ,均方回转半径及分布随温度的变化 .由于刚性壁的影响 ,使得有限链长的高分子尾形链与自由链相比 ,其表示链尺寸 温度关系的曲线要稍低 .模拟还发现 ,在高温时壁对链形状的影响比较大 ,壁垂直方向上尺寸明显大于平行方向的尺寸 ,后者接近于自由链的尺寸分量 .然而 ,低于θ温度时 ,尤其是完全塌缩之后 ,壁对链形状的影响已经很小 .     

分子链构象变化对高分子液晶相行为的影响

聚肽高分子溶解在含有机酸的有机溶剂中可以在室温条件下形成液晶．随着温度的下降,体系中的酸分子会引起聚肽分子链发生由刚性螺旋结构向柔性无规线团结构的构象转变．这种转变将导致一个由液晶态向非液晶态的相变．在Ｆｌｏｒｙ格子理论和Ｚｉｍｍ Ｂｒａｇｇ理论的基础上,作者已提出了有关这一现象的理论解释,并通过引入一个与温度有关的库恩链长径比ｘｋ,使理论进一步完善,更切实际地解释聚肽液晶的相行为．此外,还讨论了不同分子刚柔性,不同高分子 溶剂作用系数χ对液晶相行为的影响,以及研究了聚肽液晶的有序参数．     

聚N-异丙基丙烯酰胺在十二烷基硫酸钠水溶液中的线团球体转变

高分子链在溶液中,当溶剂由良变劣时,将发生线团-球体转变,而同时由于链间聚集造成的相分离,使得很难真正观察到热力学意义上稳定的高分子单链紧缩球体。表面活性剂的加入有助于阻止高分子链间发生聚集,在不同的外部条件下,表面活性剂同高分子链将形成形态迥异且又复杂有趣的复合结构。本文主要讨论了聚N-异丙基丙烯酰胺在十二烷基硫酸钠水溶液体系中的线团-球体转变行为,以及聚N-异丙基丙烯酰胺与十二烷基硫酸钠分子间的相互作用及结构模型。     

硫酸钠诱导单链聚(N-异丙基丙烯酰胺)相变的单分子力谱研究

聚（N-异丙基丙烯酰胺） （PNIPAM）具有独特的相变行为,已成为人们研究蛋白质折叠等生命过程发生机理的模型体系. 我们利用基于原子力显微镜（AFM）的单分子力谱技术（SMFS）研究了单链PNIPAM在硫酸钠诱导下的相转变过程,并定量化了相变后所形成塌缩结构的稳定性. 通过对单链PNIPAM的单分子力谱实验得知：在相变前,得到单调上升的力曲线,对应着PNIPAM无规线团结构的形变过程;相变后,得到的锯齿型力曲线,对应着PNIPAM塌缩结构在外力诱导下的解折叠过程. 首次从单分子水平观察到在外加盐的作用下,单链PNIPAM低温相转变和高温相转变的差异：相比于低温相转变,高温相转变生成的塌缩结构更加稳定.     

大分子局部链段的走向

本文以投影几何的方法,计算了锯齿型分子链局部链段的形态为折线状。孤立的高分子链,从整体来看是无规线团状,而在微观的局部是折线状。由这样的分子链组成的非晶高聚物的聚集态结构,在局部的区域中存在着有序结构。     

激光光散射研究聚（N—异丙基丙烯酰胺）单链及其智能凝胶微球在水中的相变

利用静态和动态光散射相结合的方法系统地研究了单根聚线性长链在无规线团和蜷曲线两个状态之间的转变和球形ＰＮＩＰＡＭ微凝胶的体积相变。首次在实验上证明，一根均聚物长链可以蜷 成一个稳定的蜷曲单链球以及在无规线团和蜷曲线两个状态之间存在着两个热力学稳定态；２皱缩的线团和融化的蜷曲线。     

真空浇铸聚苯乙烯薄膜的拉伸力学行为

高分子溶液的浓度从极稀到极浓的转变过程是高分子链从单链体系转变成相互穿透的多链体系的分子凝聚过程 .在极稀溶液中高分子链以无规线团状态孤立地存在于溶剂介质中 ;在良溶剂中是溶涨的无规线团 ,可以设想溶液浓度逐渐增大时 ,有一高分子线团开始相互接触的所谓接触浓度 ;随着浓度进一步增加高分子线团之间就发生交叠而相互穿透 ,这时溶液就转变成物理交联结构的浓溶液 .分子链的互穿程度会随浓度的继续增加而增加 .如果能用一些特殊的实验方法将高分子在不同浓度的溶液中的凝聚状态尽量全部或部分的保留到高分子固体中 ,则所得到的具有…     

激光光散射研究聚(N-异丙基丙烯酰胺)单链及其智能凝胶微球在水中的相变(上)

利用静态和动态光散射相结合的方法系统地研究了单根聚（Ｎ－异丙基丙烯酰胺）（ＰＮＩＰＡＭ）线性长链在无规线团（ｃｏｌｉ）和蜷曲球（ｇｌｏｂｕｌｅ）两个状态之间的转变和球形ＰＮＩＰＡＭ微凝胶的体积相变。首次在实验上证明，一根均聚物长链可以蜷曲成一个稳定的蜷曲单链球以及在无规线团和蜷曲球两个状态之间存在着两个热力学稳定态：皱缩的线团和融化的蜷曲球。另外，无规线团到蜷曲球的动力学研究结果否定了蜷曲球内存在高度链缠结的假说。作者的结果还显示，在完全蜷曲的单链球和收缩的微凝胶的流体力学体积内仍分别含有６６％和７０％的水。通过研究微凝胶与表面活性剂的相互作用，作者提出了与疏水作用不同的新的溶涨和收缩的机理。同时，作者利用核磁共振（ＮＭＲ）首次直接观察到既使在远低于临界胶束浓度时，表面活性剂分子也可在凝胶网络中形成胶束。通过比较单链和微凝胶收缩的差异，作者发现近年来观察到的大块凝胶的所谓的非连续体积变化并不是源于理论上所预测的非连续体积相变，而是由于内部不均匀收缩引致的内部应力同剪切模量之间的相互作用引起的。     

高分子链构象分布的直接观察

在动态光散射 (LLS)中 ,可以通过测定时间相关函数得到给定样品的线宽分布G(Γ) .对于刚性的胶体粒子 ,G(Γ)和流体力学尺寸分布直接相关 ,而柔性高分子链的G(Γ)不仅依赖于链长度分布 ,而且和高分子链构象的弛豫有关 .即使是单分散的高分子样品 ,仍会存在链构象的分布 .如果链构象的弛豫和平移扩散的时间尺度相近 ,如很长的高分子链在溶液中 ,构象弛豫则可能导致G(Γ)变宽 .利用聚(N 异丙基丙烯酰胺 ) (PNIPAM)链随温度升高可从伸展的有构象分布的柔性线团变成蜷曲的无构象分布的均匀小球这一事实 ,通过比较～ 2 5和～ 32℃条件下PNIPAM长链在溶液中的G(Γ) ,直接观察到由构象分布引起的G(Γ)额外增宽 .     

Histogram Monte Carlo simulation on phase transitions in single‐polymer systems

Applying the histogram Monte Carlo simulation method and the bond‐fluctuation model, various phase transitions in single‐polymer systems were investigated. The critical transition temperature (Θ point) in the coil‐globule collapse transition of a macromolecular chain is accurately determined. Finite‐size scaling results near the transition point are verified. The first‐order transition associated with the freezing/crystallization of a polymer at a temperature below the Θ point is also observed. The free energy profiles associated with these two transitions are explicitly computed. Furthermore, the unfolding phase transition associated with stretching a collapsed polymer chain is investigated. The free energy profile associated with the transition is explicitly computed. Results on the energy cumulants and free energy profiles provide direct evidences for the first‐order nature of the unfolding phase transition.     

Variations in molecular compactness and chain entanglement during the compression of grafted polymers

Characterizing the effect of geometrical confinement on mean polymer shape is an important step towards understanding and controlling molecular behaviour at interfaces. In this work, we study the configurational transitions and molecular shape changes that take place when a grafted polymer (or “mushroom”) is compressed by a hard plane. The polymer is modelled as a single, permanently‐grafted chain with a Lennard‐Jones interaction between monomer beads. For this model, we have monitored molecular size, asphericity, and chain entanglements as a function of compression, from the regime of self‐avoiding walks to the regime of collapsed polymers. With these tools, we show that strong confinement can produce chain compactization and disentanglement even in the presence of a mild attractive interaction. Our results provide limit values to the degree of compression and monomer attraction that is necessary to deform strongly collapsed polymer mushrooms.     

高取向聚对苯二甲酸乙二酯纤维的热收缩应力

为得到具有更高拉伸强度和模量的半晶聚合物纤维,需要使分子链充分结晶和取向,然而这种高度取向样品受热时,随着温度的升高,取向的非晶态分子链熵力增大,解取向可以自发进行.在外加张力较小时,纤维产生热收缩;在定长状态下,表现为外加张力增大,此过程被视为取向材料中＂冻结＂内应力的释放,通常将这种内应力称为热收缩应力。     

Intramolecularly ordered globules and the collapse of short chains

We investigate the poor-solvent collapse of short chains having different stiffness through self-consistent minimization of the intramolecular free energy under the constraint of fixed segment lengths between adjacent beads. At first the chains form the Random Gaussian Globule, where the beads are distributed at random at the same average distance from the centre of mass, while the segments show very little correlation. At a larger attractive potential, this collapsed globule undergoes a transition to one or more ordered compact states, depending on the chain stiffness. Under very strong contraction, all chains are described as a Compact Ordered Globule: the beads are again at a constant average distance from the centre of mass, while the segments jump back and forth at the globule's wall with a very large correlation. At intermediate contraction, the thinner and stiffer chains form the Oscillating Ordered Globule wherein the beads are alternatively distributed on two concentric on two concentric shells. In this case, we also find metastable states with nonsymmetrical conformations of the chain with respect to its ends. We also briefly discuss the thermodynamics of the coil-globule and globule-globule transitions, showing that in long polymer chains these ordered conformations cannot involve the whole chain. However, we suggest that they might still be found as local globules that form for kinetic reasons.     

VISCOMETRIC INVESTIGATIONS OF POLYVINYLPYRROLIDONE IN MIXED SOLVENTS AND WITH VARYING TEMPERATURE

The viscosity behavior of polyvinylpyrrolidone (PVP) has been determined at 25℃ in mixed solvents comprising water/dimethylformamide (DMF) and water /methanol (MeOH). Analysis of the data has considered the PVP as being both host and guest polymer in solution. The intrinsic viscosity of PVP in DMF is higher than in water and in MeOH, but also increases in a mixed solvent with high water content because of the effect of polymer-solvent interactions. It was also found that the intrinsic viscosity of PVP at finite concentration, [ηpvp]c decreases with an increase in the concentration of PVP in solution. The viscosity behavior of PVP in a mixed solvent is affected by the concentration-dependent intermolecular excluded volume effect, which can be quantitatively expressed by the parameter, bY, which reflects the shrinkage of PVP chain coils, resulting in a decrease of [ηpvp]c. The effect of temperature on the viscosity behavior of PVP in MeOH shows that the interaction parameter increases up to a maximum value, and then decreases after a certain temperature.     

微相分离及链结构对聚酯-聚醚嵌段共聚物分子运动的影响

本文首先研究了成型方法和热处理对聚对苯二甲酸乙二酯与聚氧四亚甲基嵌段共聚物动态力学温度谱的影响,结合应力-应变曲线讨论了微相分离与力学性能的关系。其次,比较了三种不同链结构的聚酯-聚醚嵌段共聚物在不同温控程序下的动态力学温度谱,讨论了链结构对软链段结晶的影响。最后观察了聚氨酯-聚醚嵌段共聚物双重玻璃化转变现象并作了解释。     

Role of chain stiffness on the conformation of single polyelectrolytes in salt solutions

Conformation of single polyelectrolytes in tetravalent salt solutions is investigated under the framework of a coarse-grained model, using Langevin dynamics simulations. The chain size, studied by the radius of gyration, shows three different variational behaviors with salt concentration, depending on the chain stiffness. According to the size variations, polyelectrolytes of fixed chain length are classified into three categories: (1) flexible chain, for which the variation shows a curve similar to a tilted L, (2) semiflexible chain, whose curve resembles U, and (3) rigid chain, for which the curve is a straight line. The wormlike chain model with persistence length predicted by the Odijk-Skolnick-Fixman theory is found to be able to qualitatively describe the end-to-end distance at low salt concentration not only for semiflexible and rigid chains but also for flexible chain. In a low salt region, a flexible polyelectrolyte extends more significantly than a semiflexible chain, in reference of the size of their uncharged counterparts, and in a high salt region, regardless of chain stiffness, a chain attains a dimension comparable to that of its neutral polymer. The chain stiffness influences both the local and the global chain structures. A flexible chain exhibits a zigzagged local structure in the presence of salt ions, and the condensed structure is a disordered, random globule. A semiflexible chain is locally smooth, and the condensed structure is orderly packed, taking a form such as hairpin or toroid. Moreover, the chain stiffness can also affect the nature of the coil-globule transition. The transition occurred in a discrete manner for semiflexible chain, whereas it occurred in a continuous way for flexible chain. This discrete feature happened not only at low salt concentration when a semiflexible chain collapsed but also at high salt concentration when the collapsed chain is reexpanded. At the end, the effects of chain stiffness and salt concentration on the conformation of single polyelectrolytes are summarized in a schematic state diagram.     

Monte Carlo Simulation of Coil-to-Globule Transition of Compact Polymer Chains: Role of Monomer Interacting

Coil-to-globule transitions are fundamental problems existing in polymer science for several decades; however, some features are still unclear, such as the effect of chain monomer interaction. Herein, we use Monte Carlo simulation to study the coil-to-globule transition of simple compact polymer chains. We first consider the finite-size effects for a given monomer interaction, where the short chain exhibits a one-step collapse while long chains demonstrate a two-step collapse, indicated by the specific heat. More interestingly, with the decrease of chain monomer interaction, the critical temperatures marked by the peaks of heat capacity shift to low values. A closer examination from the energy, mean-squared radius of gyration and shape factor also suggests the lower temperature of coil-to-globule transition.     

External and internal plasticization of cellulose acetate with caprolactone: Structure and properties

Cellulose acetate was modified with caprolactone in an internal mixer at temperatures between 120 and 220 °C, and reaction times between 5 and 45 min in the presence of tinoctoate catalyst. The effect of plasticization on the properties of the polymer was studied by dynamic mechanical analysis and tensile testing. The dynamic mechanical spectrum of cellulose acetate exhibits three main relaxation transitions. These can be assigned to segments (α), to smaller structural units of the main chain, probably individual glucose rings (β), and to hydroxyl or hydroxylmethyl groups (γ). Plasticization by caprolactone leads to the decrease of the glass transition temperature of CA, but also to the breakdown of relatively large segments to smaller structural units. Free hydroxyl groups interact with the plasticizer forming larger units with higher transition temperature. Grafting decreases the intensity of the γ‐transition peak. External plasticization creates a larger number of small structural units, but the external plasticizer is less efficient in the decrease of stiffness than grafted polycaprolactone chains. Internal plasticization is more advantageous because it leads to higher flexibility at larger strength than external plasticization, and the migration of the plasticizer is prevented at the same time. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 873–883, 2007     

炭黑结合橡胶对天然橡胶性能的影响

本文研究了天然橡胶(NR)与五种不同类型炭黑的结合橡胶对其混炼胶的应力-应变、流变性质等的影响。结果表明,NR与炭黑的结合橡胶量随炭黑结构和表面积增加而增加。结合橡胶的增加使NR在低剪切下的本体粘度、弹性恢复性和强度增加,塑性和粘着性降低;在高剪切下流动性变差,挤出物收缩则有所下降。此外,结合橡胶的增加也增加了硫化胶的交联度,因此模量、硬度和耐磨性提高,抗张强度和伸长率却有所下降。