聚亚甲基链在弹性形变时的链段取向研究

高聚物的弹性形变是一个重要而普遍的现象 .在弹性形变过程中链段取向问题的研究是高聚物弹态形变中一个十分重要的内容 [1～ 6 ] ,这主要是 :一方面 ,在弹性形变过程中的链段取向可用核磁共振和红外二向色性实验方法直接测定 [2～ 4 ] ,另一方面 ,它又与高聚物在弹性形变过程中统计性质密切相关[1,5,6 ] ,因此对链段取向的研究可加深对弹性形变过程的了解 .最近 Taylor等[7] 用 Monte Carlo方法研究了聚亚甲基链的链段取向问题 ,但未研究高聚物在弹性形变过程中的内能变化 [8] ,也未考虑远程相互作用和较短的高分子链情况 ,这通常与理想…     

高聚物黏弹性力学模型计算中容易被忽视的基本问题(Ⅱ)——有关Voigt-Kelvin模型和四元件模型的计算

以高分子物理教学中的几道典型习题及解析为例,阐述了在应用黏弹性力学模型模拟高聚物力学松弛现象时,不能忽视的一些基本问题.     

测定本体粘度的拉伸蠕变方法

测量高聚物粘度的方法很多。对高粘度样品经常采用拉伸蠕变方法,这时测定的是拉伸粘度习η_T: σ=η_T(?)_f其中σ是拉伸应力,(?)_f是由此引起的拉伸流动的应变速率。由于高聚物是粘弹性材料。因此必须设法区分弹性形变和流动形变,才能得到η_T值。Bueche和Kraus等曾分别用拉伸蠕变方法研究聚甲基丙烯酸甲酯和聚顺丁二烯的本体粘度。他们所用的处理方法有三     

《高分子物理》教学中“力学损耗”的讲解

"力学损耗"是介绍聚合物黏弹性中重要的概念。教材在对它进行推导计算时省去了一些说明,导致同学们对这部分的理解比较困难。为了达到更好的教学效果,作者把周期应力作用下的应变分成理想弹性形变和理想黏性流动两部分,推导了一个形变周期内的能量损耗以及任意时刻的能量储存;弄清了"为什么在1/4周期时,系统具有最大的能量储存",并得到了力学损耗的公式。实践表明,用这种方式推导,绝大多数同学都能接受并很好的理解力学损耗这部分内容。     

高聚物温度-形变曲线全自动测定仪

测定温度-形变曲线是研究高聚物力学性质的一种重要方法。在高聚物试样上加以一定的荷重,并改变温度测定在各温度条件下的相对形变,再以形变对温度作图即可得到温度-形变曲线。在曲线的两个转折范围内可以定出玻璃化转变温度 T_g 和流动温度 T_f,从而可以估计被测试样材料的适用范围和加工条件。此外曲线还可以用来配合高聚物结构的研究和估计分子量。必须指出,T_g 和 T_f 仅标志高聚物分子运动状态的区分。在 T_g 以上分子链段开始作局部运动,因此高分子表现为高弹状态,而在 T_f 以上整个分子可以     

高聚物拉伸形变中的声发射

对一系列高聚物进行了单轴拉伸过程中声发射的观察,包括玻璃态高聚物、结晶高聚物、共聚物、共混高聚物和一种交联橡胶。非晶态高聚物拉伸时声发射次数很少,伴随银纹和微裂缝的产生而出现。结晶高聚物在屈服成颈时出现强的声发射,在颈部拉伸的初期声发射较少或不出现,拉伸到接近试件断裂前声发射强烈,次数急剧增多。相同高聚物但试件加工成形历史不同会在声发射上得到反映。交联的顺丁橡胶拉伸时声发射很弱,但可以观察到,在拉力-形变曲线开始偏离线性后出现,没有Kaiser效应。共混高聚物拉伸时声发射很多。高耐冲击共混接枝塑料在断裂前不出现强烈的声发射。如试样和试件加工成形条件相同,声发射现象的重演性是相当好的。     

高聚物从高弹态到流体态的转变

将高聚物由高弹态转变为流体态的转变温度命名为流动温度Tf,该转变温度与高聚物分子量密切相关.在高聚物从高弹态转变为流体态的研究中,由于T1.1的概念忽视对高聚物分子量的依赖性,因此采用Tf的概念更为合理.本文对高聚物的流动温度Tf的讨论涉及高聚物温度-形变曲线、高弹态温区、高聚物熔体剪切粘度.从高聚物凝聚态观点来看,高聚物熔体中凝聚缠结网络中的凝聚结点是分子链的局部向列相互作用使链单元间产生平行凝聚而形成的,而高聚物从高弹态到流体态的转变正是反映了高聚物熔体中凝聚缠结网络的物理交联点,即凝聚结点状态的变化.高聚物熔体可以流动,说明熔体中凝聚网络中的凝聚结点至少是可以在瞬间内打开的,升温使凝聚结点的解凝聚状态存在的时间加长,凝聚状态存在时间减短,当升高到某一温度时,在凝聚结点解凝聚状态的时间内,分子链通过内旋转使质量中心在外加力的方向上可以发生位移,此时高聚物从高弹态转变为流体态,而此时的温度就是流动温度Tf.对高聚物流体弛豫网络的研究,是一个很有前景的研究课题.     

在“高聚物的结构与性能”课程中讲透高聚物的特点

通过对高分子链的柔性、聚合物独有的熵弹性、显著的粘弹性、特有的描述链段运动的WLF方程,可能实现的大尺寸取向和小尺寸解取向、银纹、单链凝聚态、折叠链片晶和伸直链晶体、分子量的多分散性、高分子溶液特性和高聚物熔体的弹性行为等的讨论,希望能突出“高聚物的结构与性能”课程中高聚物的特点。     

动态膜渗透压法测量中的气球效应和液体粘附效应

用动态方法测量了半透膜对溶剂的透过速率及高聚物溶液的渗透压，膜在较大静压差的作用下所发生的弹性形变和液体在毛细管管壁上的粘附影响测量的复现性，导致了H－dH/dt关系偏离直线，使上升线与下降线不对称。     

高分子黏弹性的经典唯象模型

高分子流体的黏弹性质是高分子科学和工程中一个非常重要的研究领域.与简单黏性液体和弹性固体不同,外场作用下缠结高分子流体呈现出复杂的黏弹性行为,例如应力不仅仅与应变幅度或应变速率有关,还与整个形变历史相关.近半个世纪以来,人们建立了很多描述这些复杂黏弹性质的模型和理论,其中一类是基于连续性介质力学原理的唯象模型,例如:Maxwell模型、Voigt-Kelvin模型和在时空上所有参数为常量的连续性模型;另一类是瞬态网络模型,该模型把缠结点考虑成瞬态交联点,高分子链看成珠簧链;还有一类是微观分子理论,其中最著名的是"管子模型".本文首先介绍缠结高分子流体的线性黏弹性响应和Boltzmann叠加原理的基本概念,然后,重点综述描述高分子黏弹性质仍非常有实际应用价值的3个经典唯象模型,包括Maxwell模型、Voigt-Kelvin模型和瞬态网络模型,特别是这些理论的详细推导和存在的主要问题.关于高分子黏弹性的微观理论将在其它综述中单独介绍.     

Negative thixotropy of polymer solutions. 1. A model explaining time-dependent viscosity

Negative thixotropy, also called antithixotropy, is the effect of a flow-induced increase in viscosity that has been observed for many polymer solutions. Here, a simple quantitative model describing the time dependence of the shear stress or viscosity is presented. The model assumes a dynamic gel or network in the polymer solution, whose cross-links are dynamically formed and broken. The cross-links exist with or without deformation or flow of the solution. A second property of the model network is that it cannot be deformed infinitely, which is also true for any real network. The dynamic network solution is characterized by four parameters: its elastic shear modulus, its maximum degree of deformation, the rate with which the dynamic cross-links form and break and the viscous contribution of the polymer solution. The first two parameters can be related to each other, so only three independent parameters enter the model. An analytical solution is obtained which describes the flow-induced increase in viscosity, the minimum shear rate required for negative thixotropy and the dependence of the induction time on the shear rate. The results are shown to be in agreement with reported experimental results.     

基于多链模型的磁流变弹性体剪切模量的数值分析

Based on the magnetic interaction energy, using derivative of the magnetic energy density, a model is proposed to compute the magnetic-induced shear modulus of magnetorheological elastomers. Taking into account the influences of particles in the same chain and the particles in all adjacent chains, the traditional magnetic dipole model of the magnetorheological elastomers is modified. The influence of the ratio of the distance etween adjacent chains to the distance between adjacent particles in a chain on the magnetic induced shear odulus is quantitatively studied. When the ratio is large, the multi-chain model is compatible with the single chain model, but when the ratio is small, the difference of the two models is significant and can not be neglected. Making certain the size of the columns and the distance between adjacent columns, after constructing the computational model of BCT structures, the mechanical property of the magnetorheological elastomers composed of columnar structures is analyzed. Results show that, conventional point dipole model has overrated the magnetic-induced shear modulus of the magnetorheological elastomers. From the point of increasing the magnetic-induced shear modulus, when the particle volume fraction is small, the chain-like structure exhibits better result than the columnar structure, but when the particle volume fraction is large,the columnar structure will be better.     

Measurement of the Low-Frequency Shear Modulus of Polymeric Liquids

Abstract

The present work describes the resonance method for measurement of a low-frequency (about 10⁵ Hz) complex shear modulus of liquids by the use of a piezoquartz crystal. The problem of interaction of an oscillating system of the type piezoquartz-liquid interlayer-cover plate is analyzed. From the analysis of the problem there follow three methods for measuring the elasticity modulus of liquids. The investigation results of a homologous series of polymethyl siloxane liquids are presented. It has been shown that as the molecular weight of the series being investigated increases, the elasticity modulus value also increases, while the mechanical losses angle tangent passes through its maximum.     

Elastic properties of crosslinked poly(vinyl alcohol) gels: Network topology

Current network theory exhibits inconsistencies which show up particularly clearly in deformation of networks prepared by crosslinking a polymer in solution. A check of theory can be obtained if one knows precisely the number of crosslinks in the network and if a range of deformations is applied to the network. In an effort to explore this problem we have examined the relation of shear modulus to crosslink density, primary molecular weight, and polymer concentration for a series of poly(vinyl alcohol) gels at low to intermediate concentrations. Aqueous poly(vinyl alcohol) solutions were crosslinked to form infinite networks using terephthalaldehyde. We find a large discrepancy with these poly(vinyl alcohol) gels between measured shear modulus and that calculated from classical elasticity theory assuming quantitative reaction of crosslinking. The ratio of measured to calculated modulus is independent of crosslink density for a given primary molecular weight and concentration. It shows linear dependence on polymer concentration prior to crosslinking and extrapolates to a critical concentration which is consistent with the effective sizes of the polymer molecules.     

Giant Complex Modulus Reduction of κ‐Carrageenan Magnetic Gels

Summary: Effects of magnetization on the complex modulus of κ‐carrageenan magnetic gels have been investigated. The magnetic gel was made of a natural polymer, κ‐carrageenan, and a ferromagnetic particle, barium ferrite. The complex modulus of the magnetic gel was investigated by dynamic viscoelastic measurements with a compressional strain. It was first observed that the magnetic gels showed giant storage modulus reduction ≈10⁷ Pa before and after magnetization. The reduction was nearly independent of the frequency, and it increased with increasing the volume fraction of the ferrite. The maximum reduction in the storage modulus reached 14.9 MPa which corresponds to 76.5% of the modulus before magnetization. It was also found that the change in the modulus was nearly independent of a magnetization direction. Magnetism and morphology of the magnetic gels were also presented.

Strain dependence of the storage modulus at 1 Hz for κ‐carrageenan gel (□) and its magnetic gel before (○) and after (•) magnetization (ϕ = 0.39). The geometry of magnetization and strain directions is perpendicular.     

耐温抗盐驱油聚合物溶液黏弹性

对3种不同结构类型的耐温抗盐驱油聚合物〔高分子量聚丙烯酰胺(HPAM)、磺化聚丙烯酰胺(S-HPAM)和疏水缔合聚丙烯酰胺(A-HPAM)〕的溶液黏弹性能进行了研究。在温度85℃下,通过稳态剪切和动态剪切试验,考察了质量浓度和矿化度对聚合物溶液黏弹性的影响。结果表明,随剪切速率增加,溶液表观黏度逐渐降低。质量浓度越高,溶液的储能模量(G')和损耗模量(G″)越大。由动态剪切实验数据,计算得到第一法向应力差(N1)。随质量浓度增加,聚合物溶液的N1逐渐增大;随矿化度增加,聚合物溶液的N1出现不同盐敏感区域,说明不同结构类型的驱油聚合物溶液对矿化度的弹性响应不同。研究结果为高温高盐油藏聚合物驱剂的选择及开发提供了理论参考。     

Elastic shear modulus of biphasic gels

The effect on rheological properties on mixing one gel-forming and one nongelling polymer is investigated. It is found that on addition of a nongelling polymer to a constant amount of gel-forming polymer, the shear modulus of the resulting gel can either decrease or increase depending on the polymers. The results are interpreted within a simple qualitative model based on polymer incompatibility in combination with percolation theory and a uniform stress approximation.     

Characterization of thermo-reversible gels by means of sedimentation equilibria

This paper describes the deformation of gels in a centrifugal field leading to a continuous equilibrium. A gel is considered to be a binary mixture of cross-linked polymer and solvent and is assumed to remain isotropic during the deformation. From the equation for the osmotically effective pressure, called swelling pressure, the thermodynamic properties of a gel can be calculated. For highly swollen gels the expression of Svedberg and Pedersen is obtained. It is shown that the complete concentration dependence of the swelling pressure in the concentration range of the maximally swollen gel up to that at the cell bottom can be measured in a single equilibrium experiment. The homogeneity of weakly cross-linked gels can be examined by means of the method described. Soluble parts which are not incorporated into the polymer network can also be detected if they are present. From the swelling pressure-concentration curves it is possible to derive the thermodynamic properties of the physically crosslinked gelatin/water gels that were investigated. These gels can be described by means of a slightly modified Flory-Huggins equation with an interaction parameter χw in the weight fraction scale, which depends linearly on concentration. The interaction parameters show a dependence on concentration which is explained by an increased branching and crosslinking of the polymer with increasing initial polymer concentration of the gels. At low initial polymer concentration, the primary chains have to aggregate to build up relatively long chains between the network junctions. The static shear modulus G which can be calculated from the network term has the same order of magnitude as the real part of the complex shear modulus which is measured at low frequency.     

Comparison of ultrasonic shear wave and dynamic-mechanical measurements in acrylic-type copolymers

An ultrasonic shear wave reflection method was applied to study film formation and temperature dependence of the complex shear modulus (G^*G′ + iG″) in different amorphous films made of aqueous dispersions of acrylic-type copolymers. The data are compared with dynamic-mechanical measurements in the low frequency range. It is shown that the temperature dependence of the storage (G′) and the loss modulus (G″) for both methods can be fitted by the same set of parameters using the Havriliak–Negami function incorporating the Vogel–Fulcher–Tamman–Hesse equation for the temperature dependence of relaxation times. The temperature dependence of the relaxation times obtained from the fits to the ultrasonic shear modulus is compared to the shift factors of the dynamic-mechanical measurements. The agreement between both methods is good. This suggests an almost thermorheological simplicity of the samples for the main glass–rubber relaxation and demonstrates the capacity of the ultrasonic rheometer. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1703–1711, 1998     

A RHEOLOGICAL MODEL FOR POLYMER MELTS WITH INTERNAL STRUCTURE IN FLOW FIELDS*

Conceptually, an imagined conformation ellipsoid is supposed to represent the shape of a polymerchain for polymer melts in flow fields and to be equivalent to the volume element in a mathematical sense incontinuum mechanics. A power law dependence of shear modulus of polymer melts on detC, referred to asenvelope volume, is proposed. Based on those assumptions and the non-linear relation of shear modulus, aphenomenological viscoelastic model is derived. The model is tested in simple shear flow, simpleelongational flow, oscillatory shear flow, and relaxation process after flow suddenly stopped. The resultsshow that the model works well to predict the change of internal structure and viscoelastic performance ofpolymer melts in flow fields.