聚合物银纹化的分子机理

本文综述了近年来有关聚合物银纹化分子机理方面研究的进展情况。内容包括银纹的起源、生长、断裂过程以及各种结构关系对银纹的影响，并对几种典型的聚合物银纹形态进行了描述。     

物理老化对聚甲基丙烯酸甲酯薄膜的玻璃化转变、银纹化特征及力学性能的影响

物理老化对聚甲基丙烯酸甲酯薄膜的玻璃化转变、银纹化特征及力学性能的影响沈静姝，叶卫君（中国科学院化学研究所北京１０００８０）关键词聚甲基丙烯酸甲酯，玻璃化转变，银纹化，物理老化银纹化是聚合物中特有的现象，在应力作用下，许多非晶聚合物、一些半结晶性聚合...     

侧链含有蓝相液晶基元的聚硅氧烷液晶的合成及表征

采用蓝相小板块液晶单体反式-4-乙烯基-反式-4′-丙基双环己烷（3HHV）和反式-4-丙烯基-反式-4′-丙基双环己烷（4HHV）同时接枝到聚甲基含氢硅氧烷上,制备了聚硅氧烷侧链液晶聚合物。采用红外光谱和核磁共振氢谱对液晶单体及相应的聚合物进行结构表征,采用热台偏光显微镜,X-射线衍射和热分析对单体和聚合物的液晶行为及热性能进行研究。结果表明：液晶单体3HHV显示蓝相镶嵌织构,液晶单体4HHV显示胆甾相油纹状织构,它们的介晶区间温度分别为30.6°C和49.7°C,且均在低于室温就显示出液晶性。相应的液晶聚合物显示向列相纹影织构,介晶区间温度为192.6°C,在低于室温时也显示出液晶性,且热分解温度达到310°C以上,比其他环芳烃类介晶基元接枝聚硅氧烷主链的液晶聚合物具有更优越的热稳定性。     

物理老化对聚苯基单醚喹啉薄膜银纹化的影响

物理老化实质上是聚合物材料在 Tg 以下存放过程中 ,其凝聚态结构通过链段或更小运动单元的运动 ,从热力学非平衡态向平衡态过渡的一个结构弛豫过程[1] .在这一过程中 ,聚合物的密度、自由体积、焓、熵和力学性质随温度和时间产生变化 .因为银纹化是聚合物的特性 ,所以银纹化也将随结构回复过程而产生变化 .有关物理老化对聚合物银纹化的影响尚未得出一致的结论 [2～ 4 ] .聚苯基单醚喹啉 (结构见 Scheme1 )是一种高性能的芳杂环聚合物 [5] ,它可以在比较苛刻的条件下作为绝缘材料和膜材料使用 .有关这类高性能的芳杂环聚合物的物理老化…     

硬质PVC复合改性界面研究进展

综述了增强增韧硬质PVC方面所做的研究工作及最新的研究进展,探究了增强、增韧PVC的方法以及机理,机理包括:多重银纹,剪切屈服,剪切屈服-银纹化,逾渗,空穴。目前的改性方法包括:改性无机粒子增强增韧PVC,如微米粒子、纳米粒子、"核-壳"结构粒子、其它无机粒子;聚合物和无机粒子/聚合物以及接枝改性增强增韧PVC。     

聚苯基单醚喹噁啉薄膜的形变机理

非晶聚合物塑性变形机理主要包括银纹化和剪切屈服[1 ,2 ] .银纹化是链段局部排列疏松区域或缺陷在膨胀应力作用下成为银纹核 ,引发银纹 ,银纹 本体界面应变软化 ,银纹微纤拉伸的应变硬化过程 ,使得聚合物银纹微纤沿拉伸方向取向 ,伴随这一过程聚合物的体积增大[3] .剪切屈服是分子链沿拉伸方向的流动以及分子链间的滑移过程 ,这一过程使聚合物形状改变而体积不变 .聚合物的形变机理与聚合物的内在性质如临界缠结分子量 ,缠结密度或硬度等有关[4] .聚苯基单醚喹啉是一种高性能的芳杂环聚合物 ,它的玻璃化转变温度是 2 98℃ ,它具有耐高温…     

光学显微镜研究交联有机玻璃断面上的肋状形态

用光学显微镜观察了交联有机玻璃断面上的肋状形态。发现断面形态、裂纹路径以及肋状区裂端簇射状银纹群之间有直接联系。每一肋条由一细砂带和一粗破带构成。前者对应于裂端楔形银纹/固体聚合物之间界面的剥离;后者对应于剥离后锐化裂端银纹群之间的剪切;这两个交替过程可以用“滑-粘”模型来解释。在不稳定肋状区发现到裂纹在霉纹区和肋状区的扩展机理是可以相互转化的。     

聚丙烯酸酯型高分子侧链液晶的合成及其对聚乙烯成核结晶行为的影响

基于聚烯烃用成核剂的结构特征设计合成了两种极性基团和非极性基团交替排列的乙烯基单体,并利用自由基引发聚合,制备出相应的侧链型液晶聚合物.采用元素分析、红外光谱和核磁共振氢谱对所合成单体和聚合物的结构进行了确认.并采用热失重(TGA)和差示扫描量热仪(DSC)研究了聚合物的热稳定性和相转变温度.结果表明,所合成聚合物的起始热分解温度均在337℃以上,具有优异的热稳定性;液晶相变温度区间可达186 K,具有较宽的液晶态温度范围.热台偏光显微镜(HS-POM)研究结果表明,聚合物均呈现出纹影织构,证明所合成的聚合物均为热致向列型侧链液晶高分子.采用DSC和HS-POM研究了所合成的侧链液晶聚合物对高密度聚乙烯(HDPE)异相成核结晶行为的影响.结果表明,侧链型液晶聚合物在提高HDPE结晶温度、结晶度以及降低HDPE晶粒的尺寸及分布方面均有优异的效果,是一类HDPE有效的成核剂.     

聚甲基丙烯酸甲酯浇铸成膜的银纹形态与其成膜浓度的关系

聚甲基丙烯酸甲酯浇铸成膜的银纹形态与其成膜浓度的关系叶卫珺，沈静姝（中国科学院化学研究所高物开放实验室北京１０００８０）关键词银纹，缠结密度，均匀形变区，聚甲基丙烯酸甲酯非晶态聚合物在拉伸应力作用下，会在材料表面或内部产生能反射光线的微小而稠密的裂痕...     

橡胶增韧塑料机理的探讨

本实验采用透射电镜及新的ＲｕＯ_４染色方法，观察研究了ＰＣ／ＰＢＴ，ＰＣ／ＭＢＳ／ＰＳ共混体系和ＡＡＳ共聚共混物的银纹结构形态。结果表明：不同聚合物体系银纹产生的数量，银纹的发展、终止及支化各不相同。这时研究塑料增韧机理很有意义。     

Cyclic stress–strain behavior of the dry polycarbonate craze

Equipment and methods have been developed which allow photomicrographic determination of the stress–strain properties of the individual craze. Serial cyclic tensile tests on polycarbonate crazes are described. Under stress the typical dry polycarbonate craze thickens solely by straining; no adjacent polymer of normal density is converted to craze material. The craze exhibits a yield stress followed by a recoverable flow to roughly 40–50% strain at 6000–8000 psi. On return to zero stress the craze exhibits creep recovery at a decelerating rate. The yield stress and loss factor of each cycle decrease with increasing initial strain and cycles initiating at 50% strain or more show completely Hookean behavior. Creep recovery results in recovery of yield stress and loss factor also. Craze tensile behavior is suggested to be essentially an extension of the craze formation process. Decrease in elastic modulus and yield stress with increasing strain are rationalized in terms of strain-produced decrease in density and resultant increase in stress concentration factor on the microscopic polymer elements of the craze. Polymer surface tension and the large internal specific surface area of the craze are suggested to be important factors in the large creep recovery rates of the craze.     

用透射电镜研究PS薄膜银纹的微观结构、变形特性和破坏过程

本文介绍了用透射电镜观察PS薄膜银纹的微观结构、变形特性和破坏过程。实验观察到PS银纹质完整的网络结构和取向银纹质断裂以后的松弛特性。实验发现PS银纹质断裂转变成微裂纹的过程类似有机玻璃慢裂纹区的“撕布”模式,裂端银纹的外形符合Dugdale模型。     

Mechanical properties of methanol crazes in poly(methyl methacrylate)

Methanol crazes are grown from sharp cracks in poly(methyl methacrylate) (PMMA). The craze thickness profile is measured using a replica technique after the craze opening displacement profile of the growing craze has been measured with holographic interferometry. The craze strain profile is then computed from these data. The craze surface stress profile is determined by two methods: (1) from the uniaxial strain profile of regions adjacent to the craze as measured from the fringe spacing on the reconstructed hologram and (2) from the craze opening displacement profile using the Fourier transform method of Sneddon. From the surface stress and craze-strain profiles a true stress-strain curve for the craze fibrils has been constructed. The extrapolated fibril yield stress is in good agreement with the yield stress of bulk PMMA plasticized with methanol indicating that surface tension effects do not contribute importantly to craze fibril mechanical properties at room temperature. The craze strain increases from 0.4 near the craze tip to 1.4 near the craze base implying that methanol crazes in PMMA thicken by further straining of the existing craze fibrils and not by drawing new material into the craze from the craze surfaces. The primordial craze thickness, i.e., the original thickness of polymer which fibrillates to form the craze fibrils, is approximately 1 μm and is constant over most of the craze length. This thickness may be determined by diffusion of methanol normal to the craze surfaces in a process zone just behind the craze tip.     

Molecular conformation and craze fracture

A craze may fracture either by the breaking of covalent bonds or by a process of “viscous rupture” involving the movement of bulk material in the craze. In the latter case it is necessary that the majority of the chain ends of the polymer molecules passing through the craze-matrix interface terminate within the craze. We have therefore calculated the probability of a polystrene macromolecule spanning a thin craze and shown that for viscous rupture a craze in a normal commercial polystyrene must be something more than 40 nm thick. As the measured craze thicknesses have generally exceeded 100 nm, a viscous fracture process is clearly possible, though, of course, chain rupture is not excluded by the argument. More difficulties arise when fracture occurs within a specified region of the craze and the possibility of a bond fracture under these circumstances is briefly discussed.     

Analyzing polymer crazing as quasifracture

This paper deals with a viscoelastic boundary element method for analyzing a polymer quasifracture usually called a craze in polymers. A time-dependent boundary stiffness is considered on the quasifracture envelope surface. The viscoelastic property of the glassy polymer is represented by a generalized Kelvin model with multiple retardation times. According to the linear viscoelastic correspondence principle, the associated elasticity solution can be solved by applying the general integral boundary element method. Then the viscoelastic solution in the time domain can be obtained by applying a collocation Laplace inversion transformation. Using these methods, the quasifracture problem composed of an isolated craze opening with time-dependent stiffness traction in a stressed rectangular plate is analyzed. The displacement profile and the stress distribution around the craze envelope surface are computed.     

Mechanism of fracture in glassy polymers. III. Direct observation of the craze ahead of the propagating crack in poly(methyl methacrylate) and polystyrene

Observation of optical interference fringes at the tip of a crack in a glassy polymer allows the construction of the configurations of the crack tip and the craze that precedes it. The craze extends 25 μ beyond the crack tip in poly(methyl methacrylate) and 550 μ beyond the tip in the polystyrene studied. The craze at the crack tip in PMMA may be seen to deform elastically as much as 100% under stress before crack propagation recommences. Such deformation is estimated to account for as much as 40% of the nominal Griffith energy of crack propagation.     

Effect of orientation on the mechanism of plastic yielding of poly(ethylene terephthalate) in adsorption-active media

The effect of the preliminary orientation on the formation of crazes in poly(ethylene terephthalate) during straining in adsorption-active liquids is studied. Poly(ethylene terephthalate) is oriented by drawing at a temperature of 80°C, which is somewhat higher than its glass-transition temperature (～75°C). After orientation, samples are tested in tension in organic liquids at room temperature. At low degrees of preliminary drawing, the shear yield stress during straining in air does not increase significantly. However, the stress of craze widening rises in proportion to the degree of preliminary drawing. Thus, the orientation suppresses crazing and leads to the transition to shear flow. A model is proposed to explain the effect of orientation on crazing. According to this model, craze widening and pulling of a nonoriented polymer into the craze volume result from the formation of pores in the bases of fibrils. The formation of fibrils is caused by straining of the polymer between pores.     

A theory for environmental craze yielding of polymers at low temperatures

It has been recently discovered that polymers craze at low temperatures in the presence of nitrogen or argon. A quantitative theory has been developed which explains (1) the critical temperature above which the phenomenon disappears, (2) the critical stress for nucleating a craze, (3) the effect of strain rate on the yield point and size of crazes, (4) the drop in the load during craze yielding, and (5) the increase in strength of the polymer in N₂ or Ar at high strain rates so that the ultimate strength may exceed that in He or vacuum. The crazing action of the gases is described qualitatively at the molecular level.