聚合物的银纹研究进展

综述了国内外有关聚合物银纹研究的进展,内容包括银纹的定义、分类、引发、生长、断裂及结晶聚合物中银纹的情况。     

分子量对聚丙烯银纹形态的影响

<正> 聚合物在拉伸状态下发生脆性破坏和银纹的形成与发展有着密切联系,银纹与其它局部塑性形变的本质区别在于银纹中存在的微纤,它将两个银纹面连接起来,并能在其中传递载荷,在拉伸应力的作用下,银纹微纤断裂发展成为裂纹,最后导致材料破坏。 最近十几年里,对以PS、PMMA、PC为代表的非晶态聚合物中的银纹化现象作了比较广泛、深入的研究(如不同热历史、不同的银纹化环境等),对银纹的引发、增长、微纤的断裂等现象进行了大量的观察,也提出了一些理论模型来解释银纹化的全过程,这是因为非晶态聚合物具有相对简单的三维空间结构。     

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...     

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。     

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…     

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...     

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…     

凝聚条件对聚甲基丙烯酸甲酯薄膜银纹化现象的影响

<正> 当玻璃态聚合物受张力作用时,常可以观察到银纹形成,它是聚合物材料内部断裂的先兆,银纹是垂直于拉伸方向的平面缺陷,与正常裂纹不同,银纹的质量不是零,而是由沿拉伸方向排列的高度应变的微纤及孔穴组成,银纹的典型尺寸约为长100μm,宽1—2μm,微纤的直径约5—15nm,微纤的总体积分数约占20—50％,微纤能支撑负荷,因此银纹在控制聚合物屈服以后的力学行为中的作用一直是个重要的研究领域。近年来从聚合物分子缠结网对银纹生长,微纤断裂及银纹稳定性的影响方面做了一些有意义的工作。     

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。     

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。     

Physical Causes of Aging in Plastics

A number of physical changes that take place in a polymer below the glass transition temperature without the action of a medium are first described, and are then explained on the basis of changes in supramolecular order. Pure stress crazing with the characteristic self-limitation of craze growth is then considered. Models are developed to explain stress crazing under the influence of a wetting medium. Attempts to reduce stress crazing are then treated and the article closes with a discussion of the influence of morphological structure on crazing and cracking.     

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.     

Progress and challenge in polymer crazing and fatigue

In this review on polymer crazing and fatigue three aspects have been treated more explicitely: the molecular rearrangements preceding and provoking craze initiation, the competition between disentanglement and chain scission during lateral craze growth, and the distinct fatigue failure mechanism occurring in cyclically loaded PET and PA fibers. An overview on other aspects is given including references to work in progress.     

SEM OBSERVATION OF THE CRAZING FOR POLYPHENYLQUINOXALINE FILMS DURING IN SITU STRETCHING*

The crazing of polyphenylquinoxaline (PPQ-E) films during in situ stretching has been observedby SEM. The crazing phenomena and craze morphology of PPQ-E films were interpreted. The strain values atcritical crazing and yielding and the craze stability of PPQ-E samples depend on the thermal-dealingcondition for the samples. From the point of view of cohesional entanglements and energy absorbed bysamples, the experiment results were explained.     

Crazing and fracture in crystalline,isotactic polypropylene and the effect of morphology,gaseous environments,and temperature

Stress crazing is studied in three forms of crystalline, isotactic polypropylene (PP): (1) smectic/nonspherulitic, (2) monoclinic/nonspherulitic, and (3) monoclinic/spherulitic PP. Optical and scanning electron microscopy as well as stress—strain measurements are used to characterize crazing behavior in these three forms as a function of temperature (?210 to 60°C) and of the gaseous environment (vacuum, He, N₂, Ar, O₂, and CO₂). Forms 1 and 2 are found to craze much like an amorphous, glassy polymer in the temperature range between ?210 and ?20°C, irrespective of environment. The plastic crazing strain is large close to the glass-transition range (ca. ?20°C) of amorphous PP and in the neighborhood of the condensation temperature of the environmental gas. Near condensation, the gas acts as a crazing agent inasmuch as the stress necessary to promote crazing is lower in its presence than in vacuum. A gas is the more efficient as a crazing agent, the greater is its thermodynamic activity. Spherulitic PP (form 3) crazes in an entirely different manner from an amorphous, glassy polymer, showing that the presence of spherulites influences crazing behavior much more profoundly than the mere presence of a smectic or monoclinic crystal lattice. Below room temperature, crazes are generally restricted in length to a single spherulite, emanating from the center and going along radii perpendicular, within about 15°, to the direction of stress. They never go along spherulite boundaries. Gases near their condensation temperature act as crazing agents much as in nonspherulitic PP. Above room temperature the crazes are no longer related to the spherulite structure, being extremely long and perfectly perpendicular to the stress direction. Apparently the crystals are softened enough by thermally activated segmental motion to permit easy propagation of the craze. The morphology of the fracture surfaces and its dependence on temperature and environment is described and discussed. Concerning the action of gases as crazing agents it is argued that the gas is strongly absorbed at the craze tip, where stress concentration increases both the equilibrium gas solubility and the diffusion constant. Hence, a plasticized zone is formed having a decreased yield stress for plastic flow. This is considered to be the main mechanism by which the gas acts as a crazing agent. In addition, reduction of the surface energy of the polymer by the adsorbed gas eases the hole formation involved in crazing.     

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.     

Specific features of the formation of polymer-dye systems based on nanostructured polymer matrices prepared by solvent crazing

Specific features of the formation of polymer-dye systems based on various nanostructured polymer matrices prepared by the method of solvent crazing are discussed. In the general case, the formation of polymer-dye composites includes four main stages: sorption of dye molecules by the highly disperse fibrillar material of crazes, shrinkage of the polymer composite due to the removal of the solvent, migration of dye molecules from their localized sites on the surface of fibrils, and healing of the structure of crazes (internal interfacial boundaries) under thermal treatment. Analysis of the migration of dye molecules in the polymer matrix includes the following assumptions: first, a metastable (nonequilibrium) state of the system after solvent crazing and introduction of dye molecules into the fibrillar craze material and, second, the statement according to which both the depth and direction of the above migration processes are controlled by the free energy of mixing of components. For amorphous glassy systems (PVC, PS, PC), healing of the fibrillar craze material (after shrinkage and removal of the solvent) is observed. In the case of semicrystalline polymers (PP, vinylidene fluoride-trifluoroethylene copolymer) and amorphous crystallizable polymer matrices (PET), the intensity of healing upon thermal treatment decreases due to the presence of crystalline regions, which slow down the motion of macromolecules.     

The effect of preliminary orientation of polymers via tensile drawing at elevated temperature on solvent crazing

We studied how the preliminary orientation of an amorphous glassy PET via its uniaxial tensile drawing above the glass transition temperature affects the deformation behavior during subsequent tensile drawing in the presence of adsorptionally active environments. The tensile drawing of the preoriented PET samples with a low degree of preliminary orientation (below 100%) in the presence of liquid environments proceeds via the mechanism of solvent crazing; however, when a certain critical tensile strain is achieved (150% for PET), the ability of oriented samples to experience crazing appears to be totally suppressed. When the tensile drawing of preoriented samples is performed at a constant strain rate, the craze density in the sample increases with increasing degree of preliminary orientation; however when the test samples are stretched under creep conditions, the craze density markedly decreases. This behavior can be explained by a partial healing and smoothening of surface defects during preliminary orientation and by the effect of entanglement network. The preliminary orientation of polymers provides an efficient means for control over the craze density and the volume fraction of fibrillar polymer material in crazes.     

Solvent-induced embrittlement in a crystallizable polyarylate

The effects of solvent-induced crystallization on the micromechanical properties of thin films of polyarylate (PAr) were studied. Under uniaxial extension amorphous polyarylate was observed to deform exclusively by shear deformation with no evidence of crazing. Upon exposure to methylethyl ketone, vapor, or liquid, PAr crystallizes and is subsequently embrittled. Our transmission electron microscopy results clearly show that this embrittlement results from a transition in plastic deformation mechanism from shear yielding to crazing. A detailed examination of the samples revealed that the crazes formed preferentially within the noncrystalline regions and that the craze tips followed a complex trajectory around the crystallites. In some cases the craze tip advance deviated by as much as ±30 from a direction normal to the tensile axis. Because crazes are inherently more susceptible to forming cracks than shear deformation zones, crystallization reduces the fracture toughness of the polymer. This type of embrittlement, via a transition in plastic deformation mechanism, is believed to be a general behavior for solvent-crystallizable thermoplastics.     

The deformation behavior of polyethersulfone and polycarbonate

In thin films of polyethersulfone and polycarbonate it is shown that crazing becomes increasingly likely to occur as the temperature is raised. The transition temperature depends on strain rate and molecular weight. Three regimes of behavior can be identified. In both the low-temperature (shear deformation) and high-temperature (crazing) regimes the strain to craze is independent of molecular weight. However, in the intermediate crazing regime chain length is important, indicating the importance of disentanglement over this temperature range. It is thought that at the highest temperatures disentanglement is still occurring, but the rate-determining step is now general plastic flow into the craze fibrils.