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…     

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.     

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 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.     

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。     

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。     

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.     

Kinetics of craze initiation in polystyrene in N-alcohols

The kinetics of craze initiation has been investigated for unmodified and rubber-modified polystyrenes in n-alcohols. The dependence on time and temperature of the critical strain at which crazes could be detected visually was determined with a Bergen elliptical strain device. Sorption studies were also conducted at room temperature on films exposed to the saturated vapor of n-alcohol. The analysis of crazing data in terms of the Eyring model gave activation energies from 9.4 to 17.4 kcal/mole, increasing with increasing chain length of n-alcohol and increasing rubber content. The activation volume multiplied by a stress concentration factor decreased with increasing rubber content and was nearly independent of the chain length of the n-alcohol. The larger the diffusion coefficient, which we measured by sorption experiments, the smaller was the activation energy for craze initiation. The values of diffusion coefficients, estimated from the experimental data on craze initiation, were found to be comparable with those from the sorption experiments. It was concluded that the rate of craze initiation on exposure to liquids is controlled by the diffusion of the molecules of liquid into polymer.     

Crazing of glassy polymers in alcohols and hydrocarbons

In the crazing of glassy amorphous polymers, wetting ability and penetration of the fluid are the important practical parameters governing the activity of the fluid. Higher molecular weight and the presence of polar groups in the fluids result in an increase in the critical stress for craze initiation in polystyrene and polycarbonate. The Eyring treatment of the craze process can describe fairly well the temperature and strain rate dependence of the critical stress. The parameters involved in the Eyring theory suggest that the crazing takes place by a molecular motion of lower energy than does macroscopic yielding.     

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.     

Craze initiation in poly(methyl methacrylate) under biaxial stress

Criteria for craze initiation in poly(methyl methacrylate) have been investigated under various combined loadings including biaxial tension and torsion-compression at 65°C in air and at room temperature in a crazing agent, kerosene. Environmental crazes are observed even under torsion-compression loading when air crazing does not occur, and the stress locus for environmental crazing is very different from that for air crazing. A theoretical model analogous to the Cottrell model in crystal plasticity is proposed. Theoretical crazing loci derived from the model are compared with the experimental results.     

Energy absorption in polymer crazing

The total energy absorbed by a craze during its development in creep is analyzed and calculated on the basis of a time-dependent theory of crazing. Experimental measurements of the craze length have been utilized in the energy calculations. For polystyrene the initial energy absorption in the craze region is found to be several hundred times that in the uncrazed medium. This ratio decreases sharply in a short period of time to about 50 to 1 and less and remains low afterward. For polycarbonate, somewhat similar behavior has been found. The initial strain energy absorption by crazing is about 200 times that in the uncrazed region. The energy ratio reduces rapidly to about 55 to 1 and tends to level off thereafter. However, in general, the amount of strain energy absorbed does increase as a function of time, as it should.     

Ar atom emission as a probe of craze formation and craze growth in polystyrene

A report of measurements of Ar emission during the loading of polystyrene and high impact polystyrene in vacuum is presented. Argon was introduced into the material prior to the experiment by storing the samples in an Ar atmosphere. The development of crazes during loading was monitored by videotaped visual observations and scattered light measurements. Increased Ar emission is observed at the onset of crazing, provided that the crazes intersect the surface. The strength of the Ar signal depends upon the extent of crazing; especially intense signals are observed from samples which display significant crazing prior to fracture. High-impact polystyrene shows intense emissions at yield which soon decay due to the depletion of Ar from the near surface material. The emission intensity rises again prior to fracture, when surface crazes become connected to crazes in the bulk. Thus the emission of volatile species during deformation reflects the growth of crazes intersecting the surface, as well as changes in the “connectivity” of the craze network. © 1993 John Wiley & Sons, Inc.     

Micro and nano layered polymers

The crazing behavior of coextruded microlayer sheets consisting of alternating layers of polycarbonate (PC) and styreneacrylonitrile copolymer (SAN) was investigated as a function of PC and SAN layer thicknesses. In this study, the total sheet thickness remained essentially constant and the PC and SAN layer thicknesses were changed by varying both the total number of layers from 49 to 1857 and the PC/SAN volume ratio.^[1,2] Photographs of the deformation processes were obtained when microspecimens were deformed under an optical microscope. Three different types of crazing behavior were identified: single crazes randomly distributed in the SAN layers, doublets consisting of two aligned crazes in neighboring SAN layers, and craze arrays with many aligned crazes in neighboring SAN layers. The transition from single crazes to doublets was observed when the PC layer thickness was decreased to 6 microns. Craze array development was prevalent in composites with PC layer thickness less than 1.3 microns. It was concluded that SAN layer thickness was not a factor in formation of arrays and doublets; formation of craze doublets and craze arrays was dependent only upon PC layer thickness.     

Microvoid formation during deformation of high-impact polystyrene

Small-angle x-ray scattering (SAXS) has been used to study the formation of microvoids in polymers which craze or stress-whiten extensively. Specimens are subjected to a stepwise uniaxial strain, with scattering curves being obtained at each step. The increase in scattering intensity upon crazing is attributed to the formation of microvoids, and the relative size, shape, and concentration of the scattering elements are determined by a Porod analysis of the SAXS curves. The major portion of our work has been on high-impact polystyrene which shows a large increase in SAXS intensity as crazing occurs. We are able to follow the changes in void size and concentration during craze initiation and growth. Effects of temperature, molecular orientation, and matrix molecular weight have also been studied. The results add to the information on craze growth and microstructure known from electron microscopy and dilatometry. In addition, a qualitative physical model for microvoid nucleation is proposed, and the implications for toughness are discussed.     

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.     

Growth kinetics of solvent crazes in glassy polymers

The kinetics of craze growth from sharp cracks in polystyrene (PS) and poly(methyl methacrylate) (PMMA) in contact with liquid methanol were measured with time-lapse photography as a function of the stress intensity factor K_I. At high K_I the craze length in both systems increases as √t if the sides of the craze are protected from methanol and as t if they are not, where t is the elapsed time after loading. If such a side-protected craze is dried under load and then methanol is reintroduced to the crack tip, the methanol front advances with the same kinetics as the original craze growth. This experiment Proves that solvent crazing velocities are limited by the hydrodynamic transport of solvent through the porous craze structure under a capillary pressure driving force (which can be as high as 100 atm). An improved model of fluid flow through the craze is developed and shown to predict craze growth kinetics in good agreement with those observed. The hydraulic permeability of methanol crazes in PS was found to be independent of craze length at small craze length and to be independent of K_I except at very low K_I. Although increases in molecular weight in the range M_w = 200,000 to M_w = 670,000 do not markedly affect the crazing kinetics, they greatly increase the time to fracture of the craze.     

Environmental stress cracking of poly(vinyl chloride) in alkaline solutions

The environmental stress cracking (ESC) effects on PVC of various high pH sodium hydroxide environments have been studied. The behaviour of PVC specimens in air and pH 12, 13, 13.5 and 14.39 sodium hydroxide solutions has been examined under three-point bend, tensile and creep conditions. Two parameters were used in three-point bend testing to determine the effect of an applied strain and high pH environment on the stability of PVC, namely time to craze initiation and width of crazing. It was found that, in general, crazing occurred sooner and to a greater degree with increasing strain and pH, although there was some evidence that craze growth was most rapid at pH 13.5. The results also indicated a critical strain value of 1.5–1.6%, below which crazing was not observed in any of these alkaline environments. Creep and tensile testing revealed that the time for which a PVC specimen was immersed in the environment was very important in determining the severity of the environmental effect. Creep tests at elevated temperatures showed that the time for the effects to be manifest decreased with increasing temperature. Creep rates were highest in pH 13.5 sodium hydroxide solution indicating that this was the most hostile of the environments considered.     

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.     

Creep deformation caused by crazing

Creep deformation caused by crazing is analyzed using an analog of dislocation dynamics. Results are compared with experiments on polycarbonate and poly(vinyl chloride) subjected to the action of kerosene as a crazing agent. Good agreement between the theory and experiment shows the value of the dislocation analog approach. The theoretical craze creep strain is found to be numerically approximated by the commonly used law similar to the Nutting equation, and may provide a physical foundation for this widely used equation formally derived from rate theory.