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。     

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.     

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。     

ACOUSTIC EMISSION DURING STRETCHING OF POLYMERS

Acoustic emission has been studied for a wide range of polymers including amorphous glasses, semi-crystalline polymers, copolymers, polymer blends and a crosslinked rubber during the course of uni-axial stretching at room temperature. For non-crystalline polymers acoustic emission occurred in rather small number of events accompanied by crazing and micro-crack formation. Strong acoustic activity appeared during yielding and necking of crystalline polymers. Rather small number or none of acoustic bursts occurred during the initial stage of neck drawing but numerous strong bursts appeared when drawing proceeded approaching specimen break. Specimens of the same polymer but of different fabrication history may be reflected in their acoustic emission behavior. Acoustic emission during stretching crosslinked polybutadiene rubber was very weak but observable when the force-elongation curve started to deviate from the linear region. No Kaiser effect was observed for the rubber. Very strong and numerous acoustic emission was observed during stretching specimens of polymer blends. High impact resistant polymer modifications showed no sharp increase of acoustic activity before specimen break. So long as the polymer and conditions of specimen fabrication are the same quite reproducible acoustic emission behavior could be observed.     

<Emphasis Type="Italic">New Ideas and Hypotheses:</Emphasis> Acoustic emission on phase transformations in aqueous medium

Acoustic emission on phase transitions in aqueous medium, including ice melting, was experimentally studied. It was shown that the frequency, time, and other parameters of induced acoustic pulses depend on the nature of the substance and on outer conditions. Acoustic emission in melt water (homogeneous liquid) was reliably detected. This finding shows that acoustic emission can be used to control the technological processes involving metastable substances, and it can prove to be the only suitable technique for such processes.     

Nucleation and growth of crazes in amorphous polychlorotrifluoroethylene in liquid nitrogen

The density of mature crazes initially increases linearly with stress and then more rapidly at higher stresses. Once the crazes become observable then density was independent of time. The lowest stress at which an appreciable density of crazes was produced corresponds to the proportional limit. The average velocity of mature crazes was constant for a given stress and varied exponentially with the stress. The velocity depended on stress in the same way that the post-yield point stress depended on strain rate, whereas the yield point varied differently being a nonlinear function of the logarithm of the strain rate. The density of crazes was quantitatively related to the concentration of surface defects at which the crazes nucleate. The craze velocity was directly related to the diffusion coefficient of N₂ into the polymer. The analysis indicates that bulk diffusion of the N₂ governs the craze velocity and that plasticization of the tip of the craze is most important for the nucleation and growth of a craze in PCTFE.     

Contribution of crazing to the toughness of amorphous and semicrystalline polymers

Crazes or craze-like deformation bands occur in many different polymers. Mechanisms of initiation and growth of the crazes have been studied using different techniques of electron microscopy. Examples of modifying amorphous and semi-crystalline polymers are given to demonstrate to which extent the macroscopic toughness of the polymers is affected by changes in the microscopic structure and by the amount of crazes.     

Craze initiation of glassy polymers under the action of crazing agent

This paper deals with the formation of crazes that may be caused by an external load on glassy polymers wetted with kerosene. First, the orientation of crazes has been determined when applying a uniaxial tension to a specimen of cold-rolled polyvinyl chloride sheet at various angles to the rolling direction. The critical stress for craze initiation in poly(methyl methacrylate) and polyvinyl chloride rods has been investigated under combined tension–torsion loading. It is shown that: (1) in an anisotropic, as well as an isotropic polymer, the direction of crazes is perpendicular to that of the maximum strain calculated by taking into account the internal stress due to rolling; and (2) under the action of a crazing agent, crazing may occur even under the pure torsional load, i.e., in the absence of dilatational stress.     

Sampling statistics and considerations for single-shot analysis using laser-induced breakdown spectroscopy

A statistical analysis of single-shot spectral data is reported for laser-induced breakdown spectroscopy (LIBS). Fluctuations in both atomic emission and plasma continuum emission are investigated in concert for a homogenous gaseous flow, and fluctuations in plasma temperature are reported based on iron atomic emission in an aerosol-seeded flow. Threshold irradiance for plasma initiation and plasma absorption were investigated for pure gaseous and aerosol streams, with detailed statistical measurements performed as a function of pulse energy in the breakdown regime. The ratio of the analyte atomic emission intensity to the continuum emission intensity (peak/base) provided a robust signal for single-shot LIBS analysis. Moreover, at optimal temporal delay, the precision of the LIBS signal was maximized for pulse energies within the saturation regime with respect to plasma absorption of incident energy. Finally, single-shot temperature measurements were analyzed, leading to the conclusion that spatial variations in the plasma volume formation and subsequent plasma emission collection, play important roles in the overall shot-to-shot precision of the LIBS technique for gaseous and aerosol analysis.     

Acoustic emission potentialities for characterization of Mullins effect in natural rubber materials filled with carbon black

Acoustic Emission (AE) was investigated in order to monitor in real time the Mullins effect. Cyclic uniaxial tensile tests were carried out on two different natural rubbers. Different behaviour is revealed depending on whether or not the material undergoes the Mullins effect. The acoustic emission activity is very important during the first cycle, but decreases gradually with increasing number of cycles, when the Mullins effect is observed. On the contrary, when there is no Mullins effect no significant AE activity is recorded.     

Crazing in thin films of styrene–butadiene–styrene block copolymers

The mechanism of craze initiation and growth and its relationship to mechanical properties has been studied in thin films of styrene–butadiene–styrene (SBS) block copolymers. Optical microscopy and transmission electron microscopy were used to examine three copolymers which has a spherical rubber domain morphology but varied in rubber content from 20 to 50%. With increasing rubber content, the crazes became longer and less numerous. Widening of the crazes was at least partially responsible for the higher strains achieved in the copolymers, especially for the composition with the highest rubber content where the crazes widened to form micronecks. Transmission electron microscopy revealed that craze initiation and growth at the craze tip occurred by cavitation in the polystyrene phase. Cavitation of the continuous phase rather than the rubber domains was attributed to the concentration of chain-end flaws in the polystyrene. Crazes in the block copolymers followed a meandering pathway and the boundaries between crazed and uncrazed material were indistinct. Incorporation of fibrillated rubber particles into the craze fibrils strengthened the craze. At higher rubber content, the craze widened in the stress direction by voiding and fibrillation, which produced a cellular morphology.     

Caractérisation par émission acoustique de l’adhérence et de l’endommagement d’un revêtement : cas d’un revêtement WC–Co sur acier

This note presents a characterization method of the ‘adhesion’ of a coating by acoustic emission technique. In situ acoustic emission measurements which were investigated in terms of amplitude, absolute energy, position of the event, etc. were performed on WC–Co coated specimens prepared by HVOF (high velocity oxy fuel) during four-point bending tests. The microscopic observations of the specimens show two types of cracks: transversal cracks (regularly spaced on the coating surface) and interfacial cracks. Acoustic emission results show two different types of acoustic events in terms of absolute energy and amplitude, which are representative of two cracking mechanisms.     

高抗冲聚苯乙烯中银纹的引发与终止

银纹是由孔穴和断裂面间相联结的原纤维组成的微小裂纹,其中原纤维的体积分数可达40%.银纹的体积分数与材料的韧性成正比.银纹化是高抗冲聚苯乙烯(ＨＩＰＳ)在脆化温度以下,抵抗破坏而消耗外界能量的主要方式.银纹的产生与材料内部不均一性所导致的应力集中有关.ＨＩＰＳ中的橡胶粒子能够控制银纹在本体中均匀地发展,这是ＨＩＰＳ高韧性的原因[1].ＨＩＰＳ的分散相是由聚丁二烯(ＰＢ)为连续相,ＰＳ为分散相构成的细胞结构粒子.通常ＨＩＰＳ中ＰＢ的含量为7%～8%,而细胞结构粒子的体积分数可高达23%,可见细胞结构粒子内部ＰＳ的含量为ＰＢ的…     

第一性原理的形变势理论研究声学声子散射对电荷传输的影响

本文应用密度泛函理论和玻尔兹曼方程,在形变势理论的框架和驰豫时间近似下,研究了分子晶体中电子与声学声子散射对电荷传输的影响.针对蒽、萘、丁省和并五苯的计算表明,非局域化电子的传输过程主要受到来自于声学声子的散射.对于蒽晶体,与以前的Holstein-Peierls模型计算结果相比,发现纵向声学声子对空穴的散射强度是光学声子的3倍,所得到的空穴迁移率更接近超纯单晶样品的实验测量结果.同时,我们发现电子的本征迁移率比空穴还要大,应用前线轨道交叠分析可以合理地解释这一结果.     

Emission of high-speed electrons and other phenomena accompanying the process of breaking adhesion bonds

The process of breaking adhesion bonds is accompanied by the drawing apart of the plates of a flat condenser as formed by the double electric layer. An increase in the spacing between differently charged surfaces in the process of breaking the adhesion contact results in the falling off of a capacity, and in increasing the potential difference up to the breakdown voltage. If the breakdown occurs under conditions of a vacuum, then during the experiment a flux of free electrons is registered, whose energy amounts to a value of the order of 10⁴ to 10⁵ eV. Under ordinary conditions, owing to the ionization of the molecules of a surrounding gas by high-speed electrons, the gas-discharge processes arise accompanied by glowing, electromagnetic radiation, and acoustic emission, which are characteristic of those processes.     

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.     

Analysis of the debonding process in polypropylene model composites

Polypropylene (PP) model composites were prepared using cross-linked PMMA particles with a very narrow particle size distribution as filler in order to study the micromechanical processes, which take place during deformation. Composites containing a commercial CaCO₃ filler with a broad particle size distribution were also prepared and studied for comparison. The filler loading of the composites was changed from 0 to 0.3 volume fraction in 0.05 volume fraction steps. Measurements of acoustic emission signals during the elongation of PP/PMMA model composites allowed us to assign the debonding process, including its initiation, unambiguously to a well-defined section of the stress vs. strain curve. The number and intensity of the acoustic signals detected during the deformation of the matrix polymer and the composite, respectively, differed considerably, which made possible the separation of the various micromechanical deformation processes occurring in them. At low extensions the composite is deformed elastically, then debonding takes place in a very narrow deformation range, followed by the plastic deformation of the matrix. At small particle content debonding occurs at relatively low stresses, which differ significantly from the yield stress. Considerable plastic deformation of the matrix begins at the yield point. At larger filler content debonding and shear yielding occur simultaneously. Micromechanical deformation processes cannot be separated as clearly in composites prepared from the commercial CaCO₃ filler with a broad particle size distribution. The debonding of particles with different size occurs in a wide deformation range because of the particle size dependence of debonding stress. The analysis of characteristic values derived from acoustic emission experiments proved that the interacting stress fields of neighboring particles influence the deformation process and that even large particles may aggregate or at least associate at large filler content.     

Monitoring of a heterogeneous reaction by acoustic emission

The feasibility of monitoring the reaction of itaconic acid and 1-butanol by non-invasive acoustic emission measurements has been assessed. A piezoelectric transducer with a resonant mode at 90 kHz was attached to the external wall of a 1 L jacketed glass reactor. Acoustic emission from the oil jacket, stirrer and toluene was insignificant in comparison to that produced by the itaconic acid particles, which was transmitted through the glass walls and heating oil to the transducer. The transducer responded to acoustic emission from itaconic acid up to approximately 300 kHz, with the region around 90 kHz having the highest sensitivity. The effect of particle concentration and size on the acoustic emission generated has also been investigated, with higher concentrations and larger particles giving the greater signals. The detection limit for itaconic acid particles was 14 g dm(-3) of toluene. The effect of 1-butanol concentration and temperature on the progression of reactions was monitored using acoustic emission. It was possible to detect differences in the rate and extent of the reaction under different conditions, and also to identify when a combination of the concentration and/or size of itaconic acid particles had reached a steady state. However, it was not possible to differentiate between changes in particle size and concentration using the resonant transducer.     

Relaxation of stress and orientation in thermo-reversible networks

4-(3,5-dioxo-1,2,4-triazolidin-4-yl) benzole (U4A) or -isophthalic acid (U35A) units randomly attached to a polybutadiene backbone form extended supramolecular hydrogen bond assemblies, which act as effective junction zones in unusual thermoreversible elastomer networks. The relaxation behavior of stress and the segmental orientation induced after a sudden strain, has been investigated by means of step-strain experiments and ²H-NMR spectroscopy.The stress relaxation behavior can be described as a two-step process in which the first step is very sensitive to the stability of the supramolecular aggregates. About 20 s after reaching the initial strain, stress is reduced to a value comparable to the yield-stress in stress-strain cycles. The long-time relaxation behavior is interpreted as a reduction of the effective cross-link density due to a gradual breakdown of the hydrogen bond clusters. The relaxation data of the functionalized polybutadienes can be superimposed to give master curves, which are characteristic for the type of junction zone. The degree of aggregate degradation is estimated as a function of the initial stress.In the same type of step-strain experiment, the ²H-NMR spectra show a decay of the line splitting as well as a change in the complete lineshape.     

Thermosonimetry of the phase II/III transition of hexachloroethane

A thermosonimetric study has shown that the Phase II/III polymorphic transition of hexachloroethane emits acoustic signals. This solid-solid phase transition is known to occur by a nucleation-growth process during which a nucleus of the new phase, once formed, grows at the expense of the mother phase to form a complete crystal without fracture. Acoustic emissions from a conditioned multi-crystal sample have been used to study the transition. Acoustic activity correlated well with dilatometric measurements. Frequency analysis on waveforms of many hundreds of individual acoustic emissions revealed marked differences between individual signals. Principal-components analysis on 24 signal features revealed a single dispersed cluster with a highly non-uniform distribution of signals. These experiments provided highly reproducible average power spectra. Time-resolved acoustic power spectra were also generated. These additional types of information cannot be obtained by other techniques.