Cavitation and cavity-free deformation of filled crystalline polymer systems

Main mechanisms of tough response of polymers are described. In heterogeneous polymer systems due to mechanical misfit between heterogeneities and the matrix a high negative pressure (tri-axial stress) is generated. The excessive negative pressure is the main reason of material cavitation. Cavitation appears to be another mechanism of tough response of the material to loading. Cavitation is a massive phenomenon in crystalline polymers and in all filled polymers. Cavitation itself does not consume much energy but allows for further toughening by activating other mechanisms. Examples of polypropylene filled with chalk modified by liquid, rubber and mineral filled polypropylene and syndiotactic polypropylene filled with chalk are described. Modes of deformation with significant compressive component of stress prevents for cavitation. Materials deformed in a cavity-free manner show much higher strength. It is pointed out that high polymer crystal anisotropy is necessary for the formation of a network of easy crystallographic slip in the unusual toughening of highly filled polymers observed recently. An example of syndiotactic polypropylene filled with submicro-chalk particles is presented.     

硅橡胶/氟橡胶并用胶的制备及力学性能

硅橡胶和氟橡胶作为国防、航天等重要领域的耐热材料一直被人们青睐,但其有着各自地优缺点且价格昂贵,本文尝试将这两种橡胶制成并用胶以解决氟橡胶不耐低温和加工性差的问题,以期增大其使用温度范围。采用机械共混法制备硅橡胶/氟橡胶并用胶,研究了硅橡胶和氟橡胶的混炼工艺、并用比、共硫化体系和硫化条件对并用胶力学性能的影响。结果表明,当硅橡胶/氟橡胶的质量比为10∶90,共硫化体系为3~#硫化剂/过氧化二异丙苯(DCP),一段硫化温度为170℃、硫化压力为10MPa、硫化时间为30min,二段硫化温度为200℃、硫化时间为6h时,并用胶的力学性能达到最好。     

History of Synthetic Rubber

Synthetic rubber undoubtedly represents the earliest development of the synthesis of macromolecules. It dates back to the historic discovery by Greville Williams in 1860 that isoprene is the “mother substance” of natural rubber. Attempts to convert isoprene, and later other 1,3-dienes, to a synthetic rubber began shortly thereafter, although the first commercial production of such a material did not take place until a half century later. The period between World War I and II witnessed the first development of a true synthetic substitute for natural rubber, i.e., sodium-polymerized butadiene, which was produced in Germany as Buna rubber and in the USSR as SK rubber. However, during the 1930s, Germany developed the emulsion copolymerization of butadiene-styrene (Buna S), whereas sodium polybutadiene continued as the principal general purpose synthetic rubber in the Soviet Union. The United States which, up till then, had only developed special-purpose synthetic rubbers like neoprene, entered the synthetic rubber age during the emergency of World War II when natural rubber supplies were cut off, and developed a giant industry based on Buna S technology virtually overnight.

Among the synthetic polymers in use today, synthetic rubber is unique in that it was developed not as an interesting new material but to fill a dire need of the modern world. As a matter of fact, here in the United States, it arose solely out of the emergency of World War II.

The reason for this unique position of synthetic rubber is, of course, the unique property of rubber, the only substance which exhibits long-range elasticity, and which therefore fills a special need in modern technology. Natural rubber was discovered in the New World as early as Columbus's voyages, but its use in technology did not really take place until after the Industrial Revolution, i.e., with the start of the 19th century. However, it was not until the latter part of the last century that the first attempts were made to synthesize rubber from simple chemical compounds.     

Preparation of Hydrogenated Nitrile Rubber

Hydrogenated nitrile rubber is an oil and solvent resistant rubber and particularly give more resistant to heat, ozone, light. It is generally prepared from nitrile rubber by selective hydrogenation using a suitable catalyst system. In the present work a prepared method was adapted for the hydrogenation reaction of nitrile rubber using homogeneous tris(tri-phenlphosphine)chlorhodium(I) catalyst (RhCl(PPh3)) system. The hydrogenation reaction was carriedout at different temperature, pressure, time and catalyst concentration, the concentration, the conditions of hydrogenation are stated in table 1.     

Design and control of morphology for high performance polymer alloys

Ductile polymers are significantly toughened by the addition of an elastomeric phase. The rubber phase acts as a stress concentrator, cavitates during the loading process and initiates localized plastic deformation in matrix. This paper deals with the simulation of the deformation behavior of rubber toughened polycarbonate and the fracture process of the embedded rubber particle. A two-dimensional one particle- and two-particle model with varying surface-to-surface interparticle distances are established. The calculation showed that the polymer matrix has plastically deformed before cavitation for the one-particle model whereas cavitation occurs in the elastic state of the matrix for the two-particle model. Cavitation itself is proved to be a change from the particle-system towards a void-system for both cases. The toughness of the post-cavitated void-system is shown to be dependent on the surface-to-surface interparticle distance and the strain-hardening characteristic of the matrix polymer.     

Storage Hardening of Natural Rubber

Abstract

Natural rubber exhibits different storage properties when compared with synthetic polyisoprenes. Stored over an extended period of a few months, natural rubber is found to become progressively harder while the synthetic rubber is known to soften. This phenomenon of spontaneous crosslinking of natural rubber in storage is of considerable importance since it affects the processing properties. The process of storage hardening has been actively investigated and is believed to involve abnormal groups in the rubber molecules. This paper reviews the various proposals by different workers involving aldehyde, epoxide, and amino acids. Our recent results show that amino acids react with certain abnormal groups in rubber at the latex stage. The net effect of the reaction is to functionalize the rubber with carboxylic, hydroxylic, and amine groups in addition to the original abnormal groups. Storage of the dry rubber could lead to slow crosslinking reactions which are accelerated by anhydrous conditions.     

天然橡胶分子链双键中引入环氧基对其性能的影响

天然橡胶在乳液状态下与过氧乙酸反应，在主分子链双键中引入环氧基团，可显著提高分子极性，但其高强伸性能基本保持不变；玻璃化温度上升，冲击弹性下降，耐油性、气密性、粘合性显著改善。     

Properties of Natural Rubber/Recycled Chloroprene Rubber Blend: Effects of Blend Ratio and Matrix

The present study investigated the effects of two types of natural rubber and different blend ratios on the cure, tensile properties and morphology of natural rubber/recycled chloroprene rubber blends. The blends of natural rubber/recycled chloroprene rubber were prepared by using laboratory two-roll mill. The result showed that the cure time prolonged with the addition of recycled chloroprene rubber (rCR). Comparability, natural rubber/recycled chloroprene rubber (SMR L/rCR) blendcured rapidly than epoxidized natural rubber/recycled chloroprene rubber (ENR 50/rCR) blend. The addition of rCRalso caused a decrement in the tensile strength and elongation at break for both rubber blends. The SMR L/rCR blendsshowed higher tensile strength and elongation at break compared to those of ENR 50/rCR blends at any blend ratios.     

Effect of Ground Rubber Powder on Properties of Natural Rubber

Ground rubber powder (GRP) with three different sizes was incorporated into nature rubber matrix with different loading. Cure characteristics, swelling behaviour, crosslink density, tensile fractured surface, and mechanical properties have been studied. Based on the cure characteristics, it is evident that the processability of the rubber compounds has not changed obviously with the different GRP loading. The introduction of GRP in virgin rubber leads to the increase in swelling degree and the decrease in crosslink density. Tensile strength, hardness and abrasion resistant deteriorate with the increase of GRP loading, but the tear resistance gets better. If the ground rubber particles are smaller, the properties are more similar to the virgin rubber. Because of the phase separation of the GRP and matrix, the properties get worse with the bigger ground rubber powder.     

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.     

有机硅橡胶裂解产物气相色谱-质谱联用分析

以室温硅橡胶和高温硅橡胶产品的边角废料及次品作为实验原料,进行到催化和碱催化裂解,将裂解产物进行气相色谱－质谱（ＧＣ－ＭＳ）联用分析,经过质谱数据检索,确定了两种酸催化产物的组成,高温橡胶的酸催化裂解产物主要是环状化物合;室温橡胶的酸催化一妥产物中有太和链状两类化合物,该实验为硅像胶废料利用提供了依据。碱催化产物太复杂,产物利用存在困难。     

加成型液体硅橡胶的研究进展

结合加成型液体硅橡胶的硫化原理,综述了加成型液体硅橡胶导热性能、耐高温性能及粘结性能的最新研究进展,发现加入金属氮化物导热填料是提高加成型液体硅橡胶导热性能的有效途径;改善分子结构是提高加成型液体硅橡胶耐高温性能的主要途径;共混粘结促进剂是提高加成型液体硅橡胶粘结性能的重要途径。介绍了加成型液体硅橡胶的最新应用领域,提出功能化加成型液体硅橡胶,如3D个性化打印硅橡胶、人体器官硅橡胶、高折光封装硅橡胶等功能材料是未来加成型液体硅橡胶的发展方向。     

Rubber toughening of poly(ether imide) by modification with poly(butylene terephthalate)

Rubber toughening of poly(ether imide) (PEI) has been elusive up to now due to the high processing temperature of PEI, which leads to degradation of the rubber. In this study, by profiting from the miscibility between PEI and poly(butylene terephthalate) (PBT), and the low T_g of PBT, we prepared a blend by melt extrusion with 20 wt% PBT in an attempt to render it toughenable by decreasing its T_g and processing temperature. The PEI-rich blend was subsequently mixed with maleic anhydride (0.9 wt%) grafted poly(ethylene-octene) copolymer (mPEO) up to 30 wt%. The decrease in T_g and processing temperature resulted in no observable degradation of the mPEO, and to the formation of a homogeneous morphology of rubber particles with a fine particle size, indicating that compatibilization was achieved. Upon rubber addition, stiffness decreased, while a very large toughness increase occurred with only 15% mPEO (impact strength more than 10-fold that of the PEI-PBT matrix). Upon observation of the fracture surface, the increase in impact strength was attributed partially to the cavitation and debonding of the rubber particles, and mostly to the deformation and yielding of the PEI-PBT matrix.     

Thermal Oxidative Degradation and Ageing Performance of Silicone Rubber Filled with Attapulgite

The natural attapulgite (NAPT) was disaggregated by high-pressure homogenization technology combined with extrusion process to prepare the attapulgite with disaggregated rod crystal bundles (DAPT) and large specific surface area of 133.7 m²/g. NAPT and DAPT were incorporated into the silicone rubber to obtain the composite NAPT-SR and DAPT-SR by mechanical blending method, respectively. After thermal oxidative ageing at 300 ℃ for 0.5 h, temperature for the 5% weight loss increased greatly from 385 ℃ of the neat silicone rubber to 396℃ - 399 ℃ with addition of NAPT and DAPT. NAPT and DAPT enhanced the interaction between the filler nanoparticles and rubber matrix thus inhibited the nanoparticle agglomeration. The conservation rate of the side methyl group in NAPT-SR and DAPT-SR was greatly improved after ageing. Therefore, the thermal oxidative degradation and ageing performance of the silicone rubber composites was significantly reinforced. Moreover, DAPT could greatly restrain the growth of nanoparticles after ageing. Therefore, DAPT-SR showed the better retention of tensile strength (40.6%), elongation at break (34.9%) and tear strength (30.1%) compared with the corresponding mechanical properties of the neat silicone rubber (10.6%, 7.4%, and 5.0%) after ageing.     

Blending of Natural Rubber/Recycled Ethylene-Propylene-diene Rubber: Promoting the Interfacial Adhesion Between Phases by Natural Rubber Latex

This article deals with blends based on natural rubber (NR) and recycled ethylene-propylene-diene rubber (R-EPDM). Natural rubber latex (NRL) was introduced into the blends to enhance interfacial adhesion between NR and R-EPDM. A new route of compounding was also suggested. The blends were prepared by mixing R-EPDM and other additives in NRL before blending with natural rubber on a two-roll mill. By applying this method, the homogeneity of the blends and cross-linking distribution are significantly improved. The blends exhibited superior state of cure, swelling resistance, mechanical properties and dynamic mechanical properties. The degree of entanglement between NR and R-EPDM also increased after NRL modification.     

Pragmatic Approach to the Evaluation of the Polymer-Mediated Force and Stability Ratio of Nano-Fillers Immersed in Rubber Materials

We used self-consistent field theory to derive the expression for the potential of the polymer-mediated forces acting between non adsorbing and weakly adsorbing nanoparticles in generic excluded volume polymer systems. By way of analyzing the physical structure of the obtained exact result for the polymer-mediated potential, we developed a pragmatic approach to evaluating this potential and associated filler flocculation stability ratio in dense rubber systems. The thus obtained theoretical approximation expresses the polymer-mediated potential acting between nanoparticles immersed in rubber through the relevant experimentally accessible quantities: filler immersion free energy, compressibility, and density correlation length of a rubber. By making use of the developed pragmatic approach, we have evaluated the polymer-mediated potential and the associated filler flocculation stability ratio for selected practically important filler and rubber materials.     

一种新型硅藻土填充橡胶纳米复合材料研究

橡胶的填料问题一直是人们的研究热点,针对炭黑和白炭黑在橡胶生产中存在的污染问题,本文选用成分结构与白炭黑类似的硅藻土来填充各种橡胶。首先对硅藻土进行了改性,并对不同改性剂改性硅藻土用于填充橡胶进行了研究。结果表明2.5份偶联剂Si69的改性效果最佳。通过机械共混法制备了改性硅藻土/橡胶纳米复合材料,通过力学性能测试确定了比较适合硅藻土填充的橡胶是氟橡胶、三元乙丙橡胶和丙烯酸酯橡胶。绿色环保且价格低廉的硅藻土可以替代白炭黑增强填充氟橡胶、三元乙丙橡胶和丙烯酸酯橡胶。     

NMR Study of Vulcanized Rubber

It is shown that NMR-linewidth measurements are useful to obtain information about the cross-linkage density and the average distance between the cross-links in vulcanized rubber. Inhomogeneous structure of the rubber phase in carbon-filled rubber is evidenced and the thickness of the rubber layer on carbon is evaluated at 50 Å.     

硫化天然橡胶的本征自修复与固相回收加工

通过小分子模拟试验和应力松弛,发现甲基丙烯酸铜(MA-Cu)比氯化铜(CuCl_2)更适合用作硫化天然橡胶中二硫键交换反应催化剂,并且硫化天然橡胶中的二硫键交换反应需要在高于120°C的温度下才能高效进行,这保障了相关制品在较低温工作时的结构与性能稳定.进一步的实验结果表明,硫化天然橡胶在MA-Cu辅助作用下获得了多次自修复与固相回收加工性能,损伤自修复后的硫化天然橡胶与固相回收加工的再生硫化天然橡胶,其拉伸强度均可恢复到原始材料强度的80%左右.     

Cure Kinetics of a Tetrafunctional Rubber Modified Epoxy-amine System

In this work the curing kinetics behaviour of a rubber modified epoxy amine system is investigated through calorimetric analysis. This study is part of a wider investigation on new epoxy formulations to be used as matrices of composite materials. The aim is to enhance both the processing behaviour and the mechanical properties of the matrix in order to obtain higher performance composites for more demanding applications. The epoxy system is blended with a high molecular mass rubber containing functional groups reactive towards the epoxies. The formation of a rubber/epoxy network can be achieved by means of a 'pre-reaction' between the epoxy monomers and the rubber functional groups, carried out in the presence of a suitable catalyst and before the resin is cured with the amino hardener. In this work the influence of both the rubber and the catalyst on the resin cure kinetics is analysed. This revised version was published online in July 2006 with corrections to the Cover Date.