Thermal stability of acrylonitrile/chlorosulphonated polyethylene rubber blend

The properties of chlorosulphonated polyethylene (CSM) rubber, acrylonitrile rubber (NBR) and their blend (50/50 w/w) were studied. Fourier transform infrared (FTIR) studies supported that CSM/NBR rubber blend is self curable, when cross-linking takes place between acrylonitrile groups of NBR and –SO₂Cl groups or in situ generated allyl chloride moieties of CSM. The thermal stability of vulcanizates was analyzed in nitrogen by thermogravimetry. It was found that the initial degradation temperature of elastomer based on CSM rubber is lower than of pure NBR rubber. By adding NBR to CSM rubbers, the degradation temperature of crosslinked material increased, indicating higher thermal stability. The activation energy for the degradation are determined using the Arrhenius equation The activation energies for the rubber blends are higher than for elastomers based on pure rubbers. It was found that the mass loss of the blends at any temperature was between those of the pure rubbers. The differential scanning calorimetry (DSC) was used for the glass transition temperature determination. It is estimated thermodynamic immiscibility of NBR/CSM blend based on noticed two different glass transition temperatures, corresponding to CSM and NBR rubbers.     

Thermal behaviour of styrene butadiene rubber/poly(ethylene-co-vinyl acetate) blends

The thermal behaviour of styrene butadiene rubber (SBR)/poly (ethylene-co-vinyl acetate) (EVA) blends was studied by using thermogravimetry (TG) and differential scanning calorimetry (DSC). The effects of blend ratio, cross-linking systems and compatibilization on the thermal stability and phase transition of the blends were analyzed. It was found that the mass loss of the blends at any temperature was lower than that of the components, highlighting the advantage of blending SBR and EVA. The addition of compatibilizer was also found to improve the thermal stability. DSC studies indicated the thermodynamic immiscibility of SBR/EVA system even in the presence of the compatibilizer. This is evident from the presence of two different glass transition temperatures, corresponding to SBR and EVA phases in both compatibilized and uncompatibilized blends.     

Thermal stability of CR/CSM rubber blends filled with nano- and micro-silica particles

The properties of filled polymers depend on the properties of the matrix and the filler, the concentration of the components and their interactions. In this research we investigated the rheological and mechanical properties and thermal stability of polychloroprene/chlorosulfonated polyethylene (CR/CSM) rubber blends filled with nano- and micro-silica particles. The density of the nano-silica filled CR/CSM rubber blends was lower than that of the micro-silica filled samples but the tensile strength and elongation at break were much higher. The nano-silica filled CR/CSM rubber blend has higher V _r0/V _rf values than micro-silica composites and show better polymer–filler interaction according to Kraus equation. The nano-silica filled CR/CSM rubber blends were transparent at all filler concentration, and have higher glass transition values than micro-silica filled compounds. The higher values of the glass transition temperatures for the nano- than the micro-filled cross-linked systems are indicated by DMA analysis. The nano-filled cross-linked systems have a larger number of SiO–C links than micro-filled cross-linked systems and hence increased stability.     

Influence of structure on the impact behaviour of nylon-rubber blends

Blends of nylon-6 and EPDM rubber were prepared by reaction blending to study the influence of rubber concentration, rubber particle size and interfacial adhesion on the impact strength. Rubber particles induce a sharp brittle-tough transition which is independent of the glass transition of the nylon matrix. Increasing the rubber concentration or decreasing the particle diameter shifts the brittle-tough transition temperature for notched Izod impact tests to lower values. A toughening mechanism is proposed in which the interparticle distance, the rubber modulus and the temperature play crucial roles.     

Headspace gas analysis: Comparison of the efficiency of thick film,ultra thick film,and activated charcoal open tubular capillary traps for the concentration of volatile,airborne, organic compounds

Determination of the rate at which volatile organic molecules diffuse through the wall of a polysiloxane rubber tube, shows that the full depth of the rubber lining of ultra-thick film open tubular traps is utilized for the retention of volatile organic compounds in headspace gas analysis. Small apolar molecules migrate rapidly through the rubber, but larger molecules and polar compounds diffuse relatively slowly into the rubber. Neither traps with a thick film of an apolar stationary phase, nor those with an ultra thick polysiloxane rubber lining retain highly volatile compounds very effectively. Traps containing activated charcoal particles fused into their inside glass surface have a much higher capacity than those with activated charcoal particles embedded in a layer of stationary phase.     

Effect of relaxation properties on the adhesion of rubber

The adhesion to glass of rubbers with different relaxation properties but similar surface condition has been compared using the thin film peel test. At higher peeling stresses, the rubber–glass interface fractured at constant velocity and all rubbers gave the same adhesive energy values. However, at lower peel stresses, the lossy rubber appeared to adhere more strongly due to a crack-slowing phenomenon at the rubber–glass interface.     

Rubber particle agglomeration phenomena in acrylonitrile-butadiene-styrene (ABS) polymers II. Rubber particle agglomeration elucidated by a thermodynamic theory

A thermodynamic theory incorporating Flory-Huggins thermodynamics was developed to elucidate the observed rubber particle agglomeration phenomena in ABS molded under a severe condition. When the particle size of ABS is smaller than a thermodynamically stable domain size (D_s), rubber particle agglomeration can occur. Based on this criterion, rubber particle agglomeration can be explained semiquantitatively, especially for materials which do not have too insufficient graft level and nearly no compositional acrylonitrile mismatch. This finding suggests that the agglomeration results mainly from a driving force produced by thermodynamic incompatibility between components. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 553–562, 1997     

Thermal properties of compatibilized and filled natural rubber/acrylonitrile butadiene rubber blends

The thermal behaviour of natural rubber/acrylonitrile butadiene rubber (NR/NBR) was studied using thermogravimetry (TG) and differential scanning calorimetry (DSC) in terms of blend ratio, crosslinking systems, fillers and compatibilizer (neoprene) were analyzed. The presence of NBR markedly increases the thermal stability of their blends and it lies in between NR and NBR. DSC studies revealed the thermodynamic immiscibility of the NR/NBR blends by the presence of two distinct glass transition temperatures and the immiscibility was prominent even in the presence of a compatibilizer.     

Isochoric and isobaric glass formation: Similarities and differences

Pressure-volume-temperature (PVT) studies were performed on a glass-forming polymer, poly(carbonate) (PC), under both isobaric and isochoric (constant volume) conditions. An isochoric glass transition was observed and the formation points were found to be consistent with those obtained isobarically. Although the isobaric and isochoric responses were, as expected, the same in the rubbery state, the glassy state values were found to be different and dependent upon the glass formation history. The isobaric data exhibited larger changes in going from the rubber to the glass, hence a “stronger” glass transition, than did the isochoric data. Inserting the experimental values for the thermal expansion coefficient α and isothermal compressibility β, into appropriate thermodynamic relations, measures of the strength of each transition are defined. Strength estimates based on literature values of α and β are compared to the experimental measures of the isochoric and isobaric transitions. In addition, both the isobaric and isochoric PVT results were analyzed in terms of the Fox and Flory free volume theory which assumes that the glass transition is an iso-free volume state. While the isobaric results were consistent with the Fox and Flory theory, the isochoric results were not consistent with the idea of an iso-free volume glass transition. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1561–1573, 1997     

Transition temperatures and structural correlations for cellulose triesters

Six homologs of the cellulose triester series were found to exhibit, in general, three second-order transitions as determined dilatometrically. A parallel study of torsional modulus versus temperature revealed one glass–rubber transition, which allowed molecular assignment of one of the above. The dependence of the remaining two transition temperatures on length of the ester group permits some speculation with regard to their origin. The glass–rubber and secondary transitions exhibit an inversion for cellulose trivalerate and higher homologs, the two secondary transitions occurring at temperatures higher than the glass–rubber transition. A possible explanation for this anomaly in terms of side-chain crystallization is discussed.     

磺化丁基橡胶离聚体及其共混物的动态力学性质

<正> 含10％摩尔以下的离子且主链为柔性的离聚体是一种热塑性弹性体。在动态力学性质方面呈现特殊的行为,表现在贮能模量(1gE′)与温度的关系中有橡胶态平台出现。最早Otocka等指出,(丁二烯-甲基丙烯酸)共聚物无橡胶态平台,经金属离子中和后产生橡胶态平台,且E′增加。Agarwal,Makowski等则报道磺化乙丙胶离聚体的橡胶态平台随离子含量提高而加宽,随硬脂酸锌的加入而缩短。Fitzgerald及Weisst结合X-射线小角散射研究了甘油及邻苯二甲酸二辛酯对磺化聚苯乙烯离聚体的动态力学性质的影响。     

胶粉在改性沥青中的物化行为分析

生产胶粉改性沥青(CRMA)是实现废橡胶资源化利用及减轻环境污染的有效途径。为了研究胶粉在沥青中的物理及化学行为,采用邻苯二甲酸二丁酯(DBP)模拟沥青的轻组分,将胶粉置入DBP中,在175℃下,反应1.5 h后分离胶粉与轻组分,对轻组分进行气相色谱与质谱联用(GC-MS)分析,讨论胶粉与轻组分发生的物理化学作用;对不同条件下制备的胶粉改性沥青分离胶粉后进行红外光谱(IR)和差示扫描量热(DSC)分析,研究橡胶改性沥青中的官能团变化和热力学特性。结果表明,分离胶粉后的DBP中存在19种检出物,除含量最高的DBP外,其余物质均为胶粉浸出物或与轻组分的反应产物,即胶粉在轻组分中发生了复杂的物理化学反应。胶粉沥青样品中的—CH_2和C=C双键等特征官能团吸收峰大幅增强,橡胶分子在沥青中发生断链降解释放出小分子物质溶于沥青组分发挥改性作用;195℃、1.5 h和175℃、3.0 h制备的沥青样品DSC谱线出现了强烈的吸热峰,即处理温度过高或时间过长,可能发生胶粉过度降解、胶粉团聚或沥青老化行为,使胶粉改性沥青的物化状态发生改变,导致性能劣化。从胶粉物化变化的角度,建议制备胶粉改性沥青时,胶粉掺量(质量分数)应在20%左右,处理温度不高于195℃,处理时间不超过1.5 h。     

间甲钴黏合体系在轮胎骨架材料中的黏合机理研究

为验证与进一步探索黏合树脂及钴盐对轮胎与镀铜钢丝帘线的增黏作用机理,选取传统黏合树脂R80与2种新型黏合树脂HT1005和H620,通过对2种新型黏合树脂的结构分析、橡胶硫化特性、静态T抽出测试与力学性能测试,并设计了一种新的黏合层强度测试方法与黏合层表征方法,进行机理探索,得出如下结论:含有羟基的极性黏合树脂在橡胶硫化时,会由于与非极性天然橡胶的极性差异产生的热力学不相容从而产生自动相分离,向橡胶与镀铜钢丝的界面层进行迁移汇集,且极性越高迁移能力越强,产生一个介于橡胶与镀铜钢丝之间的树脂富集层.因为黏合树脂交联反应温度为140℃左右,会在天然橡胶硫化反应时发生同步交联反应,黏合树脂形成的网络模量高于橡胶硫化网络,会增强镀铜钢丝与橡胶之间的黏合层强度,并形成一个镀铜钢丝与橡胶之间的模量过渡层,进一步增强黏合层.且极性越强,树脂网络交联程度与橡胶硫化网络交联程度越接近,增黏效果越好;钴盐会活化橡胶中的S,使更多的S迁移到镀铜钢丝表面从生成更多硫化亚铜键,增强黏合.     

Effect of 200 keV proton irradiation on the properties of methyl silicone rubber

The effects of 200 keV proton irradiation on methyl silicone rubber were studied. The changes in surface morphology, mechanical properties, cross-linking density, glass transition temperature, infrared attenuated total reflection spectrum and mass spectrum indicated that, at lower fluence, the proton irradiation induced cross-linking, resulting in an increase in tensile strength and hardness of the methyl silicone rubber. However, at higher proton fluence, radiation-induced degradation, which decreased the tensile strength and hardness, became dominant. A macromolecular-network destruction model for silicone rubber irradiated with protons was proposed.     

Gas permeation properties of poly(silamine) membrane

The gas permeation characteristics of poly(silamine) membrane, which consists of alternating 3,3-dimethyl-3-silapentane and N,N′-diethylethylenediamine units in the main chain, were investigated. Though poly(silamine) shows high flexibility (glass transition temperature of −88°C), the gas permeabilities were much lower than those of other rubbery polymers such as poly(dimethylsiloxane) and natural rubber. The activation energies of diffusion in poly(silamine) were much higher than that of natural rubber. On the basis of these results, we propose a model such that the interaction between the Si atom and gas molecules (O₂ and N₂) prevents the free diffusion of the gas molecule in the poly(silamine) membrane. © 1997 John Wiley & Sons, Ltd.     

玻璃化转变的热力学理论错在哪里？

现行国内高分子物理学教科书上都介绍玻璃化转变的热力学理论,其把玻璃化转变描述成为一个二级相转变.但是现在人们已经普遍接受玻璃化转变的本质是一个动力学过程的观点.我们通过讨论玻璃化转变热力学理论的来历,试图弄清这一理论到底错在哪里.首先,该理论所基于的Kauzmann佯谬可能不是一个真正的佯谬;其次,半柔顺链高分子溶液的经典格子统计理论结果中所谓的熵灾难可能是出于对构型熵的错误理解所致.因此,把以上二者联系起来构成玻璃化转变热力学理论的基本假定就从根本上来说是不可靠的.     

Waste Cooking Oil-Modified Epoxy Asphalt Rubber Binders with Improved Compatibility and Extended Allowable Construction Time

The application of crumb rubber from end-of-life tires and waste cooking oil (WCO) in road pavements is of significant importance from an economic and environmental viewpoint. However, the incorporation of crumb rubber greatly shortens the allowable construction time of epoxy asphalt binders due to the high viscosity of the epoxy asphalt rubber (EAR) binder and poor compatibility between crumb rubber and asphalt binder. To lower the viscosity of asphalt rubber, extend the allowable construction time and improve the compatibility of EAR binder, waste cooking oil (WCO) was introduced. The effect of WCO on the viscosity–time behavior, thermal stability, dynamic modulus, glass transitions, crosslink density, damping ability, compatibility, mechanical properties and phase separation of WCO-modified EAR binders was investigated by using the Brookfield viscometer, thermogravimetric analysis, dynamic mechanical analysis, universal testing machine and laser confocal microscopy. The test results demonstrated that the incorporation of WCO declined the viscosity and extended the allowable construction time of the unmodified EAR binder. The inclusion of WCO improved the compatibility between asphalt and crumb rubber and the damping ability and elongation at the break of the unmodified EAR binder. The presence of WCO had a marginal effect on the thermal stability of the unmodified EAR binder. Confocal microscopy observation revealed that asphalt rubber particles aggregated in the epoxy phase of the unmodified EAR binder. With the inclusion of WCO, co-continuous asphalt rubber particles became more spherical.     

轮胎橡胶多组分分析方法的研究

轮胎橡胶物证是涉车案件中常见物证,对于相关案件的侦破具有重要的物证价值。本文根据轮胎橡胶组分体系的特点,设计了以大型仪器为主线的多组分分析方案。所选用的仪器设备及方法有:裂解气相色谱仪(Py-GC)、裂解气相色谱与质谱联用仪(Py-GCMS)、差示扫描量热仪(DSC)、热重分析仪(TGA)、原子吸收分光光度计(AAS)、化学法;实验中,测试了轮胎橡胶的胶型、配合剂定性(防老剂定性、促进剂定性、其他助剂定性)、玻璃化温度,焓值,高聚物含量、配合剂含量、炭黑含量、无机填料(盐酸不溶物、氧化锌含量、二氧化硅含量)、硫含量等十三个测试项目;并将已知配方的硫化胶理论值与测试样品结果比对分析。分析结果表明:建立的系列方法的测试结果准确、可靠,可以为轮胎橡胶的分析鉴别提供技术支持。     

Equilibrium density of states and thermodynamic properties of a model glass former

This paper presents an analysis of the thermodynamics of a model glass former. We have performed equilibrium sampling of a popular binary Lennard-Jones model, employing parallel tempering Monte Carlo to cover the crystalline, amorphous, and liquid regions of configuration space. Disconnectivity graphs are used to visualize the potential energy landscape in the vicinity of a crystalline geometry and in an amorphous region of configuration space. The crystalline global minimum is separated from the bulk of the minima by a large potential energy gap, leading to broken ergodicity in conventional simulations. Our sampling reveals crystalline global minima that are lower in potential energy than some of the previous candidates. We present equilibrium thermodynamic properties based on parallel tempering simulations, including heat capacities and free energy profiles, which depend explicitly on the crystal structure. We also report equilibrium melting temperatures.     

Studies on the nature of multiple glass transitions in low acrylonitrile,butadiene–acrylonitrile rubbers

A study of the occurrence of multiple glass transitions in acrylonitrile–butadiene rubbers (NBR) has been made. Copolymerization theory was used to predict the change in comonomer composition with conversion for comonomer ratios both above and below the calculated azeotropic composition of 64% butadiene/36% acrylonitrile by weight. The results of these calculations suggested that multiple glass transitions, which occur only in NBR of less than 36% acrylonitrile, were due to an incompatibility of copolymer species of divergent comonomer compositions. This was shown by differential thermal analysis to be the case for various experimental polymers of known comonomer composition. A series of NBR's was prepared by incremental addition of acrylonitrile monomer during polymerization, and the resultant glass transition temperatures were evaluated. Results obtained showed that experimental samples which had single glass transitions also had a much narrower spread of comonomer species than the corresponding rubber polymerized with the use of full initial charge of both monomers. The data indicate that NBR's having a single glass transition, regardless of acrylonitrile content, may be prepared by incremental addition of acrylonitrile monomer during polymerization. Existing copolymerization theory appears to be adequate for predicting incremental monomer addition schedules suitable for the polymerization of NBR's having a single glass transition.