Rubber particle size and cavitation process in high impact polystyrene blends

The rubber particle size and its volume fraction are recognised as being important factors in determining the yield and fracture behaviour of high impact polystyrene (HIPS). However, correlations between the average particle size and cavitation in the rubber with toughening efficiency have only recently been established theoretically. This work provides further evidence on how the deformation kinetics in HIPS are affected by variations in the average rubber particle size highlighting along the way the role of rubber cavitation in the process. Variations in the average particle size were achieved by melt blending different proportions of two commercial grades of HIPS that had the traditional multiple inclusion particle morphology. Tensile and impact properties of the blends were measured and correlated to morphological parameters determined by quantitative image analysis. It was found that yield and fracture behaviour in tensile and impact test were strongly dependent on the amount of sub-micron particles in the blend. At high rates, toughness drops steeply with particle size. It was proposed that stress at yield and post yield strain hardening are controlled by particle size and rubber stretching respectively. Microfracture analysis by transmission electron microscopy lent support to the arguments presented. This revised version was published online in November 2006 with corrections to the Cover Date.     

Rubber toughening of plastics

Electron microscopy of a high-impact polystyrene (HIPS) polymer, containing 8.5 wt% polybutadiene, shows that the volume fraction, , of composite rubber particles is 35%. The rubber particle size distribution has 8 median diameter of 1.6 µm. By making a series of blends between this HIPS and polystyrene, it is shown that Young's modulus decreases linearly with . Dilution with polystyrene results in a sharp drop in notched Charpy impact strength. The relevance of these data to the interpretation of structure-property relationships for a wide range of HIPS morphologies is discussed.     

Rubber toughening of plastics

Measurements of particle size distribution, particle volume fraction?/, Young's modulus, tensile and compressive yield stress and Charpy impact strength were made on a series of 14 high-impact polystyrene (HIPS) polymers of widely varying structure. In materials throughout the series containing 8.5 wt % polybutadiene, it was found that?/ varied between 0.17 and 0.44 as the mean particle size increased from 0.2 to 1.8 μm. Modulus and yield stresses depended principally upon particle volume fraction but the ratio of polybutadiene to polystyrene within the particles also appeared to have some influence upon properties. By contrast, variations in ? provided only a partial explanation for the observed differences in Charpy impact strength. It is concluded that impact strength is affected by rubber particle size to a much greater extent than properties measured at low strain rates.     

不同冲击断裂方式下橡胶粒子形态对HIPS脆韧转变的影响

核-壳型/蜂窝型高抗冲聚苯乙烯(HIPS)树脂在Izod冲击和落锤冲击断裂过程中的脆-韧转变行为不同。透射电镜(TEM)对亚断裂形变区的观察表明,蜂窝型HIPS对落锤冲击作用下的脆韧转变敏感,应力集中能有效引发基体的塑性形变,呈韧性断裂,但在v-notched Izod冲击断裂过程中,却呈脆性;而核-壳型HIPS的冲击断裂性能与之相反。将LDO假说引入冲击破坏研究并结合损伤竞争准数Da和Vincent图探讨了分散相特性及冲击方式对脆韧转变行为的影响。     

Computer modelling of rubber-toughened plastics

A computer model has been developed which shows that high-impact polystyrene (HIPS) surface roughness (gloss) depends heavily on rubber phase volume and rubber particle size distribution parameters. The model has been developed in a series of steps. First, several tools have been created for isolation and display of rubber particles near the surface of computer-generated resins. Next, a technique for choosing surface points has been devised, using an algorithm which allows the surface to be disturbed by any particle near the surface. In step three, a non-linear fit of the surface points produces an abstract surface in the form of a grid. The variability in the array of grid points is a measure of surface roughness. The measured surface roughness of conventional high-impact polystyrene resins correlates to the variables identified by the model. A high percentage of the surface roughness variability has been explained in a correlation using average rubber particle size and rubber phase volume, showing the linear regression approach to be good for prediction of the surface roughness of conventional HIPS resins.     

Computer modelling of rubber-toughened plastics

Coarse models of high-impact polystyrene (HIPS) have been created by computer simulation of the rubber particle spacing in the resin. Interparticle surface-surface distance parameters can be calculated from the models to help explain properties of real materials and predict the properties of hypothetical impact-polystyrene resins. Calculations of the geometric spacing of rubber particles in a group of hypothetical HIPS resins show that a narrow rubber-particle size distribution gives smaller interparticle distance and more reinforcing particles compared to broad distributions for a given average particle size.     

HIPS性能与橡胶粒子结构的关联及落锤冲击断裂的增韧机理

研究了橡胶粒子的结构对高抗冲聚苯乙烯(HIPS)性能及落锤冲击断裂的影响。结果表明,屈服强度随着橡胶体积分数的增加而线性递减;材料的落锤冲击韧性主要由分散相粒子的形态及粒子-界面间的粘接强度决定。透射电子显微镜(TEM)和扫描电镜(SEM)对落锤冲击断裂下的微观形变机理研究显示:(1)塑性形变或多重银纹是落锤冲击断裂过程中主要的能量耗散形式;(2)落锤冲击增韧机理可以通过橡胶粒子的形态设计及组成进行调控。另外,采用热重分析法(TGA)研究了HIPS中基质和凝胶的热稳定性。     

丁羟包覆层老化宏微观特性相关性及贮存寿命预估

为了研究固体火箭发动机中丁羟包覆层的宏微观特性相关性并准确预估其材料的贮存寿命,开展了50℃、60℃、70℃和80℃温度下的加速老化试验,建立了交联密度和最大延伸率的相关性函数关系,并用对数模型、幂函数模型和指数模型研究了交联密度随贮存时间的变化规律。以交联密度为老化性能表征量,选用修正Arrhenius法预估了试样的常温贮存寿命。结果表明,α=0.3时的幂函数模型能够较好地描述丁羟包覆层交联密度的变化规律,修正Arrhenius法求得的表观活化能与温度之间具有线性关系。分别以最大延伸率下降50%时的线性函数和二次多项式对应的交联密度值作为失效判据,预估丁羟包覆层的在常温298.15 K下的贮存寿命为17.38年和16.14年,结果与用最大延伸率预估的寿命具有很好的一致性,且能够满足包覆层的老化性能要求。      

硬脂酸钙在环氧化天然橡胶中的应用

在半有效硫化体系中,研究硬脂酸钙用量对环氧化程度为25的环氧化天然橡胶(ENR25)的硫化特性以及硫化胶的物理力学性能、交联密度、耐热空气老化性能、热稳定性及热降解动力学的影响。结果表明,硬脂酸钙用量为1phr时,胶料的焦烧时间tS1较长,硫化速度较快,交联密度较高,物理力学性能较好;随着硬脂酸钙用量的增加,ENR25硫化胶的耐热老化性能提高,热降解反应的表观活化能E增大,热稳定性提高。     

ABS增韧树脂的本体法制备和力学性能

以聚丁二烯橡胶为增韧剂,用本体聚合方法合成了一系列丙烯腈-丁二烯-苯乙烯三元共聚物(ABS),并研究其力学性能。结果表明:高顺胶BR9004的增韧效果最好,IZOD缺口冲击强度高达236.1 J/m,与低顺胶700A的复合可使后者的综合力学性能提高(可与高桥8434牌号产品相媲美);随着丙烯腈含量和树脂相分子量的增加,材料的IZOD缺口冲击强度、拉伸强度和断裂伸长率均有所提高;而树脂的拉伸强度则随着橡胶含量的增加而降低;在橡胶含量低于20%时冲击强度随着橡胶含量增长迅速,高于20%时增长缓慢。     

Model filled rubber IV: Dependence of stress-strain relationship on filler particle morphology

The addition of monodisperse size crosslinked polystyrene (PS) particles, synthesized by emulsifier-free emulsion polymerization, to polysulfide matrix enhanced mechanical properties of the cured rubbery composites. The modulus, fracture strength, and elongation at break increased with increasing filler volume fraction up to 30 wt % PS particles. The strength and elongation at break decreased with increasing particle diameter from 0.315 to 1.25 m. The strength at break increased, but the extension decreased, as the particle crosslink density increased from 0 to 5 mol % DVB. Interparticle interactions are dominant and lead to the formation of clusters which form a network structure in PS particle filled composites. Since the number density, as well as the total surface area, of particles increase with decreasing particle diameter, interparticle attractions are enhanced, the tendency for cluster formation increased with decreasing particle size from 1.25 to 0.315 m. As particle crosslink density was reduced, the porosity and surface roughness of particles increased. Then, the dispersion of particles in the matrix was enhanced and particle agglomeration reduced but more polymer matrix was adsorbed on the particles. These particles or clusters act as physical crosslinks, resulting in an increased total effective crosslink density in the filled composites.     

Correlation between the acoustic and dynamic mechanical properties of natural rubber foam: Effect of foaming temperature

Acoustic absorbing foam materials are produced from dry natural rubber (NR) with the addition of sodium bicarbonate as a blowing agent. The acoustical efficiencies of NR foams were studied, and the results show a significant influence of the viscoelastic and damping properties of the base matrix. Both of these properties are governed by the average cell size, relative density, crosslink density and number of cells per unit volume. The lowest foaming temperature, 140 °C, yielded the NR foam (NR 140) with the highest relative density, crosslink density, smallest average cell size and greatest number of cells per unit volume. Consequently, these foam cell characteristics resulted in a superior sound absorption coefficient and a high storage modulus, which indicates that the NR 140 foam exhibits a better elastic behavior. On the other hand, the NR foam that expanded at 160 °C (NR 160) exhibited great potential for insulating sound and possessed good damping properties, which was characterized by its high transmission loss and tan δ values.     

Internal structure of rubber particles and craze break-down in high-impact polystyrene (HIPS)

Polystyrene can be substantially toughened by the addition of rubber particles, their role being to act as craze initiators permitting substantial plastic deformation to occur prior to fracture. The internal structure of these particles is variable: typically the smaller (1 m) particles are solid rubber and the larger particles contain sub-inclusions of polystyrene. Thin films of a toughened high-impact polystyrene (HIPS) suitable for optical and transmission electron microscopy (TEM) have been prepared, and the interplay between the internal structure of the particles and the crazes they generate has been examined by TEM. It is found that as crazes form around the solid rubber particles, significant lateral contraction occurs accompanying their elongation in the tensile direction. As this contraction proceeds, decohesion occurs just beneath the particlecraze interface, resulting in the formation of a void. This void will grow under increasing stress, leading to premature failure of the craze. In contrast to this behaviour, occluded particles can accommodate the displacements due to crazing by local fibrillation of the rubber shell which surrounds each sub-inclusion, without the formation of large voids. Consequently, the occluded particles do not act as sites for early craze break-down. These results suggest that the optimum morphology for rubber particles in HIPS will consist of a large number of small PS occlusions, each surrounded by a thin layer of rubber, in which case the size of the inherent flaws introduced during crazing will be minimized.     

Measurement of rubber particle fraction in high-impact polystyrene

The rubber particle fraction in high-impact polystyrene (HIPS) can be separated efficiently from the polystyrene matrix if the rubber phase is cross-linked using heat-treatment. A conventional gel test to measure the rubber particle weight fraction has been used on HIPS, which has been heat-treated to cross-link the rubber phase. The rubber particle fraction results obtained by the gel test method are shown to agree with results from an alternative method where the rubber particle fraction is calculated using measurements taken directly from transmission electron photomicrographs.     

高氯酸锂改性丁腈橡胶抗静电性能研究

采用熔融共混法,制备丁腈橡胶/高氯酸锂(NBR/LiClO_4)抗静电复合材料,研究LiClO_4的用量对复合材料硫化性能、力学性能及电性能的影响。结果表明:LiClO_4对NBR的硫化起到了促进作用,提高了其交联密度;NBR的力学强度随着LiClO_4用量的增加而提高;LiClO_4的加入降低了NBR的体积电阻率和表面电阻率,使其由绝缘材料转变为抗静电材料。当LiClO_4的用量为40份时,NBR复合材料的体积电阻率、表面电阻率分别达1.1×108·cm和2.0×109。     

Effect of silica particles modified by in-situ and ex-situ methods on the reinforcement of silicone rubber

In-situ and ex-situ methods were applied to modify silica particles in order to investigate their effects on the reinforcement of silicone rubber. Surface area and pore analyzer, laser particle size analyzer, Fourier-transform infrared spectroscopy (FTIR), contact-angle instrument, and transmission electron microscope (TEM) were utilized to investigate the structure and properties of the modified silica particles. Dynamic mechanical thermal analyzer (DMTA) was employed to characterize the vulcanizing behavior and mechanical properties of the composites. Thermogravimetric analysis (TGA) was performed to test the thermal stability of the composites. FTIR and contact angle analysis indicated that silica particles were successfully modified by these two methods. The BET surface area and TEM results reflected that in-situ modification was more beneficial to preparing silica particles with irregular shape and higher BET surface area in comparison with ex-situ modification. The DMTA and TGA data revealed that compared with ex-situ modification, the in-situ modification produced positive influence on the reinforcement of silicone rubber.     

Preparation and properties of hollow glass bead filled silicone rubber foams with low thermal conductivity

Silicone rubber foams filled with various content and different particle size of hollow glass bead (HGB) were prepared by compression molding. It was revealed that compared with silica filled silicone rubber foams, HGB filled materials achieved higher foaming extent, lower thermal conductivity, and lower hardness, which can be significant for thermal insulation materials. For HGB filled materials, the morphology indicated the average cell size decreased with higher HGB content and larger particle size of HGB. The density, thermal conductivity, hardness and tensile strength increased with higher HGB content and larger particle size of HGB.     

Polymers toughened with rubber microspheres: an analytical solution for stresses and strains in the rubber particles at equilibrium and rupture

Large strains in rubber toughened polymers cause void formation and growth in the rubber particles and yielding in the matrix. Void formation usually precedes plasticity in the matrix around the particle and previous papers have proposed models for the relationship between rubber surface energy, volume strain energy and void growth. In this paper, it is shown that another volume criterion must also be satisfied arising from the fact that in all these models, no decohesion is allowed at the particle-matrix interface. A fracture mechanics approach, where linear and nonlinear elasticity are assumed for the matrix and the rubber particle, respectively, is used to define a void formation criterion depending on the rubber fracture surface energy. After formation, the stability of the void is examined, taking into account the volume conservation between matrix and particle and the stress due to surface tension when the void size is very small. A size effect is observed, indicating that voids cannot grow in small particles. The required value of fracture energy in a particle on a microscopic scale is discussed.     

The effect of silane coupling agent on iron sand for use in magnetorheological elastomers Part 1: Surface chemical modification and characterization

Bis-(3-triethoxysilylpropyl) tetrasulphane (TESPT) was employed for surface modification of iron sand for use in magnetorheological elastomers (MREs). The amount of TESPT was varied at five levels (2, 4, 6, 8 and 10 wt%) relative to iron sand content to assess the optimum amount of coupling agent for interfacial bonding and damping performance. Evidence that coupling had occurred between iron sand and TESPT was identified by Raman Spectroscopy and the grafting percentage was determined by thermogravimetric analysis. Subsequently, isotropic MREs containing unmodified and modified iron sand particles and natural rubber were prepared. Crosslink density assessment by swelling testing provided evidence that the tetrasulphane group of TESPT formed crosslinks with the rubber chains. The results exhibited the advantages of TESPT as a coupling agent between iron sand particles and rubber and also revealed that 6% TESPT content produced the highest crosslink density. The effects of the amount of TESPT on dynamic mechanical properties the morphological characteristics of the MREs were also investigated.