Toughening of polystyrene by natural rubber-based composite particles: Part I Impact reinforcement by PMMA and PS grafted core-shell particles

This work was focused on the influence of the morphology of composite natural rubber (NR)-based particles on the toughness of polystyrene (PS). Emulsion polymerization processes were used to adjust the microstructure of the latex particles. In order to be suitable for the reinforcement of PS, the NR-based particles were coated with a shell of crosslinked polymethyl methacrylate (PMMA) or PS. Furthermore, PS subinclusions were introduced into the natural core. A continuous extrusion process was adapted for the incorporation of these natural rubber based impact modifiers into thermoplastics. High deformation speeds (impact testing) were necessary in order to evaluate the mechanical properties of PS blends with a series of the prepared structured latexes. PS could only be toughened by core-shell particles. A PMMA shell proved to be advantageous because it is easier to produce by emulsion polymerization than a hydrophobic PS shell. Pre-vulcanized NR-based particles, which do not cavitate easily, were ineffective. Core-shell particles based on NR-containing PS subinclusions toughened PS more effectively. Solid NR particles caused premature craze and polymer fracture, as the rubber particles break down, debond from the matrix and form large voids at the craze/particle interface. Scanning electron microscopy (SEM) of Izod fracture surfaces showed clearly the cavities of debonded solid rubber particles and demonstrated that subinclusions within the rubber core permitted a larger volume of plastic deformation before failure. This revised version was published online in November 2006 with corrections to the Cover Date.     

Toughening of polystyrene by natural rubber-based composite particles: Part II Influence of the internal structure of PMMA and PS-grafted core-shell particles

This work was focused on the influence of the internal structure of natural rubber (NR)-based core-shell particles on the toughness of polystyrene (PS). Several emulsion polymerization processes were used to control the degree of grafting of the NR phase and the site of polymerization, which determines the final morphology of the prepared composite NR-based particles. PS subinclusions were introduced into the NR core in order to determine their influence on the deformation behaviour of PS. A continuous extrusion process was adapted for the direct feeding of the wet NR-based latexes into the molten PS matrix. Impact testing indicated that core-shell particles based on NR containing a large number of small crosslinked PS subinclusions toughened PS most effectively. A very effective toughening agent is obtained if a hard shell of 25 wt% crosslinked PMMA surrounds the composite rubber particle. Grafting of NR chains during the subinclusion synthesis has to be avoided since a high rubber particle modulus is detrimental for craze nucleation in PS. From the fracture surface morphology the craze nucleating and stabilizing efficiency of composite NR particles having different morphologies or grafting degrees could be deduced. This revised version was published online in November 2006 with corrections to the Cover Date.     

Toughening mechanisms in high impact polystyrene

In situ scanning electron microscope crack propagation experiments have been performed on a number of polystyrene and high impact polystyrene blends so that dynamic observations can be made of the mechanisms of failure. Brittle fracture is observed in low rubber phase volume systems, whereas high rubber phase volume systems exhibit a ductile tearing mode of fracture. As the rubber phase volume is increased there is an increased density of crazes, which leads to a reduction in width of material between them. The subsequent failure of the crazes leaves bridging ligaments. Under increasing load these fail in a manner dependent on their thickness such that there is a brittle-ductile transition at a ligament thickness around 3m. We argue that this alteration in mechanism could be caused by either the loss of the triaxial stress state or the reduced probability of extrinsic flaws being found in the smaller ligaments, resulting in inhibition of crazing. The stress required for failure at the crack tip consequently increases from that for craze formation to the yield stress of the dense polymer. This in turn allows a larger crazed deformation zone (already increased due to the stress relief effects of crazing) to form, hence a further toughness increase.     

核-壳聚合物粒子增韧改性工程塑料

介绍了核 -壳结构聚合物粒子的组成、制备方法及用途 ,概述了其作为抗冲改性剂和增韧剂对工程塑料的改性 ,探讨了核 -壳粒子的增韧机理     

Fracture mechanisms in polystyrene/laponite nanocomposites prepared by emulsion polymerization

Transmission electron microscopy (TEM) has been used to investigate the effect of laponite clay on microdeformation in thin latex-based polystyrene (PS) films, in which the laponite was concentrated at the original interfaces between the PS particles. At room temperature, a transition was observed from crazing in pure PS to a coarser fibrillar deformation mode as the laponite content increased. Moreover, whereas pure PS showed increasingly homogeneous deformation as T approached T_g, the fibrillar deformation zones observed in the nanocomposites persisted up to T just below T_g, and there was some evidence for yielding behaviour at even higher T in the presence of laponite. The macroscopic fracture resistance of the films, as assessed from double edge-notched tensile specimens, initially increased with laponite content, but decreased for laponite contents greater than 5 wt% with respect to the styrene monomer. This was attributed to a decrease in local ductility, consistent with the observation of reduced deformation ratios in the deformation zones by TEM, and to the intrinsic weakness of the laponite stacks and/or the PS-laponite interface. Thus, specimens with laponite contents comparable with the estimated threshold for percolation of contacts between the laponite stacks showed extremely brittle behaviour, associated with crack propagation along the interfaces between the latex particles.     

Synthesis of Janus composite particles by the template of dumbbell-like silica/polystyrene

Janus particles possess promising performances. It is challenging to develop new methods to control composition and microstructure of the particles. In this report, we describe a general template synthesis of several non-spherical Janus composite particles by the template of dumbbell-like silica/polystyrene (PS) Janus particles. Both PS and silica can be modified to introduce desired functional groups respectively, or induce crystallization of other materials on the particle surface. Especially, by favorable growth of materials within the sulfonated PS gel forming the core–shell structure at the polymer part, several new Janus hollow particles are obtained after removal of the PS core.     

Toughening and strengthening of polypropylene using the rigid-rigid polymer toughening concept Part II Toughening mechanisms investigation

Toughening mechanisms in blends of isotactic polypropylene and Noryl polyphenylene oxide/polystyrene (iPP/Noryl) are studied using optical microscopy, scanning electron microscopy and transmission electron microscopy. Large Noryl particles (10–15 m) are formed in iPP/Noryl blend and crazing is found to be the dominant toughening mechanism. A detailed investigation of fracture mechanisms reveals that Noryl particles help trigger and stabilize massive crazes in the iPP matrix. Incorporation of a small amount of styrene-ethylene-propylene (SEP) compatibilizer helps reduce Noryl particle size and improve interfacial adhesion between iPP and Noryl particles. Crazing and shear banding mechanisms are found to operate sequentially in iPP/Noryl/SEP blends. As a result, significantly improved toughness is obtained.     

聚苯乙烯/铝粉超细复合粒子制备研究

以苯乙烯(St)为原料,以过硫酸钾为引发剂,采用乳液聚合法在球形金属铝粉表面聚合并包覆聚苯乙烯(PS),制备出包覆式PS/4铝粉复合粒子.通过改变铝粉的加入量及选择不同特性的表面活性剂,确定了制备包覆完全均匀致密复合粒子的合理条件.应用扫瞄电镜、傅立叶变换红外光谱及粒度测试等分析方法对复合粒子进行表征.     

Lowering the percolation threshold of polymer matrix composite by using raspberry-like carbon black/polystyrene composite particles

Our previous studies of raspberry-like carbon black/polystyrene (CB/PS) composite particles suggested that their morphologies could be tailored as the coverage degree of CB on PS microspheres. Morphologies of these composite particles were investigated by scanning electron microscope. The CB/PS composites prepared by using raspberry-like CB/PS particles had lower percolation threshold than that of general CB/PS composites. Optical microscopy photographs indicated that hierarchical structure of composite particles enabled CB particles to form more effective networks within the matrix. Raspberry-like structure dispersed CB particles in the interfaces between polycarbonate (PC) and PS when CB/PS particles were introduced into PC as additives. The effects of concentration of PS, coverage degree of CB, and concentration of CB on electrical properties of CB/PS/PC composite were investigated. The results showed that the percolation threshold of CB/PS/PC composite was improved when PS concentration was at the range of 20–80% and coverage degree of CB was more than 5% simultaneously.     

Toughening of thermoset polymers by rigid crystalline particles

The toughening of an aromatic amine-cured diglycidyl ether of bisphenol-A epoxy with particles of crystalline polymers was studied. The crystalline polymers were poly (butylene terephthalate), nylon 6, and poly(vinylidene fluoride). Nylon 6 and poly(vinylidene fluoride) were found to toughen the epoxy about as well as did an equivalent amount of CTBN rubber. Poly(butylene terephthalate) was found to toughen the epoxy about twice as well as did the rubber. The toughness of poly(butylene terephthalate)-epoxy blends was independent of particle size for sizes in the range of tens of micrometres, but the toughness of the nylon 6-epoxy blends decreased with increasing particle size for sizes smaller than about 40 μm. There was no loss of either Young's modulus or yield strength of the epoxy with the inclusion of either nylon 6 or poly(butylene terephthalate) and less loss of these with the inclusion of poly(vinylidene fluoride) than with the inclusion of rubber. Toughness seems to have arisen from a combination of mechanisms. The poly(butylene terephthalate)-epoxy blends alone seem to have gained toughness from phase-transformation toughening. Crack path alteration and the formation of steps and welts and secondary crack bridging seem to have accounted for an especially large part of the fracture energy of the poly(vinylidene fluoride)-epoxy blends. Secondary crack nucleation contributed to the toughness of the nylon 6-epoxy blends.     

用核壳型聚合物粒子增韧改性环氧树脂

介绍了环氧树脂增韧改性的新方法,即用橡胶弹性体、热塑性树脂、刚性粒子和核壳型结构聚合物来增韧环氧树脂。采用种子乳液聚合法制备出了聚丙烯酸丁酯/聚甲基丙烯酸甲酯(PBA/PMMA)核壳型聚合物粒子,并对其表观形貌及结构进行了SEM和FTIR分析。将所制备的核壳型聚合物粒子增韧改性环氧树脂,当用量仅为环氧树脂用量2％时,冲击强度有明显提高。     

Toughening mechanisms and properties of mullite matrix composites reinforced by the addition of SiC particles and Y-TZP

Mullite matrix composites reinforced by SiC particles and Y-TZP, were fabricated by hot-pressing. The effects of adding SiC particles and Y-TZP to mullite or mullite-based materials on properties and toughening mechanisms in the composites were investigated. Crack deflection is proposed as the principal toughening mechanism, produced by the addition of SiC particles. Transformation and microcrack toughening are the two main toughening mechanisms caused by Y-TZP addition. However, the magnitude of their contribution varied with increasing Y-TZP addition. With low Y-TZP addition, the transformation toughening dominated, while at a higher Y-TZP content, the microcrack toughening was dominant. The simultaneous addition of SiC particles and Y-TZP to mullite resulted in higher increases in both flexural strength and fracture toughness, than the simple sum of those obtained by the separate processes. It appears that the two toughening processes were coupled, thereby leading to synergistic toughening and strengthening effects in the mullite composites.     

Fracture mechanisms of epoxy-based ternary composites filled with rigid-soft particles

Epoxy composites filled with different amounts of aggregate-free silica nanoparticles and phase-separated submicron rubber particles were fabricated to study the synergistic effect of multi-phase particles on mechanical properties of the composites. Compared with binary composites with single-phase particles, the ternary composites with both rigid and soft particles offer a good balance in stiffness, strength and fracture toughness, showing capacities in tailoring the mechanical properties of modified epoxy resins. It was observed that debonding of silica nanoparticles from matrix in the ternary composites was less pronounced than that in the binary composites. Moreover, the rubber particles became smaller and their shape tends to be irregular, affected by the presence of rigid silica nanoparticles. The toughening mechanisms in the epoxy composites were evaluated, and the enlarged plastic deformation around the crack tip, induced by the combination of rigid and soft particles, seems to be a dominant factor in enhancing fracture toughness of the ternary composites.     

阻燃高抗冲聚苯乙烯的增韧研究

分别以SBS和EPDM为增韧剂,研究了它们对阻燃HIPS物理机械性能和阻燃性能的影响。结果表明,以SBS为增韧剂所得复合材料的综合性能优于以EPDM为增韧剂所得复合材料的综合性能;复合材料的冲击强度随SBS用量的增大而增大,当SBS用量为12%时,其冲击强度达到9kJ/m2左右,较未经增韧改性复合材料的冲击强度增加了7kJ/m2左右,并且SBS的加入不会对复合材料的阻燃性能产生不利影响。     

Fatigue damage mechanics of composite materials Part III: Prediction of post-fatigue strength

A damage-based model for post-fatigue notch strength is presented. The model is an extension of a method developed previously to predict the notch strength of laminated composites. A simple finite element representation of the notch tip damage zone is used to obtain the localized damage-modified stress distribution. A uniaxial tensile stress failure criterion is applied to the 0° plies from which the laminate strength is evaluated. In conjunction with the fatigue damage growth law described in Part II, residual strength is calculated as a function of the applied loading conditions, specimen geometry and lay-up for (90/0)_s, (90/0)_2s and (90₂/0₂)_s T300/914C carbon-fibre/epoxy laminates subjected to tension-tension fatigue cycling.     

Toughening of calcium hydroxyapatite with silver particles

Calcium hydroxyapatite bioceramic was toughened by preparing composites with silver particles as reinforcements. The composites were fabricated from hydroxyapatite and silver oxide raw powders. The sintering behaviour was investigated using dilatometry. An optimized sintering programme was designed to promote densification and to suppress the decomposition of the hydroxyapatite matrix and the evaporation of silver. High density was achieved on both small cylinder samples and large block samples by pressureless sintering. The density of the composites is over 92.4% theoretical with silver inclusions up to 30 vol%. The strength of the composites is greater than 80 MPa as tested by four-point bending. Silver inclusions improve the toughness consistently, from 0.70 MPa m1/2 for the monolithic hydroxyapatite to 2.45 MPa m1/2 at 30 vol% silver. Studies on the toughening mechanism indicate that crack bridging and subsequent plastic work of silver are mostly responsible for the toughening, whereas crack deflection also makes some contribution.     

Strengthening mechanisms of aluminum matrix composite containing Cu-coated SiC particles produced by friction stir processing

ABSTRACT

A friction stir processing (FSP) method has been developed to fabricate a locally reinforced aluminum matrix composite (AMC) by stirring electroless-copper-coated SiC particles into AA6061 matrix. The interfacial bonding between particulate reinforcement and the matrix was enhanced by the copper coating. Effective improvement in hardness and in tensile strengths has been proved. Microstructural investigation and analyses were conducted to correlate the microstructural evidences with the possible strengthening mechanisms. The effect of copper coating on the bonding between SiC particles and Al-matrix; the role of the dispersed Cu debris and the increased Cu content in solid solution on the strengthening; and the effect of friction stir on dislocation density and on the recrystallization behavior were analyzed. Multiple strengthening mechanisms due to diffusion between copper film and matrix; dispersion of fine copper debris and Al-Cu intermetallic compounds (IMCs) in the matrix; solid solution due to increased copper content and dislocation punching were four major mechanisms in interpreting the strengthening phenomena in AMC containing copper coated SiC reinforcements.     

Effect of core–shell composite particles on the sintering behavior and properties of nano-Al2O3/polystyrene composite prepared by SLS

Nano-Al₂O₃ particles coated with polystyrene (PS) by emulsion polymerization were used as fillers to reinforce PS based composites prepared by selective laser sintering (SLS). The influences of the treated and untreated nanoparticles on the sintering behavior and mechanical properties of the laser sintered specimens were investigated. It was found that there were many uneven holes in the untreated composites. However, for the treated composites, due to the nanoparticle surfaces treated by emulsion polymerization, the absorbance of laser was improved and the nanoparticles dispersed well in the polymer matrix; a full dense structure was obtained and the properties were enhanced, such as the notched impact strength increased 50%, the maximum value was 12.1 kJ/m²; the tensile strength increased up to 300%, the maximum value was 31.2 MPa, comparing to the unfilled PS. FE-SEM studied the tensile fractured surfaces of the sintered specimens. It was noted that the fractured surfaces of composites with treated nanoparticles were rougher than those of unfilled PS and those of the untreated composite. Drawing from the results, it can be confirmed that a full dense structure can be obtained and the polystyrene matrix was strengthened and toughened when the nanoparticles were coated with PS by emulsion polymerization. This work forms a theoretical and technique basis for the production of selective laser sintered nano-Al₂O₃/PS functional products.     

Numerical analysis of intralaminar failure mechanisms in composite structures. Part II: Applications

A three-dimensional continuum damage mechanics-based material model was implemented in an implicit Finite Element code to simulate the progressive intralaminar degradation of fibre reinforced laminates based on ply failure mechanisms. This paper presents some structural applications of the progressive failure model implemented. The focus is on the non-linear response of the shear failure mode and its interaction with other failure modes. Structural applications of the damage model show that the proposed model is able to reproduce failure loads and patterns observed experimentally.