Deformation mechanism of polystyrene toughened with sub‐micrometer monodisperse rubber particles

Core–shell polybutadiene‐graft‐polystyrene (PB‐g‐PS) rubber particles with different ratios of polybutadiene to polystyrene were prepared by emulsion polymerization through grafting styrene onto polybutadiene latex. The weight ratio of polybutadiene to polystyrene ranged from 50/50 to 90/10. These core‐shell rubber particles were then blended with polystyrene to prepare PS/PB‐g‐PS blends with a constant rubber content of 20 wt%. PB‐g‐PS particles with a lower PB/PS ratio (≤70/30) form a homogeneous dispersion in the polystyrene matrix, and the Izod notched impact strength of these blends is higher than that of commercial high‐impact polystyrene (HIPS). It is generally accepted that polystyrene can only be toughened effectively by 1–3 µm rubber particles through a toughening mechanism of multiple crazings. However, the experimental results show that polystyrene can actually be toughened by monodisperse sub‐micrometer rubber particles. Scanning electron micrographs of the fracture surface and stress‐whitening zone of blends with a PB/PS ratio of 70/30 in PB‐g‐PS copolymer reveal a novel toughening mechanism of modified polystyrene, which may be shear yielding of the matrix, promoted by cavitation. Subsequently, a compression‐induced activation method was explored to compare the PS/PB‐g‐PS blends with commercial HIPS, and the result show that the toughening mechanisms of the two samples are different. Copyright © 2006 Society of Chemical Industry     

ABS/HIPS blends obtained from WEEE: Influence of processing conditions and composition

The recycling of acrylonitrile–butadiene–styrene (ABS) and high‐impact polystyrene (HIPS) from postconsumer electronic equipment housing was investigated. A preliminary study of shot size and particle size effects on the mechanical properties of ABS/HIPS (50/50) blends obtained directly via injection molding was conducted. Injection‐molded specimens of ABS/HIPS blends, obtained at different compositions with or without previous extrusion, were subjected to mechanical, thermal, and morphological testing. Preliminary studies showed that a smaller particle size resulted in higher tensile and impact strength, regardless of the shot size used during injection molding. ABS/HIPS blends obtained using previous extrusion presented a slight increase in Young's modulus and a decrease in elongation at break and impact strength. The increase in glass‐transition temperature related to the Polybutadiene (PB) phases of these blends indicated a possible increase in crosslinking structures during extrusion. In addition, these blends showed a coarse and heterogeneous morphology, suggesting that ABS did not completely mix with HIPS. Compared to processing conditions, the blend composition appeared to have a much stronger effect on the mechanical properties. The results obtained suggest the possibility of obtaining ABS/HIPS blends directly via injection molding as long as small ground particles are used. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43831.     

Comparison of the toughening mechanisms of poly(vinyl chloride)/chlorinated polyethylene and poly(vinyl chloride)/acrylonitrile–butadiene–styrene copolymer blends

In this study, the influence of chlorinated polyethylene (CPE) and acrylonitrile–butadiene–styrene copolymer (ABS) on the mechanical properties of poly(vinyl chloride) (PVC)/CPE and PVC/ABS hybrids were examined. The experimental results show that the toughness of the hybrids could be modified greatly by the introduction of CPE or ABS. The microstructure and impact surfaces of the blends were investigated by scanning electron microscopy and transmission electron microscopy. ABS dispersed in the form of particles or agglomerates in the PVC matrix, and CPE tended to disperse as a net structure. In the tensile test, ABS initiated crazes as stress concentrators to toughen the PVC matrix, whereas CPE, with the PVC matrix together, caused a yield deformation by shear stress to form a shear band. The formation of crazes and shear bands benefited the toughening of PVC, but to the different extent. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 916–924, 2003     

PVC/ABS共混体系中的银纹及其增韧作用

研究ABS用量对PVC／ABS二元体系冲击性能的影响，用电子显微镜（SEM，TEM）观察共混体系冲击断面和拉伸断面形貌，分析ABS分布形态和增韧作用。结果发现，ABS依用量不同分别以颗粒或聚集体分散在PVC连续相中，在拉伸过程中，ABS粒子产生变形并作为应力集中体引发银纹。银纹的产生，发展和缎地增韧起着重要的作用。     

PS/EPDM blends prepared by in situ polymerization of styrene

PS/EPDM blends formed by in situ polymerization of styrene in the presence of EPDM were prepared. EPDM has excellent resistance to factors such as weather, ozone and oxidation and it could be a good alternative for substituting polybutadiene‐based rubbers in PS toughening. The PS/EPDM blends present two phases, an EPDM elastomeric phase dispersed into a rigid matrix. The blends show higher thermal stability than polystyrene homopolymer due to the stabilizing effect of EPDM incorporation. The mechanical properties of in situ polymerized PS/EPDM blends with different compositions were evaluated before and after accelerated photoaging and compared with the properties of HIPS submitted to the same aging conditions. The blend containing 17 wt % of EPDM presents an increase in the impact resistance of 210% in comparison with the value of PS. Although the initial mechanical properties of HIPS are superior, a pronounced drop was observed after an exposure time. For example, after the aging period, all PS/EPDM blends showed higher strain at break than HIPS. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Micromechanics of uniaxial tensile deformation and failure in high impact polystyrene (HIPS)

While it is recognized that the heterogeneous particles in HIPS play the dual role of providing multiple sites for craze initiation in the polystyrene (PS) matrix and allow the stabilization of the crazing process through cavitation/fibrillation in the PB phase within the particle, the precise role of particle morphology is not well understood or quantified. This work probes the micromechanics of uniaxial tensile deformation and failure in rubber-toughened PS through axi-symmetric finite element representative volume element (RVE) models that can guide the development of blends of optimal toughness. The RVE models reveal the effect on craze morphology and toughness by various factors such as particle compliance, particle morphology, particle fibrillation and particle volume fraction. The principal result of our study is that fibrillation/cavitation of PB domains within the heterogeneous particle provides the basic key ingredient to account for the micro- and macro-mechanics of HIPS.     

Study of a novel halogen‐free flame retardant system through TGA and structure analysis of polymers

Butadiene‐rubber toughened styrene polymers, such as acrylonitrile‐butadiene‐styrene (ABS) copolymer and high impact polystyrene (HIPS), are noncharring polymers. They are generally blended with polycarbonate (PC) or polyphenyleneether (PPE), which are char forming polymers, to improve char forming ability for styrenic blends containing conventional phosphate flame retardants. To achieve cost effective flame retardant system, PET was selected as a potential char‐source for ABS blends through the thermogravimetric analysis (TGA) and chemical structure analysis of various polymers. PET may contribute to the enhancement of flame retardancy of ABS/PET blends, especially in the presence of small amounts of phenol novolac (PN). The effective flame retardancy of this system is believed to be accomplished through the enhancement of interchain reactions by PN. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

PE-C、ABS改性硬质聚氯乙烯的性能和增韧机理

研究不同用量的氯化聚乙烯（PE-C）和（丙烯腈/丁二烯/苯乙烯）共聚物（ABS）对硬聚氯乙烯（PVC-U）二元共混体系力学性能的影响。用电子显微镜观察了冲击断面和微观结构,结果发现,随增韧剂用量不同两种共混体系的冲击性能曲线均可分为“脆性断裂”,“脆韧转变”和“韧性断裂”三个区。不同的是,PE-C在PVC-U中形成网络结构,而ABS是以颗粒或聚集体分散在PVC连续相中,拉伸时,PE-C易与基体共同发生剪切屈服产生“剪切带”,ABS作为应力集中体引发银纹。“剪切带”和“茛纹”都对PVC-U增韧起着重要的作用。     

Phase morphologies and mechanical properties of high‐impact polystyrene (HIPS) and polycarbonate blends compatibilized with polystyrene and polyarylate block copolymer

Phasemorphology and mechanical properties of blends of high‐impact polystyrene (HIPS) and polycarbonate (PC) blends compatibilized with a polystyrene (PS) and polyarylate (PAr) (PS–PAr) block copolymer were investigated. Over a broad range of composition from 50/50 through 30/70, HIPS/PC blends formed cocontinuous structures induced by the flow during the extrusion or injection‐molding processes. These cocontinuous phases had heterogeneity between the parallel and perpendicular directions to the flow. The micromorphology in the parallel direction to the flow consisted of stringlike phases, which were highly elongated along the flow. Their longitudinal size was long enough to be longer than 180 μm, while their lateral size was shorter than 5 μm, whereas that in the perpendicular direction to the flow showed a cocontinuous phase with regular spacing due to interconnection or blanching among the stringlike phases. The PS–PAr block copolymer was found to successfully compatibilize the HIPS/PC blends. The lateral size of the stringlike phases could be controlled both by the amount of the PS–PAr block copolymer added and by the shear rate during the extrusion or injection‐molding process without changing their longitudinal size. The HIPS/PC blend compatibilized with 3 wt % of the PS–PAr block copolymer under an average shear rate of 675 s^?1 showed a stringlike phase whose lateral size was reduced almost equal to the rubber particle size in HIPS. The tensile modulus and yield stress of the HIPS/PC blends could be explained by the addition rule of each component, while the elongation at break was almost equal to that of PC. These mechanical properties of the HIPS/PC blends can be explained by a parallel connection model independent of the HIPS and PC phases. On the other hand, the toughness factor of the HIPS/PC blends strongly depended on the lateral size of the stringlike phases and the rubber particle size in the HIPS. It was found that the size of the string phases and the rubber particle should be smaller than 1.0 μm to attain a reasonable energy absorbency by blending HIPS and PC. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2347–2360, 2001     

Influence of core–shell rubber particles synthesized with different initiation systems on the impact toughness of modified polystyrene

Core–shell poly(butadiene‐graft‐styrene) (PB‐g‐PS) rubber particles were synthesized with different initiation systems by emulsion grafting polymerization. These initiation systems included the redox initiators and an oil‐soluble initiator, 1,2‐azobisisobutyronitrile (AIBN). Then the PB‐g‐PS impact modifiers were blended with polystyrene (PS) to prepare the PS/PB‐g‐PS blends. In the condition of the same tensile yield strength on both samples, the Izod test showed that the notched impact strength of PS/PB‐g‐PS(AIBN) was 237.8 J/m, almost 7 times than that of the PS/PB‐g‐PS(redox) blend, 37.2 J/m. From transmission electron microscope (TEM) photographs, using the redox initiators, some microphase PS zones existed in the core of PB rubber particles, which is called “internal‐grafting.” This grafting way was inefficient on toughening. However, using AIBN as initiator, a great scale of PS subinclusion was seen within the PB particle core, and this microstructure increased the effective volume fraction of the rubber phase with a result of improving the toughness of modified polystyrene. The dynamic mechanical analysis (DMA) on both samples showed that the glass transition temperature (T_g) of rubber phase of PS/PB‐g‐PS(AIBN) was lower than that of PS/PB‐g‐PS(redox). As a result, the PB‐g‐PS(AIBN) had better toughening efficiency on modified polystyrene than the PB‐g‐PS(redox), which accorded with the Kerner approximate equation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 738–744, 2007     

Mechanical properties and deformation behaviors of acrylonitrile‐butadiene‐styrene under Izod impact test and uniaxial tension at various strain rates

Two polybutadiene‐graft‐acrylonitrile‐styrene copolymer (PBD‐g‐SAN) impact modifiers with different rubber particle size were synthesized by seeded emulsion polymerization. Acrylonitrile‐butadiene‐styrene (ABS) blends with a constant rubber concentration of 15 wt% were prepared by blending those impact modifiers and SAN resin. The major focus was the mechanical properties and deformation mechanisms of ABS blends under Izod impact test and uniaxial tension at various strain rates from 2.564 × 10^?4 S^?1 upto 1.282 × 10^?1 S^?1. By the combination of transmission electron microscope and scanning electron microscope, it was concluded that crazes and cavitation coexisted in ABS blends. The deformation mechanisms of ABS blend containing large rubber particles was rubber particles cavitation and shear yielding in the matrix including crazes, and they do not change with the strain rate. Different from ABS blend with large rubber particles, deformation mechanism of ABS with small rubber particles under tensile condition was only involved in shear yielding in the matrix and no crazes were formed. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Mechanical Properties of Ternary Blends of ABS + HIPS + PETG

The effect of a commercial styrene/butadiene/styrene-based compatibilizer (Styroflex) on the tensile and impact properties of ternary blends of poly(acrylonitrile-co-butadiene-co-styrene) (ABS), high impact poly(styrene) (HIPS) and poly(ethylene terephthalate-co-cyclohexanedimethanol terephthalate) (PETG) was investigated. The tensile yield strengths and the moduli of the blends were of similar magnitude as the parent polymers. However, notched Charpy impact properties showed significant deviations with high synergy in ABS/PETG blends and strong antagonism in HIPS/PETG blends. Addition of Styroflex improved the impact properties of all blends containing HIPS and ABS. Dynamic mechanical analysis studies confirm the phase separated nature of ABS/PETG binary blends.     

Instability of styrene/polystyrene/polybutadiene/polystyrene‐b‐polybutadiene emulsions that emulate styrene polymerization in the presence of polybutadiene

This article investigates the room temperature demixing of oil‐in‐oil emulsions containing styrene (St), polybutadiene (PB), a St‐butadiene star block copolymer (BC), and two polystyrene (PS) samples of different molecular weights and is a contribution toward a better understanding of the stability/instability of the reaction mixture in a bulk high‐impact polystyrene (HIPS) process close to the phase inversion. Twelve bulk prepolymerizations of St in the presence of PB were emulated, at 10%, 15%, and 20% conversion; and with constant grafting efficiencies. All the blends contained 6% in weight of butadiene units. After stirring the blends for 24 h, the decantation demixing process was monitored along 30 days, with daily measurement of the interface levels after appearance of a clear interface. For some of the isolated phases, their unswollen morphologies were observed by transmission electron microscopy. All the isolated phases exhibited macrophase separation into homopolymer‐ and copolymer‐rich macrodomains with lamellar microdomains. The BC showed a greater affinity toward the PS‐rich phase. The separation of an independent BC‐rich phase in the blends containing the high molar mass PS and at high grafting efficiencies, modifies the idea of the graft‐ or BC molecules located at the interface of large PS‐rich and PB‐rich phases. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Morphology and mechanical properties of ABS blends prepared from emulsion‐polymerized PB‐g‐SAN impact modifier with AIBN as initiator

A series of PB‐g‐SAN impact modifiers (polybutadiene particles grafted by styrene and acrylonitrile) are synthesized by seed emulsion copolymerization initiated by oil‐soluble initiator, azobisiobutyronitrile (AIBN). The ABS blends are obtained by mixing SAN resin with PB‐g‐SAN impact modifiers. The mechanical behavior and the phase morphology of ABS blends are investigated. The graft degree (GD) and grafting efficiency (GE) are investigated, and the high GD shows that AIBN has a fine initiating ability in emulsion grafting of PB‐g‐SAN impact modifiers. The morphology of the rubber particles is observed by the transmission electron microscopy (TEM). The TEM photograph shows that the PB‐g‐SAN impact modifier initiated by AIBN is more likely to form subinclusion inside the rubber particles. The dynamic mechanical analysis on ABS blends shows that the subinclusion inside the rubber phase strongly influences the T_g, maximum tan δ, and the storage modulus of the rubber phase. The mechanical test indicates that the ABS blends, which have the small and uniform subinclusions dispersed in the rubber particles, have the maximum impact strength. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Thermally stimulated oxidative degradation of high impact polystyrene with nitric acid

The practical application of high impact polystyrene (HIPS) depends on the resistance to aging in aggressive environments. The investigation of morphological, mechanical, and chemical properties was made on HIPS samples of various thickness. The property deterioration of HIPS caused by concentrated nitric acid and heat was studied. The diffusion through micropores formed visible cracks that finally led to the complete destruction into a powder. The rapid loss in mechanical properties was explained in terms of scission reaction of the graft polybutadiene (PB) with the homopolystyrene (PS) matrix. Comparative measurements of pure PS and PB under the same conditions were helpful in resolving parallel reactions that preferentially take place in PS and/or in PB sequences. It was established that higher degree of nitration caused by higher temperature results in increased insolubility owing to parallel crosslinking reactions. The nitric acid attack on HIPS caused scission reactions, which also led to the oxidative degradation, more pronounced in the PS phase in the soluble part of HIPS.     

Blends of polyamide1010 with unmodified and maleic‐anhydride‐grafted high‐impact polystyrene

The crystallization behaviors, dynamic mechanical properties, tensile, and morphology features of polyamide1010 (PA1010) blends with the high‐impact polystyrene (HIPS) were examined at a wide composition range. Both unmodified and maleic‐anhydride‐(MA)‐grafted HIPS (HIPS‐g‐MA) were used. It was found that the domain size of HIPS‐g‐MA was much smaller than that of HIPS at the same compositions in the blends. The mechanical performances of PA1010–HIPS‐g‐MA blends were enhanced much more than that of PA1010–HIPS blends. The crystallization temperature of PA1010 shifted towards higher temperature as HIPS‐g‐MA increased from 20 to 50% in the blends. For the blends with a dispersed PA phase (≤35 wt %), the T_c of PA1010 shifted towards lower temperature, from 178 to 83°C. An additional transition was detected at a temperature located between the T_g's of PA1010 and PS. It was associated with the interphase relaxation peak. Its intensity increased with increasing content of PA1010, and the maximum occurred at the composition of PA1010–HIPS‐g‐MA 80/20. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 857–865, 1999     

PS SAN 和AAS对PVC／ABS体系增韧改性的研究

采用非弹性体增韧的概念,探讨了三种有机刚性粒子(PS、SAN和AAS)对PVC/ABS二元体系的增韧改性作用,分析了有机刚性粒子增韧作用的影响因素和实现途径。结果表明,有机刚性粒子对PVC/ABS二元共混体系确有一定增韧作用,不同的刚性粒子对不同韧性的二元基体,增韧改性效果各不相同。     

Characterization of the free volume in high‐impact polystyrene/polypropylene and high‐impact polystyrene/high‐density polyethylene blends probed by positron annihilation spectroscopy

The free‐volume properties of high‐impact polystyrene (HIPS)/polypropylene (PP) and HIPS/high‐density polyethylene (HDPE) blends were investigated by means of positron annihilation lifetime spectroscopy (PALS). The measured results show that the free‐volume holes in the semicrystalline polymers, such as PP and HDPE, were not large enough to accommodate the branched chains and the end groups of the macromolecular chains in HIPS to produce favorable interactions between the semicrystalline polymers and the HIPS polymer in these blends; thus immiscible blends were formed. The weak interaction between two dissimilar polymer molecules only took place in the regions between two amorphous phases. In addition, the observed negative deviations of the longest lifetime intensity and the free‐volume fraction were attributed to the influence of the interfacial polarization during PALS measurement. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1507–1514, 2003     

Molecular simulation of the effect of graft structure on the miscibility of high‐impact polystyrene blends

High‐impact polystyrene (HIPS) is a kind of thermoplastic with good impact, which is considered to derive from the biphase of microstructure studied with SEM, etc. In this article, the influence of polystyrene (PS)/polybutadiene (PB) graft structure to the behavior of HIPS was studied through molecular simulation. The analysis of Flory‐Huggis parameter χ and radial distribution function (RDF) shows that the blend system of PS/PB has the best miscibility when the mass ratio of PS/PB is 60/40. In the toughening process, however, the graft copolymer PB‐g‐S is formed. For the PS/PB‐g‐S system with the same repeat unit of PS, PB‐g‐S chains with two grafts [PB‐g‐S(G = 2)] are better than PB‐g‐S chains with one graft [PB‐g‐S(G = 1)] in miscibility, which is in accord with the study of Fischer and Hellmann. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Toughness and morphology of radiation‐crosslinked natural rubber modified polystyrene

γ‐Radiation vulcanized natural rubber (RVNR)/phase transfer/suspension polymerization technique was used to prepare high‐impact polystyrene (HIPS) in bead form. The high notched Izod impact resistance of HIPS based on RVNR was observed and compared with that of unmodified PS. The impact resistance of HIPS based on RVNR was further enhanced by addition of 10% of polystyrene‐block‐polyisoprene‐block‐polystyrene copolymer. A mesh structure of all crosslinked rubber particles containing polystyrene and long crazes in HIPS were observed under electron microscopy. Copyright © 2003 Society of Chemical Industry