Cold rolled ABS. Part 1: The effect of rubber particle size on the tensile properties of ABS before and after cold rolling

The effect of rubber particle size on the tensile properties of rolled and unrolled acrylonitrile-butadiene-styrene has been studied by considering model systems consisting of mixtures of a small particle (0.1 micron diam) rubber, S, and a large particle (0.56 micron diam) rubber, L, in an SAN matrix. Before rolling, tensile toughness is characterized by crazing. While both rubber induce matrix crazing, ABS systems containing only the S rubber exhibits early failure due to crack formation, before crazing is propagated very far along the tensile axis. The inefficiency of the small particle rubber is interpreted in terms of high composite yield stress and insufficient distance between particles to allow craze branching. The efficiency of the small particle rubber is improved via the addition of a small amount of large particle, L, rubber to the composite or by a slight degree of cold rolling, both of which enhance craze propagation in the tensile direction. With further rolling, the tensile deformation mode changes from one of localized crazing, which is propagated, to one of uniform deformation, which occurs without crazing.     

The effects of particle bulk modulus on toughening mechanisms in rubber-modified polymers

The interaction of a blunting mode I plane-strain crack tip with a periodic array of initially spherical rubber particles directly ahead of and parallel to the crack front in the effective medium is studied by the crack tip-particle interaction model. The local stress concentrations responsible for rubber cavitation, matrix crazing and shear yielding are obtained by three-dimensional large deformation elastic-plastic finite element analysis with a sub-modeling technique to explore the relationship between these toughening mechanisms. It is shown that rubber particles can act as stress concentrators to initiate matrix crazing or shear yielding but they behave differently from voids at high triaxiality because of their high bulk modulus. Particle bulk modulus affects significantly the hydrostatic stress inside rubber particles as well as the plastic deformation in the ligament between the crack tip and particles. Rubber cavitation or interface debonding relieves the triaxial stress planestrain condition so that extensive plastic deformation can be developed in the toughening process.     

Mechanical behavior and structure of rubber modified vinyl ester resins

Vinyl esters are used widely as thermoset matrix materials for reinforced composites; however, they suffer from low‐impact resistance. Substantial enhancement of the toughness of brittle polymers may be achieved by dispersing elastomeric inclusions or rubber particles in the polymer matrix, inducing multiple crazing and shear yielding of the matrix. The main objectives of this work are morphological characterization of vinyl ester/reactive rubber systems and investigation of the mechanical and fracture behavior of these systems. Additional studies focused on rubber endcapped vinyl ester in the absence and presence of added reactive rubber. The initial compatibility of the liquid rubber with the liquid resin was studied. This is a key factor, along with cure conditions, in determination of the possible morphologies, namely, the degree of phase separation and particle size. The initial rubber/resin compatibility was found poor and all attempts to improve it by means of surfactants or ultrasonic treatment have not been successful. The flexure mechanical and fracture behavior of the cured resin/rubber systems was investigated. Three basic types of crack propagation behavior, stable, unstable, and stick‐slip, were observed. Fracture toughness of various resin/rubber systems was evaluated and was found to increase with increased content of rubbery second‐phase material. However, there is some payoff in stiffness and flexural strength of the cured resins. The addition of rubber does not affect the resin toughness at impact conditions. Analysis and interpretation of fractures morphology show that both multiple crazing and external cavitation play an important role in the fracture mechanism of the rubber modified specimens. No shear yielding is evident. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 647–657, 1999     

The rubber particle size dependence of crazing in polypropylene

The tensile crazing and Charpy impact behavior of polypropylene modified with styrene-butadiene copolymer (SBR) and ethylene-propylene-diene monomer (EPDM) was studied. Various rubber particle size distributions were obtained by varying the relative viscosities between rubbery phase and PP matrix. Transmission electron microscopy and computer-aided image analysis were used to provide particle size information. In general, PP blends with smaller rubber particles are tougher and more ductile than those with larger particles, probably because the former represents a more efficient use of rubbery phase in promoting crazing and/or shear yielding. Samples with average particle diameter D? ≥ 0.5 μm were found to exhibit pronounced crazing. Within a given sample, no crazes appeared to develop around individual rubber particles with D < 0.5 μm. The higher the D, the greater the propensity to form crazes. The behavior of samples with D? ? 0.5 μm appeared to be dominated by shear yielding; very few crazes could be found. That there exists a critical rubber particle size is explained by the requirement that sufficient stress concentration be maintained to a finite radial distance to permit the initiation and growth of a craze, which requires a finite volume. Small particles, inducing smaller stress-enhanced zones, are therefore not effective in initiating crazes.     

Izod impact strength of a product molded of poly(vinyl chloride)/impact modifier containing voids (void MOD)

The Izod impact strength of a PVC (polyvinylchloride)/MOD (impact modifier) molded product was investigated by suitably reducing the amount of crosslinking agent in the rubber of MOD or by making rubber particles void when they were in the form of a latex. As a result, (1) when the amount of crosslinking agent in rubber was suitably reduced, the Izod impact strength of the PVC/MOD molded product was improved in both ordinary MOD and void MOD. However, with the extremely small amount of crosslinking agent, low Izod impact strength was exhibited. With the same amount of crosslinking agent, the void MOD showed higher Izod impact strength than the ordinary MOD. (2) SEM (scanning electron microscope) and TEM (transmission electron microscope) observations on the broken surface revealed that shear yield and crazing occurred in a whitened portion, and crazing was observed only near the surface of the broken section in a non‐whitened portion. It was also found that when the crosslinking degree of rubber was reduce, cavitations were liable to be formed in rubber under stress and expanded under rubber stress in the void MOD mor‐; than in the ordinary MOD. (3) As a result of a tensile test on the molded product, it was found that the void MOD caused lower yield stress than the ordinary MOD, thereby increasing in stress concentration. (4) P'rom these results, an estimation was earned out of the mechanism of improvement in the Izod impact strength of the MOD or void MOD using rubber with an appropriately lowered crosslinking degree.     

Synthesis of sub‐micrometer core–shell rubber particles with 1,2‐azobisisobutyronitrile as initiator and deformation mechanisms of modified polystyrene under various conditions

BACKGROUND: Sub‐micrometer core‐shell polybutadiene‐graft‐polystyrene (PB‐g‐PS) copolymers with various ratios of polybutadiene (PB) core to polystyrene (PS) shell were synthesized by emulsion grafting polymerization with 1,2‐azobisisobutyronitrile (AIBN) as initiator. These graft copolymers were blended with PS to prepare PS/PB‐g‐PS with a rubber content of 20 wt%. The mechanical properties, morphologies of the core‐shell rubber particles and deformation mechanisms under various conditions were investigated. RESULTS: Infrared spectroscopic analysis confirmed that PS could be grafted onto the PB rubber particles. The experimental results showed that a specimen with a ‘cluster’ dispersion state of rubber particles in the PS matrix displayed better mechanical properties. Transmission electron micrographs suggested that crazing only occurred from rubber particles and extended in a bridge‐like manner to neighboring rubber particles parallel to the equatorial plane at a high speed for failure specimens, while the interaction between crazing and shear yielding stabilized the growing crazes at a low speed in tensile tests. CONCLUSION: AIBN can be used as an initiator in the graft polymerization of styrene onto PB. The dispersion of rubber particles in a ‘cluster’ state leads to better impact resistance. The deformation mechanism in impact tests was multi‐crazing, and crazing and shear yielding absorbed the energy in tensile experiments. Copyright © 2009 Society of Chemical Industry     

Impact toughening mechanisms in rubber-dispersed polymer alloy

The toughening mechanisms of rubber-dispersed polymer alloys were investigated with respect to two factors: (i) characteristic ratio, C_∞, as a measure of chain flexibility of the polymer matrix and (ii) the rubber particle size in high impact polystyrene/poly(2,6-dimethyl- 1,4-phenylene ether) blend systems. Measurements of the specific gravity, synchrotron radiation small angle X-ray scattering (SR-SAXS) tests, and finite element analysis were carried out to gain understanding of plastic deformation (crazing and shear yielding) of these materials. Shear yielding was found to be enhanced when the C_∞ value of the matrix polymer was relatively low and the rubber particles were small (submicron). From these results, we presumed the impact energy absorption mechanisms to be governed by these two factors.     

Rubber-toughening in polypropylene

To deformation and fracture behavior of several polypropylene (PP) and rubber-modified PP materials have been investigated. Plastic deformation mechanisms of these systems depend upon the test rate and temperature with high rates and low temperatures being in favor of crazing. The ductility and toughness of these materials are explained in light of the competition between crack formation and the degree of plastic deformation through crazing and shear yielding. The second phase morphology with smaller average rubber particle diameter D appears to be more efficient than that with larger D in toughening PP. Theoretical calculations indicate that the stresses imposed upon the rubber particles due to volume shrinkage of PP during crystallization are sufficient to compensate for the stresses due to differential thermal contraction in cooling from solidification temperature to end-use temperature. The difference between these two is small, and therefore they provide very little contribution to interfacial adhesion between rubber particle and PP matrix, the adhesion being insufficient for the rubber particles to be effective in controlling craze propagation. The rubber particles, in addition to promoting crazing and shear yielding, can also improve the fracture resistance of PP by varying the crystalline structure of PP (e.g., reducing the spherulite dimensions).     

Fine structures and fracture processes in plastic/rubber two -phase polymer systems. I. Observation of fine structures under the electron microscope

Fine structures of several plastic/rubber two -phase polymer systems were studied by means of direct observations of ultrathin sections under the electron microscope using osmium tetroxide staining and a hardening procedure developed recently by Kato. Samples used are several types of both ABS polymers and high -impact polystyrenes, and several PVC/rubber blends and the results were discussed in relation to their dynamic viscoelastic properties. It is suggested that these studies may fruitfully be extended to clarify the structure -to property relationships by use of this method.     

New toughening mechanisms in rubber modified polymers

Abstract

Rubber toughening usually involves the addition of rubber particles to a rigid polymer in order to promote energy absorption through the initiation of local yielding, which takes the form of multiple crazing and/or extensive shear yielding. In addition to these classic mechanisms, recent studies of deformation mechanisms in various rubber modified polymers, using a range of electron microscopy techniques, have revealed two new mechanisms of energy absorption. Direct observations of micromechanical processes in high impact polystyrene and copoly(styrene/acrylonitrile)–acrylate blends, carried out in situ on the stage of a transmission electron microscope have shown that the rigid, glassy subinclusions found in both ‘salami’ and hard–soft–hard ‘core–shell’ rubber particles respond to high tensile stresses by cold drawing. Fibrillation begins in the rubber phase and then draws fibrils of glassy polymer from the subinclusions, causing initially spherical inclusions to become flattened discs before finally disintegrating. In addition, when thin sections of rubber toughened polypropylene are stretched in situ on the stage of the transmission electron microscope, hard–soft core–shell particles consisting of a polyethylene core and an ethylene/propylene copolymer rubber shell are able to initiate crazing in the matrix at -100°C, well below the glass transition temperature of the ethylene/propylene copolymer rubber. Micrographs illustrating these mechanisms are presented and discussed.     

Schädigungskriterien glasiger polymer im hinblick auf deren schlagzähmodifizierung

In rubber-modified, stiff and brittle polymers an applied stress generates multiaxial stress concentrations in the matrix material at the rubber interface and initiates a large number of limited regions of plastic deformation. In order to understand this toughening mechanism, one needs a certain knowledge of the kind of plastic flow which is initiated within a glassy polymer according to the type and amount of stress, the so-called failure criteria. Unlike criteria which apply to the onset of shear flow, craze criteria are still contro-versially discussed in the literature. Argon has suggested a theoretical criterion of bulk crazing. Sternstein et al. have studied experimentally the surface crazing of PMMA. Based on experimental results of Rehage and Goldbach and ourselves, calculations have given the following results: The Sternstein criterion, measured and formulated for surface crazing under the condition of plain stress has till now been incorrectly transformed for use in principal stress space. Correctly transformed, it deviates strongly from Argon's criterion in the range of states of stress with large portions of hydrostatic tension. The Sternstein criterion obviously lends itself to describing multiaxial corrosion. For rubber-modified systems, however, one needs bulk craze criteria, for which no experimental results exist. Preliminary results show that these can more easily be estimated for PS than for PMMA. These two polymers therefore show markedly different shapes of the failure surfaces.     

Fracture behavior of poly(vinyl chloride)/methyl methacrylate/butadiene/styrene polymer blends

The fracture mode of poly(vinyl chloride)/methyl methacrylate/butadiene/styrene (PVC/MBS) polymer blends can change from ductile to brittle in accordance with the changes in shape of the test specimen or test conditions. Therefore, the mechanisms of impact energy absorption and the main cause of stress whitening are complicated. The following results on PVC/MBS blends were obtained by carrying out fracture experiments at different test speeds and temperatures:

• (1) The ductile/brittle fracture mode of the PVC and PVC/MBS blends can be explained by σ (the craze initiation stress)/σ_y (the shear yield initiation stress), which depends on the strain rates and temperature.
• (2) The fracture behavior of the PVC/MBS blends can be classified into the following types from the standpoints of fracture mode and whitening degree: Fracture I: ductile fracture without whitening; Fracture II: ductile fracture with whitening; and Fracture III: brittle fracture without whitening.
• (3) The following concepts can be estimated from the measurements of yield stress, specific gravity and SEM, TEM and visual observations. In Fracture I, shear yield occurs mainly. In Fracture II, both shear yield and crazing occur. In Fracture III, deformation of the rubber and local crazing occur.
• (4) The main cause of stress whitening in PVC/MBS blends is light scattering by cavities in the rubber particles.
• (5) In Fracture II, at first, crazes with cavities in the rubber particles occur. Then, shear yield occurs. Finally, crazes are healed by the heat, and only the cavities in the rubber remain.

     

Particle Interaction Effects on Interfacial Stress in Extension of Rubber-Toughened Polypropylene

Polypropylene (PP) toughened with rubber particles is extensively used in polymer industry. Strength or toughness of polymer blends and polymer composites depends, to a great extent, upon their interfacial stress state. A finite element analysis of interfacial stress and its distribution during extension of PP/rubber blends was made by means ANSYS software, to investigate the effects of interaction between neighboring rubber particles on the interfacial stress and its distribution during extension of toughening PP. The simulation results showed that there was obvious stress concentration between rubber particles, especially around the equator zone of the rubber particles. Large shear stress presented at about 45 degrees between the surface and the equator of the rubber particles, and it was symmetry. The pressed and pulled effect subjected by the pole zone of the rubber particles was maximal. Furthermore, the variation extent of the interfacial stress between the particle and the matrix increased with an increase of the particle number.     

橡胶相结构特征对ABS树脂力学性能的影响

采用乳液聚合法合成了具有橡胶结构特征的丙烯腈丁二烯苯乙烯共聚物（ABS）,将其与苯乙烯丙烯腈共聚物（SAN）共混,制备了ABS/SAN共混物,并系统地研究了橡胶相结构特征的影响因素及其对共混物力学性能及其形变机理的影响。结果表明,随着聚丁二烯（PB）橡胶粒子粒径的增大,共混物的冲击强度提高,拉伸强度降低;随着橡胶粒子粒径的增大,共混物形变机理从单一的银纹向橡胶粒子空洞化诱发基体剪切屈服转变。     

Skin-Core morphology and failure of injection-molded specimens of impact-modified polypropylene blends

The structure-property relationship as well as the failure phenomena of injection molded polypropylene (PP) blends modified with ethylene/propylene/diene terpolymer (EPDM) and thermoplastic polyolefinic rubber (TPO) were investigated. Single and double-gated tensile bars were injection molded by different Injection speeds. Microscopic studies on the failure behavior of knit lines were carried out using microtomed sections taken from the doublegated specimens. It was found that during injection molding, a skin-core morphology is formed in both the continuous PP matrix as well as in the modified PP blends containing rubber particles of various deformation. The characteristics of the latter are in agreement with those described by the Tadmor flow model. The skin consists of a thin pure PP layer, whereas the subsurface layer contains more or less elongated rubbery particles due to the elongational flow at the wall. The deformation of the rubbery particles decreases, but their concentration increases with increasing distance from the skin towards the core. The deformed particles are oriented tengentionally to the flow front profile. Failure during tensile and tensile impact loading is initiated in the shear zone along the skin-core boundary. This zone has a transcrystalline character and favors the formation of crazing. Final fracture of the bars depends, however, on how crazing and shear yielding simultaneously interact. Their interaction is a function of the average particle size of the dispersed phase. Above an average particle size of 0.6 μm, crazing is prevented by shear bands. For injection molding of PP/rubber blends a moderate injection speed is recommended, if the melt viscosities of the components are closely matched. In this way a pronounced dispersion gradient of the rubber particles across the plaque thickness is avoided. However, for the blends modified with rubber of high viscosity ratio and greater melt elasticity, use of higher injection speed is advantageous. Here, the higher shear stress field decreases the average particle size taken into the direction perpen dicular to the lead, since the cross section of the stronger deformed particle decreases.     

Modification of natural rubber latex. II. Natural rubber poly(methyl methacrylate) composite latexes synthesized using an amine-activated hydroperoxide

Composite latex particles based on natural rubber latex have been synthesized to yield materials which may be formally regarded as interpenetrating polymer networks and semiinterpenetrating polymer networks. Methyl methacrylate was added to a carefully stabilized natural rubber latex and polymerized in situ using an amine-activated initiator, tert-butyl hydroperoxide. The resulting materials were cast to yield solid sheets. The morphology of the materials was determined both by transmission electron microscopy and by dynamic mechanical analysis. In addition the stress–strain behavior was studied.     

Chain structure,phase morphology,and toughness relationships in polymers and blends

We present chain structure, phase morphology, and toughness relationships in thermoplastic polymers and polymer/rubber blends. In neat polymers, molecular aspects of craze/yield behavior are controlled by two chain parameters: entanglement density ν_e and characteristic ratio C_∞. The crazing stress is proportional to ν, and the yield stress is proportional to C_∞. The dispersed rubber toughens a polymer/rubber blend mainly by promoting energy dissipation of the matrix. The toughening efficiency correlates with the rubber phase morphology and the chain structure of the matrix.     

Damage zone in PVC and PVC/MBS blends. I. The effect of rubber content and temperature

The damage zone development in poly (vinyl chloride) (PVC) and its transparent blends with methyl methacrylate-butadiene-styrene (MBS) core/shell rubber was studied as a function of temperature and rubber content in a triaxial stress state under slow tensile loading. Failure at the semicircular notch occurred by shear yielding followed by stress whitening. In unmodified PVC, the shear yielded plastic zone size was not affected by temperature in the range between —40 and 40°. In the blends, the plastic zone preceding stress whitening increased in size with temperature and rubber content, shifting the stress-whitened zone further away from the notch root. Below 0°, stress whitening initiated at the notch root and the stress-whitened zones had a crescent shape similar to those of PVC/CPE blends studied previously. In unmodified PVC, stress whitening initiated from the growth of preexisting microvoids at the tip of the shear yielded zone containing two families of curving slip lines emanating from the notch root. In contrast, stress whitening in the blends was more intense and was initiated by the cavitation of the rubber particles.     

Different deformation mechanisms of two modified‐polystyrene bimodal systems

It is well known that the dominant toughening mechanism of rubber‐modified polystyrene is multiple crazing. Some researchers have investigated polystyrene that can be modified by rubbers with dual particle sizes, leading to better mechanical properties. That is, the way to absorb energy during the deformation process is crazing and cavitation induced by rubber particles. Two types of polybutadiene‐graft‐polystyrene (PB‐g‐PS) rubber modifiers which have core‐shell structures were synthesized via an emulsion graft polymerization using redox and oil‐soluble initiators, respectively. To balance the yield strength, general‐purpose polystyrene was blended with the PB‐g‐PS modifiers, as well as commercial high‐impact polystyrene. Blends were defined as R‐bimodal and O‐bimodal corresponding to dispersed PB‐g‐PS particles formed using the redox and oil‐soluble initiators, respectively. The impact strength of R‐bimodal was improved significantly by altering the ratio of core to shell. However, little change of impact strength was observed for O‐bimodal. Transmission electron microscopy images of fracture surfaces indicated that the deformation mechanism of R‐bimodal is shear‐yielding induced by multi‐crazing. Moreover, PB‐g‐PS particles dispersed in O‐bimodal can form a ‘cluster’ structure, leading to crazing to absorb energy. Scanning electron microscopy images also showed obvious distinctness between the R‐bimodal and O‐bimodal systems due to different deformation mechanisms. Copyright © 2010 Society of Chemical Industry     

Effect of dynamic crosslinking on impact strength and other mechanical properties of polypropylene/ethylene‐propylene‐diene rubber blends

The deformation and fracture behavior of several dynamic vulcanizate blends of isotactic polypropylene with ethylene‐propylene‐diene rubber (EPDM) was examined and compared with those of uncrosslinked blends of PP/EPDM. These blends were prepared by melt mixing in an internal mixer at 190°C in a composition range of 10–40 wt % EPDM rubber. The variation in yield stress, the strength of fibrils of the craze, and the number density of the EPDM rubber domains (morphology fixation) that are dominant factors for enhancing interfacial adhesion and toughness in dynamic vulcanizate blends were evaluated. The ductility and toughness of these materials were explained in light of the composition between crack formation and the degree of plastic deformation through crazing and shear yielding. The physicomechanical properties including the hardness, yield stress, Young's modulus, percentage elongation, impact strength, flexural strength, and flexural modulus of dynamic vulcanized blends were found to be consistent and displayed higher values compared with uncrosslinked blends. The nucleation effect of the crosslinked particles and the decrease of crystallinity of the EPDM rubber were also considered to contribute to the improvement in the impact strength. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2089–2103, 2000