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.     

Fracture behavior of styrene‐ethylene‐propylene rubber‐toughened polypropylene

The morphology and fracture behavior of isotactic polypropylene toughened by styrene‐ethylene‐propylene (PP/SEP) were investigated. The SEP rubber, having an average particle size of 0.2 µm, is found to be well dispersed in the PP matrix. The fracture toughness of SEP‐modified PP is greatly improved. The toughening mechanism investigation shows that a widespread crazing zone is generated in the crack tip damage zone. An intense narrow damage band in the center of crazed zone is formed. Crazing and shear yielding are found to be the dominant toughening mechanisms in PP/SEP. The crazes are initiated only by large SEP particles in the blend. The small SEP particles (< 0.3 µm) can neither cavitate nor trigger crazing. As a result, large scale shear deformation is suppressed in this blend. These findings are consistent with the notion that the crack tip plane strain constraint has to be relieved in magnitude in order for the deviatoric stress to reach a critical value for widespread shear banding.     

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.     

Mechanism of Toughening in Rubber Toughened Polyolefin—A Review

The recent advances and theories in the studies of the toughening mechanism have been reviewed to explain the effect of rubber particles in different rubber modified Polyolefin materials. To elucidate toughening effect, major theories e.g., critical particle distance, particle size, micro deformation by stress field of rubber, shear yielding and crazing phenomena has been reviewed. Based on these theories, variety of blends of rubber modified Polyolefin materials has been compared but no one of these provided adequate information to be considered as total theory of toughening. To achieve the objective of toughening, it is important to maintain critical particle size, uniform particle distribution and good interfacial adhesion by inclusion of suitable compatibilizer in the matrix. Particular attention has been paid to study the type of morphology and bimodal distribution of rubber particles to elucidated toughening effect. Rubber particle cavitation, which comes from micro-voids and rubber phase interface are then further discussed.     

Deformation,yield and fracture of elastomer‐modified polypropylene

In recent decades, great attention has been devoted to the toughening of isotactic poly(propylene) (PP) with elastomers such as ethylene–propylene rubber (EPR). The most important reasons for this interest are the moderate cost and favorable properties of PP. This article is focused on the role of EPR in the deformation and fracture mechanism of PP/EPR blends with different volume fractions of elastomer phase. Differential scanning calorimetry (DSC), tensile tests, and microscopy techniques were used in this study. The fracture mechanism of isotactic PP toughened by EPR (PP/EPR) has also been studied by three point bending (3‐PB) and four point bending (4‐PB) tests. Rubber particle cavitation appears to be the main mechanism of microvoid formation, although some matrix/particle debonding was observed. The investigation of the toughening mechanism shows that a wide damage zone spreads in front of the pre‐crack. Optical microscopy (OM) illustrates that, in pure PP, crazing is the only fracture mechanism, and no evidence of shear yielding is found, while in PP blends craze‐like features associated with shear yielding are observed, which have been identified as high shear localized dilatational bands. This type of deformation pattern supports a model previously proposed by Lazzeri 1 to explain the interparticle distance effect on the basis of the stabilization effect on dilatational band propagation exerted by stretched rubber particles. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3767–3779, 2003     

Sequences of fracture toughness micromechanisms in PP/CaCO3 nanocomposites

Mechanical properties and fracture toughness micromechanisms of copolypropylene filled with different amount of nanometric CaCO₃ (5–15 wt %) were studied. J‐integral fracture toughness was incorporated to measure the effect of incorporation of nanoparticle into PP matrix. Crack‐tip damage zones and fracture surfaces were studied to investigate the effect of nanofiller content on fracture toughness micromechanisms. It was found that nanofiller acted as a nucleating agent and decreased the spherulite size of polypropylene significantly. J‐integral fracture toughness (J_c) of nanocomposites was improved dramatically. The J_c value increased up to approximately two times that of pure PP at 5 wt % of nano‐CaCO₃. The fracture micromechanisms varied from rubber particles cavitation and shear yielding in pure PP to simultaneous existence of rubber particles cavitation, shear yielding, filler particles debonding, and crazing in PP/CaCO₃ nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of compatibilizer on micromehanical deformations and morphology of dispersion in PP/PDMS blend

Role of maleic anhydride grafted polypropylene (PP‐g‐MAH) in interface modification in polypropylene (PP)/poly(dimethylsiloxane) (PDMS) elastomer blend has been investigated in this article through its effects on morphology of dispersion, micromechanical deformations such as voiding, crazing, shear yielding, fibrillation, and tensile behavior. During tensile deformation, PP/PDMS blend without the compatibilizer showed debonding at the elastomer‐matrix interface and it induced shear yielding and subsequently fibrillation in the matrix. The compatibilizer improved the interfacial adhesion between the PDMS domains and PP matrix, which prevented the debonding at elastomer‐matrix interface and the resulting shear yielding, and fibrillation was absent and rather caused extensive crazing in the matrix. Addition of PP‐g‐MAH reduced the size of dispersed PDMS domains, and narrowed the domain size distribution, which is attributed as an effect of interfacial adhesion produced by PP‐g‐MAH. Stress–strain curve and fibrillation also show similar effect of the interfacial adhesion caused by the compatibilizer. All these observations consistently lead to conclude that PP‐g‐MAH acts as a good compatibilizer for PP/PDMS blend. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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     

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.     

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.     

Mechanical behavior of dual-rubber-modified SAN

The use of either an SBS block copolymer or an emulsion-made methyl-methacrylate-grafted rubber alone failed to give any significant increase in the toughness of brittle poly(styrene-co-acrylonitrile) (SAN), even at concentrations up to 50%. However, a combination of the two rubber modifiers produced a strong synergistic toughening. All specimens were prepared by injection molding; however, annealing to relax orientation did not significantly alter this synergistic effect. The use of mechanical dilatometry showed that post-yield deformation of blends containing both modifiers involved some crazing just after yielding but subsequent deformation was mostly due to shear yielding. Addition of SBS alone to SAN resulted in a mixed crazing/shear yielding mode of post-yield deformation with the relative proportions of the two mechanisms being constant up to failure. In contrast, the small emulsion graft particles alone gave rise to a predominant shear yielding deformation. A qualitative mechanism for the synergism is discussed.     

Fractographic analysis of the crack resistance of styrene–acrylonitrile/polybutadiene‐g‐styrene–acrylonitrile blends as evaluated by the essential work of fracture method

The fracture surfaces and deformation micromechanisms of styrene‐co‐acrylonitrile (SAN)/polybutadiene‐g‐styrene‐co‐acrylonitrile (PB‐g‐SAN) blends with the compositions ranging from 65/35 to 0/100 were studied with a scanning electron microscopy technique. The results were compared to the essential work of fracture parameters obtained in a previous study conducted on double‐edge notched tension specimens. Different plastic damage mechanisms were observed, and they depended on the blend composition. For blends of 65/35 and 45/55, a high degree of rubber particle cavitation and multiple cracking followed by the massive shear yielding of the matrix were found to be the main source of energy dissipation during crack growth. Within this compositional range, more intense plastic damage in a larger volume of material, especially at the notched region, was observed as the concentration of the rubbery phase increased. For the 25/75 blend, the prevailing mechanism was pure shear yielding without any sign of cavitation inside the particles, and the fracture surface became relatively flat and was covered with aligned small microcracks. This sample showed the highest specific essential work (w_e) value among the blends examined in the previous study. For the samples containing concentrations of dispersed phase higher than 75%, the shear yielding process gradually became less important with the progressive importance of multiple crazing so that high‐magnification micrographs revealed extensive microcracking/crazing both inside and between the rubber particles, as the only active deformation micromechanism for neat PB‐g‐SAN. The variation w_e and specific plastic work of fracture with the PB‐g‐SAN phase content were successfully explained in terms of prevalent deformation mechanisms. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40072.     

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     

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     

Notched impact behavior of polymer blends: Part 1: New model for particle size dependence

A model is proposed to explain the observed relationships between particle size and fracture resistance in high-performance blends, which typically reach maximum toughness at particle diameters of 0.2–0.4 μm. To date there has been no satisfactory explanation for the ductile–brittle (DB) transition at large particle sizes. The model is based on a recently developed criterion for craze initiation, which treats large cavitated rubber particles as craze-initiating Griffith flaws. Using this criterion in conjunction with Westergaard's equations, it is possible to map the spread from the notch tip of three deformation mechanisms: rubber particle cavitation, multiple crazing and shear yielding. Comparison of zone sizes leads to the conclusion that maximum toughness is achieved when the particles are large enough to cavitate a long way ahead of a notch or crack tip, but not so large that they initiate unstable crazes and thus reduce fracture resistance.     

Rubber toughening in polypropylene: A review

The recent advances in the studies of the toughening methods and theories of polypropylene (PP)–elastomer blends are reviewed in the present article. Inclusions are key to toughening PP; they can play the role of agent‐induced crazing, cause shear yielding of the matrix around them, and end the propagation of cracks. The major theories interpreting the toughening mechanisms of the blends are: multiple crazing, damage competition theory, shear‐yielding theory, microvoids, and cavitation theories. The factors affecting the toughening effect are relatively complicated. Therefore, these theories have been verified only in some cases when they have been applied in relevant conditions. To achieve the objective of better toughening, it is important to improve the uniform distribution of dispersed‐phase particle size and suitable filler size, as well as improving the dispersion of the inclusions formed in the matrix; in addition the matrix materials or fillers must be functional with suitable modifier in order to enhance the interfacial adhesion or to improve the interfacial morphological structure between the filler and matrix. However, the exact toughening mechanisms for PP–rubber blends have to be studied further because of complications resulting from the crystallinity of the matrix. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 409–417, 2000     

Microdeformation mechanisms in propylene–ethylene block copolymer

Blends of propylene–ethylene block copolymer (PEB) and propylene homopolymer (PP) were prepared to give various rubber contents (4–20 wt %). By diluting the PEB with PP with molecular weight equal to that of the PEB matrix, molecular characteristics of all the blends were kept constant. The rubber particle size and size distribution of all the blends were almost constant, so that the interparticle distance decreased with increased rubber content. According to the observation of the fracture behavior at ?20°C, a brittle to ductile transition was found at the rubber content of 16 wt %. Microdeformation behavior of the blends was investigated in the region of brittle to ductile transition by using transmission electron microscopy. In the case of the brittle sample with low rubber content, crazing and voiding were observed. Whereas even in the ductile sample with high rubber content, crazing certainly took place before shear yielding. The origin of ductile fracture could possibly be attributed to the relaxation of strain constraint by the microvoids contained in the craze. © 1993 John Wiley & Sons, Inc.     

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.     

Deformation mechanisms in rubber toughened semicrystalline polyethylene terephthalate

The deformation mechanisms of rubber toughened polyethylene terephthalate (PET) are studied with fractography of impact fractured samples and tensile dilatometry. The dispersed phase consists of a mixture of an ethylene-co-propylene rubber (EPR) and a compatibilising agent (E-GMA8: copolymer of ethylene and 8 wt% of glycidyl methacrylate). It is found that the ductile fracture behaviour, above the brittle-ductile transition temperature (T_bd), consists of a high degree of rubber cavitation and extensive matrix shear yielding, both in the fracture plane and the stress whitened zone surrounding the crack. A steep increase in the volume strain upon tensile loading confirms the presence of the rubber voiding mechanism in the PET/(EPR/E-GMA8) blend system. It is seen that the stress whitened zone below the impact fracture surface consists of different zones, depending on the test temperature. Below T_bd, a layer of a highly deformed structure is followed by a cavitation layer containing only a limited number of cavitaties. Increasing the temperature, causes the deformation layer to be replaced by a zone lacking structure. It is believed that part of the fracture energy has been dissipated in the form of heat inducing a relaxation in the structure. Dynamical mechanical analysis under superimposed axial stresses reveals that the dispersed rubber particles internally cavitate in the presence of volume strain. At increased volume strains, the biaxial stress state in the cavitated particle is disturbed, resulting in the rupture of the rubber chains closest to the void by a tearing mechanism; revealing that the rubber particle is damaged upon cavitation.