Crazing and shear deformation in glass bead-filled glassy polymers

The competition between craze formation and shear band formation at small glass beads embedded in matrices of glassy polymers has been investigated. This has been done by performing constant strain rate tensile tests over a wide range of strain rates and temperatures, and examining the deformation pattern formed at the beads with a light microscope. The glassy polymers under investigation were polystyrene, polycarbonate, and two types of styrene—acrylonitrile copolymer. It was found that besides matrix properties, strain rate and temperature, the degree of interfacial adhesion between the glass beads and the matrix also has a profound effect on the competition between craze and shear band formation: at excellently adhering beads craze formation is favoured, whereas at poorly adhering beads shear band formation is favoured. This effect is caused by the difference in local stress situation, craze formation being favoured under a triaxial stress state and shear band formation under a biaxial stress state. The kinetics of crazing and shear deformation have also been studied, using a simple model and Eyring's rate theory of plastic deformation. The results suggest that chain scission may be the rate-determining step in crazing but not in shear deformation.     

Craze yielding and fracture mechanism in PE/PS/PE laminated films

The change in polystyrene (PS) layer thickness, which has been simultaneously determined during post-yield deformation, shows that crazing is the basic mechanism of toughening in all laminated films, and that shear deformation supplements the contribution of crazing especially for samples with high polyethylene (PE) volume fractions. Crazes formed in PS layers in the laminated films are slender and regular compared with the short and lenticular crazes formed in bulk PS film. When PE volume fraction increased, craze advance speed decreased because of the reduction of the stress concentration effect at craze tips. The life-time of the first mature craze to be formed at a given strain rate increased with PE volume fraction because the PE supporting the mature crazes could effectively inhibit craze rupture and blunt out the propagating crack by absorbing the stored elastic energy in the PS layer that would have been dissipated as fracture surface energy.     

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

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

Crazing mechanisms and craze healing in glassy polymers

When held at temperatures above the glass transition temperature, crazes in certain polymers may be made to heal; that is, the crazed material may be made to recover the mechanical properties it had prior to crazing. Using thin films of a variety of polymers, we have investigated whether the mechanism of entanglement loss during crazing influences the heat treatment time necessary for healing. We find that under experimental conditions for which there is evidence of disentanglement during crazing, and if the crazes do not break down, healing occurs after heat treatment times of the order of those necessary to make the craze disappear optically. Similar heat treatments applied to scission mediated crazes however, do not result in healing. We argue that scission crazing results in a high proportion of chain fragments which are unable to contribute to the entanglement network. Since the heat treatments are not sufficiently long to disperse these fragments, and hence to restore the original local entanglement density, healing does not take place. Disentanglement should not result in such damage, so, consistent with our observations, healing times should be relatively short. Hence, these results provide independent evidence for disentanglement during crazing.     

The structure of solvent crazes in polystyrene

The structure of crazes grown in polystyrene (PS) immersed inn-heptane and methanol at room temperature has been determined using refractive index measurements, transmission electron microscopy, and fractographic analysis of craze fracture surfaces.n-heptane crazes in thin films exhibit a low number density of thick, load-bearing fibrils whereas methanol crazes consist of a highly interconnected network of fibrils not unlike the craze structure found in crazes grown in air. A row of large voids at the centre line of the craze which is typical of the structure observed in air crazes is not found, however, in either methanol orn-heptane crazes, indicating a different growth mechanism for the solvent crazes. The craze structure found in thin films is in agreement with the void contents determined from refractive index measurements and with the results from scanning electron microscopy of fracture surfaces of bulk crazes grown with methanol andn-heptane. Glass transition temperature measurements of equilibrium swollen PS films giveT _g=91° C for methanol andT _g=6° C forn-heptane. The results suggest that the structure of crazes grown with slowly diffusing crazing agents (methanol andn-heptane) is strongly dependent on whether the growth temperature is above or belowT _g, the glass transition temperature of the plasticized region just ahead of, and in, the craze. IfT _g is below the growth temperature, weak crazes are formed with a large void content. During the growth, thin fibrils break by viscous flow leaving only a small number of load-bearing fibrils. The stress in the neighbourhood of the growing craze is strongly relieved favouring propagation of a single craze. IfT _g is above the growth te'mperature, strong crazes are formed with the fibrils strain-hardened during the growth process. There is hardly any change in stress next to the craze and therefore multiple crazing (craze bundles) is favoured over the propagation of a single craze.     

Crazing behaviour in oriented poly(ethylene terephthalate)

A study has been made of the two types of crazes formed in oriented sheets of poly(ethylene terephthalate). The crazes have been termed tensile crazes and shear crazes. The tensile crazes formed parallel to the initial draw direction (IDD) whereas the shear crazes formed in a direction close to that of the deformation bands observed when the material yields.The possibility of applying a yield criterion to shear craze formation has been examined and there appears to be fairly good agreement between theory and experiment. Measurements of crazing stress on the tensile crazes indicated that the criterion for tensile craze formation is not purely dependent on the component of stress normal to the extended chains.It is concluded that the two types of crazes are formed by two quite different mechanisms, although the exact nature of these mechanisms is still uncertain.     

Shear and craze development in the fatigue of ductile amorphous polymers

The competitive interplay between shear and craze deformation in the fatigue of ductile amorphous polymers leads to the formation of intricate fatigue crack shapes and stable crack growth. The craze/shear dual deformation mode is expressed in a unique crack tip plastic zone, which has been observed in polycarbonate, polysulfone, a polyarylate block copolymer and a polyestercarbonate copolymer. The fatigue crack growth resistance in these polymers is high, and factors which affect the relative ease of shear flow and crazing are expected to affect their fatigue endurance.     

The effect of cross-linking on crazing in polyethersulphone

Cross-links have been introduced into thin films of PES (polyethersulphone)/1 wt% sulphur by heating them in air at 350 °C. The effect of this is to suppress crazing in favour of shear deformation in high-temperature regimes where disentanglement crazing dominates for uncross-linked films of the same composition. We argue that light cross-linking (one or two cross-links per chain) is sufficient to give rise to a finite gel fraction in the films which, because it effectively forms an infinite network, cannot disentangle. Thus for crazing to occur, chains which form part of the gel fraction must always break rather than disentangle. This has the effect of raising the crazing stress relative to the yield stress in the weakly temperaturedependent regime of crazing at high temperature, where disentanglement is normally considered sufficiently rapid for entanglement loss not to contribute to the crazing stress. Hence as the gel fraction is increased by increasing the heat-treatment time, crazing is suppressed at the highest temperatures with respect to shear deformation, leading to a second transition, this time from crazing back to shear.     

Ductility of polylactide composites reinforced with poly(butylene succinate) nanofibers

Sustainable “green nanocomposites” of polylactide (PLA) and poly(1,4-butylene succinate) (PBS) were obtained by slit die extrusion at low temperature. Dispersed PBS inclusions were sheared and longitudinally deformed with simultaneous cooling in a slot capillary and PBS nanofibers were formed. Shearing of PBS increases nonisothermal crystallization temperature by 30 °C. Tensile deformation was investigated by in-situ experiments in SEM chamber. Dominant deformation mechanism of PLA is crazing, however, there are dormant shear bands formed during slit die extrusion. Pre-existing shear bands are inactive in tensile deformation but contribute to ductility by blocking, initiating and diffusing typical craze growth. PBS nanofibers are spanning PLA craze surfaces and bridging craze gaps when PLA nanofibrils broke at large strain. Straight crazes become undulated because either dormant or new shear bands become activated between crazes. Due to interaction of crazes and shear bands the ductility increases while high strength and stiffness are retained.     

Similarity between craze morphology and shear-band morphology in polystyrene

The formation of shear bands and crazes in thin films as well as in bulk samples of polystyrene were examined in the electron microscope using a variety of replication techniques. The morphologies of shear bands and crazes are quite similar both depending initially upon the relative shear displacement of 400 to 1000 Å domains. As deformation continues and orientation increases, fibrils varying from 50 to 700 Å are formed within the deformation zone, lateral constraint of the normal Poisson contraction causing voids to form in the crazes but not in the shear bands. Shear-band width was found not to be a unique function of either temperature or strain-rate and both craze and shear-band morphologies were found not to be strong functions of molecular weight. Regardless of molecular weight, fibrils formed within the deformation zone were always on the order of a few hundred Angstroms in diameter. However, for thin films of molecular weight less than 20 000 insufficient numbers of tie molecules between fundamental structural units or domains made it difficult for these fibres to span the craze width.     

Interaction of crazes with pre-existing shear bands in glassy polymers

Shear bands have been grown in bulk specimens of P₃O(poly 2,6 diphenyl 1,4 phenylene oxide) and in thin films of two blends of polystyrene with poly(xylenyl ether). The subsequent interaction of crazes with these shear bands has been characterized by transmission electron microscopy. For the case of shear bands grown under the plane stress conditions of thin films, it is found that the bands act as preferential sites for craze nucleation. A fairly regularly-spaced array of short crazes grows within the shear bands and these crazes may thicken sufficiently to coalesce. When the crazes reach the end of the shear band they emerge and propagate into the unoriented polymer matrix. Within the shear band the craze growth direction does not lie normal to the tensile axis, but is rotated due to the molecular orientation of the shear band. The direction of craze growth is also affected under the plane strain conditions of bulk specimens. In this case the craze is diverted along the shear band before re-emerging into the matrix. Measurements of the craze fibril extension ratio, , within the shear band show an increase over typical values obtained outside the shear band in the same polymer. This high value of leads to an increased likelihood of craze break-down and crack nucleation within the shear band.     

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.     

The effect of temperature on crazing mechanisms in polystyrene

At room temperature scission is the dominant mechanism for the modification of the entanglement network required for craze formation in polystyrene, but as the temperature is increased towardsT _g, there is the possibility that disentanglement processes may contribute. These will be most important for short chains. If disentanglement can occur, a molecular weight dependence of the crazing stress as a function of temperature will result. This prediction is tested by straining thin films of a range of monodisperse samples of polystyrene at temperatures between 40 and 90° C. The nature of the ensuing deformation has been characterized by transmission electron microscopy. It is observed that whereas only crazing occurs over the entire temperature range for the lowest molecular weight sample, shear processes become important for higher molecular weight materials. For the longest chains, crazing is almost entirely suppressed at 80° C, with the preferential formation of shear deformation zones occurring. These observations are consistent with the idea that disentanglement is playing a significant role in craze formation at sufficiently high temperatures.     

Microstructure and origin of cross-tie fibrils in crazes

Crazes were grown in thin films of polystyrene (PS) at various temperatures and the resulting craze fibril microstructures were examined using low-angle electron diffraction (LAED). A quasi-regular array of cross-tie fibrils pull the main fibrils away from the tensile axis by an angle ± /2°. As a result, the LAED patterns from crazes grown at temperatures T<50°C exhibited split diffraction lobes centred about the equatorial axis of the LAED pattern. It was found that decreased with increasing crazing temperature and that the split lobes could no longer be resolved at the highest temperatures. Diffuse meridional diffraction spots due to scattering from the quasi-regular array of cross-tie fibrils were seen in the LAED patterns from crazes grown at low temperatures. The spacing of the cross-tie fibrils, R, determined from these patterns, was found to increase with the crazing temperature. A new model of craze widening was proposed that accounts for the formation of cross-tie fibrils by allowing some of the entangled polymer strands which bridge two fibrils in the active zone to survive fibrillation. Cross-tie fibrils are created when several such strands pile up locally, and the craze/bulk interface bypasses the pile-up.     

The effect of specimen size on the mechanical behaviour associated with crazing

Since crazes generally nucleate at the surface it is expected that the size of the specimen, as described by the ratio of surface area to volume, should affect the mechanical behaviour of polymers which deform primarily by crazing. The stress relaxation curves and the stress-strain curves of PS, PMMA, PTFE, and PC were measured in liquid nitrogen for specimens of different size which were machined from the same rod. The predicted size effect was observed in that the smaller (6.4mm diameter) specimens stress-relaxed faster and the stress to produce a given amount of craze deformation was lower than for the larger (12.7 mm diameter) specimens. The range of the tensile strength from 0 to size is also presented based on the stress to nucleate the first craze and on the tensile strength that is observed when no crazing occurs     

Three-dimensional interaction of crazes and micro-shearbands in PC-SAN microlayer composites

The three-dimensional interaction of crazes and micro-shearbands in co-extruded microlayer sheets with 49 alternating layers of polycarbonate (PC) and styrene-acrylonitrile copolymer (SAN) was investigated as a function of the relative layer thickness. The deformation processes were observed when microspecimens were deformed under an optical microscope. Deformed specimens were sectioned and examined further in the transmission electron microscope. Two types of craze were observed in the SAN layers: surface crazes initiated at a strain of about 1.8% and gradually lengthened to a maximum of 70 m when they were arrested by micro-shearbands at 4.2% strain, while tunnel crazes appeared above 4.2% strain and rapidly grew through the entire SAN layer. Surface crazes did not prevent yielding and stable neck propagation, while tunnel crazes were responsible for fracture prior to neck formation. The density of surface crazes relative to tunnel crazes increased as the PC-SAN ratio increased or as the strain rate decreased. The surface crazes stimulated micro-shearbanding in both PC and SAN layers. After micro-shearbands initiated in the PC layers where the craze impinged on the PC-SAN interface, they propagated rapidly along the edges of the craze. As they overtook the craze tip, the micro-shearbands penetrated through the PC-SAN interface and continued around the craze tip to entirely engulf the craze. This terminated craze growth, and further strain in the SAN layer was accommodated by shear deformation.     

Methanol crazing of coarse shear bands in polystyrene

A specimen with coarse shear bands produced at stress concentrations by compression was immersed in methanol to observe craze formation. Thin crazes were initiated at shear bands and joined together while propagating to form thick crazes. Crazes were formed only on the tension side of shear bands with the craze planes perpendicular to the shear bands. When a craze propagated through a shear band, each displaced the other at intersections. Some secondary shear bands were transformed partly into crazes resulting in about a factor of ten increase in thickness. This transformation was achieved by a tensile deformation of fibrous sheets in the shear band with simultaneous production of fine fibres.     

Correlation between craze formation and mechanical behaviour of amorphous polymers

The formation, growth and fracture of crazes have been studied for several amorphous polymers (PS, PMMA, SAN, NEC, PC). From bulk polymeric materials 0.5 to 5m thick sections were prepared and investigated after uniaxial deformation or duringin situ deformation in a 1000 kV high voltage electron microscope (HVEM). The use of the HVEM also allows one to study irradiation-sensitive polymers (PMMA and PC). The size of crazes (length and thickness), the shape (opening angle at the craze tip, craze thickness profile), the thickness of a pre-craze zone, the structure of the material inside the craze (fibrillar or more homogeneous), and the degree of deformation were measured. Correlations have been found between the type and the size of crazes and their mechanical properties, particularly fracture toughness and elongation at break. There are notable differences between unannealed and annealed samples (SAN and PC) as well as in the craze formation and in the fracture toughness.     

Rubber-toughening of plastics

Mechanisms of deformation in an ABS emulsion polymer were studied quantitatively by a uniaxial tensile creep method. Craze formation was measured in terms of volume strain, which was calculated from simultaneous observations of longitudinal and lateral strains, and shear deformation was measured in terms of lateral strain. The experiments showed that shear deformation predominated during the early stages of creep, but that the rate of shear deformation fell with time. At stresses below 27 MN m⁻², specimens reached extensions of 5% without significant craze formation: at higher stresses, crazing was observed at strains above about 21/2%. Rates of crazing increased with time and with stress, so that the contribution of crazing to creep was greatest during the later stages of the test, and at the higher stresses. The relevance of these results to engineering applications of ABS polymers is discussed.