Shear ductility and toughenability study of highly cross-linked epoxy/polyethersulphone

The objective of the present study was to determine whether the ductility and toughenability of a highly cross-linked epoxy resin, which has a high glass transition temperature, T _g, can be enhanced by the incorporation of a ductile thermoplastic resin. Diglycidyl ether of bisphenol-A (DGEBA) cured by diamino diphenyl sulphone (DDS) was used as the base resin. Polyethersulphone (PES) was used as the thermoplastic modifier. Fracture toughness and shear ductility tests were performed to characterize the materials. The fracture toughness of the DDS-cured epoxy was not enhanced by simply adding PES. However, in the presence of rubber particles as a third component, the toughness of the PES–rubber-modified epoxy was found to improve with increasing PES content. The toughening mechanisms were determined to be rubber cavitation, followed by plastic deformation of the matrix resin. It was also determined, through uniaxial compression tests, that the shear ductility of the DDS-cured epoxy was enhanced by the incorporation of PES. These results imply that the intrinsic ductility, which had been enhanced by the PES addition, was only activated under the stress state change due to the cavitation of the rubber particles. The availability of increasing matrix ductility seems to be responsible for the increase in toughness. This revised version was published online in November 2006 with corrections to the Cover Date.     

Influence of particle size and particle size distribution on toughening mechanisms in rubber-modified epoxies

The principal toughening mechanism of a substantially toughened, rubber-modified epoxy has again been shown to involve internal cavitation of the rubber particles and the subsequent formation of shear bands. Additional evidence supporting this sequence of events which provides a significant amount of toughness enhancement, is presented. However, in addition to this well-known mechanism, more subtle toughening mechanisms have been found in this work. Evidence for such mechanisms as crack deflection and particle bridging is shown under certain circumstances in rubber-modified epoxies. The occurrence of these toughening mechanisms appears to have a particle size dependence. Relatively large particles provide only a modest increase in fracture toughness by a particle bridging/crack deflection mechanism. In contrast, smaller particles provide a significant increase in toughness by cavitation-induced shear banding. A critical, minimum diameter for particles which act as bridging particles exists and this critical diameter appears to scale with the properties of the neat epoxy. Bimodal mixtures of epoxies containing small and large particles are also examined and no synergistic effects are observed.     

Damage zone around crack tip and fracture toughness of rubber-modified epoxy resin under mixed-mode conditions

Damage zones that form around crack tips before the onset of fracture provide significant data for evaluating the fracture behavior of polymeric materials. The size of the damage zone correlates closely with the fracture toughness of the resin. In this study, we investigate the relationship between the fracture toughness and damage zone size around crack tips of a rubber-modified epoxy resin under mixed-mode conditions. The fracture toughness, G_C, based on the energy release rate, is measured using an end-notched circle type (ENC) specimen. The deformation of rubber particles in the damage zones is also observed using an optical microscope. The results show that the fracture toughness, G_C, of the rubber-modified epoxy resin is closely related to the area of the damage zone. In the specimen with a loading angle of 30°, the rubber particles were deformed ellipsoidally due to the difference between the first and second principal stresses.     

Low-temperature behaviour of epoxy-rubber particulate composites

Toughness and mechanical property data are presented for a carboxyl-terminated acrylonitrile butadiene (CTBN) rubber-modified epoxy resin in the temperature range 20 to – 110° C. A toughening model based on ultimate strain capability and tear energy dissipation of the rubber, present as dispersed microscopic particles in an epoxy matrix, is used to explain the suppression of composite toughness (G _Ic ) below – 20° C. The toughness loss is attributed to a glass transition in the rubber particles, and to a secondary transition in the epoxy resin, both occurring in the range – 40 to – 80° C. Strain-tofailure and modulus measurements on bulk rubber-epoxy compounds, formulated to simulate rubber particle compositions, confirm a decrease in rubber ductility coincident with the onset of composite toughness loss. An increase in rubber tear energy associated with its transition to a rigid state can explain the observation that even at low temperatures composite toughness generally remains significantly higher than that of pure epoxy. Although the low-temperature epoxy transition reduces molecular mobility in the matrix phase, residual ductility in, and energy dissipation by, the rubber particles determine the extent of composite toughness suppression. The low-temperature data bear out the particle stretching-tearing model for toughening.     

Fracture mechanism of toughened epoxy resin with bimodal rubber-particle size distribution

A bimodal rubber-particle distributed epoxy resin was made by simultaneous addition of two kinds of liquid rubbers, CTBN1300X9 and CTBN1300X13. These rubbers were added at a constant total rubber content but with varying weight ratios. The microstructure and fracture behaviour of these rubber-modified epoxy resins have been studied. A strong increase in the fracture resistance was found for the bimodal rubber-particle distributed epoxy resin. The role of the small particle is thought to toughen the shear bands between large particles. The role of large particle is thought to induce a large-scale shear deformation in the crack front. The synergistic effect of these particles gives rise to a strong increase in the toughness of these bimodal rubber-particle distributed epoxy systems.     

Toughening mechanism for a rubber-toughened epoxy resin with rubber/matrix interfacial modification

For a rubber-toughened piperidine-DGEBA epoxy resin, the interface between the rubber particle and the epoxy resin matrix was modified by an epoxide end-capped carboxyl terminated butadiene and acrylonitrile random copolymer (CTBN). The end-capping epoxides used were a rigid diglycidyl ether of bisphenol-A (Epon 828), a short-chain flexible diglycidyl ether of propylene glycol (DER 736), and a long-chain flexible diglycidyl ether of propylene glycol (DER 732). The microstructures and the fracture behaviour of these rubber-modified epoxy resins were studied by transmission electron microscopy and scanning electron microscopy. Their thermal and mechanical properties were also investigated. In the rubber-modified epoxy resins, if the added CTBNs were end-capped by a flexible diglycidyl ether of propylene glycol (DER 732 or DER 736) before curing, the interfacial zone of the undeformed rubber particle, the degree of cavitation of the cavitated rubber particle on the fracture surface and the fracture energy of the toughened epoxy resin were all significantly increased. The toughening mechanism based on cavitation and localized shear yielding was considered and a mechanism for the interaction between cavitation and localized shear yielding that accounts for all the observed characteristics is proposed.     

Fatigue of rubber-modified epoxies: effect of particle size and volume fraction

A change in crack-tip plastic zone/rubber particle interactions induces a transition in the fatigue crack propagation (FCP) behaviour of rubber-modified epoxy polymers. The transition occurs at a specific K level, K _T, which corresponds to the condition where the size of the plastic zone is of the order of the size of the rubber particles. At K>K _T, rubber-modified epoxies exhibit improved FCP resistance compared to the unmodified epoxy. This is because the size of the plastic zone becomes large compared to the size of the rubber particles and, consequently, rubber cavitation/shear banding and plastic void growth mechanisms become active. At K>K _T, both neat and rubber-modified epoxies exhibit similar FCP resistance because the plastic zone size is smaller than the size of the rubber particles and hence, the rubber cavitation/shear banding and plastic void growth mechanisms are not operating. As a result of these interactions, the use of smaller 0.2 m rubber particles in place of 1.5 m rubber particles results in about one order of magnitude improvement in FCP resistance of the rubber-modified system, particularly near the threshold regime. Such mechanistic understanding of FCP behaviour was employed to model the FCP behaviour of rubber-modified epoxies. It is shown that the near threshold FCP behaviour is affected by the rubber particle size and blend morphology but not by the volume fraction of the modifiers. On the other hand, the slope of the Paris-Erdogan power law depends on the volume fraction of the modifiers and not on the particle size or blend morphology.     

Possible phase transformation toughening of thermoset polymers by poly(butylene terephthalate)

Mechanisms were explored by which particles of poly(butylene terephthalate) (PBT) are able to toughen a brittle epoxy. The epoxy studied was an aromatic amine-cured diglycidyl ether of bisphenol-A, which was toughened at about twice the rate with particles of poly(butylene terephthalate) as with particles of nylon 6, poly(vinylidene fluoride), or CTBN rubber. Many of the mechanisms of toughening are visible on the fracture surface of the PBT-epoxy blend, but a mechanism suggested to account for perhaps half of the increased toughness with PBT, phase transformation toughening, is not. The two types of experiment performed to detect phase transformation toughening were: (1) measurements of the rubber cavitation zone in PBT-CTBN rubber-epoxy ternary blends, which would detect an expansion of the PBT particles during fracture if it occurred, and (2) measurements of the fracture energy in PBT-epoxy blends in which the various mechanisms of toughening were selectively suppressed. Both types of experiment indicated the occurrence of phase transformation toughening in these PBT-epoxy blends.     

Comparison of failure mechanisms between rubber-modified and unmodified epoxy adhesives under mode II loading condition

The effect of rubber modification on fracture toughness of adhesive joints under mode II loading condition was investigated in comparison with that under mode I loading, wherein the two adhesives rubber-modified and unmodified were used. To evaluate the fracture toughness on the basis of R-curve characteristics under mode II loading condition, four-point bend tests had been conducted for the adhesively bonded end-notched flexure (ENF) specimens. Thus obtained R-curves revealed the following trend: its behavior did not appear for the unmodified adhesive, whereas the rubber-modified adhesive exhibited a typical behavior. In the initial stage of crack propagation, G _IIC of the rubber-modified adhesive is lower than that of the unmodified adhesive, but becomes greater in the range of Δa > 25 mm. Nevertheless, the significant improvement of the fracture toughness with the rubber modification under mode I loading condition was not observed under mode II loading. Moreover, FEM analysis was made to elucidate the relation between the above fracture behavior and stress distributions near the crack tip. The results gave the reasonable relationship between evolution of plastic zone and the area with high void-fraction as well as the R-curves behavior. In addition, macroscopic and SEM observations for the fracture surfaces were also conducted.     

Failure mechanisms in toughened epoxy resins—A review

The subject of improving the fracture toughness of brittle epoxy resins is receiving significant attention in order to improve the design strain of fiber-reinforced composites for aerospace structural applications. Various rubber-modified and particle-filled epoxy resins have been considered as candidate materials. Such modified resins have been observed to yield a ten- to thirty-fold increase in fracture toughness compared to the unmodified material. In order fully to utilize the potential of such materials, it is necessary to understand the failure mechanisms leading to the improvement in toughness. This paper provides a critical review of the existing theories that have been proposed for the various toughening mechanisms related to modified epoxy resins.     

Modes of deformation in rubber-modified thermoplastics during tensile impact

Real-time small-angle X-ray scattering (RTSAXS) studies were performed on a series of rubber-modified thermoplastics. Scattering patterns were measured at successive time intervals as short as 1.8 ms and were analysed to determine the plastic strain due to crazing. Simultaneous measurements of the absorption of the primary beam by the sample allowed the total plastic strain to be computed. The plastic strain due to other deformation mechanisms, e.g. particle cavitation and macroscopic shear deformation was determined by the difference. Samples of commercial thicknesses can be studied at high rates of deformation without the inherent limitations of microscopy and its requirement of thin samples (i.e., plane strain constraint is maintained on sample morphology). Contrary to the conclusions drawn from many previous dilatation-based studies, it has been demonstrated that the strain due to non-crazing mechanisms, such as rubber particle cavitation, and deformation of the glassy ligaments between rubber particles, occurs before that due to crazing mechanisms. Crazing accounts for at most only half of the total plastic strain in HIPS (high impact polystyrene) and ABS (rubber-modified styrene-acrylonitrile copolymer) materials. The proportion of strain attributable to crazing can be much less than half the total in thermoplastic systems with considerable shear yield during plastic deformation. The predominant deformation mechanism in polycarbonate-ABS blends is shear in the PC (polycarbonate) with associated rubber gel particle cavitation in the ABS. This cavitation means that there appears to be a direct relationship between gel particle rubber content in the ABS and toughness of the blend. The mechanism is the same whether the tensile stress is in the direction parallel or perpendicular to the injection-moulded orientation, with simply less total strain being reached before fracture in the weaker perpendicular direction. Crazing, although the precursor to final fracture, occurs after the predominant mechanism and contributes only a few per cent to the total plastic deformation.     

Mechanical properties and fracture behaviors of epoxy composites with multi-scale rubber particles

In this work, we developed a strategy to balance the toughness and thermal resistance of epoxy composites by incorporating the multi-scale rubber particles. Two types of rubber i.e. the phase-separation-formed submicron liquid rubber (LR) and preformed nano-scale powered rubber (PR) particles were chosen as tougheners. It was found that the combination of these multi-scale rubber particles not only provides superior efficiency in enhancing the impact resistance of epoxy composites, but also results in balanced glass transition temperature. In particular, the highest gain in impact strength was obtained for the ternary composites containing 9.2 wt% submicron liquid rubber and 9.2 wt% nano-sized powered rubber which were ∼112% higher than the maximum enhancements of ∼49% and ∼66% for the corresponding binary composite systems with the single-phase rubber, respectively. The damage zone observation and fracture surface analysis suggested that the combined use of multi-scale particles was effective to promote matrix plastic deformation including void growth and shear banding induced by the improved rubber cavitation/debonding, which is likely responsible for the highly improved impact resistance of the ternary composites.     

Dilatational bands in rubber-toughened polymers

A theory is advanced to explain the effects of rubber particle cavitation upon the deformation and fracture of rubber-modified plastics. The criteria for cavitation in triaxially-stressed particles are first analysed using an energy-balance approach. It is shown that the volume strain in a rubber particle, its diameter and the shear modulus of the rubber are all important in determining whether void formation occurs. The effects of rubber particle cavitation on shear yielding are then discussed in the light of earlier theories of dilatational band formation in metals. A model proposed by Berg, and later developed by Gurson, is adapted to include the effects of mean stress on yielding and applied to toughened plastics. The model predicts the formation of cavitated shear bands (dilatational bands) at angles to the tensile axis that are determined by the current effective void content of the material. Band angles are calculated on the assumption that all of the rubber particles in a band undergo cavitation and the effective void content is equal to the particle volume fraction. The results are in satisfactory agreement with observations recorded in the literature on toughened plastics. The theory accounts for observed changes in the kinetics of tensile deformation in toughened nylon following cavitation and explains the effects of particle size and rubber modulus on the brittle-tough transition temperature.     

Toughening mechanisms of modified unsaturated polyester with novel liquid Polyurethane rubber

Unsaturated polyester (UPE) has been toughened by incorporating novel liquid polyurethane (PU) rubber. PU rubber was synthesized using toluene di-isocyanate and polyols such as poly (propylene glycol) and poly (tetramethylene ether) glycoi, whose molecular weights vary from 650 to 4000. Particle size was varied from 0.1 to 3 m by changing the polyol and the molecular weight of PU rubber, and the effects of particle size on the fracture toughness of PU rubber-modified UPE were investigated. Hydroxyl terminated PU rubber (HTPU) and isocyanate terminated PU rubber (ITPU) were used to study the effects of rubber-matrix adhesion. The toughening mechanisms observed by scanning electron microscope are debonding between rubber and matrix in HTPU-modified UPE, and cavitation in the rubber particle in ITPU-modified UPE. However, shear bands were not observed as UPE is a highly cross-linked thermoset with very short chain length between the cross-links. A 1.9-times increase in fracture toughness of UPE was achieved with the formation of cavitated particles. In order to measure the process zone size at the crack tip, the thin sections of tested double-notched four-point bending specimens were examined by optical microscope.     

Numerical and experimental studies on the fracture behavior of rubber-toughened epoxy in bulk specimen and laminated composites

To study the toughening mechanisms of liquid rubber (LR) and core-shell rubber (CSR) in bulk epoxy and composite laminate, experimental and numerical investigations were carried out on compact tension (CT) and double-cantilever-beam (DCB) specimens under mode-I loading. The matrix materials were pure epoxy (DGEBA), 15% LR (CTBN) and 15% CSR modified epoxies. Experimental results and numerical analyses showed that both liquid rubber (LR) and core-shell rubber (CSR) could improve significantly the fracture toughness of pure epoxy (DGEBA). However, the high toughness of these toughened epoxies could not be completely transferred to the interlaminar fracture toughness of the unidirectional carbon fibre reinforced laminate. The main toughening mechanism of CSR in bulk epoxy was the extensive particle cavitation, which greatly released the crack-tip triaxiality and promoted matrix shear plasticity. The poor toughness behavior of CSR in the carbon fibre laminate was thought to be caused by the high constraint imposed by the stiff fibre layers. No particle cavitation had been observed in LR modified epoxy and the main toughening mechanism was merely the large plastic deformation near the crack-tip due to the rubber domains in the matrix which results in a lower yield strength but a higher elongation-to-break.     

Three-dimensional elastoplastic finite element modelling of deformation and fracture behaviour of rubber-modified polycarbonates at different triaxiality

A periodic face-centred cuboidal cell model is provided to account for inter-particle interaction, and a particle-crack tip interaction model is developed to study the interaction between a blunting model I crack tip and the closest array of initially spherical rubber particles in an effective medium. Three-dimensional elastoplastic finite element analysis has been preformed to study the deformation and fracture behaviour of rubber-modified polycarbonates. The effective elastoplastic constitutive relation is derived by the method of homogenisation and local stress and strain distributions are obtained to explore the role of rubber cavitation in the toughening process at different stress triaxiality. 3D elastoplastic finite element results are compatible with experimental observations, that is, rubber particles can act as stress concentrators to initiate crazing or shear yielding in the matrix but they behave differently from voids at high triaxiality. Rubber cavitation plays an important role in the toughening process under high tensile triaxial stresses.     

Effect of hybridization of liquid rubber and nanosilica particles on the morphology, mechanical properties, and fracture toughness of epoxy composites

A liquid carboxyl-terminated butadiene–acrylonitrile copolymer (CTBN) and SiO₂ particles in nanosize were used to modify epoxy, and binary CTBN/epoxy composites and ternary CTBN/SiO₂/epoxy composites were prepared using piperidine as curing agent. The morphologies of the composites were observed by scanning electron microscope (SEM) and transmission electron microscope (TEM), and it is indicated that the size of CTBN particles increases with CTBN content in the binary composites, however, the CTBN particle size decreases with the content of nanosilica in the ternary composites. The effects of CTBN and nanosilica particles on the mechanical and fracture toughness of the composites were also investigated, it is shown that the tensile mechanical properties of the binary CTBN-modified epoxy composites can be further improved by addition of nanosilica particles, moreover, obvious improvement in fracture toughness of epoxy can be achieved by hybridization of liquid CTBN rubber and nanosilica particles. The morphologies of the fractured surface of the composites in compact tension tests were explored attentively by field emission SEM (FE-SEM), it is found that different zones (pre-crack, stable crack propagation, and fast crack zones) on the fractured surface can be obviously discriminated, and the toughening mechanism is mainly related to the stable crack propagation zone. The cavitation of the rubber particles and subsequent void growth by matrix shear deformation are the main toughening mechanisms in both binary and ternary composites.     

Influence of stress state and strain rate on the behaviour of a rubber-particle reinforced polypropylene

This article presents an experimental investigation of a ductile rubber-modified polypropylene. The behaviour of the material is investigated by performing tension, shear and compression tests at quasi-static and dynamic strain rates. Subsequently, scanning electron microscopy is used to analyse the fracture surfaces of the tension test samples, and to relate the observed mechanical response to the evolution of the microstructure. The experimental study shows that the material is highly pressure and strain-rate sensitive. It also exhibits significant volume change, which is mainly ascribed to a cavitation process which appears during tensile deformation. Assuming matrix-particle debonding immediately after yielding, the rubber particles might play the role of initial cavities. It is further found that the flow stress level is highly dependent on the strain rate, and that the rate sensitivity seems to be slightly more pronounced in shear than in tension and compression. From the study of the fracture surfaces it appears that the fracture process is less ductile at high strain rates than under quasi-static conditions.     

Impact properties of epoxy polymers

Instrumented impact tests havé been conducted on both a simple unmodified and a rubber-modified epoxy polymer over a range of impact velocities. Single-edge notched three-point bend and double-edge notched tensile specimens have been employed and, from the measured force-time response, values of the fracture energy,G _lc, and the fracture toughness,K _lc, have been determined and shown to be independent of the geometry of the test specimen. However, the measured value of the toughness is found to be dependent upon the impact velocity of the pendulum striker and this dependence appears to largely arise from dynamic effects present in the test technique. The nature of these effects are discussed and modelled and the hue material impact resistance of the epoxy polymers determined. These studies clearly reveal that the multiphase microstructure of the rubber-modified epoxy leads to a significant improvement in the impact behaviour of cross-linked epoxy polymers.     

Toughening of epoxy using core–shell particles

An epoxy resin, cured using an anhydride hardener, has been modified by the addition of preformed core–shell rubber (CSR) particles which were approximately 100 or 300 nm in diameter. The glass transition temperature, T _g, of the cured epoxy polymer was 145 °C. Microscopy showed that the CSR particles were well dispersed through the epoxy matrix. The Young’s modulus and tensile strength were reduced, and the glass transition temperature of the epoxy was unchanged by the addition of the CSR particles. The fracture energy increased from 77 J/m² for the unmodified epoxy to 840 J/m² for the epoxy with 15 wt% of 100-nm diameter CSR particles. The measured fracture energies were compared to those using a similar amount of carboxyl-terminated butadiene-acrylonitrile (CTBN) rubber. The CTBN particles provided a larger toughening effect when compared to CSR particles, but reduced the glass transition temperature of the epoxy. For the CSR-modified epoxies, the toughening mechanisms were identified using scanning electron microscopy of the fracture surfaces. Debonding of the cores of the CSR particles from the shells was observed, accompanied by plastic void growth of the epoxy and shell. The observed mechanisms of shear band yielding and plastic void growth were modelled using the Hsieh et al. approach (J Mater Sci 45:1193–1210). Excellent agreement between the experimental and the predicted fracture energies was found. This analysis showed that the major toughening mechanism, responsible for 80–90% of the increase in fracture energy, was the plastic void growth.