Toughening performance of glass fibre composites with core–shell rubber and silica nanoparticle modified matrices

The fracture energies of glass fibre composites with an anhydride-cured epoxy matrix modified using core–shell rubber (CSR) particles and silica nanoparticles were investigated. The quasi-isotropic laminates with a central 0°/0° ply interface were produced using resin infusion. Mode I fracture tests were performed, and scanning electron microscopy of the fracture surfaces was used to identify the toughening mechanisms.The composite toughness at initiation increased approximately linearly with increasing particle concentration, from 328 J/m² for the control to 842 J/m² with 15 wt% of CSR particles. All of the CSR particles cavitated, giving increased toughness by plastic void growth and shear yielding. However, the toughness of the silica-modified epoxies is lower as the literature shows that only 14% of the silica nanoparticles undergo debonding and void growth. The size of CSR particles had no influence on the composite toughness. The propagation toughness was dominated by the fibre toughening mechanisms, but the composites achieved full toughness transfer from the bulk.     

Role of rigid nanoparticles and CTBN rubber in the toughening of epoxies with different cross-linking densities

Experimental investigations were conducted to characterize the fracture behaviours of Bisphenol A diglycidyl ether (DGEBA) epoxies modified with rigid nanoparticles (nanosilica or halloysite) and a reactive liquid carboxylterminated butadiene–acrylonitrile (CTBN) liquid rubber to identify toughening mechanisms and toughenability in the cured epoxies with different cross-linking densities. The epoxy was cured using three different hardeners, a heterocyclic amine (piperidine), a cycloaliphatic polyamine (Aradur 2954) and an aromatic amine [4,4′-Diaminodiphenyl sulfone (DDS)] to form nanocomposites with different cross-linking densities. It was found that both the hybrid particles, nanosilica with CTBN rubber and halloysite with CTBN rubber, were effective additives that clearly increased the fracture toughness of the three epoxy composites. In particular, the use of halloysite nanoparticles as additives for the epoxies showed greater potential than nanosilica to increase strength and modulus due to the reinforcing effect of the halloysite nanotubes (HNTs). The epoxy systems cured with the hardeners (Aradur 2954 and DDS), which generated relatively high cross-linking densities, evidenced inferior toughenability of the hybrid particles, compared with the epoxy systems cured using the hardener (piperidine), which produced lower cross-linking densities. The CTBN rubber formed dissimilar domains in different epoxy systems, features which were attributed to the different toughenability of the hybrid particles in the systems due to variations in the dominant toughening mechanisms involved.     

Improving interlaminar fracture toughness of carbon fibre/epoxy laminates by incorporation of nano-particles

Double-cantilever-beam tests were applied to investigate the mode I interlaminar fracture toughness of carbon fibre/epoxy laminates, in which the epoxy matrices were incorporated with rubber and silica nano-particles, either singly or jointly. It is shown that the toughness is improved owing to the presence of these nano-particles although nano-rubber is more effective than nano-silica. Further, by keeping the total particle weight percentage constant in epoxies (e.g., at 8 and 12 wt.%) filled with equal amount of nano-silica and nano-rubber, the interlaminar toughness values of the hybrid laminates are always higher than those with nano-silica filled epoxies but lower than those with nano-rubber filled matrices. Scanning electron microscopy examination of the delaminated surfaces of composite laminates filled with nano-particles revealed that cavitation of nano-rubber particles/void growth and debonding of nano-silica from epoxy matrix are responsible for the improved interlaminar toughness observed. It is also shown that the bulk toughness of nano-particle filled epoxies cannot be fully transferred to the interlaminar toughness of composite laminates, being limited by the constraint effect imposed by the carbon fibres. Finally, the role of fibre-bridging on the delaminated crack and hence delamination toughness is discussed.     

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.     

Fracture behaviour of unmodified and rubber-modified epoxies under hydrostatic pressure

The fracture toughness and uniaxial tensile yield strengths of unmodified and CTBN-rubber-modified epoxies were measured under hydrostatic pressure. The purpose of these experiments was to learn how suppressing cavitation in rubber particles affects the deformation mechanisms and the fracture toughness of rubber-modified epoxy. It was found that the cavitation of CTBN-rubber could be suppressed at a relatively low pressure (between 30 and 38 M Pa). With cavitation suppressed, the rubber particles are unable to induce massive shearyielding in the epoxy matrix, and the fracture toughness of the rubber-modified epoxy is no higher than that of the unmodified epoxy in the pressure range studied. Unmodified epoxy shows a brittle-to-ductile transition in fracture toughness test. The reason for this transition is the postponement of the cracking process by applied pressure.Work performed while on a sabbatical leave at the University of Michigan.     

The importance of constraint relief caused by rubber cavitation in the toughening of epoxy

Many rubber-toughened epoxies are thought to derive the bulk of their toughness through the processes of rubber cavitation and plastic shear-yielding in the epoxy matrix. Constraint relief has been considered to be a key mechanism which allows extra plastic shear deformation to occur. The present work attempts to provide direct experimental evidence of the constraint relief effect by combining testing geometries that vary the degree of constraint with microscopic observations. The results show that the success of a rubber as a toughening agent for epoxies is closely related to its ability to cavitate. Evidence for local constraint relief is presented. Upon cavitation of the rubber, the stress state in a specimen with initial constraint is found to change to a plane stress state. The constraint relief circumvents or delays the crack initiation in the matrix, which allows more plastic deformation to occur.     

Interlaminar fracture toughness and associated fracture behaviour of bead-filled epoxy/glass fibre hybrid composites

To investigate enhancement of matrix-dominated properties (such as interlaminar fracture toughness) of a composite laminate, two different bead-filled epoxies were used as matrices for the bead-filled epoxy/glass fibre hybrid composites. The plane strain fracture toughness of two different bead-filled epoxies have been measured using compact tension specimens. Significant increases in toughness were observed. Based on these results the interlaminar fracture toughness and fracture behaviour of hybrid composites, fabricated using bead-filled epoxy matrices, have been investigated using double cantilever beam and end notch flexure specimens for Mode I and Mode II tests, respectively. The hybrid composites based on carbon bead-filled matrix shows an increase in both G _IC initiation and G _IIC values as compared to a glass fibre reinforced plastic laminate with unmodified epoxy matrix. The optimum bead volume fraction for the hybrid composite is between 15% and 20%. However, the unmodified epoxy glass-fibre composite shows a higher G _IC propagation value than that of hybrid composites, due to fibre bridging, which is less pronounced in the hybrids as the presence of the beads results in a matrix-rich interply region.     

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.     

The toughness of epoxy polymers and fibre composites modified with rubber microparticles and silica nanoparticles

The present paper investigates the effect of adding silica nanoparticles to an anhydride-cured epoxy polymer in bulk and when used as the matrix of carbon- and glass-fibre reinforced composites. The formation of ‘hybrid’ epoxy polymers, containing both silica nanoparticles and carboxyl-terminated butadiene-acrylonitrile (CTBN) rubber microparticles, is also discussed. The structure/property relationships are considered, with an emphasis on the toughness and the toughening mechanisms. The fracture energy of the bulk epoxy polymer was increased from 77 to 212 J/m² by the presence of 20 wt% of silica nanoparticles. The observed toughening mechanisms that were operative were (a) plastic shear-yield bands, and (b) debonding of the matrix from the silica nanoparticles, followed by plastic void-growth of the epoxy. The largest increases in toughness observed were for the ‘hybrid’ materials. Here a maximum fracture energy of 965 J/m² was measured for a ‘hybrid’ epoxy polymer containing 9 wt% and 15 wt% of the rubber microparticles and silica nanoparticles, respectively. Most noteworthy was the observation that these increases in the toughness of the bulk polymers were found to be transferred to the fibre composites. Indeed, the interlaminar fracture energies for the fibre-composite materials were increased even further by a fibre-bridging toughening mechanism. The present work also extends an existing model to predict the toughening effect of the nanoparticles in a thermoset polymer. There was excellent agreement between the predictions and the experimental data for the epoxy containing the silica nanoparticles, and for epoxy polymers containing micrometre-sized glass particles. The latter, relatively large, glass particles were investigated to establish whether a ‘nano-effect’, with respect to increasing the toughness of the epoxy bulk polymers, did indeed exist.     

Fracture resistance of polyblends and polyblend matrix composites Part III Role of rubber type and location in nylon 6,6/SAN composites

The role of rubber particle type, location and morphology on toughening in blends of nylon 6,6 with styrene acrylonitrile (SAN), with and without fibre reinforcements was examined in this study. The rubber used was ethylene propylene diene monomer (EPDM) rubber and the results were compared to a previous study that used butadiene rubber. The compositions of the blends ranged from pure nylon 6,6 to pure SAN. EPDM rubber was chemically compatibilized with one of the matrix phases rather than grafted, as in the ABS. In order to study the effect of rubber location on fracture behaviour, the approach was to compatibilize EPDM with either the minor phase or the major phase component of the blend. Attention was focused on fracture initiation toughness and fracture propagation toughness, measured through the parameters J _IC and J _SS, respectively. J _SS refers to the steady-state, or plateau value of the material R-curve and was therefore a measure of total toughness which included the additional component derived from crack extension. The results indicated that EPDM rubber was not as effective a toughening agent as was butadiene in the Acrylonitrile Butadiene Styrene (ABS) system, primarily due to the morphology of EPDM and its interface character with the nylon 6,6 or SAN matrix. It was demonstrated that the embrittlement effects of a second rigid polymer phase can be mitigated by selectively adding rubber to that phase in the alloy or blend. With regard to the role of fibre reinforcement, a strong fibre matrix interface was found to be essential for toughening. Further, the extent of rubber toughening was larger when fibres were present than when fibres were absent, provided the fibre matrix interface was strong. Fibres also, like rubber, enhanced local matrix plasticity as well as reduced the embrittlement effects associated with a second polymer phase.     

热塑性树脂含量对CCF800H碳纤维环氧复合材料Ⅰ型层间断裂韧度的影响

采用国产CCF800H高强中模碳纤维增强环氧制备了复合材料,研究不同热塑性树脂含量对复合材料张开(Ⅰ)型层间断裂韧度的影响,研究表明:随着热塑组分含量的提高,复合材料的裂纹起始应变能量释放率(GⅠC-init)与裂纹稳态扩展应变能量释放率(GⅠC-prop)都获得了大幅度提升,在增韧组分质量分数大于20%时,增韧聚芳醚酰亚胺粉体可在复合材料层间富集形成层间高韧区,并在复合材料层间形成了由"连续相"和"分散相"组成的层间增韧结构。     

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.     

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.     

Improved fracture toughness and fatigue life of carbon fiber reinforced epoxy composite due to incorporation of rubber nanoparticles

In this study, core–shell rubber (CSR) nanoparticles with approximate particle size of 35 nm were used as a modifier for the epoxy polymer. The effects of various CSR contents in the epoxy matrix on mode I interlaminar fracture toughness, tensile strength, and fatigue life of the carbon fabric reinforced epoxy (CF/EP) composites were investigated. The experimental results showed that the mode I interlaminar fracture toughness at crack initiation and propagation significantly improved by 71.21 and 58.47 %, respectively, when 8.0 wt% CSR was dispersed in the epoxy matrix. The fatigue life of the modified CF/EP composites at all of CSR contents dramatically increased 75–100 times longer than that of the unmodified CF/EP composites at high cycle fatigue while tensile strength slightly increased by about 10 %. Field emission scanning electron microcopy (FESEM) observations of the fracture surfaces were conducted to explain failure mechanisms of CSR addition to the CF/EP composites. The evidences of the rubber nanoparticle debonding, plastic void growth, and microshear banding were credited for delaying the onset of matrix crack, and reducing the crack growth rate, as a result, attributed to increase in the mechanical properties of the CF/EP composites.     

Morphology and toughening mechanisms in clay-modified styrene-butadiene-styrene rubber-toughened polypropylene

Clay-modified styrene-butadiene-styrene (SBS) rubber is utilized to toughen polypropylene (PP). The SBS rubber is found to have good compatibility with clay particles. SBS rubber helps to finely disperse clay particles in PP matrix. Mode-I fracture mechanisms are investigated using optical microscopy and transmission electron microscopy techniques. Rubber particle cavitation and matrix shear yielding are found to be the main toughening mechanisms in PP/SBS system. In the case of PP/SBS/clay system, widespread rubber particle cavitation, which appears to be facilitated by the presence of clay particle inclusions inside the SBS rubber particles, takes place in the PP matrix. This, in turn, leads to the formation of a bigger shear yielded zone in PP matrix. As a result, an enhanced toughness is observed.     

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.     

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.     

Ultimate properties of rubber and core-shell modified epoxy matrices with different chain flexibilities

Preformed polystyrene-co-butylacrylate (PScoBu) core-shell particles and polystyrene microspheres as well as amine-terminated butadiene nitrile (ATBN) rubber have been used for modification of both rigid and more flexible crosslinked DGEBA-based epoxy networks having significantly different crosslink densities. Some variations in cure kinetics have been shown by both thermal and rheological measurements. Independently of the crosslink density of the neat epoxy matrix, function of the cycloaliphatic or aliphatic hardener used, the toughening effect via core-shell modification has been found as good as that for rubber modification but with a better retention of thermal properties. Results are investigated as a function of the morphologies obtained by scanning electron microscopy (SEM) but also by atomic force microscopy (AFM). Larger fracture toughness was obtained for every-unmodified and modified- epoxy matrices cured with the aliphatic hardener as a consequence of the lower crosslink density of the corresponding mixtures.     

Fracture toughness and fracture mechanisms of PBT/PC/IM blend

Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques were employed in the morphology and fracture mechanisms studies on a commercial polybutylene terephthalate/polycarbonate/impact modifier (PBT/PC/IM) blend. The fracture mechanisms involved at different temperatures under both impact and static loading were revealed. It was found that massive plastic deformation of the matrix material occurred after rubber particle cavitation; and it was this plastic deformation that was responsible for the drastic enhancement in fracture toughness although the widespread cavitation did absorb a considerable amount of energy as well. The major source of toughness was the same for both impact and static fracture tests, but the toughening processes became effective at a much lower temperature under static than impact conditions. The sequence of toughening events was also observed using TEM.     

Fracture resistance of polyblends and polyblend matrix composites: Part II Role of the rubber phase in Nylon 6,6/ABS alloys

A comprehensive study was undertaken on the specific role of rubber on toughening when other rigid polymer or non-polymer phases were present. Nylon 6,6/SAN blends of various SAN concentrations ranging from pure SAN to pure nylon 6,6 were investigated with and without fibre reinforcements. These results could be compared with the toughness values of unreinforced and fibre-reinforced nylon 6,6/ABS alloys from a previous study in order to elucidate the role of rubber. Fracture behaviour was investigated rigorously by characterizing the fracture initiation toughness, JIC, and the steady-state fracture toughness, Jss. These were then related to the microstructure and failure modes determined by microscopy and fractography methods. It was found that rubber increased both fracture initiation and propagation toughness in the presence of the rigid phase, while the rigid phase toughened the alloy only when the rigid phase/matrix interface was strong enough. The role played by glass fibres was found to be critically related to the fibre/matrix interfacial strength. Toughening was generally observed, both in the presence and absence of rubber, when the interface was strong. In all cases toughening could be related to the enhancement of plasticity in the crack tip by the presence of the rubber phase or the reinforcing glass phase. This revised version was published online in November 2006 with corrections to the Cover Date.