A study of polymer fracture surface features and their relationship to toughness

The aim of this study was to research fracture surface features for polymers of different toughness and type. The materials chosen provided for an interesting comparison of fracture surfaces. Two brittle amorphous thermoplastics (SAN & PMMA) of the same toughness had very different fracture surfaces. An amorphous thermoplastic (PC) exhibited similar features as both SAN and PMMA but had a higher toughness. Two semi-crystalline thermoplastics (PE1 & PE2) had similar fracture surface features but one was twice the toughness of the other. A rubber toughened polymer (ABS) showed a very different fracture surface to SAN (the host material) and all the other polymers studied. A particular interest was to use the comparison of the fracture surfaces of the above materials to investigate the toughening effects of rubber particles in ABS.     

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.     

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.     

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.     

On fracture toughness of nano-particle modified epoxy

A systematic study on the effects of silica and rubber nano-particles on the fracture toughness behavior of epoxy was conducted. Mode I fracture toughness (G_IC) of binary silica/epoxy, binary rubber/epoxy and ternary silica/rubber/epoxy nanocomposites with different particle weight fractions was obtained by compact tension tests. It is found that G_IC of epoxy can be significantly increased by incorporating either rubber or silica nano-particles. However, hybrid nanocomposites do not display any “synergistic” effect on toughness. Microstructures before and after fracture testing were examined to understand the role of nano-particles on the toughening mechanisms.     

The microstructure and fracture performance of styrene–butadiene–methylmethacrylate block copolymer-modified epoxy polymers

The microstructure and fracture performance of an anhydride-cured epoxy polymer modified with two poly(styrene)-b-1,4-poly(butadiene)-b-poly(methyl methacrylate) (SBM) block copolymers were investigated in bulk form, and when used as the matrix material in carbon fibre reinforced composites. The ‘E21’ SBM block copolymer has a higher butadiene content and molecular weight than the ‘E41’. A network of aggregated spherical micelles was observed for the E21 SBM modified epoxy, which became increasingly interconnected as the SBM content was increased. A steady increase in the fracture energy was measured with increasing E21 content, from 96 to 511 J/m² for 15 wt% of E21. Well-dispersed ‘raspberry’-like SBM particles, with a sphere-on-sphere morphology of a poly(styrene) core covered with poly(butadiene) particles, in an epoxy matrix were obtained for loadings up to 7.5 wt% of E41 SBM. This changed to a partially phase-inverted structure at higher E41 contents, accompanied by a significant jump in the measured fracture energy to 1032 J/m² at 15 wt% of E41. The glass transition temperatures remained unchanged with the addition of SBM, indicating a complete phase separation. Electron microscopy and cross polarised transmission optical microscopy revealed localised shear band yielding, debonding and void growth as the main toughening mechanisms. Significant improvements in fracture energy were not observed in the fibre composites, indicating poor toughness transfer from the bulk to the composite. The fibre bridging observed for the unmodified epoxy matrix was reduced due to better fibre–matrix adhesion. The size of the crack tip deformation zone in the composites was restricted by the fibres, hence reducing the measured fracture energy compared to the bulk for the toughest matrix materials.     

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.     

A model for the toughness of epoxy-rubber particulate composites

Epoxy resins are toughened significantly by a dispersion of rubber precipitates. Microscopic examinations of propagating cracks in epoxy-rubber composites reveal that the brittle epoxy matrix cracks, leaving ligaments of rubber attached to the two crack surfaces. The rubber particles are stretched as the crack opens and fail by tearing at large, critical extensions. This fracture mechanism is the basis of a new analytical model for toughening. An increase in toughness (G _IC) of the composite is identified with the amount of elastic energy stored in the rubber during stretching which is dissipated irreversibly (e.g. as heat) when the particles fail. The model predicts the failure strain of the particles in terms of their size. It also relates the toughness increase to the volume fraction and tearing energy of the rubber particles. Direct measurements of the tearing strains of rubber particles, and toughness data obtained from epoxy-rubber composites, are in good agreement with the model. The particle-stretching model provides a quantitative explanation, in contribution to existing qualitative theories, for the toughening of epoxy-rubber composites.     

橡胶增韧环氧树脂的增韧力学模型综述

对橡胶增韧环氧树脂的增韧机理模型进行了回顾,其主要增韧机理为局部部切屈服,孔洞或空穴的塑料性体积膨胀和橡胶颗粒桥联,在细观结构上采用典型轴对称单元的有限元分析来预测增韧环氧树脂的力学行为,断裂力学的J积分模型可用于估算增韧程序,基于断裂韧性GIC的增韧模型定量分析已取得一定进展。     

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.     

Behavior of particle-filled polymer composite under static and dynamic loading

Experimental results of quasi-static and dynamic fracture of particle-filled polymer composite (PFPCM) “ALTUGLAS EI CH25” with a matrix of polymethylmethacrylate (PMMA) are reported in this paper. PMMA matrix is filled with rubber particles, as result a shock-resistant transparent composite is produced. The main task was to investigate experimentally and theoretically the fracture toughness of this composite under static and dynamic loading. A high-rate loading has been created by impulse magnetic field. Analysis of fracture process and its relation with the load parameters and material microstructure have been established. Application of the original testing method enabled determination of fracture toughness at very short loading times and comparison of the results with material dynamic properties. Theoretical analyses are based in general on the notion of delayed fracture. More specifically, the theoretical analysis is based on experimental results and on the hypothesis of fracture incubation time, or delay time.     

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.     

Toughening of polystyrene by natural rubber-based composite particles: Part I Impact reinforcement by PMMA and PS grafted core-shell particles

This work was focused on the influence of the morphology of composite natural rubber (NR)-based particles on the toughness of polystyrene (PS). Emulsion polymerization processes were used to adjust the microstructure of the latex particles. In order to be suitable for the reinforcement of PS, the NR-based particles were coated with a shell of crosslinked polymethyl methacrylate (PMMA) or PS. Furthermore, PS subinclusions were introduced into the natural core. A continuous extrusion process was adapted for the incorporation of these natural rubber based impact modifiers into thermoplastics. High deformation speeds (impact testing) were necessary in order to evaluate the mechanical properties of PS blends with a series of the prepared structured latexes. PS could only be toughened by core-shell particles. A PMMA shell proved to be advantageous because it is easier to produce by emulsion polymerization than a hydrophobic PS shell. Pre-vulcanized NR-based particles, which do not cavitate easily, were ineffective. Core-shell particles based on NR-containing PS subinclusions toughened PS more effectively. Solid NR particles caused premature craze and polymer fracture, as the rubber particles break down, debond from the matrix and form large voids at the craze/particle interface. Scanning electron microscopy (SEM) of Izod fracture surfaces showed clearly the cavities of debonded solid rubber particles and demonstrated that subinclusions within the rubber core permitted a larger volume of plastic deformation before failure. This revised version was published online in November 2006 with corrections to the Cover Date.     

Fracture toughness of the nano-particle reinforced epoxy composite

Although thermoset polymers have been widely used for engineering components, adhesives and matrix for fiber-reinforced composites due to their good mechanical properties compared to those of thermoplastic polymers, they are usually brittle and vulnerable to crack. Therefore, ductile materials such as micro-sized rubber or nylon particles are added to thermoset polymers are used to increase their fracture toughness, which might decrease their strength if micro-sized particles act like defects.In this work, in order to improve the fracture toughness of epoxy adhesive, nano-particle additives such as carbon black and nanoclay were mixed with epoxy resin. The fracture toughness was measured using the single edge notched bend specimen at the room (25 °C) and cryogenic temperature (−150 °C). From the experimental results, it was found that reinforcement with nano-particles improved the fracture toughness at the room temperature, but decreased the fracture toughness at the cryogenic temperature in spite of their toughening effect.     

Low temperature fracture properties of polymer-modified asphalts relationships with the morphology

A methodology for studying the relationships between fracture behavior and morphology of polymer-modified asphalts used as binders was developed by using the linear elastic fracture mechanics (LEFM) method and confocal laser scanning and environmental and cryo-scanning electron microscopies. Different types of polymers were used as modifiers: (i) copolymers from ethylene and methyl acrylate (EMA), butyl acrylate (EBA) or, vinyl acetate (EVA); (ii) diblock or star-shape triblock styrene-butadiene copolymers (SB or SBS^*). The 4 to 6 wt. % blends display an heterogeneous structure with a polymer-rich dispersed phase based on the initial polymer swollen by the aromatic fractions of the asphalt. The fracture toughness of the blends is higher than for the neat asphalt even if KIc of blends remains low compared to usual polymer blends due to the brittleness of the asphalt matrix. The fracture behavior which is strongly dependent on the nature of the polymer is discussed from the toughening mechanisms given for the filled polymers and the polymer blends. The EBA, SB, and SBS-based blends compared to the EMA and EVA-based ones display a higher KIc due to the elastomeric behavior of the polymer phase leading to a more efficient energy dissipation during crack propagation. The sample prepared with 4% crosslinked SB (Styrelf) and the corresponding physical blend (non-crosslinked) display the better fracture properties.     

半圆盘构件冲击断裂特性的动态焦散线实验研究

采用动态焦散线实验系统,对有机玻璃（PMMA）在冲击载荷下的I型和I-II混合型裂纹在起裂和扩展时的动态断裂特性进行了研究。结果表明：随着PMMA由I型断裂转变为I-II混合型断裂,从落锤作用在试件上到裂纹起裂所需时间不断增加,说明裂纹起裂需要的能量有所增加,同时从裂纹起裂到最终贯通所需时间不断减少,说明裂纹平均扩展速度也不断增大;在I型断裂中,PMMA的断裂韧度KIC为2.04 MN/m3/2,而在I-II混合型断裂中,PMMA的断裂韧度KIC低于I型断裂时的断裂韧度KIC,但是KIIC有所增大;对于I-II混合型断裂,PMMA极限扩展速度约为366m/s,当达到极限扩展速度后,裂纹尖端出现微裂纹增韧现象,使裂纹的表面能迅速增大,随后裂纹的扩展速度迅速减小。     

The effect of temperature on the fracture of rubber modified polystyrene

Brittle fractures were obtained in rubber modified polystyrene over the temperature range −120 to 20° C using the surface notch method. When compared with single edge notch data, a thickness effect was apparent and this was described in terms of plane stress and plane strain fracture toughness values. The plane strain value agreed closely with that of the polystyrene matrix indicating that the constrained region showed no toughening effect. The relaxation process of the rubber was apparent in the plane stress toughness.     

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.     

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.     

Toughened carbon/epoxy composites made by using core/shell particles

Toughened epoxy resin composites have been prepared by resin-transfer moulding by using a range of toughening agents. Two types of epoxy-functional preformed toughening particles were investigated and have a three-layer morphology in which the inner core is crosslinked poly(methyl methacrylate), the intermediate layer is crosslinked poly(butyl acrylate) rubber and the outer layer is a poly[(methyl methacrylate)-co-(ethyl acrylate)-co-(glycidyl methacrylate)]. The presence of glycidyl groups in the outer layer facilitates chemical reaction with the matrix epoxy resin during curing. Comparisons were made with acrylic toughening particles that have a similar structure, but which do not have the epoxy functionality in the outer shell, and with a conventional carboxy-terminated butadiene acrylonitrile (CTBN) liquid rubber toughening agent. The composites were characterised by using tensile, compression and impact testing. The fracture surfaces and sections through the moulded composites were examined by means of optical and scanning electron microscopy. Short-beam shear tests and fragmentation tests were used to investigate the interfacial properties of the composites. In general, use of the epoxy-functionalised toughening particles gave rise to superior properties compared with both the non-functionalised acrylic toughening particles and CTBN.