Non-stoichiometric curing effect on fracture toughness of nanosilica particulate-reinforced epoxy composites

Non-stoichiometric curing effects on the fracture toughness behaviors of nanosilica particulate-reinforced epoxy composites were experimentally investigated in this study by comparing them with bending strengths to take into consideration the effect of interaction between nanoparticles and network structures in matrix resins. The matrixes were prepared by curing them with an excess mixture of diglycidyl ether of bisphenol A-type epoxy resin as the curing agent for the stoichiometric condition. The volume fractions of the silica particles with a median diameter of 240 nm were constantly 0.2 for all composites. The neat epoxy resins and the composites were cured non-stoichiometrically to change the crosslinking densities of the neat epoxy resins and the matrix resins of the composites within 2740–490 mol/m³. The fracture toughnesses and bending strengths of the composites and the neat epoxy resins strongly depended on the crosslinking densities in the resins. Although the fracture toughness decreased monotonously from that of the stoichiometrically cured resins as the crosslinking density decreased, the fracture toughnesses of composites were largest at a slightly lower crosslinking density of approximately 2490 mol/m³ from the stoichiometric condition of 2740 mol/m³. The fracture toughness and the bending strength were improved for crosslinking densities higher than 2000 mol/m³ by adding particles. At crosslinking density lower than 2000 mol/m³, the particles worked against the mechanical properties as defects in matrix resins.     

Influence of electroless nickel-plating on fracture toughness of pitch-based carbon fibre reinforced composites

Nickel-Pitch-based carbon fibres (Ni-PFs) were prepared by electroless nickel-plating to enhance fracture toughness of Ni-PFs reinforced epoxy matrix composites (Ni-PFs/epoxy). The surface properties of Ni-PFs were determined by scanning electron microscopy (SEM), X-ray photoelectron spectrometry (XPS), and X-ray diffraction (XRD). The fracture toughness of the Ni-PFs/epoxy was assessed by critical stress intensity factor (K_IC) and critical strain energy release rate (G_IC). The fracture toughness of Ni-PFs/epoxy was enhanced compared to those of PFs/epoxy. These results were attributed to the increase of the degree of adhesion at interfaces between Ni-PFs and matrix resins in the composites.     

Mixture law including particle-size effect on fracture toughness of nano- and micro-spherical particle-filled composites

The effects of particle diameter and volume fraction on fracture toughness of nano- and micro-spherical particle-filled composites were investigated. The purpose was to create a mixture law of fracture toughness based on experimental results of spherical silica particle–filled epoxy composites and a theoretical approach. The fracture toughness of composites was found to be tailored independently by exchanging different particle sizes, and elastic and viscoelastic properties were found to be governed by the volume fraction of the particles. In a theoretical analysis, a mixture law of fracture toughness, composed of the elastic moduli, diameter, and volume fraction of particles and the elastic moduli of matrix resins was proposed. Its validity was demonstrated in a comparison with the experimental results.     

Fracture mechanisms of epoxy-based ternary composites filled with rigid-soft particles

Epoxy composites filled with different amounts of aggregate-free silica nanoparticles and phase-separated submicron rubber particles were fabricated to study the synergistic effect of multi-phase particles on mechanical properties of the composites. Compared with binary composites with single-phase particles, the ternary composites with both rigid and soft particles offer a good balance in stiffness, strength and fracture toughness, showing capacities in tailoring the mechanical properties of modified epoxy resins. It was observed that debonding of silica nanoparticles from matrix in the ternary composites was less pronounced than that in the binary composites. Moreover, the rubber particles became smaller and their shape tends to be irregular, affected by the presence of rigid silica nanoparticles. The toughening mechanisms in the epoxy composites were evaluated, and the enlarged plastic deformation around the crack tip, induced by the combination of rigid and soft particles, seems to be a dominant factor in enhancing fracture toughness of the ternary composites.     

Nanoparticle-induced enhancement in fracture toughness of highly loaded epoxy composites over a wide temperature range

The fracture toughness of an epoxy molding compound (EMC) has been enhanced over a wide temperature range by the addition of a very low volume fraction of silica nanoparticles to the EMC filled with micro-silica particles, which induces macroscopic crack deflection and plastic deformation in front of the crack tip. To evaluate the fracture toughness (G _IC) of these materials, the single edge notched bending (SENB) test was performed for a wide range of temperatures (from ambient temperature to 230°C). The fracture toughness of the nano-silica filled EMCs was found to be improved in this temperature range by as much as a factor of two. Investigation of the fracture surfaces revealed that the micro-silica particles are covered with deformed matrix materials, which implies that the silica nanoparticles induced the crack to move into the interface between the micro-silica particles. Fractography results suggest that the silica nanoparticles act as surface modifiers of the micro-silica particles, which results in crack deflection and plastic deformation.     

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.     

Fracture mechanisms of epoxy filled with ozone functionalized multi-wall carbon nanotubes

This work focused on the fracture mechanisms and reinforcing effects of ozone-treated multi-walled carbon nanotubes (MWCNTs) in epoxy matrix. Ozone functionalization of MWCNTs was found to be of help for a better dispersion and stronger interfacial bonding with epoxy matrix, which in turn improve the strength and fracture toughness of the resin. The MWCNT/epoxy composites showed complicated failure modes than the conventional fibrous composites, which have been quantitatively investigated and correlated with the fracture toughness of the nanocomposites studied.     

Thermally conducting aluminum nitride polymer-matrix composites

Thermally conducting, but electrically insulating, polymer-matrix composites that exhibit low values of the dielectric constant and the coefficient of thermal expansion (CTE) are needed for electronic packaging. For developing such composites, this work used aluminum nitride whiskers (and/or particles) and/or silicon carbide whiskers as fillers(s) and polyvinylidene fluoride (PVDF) or epoxy as matrix. The highest thermal conductivity of 11.5 W/(m K) was attained by using PVDF, AlN whiskers and AlN particles (7 μm), such that the total filler volume fraction was 60% and the AlN whisker–particle ratio was 1:25.7. When AlN particles were used as the sole filler, the thermal conductivity was highest for the largest AlN particle size (115 μm), but the porosity increased with increasing AlN particle size. The thermal conductivity of AlN particle epoxy-matrix composite was increased by up to 97% by silane surface treatment of the particles prior to composite fabrication. The increase in thermal conductivity is due to decrease in the filler–matrix thermal contact resistance through the improvement of the interface between matrix and particles. At 60 vol.% silane-treated AlN particles only, the thermal conductivity of epoxy-matrix composite reached 11.0 W/(m K). The dielectric constant was quite high (up to 10 at 2 MHz) for the PVDF composites. The change of the filler from AlN to SiC greatly increased the dielectric constant. Combined use of whiskers and particles in an appropriate ratio gave composites with higher thermal conductivity and low CTE than the use of whiskers alone or particles alone. However, AlN addition caused the tensile strength, modulus and ductility to decrease from the values of the neat polymer, and caused degradation after water immersion.     

Enhancement of fracture toughness,mechanical and thermal properties of rubber/epoxy composites by incorporation of graphene nanoplatelets

Carboxyl terminated butadiene acrylonitrile (CTBN) was added to epoxy resins to improve the fracture toughness, and then two different lateral dimensions of graphene nanoplatelets (GnPs), nominally <1 μm (GnP-C750) and 5 μm (GnP-5) in diameter, were individually incorporated into the CTBN/epoxy to fabricate multi-phase composites. The study showed that GnP-5 is more favorable for enhancing the properties of CTBN/epoxy. GnPs/CTBN/epoxy ternary composites with significant toughness and thermal conductivity enhancements combined with comparable stiffness to that of the neat resin were successfully achieved by incorporating 3 wt.% GnP-5 into 10 wt.% CTBN modified epoxy resins. According to the SEM investigations, GnP-5 debonding from the matrix is suppressed due to the presence of CTBN. Nevertheless, apart from rubber cavitation and matrix shear banding, additional active toughening mechanisms induced by GnP-5, such as crack deflection, layer breakage and separation/delamination of GnP-5 layers contributed to the enhanced fracture toughness of the hybrid composites.     

Mechanical properties of epoxy composites filled with silane-functionalized graphene oxide

In this work, the effects of as-produced GO and silane functionalized GO (silane-f-GO) loading and silane functionalization on the mechanical properties of epoxy composites are investigated and compared. Such silane functionalization containing epoxy ended-groups is found to effectively improve the compatibility between the silane-f-GO and the epoxy matrix. Increased storage modulus, glass transition temperature, thermal stability, tensile and flexural properties and fracture toughness of epoxy composites filled with the silane-f-GO sheets are observed compared with those of the neat epoxy and GO/epoxy composites. These findings confirm the improved dispersion and interfacial interaction in the composites arising from covalent bonds between the silane-f-GO and the epoxy matrix. Moreover, several possible fracture mechanisms, i.e. crack pinning/deflection, crack bridging, and matrix plastic deformation initiated by the debonding/delamination of GO sheets, were identified and evaluated.     

Enhancement of fracture toughness of hierarchical carbon fiber composites via improved adhesion between carbon nanotubes and carbon fibers

Hierarchical +1 composites consisting of carbon fibers with carbon nanotubes (CNTs) grown onto them and an epoxy matrix were processed, and the mode I fracture toughness of these composites was evaluated. The mode I fracture toughness of the initial batches of the hierarchical composites was lower than that of the baseline samples without CNTs. Hence, efforts to enhance the adhesion between carbon fibers and CNTs were made, resulting in enhanced adhesion. The enhanced adhesion was confirmed by Scotch tape tests and mode I fracture toughness tests followed by fractographic studies. The mode I fracture toughness of the hierarchical composites with enhanced adhesion was 51% and 89% higher than those of the baseline samples and hierarchical composites with poor adhesion, respectively. Moreover, fractographic studies of the fracture surfaces of the hierarchical composites with enhanced adhesion showed that CNTs were still attached to carbon fibers even after the mechanical tests.     

CF/EP composite laminates with carbon black and copper chloride for improved electrical conductivity and interlaminar fracture toughness

An experimental study was conducted to improve the electrical conductivity of continuous carbon fibre/epoxy (CF/EP) composite laminate, with simultaneous improvement in mechanical performance, by incorporating nano-scale carbon black (CB) particles and copper chloride (CC) electrolyte into the epoxy matrix. CF/EP laminates of 65 vol.% of carbon fibres were manufactured using a vacuum-assisted resin infusion (VARI) technique. The effects of CB and the synergy of CB/CC on electrical resistivity, tensile strength and elastic modulus and fracture toughness (K_IC) of the epoxy matrix were experimentally characterised, as well as the transverse tensile modulus and strength, Mode I and Mode II interlaminar fracture toughness of the CF/EP laminates. The results showed that the addition of up to 3.0 wt.% CB in the epoxy matrix, with the assistance of CC, noticeably improved the electrical conductivity of the epoxy and the CF/EP laminates, with mechanical performance also enhanced to a certain extent.     

Enhancement of mechanical performance of epoxy/carbon fiber laminate composites using single-walled carbon nanotubes

Carbon nanotubes (CNT) in their various forms have great potential for use in the development of multifunctional multiscale laminated composites due to their unique geometry and properties. Recent advancements in the development of CNT hierarchical composites have mostly focused on multi-walled carbon nanotubes (MWCNT). In this work, single-walled carbon nanotubes (SWCNT) were used to develop nano-modified carbon fiber/epoxy laminates. A functionalization technique based on reduced SWCNT was employed to improve dispersion and epoxy resin-nanotube interaction. A commercial prepregging unit was then used to impregnate unidirectional carbon fiber tape with a modified epoxy system containing 0.1 wt% functionalized SWCNT. Impact and compression-after-impact (CAI) tests, Mode I interlaminar fracture toughness and Mode II interlaminar fracture toughness tests were performed on laminates with and without SWCNT. It was found that incorporation of 0.1 wt% of SWCNT resulted in a 5% reduction of the area of impact damage, a 3.5% increase in CAI strength, a 13% increase in Mode I fracture toughness, and 28% increase in Mode II interlaminar fracture toughness. A comparison between the results of this work and literature results on MWCNT-modified laminated composites suggests that SWCNT, at similar loadings, are more effective in enhancing the mechanical performance of traditional laminated composites.     

Simultaneously enhanced cryogenic tensile strength and fracture toughness of epoxy resins by carboxylic nitrile-butadiene nano-rubber

Epoxy resins are important matrices for composites. Carboxylic nitrile-butadiene nano-rubber (NR) particles are employed to improve the tensile strength and fracture toughness at 77 K of diglycidyl ether of bisphenol-F epoxy using diethyl toluene diamine as curing agent. It is shown that the cryogenic tensile strength and fracture toughness are simultaneously enhanced by the addition of NR. Also, the fracture toughness at room temperature (RT) is enhanced by the addition of NR. On the other hand, the tensile strength at RT first increases and then decreases with further increasing the NR content up to 5 phr. 5 phr NR is the proper content, which corresponds to the simultaneous enhancements in the tensile strength and fracture toughness at RT. Moreover, the comparison of mechanical properties between 77 K and room temperature indicates that the tensile strength, Young’s modulus and fracture toughness at 77 K are higher than those at RT but the failure strain shows the opposite results. The results are properly explained by the SEM observation.     

多壁碳纳米管-有机蒙脱土协同增韧环氧树脂

采用机械搅拌和离心分散的方法制备了多壁碳纳米管-有机蒙脱土/环氧树脂复合材料。X射线衍射分析表明,当有机蒙脱土含量为2 wt%时, 蒙脱土在树脂体系中能够形成离散性结构。断裂韧性测试结果表明,多壁碳纳米管和有机蒙脱土的混杂对环氧树脂具有协同增韧的作用。当有机蒙脱土含量为2 wt%,多壁碳纳米管含量为0.1 wt%时,所得复合材料的断裂韧性是纯环氧树脂的1.77倍,是2 wt%有机蒙脱土/环氧树脂复合材料的1.45倍,是0.1 wt%多壁碳纳米管/环氧树脂复合材料的1.39倍。扫描电镜分析表明,多壁碳纳米管在环氧树脂体系中分散均匀,并与有机蒙脱土片层形成了一定程度的相互穿插和咬合,多壁碳纳米管与有机蒙脱土协同增韧的主要原因是微裂纹增韧、剪切屈服与纤维拔出。      

Synchronous effects of multiscale reinforced and toughened CFRP composites by MWNTs-EP/PSF hybrid nanofibers with preferred orientation

MWNTs-EP/PSF (polysulfone) hybrid nanofibers with preferred orientation were directly electrospun onto carbon fiber/epoxy prepregs and interlaminar synchronously reinforced and toughened CFRP composites were successfully fabricated. With MWNTs-EP loading increasing, the oriented nanofibers were obtained accompanying with enhanced alignment of inner MWNTs-EP. Flexural properties and interlaminar shear strength of composites were improved with increasing MWNTs-EP loadings, whereas fracture toughness attained maximum at 10 wt% MWNTs-EP loading and then decreased. Based on these results, multiscale schematic modeling and mechanism schematic of hybrid nanofibers reinforced and toughened composites were suggested. Due to the preferred orientation of nanofibers, MWNTs-EP was inclined to align vertically to carbon fiber direction along the in-plane of interface layer. The proposed network structures, containing four correlative phases of MWNTs-EP/PSF sphere/carbon fiber/epoxy matrix, contributed to simultaneous improvement of strength and toughness of composites, which was realized by crack pinning, crack deflection, crack bridging and effective load transfer.     

Mode I interlaminar fracture behavior and mechanical properties of CFRPs with nanoclay-filled epoxy matrix

The mechanical properties and fracture behavior of nanocomposites and carbon fiber composites (CFRPs) containing organoclay in the epoxy matrix have been investigated. Morphological studies using TEM and XRD revealed that the clay particles within the epoxy resin were intercalated or orderly exfoliated. The organoclay brought about a significant improvement in flexural modulus, especially in the first few wt% of loading, and the improvement of flexural modulus was at the expense of a reduction in flexural strength. The quasi-static fracture toughness increased, whereas the impact fracture toughness dropped sharply with increasing the clay content.Flexural properties of CFRPs containing organoclay modified epoxy matrix generally followed the trend similar to the epoxy nanocomposite although the variation was much smaller for the CFRPs. Both the initiation and propagation values of mode I interlaminar fracture toughness of CFRP composites increased with increasing clay concentration. In particular, the propagation fracture toughness almost doubled with 7 wt% clay loading. A strong correlation was established between the fracture toughness of organoclay-modified epoxy matrix and the CFRP composite interlaminar fracture toughness.     

Multi-scale reinforcement of CFRPs using carbon nanofibers

In this paper, stacked-cup carbon nanofibers (CNF) were dispersed in the matrix phase of carbon-fiber-reinforced composites based on a high-performance epoxy system with and without modification by an elastomeric triblock copolymer (TCP) for increased toughness. The addition of the TCP provided an enhancement in toughness at the cost of a slight degradation in modulus and strength. The CNFs, on the other hand, provided significantly enhanced strength and stiffness in matrix-dominated configurations, including tension of quasi-isotropic composites and short beam shear strength of both quasi-isotropic and unidirectional composites. Scanning electron microscopy revealed enhanced adhesion between the matrix and carbon fibers with the addition of either TCP or CNFs. However, CNF agglomeration in the studied systems partially offset the energy dissipation processes brought about by the nanofibers, thereby limiting interlaminar fracture toughness enhancements by CNF addition. These results show good promise for CNFs as low-cost reinforcement for composites while offering insight into the codependent morphologies of multi-scale phases and their influence over bulk properties.     

Fracture toughness and electrical conductivity of epoxy composites filled with carbon nanotubes and spherical particles

The attainment of both high toughness and superior electrical conductivity of epoxy composites is a crucial requirement in some engineering applications. Herein, we developed a strategy to improve these performances of epoxy by combining the multi-wall carbon nanotubes (MWCNTs) and spherical particles. Two different types of spherical particles i.e. soft submicron-rubber and rigid nano-silica particles were chosen to modify the epoxy/MWCNT composites. Compared with the binary composites with single-phase particles, the ternary composites with MWCNTs and spherical particles offer a good balance in glass transition temperature, electrical conductivity, stiffness and strength, as well as fracture toughness, exhibiting capacities in tailoring the electrical and mechanical properties of epoxy composites. Based on the fracture surface analysis, the complicated interactions between multiscale particles and the relative toughening mechanisms were evaluated to explain the enhancement in fracture toughness of the ternary composites.     

Reinforcement effects of MWCNT and VGCF in bulk composites and interlayer of CFRP laminates

The reinforcement effects of two nanofillers, i.e., multi-walled carbon nanotube (MWCNT) and vapor grown carbon fiber (VGCF), which are used at the interface of conventional CFRP laminates, and in epoxy bulk composites, have been investigated. When using the two nanofillers at the interface between two conventional CFRP sublaminates, the Mode-I interlaminar tensile strength and fracture toughness of CFRP laminates are improved significantly. The performance of VGCF is better than that of MWCNT in this case. For epoxy bulk composites, the two nanofillers play a similar role of good reinforcement in Young’s modulus and tensile strength. However, the Mode-I fracture toughness of epoxy/MWCNT is much better than that of epoxy/VGCF.