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.     

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 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.     

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.     

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.     

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.     

Preparation and characterization of water-borne epoxy shape memory composites containing silica

Shape memory silica/epoxy composites were successfully prepared by hydrolysis of tetraethoxysilane (TEOS) within the epoxy matrix via latex, freeze-drying, and hot-press molding method. The silane coupling agent 3-triethoxysilylpropylamine (KH550) was introduced to improve the interfacial properties between the in-situ generated silica particle and epoxy matrix. The morphology structure and the effect of the content of the in-situ formed silica on the mechanical and shape memory properties of the silica/epoxy composites were studied. The experimental results indicated that the silica particles were homogenously dispersed and well incorporated into the epoxy matrix. Significant improvements were achieved in the mechanical property of the organic–inorganic hybrid materials. The silica/epoxy composites exhibited high shape recovery and fixity ratio approximately 100% even after 10 thermo-mechanical cycles.     

Delamination resistance of GFRP‐epoxy rods with nanoparticle‐ and microparticle‐modified matrix and its correlation with the fracture properties of epoxy nanocomposites

Pultruded glass fiber–reinforced plastic (GFRP) rods are industrially produced for various applications. The mechanical properties of GFRP rods can be tailored, eg, with modified epoxy matrix by adding microsized and nanosized fillers. In this work, we investigated the transferability of the fracture properties of epoxy nanocomposites to GFRP epoxy rods. For this purpose, nanosilica particles, micron‐sized rubber, and micron‐sized calcium carbonate were used as fillers. Firstly, epoxy plates with different combinations of nanosized and micron‐sized fillers were produced and their fracture toughness evaluated. Secondly, using binary and ternary epoxy filler systems as matrices, GFRP rods were produced, and their fracture toughness was determined using a modified testing procedure derived from standard composite double cantilever beam specimens. Lastly, the correlation between fracture properties of epoxy nanocomposites and GFRP rods was analysed. Besides that, the fractographic investigations of both epoxy nanocomposites and GFRP rods were carried out and discussed.     

Micro- and nano-scale deformation behavior of nylon 66-based binary and ternary nanocomposites

The primary aim of this paper is to provide an insight on the effect of the location of organoclay on the micro- and nano-scale deformation processes in melt-compounded nylon 66/organoclay/SEBS-g-MA ternary nanocomposites prepared by different blending sequences. In addition, the deformation processes of the ternary nanocomposites were compared to the binary nanocomposites (nylon 66/organoclay and nylon 66/SEBS-g-MA) and neat nylon 66. The incorporation of SEBS-g-MA particles toughened nylon 66 markedly; but the flexural modulus and strength were both reduced. Conversely, the use of organoclay increased the modulus but decreased the fracture toughness of nylon 66. Nylon 66/SEBS-g-MA/organoclay ternary nanocomposites exhibited balanced elastic stiffness and toughness. Stress-whitening studies of the fracture surfaces in terms of gray level were also performed and an attempt was made to correlate the optical reflectivity characteristics with fracture toughness. It was concluded that the capability of SEBS-g-MA particles to cavitate was decreased by the presence of organoclay in the SEBS-g-MA phase, resulting in reduced toughening efficiency. The best micro-structure for toughness and other mechanical properties is thus to maximize the amount of exfoliated organoclay in the nylon 66 matrix rather than to have it embedded in the finely dispersed SEBS-g-MA particles.     

Ternary nano-CaCO3/poly(ethylene terephthalate) fiber/polypropylene composites: Increased impact strength and reinforcing mechanism

The binary nano-CaCO₃/polypropylene (PP), poly(ethylene terephthalate) (PET) fibers/PP and ternary nano-CaCO₃/PET fibers/polypropylene composites were prepared by melt blending method, and their structure and mechanical properties were investigated. The results show that the ternary nano-CaCO₃/PET fibers/PP composite displays significantly enhanced mechanical properties compared with the binary PET fibers/PP and nano-CaCO₃/PP composites, and neat PP. The X-ray diffraction, dynamic mechanical analysis, scanning electron microscopy and analysis of the non-isothermal crystallization kinetics were used to investigate the reinforcement mechanism of composites. The results indicate that the interfacial action and compatibility between PET fiber and PP are obviously enhanced by the addition of modified nano-CaCO₃ particles in the ternary composites and the mechanical property enhancement in the ternary system may be mainly originated from the formation of β-form crystallites of PP induced by the synergistic effect between PET fibers and nano-CaCO_3.     

Modification of surface functionality of multi-walled carbon nanotubes on fracture toughness of basalt fiber-reinforced composites

In this work, we studied the influence of surface functionality of multi-walled carbon nanotubes (MWCNTs) on the mechanical properties of basalt fiber-reinforced composites. Acid and base values of the MWCNTs were determined by Boehm's titration technique. The surface properties of the MWCNTs were determined FT-IR, and XPS. The mechanical properties of the composites were assessed by measuring the interlaminar shear stress, fracture toughness, fracture energy, and impact strength. The chemical treatments led to a change of the surface characteristics of the MWCNTs and of the mechanical interfacial properties of MWCNTs/basalt fibers/epoxy composites. Especially the acid-treated MWCNTs/basalt fibers/epoxy composites had improved mechanical properties compared to the base-treated and non-treated MWCNTs/basalt fibers/epoxy composites. These results can probably be attributed to the improved interfacial bonding strength resulting from the improved dispersion and interfacial adhesion between the epoxy resin and the MWCNTs.     

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.     

Cyclic fatigue crack propagation of nanoparticle modified epoxy

An experimental study on the fatigue performance of nanoparticle modified epoxy was conducted. Seven material systems were examined which were: neat epoxy (E), 6 and 12 weight percent (wt.%) silica nanoparticle modified epoxy (S6, S12), 6 and 12 wt.% rubber nanoparticle modified epoxy (R6, R12), 3 wt.% each of silica and rubber nanoparticle modified epoxy (S3R3) and 6 wt.% each of silica and rubber nanoparticle modified epoxy (S6R6). Effects of those nanoparticles on the fatigue threshold (ΔG_th and ΔK_th) and fatigue crack propagation rates (da/dN) were studied. It was found that, compared to neat epoxy (E), nanosilica (S6, S12) increased ΔG_th (and ΔK_th) but nanorubber (R6 and R12) did not. However, a synergistic effect was observed on the fatigue threshold when both silica and rubber nanoparticles were added into epoxy. All these nanoparticles, individually or conjointly, decreased da/dN with silica the most effective. Morphology of the fracture surface was examined to understand the role of nanoparticles on toughening mechanisms under cyclic loading, which depended on the applied ΔG levels.     

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.     

Temperature dependence of fracture toughness of silica/epoxy composites: Related to microstructure of nano- and micro-particles packing

Temperature dependence of the fracture toughness of epoxy composites reinforced with nano- and micro-silica particles was evaluated. Epoxy composites containing varied composition ratios Φ_SP of spherical nano- and micro-silica particles, 240 nm and 1.56 μm, were prepared at a fixed volume fraction (V_P = 0.30). The thermo-viscoelasticity and fracture toughness of the composites and neat epoxy were measured at 143 K, 185 K, 228 K, 296 K, 363 K, and 399 K. Experimental results revealed that fracture toughness strongly depended on the microstructure of nano- and micro-particles bidispersion as well as its interactions with the matrix at all temperature, but depended on toughened matrix due to increase in mobility of matrix at the relaxation temperatures.     

微纳米SiO2/PP复合材料增强增韧的实验研究

为了研究无机刚性颗粒对通用塑料聚丙烯 (PP) 的力学性能的影响, 采用熔融共混方法制备了经硅烷偶联剂A-151处理的SiO₂/PP 复合材料, 并通过其缺口冲击、 拉伸、 弯曲试验和冲击断面的形貌观察, 分析研究了微纳米SiO₂颗粒大小、 填充量、 表面改性以及不同颗粒大小SiO₂混合物对PP复合材料增韧、 增强效果的影响。实验结果表明: 纳米SiO₂的加入可以同时改善其韧性、 刚性和强度; 填充量相同, 颗粒越细, SiO₂/PP复合材料的力学性能越好。SiO₂经改性后填充到PP基体中, 明显改善了颗粒在基体中的分散性及基体与颗粒之间界面结合性能, 使复合材料的综合力学性能得到提高。不同颗粒大小的SiO₂混合后填充到PP基体中, 混合SiO₂的协同效应使复合材料拉伸、 弯曲性能进一步提高, 对PP基体具有更好的增强效果, 但其冲击性能下降。      

Influence of addition of silica particles on reaction-induced phase separation and properties of epoxy/PEI blends

Polyether imides (PEI)/silica nanocomposites, prepared by sol–gel process, were used to modify the epoxy resin (ER), and the effect of silica particles on reaction-induced phase separation and mechanical properties of these systems were investigated. SEM images of the fracture surface of ER/PEI/silica composites showed an interesting morphology transformation with the increase of silica particle content. SEM–EDX results indicated that silica particles once formed in the PEI gradually migrated and concentrated in epoxy-rich region during the phase separation because of the better affinity between silica particles and epoxy resin. FTIR measurement and rheological test confirmed that the silica particles make the polymerization reaction of epoxy faster and the dynamic DSC results demonstrated that the activation energy of these systems decreased with the increase of the silica particles. Mechanical measurements approved that the introducing of PEI/silica nanocomposites into the epoxy could lead to great improvement of the impact strength and storage module.     

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.     

Cyclic fatigue of polymer nanocomposites

This paper presents an experimental study on cyclic fatigue of two polymer nanocomposites in two common failure modes: mechanical failure in epoxy nanocomposites and thermal softening in polyamide (PA, nylon) 6 nanocomposites. For epoxy nanocomposites, the effects of hard (silica) and soft (rubber) nano-particles on un-notched samples under constant cyclic stress amplitude fatigue were studied. Hard particles were shown to increase but soft particles decrease the fatigue life of nanocomposites compared to unmodified epoxy. At the same stress amplitude, the extent of fatigue crack growth prior to fast fracture was largest in rubber nanocomposites and least in pure epoxy, reflecting the differences in their fracture toughness values. Ternary nanocomposites with both hard and soft (silica and rubber) particles were also investigated and their fatigue performances were compared to the binary nanocomposites. Further, the stress (σ_a) versus life (N_r) test data of pure epoxy and its binary and ternary nanocomposites are well described by Basquin’s law.PA6 nanocomposites exhibited fatigue failure due to thermal softening when the maximum local temperature of the specimens subjected to cyclic loading reached the glass transition temperature, T_g, of the material. Critical stress (σ_a) versus frequency (ω) envelopes for design against thermal failure were obtained for PA6/organoclay, PA6/POE-g-MA and PA6/pristine clay. Experimental results compared favorably with theoretical predictions.     

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.