Effects of surface treatment and weave structure on interlaminar fracture behaviour of plain glass woven fabric composites: Part II. Report of the 2nd round robin test results

This paper reports the second part of the results from the round robin test program proposed by the Society of Interfacial Materials Science (SIMS) to characterise the interlaminar fracture behaviour of E-glass woven fabric reinforced vinylester composites. Special emphasis was placed on the study of loading direction (i.e. weft and warp directions) effect on interlaminar shear strength and fracture toughness. Ten laboratories worldwide participated in this test (Table 1). Each laboratory was supplied with composite laminates and conducted the tests according to its own procedure. The results showed that although there were large variations in absolute magnitude between laboratories, a general trend was established with higher interlaminar fracture resistance in the weft direction than in the warp direction for a given silane agent. The larger number of strands running in the warp direction with rougher, more undulating areas perpendicular to the direction of crack propagation was mainly responsible for this result. The results also confirmed the previous finding that the mode I interlaminar fracture toughness increased with increasing silane agent concentration.     

Annealing effect in glass woven fabric composites,Part I. Mode I and mode II interlaminar fracture behavior

Mode I and mode II interlaminar fracture behavior of plain glass woven fabric composites with different silane concentration was investigated on the basis of a discussion of the effects of annealing on the fracture behavior. The fracture mode changed by annealing from stable to unstable manner in lower silane concentration and from unstable to stable manner in higher silane concentration specimens in mode I fracture. In the mode II fracture, the initiation values of fracture toughness increased by annealing without respect to silane concentration.     

Effect of surface treatment condition on interfacial degradation behavior in GFRP under acidic conditions

Interfacial degradation behavior of E-glass cloth reinforced vinyl ester resin under acidic conditions has been investigated. Specimens with different surface treatment conditions were prepared. Mode I fracture toughness tests were performed using DCB specimen, and the effect of surface treatment condition and immersion time on the crack propagation behavior is discussed. The crack propagation behavior changes as a function of the condition of the silane coupling agent and the immersion time due to the degradation of the interphase. A technique is proposed to evaluate the interfacial property. The change of fracture toughness of interphase and resin as a function of immersion time is studied by the crack propagation behavior and the fracture toughness of interphase and resin evaluated by this technique. The fracture toughness of interphase decreases rapidly with immersion in acidic solution.     

Effects of fibre surface treatment on fracture-mechanical properties of sisal-fibre composites

Sisal fibre reinforced composites, one class of a broad range of eco-composite materials, were studied in connection with the effects of fibre surface treatment on their fracture-mechanical properties. Previous investigations on sisal fibre and its composites have been fully reviewed [1], which provided an impetus for this research. Two fibre surface treatment methods, chemical coupling based on silane and oxidization based on permanganate and dicumyl peroxide, together with untreated sisal fiber composites were used to set up different levels of interface bonding strength. The interface effects on the mechanical properties and fracture toughness of sisal fibre reinforced vinyl-ester composites were completely assessed based on the test results obtained and theoretical analyses. Many aspects of studies reported in this paper are original, such as single fiber pull-out tests and toughness evaluation of sisal composites aided by scanning electron microscopy. The results showed that fibre surface treatment could improve interfacial bonding properties between sisal fibre and vinylester resin. These in turn influenced the fracture-mechanical characteristics of this class of ecocomposites.     

Mode I and Mode II interlaminar fracture toughness of CFRP/magnesium alloys hybrid laminates

The fiber metal laminates (FML), consisting of carbon fiber reinforced polymer prepregs and magnesium alloys sheets, were introduced, and the Mode I (peel) and Mode II (shear) interlaminar fracture toughness of the FMLs were investigated. The results show that the Mode I interlaminar toughness (0.23 kJ/m²) of the FMLs is much lower than the Mode II interlaminar toughness (5.81 kJ/m²), due to the fact that the effects of mechanical interlock to hinder crack propagates is smaller under Mode I loading conditions than under Mode II. The FMLs mainly show adhesive failure and interfacial failure under Mode I loading conditions, while for Mode II loading, it exhibits a degree of epoxy cohesive failure except the adhesive failure and interfacial failure.     

Roles of interfaces between carbon fibers and epoxy matrix on interlaminar fracture toughness of composites

The effect of atmospheric-pressure plasma treatment on high strength PAN-based carbon fibers had been studied in terms of fiber surface energetics and mode I and II interlaminar fracture toughness of unidirectional carbon fibers/epoxy matrix composites. The surface characterization of plasma treated carbon fibers was investigated by X-ray photoelectron spectroscopy (XPS) and contact angles. As a result, the plasma treatment changed the surface properties of the carbon fibers, mainly through formation of oxygen functional groups like hydroxyl, carbonyl, and carboxyl groups. According to contact angle measurements, it was observed that plasma treatment led to an increase in surface free energy of the fibers, mainly due to the increase of its specific component. Fracture toughness test results employing double-cantilever beam (DCB) and end notched flexure (ENF) specimens also showed that the increase in specific components or hydrogen bonding between the –OH groups on carbon fibers and the =O ring in epoxy matrix resins played an important role in improving the degree of adhesion at interfaces, resulting in an increase in the interfacial fracture toughness of the composites studied.     

A novel surface treatment process for enhanced adhesion of ultra-high modulus polyethylene fibres to epoxy resins

Ultra-high modulus polyethylene (UHMPE) fibres have been treated using a novel 'non-plasma' treatment allowing the incorporation of various chemical functional groups onto the polymer surface. The process comprises two steps: corona discharge treatment, followed by silanization of the polymer surface by a solution of an organo-functional silane. Corona discharge treatment incorporates oxygen-containing functionalities, e.g. reactive hydroxyl groups, onto the polymer surface. The presence of reactive -OH groups provides the possibility of covalent linkage of any organo-functional silane to the corona discharge-treated polymer in the form of a fibre, film, sheet, or powder. The effectiveness of the process was assessed by examining the interlaminar fracture energy and flexural modulus and by SEM analysis of the fracture surfaces of composites fabricated from the untreated, corona discharge-treated, ammonia plasma-treated, and the amine-grafted (using the novel process) UHMPE fabric. A significant improvement in interfacial adhesion was confirmed by increases in the interlaminar fracture energies and flexural moduli. The effectiveness of the process investigated is similar to the ammonia plasma treatment. SEM analysis of the fracture surfaces indicated a change in the fracture mode from purely adhesive for unmodified fibres, through to mixed failure mode for corona-treated material, to highly cohesive-in-fibre surface for amine-grafted UHMPE fibres. XPS analysis confirmed the incorporation of the amine groups onto the surface of polyethylene treated using the novel method.     

Mixed mode I/II fracture investigation of Perspex based on the averaged strain energy density criterion

In this work, some recent mixed mode I/II fracture toughness results obtained from Perspex (or polymethylmethacrylate (PMMA)) with four simple cracked specimens subjected to the conventional three-point bend loading are reanalysed based on local energy concept. Although all the mentioned samples have been tested under the same and similar mode mixities, different fracture toughness envelopes were obtained for mixed mode I/II fracture of PMMA. The averaged strain energy density (SED) criterion has been applied in the past for different types of notched specimens (including U, V, O and keyhole notches). It is shown that the mixed mode tensile-in plane shear fracture toughness data obtained from the semicircular and triangular crack type specimens are successfully predicted for sharp cracked PMMA samples using the SED criterion.     

Microcellular and Solid Polylactide–Flax Fiber Composites

Polylactide–flax fiber composites with 1, 10 and 20 wt% fiber were melt-compounded and subsequently molded via the conventional and microcellular injection-molding processes. Silane was used as a coupling agent. The effects of fiber and silane content on cell morphology, static and dynamic mechanical properties, and crystallization properties have been studied. The average cell size decreased while the cell density increased with the fiber content. The degree of crystallinity increased with the fiber content. Silane treatment of fibers affected neither the cell morphology nor the degree of crystallinity. The toughness and strain-at-break of solid samples decreased with the fiber content while silane treatment increased both properties; however, neither fiber content nor silane treatment had much influence on the toughness and strain-at-break of microcellular samples. The specific modulus of both solid and microcellular samples increased with the fiber content. The specific strength of the solid and microcellular PLA–flax composites were only slightly lower than that of their solid and microcellular pure PLA counterparts. Overall, the toughness, strain-at-break, and specific strength of microcellular samples were found to be lower than that of their solid counterparts. The storage modulus of the PLA–flax composites with 10 and 20% fiber contents was higher than that of pure PLA.     

Effect of Modified Nano-Silica on the Reinforcement of Styrene Butadiene Rubber Composites

The performance of styrene butadiene rubber (SBR) composites filled with nano-silica has been improved by surface modification of the nano-silica using silane coupling agents. The dispersion of nano-silica in SBR rubber and the bonding force of nano-silica with SBR were significantly improved, and the physical and mechanical properties of the vulcanized rubber were greatly improved. The results showed Si69 (bis-(γ- triethoxysilylpropyl)-tetrasulfide) was the best modifier among the six silane coupling agents used in the experiments, and its optimum amount was 12% (wt) of nano-silica.     

Influence of Cell Topology on Mode I Fracture Toughness of Cellular Structures

A cellular structure is made up by an interconnected network of beams or plates which forms the edges and faces of cells. This paper proposes three different micromechanical models to determine the fracture toughness values of cellular materials such as rigid polyurethane foams using the finite element micromechanical analysis and Abaqus software. This study was carried out for mode I fracture and fracture toughness was predicted based on linear elastic fracture mechanics. Models of two-dimensional cellular solids with square, hexagonal and circular cells were generated for five different relative densities (0.077, 0.105, 0.133, 0.182 and 0.333). A study of the influence of geometrical parameters on fracture toughness was also conducted. Based on the finite-element simulations, three linear correlations are proposed which could be useful for estimation of fracture toughness values if relative densities are in the considered range of 0.077 (90 kg/m³ density) and 0.333 (390 kg/m³ density). Finally, the authors validate their proposed micromechanical models presenting a comparison of analytical, numerical and experimental results of fracture toughness of cellular materials. It was found that at low relative densities (between 0.077 and 0.333), the proposed micromechanical models predict the fracture toughness values similar to experimental and numerical ones, but they must be used according with the real cellular structure.     

The measurement of cohesive and interfacial toughness for bonded metal joints with epoxy adhesives

The types of crack growth in adhesive joints are reviewed and three are identified, namely central cohesive, asymmetric cohesive and interfacial. Test methods for measuring fracture toughness associated with these cracks are then outlined and include a Tapered Double Cantilever Beam (TDCB) test for a central cohesive crack and peel tests on flexible laminates for the other types of crack. In particular, fixed arm and mandrel peel tests are used. Two aerospace adhesives are used to prepare test specimens in order to conduct these tests. For one of these adhesives, all three types of crack growth were recorded and this provided an opportunity to make detailed comparisons of the three associated fracture toughness values. Of particular interest was the use of the mandrel peel method because it enabled a fracture transition (asymmetric cohesive to interfacial fracture) to be observed during the test. The fracture toughness value associated with a central cohesive crack was similar in magnitude to that for an asymmetric cohesive crack. However, the fracture toughness for interfacial fracture was much lower, but similar in magnitude to the expected value of half the fracture toughness from a TDCB test.     

Evaluation of Synthetic Magnesium Silicate as a New Polymer Filler

The paper reports on the performance of highly dispersed synthetic magnesium silicate as a filler of the styrene–butadiene rubber (SBR). The magnesium silicate has been precipitated and characterized by determination of particle size distribution, electrokinetic potential, nitrogen adsorption/desorption isotherms and SEM observation. At the subsequent stage of the study its surface has been modified by silane coupling agents. The unmodified and silane-grafted magnesium silicate samples have been used as fillers of SBR of standard testing composition. The vulcanizates obtained with the fillers have been tested as to their physical and mechanical performance. The vulcanizates filled with synthetic magnesium silicate have been found to show much better mechanical parameters than unfilled rubber. Modification of the synthetic magnesium silicates with silane coupling agents has further improved the mechanical characteristics of the vulcanizates.     

Effect of surface treatment of nanoclay on the mechanical properties of epoxy/glass fiber/clay nanocomposites

A new method of silane treatment of nanoclays is reported where in the clay is nanodispersed in hydrolyzed silanes. The surface functionalization of Cloisite^® 15A nanoclay has been carried out using two different silane coupling agents: 3-aminopropyltriethoxy silane and 3-glycidyloxypropyltrimethoxy silane using varied amounts of silane coupling agents, e.g. 10, 50, 200, and 400 wt% of clay. The surface modification of Cloisite^® 15A has been confirmed by Fourier transform infrared spectroscopy. The modified clays were then dispersed in epoxy resin, and glass fiber-reinforced epoxy clay laminates were manufactured using vacuum bagging technique. The fiber-reinforced epoxy clay nanocomposites containing silane modified clays have been characterized using small angle X-ray scattering, transmission electron spectroscopy and differential scanning calorimetry. The results indicate that the silane treatment of nanoclay aided the exfoliation of nanoclay and also led to an increase in mechanical properties. The optimized amount of silane coupling agents was 200 wt%. The nanocomposites containing clay modified in 200 wt% of silanes exhibited an exfoliated morphology, improved tensile strength, flexural modulus, and flexural strength. The improved interfacial bonding between silane modified nanoclays and epoxy matrix was also evident from significant increase in elongation at break.     

Enhanced interlaminar fracture toughness of unidirectional carbon fiber/epoxy composites modified with sprayed multi-walled carbon nanotubes

A recently reported solvent spraying technique was used herein for incorporation of multi-walled carbon nanotubes (MWCNTs) on unidirectional carbon fiber/epoxy prepregs. The role of the agglomerates reduction of oxidized MWCNTs on Mode-I interlaminar fracture toughness (G_IC) of laminated composites was investigated using double cantilever beam tests. Multiscale laminate composites were fabricated using MWCNTs without and with an acid oxidation, agglomerates reduction (AR) and a sequential treatment based on oxidation and AR. For comparison, specimens without MWCNTs were also prepared and tested. Fourier transform infrared analysis shows evidence of an important amount of oxygenated functional groups on the surface of as-received and oxidized MWCNTs. The results also show Mode-I fracture toughness improvements for all the laminated composites compared to reference samples. A substantial 52% increase in the average G_IC initiation was achieved for laminated composites reinforced with oxidized AR-MWCNTs prepared with only 0.05 wt.% MWCNTs.     

Annealing effect in glass woven fabric composites,Part II. Bending properties

Effects of annealing on bending properties of composites reinforced with plain glass woven fabrics that were treated with different concentrations of silane coupling agent were investigated in this paper. Bending strength increased by annealing in the specimen treated with lower silane concentration. Higher annealing temperature in a range from 80°C to 150°C led to higher bending strength. Then, the fracture mode changed from a micro-crack type (low strength type) to a branched matrix crack type (high strength type) by annealing.     

Tensile properties of styrene-butadiene rubber/silica composites with mercapto functional silane coupling agents: influences of loading method and alkoxy group number

The influences of alkoxy group number and loading method of silane coupling agents on the mechanical properties of a styrene-butadiene rubber/silica composite were investigated. Mercapto functional silane coupling agents with dialkoxy and trialkoxy structures were used. The pre-treatment method and the integral blend method were compared. Both the fracture stress and modulus at 200% strain were higher in the pre-treatment than in the integral blend for dialkoxy type composites. However, they were higher in the integral blend than in the pre-treatment for trialkoxy-type composites. The interaction between the silane chains on the silica surface and the rubber molecular chains at the interfacial region was estimated by ¹H pulse nuclear magnetic resonance spectroscopy using an unvulcanized silica/rubber mixture. It was found that the binding of rubber molecular chains by the silane chains was higher in the pre-treatment system for dialkoxy-type composites, whereas it was higher in the integral blend for trialkoxy-type composites. The reason is proposed as follows: in the pre-treatment for dialkoxy type, a linear silane chain formed in the case of multi-layer coverage. The silane chain entangled with the rubber chain in the interfacial region and improved the reinforcement effect. For the trialkoxy type, a network structure formed using the pre-treatment method, lowering the amount of entanglement. However, in the integral blend for trialkoxy type, the formation of the silane network and the entanglement progressed simultaneously during the preparation process. A well-entangled interfacial region was formed.     

Small-scale fracture toughness of ceramic thin films: the effects of specimen geometry,ion beam notching and high temperature on chromium nitride toughness evaluation

For the implementation of thin ceramic hard coatings into intensive application environments, the fracture toughness is a particularly important material design parameter. Characterisation of the fracture toughness of small-scale specimens has been a topic of great debate, due to size effects, plasticity, residual stress effects and the influence of ion penetration from the sample fabrication process. In this work, several different small-scale fracture toughness geometries (single-beam cantilever, double-beam cantilever and micro-pillar splitting) were compared, fabricated from a thin physical vapour-deposited ceramic film using a focused ion beam source, and then the effect of the gallium-milled notch on mode I toughness quantification investigated. It was found that notching using a focused gallium source influences small-scale toughness measurements and can lead to an overestimation of the fracture toughness values for chromium nitride (CrN) thin films. The effects of gallium ion irradiation were further studied by performing the first small-scale high-temperature toughness measurements within the scanning electron microscope, with the consequence that annealing at high temperatures allows for diffusion of the gallium to grain boundaries promoting embrittlement in small-scale CrN samples. This work highlights the sensitivity of some materials to gallium ion penetration effects, and the profound effect that it can have on fracture toughness evaluation.     

Determination of interfacial material constants in plain glass woven fabric composites using finite element analysis

Numerical analysis with the finite element method (FEM) was used in order to identify interfacial material constants of plain glass woven fabric composites under mode I loading. Relations between strength, stress intensity factor, and modulus in the interphase which were correlated with the onset of unstable fracture were determined. As a result, it was reasonable that the interfacial moduli were between 2.8 and 8.4 GPa which corresponds to one to three times the resin modulus. It was suggested that the increase of concentration of silane coupling agent has led to an increase of the interfacial strength. Changing of fracture mechanisms from unstable to stable crack propagations was explained through the interfacial material constants.     

Preparation and Characterization of Nano-Calcium Carbonate/Silane Coupling Agent Master Batch and Its Effect on Epoxy Resin

A nano-calcium carbonate (CaCO₃)/silane coupling agent (NCC/SCA) master batch was prepared by the reaction of SCA (γ-aminopropyl triethoxy silane, trade name KH550) with the hydroxyl groups of nano-CaCO₃. Both Fourier transform infrared spectroscopy and thermal gravimetric analysis indicated that the nanoparticles were grafted by SCA. An epoxy resin was modified by adding the NCC/SCA master batch. A simple dipping test suggested that a better dispersion of the treated NCC in epoxy could be obtained than that of the untreated NCC. Then samples of epoxy nano-composites were prepared by a hot press process. The compressive property of epoxy nano-composites was investigated; the results of these mechanical property tests revealed that the compressive strength, elastic modulus, and the total fracture work of the epoxy matrix filled with the treated NCC were significantly improved relative to that filled with the untreated NCC.