Environmentally benign green composites based on epoxy resin/bacterial cellulose reinforced glass fiber: Fabrication and mechanical characteristics

Bio-based bacterial cellulose (BC) epoxy composites were manufactured and their mechanical properties were examined. The BC was initially fabricated from Vietnamese nata de coco by means of alkaline pretreatment followed by solvent exchange. The obtained fibers were dispersed in epoxy resin (EP) by both mechanical stirring and ultrasonic techniques. The resulting blend was used as the matrix for glass-fiber (GF) composite fabrication using a prepreg method followed by multiple hot-press-curing steps. The morphology, mechanical characteristics and mode-I interlaminar fracture toughness of the fabricated composites were investigated. With a 0.3-wt% BC content, the mode-I interlaminar fracture toughness for both crack initiation and crack propagation were improved by 128.8% and 1110%, respectively. The fatigue life was dramatically extended by a factor of 12, relative to the unmodified composite. Scanning electron microscopy images revealed that the BC plays a vital role in increasing the interlaminar fracture toughness of a GF/EP composite via the mechanisms of crack reflection, debonding and fiber-bridging.     

Improving the interlaminar fracture toughness of carbon fiber/epoxy composites using clustered microcapsules

The composite laminates are susceptible to delamination between reinforcing plies during their long-term service. In this paper, we propose a modified carbon fiber/epoxy composite laminate with embedded clustered dual-component microcapsules in order to increase the interlaminar fracture toughness of the lamina. The details of microcapsules were illustrated using scanning electron microscope (SEM). The modified CF/EP composite laminates were fabricated using hot-compaction technique. Mode I interlaminar fracture tests were conducted using double cantilever beam specimens, then the values of opening fracture toughness G_IC were calculated to evaluate the toughening effect of modified laminates. The toughening mechanism was revealed and discussed through micrographs of the fracture surfaces obtained by ultra-depth microscope and SEM. The results show that clustered microcapsules after polymerization are equal to special Z-pinning, significantly enhancing the ability of crack arrest, and largely and roundly improved the G_IC values of resultant composite laminates. Meanwhile, the clustered microcapsules and matrix resin formed a second-phase material layer, which also absorbed the fracture energy and suppressed the expansion of cracks.     

Thermally conductive and electrically insulative nanocomposites based on hyperbranched epoxy and nano‐Al2O3 particles modified epoxy resin

Novel epoxy nanocomposites based on a diglycidyl ether of bisphenol A (DGEBA) epoxy, an epoxy functionalized hyperbranched polymer (HTTE) and nano‐Al₂O₃ were synthesized with the aim of determining the effect of the nano‐Al₂O₃ particles and HTTE on the structure and properties of epoxy nanocomposites. The mechanical properties, thermal conductivity, bulk resistivity, and thermal stability of the nano‐Al₂O₃/HTTE/DGEBA ternary composites were evaluated and compared with the corresponding matrix. The improvement in impact properties of these nanocomposites was explained in terms of fracture surface analysis by SEM. The results indicate that the incorporation of nanoparticles and hyperbranched epoxy effectively improved the toughness of epoxy composites without sacrificing thermal conductivity and bulk resistivity compared to the neat epoxy and Al₂O₃/DGEBA, obtaining a well dispersion of nanoparticles in epoxy matrix and solving the drawbacks for single fillers filled epoxy nanocomposite. Copyright © 2010 John Wiley & Sons, Ltd.     

Tough and Conductive Nacre-inspired MXene/Epoxy Layered Bulk Nanocomposites

A long-standing quest in materials science has been the development of tough epoxy resin nanocomposites for use in numerous applications. Inspired by nacre, here we report tough and conductive MXene/epoxy layered bulk nanocomposites. The orientation of MXene lamellar scaffolds is enhanced by annealing treatment. The improved interfacial interactions between MXene lamellar scaffold and epoxy through surface chemical modification resulted in a synergistic effect. Tailoring the interlayer spacing of MXene nanosheets to a critical distance resulted in a fracture toughness about eight times higher than that of pure epoxy, surpassing other epoxy nanocomposites. Our nacre-inspired MXene/epoxy layered bulk nanocomposites also show high electrical conductivity that provides self-monitoring capability for structural integrity and exhibits an excellent electromagnetic interference shielding efficiency. Our proposed strategy provides an avenue for fabricating high-performance epoxy nanocomposites.     

Experimental fracture study of MWCNT/epoxy nanocomposites under the combined out-of-plane shear and tensile loading

In order to explore the role of multi-walled carbon nanotubes (MWCNTs) on the fracture behavior of epoxy-based nanocomposites, fracture tests were conducted under the combined out-of-plane shear and tensile loading. Epoxy resin LY-5052 together with MWCNT contents of 0.1, 0.5 and 1.0 wt% were used to produce nanocomposite specimens. The results showed that increasing the contribution of out-of-plane shear from pure mode I towards pure mode III enhanced fracture toughness for both pure epoxy and nanocomposites. Additionally, it was found that in both loading conditions of pure mode III and mixed mode I/III, increasing MWCNT content up to 1.0 wt% enhanced fracture toughness with an ascending trend. The mechanisms involved in the fracture behavior of polymer-based nanocomposites were also studied in detail using the photographs taken from the fracture surfaces by scanning electron microscopy.     

Ultra‐Tough Inverse Artificial Nacre Based on Epoxy‐Graphene by Freeze‐Casting

Epoxy nanocomposites combining high toughness with advantageous functional properties are needed in many fields. However, fabricating high‐performance homogeneous epoxy nanocomposites with traditional methods remains a great challenge. Nacre with outstanding fracture toughness presents an ideal blueprint for the development of future epoxy nanocomposites. Now, high‐performance epoxy‐graphene layered nanocomposites were demonstrated with ultrahigh toughness and temperature‐sensing properties. These nanocomposites are composed of ca. 99 wt % organic epoxy, which is in contrast to the composition of natural nacre (ca. 96 wt % inorganic aragonite). These nanocomposites are named an inverse artificial nacre. The fracture toughness reaches about 4.2 times higher than that of pure epoxy. The electrical resistance is temperature‐sensitive and stable under various humidity conditions. This strategy opens an avenue for fabricating high‐performance epoxy nanocomposites with functional properties.     

Coupon Tests on z-Pinned and Unpinned Composite Samples for Damage Resistant Applications

The main objective of the work was to determine the mechanical properties of Z-pinned and unpinned composites samples. Tensile and interlaminar fracture tests under mode I have been carried out on thermoset polymer matrix composite samples composed of CYTEC 977-2 and carbon fibre yarn HTA-12K/35. The presence of the Z-pins has been found to significantly increase the interlaminar fracture toughness. The crack resistance improvement has been found to be accompanied by a small reduction of the in-plane stiffness properties for a Z-pins density of 2%. The results are presented in relation to the size and pinning quality and are rationalised on the basis of the location of Z-pin block within the sample.     

Influence of the network chain orientation on the fracture toughness of a mesogenic epoxy resin modified with CTBN

A biphenol‐type epoxy resin, which had a mesogenic group in the backbone moiety, was modified with carboxy‐terminated butadiene acrylonitrile copolymer (CTBN) as a reactive elastomer, and its fracture toughness was measured. With the addition of CTBN, the fracture toughness of the biphenol‐type epoxy resin significantly increased and became significantly higher than that of a bisphenol A‐type epoxy resin modified with CTBN. The network chain orientation in the cured biphenol‐type epoxy resin system was clearly observed during the fracture process with polarized microscopy Fourier transform infrared measurements, although such a phenomenon was not observed in the bisphenol A‐type epoxy resin system. The high toughness of the cured biphenol‐type system was clearly due to the consumption of the mechanical energy by a large deformation of the matrix resin due to the orientation of the network chains during the fracture process. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1198–1209, 2003     

Effect of phase change microcapsules on the thermo-mechanical,fracture and heat storage properties of unidirectional carbon/epoxy laminates

This work aims at producing and characterizing unidirectional carbon/epoxy composites containing different fractions of paraffin microcapsules (MC) for thermal management applications. The viscosity of the epoxy/MC mixtures increases with the MC content, thereby increasing the final matrix weight and volume fraction and reducing that of the fibers. This is at the basis of the decrease in mechanical properties of the laminates with high MC concentration (the elastic modulus decreases up to 53% and the flexural strength up to 67%), but the application of theoretical models shows that this decrease is only due to the lower fiber volume fraction, and not to a change in the properties of the constituents or the fiber/matrix interaction. The MC phase is preferentially distributed in the interlaminar zone, which leads to a thickening of this region and a decrease in matrix-related properties, such as the interlaminar shear strength, which decreases of up to 70%. However, a modest MC fraction causes an increase in the mode I interlaminar fracture toughness of 48%, due to the introduction of new toughening mechanisms. On the other hand, an excessive MC content lets the crack propagating through the matrix and not at the fiber/matrix interface, thereby reducing the toughening mechanism provided by fiber bridging. For the thermal properties, the phase change enthalpy increases with the MC fraction up to 48.7 J/g, and this is reflected in better thermal management performance, as proven by thermal imaging tests. These results are promising for the development of multifunctional polymer composites with thermal energy storage and thermal management properties, and future works will be focused on a deeper study of the micromechanical properties of PCM microcapsules and on the improvement of the capsule/matrix adhesion.     

Interfacial adhesion and microfailure modes of electrodeposited carbon fiber/epoxy-PEI composites by microdroplet and surface wettability tests

Interfacial properties and microfailure modes of electrodeposition (ED)-treated carbon fiber-reinforced polyetherimide (PEI) toughened epoxy composite were investigated using microdroplet test and the measurement of surface wettability. ED was performed to improve the interfacial shear strength (IFSS). As PEI content increased, IFSS increased due to enhanced toughness and plastic deformation of PEI. In the untreated case, IFSS increased with adding PEI content, and the IFSS of the pure PEI matrix showed the highest. On the other hand, for the ED-treated case IFSS increased with PEI content with rather low improvement rate. In the untreated case, neat epoxy resin appeared brittle microfailure mode, whereas the pure PEI matrix exhibited a more likely ductile microfailure mode. In the ED-treated case, neat epoxy exhibited a more ductile fracture than that of the untreated case. Critical surface tension and polar surface free energy of ED-treated carbon fiber was higher than those of the untreated fiber. The work of adhesion between fiber and matrix was not directly proportional to IFSS for both the untreated and ED-treated cases. The matrix toughness might contribute to IFSS more likely than the surface wettability. Interfacial properties of the epoxy-PEI composite can be affected efficiently by both the control of matrix toughness and ED treatment.     

Effect of scale and surface chemistry on the mechanical properties of carbon nanotubes‐based composites

In this article, Multi‐Walled Carbon Nanotubes (MWCNTs) of varying diameters, both untreated and polycarboxylated, were dispersed at constant weight percentage in an epoxy matrix, and resulting fracture toughnesses (K_Ic) were measured in each case. We show that changing the MWCNT diameter has two effects on the composite fracture toughness: (i) a small MWCNT diameter enables larger interfacial surface for adhesion maximization, which increases toughness; (ii) at the same time, it limits the available pull‐out energy and reduces the MWCNT ability to homogeneously disperse in the matrix due to this same large active surface: this decreases toughness. Most commercially available MWCNTs have a length range of several μm, thus an optimal diameter exists which depends on MWCNT wall thickness and surface treatment. Such optimal diameter maximizes pull‐out energy and thus composite fracture toughness. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Graft interpenetrating polymer networks of polyurethane and epoxy. II. Toughening mechanism

Graft interpenetrating polymer networks (graft-IPNs) of polyurethane (PU) and the diglycidyl ether of bisphenol A (epoxy) were prepared by first grafting excess PU prepolymer to the epoxy and then simultaneously polymerizing the PU prepolymer and epoxy. The fracture properties, at high shear rate (e.g., impact) and low shear rate (e.g., pseudostatic tensile fracture energy measurement) of these graft-IPNs exhibit opposite behavior. Although dispersed rubber particles can enhance the Izod impact strength, toughening of the matrix of graft-IPNs was found to be the main contribution. In contrast, it was found that a heterogeneous morphology with suitably dispersed rubber domains of appropriate size as well as the toughness of the matrix are requirements for effectively increasing the fracture energy at low shear rate. A reinitiating crack in the plastic matrix is proposed as the main toughening mechanism and can be invoked to interpret the fracture behavior at high and low shear rates of the graft-IPNs.     

Effect of acidic surface treatment of red mud on mechanical interfacial properties of epoxy/red mud nanocomposites

In this work, red mud (RM) was chemically modified by 0.1, 1, and 5 M H(3)PO(4) solution to prepare epoxy/RM nanocomposites. The effect of chemical treatment on a RM surface was studied in terms of pH, acid-base values, N(2)/77 K gas adsorption, equilibrium spreading pressure (pi(e)), and surface free energy. The mechanical interfacial properties of epoxy/RM nanocomposites was measured in the context of critical stress intensity factor (K(IC)) and critical strain energy release rate (G(IC)) measurements. From the experimental results, the acidic surface treatment led to a modification of the RM surface properties, such as the surface acid values, porosity, specific surface area, pi(e), and London dispersive component (gamma(S)(L)) of surface free energy of the treated RM as an increase of the treatment concentration. In the fracture toughness (K(IC) and G(IC)) measurements, the mechanical interfacial properties of epoxy/treated RM nanocomposites were intimately correlated with the improvement of interfacial adhesion between the RM surface and a matrix and the increase of gamma(S)(L) of surface free energy of the RM due to the development of S(BET) or porosity of RM surfaces.     

Comparison of static and fatigue interlaminar testing methods for continuous fiber reinforced polymer composites

Two different interlaminar fatigue testing methods have been compared by testing a carbon fiber reinforced epoxy (CF/EP) composite and a carbon fiber/multiwalled carbon nanotube reinforced epoxy (CF/MWCNT/EP) hybrid nanocomposite. The first, conventional fatigue testing method was the end-notched flexure (ENF) test, which was used as a reference. The second, novel technique was the fatigue interpretation of the double-notch shear (DNS) test. Both tests have been performed with static and cyclic loading to compare the evaluated properties of the different systems, the effect of transition from cyclic to fatigue loading and to demonstrate if the complex ENF test can be replaced by the simpler DNS test.The test results showed the slight beneficial effect of the nanoreinforcement in both static and cyclic load conditions, and the possibility to use the DNS test for fatigue testing of continuous fiber reinforced composites. The SEM micrographs taken of the fracture surfaces of the composites after the different interlaminar tests provide valuable data on the interlaminar failure phenomena of hybrid nanocomposites in both static and fatigue loading conditions.     

Toughening of Epoxy Nanocomposites: Nano and Hybrid Effects

In this paper, we review recent progress made in the field of epoxy-based binary and ternary nanocomposites containing three-, two-, and one-dimensional (i.e., 3D-, 2D-, and 1D) nano-size fillers with a special focus on their fracture behaviors. Despite investigations conducted so far to evaluate the crack-resistance of epoxy nanocomposites and attempts made to clarify the controlling toughening mechanisms of these materials, some questions remain unsolved. It is shown that silica nanoparticles can be as effective as rubber particles in improving the fracture toughness/energy; but incorporation of carbon nanotubes (CNTs) or clay platelets in epoxy matrices delays crack growth only modestly. The “nano” effects of silica (<25 vol.%) and rubber (>10 wt.%) nanoparticles in toughening epoxy resin are confirmed by comparison with silica and rubber micro-particles of the same loading. There is clear evidence of both synergistic and additive toughening effects in the silica/rubber/epoxy ternary nanocomposites. In addition, positive hybrid toughening effect has been observed in the nano-rubber/CNT/epoxy composites; however, a negative hybrid effect is predominant in nano-clay/nano-rubber/epoxy ternary nano-composites. Future research directions for epoxy-based nanocomposites towards multi-functional applications are discussed.     

Studies on PAN-based carbon fibers irradiated by Ar+ ion beams

In this work, the effects of Ar+ ion beam irradiation on carbon fibers were studied using tensile and surface analytical techniques. The single-fiber pull-out test was executed in order to characterize the fiber/epoxy matrix interfacial adhesion. The Ar+ ion beam was irradiated using an ion-assisted reaction (IAR) method in reactive gas conditions under an oxygen environment with 1 x 10(16) ions/cm(2) Ar+ ion dose (ID), 6 sccm blown gas flow rate, and different ion beam energy intensities. From the experimental results, both the interfacial shear strength (IFSS) and fracture toughness (Gi) were found to increase with increasing Ar+ ion irradiation intensity. This was probably due to the fact that Ar+ ion beam irradiation on carbon fibers was effective in altering their surface physical chemistry and structural morphology, resulting in improved interfacial adhesion in the fiber/epoxy matrix. The reliability of single-fiber pull-out test data could be improved by statistical analysis using the Weibull distribution, which served to predict the variation of the mechanical interfacial properties in a composite system.     

Development and thermo‐mechanical behavior of nanocomposite epoxy adhesives

Two kinds of organo‐modified (OM) clays were dispersed in an epoxy resin for the preparation of nanocomposite adhesives at various filler amounts. XRD tests evidenced the formation of intercalated structures, increasing the intercalation degree with the clay hydrophilicity. The original transparency of the samples was retained up to a filler content of 3 wt%, and then decreased due to filler agglomeration. The glass transition temperature of nanocomposites filled with the more hydrophilic clay (30B) raised up to a filler content of 3 wt% and then decreased, probably because of the concurrent and contrasting effects of the physical chain blocking and reduction of the cross‐linking degree. Also elastic modulus, stress at break, and fracture toughness were sensibly improved by nanoclay addition up to filler loadings of 0.5–1 wt%. For higher concentrations the positive contribution of clay nanoplatelets was counterbalanced by the presence of agglomerated tactoids in the matrix. Mechanical tests on single‐lap composite (epoxy/glass) bonded joints evidenced an enhancement of the shear strength by about 25% for an optimal filler content of 1 wt%. Therefore, it was concluded that the addition of a proper amount of OM clay to epoxy adhesives could represent an effective way to improve the shear resistance of adhesively bonded composite structures. Copyright © 2011 John Wiley & Sons, Ltd.     

Clay dispersibility and mechanical property of the epoxy/clay nanocomposites prepared by different treatment methods

The bisphenol‐A type epoxy resin was combined with layered clays. Three types of epoxy/clay nanocomposites were prepared by different clay pretreatment methods, that is, the slurry (clay swelling with polar solvent), organo, and solubilization (organoclay swelling with polar solvent) methods. The organo and solubilization systems showed good dispersibility. The basal spacing of the layered clays in the obtained nanocomposites was evaluated by XRD and TEM observations. The basal spacing of the nanoclay in the solubilization system drastically increased. The mechanical properties were improved with the increase in the clay dispersion. A high modulus and fracture toughness were obtained by improvement of the clay dispersion into the matrix. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1753–1761, 2009     

Polymer blends based on epoxy resin and polyphenylene ether as a matrix material for high-performance composites

The application of poly(2,6-dimethyl-1,4-phenylene ether), PPE, as a matrix material for continuous carbon fibre reinforced composites has been studied. Due to the intractable nature of PPE melt impregnation is not feasible and a novel impregnation route, using epoxy resin as a reactive solvent, was developed. The introduction of epoxy resin results in enhanced flow and a reduced processing temperature, enabling the processing of PPE and the preparation of high quality composites. Upon curing, phase separation is initiated and epoxy resin is converted into a second phase. In composites, epoxy resin preferentially accumulates at the polar fibre surface, resulting in an epoxy layer around the fibres, providing a high level of interfacial adhesion. For a high fibre volume fraction (> 50%) this results in the ultimate morphology of epoxy coated fibres in a neat PPE matrix. Due to this unique morphology the composite materials reveal outstanding mechanical properties in terms of interlaminar toughness and impact performance.     

Interlaminar Fracture Toughness Characterization of Laminated Composites: A Review

Abstract

Interlaminar fracture toughness had been the subject of great interest for several years and is still interesting to the research community. In this article, a comprehensive analysis of fracture toughness in FRP laminates is presented. Primarily, toughness studies are undertaken on glass and carbon fiber reinforced composites under mode-I and mode-II loading conditions. The fracture behavior and its failure pattern depend on a number of parameters: fiber sizing/coating, matrix modification, insert film, fiber volume fraction, stacking sequence, specimen geometry, loading rate and temperature change. In fact, a state-of-the-art process enables increasing fracture resistance with “matrix toughening by carbon nanotubes (CNT) inclusion”. It enables production of materials having ultra-high strength and low weight. The present study has highlighted the available techniques of CNT incorporation: mechanical mixing, grafting and interleaving. Other aspects, such as the dispersion level, matrix viscosity, fiber surface roughness, loading weight %, bonding strength with epoxy, height and density of grown CNT, energy absorption mechanism during delamination, etc., have been examined as well. Although a clear correlation of all these parameters with fracture toughness is hard to establish, there is growing understanding of the surface-grown CNTs and interleaving processes as they ensure significant increase in fracture toughness.