Characterisation of nanoclay dispersion in resin transfer moulded glass/nanoclay/epoxy composites

Abstract

A novel approach for characterisation of nanoclay dispersion in polymeric composites using electron microprobe analysis (EMPA) is presented. Dispersion analysis was performed on three sets of centre-gated discs fabricated by resin transfer moulding. The first set was neat epoxy polymer without reinforcement, whereas the second set comprised 17 vol.-% randomly oriented chopped glass fibre preforms. The last set, in addition to the glass fibre reinforcement, contained 1·7 wt-% Cloisite 25A nanoclay. Upon completion of curing, a sample along the radius of a nanoclay reinforced disc was analysed on a Cameca SX50 electron microprobe analyser. The results from scanning electron micrographs indicated that nanoclay exists in clusters of various sizes ranging from over 10 μm down to submicrometre scale. Nanoclay clusters larger than 1·5 μm, were analysed by digital image processing on the scanning electron micrographs taken along the part's radius. The dispersion of nanoclay smaller than 1·5 μm was quantified by compositional analysis via wavelength dispersive spectrometry (WDS). Distribution of nanoclay clusters larger than 1·5 μm was found to be approximately constant along the radius with an average value of 1·4% by volume. Similarly, nanoclay clusters smaller than 1·5 μm were found to be distributed evenly with an average value of 0·41 wt-%. To investigate the effect of nanoclay on thermo-mechanical properties, glass transition temperature of moulded samples was measured under oscillatory shear. At the current dispersion state, the glass transition temperature improved 11% with the addition of nanoclay.     

Influence of silane coupling agents on the surface energetics of glass fibers and mechanical interfacial properties of glass fiber-reinforced composites

The effect of various silane coupling agents on glass fiber surfaces has been studied in terms of the surface energetics of fibers and the mechanical interfacial properties of composites. γ-Methacryloxypropyltrimethoxysilane (MPS), γ-aminopropyltriethoxysilane (APS), and γ-glycidoxypropyltrimethoxysilane (GPS) were used for the surface treatment of glass fibers. From contact angle measurements based on the wicking rate of a test liquid, it was observed that silane treatment of glass fiber led to an increase in the surface free energy, mainly due to the increase of its specific (or polar) component. Also, for the glass fiber-reinforced unsaturated polyester matrix system, a constant linear relationship was observed in both the interlaminar shear strength (ILSS) and the critical stress intensity factor (K_IC) with the specific component, γ_S ^SP, of the surface free energy. This shows that the hydrogen bonding, which is one of the specific components of the surface free energy, between the glass fibers and coupling agents plays an important role in improving the degree of adhesion at the interfaces of composites.     

Modification of Glass Fiber-Reinforced Epoxy with Amine Functional Aniline Formaldehyde Condensate (AFAFC)

Unmodified epoxy glass fiber laminates are brittle by nature. In this study, an improvement of the mechanical properties, such as impact, tensile and flexural strengths of the reinforced glass fiber diglycidyl ether of bisphenol-A based epoxy laminate, was carried out by incorporating an amine functional aniline formaldehyde condensate (AFAFC) modifier. AFAFC was synthesized by reacting aniline and formaldehyde in an acid medium (pH 4) and was characterized by FT-IR and 1-H NMR spectroscopy, viscosity measurements, elemental analysis and potentiometric titration. The fracture energies of the modified glass fiber composite were vastly improved and the improvement depended on the concentration of the modifier. The optimum properties were obtained by adding 10 phr (parts per hundred parts of epoxy resin) of the modifier. Furthermore, the fracture energies of the modified glass fiber composite increased with increasing the number of glass fiber layers. Scanning electron microscopy showed that round shaped AFAFC oligomer domains were formed in the matrix. These oligomer domains led to improved strength and toughness due mainly to the 'rubber toughening' effect in the brittle epoxy matrix. The thermal stability of the modified epoxy composites by thermogravimetric analysis was also reported.     

Wettability of glass fibers by reactive thermoplastic/polyester blends: comparison between compatible and incompatible blends

The evolution of morphology of reactive thermoplastic/unsaturated polyester blends at the surface of glass fibers is investigated during curing. The study focuses on two different types of thermoplastics, incompatible and compatible respectively with the polyester resin. Poly(dimethylsiloxane) and poly(methyl methacrylate) are chosen as incompatible thermoplastics, and poly(vinyl acetate) as a compatible thermoplastic. In the presence of incompatible thermoplastics, the blends form an emulsion during the entire course of curing. In that case, a correlation exists between the surface tensions of the components of the blend measured before curing and the final morphology at the surface of the fibers. For a compatible thermoplastic, on the other hand, a reaction-induced phase separation occurs during curing. In that case, the morphology at the surface of the fiber after phase separation cannot be fully determined by the surface tensions of the components.     

Processing and properties of co-injected resin transfer molded vinyl ester and phenolic composites

Vacuum Assisted Resin Transfer Molding type processes have been proven to be cost effective manufacturing techniques for large composite structures. However, their use has been limited to a single resin system. A large variety of composite structures require multiple resins to serve different purposes while being integrated into a single structure. Co-Injection Resin Transfer Molding (CIRTM) is a new manufacturing process, developed at the University of Delaware's Center for Composite Materials in collaboration with the U.S. Army Research Laboratory, that enables the user to manufacture multi-layer hybrid composite parts in a single processing step (1). In this paper, CIRTM is used to manufacture a dual layered structure consisting of a vinyl ester layer for structural integrity and a phenolic layer for fire, smoke, and toxicity protection. The two resins are simultaneously injected into a mold filled with a stationary fiber bed and are co-cured. Resin separation is maintained by a 0.0254 mm (0.001 in) thick polysulfone film sandwiched between two layers of 0.165 mm (0.0065 in) thick adhesive. A Differential Scanning Calorimeter (DSC) is used to select the optimum cure cycle for all of the materials. Mechanical testing is used to evaluate the performance of the interphase formed between dissimilar materials. Short beam shear (SBS) is used to evaluate the overall quality of the part produced. Double cantilever beam (DCB) is used to quantify the fracture toughness of the interphase, and the wedge test is used to evaluate the durability of the interphase. Experimental results show that co-injected, co-cured materials offer properties equivalent, or in some cases, superior, to those provided by single injection resin composites. This case is used to develop and present a methodology that can be followed to co-inject different resins.     

Modification of epoxy resin by polysulfone to improve the interfacial and mechanical properties in glass fibre composites. I. Study of processes during matrix/glass fibre interface formation

The rheology of epoxy resin-polysulfone blends and wetting at the blend/glass fibre interface have been studied. Measurements were made in a rotary viscometer and in a modified Wilhelmy apparatus. It was shown that none of the blends investigated revealed non-Newtonian behaviour in the range of shear rates used. The viscosity of the blends increased as polysulfone content increased. Introduction of hardener resulted in a significant increase of the blends viscosity up to 2-3 orders of magnitude. Rheological tests suggested that 15 wt% polysulfone was the highest concentration useful for obtaining composites by solvent-free impregnation technique. These tests suggested that the structure of the cured epoxy-polysulfone blends depended on the modifier concentration. The structures of the blends differed for the blends containing 5 wt% polysulfone and 10-15 wt% polysulfone. All the blends (with the hardener) required at least 30 min at 180°C to achieve final values of the mechanical properties such as storage and loss moduli, loss tangent and complex viscosity. For all epoxy resin-polysulfone/glass fibre systems a complete wetting of the fibres was observed. Surface tension vs. polysulfone content dependency was found to be nonadditive. Surface tension measured was minimal for epoxy resin-5% polysulfone blend, while for other systems the values were close to that of epoxy resin. Modification of epoxy resin by polysulfone did not change the kinetics of the fibres wetting by the blends.     

The effect of silica (SiO2) nanoparticles and ammonia/ethylene plasma treatment on the interfacial and mechanical properties of carbon-fiber-reinforced epoxy composites

A nanoparticle dispersion is known to enhance the mechanical properties of a variety of polymers and resins. In this work, the effects of silica (SiO₂) nanoparticle loading (0–2 wt%) and ammonia/ethylene plasma-treated fibers on the interfacial and mechanical properties of carbon fiber–epoxy composites were characterized. Single fiber composite (SFC) tests were performed to determine the fiber/resin interfacial shear strength (IFSS). Tensile tests on pure epoxy resin specimens were also performed to quantify mechanical property changes with silica content. The results indicated that up to 2% SiO₂ nanoparticle loading had only a little effect on the mechanical properties. For untreated fibers, the IFSS was comparable for all epoxy resins. With ethylene/ammonia plasma treated fibers, specimens exhibited a substantial increase in IFSS by 2 to 3 times, independent of SiO₂ loading. The highest IFSS value obtained was 146 MPa for plasma-treated fibers. Interaction between the fiber sizing and plasma treatment may be a critical factor in this IFSS increase. The results suggest that the fiber/epoxy interface is not affected by the incorporation of up to 2% SiO₂ nanoparticles. Furthermore, the fiber surface modification through plasma treatment is an effective method to improve and control adhesion between fiber and resin.     

Mechanical and dynamic mechanical analysis of hybrid composites molded by resin transfer molding

This work aims to evaluate the performance of glass/sisal hybrid composites focusing on mechanical (flexural and impact) and dynamic mechanical analyses (DMTA). Hybrid composites with different fiber loadings and different volume ratios between glass and sisal were studied. The effect of the fiber length has also been investigated. The densities of the composites were compared with the theoretical values, showing agreement with the rule of mixtures. The results obtained in the flexural and impact analysis revealed that, in general, the properties were always higher for higher overall reinforcement content. By DMTA, an increase in the storage and loss modulus was found, as well as a shift to higher values for higher glass loading and overall fiber volume. It was also noticed an increase in the efficiency of the filler and the calculated activation energy for the relaxation process in the glass transition region. The fiber length did not significantly change the results observed in all analyses carried out in this work. The calculated adhesion factor increased for higher glass loadings, meaning the equation may not be applied for the system studied and there are other factors, besides adhesion influencing energy dissipation of the composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Matrix formulation and interfacial enhancement of an aeronautical carbon fabric/epoxy composites fabricated via resin transfer molding (RTM) technique

Flexural strength and interlaminar shear strength of fiber-reinforced composites are among the most concerned properties in the aeronautical sector, which are ameliorated in combination through matrix formulation and interfacial enhancement in this study. A thermosetting matrix resin consisting of diglycidyl ether of bisphenol A and diglycidyl ester of aliphatic cyclo was formulated to cater to the requirements of carbon fabric/epoxy composites fabricated by resin transfer molding (RTM) technique. The toughness and thermal stability of the formulated epoxy resin were studied in consideration of the compromise among processability, thermal and mechanical properties for potential aeronautical applications. The processability of the matrix resin suitable for RTM technique was evaluated with respect to temperature-dependent and time-dependent viscosity. A regime for the curing and post-curing cycles was established according to the differential scanning calorimeter data. Air plasma is introduced herein as a technique to enhance the interfacial adhesion of carbon fabric/epoxy composites. Composites based on the epoxy system and plasma-treated carbon fabric were fabricated using the RTM technique. The reactive groups introduced by plasma treatment are responsible for the significant improvements of mechanical properties of the resulting composites. The microscopy pictures of the fracture surfaces confirm that the failure mode of carbon fabric/epoxy composites has changed initially from primarily adhesive failure to cohesive failure.     

Surface structure of silane-treated glass beads and its influence on the mechanical properties of filled composites

The surface treatment of glass beads, chosen as a model filler, was carried out using four different silane coupling agents with multilayer coverage. For this purpose, silanes having an aminopropyl or a methacryloxypropyl group as an organofunctional group with di- or tri-alkoxy structures were used. The amount of silane detected on the bead surface was four to six times that required for a monolayer coverage. The topography of the silane layer on the bead surface was observed using an atomic force microscope. The topography was strongly affected by the composition of the silane solution and the number of alkoxy groups in the silane. The effects of the organofunctional group and the number of alkoxy groups of the silanes on the mechanical properties of bead-filled poly(vinyl chloride), chosen as a typical ductile polymer, were investigated. A higher yield stress was observed for the silane with an aminopropyl group than for that with a methacryloxypropyl group. Furthermore, for each organofunctional group, the yield stress was higher for the silane with a dialkoxy structure than for that with a trialkoxy structure. However, their effects on the elongation-at-break were contrary to the above tendencies.     

Structural composites formed by reaction injection moulding Interlaminar fracture properties of glass fibre mat-copoly(urea/isocyanurate) resin composites

Abstract

Structural (SRIM) composites, comprising up to 40% by volume of random continuous glass fibres in a specially developed copoly(urea/isocyanurate) (PUrI) matrix, have been formed via reaction injection moulding (RIM). The two stage polymerisation process of the PUrI matrix provided low initial viscosity during mould filling followed by a 'snap cure' to give tough composite materials in <30 s. Characterisation by DMTA confirmed the two phase morphology of the rubber toughened glassy matrix. Mode I and mode II interlaminar fracture tests, carried out in accordance with the ESIS protocol, gave values of G _Ic and G _IIc in the ranges 1·4-2·8 kJ m^-2 and 3·3-5·0 kJ m^{- 2}, respectively, and were an order of magnitude greater than those determined for unidirectional carbon fibre-epoxy composites. The G _Ic values for the SRIM composites are a factor of 2-3 greater than that (0·8 kJ m^-2) for the unreinforced PUrI matrix and show significant variation due to extensive fibre bridging during crack propagation.     

The role of multi‐walled carbon nanotubes in epoxy nanocomposites and resin transfer molded glass fiber hybrid composites: Dispersion,local distribution,thermal, and fracture/mechanical properties

Hybrid composites containing endless glass fiber reinforcement and surface‐functionalized carbon nanotubes (CNTs) dispersed in the matrix phase were produced by resin transfer molding (RTM). An efficient surface modification of the nanotubes enhances the compatibility with the matrix system and the dispersion quality, enabling the impregnation process via liquid composite molding. We assessed the quality of the RTM process by newly developed methodologies for the quantification of the filtering of CNTs. First, we established a method to analyze the CNT length distribution before and after injection for thermosetting composites to characterize length‐dependent withholding respectively the size distribution of nanotubes in the hybrid composites. Second, the resulting test laminates were locally examined by Raman spectroscopy and compared to reference (nanocomposite) samples of known CNT content to non‐destructively quantify the local CNT concentration along the resin flow path. Moreover, the thermal and mechanical properties of the modified composites were investigated. The nanocomposites containing 0.5 wt% surface‐functionalized CNTs exhibited superior ductility and increased fracture toughness. Glass fiber hybrid composites containing 0.5 wt% functionalized CNTs in the resin phase exhibited increased fracture toughness in mode I and a slight deterioration in mode II due to the constrained formation of hackles. POLYM. COMPOS., 38:1849–1863, 2017. © 2015 Society of Plastics Engineers     

Moisture sorption on the wetting behavior of poly(p-phenylene terephthalamide) fibers in water and epoxy resin

The moisture sorption of poly(p-phenylene terephthalamide) (PPTA) fibers and the effects of moisture on the wetting behavior of these fibers in water and in an epoxy resin were studied. The moisture regains in the Kevlar 149 fibers followed a third order polynomial dependency on increasing relative humidity at 23°C. When preconditioned at 0% relative humidity (R.H.), water wettability of Kevlar 49 fibers was superior to that of Kevlar 149 fibers. Resin wettability of the dried Kevlar 49 fibers, on the other hand, was lower than that of Kevlar 149 fibers. Wettability in water and resin of these two fiber types was affected differently by moisture. Exposure to 97% R.H. moisture level significantly lowered water wettability of Kevlar 49 fibers but did not affect the wettability of Kevlar 149 fibers in water. Resin wettability of Kevlar 49 fibers was improved upon exposure to moisture, but the opposite was observed on Kevlar 149 fibers.     

Study of miscibility of melamine-formaldehyde resin and poly(vinyl acetate) blends for use as adhesives in engineered flooring

The objective of this research was to investigate the miscibility behavior of melamine-formaldehyde (MF) resin and poly(vinyl acetate) (PVAc) blends for their use as adhesives for bonding fancy veneer and plywood in engineered flooring, by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR). Blends of various compositions of MF resin/PVAc were prepared. To determine and compare the effect of PVAc content, blends with PVAc to MF resin weight ratios of 0, 30, 50, 70 and 100% were prepared. These blends displayed a single cure temperature over the entire range of compositions indicating that this blend system was miscible in the amorphous phase due to the formation of hydrogen bonding between the amine groups of the MF resin and the carbonyl groups of PVAc.     

Mechanical properties of poly(styrene‐co‐acrylonitrile)‐modified epoxy resin/glass fiber composites

Poly(styrene‐co‐acylonitrile) was used to modify diglycedyl ether of bisphenol‐A type epoxy resin cured with diamino diphenyl sulfone and the modified epoxy resin was used as the matrix for fiber‐reinforced composites (FRPs) to get improved mechanical properties. E‐glass fiber was used as fiber reinforcement. The tensile, flexural, and impact properties of the blends and composites were investigated. The blends exhibited considerable improvement in mechanical properties. The scanning electron micrographs of the fractured surfaces of the blends and tensile fractured surfaces of the composites were also analyzed. The micrographs showed the influence of morphology on the properties of blends. Results showed that the mechanical properties of glass FRPs increased gradually upon fiber loading. Predictive models were applied using various equations to compare the mechanical data obtained theoretically and experimentally. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical and thermal properties of environment-friendly “green” composites made from pineapple leaf fibers and poly(hydroxybutyrate-co-valerate) resin

This paper presents the mechanical and thermal properties of unidirectional, degradable, environment-friendly “green” composites made from pineapple fibers and poly(hydroxybutyrate-co-valerate) (PHBV) resin. Tensile and flexural properties of the “green” composites with different fiber contents were measured in both longitudinal and transverse directions. Compared to those of virgin resin, the tensile and flexural strengths of “green” composites are significantly higher in the longitudinal direction while they are lower in the transverse direction. However, the mechanical properties are lower than those predicted by simple models. Scanning electron microscope (SEM) photomicrographs of the tensile fracture surfaces demonstrate fibers being pulled out from the matrix, the interfacial failure, fiber fibrillation, and the nonunidirectional nature of the “green” composites. The thermal behavior of the “green” composites, studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), showed that the presence of pineapple fibers does not affect the nonisothermal crystallization kinetics, crystallinity, and thermal decomposition of PHBV resin.     

Determining the mechanical properties of epoxy resin (DGEBA) composites by ultrasonic velocity measurement

In this study, the composites of diglycidyl ether of bisphenol A (DGEBA) epoxy resin that have been formed by mixing epoxy resin with allyl glycidyl ether (AGE) and 2,3‐epoxypropyl methacrylate [glycidyl methacrylate (GMA)] were prepared in weight % ratios of 90 : 10, 80 : 20, and 70 : 30. A computer controlled analyzer with 35 MHz and a digital oscilloscope with 60 MHz were used for measuring the velocities of ultrasonic wave. The measurement of ultrasonic velocity carried out by pulse echo method at frequencies of 2.25 and 3.5 MHz at room temperature. The values of acoustic impedance (Z), Poisson ratio (μ), and coefficients of elasticity (L, G, K, E) of composites were calculated by values of densities and velocities that obtained. Thus, the effect of modificating epoxy resin (DGEBA) by AGE and GMA on mechanical properties of DGEBA was investigated using the ultrasonic method. Atomic force microscopy has been used for determining the microstructure of composites. By the results obtained from the investigation, it have been established that the longitudinal and shear ultrasonic wave velocities, and the values of all the elasticity constants of DGEBA were increased by modification with AGE and GMA. Also the most suitable combination ratio for the compound of DGEBA : AGE and DGEBA : GMA has been found as 80 : 20. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Microstructure and properties of polypropylene/glass fiber composites grafted with poly(pentaerythritol triacrylate)

Isotactic polypropylene(PP)/glass fiber(GF) composites were modified by grafting polymerization of polyfunctional monomer, pentaerythritol triacrylate (PETA), in the presence of 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane peroxide (DDHP) via melt extrusion. Fourier transform infrared spectroscopy (FTIR), melt strength test (MS), mechanical property test, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) were used to characterize the microstructure and properties of the modified composites. The crystallization kinetics was investigated by Mo method while apparent activation energy of crystallization of the composites was determined by Kissinger method. The FTIR results showed that the acrylic polymers were grafted onto the polypropylene chains. The grafting made the melt strengths and the mechanical properties of the modified composites, and the interfacial adhesion between PP and glass fiber all enhanced. High melting and crystallization temperatures, high crystallization rate and large activation energy of crystallization were also obtained after grafting. In addition, the grafted acrylic polymers recovered the depressed crystallization of polypropylene and restrained α-β transition in fatigue experiment.     

Thermal properties of extruded injection‐molded poly(lactic acid) and milkweed composites: Degradation kinetics and enthalpic relaxation

To determine the degree of compatibility between poly(lactic acid) (PLA) and different biomaterials, PLA was compounded with milkweed fiber, a new crop oil seed. After oil extraction, milkweed remaining cake retained approximately 10% residual oil, 47% protein, and 10% moisture. The fiber (300 μm) was added at 85 : 15 and 70 : 30 PLA : Fiber and blended by extrusion (EX) followed by injection molding (IM). Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used for testing the composites. After melting in the DSC sealed pans, composites were cooled by immersion in liquid nitrogen and aged (stored) at room temperature for 0, 7, 15, and 30 days. After storage, samples were heated from room temperature to 180°C at 10°C/min. The pure PLA showed a glass transition (T_g) at 60.3°C and the corresponding ΔCp was 0.464 J/g/°C followed by crystallization and melting transitions. The enthalpic relaxation (ER) of neat PLA and composites steadily increased as a function of storage time. Although the presence of fiber had little effect on ER, IM reduced it. The percentage crystallinity of neat unprocessed PLA dropped by 95 and 80% for the EX and IM, respectively. The degradation activation energy (E_a) of neat PLA exhibited a significant drop in nitrogen environment, whereas increased in air, indicating PLA resistant to heat degradation in the presence of oxygen. Overall, IM appeared to decrease E_a of the composites, whereas milkweed significantly reduced E_a values in nitrogen environment. Enzymatic degradation of the composites revealed higher degradation rate for the EX samples versus IM, whereas 30% milkweed exhibited higher weight loss compared to the 15%. The degradation mechanism was observed by looking at the percent conversion as a function of E_a from the TGA data, where multisteps degradation occurred mostly in air. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

DSC analysis of crystallization and melting behavior of polypropylene in model composites with glass and poly(ethylene terephthalate) fibers

Isothermal and nonisothermal crystallization of maleic anhydride grafted polypropylene (PP), which is used for the production of split warp knit composite preforms,¹ are analyzed in model composites to determine the influence of reinforcement glass fibers (GF) and poly(ethylene terephthalate) (PET) binding yarns on the crystallization kinetics. Basic energetic parameters of crystallization are determined, and the melting behavior of PP in model composites is analyzed. The crystallization of PP carried out in nonisothermal and isothermal regimes is facilitated in the presence of GF, and the additional effects of PET fibers are also shown. Better conditions for nucleation, resulting in lower energy for formation of a stable nucleus and lower critical dimensions, are proposed as a reason for this. The crystal structure of PP in model composites exhibits lower lamellae thickness and is less disposed to recrystallization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 239–246, 1999