Micromechanics for fiber volume percent with a photocure vinyl ester composite

Micromechanics for fiber volume percent (V_f) from 0.0V_f to 54.0 V_f were conducted using (3 mm long × 9 μm diameter) high‐purity quartz fibers in a visible‐light vinyl ester particulate‐filled photocure resin. MTS fully articulated four‐point bend fixtures were used with a 40 mm test span and 50 × 2 × 2 mm³ sample dimensions. Specimens were tested following the combined modified ASTM standards for advanced ceramics ASTM‐C‐1161–94 and polymers ASTM‐D‐6272–00 for modulus, flexural strength, and yield strength. Experimental data provided reliable statistical support for the dominant fiber contribution expressed through the rule‐of‐mixtures theory as a valid representation of micromechanical physics. The rule‐of‐mixtures micromechanics described by V_f could explain 92, 85, and 78% of the variability related to modulus, flexural strength, and yield strength respectively. Statistically significant improvements with fiber addition began at 10.3V_f for modulus, 5.4V_f for flexural strength, and 10.3V_f for yield strength, p < 0.05. In addition, correlation matrix analysis was performed for all mechanical test data. An increase in V_f correlated significantly with increases in modulus, flexural strength, and yield strength as measured by the four‐point bending test, p < 10⁻¹⁰. All mechanical properties in turn correlated highly significantly with one another, p < 10⁻⁹. POLYM. COMPOS., 28:294–310, 2007. © 2007 Society of Plastics Engineers     

Effect of thermoplastic veils on interlaminar fracture toughness of a glass fiber/vinyl ester composite

The effects of two thermoplastic micro‐veils, polyamide (PA) and polyethylene terephthalate (PET) veil, on the interlaminar fracture toughness of a glass fiber/vinyl ester (GF/VE) composite were investigated. The veils incorporated into the composite as interleaving materials were first characterized via scanning electron microscopy (SEM), differential scanning calorimetry (DSC), contact angle and tensile testing in order determine the best candidate as toughening agent for the GF/VE composite. Composite laminates were manufactured by vacuum‐assisted resin infusion process. Double cantilever beam (DCB) testing was performed to investigate the Mode I type interlaminar fracture toughness of the composites, which was characterized by critical strain energy release rate (G _IC). An increased G _IC was obtained by incorporating the PA veil, but it changed negligibly by the addition of the PET veil. The analysis of the composites fracture surface via SEM revealed increased fiber bridging between adjacent plies in the case of PA veil interleaved composites which played a key role in enhancing the Mode I interlaminar fracture toughness. However, the PET veil present in the interlaminar region did not take part in any energy absorbing mechanism during the delamination, thus keeping the G _IC of the composite unaltered. POLYM. COMPOS., 38:2501–2508, 2017. © 2015 Society of Plastics Engineers     

Aryl phosphate ester fire‐retardant additive for low‐smoke vinyl applications

Additives that act as flame retardants can contribute significantly to smoke generation because they decrease the efficiency of the fuel source and, as a result, create a sooty combustion. Work on a new phosphate ester material has shown interesting results and synergies that complement both flame retardancy and low smoke generation in flexible vinyl compositions. This new proprietary aryl phosphate was examined in both neat and blended systems and compared to other typical phosphate ester fire‐retardant (FR) compounds for vinyl. Additionally, the flammability and smoke effects were measured with and without other common vinyl FR additives (zinc borate and ammonium octamolybdate). J. Vinyl Addit. Technol. 10:187–192, 2004. © 2004 Society of Plastics Engineers.     

Plasma‐graft polymerization of a monomer with double bonds onto the surface of carbon fiber and its adhesion to a vinyl ester resin

Double bonds reactive with active radical species were introduced onto the surface of carbon yarn by the plasma‐graft polymerization of adipic acid divinyl ester and ethylene glycol dimethacrylate monomers to increase the adhesive strength in the interface between the carbon yarn and a vinyl ester resin. The degree of grafting increased with increasing polymerization time and polymerization temperature. The degree of grafting depended on both the solvent and the monomer species used in the polymerization, and a high degree was obtained with ethylene glycol dimethacrylate as the conjugated monomer and in a mixture of methyl isobutyrate and water. The grafted yarn, whose surface layer contained double bonds, was reacted with a vinyl ester resin containing benzoyl peroxide and N,N‐dimethylaniline. The pull‐out force of the yarn embedded in the resin increased with increasing degree of grafting. The failure in pulling out the yarn was cohesive. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2415–2419, 2003     

Ion‐leaching behaviors and corrosion morphology of glass fiber reinforced vinyl ester composites in sulfuric acid solution

The corrosion mechanism of glass‐fiber reinforced vinyl ester composites was investigated by immersing composite samples in 40 wt% sulfuric acid solution at constant temperature of 35°C, 55°C, 65°C, and 75°C for periods up to 10,500 h. Results were characterized through weight gain tests, inductively coupled plasma analysis, and scanning electron microscope (SEM). Weight gains and ion‐leaching behaviors show that the composite interface has undergone significant changes due to a long corrosive environment, and the interface corrosion of composite increases with increasing the temperature. SEM images of surface and cross‐section of samples indicated that there exit in irreversible degradation reaction on resin matrix and interface in composite, which lead to the increase of weight gain and ion leachability, especially at high temperatures. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Aramid‐short‐fiber reinforced rubber as a tire tread composite

Mechanical and dynamic‐mechanical properties of a typical tire tread compound reinforced with one part aramid short fibers were investigated in order to predict the effects of fibers on tire tread performances such as rolling resistance and traction. Rubber processing, including mixing and extrusion, was performed in an industrial scale. Fiber orientation as a result of extrusion was evaluated quantitatively and qualitatively using mechanical anisotropy in swelling and scanning electron microscopy, respectively. Unidirectional tensile tests revealed higher modulus, but slightly lower strength and elongation at break for the composites stretched in the longitudinal (orientation) and transverse directions than those for the isotropic reference compound with no fiber. Dynamic mechanical thermal analysis showed that relative values of loss factor for the longitudinal and transverse composites and the reference compound depended on the state of polymer as glassy or rubbery. Therefore, a high loss factor at lower temperatures and a low loss factor at higher temperatures predicted a balanced improvement of tire traction and rolling resistance as a result of fiber addition. Heat build‐up and abrasion experiments showed that addition of fiber did not deteriorate other performances of tire tread. Also, the fibers had negligible effects on processing and vulcanization characteristics of the composite. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Toughening vinyl ester networks with polypropylene meso-fibers: Interface modification and composite properties

Polymer-polymer composites comprised of vinyl ester matrices (VE) and polypropylene (PP) fiber meshes were fabricated and tested in this investigation. Results indicated that PP fibers greatly enhanced fracture toughness; however, strength of the VE was significantly reduced as voids were observed at the interface of the PP and VE. A two-step surface modification, oxygen plasma treatment followed by grafting vinyltrimethoxysilane (VTMS), was conducted on PP fibers in an effort to improve interfacial strength. Interfacial discontinuities of composites were improved after surface modification of PP. The oxygen plasma treatment added hydrophilic functional groups but caused surface roughness. Surface treatment of PP slightly increased fracture toughness of the PP-VE composite by enhancing energy absorption capacity at the interface. However, mechanical strength and modulus did not significantly increase for the composite using VTMS grafted PP fibers due to the weak fiber material. Small PP fibers with higher strength may attain the expected improvement in mechanical properties after surface treatment.     

High‐performance thermosets with tailored properties derived from methacrylated eugenol and epoxy‐based vinyl ester

A renewable chemical, eugenol, is methacrylated to produce methacrylated eugenol (ME) employing the Steglich esterification reaction without any solvent. The resulting ME is used as a low‐viscosity co‐monomer to replace styrene in a commercial epoxy‐based vinyl ester resin (VE). The volatility and viscosity of ME and styrene are compared. The effect of ME loading and temperature on the viscosity of the VE–ME resin is investigated. Moreover, the thermomechanical properties, curing extent and thermal stability of the fully cured VE–ME thermosets are systematically examined. The results indicate that ME is a monomer with low volatility and low viscosity, and therefore the incorporation of ME monomer in VE resins allows significant reduction of viscosity. Moreover, the viscosity of the VE–ME resin can be tailored by adjusting the ME loadings and processing temperature to meet commercial liquid molding technology requirements. The glass transition temperatures of VE–ME thermosets range from 139 to 199 °C. In addition, more than 95% of the monomer is incorporated and fixed in the crosslinked network structure of VE–ME thermosets. Overall, the developed ME monomer exhibits promising potential for replacing styrene as an effective low‐viscosity co‐monomer. The VE–ME resins show great advantages for use in polymer matrices for high‐performance fiber‐reinforced composites. This work is of great significance to the vinyl ester industry by providing detailed experimental support. © 2018 Society of Chemical Industry     

Thermo‐physical,thermal degradation,and flexural properties of betel nut husk fiber reinforced vinyl ester composites

This study aims to investigate the thermo‐physical, mechanical, and thermal degradation properties of betel nut husk (BNH) fiber reinforced vinyl ester (VE) composites. These properties were evaluated as a function of fiber maturity, fiber content, and fiber orientation. Thermo‐physical properties were analyzed experimentally using a hot disk TPS method. The introduction of BNH was found to reduce the thermal conductivity of neat VE. The thermal conductivity and thermal diffusivity of BNH reinforced VE composites decreased with the increase in fiber content. Short fiber BNH reinforced VE composites showed the lowest thermal conductivity as compared to the unidirectional and random nonwoven composites. The TGA analysis shows lower resin transition peak for the BNH reinforced VE composites than the peak of neat VE. Fiber maturity had a notable effect on the flexural modulus of the BNH fiber reinforced VE composites. Incorporation of 10 wt% BNH fibers into the composite has increased the composites' flexural modulus by 46.37%. However, further increases in the fiber content reduced both flexural strength and modulus of the composites. POLYM. COMPOS., 37:2008–2017, 2016. © 2015 Society of Plastics Engineers     

Processing and mechanical properties of bio‐derived vinyl ester resin‐based composites

A “green” vinyl ester resin (GVER) is investigated for use in structural applications. The GVER was formulated using a monodisperse vinyl ester created via a novel synthetic route capable of using bio‐waste material from paper and biodiesel industries. The GVER was used either as a neat resin or as blended with a commercial vinyl ester resin. The processing viscosity and gel times are investigated. The GVER reaches a similar viscosity as the commercial resin with only half the styrene monomer content, thereby reducing the volatile organic compounds associated with manufacturing. Composites of the GVER matrix reinforced by carbon fabric were tested for their tensile and flexural properties. The mechanical performance of the GVER compares favorably with commercial resin and provide a route for composites manufacturing from sustainably sourced vinyl ester matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44642.     

Mechanical properties of particulate‐filler/woven‐glass‐fabric‐filled vinyl ester composites

Studies of the effect of particulate fillers on specific mechanical properties of vinyl ester epoxy (VE) reinforced with woven glass fiber composites were carried out with different filler types and particulate filler contents (1%, 3%, and 5% by weight). Two types of particulate filler were used, i.e., calcium carbonate (CC) and phenolic hollow microspheres (PHMS). The composites were prepared by using a hand lay‐up and vacuum bagging method. Woven glass fabric composites filled with particulate PHMS were observed to have better specific flexural strength and specific impact strength, as well as lower density, than those filled with particulate CC. Morphological features determined by scanning electron microscope (SEM) proved that the PHMS filler experienced good bonding in the VE matrix, a feature which contributed to the improvement in the properties of the composites. The incorporation of particulate fillers into the composites also influenced the storage modulus with a minimal effect on T_g. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Thermal behavior of vinyl ester resin matrix composites reinforced with alkali‐treated jute fibers

The thermal behavior of vinyl ester resin matrix composites reinforced with jute fibers treated for 2, 4, 6, and 8 h with 5% NaOH was studied with Thermo‐gravimetric analysis and differential scanning calorimetry. The moisture desorption peak shifted to a higher temperature, from 37 to 58.3°C, for all the treated‐fiber composites because of improved wetting of the fibers by the resin and stronger bonding at the interface. The degradation temperature of the vinyl ester resin in the composites was lowered to 410.3°C from that of the neat resin, 418.8°C. The X‐ray diffraction studies showed increased crystallinity of the treated fibers, which affected the enthalpy of the α‐cellulose and hemicellulose degradation. The hemicellulose degradation temperature remained the same (299.7°C) in all the treated‐fiber composites, but the enthalpy associated with the hemicellulose degradation showed an increasing trend in the treated composites with a small increase in the weight loss. This could be attributed to the increased hydrogen bonding between the more accessible ? OH groups of the hemicellulose in the noncrystalline region of the jute fiber and the resin. The degradation temperature of α‐cellulose was lowered from 364.2 to 356.8°C in the treated composites. The enthalpy of α‐cellulose degradation showed a decreasing trend with a lowering of the weight loss. The crystalline regions of the fiber, consisting of closely packed α‐cellulose chains, were bonded with the resin mainly on the surface through hydrogen bonds and became more resistant to thermal degradation; this reduced the weight loss. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 123–129, 2004     

Epoxy‐modified cyanate ester resin and its high‐modulus carbon‐fiber composites

Epoxy E51‐modified bisphenol A dicyanate (BADCy) and its high‐modulus carbon fiber (M40) reinforced composites were prepared in this research. The carbon‐fiber composites were prepared by autoclave molding. Differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy of BADCy‐E51 blend systems showed that polycyclotrimerization of BADCy primarily took place at low temperature. Epoxy group reacted with triazine ring group and produced oxazolidinone at high temperature. The data of mechanical properties, water absorption, and heat deflection temperature (HDT) of cured castings showed that the matrix system containing 95 wt% BADCy and 5 wt% E51 had optimum characteristics. Scanning electron microscopy (SEM) analysis of M40 fiber and the fracture surfaces of M40/BADCy‐E51 composite displayed that the adhesion between M40 fiber and BADCy was good though the surface of M40 was inert. The high retention of mechanical properties of M40/BADCy‐E51 composite after long‐term exposure to environmental conditions indicated that the M40/BADCy composite was suitable for space applications. POLYM. COMPOS., 27:402–409, 2006. © 2006 Society of Plastics Engineers     

Morphology of rubber‐modified vinyl ester resins cured at different temperatures

The morphologies of styrene (St) crosslinked divinylester resins (DVER) modified with elastomers were analyzed. The primary focus of this study was on the effect of the molecular weight of the resins, the reactivity of the elastomeric modifiers, and the temperature of curing. All of these variables have a strong influence on both the miscibility and the viscosity of the system, affecting the phase‐separation process that takes place in the unreacted and the reacting mixture. The selected liquid rubbers were carboxyl‐terminated poly(butadiene‐co‐acrylonitrile) (CTBN), a common toughening agent for epoxy resins, and an almost unreactive rubber with the DVER; and St comonomers and vinyl‐terminated poly(butadiene‐co‐acrylonitrile (VTBN), a reactive rubber. Different morphologies potentially appear in these systems: structures formed by DVER–St nodules surrounded by elastomer and spanning the whole sample; dual cocontinuous micron‐size domains formed by elastomer‐rich or resin‐rich domains; and a continuous DVER–St‐rich phase with included complex nodular domains. These microstructures can be varied by just changing the nature and concentration of the elastomer, the molecular weight of the resin, or the curing temperature. The appearance of these morphologies is discussed as a function of the above variables. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 274–283, 2003     

Experimental investigation of the cure‐dependent response of vinyl ester resin

The objective of this research is to understand the influence of the thermochemical and thermomechanical material response of low temperature cured vinyl ester resin (Dow Derakane 411‐C‐50) on the development of residual stress and warpage during processing. The primary experimental technique is the bimaterial specimen experiment, in which the warpage of a bimaterial beam is used as a measure of residual stress. The bimaterial specimen experiment was developed to isolate the chemical and thermal contributions to curvature. Existing material models for shrinkage, modulus, and glass transition temperature as a function of cure were evaluated. These material models were used as input into the bimaterial equation for curvature prediction. The predicted curvatures were used along with the experimental curvatures to evaluate the material models and their ability to accurately describe the material response of the vinyl ester resin. Results showed that the model captured the overall experimental trend in curvature buildup during processing but overestimated the curvature from chemical effects during isothermal cure. Improved correlation was achieved by incorporating a time shift in the model to account for viscoelastic stress relaxation of the resin.     

Reactive and non‐reactive binders in glass/vinyl ester composites

This study characterizes and evaluates two types of preform binders: reactive thermosets, and non‐reactive thermoplastics. The interply adhesion between woven glass plies was measured as a function of binder type, concentration, and preforming conditions. It was found that reactive binders offer the potential to provide much larger interply adhesions between glass plies in a preform than thermoplastics, and are thus superior choices for the fabrication of complex‐shaped preforms requiring little or no springback. Laminated composite panels fabricated from preforms with varying binder concentrations were evaluated in regards to their interlaminar properties. It was found that both binder types degraded the interlaminar shear strength of a woven glass reinforced vinylester composite. Additionally, composite laminates made from preforms containing the thermoplastic binder showed decreases in the interlaminar fracture toughness of the composite by approximately 60%. However, composite laminates fabricated from preforms utilizing the reactive epoxy binder showed an increase in fracture toughness of approximately 47%. Hence, it is concluded that a range of interlaminar properties can be achieved depending on the type of binder, the amount of binder, and the processing of the binder and also that of the composite itself. POLYM. COMPOS., 26:377–387, 2005. © 2005 Society of Plastics Engineers     

Use of allyl‐functional benzoxazine monomers as replacement for styrene in vinyl ester resins

New vinyl ester systems are prepared using allyl‐functional benzoxazine monomers, 3‐allyl‐6‐methyl‐3,4‐dihydro‐2H‐benzo[e][1,3]oxazine (pC‐ala) or bis(3‐allyl‐3,4‐dihydro‐2H‐benzo[e][1,3]oxazin‐6‐yl)methane (BF‐ala), as reactive diluents for vinyl ester resins derived from an epoxy resin, diglycidyl ether of bisphenol A, instead of using styrene. Different initiators are used to investigate the copolymerization of allyl function from pC‐ala with vinyl function from vinyl ester resin prepolymer. The temperature dependence of viscosity is studied to demonstrate the retention of processability of the new vinyl ester resins. Dynamic mechanical and thermogravimetric analyses are used to investigate the dynamic mechanical properties and thermal stability of the new resins. Copyright © 2012 Society of Chemical Industry     

Free‐radical grafting of 4‐vinyl pyridine onto nylon 6 fiber

The chemistry of free‐radical graft copolymerization initiated with peroxomonosulfate (PMS)–thioglycolic acid (TGA) redox system has been investigated by using 4‐vinyl pyridine (4VP) as a model for nylon 6 fiber in aqueous solution under nitrogen atmosphere. Effects of concentration of 4VP, PMS, TGA, nylon 6, time, and temperature on R_h and graft parameters were studied. The FTIR spectrum of nylon 6‐g‐4VP was reported. Water retention capacity (WRC) of the grafted fiber was tested. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3108–3113, 2002     

Preparation of vinyl amine‐co‐vinyl alcohol/polysulfone composite membranes and their carbon dioxide facilitated transport properties

A vinyl amine–vinyl alcohol copolymer (VAm–VOH) was synthesized through free‐radical polymerization, basic hydrolysis in methanol, acidic hydrolysis in water, and an anion‐exchange process. In the copolymer, the primary amino groups on the VAm segment acted as the carrier for CO₂‐facilitated transport, and the vinyl alcohol segment was used to reduce the crystallinity and increase the gas permeance. VAm–VOH/polysulfone (PS) composite membranes for CO₂ separation were prepared with the VAm–VOH copolymer as a selective layer and PS ultrafiltration membrane as a support. The membrane gas permselectivity was investigated with CO₂, N₂, and CH₄ pure gases and their binary mixtures. The results show that the CO₂ transport obeyed the facilitated transport mechanism, whereas N₂ and CH₄ followed the solution–diffusion mechanism. The increase in the VAm fraction in the copolymer resulted in a carrier content increase, a crystallinity increase, and intermolecular hydrogen‐bond formation. Because of these factors, the CO₂ permeance and CO₂/N₂ selectivity had maxima with the VAm fraction. At an optimum applied pressure of 0.14 MPa and at an optimum VAm fraction of 54.8%, the highest CO₂ permeance of 189.4 GPU [1 GPU = 1 × 10^?6 cm³(STP) cm^?2 s^?1 cmHg^?1] and a CO₂/N₂ selectivity of 58.9 were obtained for the CO₂/N₂ mixture. The heat treatment was used to improve the CO₂/N₂ selectivity. At an applied pressure of 0.8–0.92 MPa, the membrane heat‐treated under 100°C possessed a CO₂ permeance of 82 GPU and a CO₂/N₂ selectivity of 60.4, whereas the non‐heat‐treated membrane exhibited a CO₂ permeance of 111 GPU and a CO₂/N₂ selectivity of 45. After heat treatment, the CO₂/N₂ selectivity increased obviously, whereas the CO₂ permeance decreased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40043.