Control of shrinkage and final conversion of vinyl ester resins cured in low‐temperature molding processes

Vinyl ester resin is a major thermoset polymer used in low‐temperature composite manufacturing processes such as the Seemann composite resin infusion‐molding process (SCRIMP). Volume shrinkage and residual styrene are important concerns for composites produced in such processes. A low‐shrinkage additive (LSA) is a typical agent added to control the volume shrinkage of vinyl ester resins during molding. In this study, the effects of LSA content and the temperature profile (the temperature gradient and peak temperature) on the volume shrinkage control of a vinyl ester resin were investigated. The reaction kinetics of the resin system were also studied. We achieved good volume shrinkage control if we raised the curing temperature slowly to allow sufficient time for phase separation and if the curing temperature reached a high value after phase separation to allow microvoid formation. On the basis of experimental results, we designed an improved SCRIMP to increase resin conversion, reduce resin shrinkage, and produce composites with better properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1486–1496, 2003     

Enhancing thermal and dynamic-mechanical properties of epoxy reinforced by amino-functionalized microcrystalline cellulose

In this study, microcrystalline cellulose (MCC) was chemically modified with 3-(aminopropyl)triethoxysilane and added to epoxy to improve chemical, thermal and dynamic-mechanical characteristics of the composites. The composites were manufactured aided by sonication with 1.0%, 2.5%, or 5.0% wt/wt of untreated MCC or amino-functionalized MCC (MCC-Si). The epoxy/MCC-Si composites showed a decrease in the ─OH band by Fourier-transform infrared spectroscopy, and X-ray diffraction analysis indicated better dispersion. The incorporation of MCC-Si in epoxy resin decreased the heat of reaction, increased activation energy values (E_a) and pre-exponential factor (A), and did not affect thermal degradation. All conversion degree (α) versus temperature curves for the composites showed a sigmoidal shape. MCC-Si composites showed better dynamic-mechanical properties than the MCC counterparts, and the functionalization effect was evidenced in storage modulus (E') and loss modulus (E"). At 2.5% wt/wt of MCC-Si content an increase of 119% in E' at the glassy region, 127% in E' at the rubbery region and 173% in E" was observed compared to the neat resin, whereas the T_g barely changed among samples. Good adhesion between the amino-functionalized MCC and the epoxy matrix was observed at the fracture surface, evidencing that surface modification of MCC improves their chemical interaction.     

Aromatic bisphenol A-based elastomers via hydrosilylation chemistry

The preparation of highly aromatic elastomers from a bisphenol A-based divinyl-terminated resin and polymerization with various aromatic silane containing compounds utilizing a room temperature hydrosilylation reaction is demonstrated. The polymers exhibit high thermal and oxidative stability with 5% weight losses around 430 and 350°C and char yields ranging from 35% to 40%. The thermosets maintained their elastomeric properties with good hardness and mechanical properties as measured by elongation measurements. The toughness of the thermosets was not improved with the inclusion of aromatic moieties but the hardness did appear to increase with the addition of more aromatic groups.     

Epoxidized soybean oil modified using fatty acids as tougheners for thermosetting epoxy resins: Part 2—Effect of curing agent and epoxy molecular weight

A series of bio-rubber (BR) tougheners for thermosetting epoxy resins was prepared by grafting renewable fatty acids with different chain lengths onto epoxidized soybean oil at varying molar ratios. BR-toughened samples were prepared by blending BRs with diglycidyl ether of bisphenol A resins, Epon 828 and Epon 1001F, at different weight fractions and stoichiometrically cured using an amine curing agent, 4, 4′-methylene biscyclohexanamine (PACM). Fracture toughness properties of the unmodified and BR toughened polymer samples—including critical strain energy release rate (G_Ic), and critical stress intensity factor (K_Ic)—were measured to investigate the toughening effect of prepared BRs. It was found that the degree of phase separation and toughening were more controllable relative to similar polymers cured using the aromatic curing agent Epikure W, and the use of higher molecular epoxy resins produces a synergistic effect increasing the toughness much more than similar polymers made with lower molecular weight epoxy resins. Average BR domain sizes ranging from 200 to 900 nm were observed, and formulations with G_Ic, values K_Ic as high as 1.0 kJ/m² and 1.4 MPa m^1/2 were attained respectively for epoxy systems with T_g greater than 130°C.     

Aramid pulp treated with imidazolium ionic liquids as a filler in rigid polyurethane bio-foams

This article reports an aramid pulp (AP) treated with two ionic liquids (IL), namely 1-n-butyl-3-methylimidazolium chloride (C₄.Cl) and 1-carboxymethyl-3-methylimidazolium chloride (HO₂C), and its use as a filler in reinforced rigid polyurethane foams (RPUF). The RPUF were incorporated with the treated AP at three weight fractions (c.a. 0.1, 0.5, and 1.0 wt%) and were produced by the free rising method. The results showed that the studied IL promoted a better interaction between the AP and the RPUF system, which increased the overall reactivity, imparting a higher cell anisotropy. This also yielded a positive effect in mechanical properties and thermal stability of the RPUF. Compared to the neat RPUF, outstanding increases of approximately 50 and 20% were achieved in compressive modulus and strength, respectively. In all, the use of IL promoted increased compatibility between matrix and reinforcement, especially that HO₂C IL.     

Epoxidized soybean oil modified using fatty acids as tougheners for thermosetting epoxy resins: Part 1

A series of bio-rubber (BR) reactive tougheners for thermosetting epoxy resins was prepared by grafting renewable saturated fatty acids of different chain lengths (C6-C14) onto epoxidized soybean oil (ESO) at varying molar ratios. The tunable nature of the BR systems derives from the architecture and functionality of naturally occurring molecules. Control of BR reactivity and molecular weight by varying the degree of grafting and the chain length of the fatty acid was demonstrated. The BR-toughened samples were prepared by blending BRs with diglycidyl ether of bisphenol A (DGEBA), Epon 828, and stoichiometrically curing the mixture using an aromatic amine hardener, diethyl toluene diamine (Epikure W). Fracture surface morphology studies showed that tuning of phase separated particle sizes was possible depending on the BR type and weight fraction. The resulting toughening effect was evaluated by measuring the fracture toughness of control and toughened polymer samples. The use of BRs significantly improved the critical strain energy release rate and critical stress intensity factor values of thermosetting polymer samples without significantly reducing T_g and modulus. In addition to toughening and adding renewable content to petroleum-based thermosetting epoxy systems these new tougheners have low viscosity compared to common alternatives and aid ease of processing.     

A (4-fluorophenyl)(phenyl)phosphine oxide-modified epoxy resin with improved flame-retardancy,hydrophobicity, and dielectric properties

The compound (4-fluorophenyl)(phenyl) phosphine oxide (4-FPO) was designed, synthesized, and used in the modification of epoxy resin (EP). The 4-FPO-modified EP was prepared by curing the reaction mixture of diglycidyl ether of bisphenol A (DGEBA) and 4-FPO in the presence of 4,4′-diaminodiphenylsulfone (DDS). Compared with the unmodified EP, the limiting oxygen index value of the EP/4-FPO-0.6 (4-FPO-modified EP with 0.6 wt% of phosphorus) increased to 31.6%, and the sample achieved UL-94 V-0 rating. The peak of the heat release rate, average of the heat release rate, and total heat release of EP/4-FPO-0.6 were reduced by 39, 24, and 19%, respectively. Mechanism study showed that the quenching effect in the gas and barrier effect in the condensed phase were responsible for the enhanced flame-retardant properties of the 4-FPO-modified EP. The results showed that hydrophobicity and dielectric properties of the modified EP were clearly improved.     

Structural,thermal, and mechanical properties of silanized boron carbide doped epoxy nanocomposites

In the presented study, the structural, thermal, and mechanical properties of the nanocomposites were investigated by doping silanized hexagonal boron carbide (h-B₄C) nanoparticles in varying proportions (0.5%, 1%, 2%, 3%, 4%, and 5%) into the epoxy resin by weight. For this purpose, the surfaces of h-B₄C nanoparticles were silanized by using 3-(glycidyloxypropyl) trimethoxysilane (GPS) to improve adhesion between h-B₄C nanoparticles and epoxy matrix. Then, the silanized nanoparticles were added to the resin by ultrasonication and mechanical stirring techniques to produce nanocomposites. The bond structure differences of silanized B₄C nanoparticles (s-B₄C) and nanoparticle doped composites were investigated by using Fourier transform infrared spectroscopy. Scanning electron microscopy and energy dispersion X-ray spectroscopy (SEM-EDS) technique was used to examine the distribution of nanoparticles in the modified nanocomposites. Differential scanning calorimetry and thermogravimetric analysis techniques were used to determine the thermal properties of the neat and s-B₄C doped nanocomposites. The tensile test and dynamic mechanical analysis were performed to determine the mechanical properties. When the experimental results were examined, changes in the bonding structure of the s-B₄C nanoparticles doped nanocomposites and significant improvements in the mechanical and thermal properties were observed. The optimum doping ratio was determined as 2% by weight. At this doping ratio, the T_g, tensile strength and storage modulus increased approximately 18%, 35%, and 44% compared to the neat composite, respectively.     

High-thermal conductivities of epoxy composites via p-phenylenediamine interfacial modification and process intensification

High loadings of fillers are usually needed to achieve high-thermal conductivity (TC) of polymer-based composites, which inevitably sacrifices processability and meanwhile causes high-cost. Therefore, it is of great significance to achieve high-TC composites under low-filler loading. Here, a novel p-phenylenediamine (PPD) modified expanded graphite (EG-PPD)/epoxy (EP) composite with high TC and low-filler content was successfully prepared via pre-dispersion and vacuum assisted mixing strategy. With the improved interfacial compatibility between EG and EP by PPD, the prepared EG-PPD/EP composite exhibited excellent thermal management performance, resulting in the TC of which reached 4.00 W·m⁻¹·K⁻¹ with only 10 wt% (5.59 vol%) of EG-PPD, which is approximately 19 times higher than that of pure EP. Meantime, the interface thermal resistance of EG-PPD/EP composite between EG-PPD and EP is reduced by 33% compared with EG/EP composite. This composite with excellent TC property is expected to be used in thermal management field.     

Evaluation of the complex hygrothermal behaviors of epoxy–amine systems

In this study, the complex hygrothermal behavior of two epoxy systems used for strengthening applications was studied. In these systems, property loss by plasticization simultaneously occurred with property gain during additional curing. A comparison of the changes in the glass-transition temperature (T_g) and crosslink density with water immersion at different temperatures clearly showed that the two effects of additional curing by a postcuring reaction and plasticization by water absorption were in competition with each other during the exposure. The changes in the conversion with different exposure conditions suggested that water accelerated the postcuring reaction, even at low temperatures; this resulted in a significant difference in the postcuring reaction between unexposed and exposed epoxies. The construction of the plot of T_g versus conversion for the unexposed system and the placement of the T_g for exposed systems onto this master plot provided a method for evaluating the plasticization effect while excluding the influence of additional curing. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012