Rheological and mechanical properties of DGEBA‐S epoxy copolymer initiated by N‐benzylquinoxalinium hexafluoroantimonate

The rheological and mechanical properties of the DGEBA‐S epoxy copolymer initiated by N‐benzylquinoxalinium hexafluoroantimonate (BQH) as a cationic latent thermal catalyst were investigated. The rheological properties of the DGEBA‐S/BQH system were investigated using a rheometer under isothermal conditions, and the mechanical properties of the casting specimens, involving flexure and impact tests, were also performed. The crosslinking activation energy and mechanical properties of the DGEBA‐S/BQH system were higher than those of the DGEBA/BQH system. This could be attributed to the introduction of sulfone groups with a polar nature to the main chain of the epoxy resins which led to a decrease of molecular motion and an improvement in the toughness of the cured epoxy copolymers. Copyright © 2005 Society of Chemical Industry     

Experimental modeling of the cure behavior of a formulated blend of DGEBA epoxy and C12‐C14 glycidyl ether as a reactive diluent

Microwave curing of polymer matrix composites has been suggested as an attractive substitute for conventional thermal curing. Formulations of epoxy and reactive diluents have the advantage of better wettability and uniform fiber impregnation. However, higher peak exotherms in large masses, and thus thermal overshoot, presents a challenge for cure cycle optimization. Therefore, building a reliable curing model will not only predict the behavior of these materials during actual processing, but also facilitate numerical modeling of the process and comparison of other resin formulations. In this study the effect of the reactive diluent on the isothermal cure kinetics of low viscosity epoxy was investigated using differential scanning calorimetry (DSC). A formulated blend of diglycidyl ether of bisphenol A (DGEBA) and C₁₂–C₁₄ aliphatic glycidyl was cured using diethylene triamine as the curing agent. Using a standardized procedure, ISO 113571‐5, the epoxy formulation was isothermally cured at several temperatures and the heat flow monitored and recorded. Using the heat flow data from DSC, the rate of cure was determined experimentally and a proper autocatalytic model with a total order of about 2.3 was fit to describe the process. Least‐square regression and isoconversion methods were used to find the model parameters and the activation energy, respectively. The accuracy of the model shows fine correlation with experimental data. By comparison to other epoxy resin without diluents, the analysis of the data shows that the reactive diluent increased the curing rate, while the values of activation energy and process parameters remained within the typical values of epoxy formulations. Based on these data, the future use of these types of resins in nonthermal curing of epoxy matrix composites is discussed. POLYM. COMPOS., 26:593–603, 2005. © 2005 Society of Plastics Engineers     

Analysis of laser/IR‐assisted microembossing

To shorten the cycle time in conventional hot embossing, an infrared laser (laser/IR)‐assisted microembossing process was investigated in this study. Since the laser/IR heats the substrate rapidly and locally, the heating and cooling time can be substantially reduced. Two different modes of IR embossing were tested. In one case, the polymer substrate was the IR‐transparent poly(methyl methacrylate) (PMMA) and a carbon black‐filled epoxy mold was used. In the second case, the polymer substrate was an IR‐absorbent PMMA, and an IR transparent epoxy mold was used. The experimental results showed that both a shorter cycle time and good replication accuracy could be achieved. A commercially available finite element (FEM) code, DEFORM?, was used for process simulation. The relationship between the penetration of radiation energy flux from the laser/IR heating source and temperature distribution inside the polymer substrate was considered in the simulation. The flow pattern observed in the experiments agreed well with the numerical simulation. However, the displacement curve showed a discrepancy. POLYM. ENG. SCI., 45:661–668, 2005. © 2005 Society of Plastics Engineers     

Latent catalyst effects in halogen‐free epoxy molding compounds for semiconductor encapsulation

Latent catalyst effects were investigated to improve the physical properties of halogen‐free epoxy molding compounds (EMCs) for semiconductor encapsulation. In this study, biphenyl‐type resins were used as the epoxy and hardener resin for halogen‐free EMCs to obtain high flame‐retardant properties and high filler contents. Latent catalyst effects were examined with two kinds of EMC compositions, halogen‐free EMCs and conventional EMC compositions. We used triphenylphosphine‐benzoquinone salt (TPP‐BQ) as a latent catalyst. Spiral flow and gel time were measured to investigate the change in moldability with the latent catalyst. We measured package fail, moisture absorption, and delamination for reliability evaluation and flexural strength, flexural modulus, and adhesion for mechanical properties to examine latent catalyst effects. An improvement in moldability, reliability, and the mechanical properties were observed in two types of halogen‐free EMCs with TPP‐BQ as a latent catalyst. These phenomena were seen in conventional EMCs, including o‐cresol novolac epoxy resin. The cure kinetics of these systems were investigated by differential scanning calorimetry with an isothermal approach to explain these phenomena. The results indicate that the improvement in moldability in halogen‐free EMCs with TPP‐BQ was due to the low conversion rate of this system, and the increase in mechanical properties was attributed to the high conversion of curing reaction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2287–2299, 2005     

Curing kinetics and reaction‐induced homogeneity in networks of poly(4‐vinyl phenol) and diglycidylether epoxide cured with amine

Mixtures of diglycidyl ether of bisphenol‐A (DGEBA) epoxy resin with poly(4‐vinyl phenol) (PVPh) of various compositions were examined with a differential scanning calorimeter (DSC), using the curing agent 4,4′‐diaminodiphenylsulfone (DDS). The phase morphology of the cured epoxy blends and their curing mechanisms depended on the reactive additive, PVPh. Cured epoxy/PVPh blends exhibited network homogeneity based on a single glass transition temperature (T_g) over the whole composition range. Additionally, the morphology of these cured PVPh/epoxy blends exhibited a homogeneous network when observed by optical microscopy. Furthermore, the DDS‐cure of the epoxy blends with PVPh exhibited an autocatalytic mechanism. This was similar to the neat epoxy system, but the reaction rate of the epoxy/polymer blends exceeded that of neat epoxy. These results are mainly attributable to the chemical reactions between the epoxy and PVPh, and the regular reactions between DDS and epoxy. Polym. Eng. Sci. 45:1–10, 2005. © 2004 Society of Plastics Engineers.     

Epoxy‐silica nanocomposites: Preparation,experimental characterization,and modeling

Silica nanoparticles having different sizes were obtained by the sol‐gel process and characterized. The prepared nanoparticles were subsequently used as reinforcing fillers to prepare epoxy‐based composites with a silica content ranging from 1 to 5 wt %. SEM analysis and tensile tests carried out on the silica‐epoxy nanocomposites indicated the absence of particle aggregation and a reinforcing effect in terms of increased elastic modulus. Mechanical properties were also modeled by using a finite element code able to construct a numerical model from a microstructural image of the material. A more reliable model was prepared by considering the presence of an interphase layer surrounding the particles with intermediate elastic properties between the epoxy and the inclusions and a characteristic size proportional to the particle radius. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2382–2386, 2005     

Preparation and characterization of polysiloxane‐modified epoxy resin aqueous dispersions and their films

Polysiloxane‐modified epoxy resin aqueous dispersions were prepared by the reaction of amino‐polysiloxane (APS) with a graft epoxy resin that was synthesized with a diglycidyl ether of bisphenol A type epoxy resin and styrene/acrylic acid. The measurements of the epoxy values and FTIR spectra confirmed that this reaction really took place. The modified aqueous dispersion exhibits high viscosity, small particle size, and nearly the same surface tension as the unmodified one. Therefore, this indicates that the siloxane segments could be encapsulated into graft epoxy resin particles during the water dispersion process. For APS‐modified films, the thermal stability and water resistance are remarkably enhanced. Furthermore, lowering of the hardness and surface tension for these films was also observed and the surface composition was measured by X‐ray photoelectron spectroscopy. The experimental data indicate that the siloxane segments easily migrate onto the surface during the film formation process and finally enrich on the surface of the APS‐modified film. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 880–885, 2005     

Consolidation simulation of composite laminates: Formulation and validation verification

Advanced fiber‐reinforced polymer composites have been increasingly used in various structural components. One of the important processes to fabricate high‐performance laminated composites is an autoclave‐assisted prepreg lay‐up. Since the quality of laminated composites is largely affected by the cure cycle, selection of the cure cycle for each application is important and must be optimized. Thus, some fundamental model of the consolidation and cure processes is necessary to properly select the suitable parameters for each application. This article is concerned with the “flow‐compaction” model during the autoclave processing of composite materials. By using a weighted residual method, a two‐dimensional finite element formulation for the consolidation process of thick thermosetting composites is presented and the corresponding finite element code is developed. Numerical examples, including comparison of the present numerical results with one‐dimensional and two‐dimensional analytical solutions, are given to indicate the accuracy and effectiveness of the finite element formulation. In addition, a consolidation simulation of AS4/3501‐6 graphite/epoxy laminate is performed and is compared with the experimental results available in the literature. POLYM. COMPOS., 26:813–822, 2005. © 2005 Society of Plastics Engineers     

Coating the inner surfaces of pipes with high-viscosity epoxy in annular flow

Applying a thin, protective coating of a nontoxic, chemically resistant epoxy to the interior of existing pipes is an alternative method to pipe replacement. In order to find the controlling parameters in this method, in this study, viscous epoxy was propelled by compressed air through clear polyvinyl chloride (PVC) pipes. Epoxy flow was annular, and it hardened to form a thin, uniform coating on the inner pipe surface. A video camera was employed to record fluid motion, and the thickness of the coating was measured using an image analysis program named ImagJ. Tests were done with varying air temperature, airflow rate, piping configuration, and epoxy temperature. A one-dimensional numerical algorithm was developed to model fluid flow, heat transfer, and epoxy curing. Heating the epoxy makes it move faster because liquid viscosity decreases with increasing temperature. The coating was significantly thicker at the bottom of a horizontal pipe than at the top due to sagging of the epoxy coating after it had been applied, resulting in flow from the top to the bottom of the pipe. Sagging could be reduced by maintaining airflow until curing was almost complete and the epoxy had hardened enough to prevent it from moving easily. The combination of the experimental results and numerical modeling showed that the most important parameters controlling the speed of the epoxy and coating thickness were the air flow rate and temperature, since they determine the shear forces on the epoxy layer and the rate at which the epoxy cures. Raising air temperature increases the reaction rate and therefore decreases the time required for the epoxy to cure inside the pipe. The results of the simulation showed a very good agreement with the experimental results in pipes with 1-in diameter or less.     

Application of a Two-Dimensional Computer Simulation to Cake Growth in Slip Casting with Complicated-Shape Gypsum Molds

A two-dimensional computer simulation method, developed by the authors using the method of finite differences, was applied to estimate the cake growth in slip casting of alumina with a triangular gypsum mold and a box-type gypsum mold with a convex bottom. The cake growth patterns, water penetration patterns, water flow rate distributions, and pressure distributions were simulated in the molds and/or cakes. The simulated cake growth patterns were in good agreement with those observed experimentally in both molds. Moreover, the cake growths could be well understood from the results of the water flow rate distributions in each case. The present method is applicable to cake growth simulation in slip casting with complicated-shape gypsum molds.     

Cure kinetics and modeling of an epoxy resin cross‐linked in the presence of two different diamine hardeners

An epoxy resin diglycidyl ether of bisphenol A (DGEBA) is cross‐linked with the help of two aromatic diamine 4,4′‐diaminodiphenylsulfone (DDS) + 4,4′‐methylenebis 3‐chloro 2,6‐diethylaniline (MCDEA) of nearly equal flexibility but different reactivities. The ratio of the two amines is varied while keeping the stoichiometry of the epoxy/amino hydrogen groups constant. The experimental cure kinetics are studied at four different isothermal temperatures. Their modeling is carried out by a phenomenological Kamal‐Sourour kinetic model. The procedure is two‐fold: 1) linear combinations of the values of rate constants from the two neat thermosets (based on only one amine) and 2) values calculated directly from isothermal cures of reactive amine mixtures. A good correlation was observed between the experimental data and the model predictions (both procedures). These amine formulations provide “mixed” epoxy thermosets and will be used later to control thermoset/thermoplastic blend morphologies for which reaction kinetics need to be predicted. POLYM. ENG. SCI. 45:1581–1589, 2005. © 2005 Society of Plastics Engineers     

Mechanical properties of copper‐clad laminate using composite naphthalene–phenyl‐based epoxy as prepreg

A composite was prepared that contained diglycidyl ether of tetrabromobisphenol A (DGETBA) and 1,5‐di(2,3‐epoxypropoxy)naphthalene (A), 4,4′‐bis(2,3‐epoxypropoxy)benzylideneaniline (B), or 4,4′‐bis(2,3‐epoxypropoxy)biphenyl (C), and then was cured using different ratios of dicyandiamide (DICY). The results of DSC, TGA, coefficient of thermal expansion, dielectric constant, and dissipation factor testing of the composite epoxy resins were analyzed, and investigation of the copper‐clad laminate using the composite epoxy resins as prepreg was also performed. Additionally, moisture absorption, peel strength, arc resistance, comparative tracking index, and flammability of the copper‐clad laminate were examined. Clearly, some of the physical or mechanical properties of the composite and the copper‐clad laminate can be improved by optimal addition of naphthalene–phenyl‐based epoxy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1485–1492, 2005     

Morphology of epoxy resin modified with silyl‐crosslinked urethane elastomer

Silyl‐crosslinked urethane elastomer modifying epoxy resin has drawn much interest. Here the triethoxysilyl‐terminated polycaprolactone elastomer (PCL‐TESi) modifying diglycidylether of bisphenol A epoxy resins (DGEBA) system was chosen, and then the effect of the type of curing agent on the phase structure of the studied epoxy resin system was investigated. The modified systems were obtained with different phase structures by varying the formulations of the curing agent. It was experimentally shown that with the addition of aminosilane (KBE‐9103), the crosslinked density was greatly increased. The cured system also showed from SEM and TEM analysis that addition of KBE‐9103 increased the compatibility between the PCL‐TESi and DGEBA, which made the ductility of the system decrease, but also indicated from TEM that addition of much KBE‐9103 made the reacted silicone particles coagulate each other. The state of phase separation from TEM in the cured system was theoretically explained. These would serve the deeper studies of the mechanism of silyl‐crosslinked urethane elastomer modifying epoxy resin in the future. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 611–619, 2005     

Use of epoxy–phenolic lacquers in food can coatings: Characterization of lacquers and cured films

Liquid and cured epoxy–phenolic lacquers used as can coatings were characterized. Tinplate was used as the base material, which was coated with lacquers of different epoxy to phenolic ratios (EPRs) from a commercial source. Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) were used together to obtain helpful information about the degree of curing and the composition of the lacquers. From FTIR analysis, we were able to infer that the lacquers were composed of a high‐molecular‐weight diglycidyl ether of bisphenol A type epoxy resin and a resol‐type phenolic resin. In addition, from FTIR spectra, we estimated the EPRs of lacquers applied on the tinplate and detected if they had been overcured. The EPRs of the applied lacquers were estimated also from DSC analysis. From TGA, we detected undercuring in the applied lacquers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1448–1458, 2005     

Synthesis and evaluation of liquid amine‐terminated polybutadiene rubber and its role in epoxy toughening

Epoxy resin is widely used for coatings, adhesives, castings, electrical insulation materials, and other applications. However, unsolved problems still remain in its applications. The main problem is low toughness: cured epoxy resin is rather brittle, with poor resistance to the propagation of cracks derived from the internal stress generated by shrinkage in the cooling process from cure temperature to room temperature. The objective of this study was to improve the flexibility and toughness of diglycidyl ether of bisphenol A based epoxy resin with a liquid rubber. For this purpose, amine‐terminated polybutadiene (ATPB) was synthesized. The product was characterized by Fourier transform infrared and NMR spectroscopy and elemental analysis. ATPB‐modified epoxy networks were made by curing with an ambient‐temperature curing agent, triethylene tetramine. We varied the epoxy/liquid rubber compositions to study the effect of toughener concentration on the impact and thermal properties. Higher mechanical properties were obtained for epoxy resins toughened with 1 phr ATPB. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2446–2453, 2005     

Improvement of the polarity of polyethylene with oxidized Fischer–Tropsch paraffin wax and its influence on the final mechanical properties

The easy, low‐cost modification of the polarity of low‐density polyethylene (LDPE) and high‐density polyethylene (HDPE) through blending with oxidized Fischer–Tropsch wax was investigated. A 10 wt % concentration of the wax increased the polar component of the total surface free energy 10 times for LDPE and 4.5 times for HDPE. Modified LDPE also had significantly higher adhesion to the polar substrate, which was represented by a crosslinked epoxy‐based resin. This behavior was not observed for HDPE. The conservation of the good mechanical properties of polyethylene was observed. The wax content had only a moderate influence on the mechanical properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1164–1168, 2005     

Moisture effects on FM300 structural film adhesive: Stress relaxation,fracture toughness,and dynamic mechanical analysis

The behavior of cured FM300 epoxy, a structural film adhesive, subjected to partial and full moisture saturation has been evaluated. Three separate but interrelated test methods were used: stress relaxation, fracture toughness, and dynamic mechanical testing. The mechanical response of the epoxy due to increasing moisture content was dependent on the testing method. In stress relaxation testing, the epoxy was plasticized when partially saturated with moisture, but it became more rigid when fully saturated. The plasticization‐to‐stiffening transition was not observed in the other two test methods. Fracture testing showed that the material toughness increased with increasing moisture concentration: plasticization effects were dominant. Similar changes in the loss modulus were found in dynamic mechanical analysis. We propose that the differences in behavior have been due to differences in load levels and loading rates used in these probing techniques. Stress relaxation testing, at a relatively lower load and loading rate, appeared to be more sensitive to the localized interactions between the absorbed water molecules and the crosslinked structure. Higher loads and loading rates tended to reveal the bulk effects of plasticization only. Nevertheless, there was also strong evidence from glass‐transition temperature measurements that these moisture effects were mostly reversible. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95:1285–1294, 2005     

常温固化环氧树脂浇铸体的制备与力学性能

利用活性稀释剂在常温常压下合成了无气泡的环氧树脂浇铸体，测试了浇铸体的冲击、弯曲和压缩等力学性能，对环氧树脂的环氧值凝胶时间和固化配方进行了研究。结果表明：采用活性稀释剂配制的环氧—乙二胺固化体系有较好的常温固化性能，可用于常温固化粘合剂及物体表面防腐，通过纤维增强改性提高力学性能，可用于工程材料     

Corrosion protection of epoxy‐coated steel using different silane coupling agents

To suppress steel corrosion at elevated temperature and in humid condition, silane coupling agents N‐β‐aminoethyl aminopropyltrimethoxysilane (AAPS), γ‐glycidoxypropyltrimethoxysilane (GPS), and bis[3‐(trimethoxysilyl)‐1‐phenylpropyl]tetrasulfide (RC‐2) were introduced as primers into an epoxy/steel system. Silane coupling agents and epoxy were coated onto the steel surface using the solution casting method. The polymer degradation and steel corrosion formation after heat and humid treatment were investigated by Fourier transform infrared reflection and absorption spectroscopy (FTIR–RAS) and scanning electron microscopy (SEM). Compared to various silane treated epoxy/steel systems, the AAPS‐treated epoxy/steel (AAPS/epoxy = 6 : 4) system suppressed steel corrosion at 400°C for 10 min in air and for 5 days at 60°C in 100% relative humidity. This is due to the formation of Si O Si linkage and Fe O Si bond on steel surface, which are resistant to water diffusion and thermally stable at elevated temperature. The relationship between chemical bonding at the steel–epoxy interface and corrosion protection on the steel surface was also investigated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 585–593, 1999     

Reactive blending of functionalized acrylic rubbers and epoxy resins

A high molecular weight acrylonitrile/butadiene/methacrylic acid (Nipol 1472) rubber is chosen to control processability and mechanical properties of a TGDDM (tetra glycidyl diphenyl methane) based epoxy resin formulation for aerospace composite applications. The physical blend of rubber and epoxy resin, achieved by dissolution of all the components in a common solvent, forms a heterogeneous system after solvent removal and presents coarse phase separation during cure that impairs any practical relevance of this material. A marked improvement of rubberepoxy miscibility is achieved by reactive blending (‘pre‐reaction’) the epoxy oligomer with the functional groups present in the rubber. The epoxy‐rubber ‘adduct’ so obtained appears as a homogeneous system at room temperature and also after compounding with the curing agent. Depending on the nature and extent of interactions developed between the rubber and the epoxy resin during ‘pre‐reaction,’ materials with different resin flow characteristics, distinctive morphologies and mechanical properties after curing were obtained. The effect of ‘pre‐reaction’ on the resin cure reaction kinetics has been also investigated.