Comparison between microwave and thermal curing of glass fiber–epoxy composites: Effect of microwave‐heating cycle on mechanical properties

The objective of this study was to compare the mechanical properties between epoxy composites cured by thermal heating and microwave heating. Epoxy‐anhydride resins reinforced with glass fiber were cured in a domestic microwave oven and in a thermal oven. Hardening agents included methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride. Microwave curing was carried out at various conditions, including 1‐, 2‐, and 3‐step heating cycle, whereby each cycle employed different power level and time. Mechanical properties were tested according to ASTM standards. It is found that the microwave‐cured composites produced mechanical properties as good as the thermally cured composites. The 2‐ and 3‐step heating cycle used in the microwave curing process produced better mechanical properties higher than those obtained from the microwaved 1‐step and thermally curing process. This is attributed to the slow increase in temperature during the beginning of the microwave curing process whereby the very low power level was applied in the first cycle of the multistep heating process. This affected the slower rate of viscosity increment, resulting in better wettability of the glass fiber with enhanced interfacial adhesion between the fibers and the resins. The viscosity of resins affected the homogeneity of the crosslinked structure. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1059–1070, 2006     

Synthesis of rosin‐based flexible anhydride‐type curing agents and properties of the cured epoxy

BACKGROUND: Although rosin acid derivatives have received attention in polymer synthesis in recent years, to the best of our knowledge, they have rarely been employed as epoxy curing agents. The objective of the study reported here was to synthesize rosin‐based flexible anhydride‐type curing agents and demonstrate that the flexibility of a cured epoxy resin can be manipulated by selection of rosin‐based anhydride‐type curing agents with appropriate molecular rigidity/flexibility. RESULTS: Maleopimarate‐terminated low molecular weight polycaprolactones (PCLs) were synthesized and studied as anhydride‐type curing agents for epoxy curing. The chemical structures of the products were confirmed using ¹H NMR spectroscopy and Fourier transform infrared spectroscopy. Mechanical and thermal properties of the cured epoxy resins were studied. The results indicate that both the epoxy/anhydride equivalent ratio and the molecular weight of PCL diol play important roles in the properties of cured resins. CONCLUSION: Rosin‐based anhydride‐terminated polyesters could be used as bio‐based epoxy curing agents. A broad spectrum of mechanical and thermal properties of the cured epoxy resins can be obtained by varying the molecular length of the polyester segment and the epoxy/curing agent ratio. Copyright © 2009 Society of Chemical Industry     

Benzoxazine–epoxy copolymers: effect of molecular weight and crosslinking on thermal and viscoelastic properties

Bisphenol‐A‐based benzoxazine was copolymerized with epoxy and chain‐extended epoxies in order to study the effect of molecular weight on cured resin properties. Cure behaviour of the copolymers was studied using differential scanning calorimetry, which indicated a single exothermic curing peak at 248 °C. Dynamic mechanical thermal analysis was used to study the viscoelastic properties of the cured resins. A decrease in tan δ peak position and an increase in storage modulus and tan δ peak height were observed due to chain extension. Higher char yield was observed for the copolymer chain extended with tetrabromobisphenol‐A. Copyright © 2005 Society of Chemical Industry     

Microwave processing of thermosets: non-contact cure monitoring and fibre optic temperature sensors

Abstract

Conventionally, curing thermosetting resins involves heating the sample in an autoclave or an oven where heat is transferred to the sample through conduction and convection involving long processing time. Microwave curing offers an efficient alternative to thermal processing as heating occurs directly inside the sample resulting in lower energy consumption and faster curing. However, it requires non-metallic cure monitoring systems. In this study, a non-contact fibre optic probe was constructed and deployed inside a custom-modified microwave oven to record near-infrared (NIR) spectra, in real-time, of a thermoset undergoing cure. Simultaneous spectroscopic and temperature data on the sample during cure have been obtained for a range of microwave power levels. Comparison is also made between a sample cured in the microwave oven with one cured conventionally. In the final part, two optical fibre temperature sensors were designed and evaluated with an aim to use them in the microwave oven for temperature metrology. The sensors were based on the Fabry-Perot interferometer. The first sensor was evaluated from ambient to 400°C with an accuracy of ± 1·0°C, while the second sensor was tested from ambient to 300°C. The accuracy of the second sensor was ± 0·5°C.     

Comparison of microwave and thermal cure of unsaturated polyester resin

Abstract

A commercial unsaturated polyester resin, Beetle R 8592 from BIP Chemical Limited has been cured using a microwave oven. Thermal curing was also carried out as a comparative study. The cured resins were compared using differential scanning calorimetry, Fourier transform infrared spectroscopy, dynamic mechanical analysis, scanning electron microscopy, solid state NMR spectroscopy, and flexural properties. The DSC analysis showed that microwave curing was much faster than thermal curing. However, within the limits of experimental error, it was found that the shear modulus, the number average molecular weight M _c, flexural modulus and strength were not significantly different. Solid state NMR also showed similar spectra for both microwave and thermal cured samples, which suggests that the same curing reactions took place in each case.     

Synthesis and properties of fluorinated biphenyl‐type epoxy resin

A novel fluorinated biphenyl‐type epoxy resin (FBE) was synthesized by epoxidation of a fluorinated biphenyl‐type phenolic resin, which was prepared by the condensation of 3‐trifluoromethylphenol and 4,4′‐bismethoxymethylbiphenyl catalyzed in the presence of strong Lewis acid. Resin blends mixed by FBE with phenolic resin as curing agent showed low melt viscosity (1.3–2.5 Pa s) at 120–122°C. Experimental results indicated that the cured fluorinated epoxy resins possess good thermal stability with 5% weight loss under 409–415°C, high glass‐transition temperature of 139–151°C (determined by dynamic mechanical analysis), and outstanding mechanical properties with flexural strength of 117–121 MPa as well as tensile strength of 71–72 MPa. The thermally cured fluorinated biphenyl‐type epoxy resin also showed good electrical insulation properties with volume resistivity of 0.5–0.8 × 10¹⁷ Ω cm and surface resistivity of 0.8–4.6 × 10¹⁶ Ω. The measured dielectric constants at 1 MHz were in the range of 3.8–4.1 and the measured dielectric dissipation factors (tan δ) were in the range of 3.6–3.8 × 10^?3. It was found that the fluorinated epoxy resins have improved dielectric properties, lower moisture adsorption, as well as better flame‐retardant properties compared with the corresponding commercial biphenyl‐type epoxy resins. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Comparison between microwave and thermal curing of a polyimide adhesive end-caped with phenylethynyl groups

Microwave energy was investigated to cure phenylethynyl-end-capped polyimide adhesive using an industrial microwave oven at a frequency of 2.45 GHz and the adhesive properties, thermal performance and curing mechanism for bonding stainless steel were evaluated. The results are compared with those of thermal cured samples. It was demonstrated that while the lap shear strength properties and thermal performance of microwave cured samples were almost as good as those cured via a thermal process, the microwave curing process resulted in a significant reduction in the process cycle time and power consumption. The Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis of the cured resin structures suggested that there was no obvious difference in the chemical reactions taking place during the microwave and the thermal cure processes.     

Curing Characteristics and Thermal Properties of Epoxidized Soybean Oil Based Thermosetting Resin

Epoxidized soybean oil (ESO) was thermally cured using methylhexahydrophthalic anhydride (MHHPA) curing agent in the presence of 2-ethyl-4-methylimidazole (EMI) catalyst. The curing characteristics of ESO/MHHPA/EMI systems were characterized using Fourier transform infrared spectroscopy (FTIR), a dynamic mechanical analyzer (DMA) and a differential scanning calorimeter (DSC). FTIR spectra showed that the polyesterification rate in ESO/MHHPA/EMI systems increased with increasing of the catalyst concentration. DSC thermograms indicated that EMI-catalyzed ESO/MHHPA systems experienced enthalpy relaxation at low EMI concentration whereas the extent decreased with increasing of the EMI concentration. There is a direct relationship between the degree of conversion and crosslink density of the thermal cured ESO/MHHPA/EMI systems with EMI concentration. The curing characteristics of thermal curable ESO thermosetting resins were found to have influence on the thermal properties of the ESO systems. It was determined that the glass transition temperature (T _g) and storage modulus (E′) of cured ESO increased with increasing the EMI concentration whereas the damping properties of the ESO/MHHPA/EMI systems exhibited the reverse trend. It was found that the thermally curable ESO thermosetting resins experienced a two-stage thermal decomposition process.     

Effect of curing method on mechanical and morphological properties of carbon fiber epoxy composites for solid rocket motor

Microwave (MW) curing and conventional thermal curing techniques were utilized to cure carbon fiber epoxy composites for solid rocket motor to investigate the effect of curing method on their mechanical and morphological properties. In this work, tensile and inplane shear strength properties together with morphological properties were compared between MW cured and thermally cured composites, and the mechanism for MW curing was analyzed. The study shows that 83% cure cycle time reduction is achieved through MW curing. Mechanism analysis for MW curing indicates the resin at the surface layer and interior parts of the composites is cured with different forms. Temperature monitoring during MW processing indicates the uneven electric field distribution in the domestic MW oven. Fourier transform infrared spectrum measurements reveal that MWs do not initiate any new chemical reactions during the curing process of the composites. Thermal analysis using differential scanning calorimeter reveals higher glass transition temperature (T_g) of MW cured composites compared with thermally cured counterparts. Moreover, the MW cured composites show 17% lower tensile strength than thermally cured composites, whereas a 3% increase of the inplane shear strength is observed for MW cured composites, which is also confirmed via scanning electron microscope by means of better coating the fibers with resin, increased fiber wetting and less fiber pullout. POLYM. COMPOS., 36:1703–1711, 2015. © 2014 Society of Plastics Engineers     

Thermal and mechanical properties of microwave‐ and heat‐cured poly(methyl methacrylate) used as dental base material

The thermal and mechanical properties of dental base materials cured by microwave and conventional heat methods were studied. The commercial dental base poly(methyl metacrylate) (PMMA) powder and liquid were mixed in a 3/1 ratio. They were polymerized by a peroxy catalyst at 65°C, then cured with a boiling water temperature and microwave radiation for periods of 5, 10, 15, 20, 25, 30, and 35 min for heat curing and 1, 2, 3, 5, and 7 min for microwave radiation. The microwave radiation outputs used were 500 and 700 W. The products of 5‐min heat curing and 1‐, 2‐, and 7‐min microwave curing were soluble in chloroform. All the others were partially soluble. The viscosity‐average molecular weights of the soluble samples were about 1 × 10⁶. The thermal properties of the polymer samples were studied by differential scanning calorimetry (DSC). For the samples that were not cured completely, broad exothermic peaks at around 125°C were obtained in the DSC thermograms. The glass‐transition temperatures for completely cured samples were 110–120°C. The mechanical properties of the samples were determined from tensile and three‐point bending tests. The elastic modulus was highest for samples obtained by the conventional method with a 30‐min curing period. However, the bending modulus was highest for 7‐min cured samples in a 700‐W microwave. The mechanical strengths of the 700‐W output were higher than those at 500 W. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 251–256, 2003     

微波技术在环氧树脂及其复合材料中的应用

论述了近年来微波固化技术在环氧树脂及其复合材料固化中的应用,重点比较了微波固化与传统热固化后环氧树脂及其复合材料的力学性能、热性能和粘结强度的变化,并对环氧树脂复合材料微波固化的研究进行了展望。     

Thermally curable adhesive tapes with complex catalyst system for fabricating semiconductor packages

Thermal curing of adhesive films was investigated to facilitate the fabrication of a reliable bonding for semiconductors. The formulated adhesive films contained acrylic polymer, epoxy resins, phenol resin, and an imidazole derivative that was the catalyst for curing the epoxy resins with phenol resin. The solubility, thermally latent characteristics, mechanical and adhesive properties of 2‐methylimidazole/boron trifluoride (2MZ/BF3), and 2MZ/aluminum trisacetylacetonate (AlAC) were investigated. It was found that 2MZ/BF3 and 2MZ/AlAC had excellent solubility in adhesive materials and they had excellent latent characteristics as thermal curing catalysts for epoxy resins, whereas conventional catalysts (2MZ and 2‐phenyl‐4, 5‐dihydroxymethylimidazole (2PHZ)) could not achieve both excellent solubility and thermally latent characteristics. The mechanical and adhesive properties of the post‐thermal‐cured adhesive film that contained 2MZ/BF3 or 2MZ/AlAC were comparable to those of the post‐thermal‐cured adhesive films that contained conventional catalysts. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Use of eugenol and rosin as feedstocks for biobased epoxy resins and study of curing and performance properties

In this study, an epoxy based on eugenol and an anhydride curing agent based on rosin were prepared. Curing of the eugenol epoxy with a commercial anhydride curing agent and with the rosin‐derived anhydride curing agent was studied. For comparison, a commercial bisphenol A type epoxy, DER353, was also selected in the curing study. The syntheses of the eugenol epoxy and rosin anhydride were investigated and the chemical structures of the products and intermediates were characterized using ¹H NMR and Fourier transform infrared spectroscopies. Non‐isothermal curing of the eugenol epoxy with hexahydrophthalic anhydride and the rosin‐derived maleopimaric acid was studied using differential scanning calorimetry. Thermomechanical properties and thermal stability of the cured epoxy resins were evaluated using dynamic mechanical analysis and thermogravimetric analysis, respectively. Addition of 2‐ethyl‐4‐methylimidazole as catalyst greatly decreased the curing temperature and promoted the completion of cure reactions. The results suggest that the eugenol epoxy and the bisphenol A type epoxy have similar reactivity, dynamic mechanical properties and thermal stability. © 2013 Society of Chemical Industry     

Effects of chemical structure changes on thermal,mechanical, and crystalline properties of rigid rod epoxy resins

Effects of chemical structure changes on the thermal, mechanical, and crystalline properties of rigid rod epoxy resins have been studied for azomethine epoxy, biphenol epoxy, and tetramethyl biphenol epoxy. Rigid rod epoxies have exhibited better properties than those of the flexible bisphenol A epoxy. The chemical structures of both rigid rod epoxy and curing agent control the properties of cured rigid rod epoxies. When a flexible curing agent (methyl cyclohexane 1,2‐dicarboxylic anhydride) was used, the chemical structure of rigid rod epoxy has dominated effects on the properties. Thus, the azomethine epoxy has shown the best thermal and mechanical properties among three rigid rod epoxies. While a rigid curing agent (sulfanilamide) was used, the physical properties of cured epoxies are not only dependent on the chemical structures of epoxies but also on the ease of formation of ordered network. Among the cured rigid rod epoxies, only the biphenol epoxy cured by sulfanilamide exhibits a liquid crystalline network. It has the highest glass transition temperature (219°C) and the lowest coefficient of thermal expansion (20.8 μm/m°C). However, the most thermal stable system is azomethine epoxy cured with sulfanilamide. It has a weight loss (39%) at 450°C. Their excellent thermal and mechanical properties of rigid rod epoxies are useful in composites, printed wiring boards, integrated circuit encapsulations, etc. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 446–451, 2000     

Thermal and dynamic mechanical properties of microwave and heat‐cured poly(methyl methacrylate) used as dental base material

In this study, the particle size distribution, molecular weight, thermal analysis (TGA) differential scanning calorimetry (DSC) and thermogravimetric analysis, and dynamic mechanical analysis (DMA) of poly(methyl methacrylate) used as dental base material were investigated. The commercial raw material used were prepared for microwave curing, and they were cured by microwave and conventional heat methods. The average particle size of the powder studied (103.1 μm) were much larger than that of the commercial powders (50–78 μm) for conventional curing. The particle size dietribution were almost symmetrical and narrow. The viscosity‐average molecular weight were larger for microwave curing and increased with curing time. The glass transition temperature T_g measured (about 110°C) by DSC increased with curing period in microwave oven. The values of T_g were close to each other for both curing techniques. The degradation temperature range observed by TGA were 200–377°C. The movements of molecular chains in their conformations were studied by DMA in the form of changes in different mechanical properties with temperature. It was shown that crosslinking increased with increase of curing time. The changes were more noticeable in microwave curing compared to conventional heat curing. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2971–2978, 1999     

Thermal properties of chlorendic acid based polyester resins

Polyester resins were prepared from chlorendic acid, maleic anhydride, and ethylene- and/or propylene-glycol. The resins were cured at room temperature with two different crosslinking agents including styrene and methyl methacrylate. The thermal behaviour of these polyester resins and their cured products was studied. From the thermogravimetric data it was observed that the polyester resins cured with styrene are thermally more stable than the methyl methacrylate cured products. It was also observed that the polyester resin prepared from propylene glycol is thermally more stable relatively than the ethylene glycol based polyester resin. The activation energies of thermal degradation of the resins and their cured products were calculated. The implications of these results are discussed.     

Physical properties of unsaturated polyester resin from glycolyzed pet fabrics

Physical properties of unsaturated polyester resins (UPE resins) prepared from glycolyzed poly (ethylene terephthalate) (PET) and PET/cotton blended fabrics were investigated. Initially, PET and PET/cotton blended fabrics were chemically recycled by glycolysis. The depolymerizations were carried out in propylene glycol with the presence of zinc acetate as a catalyst. The reaction time was varied at 4, 6, and 8 h. The glycolyzed products were then esterified using maleic anhydride to obtain UPE resins. The prepared resins were cured using styrene monomer, methyl ethyl ketone peroxide, and cobalt octoate as a crosslinking agent, an initiator and an accelerator, respectively. The cured resin products were tested for their mechanical properties and thermal stability. The results indicated that, among the fabric based resins, one prepared from the 8‐h glycolyzed product possessed the highest mechanical properties those are tensile strength, tensile modulus, flexural strength, impact strength, and hardness. The highest thermal stability was also found in the cured resin prepared from the 8‐h glycolyzed product. The mechanical properties of fabric based resins were slightly lower than those of the bottle based resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2536–2541, 2007     

Variable‐frequency microwave curing of benzocyclobutene

Polymer dielectrics are widely used in the microelectronics industry for several applications including interlevel dielectrics, encapsulants, and passivating layers. To attain the desired properties, these materials need to be processed via lengthy cure cycles. Variable frequency microwave (VFM) processing has been investigated as a rapid curing alternative for the processing of thin‐film dielectrics. Previous studies on epoxies and polyimide‐based materials have shown significant reduction in cure time and improvement in properties on VFM processing. In this study, VFM curing of Dow Chemical Cyclotene? 3022 benzocyclobutene (BCB) was investigated. The kinetics of the cure reaction were studied by Fourier transform infrared (FTIR) spectroscopy. FTIR studies indicated no significant differences in chemical structure between VFM and thermally cured films. The electrical, optical, mechanical, and chemical properties of VFM‐processed films were characterized and compared with thermally processed films to determine the effectiveness of microwave processing. The results showed that VFM curing of BCB is feasible, and properties comparable to thermally cured films can be attained. The residual stress of partially cured BCB was lower for VFM processing than for traditional thermal processing. The residual stress in fully cured BCB was similar. Improvements such as shorter cure times and lower processing temperatures than conventional thermal processing can be achieved. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3055–3067, 2002; DOI 10.1002/app.10286     

棉油酸甲酯改性胺固化剂的合成及性能研究

利用棉油酸甲酯制备了一种环氧树脂固化剂棉油酸甲酯改性胺,研究了棉油酸甲酯改性胺用量对环氧树脂体系的力学性能和热性能的影响,利用红外光谱、热分析、动态力学分析讨论了棉油酸甲酯改性胺的结构、环氧树脂固化物的性能。结果表明,环氧树脂固化物的拉伸性能、弯曲性能和冲击强度随着棉油酸甲酯改性胺用量的增加而增加。     

Copolymerization modification: improving the processability and thermal properties of phthalonitrile resins with novel comonomers

Two novel tetrahydrophthalic anhydride end‐capped imide compounds (THAN and THBN) with high thermal stability were synthesized to promote the curing reaction of 1,3‐bis(3,4‐dicyanophenoxy)benzene (3BOCN), and to study the effects of comonomer structure on the curing behavior and thermal performance of phthalonitrile resins. The curing behaviors of THAN/3BOCN and THBN/3BOCN blends with various molar ratios were investigated using rheological analysis and differential scanning calorimetry, suggesting a wide processing window. Dynamic mechanical analysis and thermogravimetric analysis showed that the cured resins possessed high glass transition temperatures (> 500 °C), and superior thermal and long‐term thermo‐oxidative stabilities with weight retention of 95% ranging from about 544 to 558 °C in both nitrogen and air. All these results indicated that the processability and thermal properties of phthalonitrile resins could be improved further by modifying the structure of comonomer in this kind of curing system. © 2018 Society of Chemical Industry