Curing behavior of epoxy resin/tung oil anhydride exfoliated nanocomposite by differential scanning calorimetry

The nanocomposite of epoxy resin/tung oil anhydride/organic montmorillonite was prepared by casting and curing. The distance of the clay gallery rose and the exfoliated nanocomposite was formed. The exfoliation behaviors of the nanocomposite had been investigated by X‐ray diffraction (XRD). The curing mechanism and kinetics of epoxy resin with the different amounts of organic montmorillonite were studied using isothermal and dynamic methods by differential scanning calorimetry (DSC). Some parameters, the activation energy and reaction orders, were calculated by the modified Avrami equation in analysis of the isothermal experiment. The total curing mechanism and kinetics of curing reaction were also analyzed by the Flynn–Wall–Ozawa method. It was noted that the instantaneous activity energy during the curing process could be obtained by the Flynn–Wall–Ozawa method and the trend of the results was in agreement with those obtained from the modified Avrami equation. These results show that the activity energy decreases with the addition of organic montmorillonite. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3822–3829, 2004     

Curing behavior and thermal property of epoxy resin with boron‐containing phenol‐formaldehyde resin

The curing reaction of bisphenol‐A epoxy resin (BPAER) with boron‐containing phenol–formaldehyde resin (BPFR) was studied by isothermal and dynamic differential scanning calorimetry (DSC). The kinetic reaction mechanism in the isothermal reaction of BPAER‐BPFR was shown to follow autocatalytic kinetics. The activation energy in the dynamic cure reaction was derived. The influence of the composition of BPAER and BPFR on the reaction was evaluated. In addition, the glass transition temperatures (T_gs) were measured for the BPAER‐BPFR samples cured partially at isothermal temperatures. With the curing conditions varying, different glass transition behaviors were observed. By monitoring the variation in these T_gs, the curing process and the thermal property of BPAER–BPFR are clearly illustrated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1054–1061, 2000     

Curing kinetics and thermal properties of vinyl ester resins

The curing kinetics of dimethacrylate-based vinyl ester resins were studied by scanning and isothermal DSC, gel time studies, and by DMTA. The rate of polymerization was raised by increased methyl ethyl ketone peroxide (MEKP) concentration but the cocatalyst, cobalt octoate, retarded the reaction rate, except at very low concentrations. By contrast, the gel time was reduced for all increases in either peroxide or cobalt concentration. This contradictory behavior was explained by a kinetic scheme in which the cobalt species play a dual role of catalyzing the formation of radicals from MEKP and of destroying the primary and polymeric radicals. The scanning DSC curves exhibited multiple peaks as observed by other workers, but in the present work, these peaks were attributed to the individual influence of temperature on each of fundamental reaction steps in the free radical polymerization. Physical aging appeared to occur during the isothermal polymerization of samples cured below the “fully cured” glass transition temperature (T_g). For these undercured materials, the difference between the DSC T_g and the isothermal curing temperature was approximately 11°C. Dynamic mechanical analysis of a partially cured sample exhibited anomalous behavior caused by the reinitiation of cure of the sample during the DMTA experiment. For partially cured resins, the DSC T_g increased monotonically with the degree of cure, and this dependence was fitted to an equation related to the Couchman and DiBenedetto equations. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 769–781, 1997     

Curing kinetics and thermal property characterization of the bisphenol‐F epoxy resin and phthalic anhydride system

The curing kinetics of bisphenol‐F epoxy resin (BPFER) and curing agent phthalic anhydride, with N,N‐dimethylbenzylamine as an accelerator, were studied by differential scanning calorimetry (DSC). Analysis of DSC data indicated autocatalytic behaviour in the first stages of the cure for the system, and that this, could be well described by the model proposed by Kamal, which includes two rate constants, k₁ and k₂, and two reaction orders, m and n. The curing reaction in the later stages was practically diffusion‐controlled. To consider the diffusion effect more precisely, a diffusion factor, ??(α), was introduced into Kamal's equation. The glass transition temperatures (T_gs) of the BPFER/phthalic anhydride samples were determined by means of torsional braid analysis. The thermal degradation kinetics of cured BPFER were investigated by thermogravimetric analysis. © 2002 Society of Chemical Industry     

Curing kinetics,thermal property,and stability of tetrabromo-bisphenol-A epoxy resin with 4,4′-diaminodiphenyl ether

The curing reaction of tetrabromo-bisphenol-A epoxy resin (TBBPAER) with 4,4′-diaminodiphenyl ether (DDE) was studied by isothermal differential scanning calorimetry (DSC) in the temperature range of 110–140°C. The results show that the isothermal cure reaction of TBBPAER–DDE in the kinetic control stage is autocatalytic in nature and does not follow simple nth-order kinetics. The autocatalytic behavior was well described by the Kamal equation. Kinetic parameters, including 2 rate constants, k₁ and k₂, and 2 reaction orders, m and n, were derived. The activation energies for these rate constants were 83.32 and 37.07 kJ/mol, respectively. The sum of the reaction orders is around 3. The glass transition temperatures (T_gs) were measured for the TBBPAER–DDE samples cured partially in isothermal temperature. With the degree of cure varies, different glass transition behaviors were observed. By monitoring the variation in these T_gs, it is illustrated that the network of the system is formed via different stages according to the sequence reactions of primary and second amines with epoxides. It is due to the presence of the 4 bromine atoms in the structure of TBBPAER that this curing process can be clearly observed in DSC curves. The thermal stability of this system studied by differential thermal analysis–thermogravimetric analysis illustrates that the TBBPAER–DDE material can automatically debrominate and takes the effect of flame retarding when the temperature reaches 238.5°C. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1991–2000, 1998     

Preparation and curing kinetics of bisphenol A type novolac epoxy resins

A bisphenol A type novolac resin (Bis‐ANR) was synthesized from bisphenol A and formaldehyde; the resulting novolac was epoxidized to generate a bisphenol A type novolac epoxy resin (Bis‐ANER). The chemical structures of Bis‐ANR and Bis‐ANER were confirmed by ¹H‐NMR spectroscopy and IR spectroscopy; the molecular weights and molecular weight distributions were determined by gel permeation chromatography. In addition, the curing process of Bis‐ANER with 4,4′‐diaminodiphenyl sulfone was studied in both dynamic and isothermal modes with differential scanning calorimetry. The dynamic curing kinetic analysis was evaluated with both the Kissinger and Flynn–Wall–Ozawa methods, and the curing activation energy values were obtained. The isothermal curing reaction exhibited autocatalytic behavior, and the curing kinetics were described with the Kamal kinetics model, which accounted for both the autocatalytic and diffusion‐control effects. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 858–868, 2006     

Cure behavior of epoxy resin containing castor oil and cashew nut shell liquid and its derivative

The cure behavior of epoxy resin with a conventional amide‐type hardener (HD) was investigated in the presence of castor oil (CO), cashew nut shell liquid (CNSL), and cashew nut shell liquid–formaldehyde resin (CFR) with dynamic differential scanning calorimetry (DSC). The activation energy of the curing reaction was also calculated on the basis of nonisothermal DSC thermograms at various heating rates. A one‐stage curing was noted in the case of epoxy resin filled with CO, whereas the epoxy resin with CNSL and CFR showed a two‐stage curing process. A competitive cure reaction was noted for the epoxy resin/CNSL(or CFR)/HD blends. In the absence of HD, CFR showed lower values of curing enthalpy than that of CNSL. The activation energy of epoxy resin curing increased with increasing CNSL and CFR loading. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Cure kinetics of epoxy resin and aromatic diamines

The kinetics of curing reaction of a diglycidyl ether of a bisphenol‐A based epoxy (DGEBA) with 4,4′‐diaminostillbene (DAS) and 4,4′‐diaminoazobenzene (DAAB) as curing agents are studied by differential scanning calorimetery (DSC) using the isothermal technique. The experimental data show that the cure reaction is autocatalytic in nature, and all kinetic parameters of the curing reaction are determined using a semiempirical equation. The reaction of DGEBA with DAS is faster than that with DAAB under the same conditions and the activation energies of both systems are higher than those reported for other aromatic diamines. With increasing isothermal temperature and concentration of curing agents the rate constants are increased by the increasing of probability collisions between epoxide and primary amine groups while the activation energies remain constant. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1049–1056, 2004     

Curing kinetics and thermal property characterization of an o‐cresol formaldehyde epoxy resin and 4,4′‐diaminodiphenyl ether system

The kinetics of the curing reaction for a system of o‐cresol formaldehyde epoxy resin (o‐CFER) with 4,4′‐diaminodiphenyl ether (DDE) as a curing agent were investigated with differential scanning calorimetry (DSC). An analysis of the DSC data indicated that an autocatalytic behavior appeared in the first stages of the cure for the system, and this could be well described by the model proposed by Kamal, which includes two rate constants and two reaction orders (m and n). The overall reaction order (m + n) was 2.7–3.1, and the activation energies were 66.79 and 49.29 kJ mol^?1, respectively. In the later stages, a crosslinked network was formed, and the reaction was mainly controlled by diffusion. For a more precise consideration of the diffusion effect, a diffusion factor was added to Kamal's equation. In this way, the curing kinetics were predicted well over the entire range of conversions, covering both the previtrification and postvitrification stages. The glass‐transition temperatures of the o‐CFER/DDE samples were determined via torsional braid analysis. The results showed that the glass‐transition temperatures increased with the curing temperature and conversion up to a constant value of approximately 370 K. The thermal degradation kinetics of the system were investigated with thermogravimetric analysis, which revealed two decomposition steps. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 182–188, 2004     

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     

Curing kinetics and thermal property characterization of a bisphenol‐F epoxy resin and DDO system

The curing kinetics of a bisphenol‐F epoxy resin (BPFER)/4,4′‐diaminodiphenyl oxide (DDO) system were studied with isothermal experiments via differential scanning calorimetry. Autocatalytic behavior was shown in the first stages of the cure for the system, which was well described by the model proposed by Kamal that includes two rate constants, k₁ and k₂, and two reaction orders, m and n. The curing reaction at the later stages was practically diffusion‐controlled because of the onset of gelation and vitrification. For a more precise consideration of the diffusion effect, a diffusion factor, f(α), was introduced into Kamal's equation. In this way, the curing kinetics were predicted well over the entire range of conversion, covering both previtrification and postvitrification stages. The glass‐transition temperatures (T_g's) of the BPFER/DDO system partially isothermally cured were determined by means of torsional braid analysis, and the results showed that T_g's increased with conversion up to a constant value. The highest T_g was 376.3 K. The thermal degradation kinetics of cured BPFER were investigated with thermogravimetric analysis, which revealed two decomposition steps. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1586–1595, 2002     

Crystal structure,curing kinetics,and thermal properties of bisphenol fluorene epoxy resin

Diglycidyl ether of 9,9‐bis(4‐hydroxyphenyl) fluorene (DGEBF) monomer was successfully synthesized and characterized in detail. The crystal structure of DGEBF was measured by single‐crystal X‐ray diffraction analysis. Curing kinetics of DGEBF with 4,4‐diaminodiphenyl sulfone (DDS), thermal properties, and decomposition kinetics were investigated using nonisothermal differential scanning calorimetry (DSC) according to Kissinger, Ozawa and Crane methods. The glass transition temperature (T_g), thermal properties of cured polymer were estimated by DSC, dynamic mechanical analysis, and thermogravimetric analyses. Epoxy value of DGEBF monomer up to theoretical value leads to higher crosslink density of cured polymers. The cured DGEBF/DDS system exhibited obvious higher T_g and better thermal stability compared to those of DGEBF/diamine systems reported previously. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Comparison of microwave and thermal cure of epoxy–anhydride resins: Mechanical properties and dynamic characteristics

The objective of this work was to compare the mechanical properties of epoxy resins cured by thermal heating and microwave heating. Epoxy–anhydride (100:80) resins were cured in a domestic microwave oven and in a thermal oven. The hardening agents included methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride. Three types of accelerators were employed. Thermal curing was performed at 150°C for 20 and 14 min for resins containing 1 and 4% accelerator, respectively. Microwave curing was carried out at a low power (207 or 276 W) for 10, 14, and 20 min. All cured resins were investigated with respect to their tensile properties, notched Izod impact resistance, and flexural properties (three‐point bending) according to ASTM standards. The tan δ and activation energy values were investigated with dynamic mechanical thermal analysis, and the extent of conversion was determined with differential scanning calorimetry. The differences in the mechanical properties of the thermally cured and microwave‐cured samples depended on the resin formulation and properties. Equivalent or better mechanical properties were obtained by microwave curing, in comparison with those obtained by thermal curing. Microwave curing also provided a shorter cure time and an equivalent degree of conversion. The glass‐transition temperatures (tan δ) of the thermally and microwave‐cured resins were comparable, and their activation energies were in the range of 327–521 kJ/mol. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1442–1461, 2005     

Master curve and time–temperature–transformation cure diagram of a polyfunctional epoxy acrylic resin

The curing reaction of a well‐defined glycidyl methacrylate‐co‐butyl acrylate statistical copolymer, prepared by atom transfer radical polymerization, and a commercial linear diamine (Jeffamine D‐230) was studied with the objectives of constructing and discussing a time–temperature–transformation isothermal curing for this system. Thermal and rheological analyses were used to obtain the gelation and vitrification times. Differential scanning calorimetry data showed a one‐to‐one relationship between the glass‐transition temperature (T_g) and fractional conversion independent of the cure temperature. As a result, T_g was used as a measurement of conversion. We obtained a kinetically controlled master curve for isothermal curing temperatures from 50 to 100°C by shifting T_g versus the natural logarithm time data to a reference temperature of 80°C. We calculated the apparent activation energy by applying two different methods, gel time measurements versus shift factors, suggesting a good agreement between them. Isoconversion contours were calculated by the numerical integration of the kinetic model. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Shape memory CTBN/epoxy resin/cyanate ester ternary resin and their carbon fiber reinforced composites

Carboxylated-terminated liquid acrylonitrile rubber (CTBN) and epoxy resin (JEF-0211) were coreacted with cyanate ester (CE) to form CTBN/EP/CE ternary resin systems. Further, the ternary resin system was applied as prepreg for carbon fiber composites with vacuum bag degassing molding process. CTBN/EP/CE ternary shape memory polymer (SMP) exhibited relatively high tensile strength, Young's modulus, impact strength, and excellent shape memory properties. Compared with CTBN/EP/CE ternary SMP, CTBN/EP/CE carbon fiber composites showed much higher mechanical properties, such as their tensile strength and Young's modulus were high to 570 MPa and 36.7 GPa, respectively. Furthermore, CTBN/EP/CE carbon fiber composites exhibited good shape memory properties, their shape fixity ratio and shape recovery ratio were more than 95% after 30 times repeating shape memory tests. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48756.     

An interpenetrated system based on a tetrafunctional epoxy resin and a thermosetting bismaleimide: Structure–properties correlation

The kinetics and mechanism of the curing process of a thermosetting blend formed by tetraglycidyl-4,4′-diaminodiphenyl methane and N,N′-bismaleimido-4,4′-diphenyl methane (BMI) cured in the presence of 4,4′-diaminodiphenyl sulfone, was investigated in detail by Fourier transform infrared spectroscopy. Information on the molecular structure of the network formed upon curing was derived. Dynamic-mechanical measurements on dry samples indicated an interpenetrated polymer network-like structure. Sorption measurements at 70°C showed a reduction of the water uptake at equilibrium in the presence of substantial amounts of BMI in the system (43.5% body weight). Finally, the dynamic-mechanical analysis of wet samples demonstrated a reduction of the plasticizing efficiency of the absorbed water in the presence of BMI. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1029–1042, 1998     

Curing and thermal degradation behavior of epoxy-based vitrimers

Epoxy with associative covalent adaptable networks (CANs), called vitrimer, is reported to be promising to realize the recyclable utilization. The typical epoxy vitrimers are synthesized from diglycidyl ether of bisphenol A and dicarboxylic catalyzed by triazabicyclodecene (TBD). The study on the curing and thermal degradation behavior facilitates in-depth understanding of the associative CANs. In this work, the effect of TBD on the curing and thermal degradation behavior is investigated via curing kinetics and thermal degradation performance analysis. The results reveal that the activation energy of curing reaction is increased as the amount of TBD is increased. EST-5 has an average activation energy of 70.1 kJ/mol, while EST-15 reaches as high as 75.1 kJ/mol. Especially, when the conversion is up to 50%, the activation energy shows an obvious increment. In addition, it has been demonstrated that TBD accelerates the thermal degradation of cured networks at lower temperature and increases the amount of volatiles during thermal decomposition.     

Reaction kinetics,thermal properties of tetramethyl biphenyl epoxy resin cured with aromatic diamine

Epoxy resins, 4, 4′‐diglycidyl (3, 3′, 5, 5′‐tetramethylbiphenyl) epoxy resin (TMBP) containing rigid rod structure as a class of high performance polymers has been researched. The investigation of cure kinetics of TMBP and diglycidyl ether of bisphenol‐A epoxy resin (DGEBA) cured with p‐phenylenediamine (PDA) was performed by differential scanning calorimeter using an isoconversional method with dynamic conditions. The effect of the molar ratios of TMBP to PDA on the cure reaction kinetics was studied. The results showed that the curing of epoxy resins contains different stages. The activation energy was dependent of the degree of conversion. At the early of curing stages, the activation energy showed the activation energy took as maximum value. The effects of rigid rod groups and molar ratios of TMBP to PDA for the thermal properties were investigated by the DSC, DMA and TGA. The cured 2/1 TMBP/PDA system with rigid rod groups and high crosslink density had shown highest T_g and thermal degradation temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Curing and thermal behavior of diglycidyl ether of bisphenol A in the presence of a mixture of amines

The curing behavior of diglycidyl ether of bisphenol A (DGEBA) was investigated by differential scanning calorimetry with mixtures of silicon‐containing amide–amines and diaminodiphenyl sulfone (DDS). Silicon‐containing amide–amines were prepared by the reaction of 2.5 mol of 4,4′‐diaminodiphenyl ether (E), 4,4′‐diaminodiphenyl methane (M), 3,3′‐diaminodiphenyl sulfone (mS), 4,4′‐diaminodiphenyl sulfone (pS), bis(3‐aminophenyl) methyl phosphine oxide (B), or tris(3‐aminophenyl) phosphine oxide (T) with 1 mol of bis(4‐chlorobenzoyl) dimethyl silane. Mixtures of the amide–amines and DDS at ratios of 0:1, 0.25:0.75, 0.5:0.5, 0.75:0.25, and 1:0 were used to investigate the curing behavior of DGEBA. A single exotherm was observed on curing with a mixture of amide–amine and DDS. This clearly shows that the mixture participated in the cocuring reaction. The peak exotherm temperature depended on the structure and the molar ratio of amide–amines. With all of the amide–amines and DDS, a significant decrease in the kick‐off temperature of the curing exotherm was observed on the incorporation of a 0.25 molar fraction of amide–amines. Thus, with the mixture, the curing temperatures were reduced and were lowest for ether‐containing amide‐amines and highest for methylene‐containing amide–amines. The char yield was almost similar in the samples cured with amide–amines (E, pS, or mS) or DDS. The char yield was higher than for either of the constituents when a mixture was used. A synergistic behavior was observed when a mixture of E, M, mS, or pS and DDS was used, whereas mixture of B or T and DDS showed antigonism in the char yield. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1739–1747, 2003     

Kinetic of epoxy resin formation by high‐performance liquid chromatography

This article is focused on the following of the cure of an epoxy resin by high‐performance liquid chromatography (HPLC) and the comparison of the data obtained with those obtained by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) techniques usually employed for characterize curing processes. A reversed‐phase HPLC method with UV detection is developed to study the kinetic of the curing reaction of diglycidyl ether of bisphenol A (DGEBA) with 1,3‐cyclohexanebismethylamine (1,3‐BAC) at 60, 70, and 80°C, before and after gelation. The limits of quantification obtained permit the application of the proposed method until the last steps of the formation kinetic. HPLC and DSC analysis show a good correlation. The gel conversions obtained by HPLC and DMA agree well. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 497–504, 2003