Curing behavior of epoxy resins in two‐stage curing process by non‐isothermal differential scanning calorimetry kinetics method

In this research, a new thermal curing system, with two‐stage curing characteristics, has been designed. And the reaction behaviors of two different curing processes have been systematically studied. The non‐isothermal differential scanning calorimetry (DSC) test is used to discuss the curing reaction of two stages curing, and the data obtained from the curves are used to calculate the kinetic parameters. Kissinger‐Akahira‐Sunose (KAS) method is applied to determine activation energy (E_a) and investigate it as the change of conversion (α). Málek method is used to unravel the curing reaction mechanism. The results indicate that the curing behaviors of two different curing stages can be implemented successfully, and curing behavior is accorded with ?esták‐Berggren mode. The non‐isothermal DSC and Fourier transform infrared spectroscopy test results reveal that two different curing stages can be implemented successfully. Furthermore, the double x fitting method is used to determine the pre‐exponential factor (A), reaction order (m, n), and establish the kinetic equation. The fitting results between experiment curves and simulative curves prove that the kinetic equation can commendably describe the two different curing reaction processes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40711.     

Cure kinetics of epoxy resins by differential scanning calorimetry technique

The curing reactions of epoxy resins with aliphatic amine are investigated using the differential scanning calorimetry technique with a single dynamic scan. The rate of the reaction was followed over the temperature range 30–250°C, and the activation energy and the order of the reaction are determined using four different computational methods. The activation energy for the various epoxy systems is observed in the range 40–76 kJ mol^?1 and the order of the reaction is observed to be ? 1·0.     

Activation energy and curing behavior of resol‐ and novolac‐type phenolic resins by differential scanning calorimetry and thermogravimetric analysis

The thermal behavior, thermal degradation kinetics, and pyrolysis of resol and novolac phenolic resins with different curing conditions, as a function of the formaldehyde/phenol (F/P) molar ratio (1.3, 1.9, and 2.5 for the resol resins and 0.5, 0.7, and 0.9 for the novolac resins) were investigated. The activation energy of the thermal reaction was studied with differential scanning calorimetry at five different heating rates (2, 5, 10, 20, and 40°C/min) between 50 and 300°C. The activation energy of the thermal decomposition was investigated with thermogravimetric analysis at five different heating rates (2, 5, 10, 20, and 40°C/min) from 30 to 800°C. The low molar ratio resins exhibited a higher activation energy than the high molar ratio resins in the curing process. This meant that less heat was needed to cure the high molar ratio resins. Therefore, the higher the molar ratio was, the lower the activation energy was of the reaction. As the thermal decomposition of the resol resins proceeded, the activation energy sharply decreased at first and then remained almost constant. The activation energy of the thermal decomposition for novolac resins with F/P = 0.5 or F/P = 0.7 was almost identical in all regions, whereas that for novolac resins with F/P = 0.9 gradually decreased as the reaction proceeded. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2589–2596, 2003     

Polymers based on N,N‐diglycidylaniline. I. Investigations of the curing kinetics by dynamic differential scanning calorimetry measurements

N,N‐Diglycidylaniline was reacted with aniline (yielding polymer EP‐1) and the newly synthesized chromophore 4‐(phenylazo)aniline (yielding polymer EP‐2). The curing kinetics of these two epoxy resin systems was studied in dynamic experiments by means of differential scanning calorimetry. Kinetic parameters such as the activation energy and frequency factor were estimated with the Ozawa method [E(O) and A(O), respectively], the Kissinger method [E(K) and A(K), respectively], and the modified Avrami method [E(A) and A(A), respectively]. The activation energy and frequency factor of EP‐1 were much lower than those of EP‐2 estimated with the Ozawa, Kissinger, and Avrami methods. The activation energy and frequency factor for EP‐1 determined with the Ozawa method [E(O) = 55.8 kJ/mol, A(O) = 10 × 10³ 1/s] and the Avrami method [E(A) = 56.4 kJ/mol, A(A) = 9.2 × 10³ 1/s] were higher than those determined with the Kissinger method [E(K) = 51.0 kJ/mol, A(K) = 2 × 10³ 1/s]. In the case of EP‐2, the kinetic parameters calculated with the Ozawa model [E(O) = 140.4 kJ/mol, A(O) = 12.3 × 10¹³ 1/s] and the Kissinger model [E(K) = 139.9 kJ/mol, A(K) = 10.9 × 10¹³ 1/s] were higher than those calculated with the Avrami model [E(A) = 130.4 kJ/mol, A(A) = 7.9 × 10¹² 1/s]. The obtained polymers were characterized with Fourier transform infrared, ¹H‐NMR, differential scanning calorimetry, and ultraviolet–visible spectroscopy. The polymers exhibited low glass‐transition temperatures in the range of 57–79°C and good solubility in common organic solvents. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Cure kinetics of a glass/epoxy prepreg by dynamic differential scanning calorimetry

Dicyandiamide (DICY)‐cured epoxy resins are important materials for structural adhesives and matrix resins for fiber‐reinforced prepregs. Dynamic differential scanning calorimetry (DSC) with heating rates of 2.5, 5, 10, and 15°C/min was used to study the curing behavior of the epoxy prepreg Hexply 1454 system, which consisted of diglycidyl ether of bisphenol A, DICY, and Urone reinforced by glass fibers. The curing kinetic parameters were determined with three different methods and compared. These were the Kissinger, Ozawa, and Borchardt–Daniels kinetic approaches. The lowest activation energy (76.8 kJ/mol) was obtained with the Kissinger method, whereas the highest value (87.9 kJ/mol) was obtained with the Borchardt–Daniels approach. The average pre‐exponential factor varied from 0.0947 × 10⁹ to 2.60 × 10⁹ s⁻¹. The orders of the cure reaction changed little with the heating rate, so the effect of the heating rate on the reaction order was not significant. It was interesting that the overall reaction order obtained from all three methods was nearly constant (≅2.4). There was good agreement between all of the methods with the experimental data. However, the best agreement with the experimental data was seen with the Ozawa kinetic parameters, and the most deviation was seen with the Borchardt kinetic parameters. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Comparison of model‐fitting kinetics for predicting the cure behavior of commercial phenol–formaldehyde resins

Phenol–formaldehyde (PF) resins have been the subject of many model‐fitting cure kinetic studies, yet the best model for predicting PF dynamic and isothermal cure has not been established. The objective of this research is to compare and contrast several commonly used kinetic models for predicting degree of cure and cure rate of PF resins. Toward this objective, the nth‐order Borchardt–Daniels (nth‐BD), ASTM E698 (E698), autocatalytic Borchardt–Daniels (Auto‐BD), and modified autocatalytic methods (M‐Auto) are evaluated on two commercial PF resins containing different molecular weight distributions and thus cure behaviors. The nth‐BD, E698, and M‐Auto methods all produce comparable values of activation energies, while Auto‐BD method yields aberrant values. For dynamic cure prediction, all models fail to predict reaction rate, while degree of cure is reasonably well predicted with all three methods. As a whole, the nth‐BD method best predicts degree of cure for both resins as assessed by mean squared error of prediction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Kinetic analysis of curing behavior of diglycidyl ether of bisphenol A with imidazoles using differential scanning calorimetry techniques

The curing kinetics and mechanisms of diglycidyl ether of bisphenol A (DGEBA) using imidazole (H‐NI) and 1‐methyl imidazole (1‐MI) as curing agents are studied with differential scanning calorimetry (DSC) under isothermal (90–120°C) and dynamic conditions (50–250°C). The isothermal DSC thermograms of curing DGEBA with H‐NI and 1‐MI curing agents show two exothermic peaks. These peaks are assigned to the processes of adduct formation and etherification. These results indicate that there is no difference in the initiation mechanism of 1‐unsubstituted (H‐NI) and 1‐substituted (1‐MI) imidazoles in the curing reaction with epoxy resin. A kinetic analysis is performed using different kinetic models. The activation energies obtained from DSC scanning runs using the Ozawa and Kissinger methods are similar and in the range of 75–79 and 76–82 kJ/mol for DGEBA/H‐NI and DGEBA/1‐MI systems, respectively. These values compare well with the activation energies obtained from isothermal DSC experiments using the autocatalytic method (74–77 kJ/mol). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2634–2641, 2006     

Curing behavior of a novolac‐type phenolic resin analyzed by differential scanning calorimetry

Curing of a novolac‐type phenolic resin was studied by DSC. The kinetic analysis was performed by means of the dynamic Ozawa method at heating rates of 5, 10, 15, and 20°C/min. This analysis was used to determine the kinetic parameters of the curing process. The activation energy was found to be 144 kJ/mol. It was found that the Ozawa exponent values decreased with increasing reaction temperature from 3.5 to 1, suggesting a change in the reaction mechanism from microgel growth to diffusion‐controlled reaction. The reaction rate constant was found to range from 123.0 to 33.6 (°C/min)ⁿ. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1678–1682, 2003     

Curing kinetics of epoxy resin–imidazole–organic montmorillonite nanocomposites determined by differential scanning calorimetry

The curing kinetics of epoxy resin–imidazole–organic montmorillonite nanocomposites were investigated by differential scanning calorimetry (DSC) in the isothermal mode. X‐ray diffraction (XRD) analysis indicated the formation of a layered silicate–epoxy nanocomposite. The cure rates for the epoxy resin–imidazole–organic montmorillonite nanocomposite were lower than the values for the neat system at higher temperature (120 and 130°C), as indicated by the relation between the cure conversion and time. These results revealed that the autocatalytic model and the modified Avrami equation are both valid for describing the cure behaviors of epoxy resin–imidazole–organic montmorillonite systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2932–2941, 2003     

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     

Differential scanning calorimetry characterization of urea–formaldehyde resin curing behavior as affected by less desirable wood material and catalyst content

Differential scanning calorimetry was applied to investigate the curing behavior of urea–formaldehyde (UF) resin as affected by the catalyst content and several less desirable wood materials (e.g., wood barks, tops, and commercial thinnings). The results indicate that the reaction enthalpy of UF resin increased with increasing catalyst content. The activation energy and peak temperature of the curing UF resin generally decreased with increasing catalyst content at lower levels of catalyst content. However, with further increases in catalyst content, the changes in the activation energy and peak temperature were very limited to nonexistent. The hydrolysis reaction of the cured UF resin occurred during the latter stages of the curing process at both lower level (<0.2%) and higher level (>0.7%) catalyst contents. This indicates that there existed an optimal range of catalyst content for the UF resin. The curing enthalpy of the UF resin decreased with increasing wood raw materials present due to the effect of diffusion induced by the wood materials and the changes in the phase of the curing systems. This suggests that the curing reactions reached a lower final degree of conversion for the wood–resin mixtures than for the UF resin alone. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2027–2032, 2005     

Kinetics of aryl phosphinate anhydride curing of epoxy resins using differential scanning calorimetry

The curing reaction of two kinds of epoxy resins, (bisphenol A epoxy DER331, and novolac epoxy DEN438) with aryl phosphinate anhydride (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)-methyl succinic anhydride (DMSA), and benzyldimethylamine (BDMA) as the catalyst, was investigated by differential scanning calorimetry (DSC) using an isothermal approach over the temperature range 130–160°C. The experimental results showing autocatalytic behaviour were compared with the model proposed by Kamal, including two rate constants (k₁ and k₂) and two reaction orders (m and n). The model predictions are in good agreement with the experimental data and demonstrate that the autocatalytic model is capable of predicting the curing kinetics of both systems without any additional assumptions. The activation energies for the rate constants of DER331/DMSA and DEN438/DMSA are 77–92 kJmol^-1 and 83–146 kJmol^-1, respectively. The obtained overall reaction order of 2 is in agreement with the reaction mechanism reported by several workers. © 1998 SCI.     

Isothermal crystallization kinetics of high‐flow nylon 6 by differential scanning calorimetry

The isothermal crystallization kinetics have been investigated with differential scanning calorimetry for high‐flow nylon 6, which was prepared with the mother salt of polyamidoamine dendrimers and p‐phthalic acid, an end‐capping agent, and ε‐caprolactam by in situ polymerization. The Avrami equation has been adopted to study the crystallization kinetics. In comparison with pure nylon 6, the high‐flow nylon 6 has a lower crystallization rate, which varies with the generation and content of polyamidoamine units in the nylon 6 matrix. The traditional analysis indicates that the values of the Avrami parameters calculated from the half‐time of crystallization might be more in agreement with the actual crystallization mechanism than the parameters determined from the Avrami plots. The Avrami exponents of the high‐flow nylon 6 range from 2.1 to 2.4, and this means that the crystallization of the high‐flow nylon 6 is a two‐dimensional growth process. The activation energies of the high‐flow nylon 6, which were determined by the Arrhenius method, range from ?293 to ?382 kJ/mol. The activation energies decrease with the increase in the generation of polyamidoamine units but increase with the increase in the content of polyamidoamine units in the nylon 6 matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Curing studies of bisphenol a based bismaleimide and cloisite 15a nanoclay blends using differential scanning calorimetry and model‐free kinetics

Blends of 2,2‐bis[4‐(4‐maleimidophenoxy phenyl)]propane [bismaleimide (BMIX)] with different proportions (1, 2, 3, 4, 5, 7, and 9%) of the nanoclay Cloisite 15a were prepared with ultrasonication. Fourier transform infrared studies reveal the existence of interactions between the clay particles and the imide rings in BMIX. The difference in the melting characteristics and the decrease in the curing window caused by the incorporation of the clay particles in BMIX, as evidenced by detailed differential scanning calorimetry investigations, confirmed the existence of interactions between the nanoclay particles and BMIX molecules. The Flynn–Wall–Ozawa, Vyazovkin, and Friedman kinetics methods were used to calculate the activation energies (E_a's) for the curing of the BMIX materials. E_a for the polymerization varied, depending not only on the amount of clay loaded in the BMIX but also on the extent of the curing reaction. Because of the loss of interaction between the clay platelets and the imide rings of BMIX, a decrease in E_a at higher reaction extents was noted when there was lower clay loadings (1–4% Cloisite 15a) in BMIX. A reversal in the previous behavior was noted at higher clay loadings (7 and 9% Cloisite 15a) in BMIX and was attributed to the restriction of the molecular mobility due to the presence of increased concentrations of clay platelets and the decreased availability of reaction sites for polymerization. These two opposing factors played were equal at the optimum level of Cloisite 15a loading (5%) in BMIX, which was reflected in the constancy of E_a variation noted with increasing reaction extent. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Optimal designs for constant‐heating‐rate differential scanning calorimetry experiments for polymerization kinetics: nth‐order kinetics

Optimal designs have been constructed for differential scanning calorimetry (DSC) experiments conducted under constant‐heating‐rate conditions for materials that are a priori assumed to follow nth‐order kinetics. Two different operating scenarios are considered, including single‐scan and multiscan DSC experiments for eight different kinetic parameter combinations representing a range of typical polymeric curing reactions. The resulting designs are studied to determine which kinetic model parameters are influential in determining the optimal design. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Evaluation of the cure kinetics of isocyanate reactive hot‐melt adhesives with differential scanning calorimetry

The matrix polymer of reactive hot‐melt adhesive (RHMA) is an isocyanate‐terminated urethane prepolymer based on oligoester or oligoether diols and diisocyanates. In this study, we explored wet cure kinetics with both isothermal and nonisothermal differential scanning calorimetry methods. Second‐order autocatalytic models were successfully used to evaluate the cure process of both oligoester‐ and oligoether‐based RHMAs. The autocatalyzation effect did not to depend on the structure of diols but on the reaction nature of the end isocyanates. The apparent energy of the overall cure reaction was 86.54 and 84.46 kJ/mol, respectively, which was based on nonisothermal DSC results. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2708–2713, 2003     

Cure kinetics of the cardanyl acrylate–styrene system using isothermal differential scanning calorimetry

The curing kinetics of styrene (30 wt %) and cardanyl acrylate (70 wt %), which was synthesized from cardanol and acryloyl chloride, was investigated by differential scanning calorimetry under isothermal condition. The method allows determination of the most suitable kinetic model and corresponding parameters. All kinetic parameters including the reaction order, activation energy E_a and kinetic rate constant were evaluated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2034–2039, 2002     

Isothermal differential scanning calorimetry study of the cure kinetics of a novel aromatic maleimide with an acetylene terminal

An isothermal differential scanning calorimetry (DSC) study on the cure kinetics was performed on N-(3-acetylenephenyl)maleimide (3-APMI) monomer to determine a suitable cure model. The 3-APMI monomer reported in our prior article was a novel aromatic maleimide monomer with an acetylene terminal that would be an ideal candidate for heat-resistant composites. The isothermal DSC study was carried out in the temperature range 150–200°C. Although the cure temperatures were different, the shapes of the conversion curves were similar, and all of the cure reactions could be described by an nth-order kinetic model. In particular, the cure reaction at the initial stage was a first-order kinetic reaction. The cure kinetic parameters of the 3-APMI monomer, including the reaction model, activation energy, and frequency factor, were determined. This information was very useful for defining the process parameters, final properties, and quality control of the cured 3-APMI monomer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008