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1.
The curing reaction kinetics of the diglycidyl ether of bisphenol A‐ (DGEBA) based epoxy was investigated according to the change of curing agents. Complex curing agents based on Ni(II) and Cu(II) chelates with benzil bisthiosemicarbazone (LH6) as a ligand was studied using differential scanning calorimetry. The curing reaction was characterized by high‐activation energies (Ea), cure onset (Ti), and peak maximum (Tp) temperatures. Dynamic kinetic parameters were calculated by using Kissinger and Ozawa methods. For the NiLH6Cl2, CuLH6Cl2, and LH6 the average values of Ea were calculated to be 165.16, 165.92, and 115.75 kJ/mol, respectively. For the NiLH6Cl2 systems, their activation energies at 40 and 30 phr are equal. The Ti and Tp of the DGEBA/NiLH6Cl2 system are lower than those of DGEBA/CuLH6Cl2 system. These results indicate that NiLH6Cl2 has a higher reactivity toward epoxy resin at the beginning of the curing reaction. The effect of hardener concentration, heating rate, and type of metal ion on the cure kinetic parameters and the shape of DSC thermograms were investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
2.
A new organic–inorganic hybrid material was prepared through reactive blending of hydrogenated carboxylated nitrile rubber (HXNBR) with epoxycyclohexyl polyhedral oligomeric silsesquioxanes (epoxycyclohexyl POSS). The structure of the composite was characterized by Fourier transform infrared spectroscopy (FTIR) and solid‐state 13C Nuclear Magnetic Resonance spectra (solid‐state 13C‐NMR). The differential scanning calorimetry (DSC) at different heating rates was conducted to investigate the curing kinetics. A single overall curing process by an nth‐order function (1 ? α)n was considered, and multiple‐heating‐rate models (Kissinger, Flynn–Wall–Ozawa, and Crane methods) and the single‐heating‐rate model were employed. The apparent activation energy (Ea) obtained showed dependence on the POSS content and the heating rate (β). The overall reaction order n was practically constant and close to 1. The isoconversion Flynn–Wall–Ozawa method was also performed and fit well in the study. With the single‐heating‐rate model, the average Ea for the compound with a certain POSS content, 66.90–104.13 kJ/mol was greater than that obtained with Kissinger and Flynn–Wall–Ozawa methods. Furthermore, the calculated reaction rate (dα/dt) versus temperature curves fit with the experimental data. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 相似文献
3.
A novel imidazole derivative (named as EMI‐g‐BGE) was synthesized through the reaction of 2‐ethyl‐4‐methyl imidazole (EMI) and butyl glycidyl ether (BGE) and characterized by elemental analysis, FTIR spectroscopy, and 1H NMR spectroscopy. The curing kinetic of diglycidyl ether of bisphenol A (DGEBA) epoxy resin with EMI‐g‐BGE as curing agent was studied by nonisothermal DSC technique at different heating rates. Dynamic DSC scans indicated that EMI‐g‐BGE was an effective curing agent of epoxy resin. The apparent activation energy Ea was 71.8 kJ mol?1 calculated through Kissinger method, and the kinetic parameters were determined by Málek method for the kinetic analysis of the thermal treatment obtained by DSC measurement. A two‐parameter (m, n) autocatalytic model (?esták‐Berggren equation) was found to be the most adequate selected kinetic model. In addition, the predicted curves from the kinetic model fit well with the nonisothermal DSC thermogram. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
4.
Methyl‐di(m‐ethynylphenyl‐amino)silane (MEAS) is a new kind of silazane with ethynylphenyl groups in the end of the molecule. The studies about the curing reaction kinetics and curing reaction mechanism are important for its application and performance. In this article, differential scanning calorimeter was used to study the curing reaction kinetics of MEAS. The results showed that both of the apparent activation energy (Ea) and the reaction order (n) that were evaluated with the method of Kissinger (113.4 kJ/mol, 0.93) agreed well with those using the method of Ozawa (116.1 kJ/mol, 0.95). According to structural changes during curing characterized using Fourier‐transform infrared spectra, it was inferred that MEAS resin underwent the main four kinds of cross‐linking reaction under the condition of heating. Thermogravimetric analysis was used to characterize the heat‐resistance of MEAS thermoset. The results showed that the temperature of 5% weight loss based on the initial weight (Td5) of the thermoset was 632.4°C and the residue yield at 900°C was 86.4% in nitrogen. The thermoset sintered at 1450°C in argon transformed into a ceramic with yield of 71%, which was studied by scanning electron microscopy and X‐ray diffraction. The sintered products were smooth and hard solid and its chemical composition was made up of β‐SiC, α‐Si3N4 ceramic and free carbon. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 相似文献
5.
The curing kinetics of the diglycidyl ether of bisphenol A/melamine phosphate (DGEBA/MP) was analyzed by the DSC technique. The Kissinger and Flynn–Wall–Ozawa methods were applied to determine the dynamic kinetics of the DGEBA/MP system. The activation energies obtained by these two methods were 83.9 and 85.6 kJ/mol, respectively. An autocatalytic equation was applied to determine the isothermal curing kinetics of the DGEBA/MP system. The DGEBA/MP system exhibits autocatalytic behavior in the isothermal curing procedure, whose kinetics fits well with the autocatalytic mechanism. The obtained isothermal curing activation energy of the DGEBA/MP system was 110.0 kJ/mol. The curing mechanism of DGEBA with melamine phosphate was investigated using FTIR, 13C solid‐state NMR, and 31P solid‐state NMR. It involved an epoxide–amine reaction, etherification of phosphoric acid and epoxy, dehydration, and thermal oxidation of the hydroxyl group of the DGEBA/MP system. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 892–900, 2004 相似文献
6.
Differential scanning calorimetry, Fourier transform infrared (FTIR) spectroscopy, and 13C‐NMR were used to characterize the curing kinetics and structural changes of a copolymer of di[(N‐m‐acetenylphenyl) phthalimide] ether (DAIE) and [(methyl) diphenylacetylene] silane (MDPES). The results show that the apparent activation energy (E) and reaction order (n) calculated according to the Kissinger method were nearly the same as those calculated according to the Ozawa method. E was 160.4 kJ/mol and n was 0.96 with the Kissinger method, and E was 158.1 kJ/mol and n was 0.95 with the Ozawa method. The FTIR and solid‐state 13C‐NMR results also indicate that with increasing curing temperature, the peaks assigned to Si? H and C?C bonded to phenylene carbons decreased, broadened, and finally vanished, whereas the peaks assigned to the C?C carbons and phenyl carbons increased and broadened. Crosslinking reactions in the curing of the DAIE/MDPES copolymer were possible due to the hydrosilylation reaction and the Diels–Alder reaction. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2126–2130, 2006 相似文献
7.
Curing kinetics of bio‐based epoxy resin based on epoxidized soybean oil and green curing agent
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New thermoset with a high bio‐based content was synthesized by curing epoxidized soybean oil (ESO) with a green curing agent maleopimaric acid catalyzed by 2‐ethly‐4‐methylimidazole. Non‐isothermal differential scanning calorimetry and a relatively new integral isoconversional method were used to analyze the curing kinetic behaviors and determine the activation energy (Ea). The two‐parameter ?esták–Berggren autocatalytic model was applied in the mathematical modeling to obtain the reaction orders and the pro‐exponential factor. For anhydride/epoxy group molar ratio equal to 0.7, Ea decreased from 82.70 to 80.17 kJ/mol when increasing the amount of catalyst from 0.5 to 1.5 phr toward ESO. The reaction orders m and n were 0.4148 and 1.109, respectively. The predicted non‐isothermal curing rates of ?esták–Berggren model matched perfectly with the experimental data. © 2016 American Institute of Chemical Engineers AIChE J, 63: 147–153, 2017 相似文献
8.
A novel epoxidized hemp oil (EHO) based bioresin was synthesized by epoxidation in situ with peroxyacetic acid. In this research the cure kinetics of an EHO based bioresin system cured with triethylenetetramine (TETA) was studied by differential scanning calorimetry using both isothermal and nonisothermal data. The results show that the curing behavior can be modeled with a modified Kamal autocatalytic model that accounts for a shift to a diffusion‐controlled reaction postvitrification. The total order of the reaction was found to decrease with an increase in temperature from ~ 5.2 at 110°C to ~ 2.4 at 120°C. Dynamic activation energies were determined from the Kissinger (51.8 kJ/mol) and Ozawa‐Flynn‐Wall (56.3 kJ/mol) methods. Activation energies determined from the autocatalytic method were 139.5 kJ/mol and ?80.5 kJ/mol. The observed negative activation energy is thought to be due to an unidentified competitive reaction that gives rise to the appearance of k2 decreasing with increasing temperature. The agreement of fit of the model predictions with experimental values was satisfactory for all temperatures. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011 相似文献
9.
The curing reactions of liquid crystalline 4,4′‐bis‐(2,3‐epoxypropyloxy)‐sulfonyl‐bis(1,4‐phenylene) (p‐BEPSBP) with 4,4′‐diaminodiphenylmethane (DDM) and 4,4′‐diaminodiphenylsulfone (DDS) were investigated by nonisothermal differential scanning calorimeter (DSC). The relationships of Ea with the conversion α in the curing process were determined. The catalyzed activation of hydroxyl group for curing reaction of epoxy resins with amine in DSC experiment was discussed. The results show that these curing reactions can be described by the autocatalytic ?esták‐Berggren model. The curing technical temperature and parameters were obtained, and the even reaction orders m, n, and ΔS for p‐BEPSBP/DDM and p‐BEPSBP/DDS are 0.35, 0.92, ?81.94 and 0.13, 1.32, ?24.45, respectively. The hydroxyl group has catalyzed activation for the epoxy–amine curing system in the DSC experiment. The average Ea of p‐BEPSBP/DDM is 67.19 kJ mol?1 and is 105.55 kJ mol?1 for the p‐BEPSBP/DDS system, but it is different for the two systems; when benzalcohol as hydroxyl group was added to the curing system, the average Ea of p‐BEPSBP/DDM decreases and increases for p‐BEPSBP/DDS. The crystalline phase had formed in the curing process and was fixed in the system. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 相似文献
10.
A new curing agent containing maleimide and biphenyl moieties (MIBP) was synthesized by the condensation polymerization of 4,4′-bismethoxymethylbiphenyl and N-(4-hydroxyphenyl)maleimide (HPM). The chemical structure was characterized with Fourier transform infrared (FTIR) spectroscopy, and the molecular weight of the new curing agent was determined by gel permeation chromatography. Curing reactions of O-cresol formaldehyde epoxy (CNE) resin with MIBP were investigated under nonisothermal differential scanning calorimetry, and the exotherm exhibited two overlapping exothermic peaks during the curing process; this was demonstrated by FTIR traces. The Flynn–Wall–Ozawa and Friedman methods were used to examine the kinetic parameters and the kinetic models of the curing processes of the CNE/MIBP mixtures. Both reactions turned out to be nth-order curing mechanisms. Values of the reaction order (n) = 1.42 and activation energy (Ea) = 91.2 kJ/mol were obtained for the first reaction of the curing of the CNE/MIBP system, and values of n = 1.11 and Ea = 78.7 kJ/mol were obtained for the second reaction. The thermal properties of the cured resin were measured with thermogravimetric analysis, and the results show a high glass-transition temperature (Tg = 155°C), good thermal stability (temperature at 10% weight loss, under nitrogen and in air, ≈ 400 and 408°C, respectively), and high char yield (temperature = 800°C, char residue = 44.5% under nitrogen). These excellent thermal properties were due to the introduction of the maleimide and biphenyl groups of MIBP into the polymer structure. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 相似文献
11.
Diglycidyl ether of bisphenol A (DGEBA) is cured with a nickel complex of O‐phenylendiamine (OPD) as a ligand. The structure of the synthesized curing agent is confirmed through IR and elemental analysis. The curing kinetics of DGEBA/Ni(OPD)3Br2 system is studied by the dynamic DSC and isothermal FTIR techniques. In all cases, we have observed at least two exothermic peaks during DSC traces up to 350°C. Dynamic activation energies are calculated by using the two isoconversional, Kissinger and Ozawa, methods applied to peak maximum. A two‐parameter (m, n) autocatalytic model (Sestak–Berggren equation) is found to be the most adequate model to describe the cure kinetics of the observed thermal events. Isothermal kinetic parameters are estimated using the Horie model. The onset decomposition temperature and char yield (at 700°C) of the crosslinked material were 290°C and 27%, respectively. The activation energy of the solid‐state thermal degradation process is evaluated by Ozawa approach, resulting in 95–138 kJ/mol on a range of 2–20% decomposition conversion. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1257–1265, 2006 相似文献
12.
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 相似文献
13.
The curing kinetics of blends of diglycidyl ether of bisphenol A (DGEBA), cycloaliphatic epoxy resins, and carboxyl‐terminated butadiene‐acrylonitrile random copolymer (CTBN) in presence of 4,4′‐diamino diphenyl sulfone (DDS) as the curing agent was studied by nonisothermal differential scanning calorimetry (DSC) technique at different heating rates. The kinetic parameters of the curing process were determined by isoconversional method given by Malek for the kinetic analysis of the data obtained by the thermal treatment. A two‐parameter (m, n) autocatalytic model (Sestak‐Berggren equation) was found to be the most adequate selected to describe the cure kinetics of the studied epoxy resins. The values of Ea were found to be 88.6 kJ mol?1 and 61.6 kJ mol?1, respectively, for the studied two sample series. Nonisothermal DSC curves obtained using the experimental data show a good agreement with that theoretically calculated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 相似文献
14.
M. Barghamadi 《Polymer Composites》2010,31(8):1442-1448
The kinetics of the cure reaction for a system of bisphenol‐A epoxy resin (DGEBA), with 4, 4′‐diaminoazobenzene (DAAB), reinforced with nanosilica (NS), and nanoclay (NC) by means of isothermal technique of differential scanning calorimetry were studied. The Kamal autocatalytic‐like kinetic model was used to estimate the reaction orders (m, n), rate constants (k1, k2), and also active energies (Ea) and pre‐exponential factors (A) of the curing reaction. However, the existence of NS and NC with hydroxyl groups in the structure improves the cure reaction and influence the rate of reaction and therefore kinetics parameters. The Ea of cure reaction of DGEBA/DAAB system showed a decrease when nanoparticles were present and therefore the rate of the reaction was increased. Using the rate constants from the kinetic analysis and transition state theory, thermodynamic parameters such as enthalpy (ΔH#), entropy (ΔS#), and Gibbs free energy (ΔG#) changes were also calculated. The thermodynamic functions were shown to be very sensitive parameters for evaluation of the cure reaction. POLYM. COMPOS., 31:1442–1448, 2010. © 2009 Society of Plastics Engineers 相似文献
15.
The curing behavior of diglycidyl ether of bisphenol A (DGEBA) epoxy and specially ground mechanochemical devulcanized ground rubber tire system (GRT) in the presence of polyoxyalkyleneamine curing agent was investigated by non-isothermal differential scanning calorimetry technique at different heating rates. Scanning electron microscopic-energy dispersive X-ray spectroscopy, and attenuated total reflection infrared spectroscopy were used to characterize the GRT particles. The kinetic parameters of curing process were determined by isoconversional method given by Málek. The average activation energy E a was found to be 52.3–60.7 and 45–59.2 kJ/mol for neat epoxy amine (Epo am 31) and epoxy/amine with GRT (5 Epo am 31) systems, respectively. It was observed that the presence of GRT in epoxy/amine promotes the curing. A two parameter (m, n) autocatalytic model (SB equation) was found to be the most adequate to describe the cure kinetics of the studied epoxy/GRT system. A dominant catalyzing effect of GRT on the curing reaction was observed which is attributed to the complexity of the reaction at later stages of curing, therefore, it was not possible to model the reaction over the whole range of degree of conversion. 相似文献
16.
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 相似文献
17.
Uraiwan Pongsa Chavakorn Samthong Anongnat Somwangthanaroj 《Polymer Engineering and Science》2013,53(10):2194-2204
Directly functionalized multiwalled carbon nanotubes (MWCNTs) with benzene‐1,3,5‐tricarboxylic acid (BTC) and 3,5‐diaminobenzoic acid (DAB) were successfully accomplished with less structural damage as confirmed by XPS and FT‐Raman results. Their dispersibility and thermal stability were achieved after the functionalization. The functional groups on MWCNT surfaces can accelerate the curing reaction of epoxy composites remarkable inducing rather low exothermic peak temperature (Tp) and exothermic heat of reaction (ΔH). The values of activation energy (Ea) obtained from Kissinger and Ozawa methods obviously decreased with the introduction of MWCNTs, especially DAB‐MWCNTs. The dynamic mechanical properties notably enhanced with the incorporation of unmodified and functionalized MWCNTs. The crosslink density (ρ) increased and free volume fraction (fg) decreased, resulting in dramatic increase of glass transition temperatures (Tg) and decrease of coefficient of thermal expansion. Additionally, epoxy composites exhibited low dielectric constant close to that of neat epoxy resin. From these remarkable properties, MWCNT/epoxy composites can be considered as a good candidate for high performance insulation materials. POLYM. ENG. SCI., 53:2194–2204, 2013. © 2013 Society of Plastics Engineers 相似文献
18.
Curing behavior of epoxy resins in two‐stage curing process by non‐isothermal differential scanning calorimetry kinetics method
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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 (Ea) 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. 相似文献
19.
Two latex interpenetrating polymer networks (LIPNs) were synthesized with methyl methacrylate (MMA) and octyl acrylate (OA) as monomers, respectively. The apparent kinetics of polymerization for the LIPNs was studied. This demonstrates that network II does not have a nucleus formation stage. The monomers of network II were diffused into the latex particles of network I and then formed network II by in situ polymerization. It indicates that the polymerization of network I obeys the classical kinetic rules of emulsion polymerization. But the polymerization of network II only appears a constant‐rate stage and a decreasing‐rate stage. The apparent activation energies (Ea) of network I and network II of PMMA/POA were calculated according to the Arrhenius equation. The Ea values of POA as network I (62 kJ/mol) is similar to that of POA as network II PMMA/POA (60 kJ/mol). However, the Ea value of PMMA as network II POA/PMMA (105kJ/mol) is higher than that of PMMA as network I (61 kJ/mol). Results show that the Ea value of the network II polymerization is related to the properties of its seed latex. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 相似文献