Curing Kinetics Study Research Articles

Cure kinetics of epoxy/MWCNTs nanocomposites: Isothermal calorimetric and rheological analyses

Abstract A combinatorial route has been applied in cure kinetics study of epoxy nanocomposites containing multi-walled carbon nanotubes (MWCNTs) based on differential scanning calorimetry and rheokinetic analyses under isothermal conditions. Pristine and amine-modified MWCNTs bearing primary and secondary amines were used at very low concentrations (0.1 and 0.3 wt.% based on epoxy weight). Model-free and model-fitting methods were applied on calorimetric data, and Kamal autocatalytic model revealed good agreement with the experimental data. In case of epoxy filled with amine-modified MWCNTs, activation energy took a value lower than that obtained for sample containing pristine MWCNTs at an identical loading because of less hindrance brought about by curing. Isothermal rheokinetic studies supported formation of a filler network during processing, which hindered epoxy-anhydride cure reaction at higher MWCNTs loadings leading to a highly crosslinked epoxy network.

Curing kinetics study of benzoxazine using diaryliodonium salts as thermal initiators

In this study, the effects of three different diaryliodonium salts—diaryliodonium tetrafluoroborate (DT), diphenyliodonium hexafluorophosphate (PF) and diphenyliodonium hexafluoroarsenate (AS)—as catalysts on the thermal curing of bisphenol A‐based benzoxazine (BA) were examined. Resin systems consisting of BA and diaryliodonium salts (BA/ArIx) were prepared. The thermal curing behavior and mechanisms of BA/ArIx were investigated by differential scanning calorimetry (DSC) and in-situ Fourier transform infrared (in-situ FTIR) spectroscopy. The thermal curing kinetics and kinetic model of BA/ArIx systems were investigated by non-isothermal DSC. Based on the results obtained from in-situ FTIR, ArIx underwent a two-stage reaction for accelerating the curing of BA. Kinetic data indicate that the BA/ArIx system exhibits activation energy slightly greater than that of BA. Both BA and BA/ArIx followed an autocatalytic kinetic model based on the Friedman method, and the theoretically calculated curves exhibited good agreement with experiment data.

DSC and curing kinetics study of epoxy grouting diluted with furfural -acetone slurry

The use of furfural-acetone slurry as active diluents of Bisphenol-A epoxy resin (DGEBA) groutings has been studied by dynamic and non-isothermal DSC for the first time. Curing kinetics study was investigated by non-isothermal differential scanning calorimetries at different heating rates. Activation enery (Ea) was calculated based on Kissinger and Ozawa Methods, and the results showed that Ea increased from 58.87 to 71.13KJ/mol after the diluents were added. The furfural-acetone epoxy matrix could cure completely at the theoretical curing temperature of 365.8K and the curing time of 139mins, which were determined by the kinetic model parameters.

Different catalytic systems on hydroxyl-terminated GAP and PET with poly-isocyanate: Curing kinetics study using dynamic in situ IR spectroscopy

ABSTRACTReactions of hydroxyl-terminated glycidyl azide polymer (GAP) or poly(ethylene oxide-co-tetrahydrofuran) (PET) polymers with poly-isocyanate (N100) were monitored by dynamic in situ Fourier transform infrared spectroscopy. The influence of catalytic systems on the cure kinetics of polyurethane reaction was investigated. From the comparison between GAP/N100 and PET/N100 systems, it was found that primary and secondary hydroxyl groups were differentiated due to the effects of steric hindrance. Using Arrhenius law and Eyring equation, the activation parameters of polyurethane reaction were calculated at different catalytic systems. The negative value of the activation entropy demonstrated an associative mechanism within the transition state.

The synthesis and curing kinetics study of a new fluorinated polyurethane with fluorinated side chains attached to soft blocks

Fluorinated polyurethane with fluorinated side chains attached to soft blocks was successfully synthesized, which exhibited unique properties. And also the curing kinetics was studied using a rotational rheometer.

A cure modelling study of an unsaturated polyester resin system for the simulation of curing of fibre-reinforced composites during the vacuum infusion process

This study presents the cure kinetics and cure modelling of an ambient curing unsaturated polyester (UP) resin system for its cure simulation in the vacuum infusion (VI) process. The curing of the UP resin system was investigated using differential scanning calorimetry (DSC). The dynamic DSC test measurements were conducted to find out the ultimate heat of reaction and enable experimental conversion determination for the isothermal curing. The empirical autocatalytic cure kinetics model incorporating the Arrhenius law represented the cure behaviour. The results of the cure kinetics study, the cure model, the material properties and the boundary conditions were the inputs in PAM-RTM software for the simulation of the degree of cure and the exothermic temperature during the infusion and the room temperature curing stages. The simulation results were compared with experimentally measured data. A vacuum infusion (VI) experiment involving a non-crimp glass fibre preform was performed in order to monitor the curing using thermocouples and validate the temperature simulation result. It was shown that the degree of cure and the exothermic temperature of a room temperature curing thermoset resin system during the VI process could be predicted through the steps of this study.

Study of UV Curing Kinetics for Coating Containing Siloxane Modified Polyurethane-Acrylate

The UV curing kinetics of coating containing siloxane modified polyurethane-acrylate were studied using photo-DSC (DPC). The effects of some factors such as incident light intensity, initiator concentration, reaction temperature on the curing kinetics have been analysized from DPC data. The curing kinetic parameters (kp and kt) for prepolymers have also been determinedv by combining steady state and non-steady state kinetics.

Cure kinetic study of organoclay‐unsaturated polyester resin nanocomposites by using advanced isoconversional approach

Curing behavior of an unsaturated polyester (UP) resin containing 3 wt % Cloisite 10A (UP/10A) and 3 wt % Cloisite 30B (UP/30B) catalyzed with methyl ethyl ketone peroxide (MEKP) as initiator and promoted by cobalt naphthenate as accelerator was investigated by dynamic differential scanning calorimetry (DSC) at heating rates of 2, 2.5, 3, and 3.5°C min−1. X‐ray diffraction and transmission electron microscopy were utilized to evaluate the morphology of UP/10A and UP/30B nanocomposites. Kinetic parameters of cure reactions were evaluated using the advanced isoconversional method. The addition of nanoclay resulted in a decrease in the activation energy of the redox reaction compared to that of the neat UP resin. The pre‐exponential factor of the redox reaction for UP/10A and UP/30B was less than that of the neat UP. Results showed an increase in the concentration of styrene between Cloisite 10A platelets leading to a decrease in the intralayer styrene content. The high concentration of styrene between nanoclay layers may lead to the formation of polystyrene chains grafted on the alkyds chains. This homo‐polymerization was also observed in the variation of activation energy of UP/10A specimen versus the degree of conversion for 0.42 ≤ α ≤ 0.6 which is very close to the activation energy of free radical homo‐polymerization of styrene. POLYM. COMPOS., 34:1824–1831, 2013. © 2013 Society of Plastics Engineers

Study of Cure Kinetics of Vinyl-tri(phenylethynyl)silane Monomer

Study of Cure Kinetics of Vinyl-tri(phenylethynyl)silane Monomer

A study of the thermal cure of new trifunctional phenylethynyl terminated imide oligomers with reduced cure temperatures

A series of novel trifunctional phenylethynyl terminated imide oligomers was synthesized from two new triamines, 1,3,5-tris(3-aminophenoxy-4′-benzoyl)benzene (m-TABB) and 1,3,5-tris(4-aminophenoxy-4′-benzoyl)benzene (p-TABB), and systematically compared with the corresponding bifunctional phenylethynyl terminated imide oligomer, BPEPA. DSC isothermal cure kinetics studies were performed at the cure temperature of 320 °C, 350 °C, and 370 °C by applying two different kinetic equations, and in these cases the reaction kinetics followed first order reactions below 90% conversion. The rate of the curing reaction was observed to increase with the number of functional groups, and the TABB-based oligomers showed 20 °C lower curing temperature than the BABB-based oligomer. Tgs and thermal oxidative stabilities of imide films increased with increasing the number of the functional groups in a molecule, which may partly due to the higher crosslink densities. Moreover, trimerization or tetramerization, possible main curing reaction of trifunctional phenylethynyl terminated oligomers, based on the kinetic analysis by isothermal and ramp temperature DSC and calculation of crosslink densities, formed more thermooxidatively stable aromatic ring structures than the main polyene structures appeared in monofunctional or bifuntional phenylethynyl terminated model compounds. m-TABB-based resin exhibited the best combination of melt processibilities, curing temperatures, and thermal properties.

Isoconversional Curing and Degradation Kinetics Study of Self-assembled Thermo-responsive Resin System Bearing Oxime and Iminium Groups

This paper demonstrates synthesis of a self-assembled resin system containing p-acetylpyridine oxime, formaldehyde and p-methoxyacetophenone moieties in main chain and thermally cross-linkable periphery oxime groups, and application as antimicrobial coating in biomedical applications. The post-polymerization conversion from oxime into iminium groups was observed by heating scan, with exothermic peaks being at 194 to 247°C. Various degradation models including the Flynn-Wall-Ozawa (F-W-O), Kissinger-Akahira-Sunose (K-A-S), Tang (T) and Friedman (F) methods were employed to check the thermal stability of self-assembly by computing apparent activation energy. It has also exhibited strong biocidal properties against gram-positive and gram-negative bacteria, and fungi until the macrochain retains some positive charge. The obtained results prove that the structure of links, which combine the hydrophobic pyridine rings with the hydrophilic iminium groups, is responsible for the high biocidal activity of the resin system.

Cure Kinetics Study of Two Epoxy Systems with Fourier Tranform Infrared Spectroscopy (FTIR) and Differential Scanning Calorimetry (DSC)

This work was aimed at the study of cure kinetics of two commercial thermosetting epoxy systems, Epikote resin 816 LV/Epikure F205 and Epikote resin 240/Epikure F205, by Fourier Tranform Infrared Spectroscopy (FTIR) and Differential Scanning Calorimetry (DSC). The studied systems consist of a resin (A), based on a diglycidyl ether of bisphenol A and a hardener (B) based on the Isophorodiamine (IPDA) a cycloaliphatic diamine. These systems are used for the building and civil engineering industries, e.g. flooring compounds, adhesives, mortars and grouts. FTIR spectroscopy was employed to investigate the isothermal curing kinetics at 30, 50 or 70°C and DSC analysis to study the non-isothermal curing kinetics at different heating rates 2.5, 5, 10 and 20°C/min, from 20 to 300°C. A kinetic model was employed to simulate the FTIR isothermal experimental data using two kinetic rate constants and incorporating also diffusion control at high degrees of conversion. Finally, the variation of the effective activation energy with the extent of curing was estimated using isoconversional analysis of non-isothermal DSC data.

Cure kinetic study of epoxidized hemp oil cured with a multiple catalytic system

AbstractThe cure kinetics of two epoxidized hemp oil (EHO) based bioresins were studied and compared under both dynamic and isothermal conditions using differential scanning calorimetry (DSC). Neat triethylenetetramine (TETA) for the first system and a combination of isophorone diamine (IPD) and TETA for the second system were used as the hardeners for the two EHO‐based bioresins. Lower total heats of reaction and an approximate 10% decrease in activation energies were observed for the IPD/TETA system. Maximum conversions of the TETA/IPD system were consistently higher than those of the TETA system throughout the entire temperature range suggesting enhanced curing characteristics. Kissinger and Ozawa–Flynn–Wall models were used to determine activation energies from dynamic DSC data. Both bioresin systems were found to display autocatalytic behavior with the TETA/IPD system showing high nth order influence. Kamal's autocatalytic isothermal model, modified to account for diffusion postvitrification was found to satisfactorily describe the cure behavior of both bioresin systems. Overall, the addition of IPD was found to increase the curing rate of the EHO bioresin systems. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Effect of nanoclay and carboxyl-terminated (butadiene-co-acrylonitrile) (CTBN) rubber on the reaction induced phase separation and cure kinetics of an epoxy/cyclic anhydride system

The effects of nano clay, carboxyl-terminated (butadiene-co-acrylonitrile) (CTBN) liquid rubber and the combination of both on the cure kinetics of diglycidyl ether of bisphenol-A (DGEBA)-based epoxy resin/nadic methyl anhydride were studied. Cure kinetics studies were carried out by performing dynamic and isothermal differential scanning calorimetric (DSC) experiments. The dynamic DSC experiments were carried out at four different heating rates. Dynamic kinetic modeling was performed using Kissinger and Ozawa approaches. Since these methods are based exclusively on the maximum rate of cure, which occurs approximately at the beginning of the cure reaction, the activation energy calculated using these methods is valid only for the initial stage of the cure. The clay (3 phr) filled epoxy system has an activation energy 24 % lower than the unfilled system. The role of the surfactant chemistry on the initial stage of the cure reaction was also studied. A plausible reaction mechanism which involves the effect of the nanoclay surfactant as an accelerator of the cure reaction was proposed. The phase separated CTBN rubber hindered the cure reaction and has 3 % higher activation energy for epoxy/CTBN system than the unfilled system. In the ternary epoxy/3 phr clay/15 phr CTBN system, the accelerating effect of clay on cure was highlighted. The cure activation observed in the presence of clay overshadows the hindrance created by the phase separated CTBN. Isothermal DSC scans were carried out at five different temperatures. The experimental datas showed an autocatalytic behavior of the reaction, and the isothermal modeling was carried out by Kamal autocatalytic model. The results showed a very good agreement within the whole conversion range for the unfilled and all the filled systems. The evolution of the morphology and phase separation was also studied using optical and scanning electron microscope. Faster cure reaction resulted in smaller phase-separated CTBN particles in epoxy/clay/CTBN ternary system as compared with those observed in epoxy/CTBN binary blend.

Cure kinetics studies of cyanate ester and bisphenol‐F epoxy blend

AbstractCyanate ester and Bisphenol‐F blends with manganese acetylacetonate in nonylphenol as catalyst and cocatalysts respectively is an attractive candidate as the insulation impregnation materials for fusion grade magnets winding packs that is required to be operating in moderate irradiated environments in fusion devices like Tokamaks. The curing kinetics of this blend system as a thermosetting polymer has been investigated in this paper in detail for 60 : 40 (epoxy:ester) composition strongly driven from application interests. The order of reactions in both chemical kinetics controlled region as well as diffusion controlled regimes have been experimentally found out using Differential Scanning Calorimetric (DSC) studies. Corresponding rate constants and associated cure kinetics have been consequently determined. The second order kinetic model, as it is found, does not fit in to the epoxy‐cyanate ester reaction mechanism. The results, therefore, have been discussed in the context of widely used autocatalytic models and variable “n” kinetics models appropriate for chemical controlled region. The reaction conversion rate dα/dt of the cyanate ester‐epoxy blend is more rapid in chemical controlled regime compared to that in the diffusion controlled regime. The order of reaction is not constant throughout the reaction and is higher in chemical controlled regime. The variable “n” kinetic model has been employed to determine the hypothetical temperature (350.81 K) below which no more curing reaction would occur. The activation energy and the pre‐exponential factors have been determined in the chemical controlled regime using Arrhenius reaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Isothermal rheokinetic study of a precured resol resin beyond gelation by torsion

AbstractThe rheokinetics of the curing process of a resol resin was studied through isothermal analysis. The resin was subjected to a curing pretreatment until gelation was reached. Rectangular torsion was chosen as the appropriate strain form to carry out the study of the resin's curing kinetics, because the viscoelastic behavior of the material was closer to an ideal solid than to a Newtonian fluid. Seven operating temperatures were selected for analysis (80–110°C). The Arrhenius and Kiuna rheokinetic models were applied to the resin's complex viscosity (η*) evolution during the crosslinking of polymer. The resol resin had curing activation energies of 62.6 and 65.8 kJ/mol when the Arrhenius model was applied in four‐ and six‐parameter forms, respectively. The Kiuna model was proposed to fit the nonlinear viscosity region found at the highest temperatures. This model was suitable to predict changes in the resin's complex viscosity, obtaining a curing activation energy of 69.5 kJ/mol for the resin. In addition, the evolution of the degree of mechanical curing was obtained from the elastic modulus, rather than from the more common DSC technique. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Highly branched polyurethane acrylates and their waterborne UV curing coating

A series of UV curable highly branched waterborne polyurethane acrylates (BWPUAs) were synthesized using an “oligomeric A 2 + B 3” approach. The thiol-endcapped difunctional oligomeric A 2 was synthesized first by the addition reaction of isophorone diisocyanate, α,α-dimethylol propionic acid and 2-hydroxyethyl acrylate, then further underwent thiol-Michael reaction with 1,6-hexamethylene bis(thioglycolic acetate). Trimethylolpropane triacrylate was used as a B 3 monomer. The molecular structures were characterized with FT-IR and 1H NMR spectroscopy. 1,6-Hexanediol diacrylate (HDDA) was incorporated into the polymeric chain for preparing the HDDA-modified BWPUAs (BWPUA-Hs). For the comparison, the linear waterborne polyurethane acrylate (LWPUA) was synthesized. The UV curing kinetics study results by using the photo-DSC approach showed that the BWPUAs possessed higher photopolymerization rate and final unsaturation conversion in the UV cured films compared with the LWPUA, which increased with the increase of unsaturation concentration in BWPUA. Moreover, the photopolymerization performance, and water and solvent resistance properties were greatly enhanced by the incorporation of HDDA segment into the BWPUA chain. The dynamic mechanical thermal analysis results showed that the elastic modulus in the rubbery plateau, and the glass transition temperature of UV cured film increased with increasing unsaturation concentration in BWPUA, whereas decreased with the introduction of HDDA flexible segment. The thermogravimetric analysis confirmed the high thermal stability of UV cured BWPUA films. All UV cured BWPUA and BWPUA-H films showed better flexibility and middle refractive indices due to the thioether linkage in the polymer network.

Cure kinetics of epoxy composite applied on stator bars insulation

Cure kinetics study of epoxy resin composite, employed as stator bars insulation system, was evaluated through differential scanning calorimetry using the dynamic methodology, different heating rates. These experiments provided some important information about the system as activation energy (Ea = 65.4 kJ mol -1 ), glass transition (Tg) values on different curing stages including the final cured material information and, besides that, it enables the comparison of these data with new materials under development. The activation energy value allows the determination of different energy needs of the system under evaluation, specially temperature for the material cure, improving the possibility of comparison between different insulation systems in use in the high voltage insulation business. The composite conversion degree based on the cure enthalpy (DHcure) at different time of cure was also subject of analysis and from that it was possible to comprehend the cure pattern which allows the cure state prediction of further samples of this type of material and the more accurate evaluation of similar sam- ples acquired directly from stator bars.

Curing kinetics study of epoxy resin/hyperbranched poly(amideamine)s system by non-isothermal and isothermal DSC

AbstractCuring kinetics of epoxy resin/hyperbranched poly(amide amine)s (HPAMAM) system was studied by non-isothermal and isothermal differential scanning calorimetry (DSC). Non-isothermal DSC scans indicated that H-PAMAM was an effective curing agent of epoxy resin. The apparent activation energy (E) was 54.3 kJ/mol 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 (Sěsták-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. The isothermal DSC method was used to investigate the curing process for resin at 60, 65, 70, 75 and 80 °С, respectively. Isothermal kinetic parameters, including k1, k2, m and n, were determined based on an autocatalytic mechanism proposed by Kamal. Both models were validated for a fitting to the experimental data by the Levenberg-Marquardt method. A process to determine the initial values for the fitting procedure was also proposed. The predictions of the validated models were in good agreement with the measured data, and were therefore applicable for numerical process optimization

Cure Kinetics Study of Unfilled and Carbon Black Filled Synthetic Isoprene Rubber

Abstract The reversion type cure kinetic and induction time models were successfully utilized to predict the isothermal and nonisothermal evolution of the state of cure in vulcanization of the unfilled and carbon black (CB)-filled IR compounds measured by APA 2000. The rate constants for the reversion reaction and the formation of the stable and unstable crosslinks and the parameters of the induction time function with the Arrhenius temperature dependences were determined from the isothermal cure measurements. The equation was proposed to adequately describe the measured dependence of the difference between the maximum and minimum torques as a function of isothermal curing temperature. The measured induction time as a function of heating rate and step temperature variation was successfully predicted based on parameters of the isothermal induction time model. Isothermal cure modeling at each curing temperature individually or at all the curing temperatures simultaneously showed the excellent agreement with the experimental data for both curing and reversion. More severe reversion in the CB-filled IR in comparison with the unfilled IR was explained by comparing their reversion rate constants.