Modeling the curing kinetics of two thermoset adhesives under varying temperature conditions

This paper presents detailed curing kinetics models for two thermoset adhesives. The cure kinetics were characterized using differential scanning calorimetry in both anisothermal and isothermal modes. The Sestak–Berggren autocatalytic model was applied to describe the anisothermal cure kinetics of the two adhesives with the Malek and undetermined coefficients methods determining their kinetic parameters. The Kamal autocatalytic model was adopted for the isothermal curing processes with the Kenny analytical-graphical method determining the kinetic parameters. A modified Kamal model was developed by introducing a concept of the maximum degree of cure (DOC) and temperature-depended kinetic parameters to describe the isothermal cure kinetics of the adhesive with a typical exothermic peak, and an extended Kamal model was further proposed by adding an initial-phase-control term to the modified Kamal model to describe the isothermal cure kinetics of the adhesive with two exothermic peaks. The results showed that the presented curing kinetics models with the determined parameters can precisely predict the evolutions of the DOC of the two thermoset adhesives in both anisothermal and isothermal modes.     

Studies on low temperature curable powder coatings

The cure temperatures necessary to affect the flow and subsequent crosslinking of powder coatings has traditionally limited the substrates and thus market applications of these coating systems. This paper will discuss model studies aimed at better understanding some of the cure processes involved in the crosslinking of blocked isocyanate systems. Work done to take the learnings from these model studies and apply them to the development of fully formulated, low temperature curable powder coatings will also be discussed. By considering both the crosslinker and the nature of the polymeric resin it was possible to develop systems that cure at 129–140 °C and have excellent flow and levelling characteristics.     

Comparison of the curing kinetics of the RTM6 epoxy resin system using differential scanning calorimetry and a microwave‐heated calorimeter

The cure of a commercial epoxy resin system, RTM6, was investigated using a conventional differential scanning calorimeter and a microwave‐heated calorimeter. Two curing methods, dynamic and isothermal, were carried out and the degree of cure and the reaction rates were compared. Several kinetics models ranging from a simple nth order model to more complicated models comprising nth order and autocatalytic kinetics models were used to describe the curing processes. The results showed that the resin cured isothermally showed similar cure times and final degree of cure using both conventional and microwave heating methods, suggesting similar curing mechanisms using both heating methods. The dynamic curing data were, however, different using two heating methods, possibly suggesting different curing mechanisms. Near‐infrared spectroscopy showed that in the dynamic curing of RTM6 using microwave heating, the epoxy‐amine reaction proceeded more rapidly than did the epoxy‐hydroxyl reaction. This was not the case during conventional curing of this resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3658–3668, 2006     

Study on cure behavior of epoxy resin–BF3–MEA system by dynamic torsional vibration method

A dynamic torsional vibration method has been developed and used to investigate the isothermal cure processes of resin system of epoxy resin–boron trifluoride monoethylamine complex? SiO_2, optimizing its cure conditions and estimating the apparent dynamic parameters including gel time and rate of cure reaction and discussing the effect of filler on cure. The cure behavior of resin system has been predicted by the nonequilibrium thermodynamic theory. The theoretical prediction is in good agreement with the experimental results obtained by dynamic torsional vibration method.     

Resin flow analysis in the consolidation of multi-directional laminated composites

Advanced fiber reinforced polymer composites have been increasingly used in various structural components. One of the important processes to fabricate high performance laminated composites is an autoclave assisted prepreg lay-up. Since the quality of laminated composites is largely affected by the cure cycle, selection of the cure cycle for each application is important and must be optimized. Thus, some fundamental model of the consolidation and cure processes is necessary to properly select the suitable parameters for each application. This study applied the theory of consolidation and flow in a porous medium to provide a general model for the three-dimensional consolidation process of the laminates with fibers reinforced in multi-directions. Based on the model analysis, one can predict the pressure, velocity, and laminate thickness during consolidation process, which, as coupled with the curing analysis, can be used to properly select the cure cycle for applications of laminated composites.     

New model for characterising resin cure by dynamic differential scanning calorimetry

Abstract

In general, mould filling and resin cure are essential parts of thermoset composite manufacturing processes. While resin viscosity is a crucial property required in modelling and designing mould filling, resin cure or chemical reaction plays a key role in consolidating a composite. For a given cure cycle, resin cure is predicted by calculating the degree of cure using a cure kinetics model. Normally, cure kinetics is modelled by quantifying the extent of chemical reaction. There are many other methods for quantifying the chemical reaction and released heat was used in this study. A new model for determining cure kinetics with dynamic differential scanning calorimetry has been developed. The new method was applied to an epoxy resin system and was verified by comparison of measurement with prediction.     

Differential Scanning Calorimetry Cure Studies of Tetra-N-glycidyldiaminodiphenylmethane Epoxy Resins. Part 1 - Reaction with 4,4′-Diaminodiphenylsulphone

Rates and extents of cure are determined using differential scanning calorimetry in the isothermal mode over the temperature range 170–220°C, and from d.s.c. scans at various heating rates. The isothermal data are consistent with an autocatalytic mechanism at conversions up to about 20–30%. Data from d.s.c. scans fit a simple kinetic model which indicates that the apparent activation energy (E) for cure increases with increasing conversion, consistent with an increasing degree of diffusion control. At low levels of conversion the isothermal and dynamic data both provide estimates for E of about 70 kJ mol^?1. The heat of cure is about 105 kJ mol^?1 epoxide, and is constant over a wide range of amine concentration. This indicates that any parallel or competing processes which occur must have the same heat of reaction.     

Consolidation and cure simulations for laminated composites

Fiber reinforced polymer composites have been increasingly used in various structural components. One of the important processes for fabricating high performance laminated composites is autoclave assisted prepreg lay-up. Since the quality of laminated composites is largely affected by the cure cycle, selection of the cure cycle for each particular application is important and must be optimized. Thus, some fundamental model of the consolidation and cure processes is necessary to properly select the suitable parameters for each application. This study used the viscoelastic solid model for the consolidation of the laminate. In addition, variations of permeability and thermal properties caused by the change of the fiber volume content during the consolidation process were also included. Simulated thickness variations of epoxy continuous carbon fiber prepreg (AS4/3501-6 from Hercules) laminate under consolidation were compared to the experimental results to test the model. Based on the model analysis, one can predict the pressure, velocity, and laminate thickness during the consolidation process, which can be used to properly select the cure cycle for applications of laminated composites.     

A novel rapid cure epoxy resin with internal mold release

Mold preparation, material layup, and cure times for thermoset-based composites often limit their use in high-volume applications. As such, new rapid cure epoxy resins are being developed to achieve a complete cycle time within 3 min. In this research, calorimetry and rheometry are used to examine and model two novel rapid cure epoxy resin systems with internal mold release. The rapid cure epoxy resins followed an autocatalytic cure kinetic and William–Landel–Ferry diffusion model. The rapid cure epoxy resin was shown to achieve 94% cure in 2 min at 150°C. However, adding an additional 2.5 wt% internal mold release hindered the first step of the reaction, which delayed the second reaction step since the final degrees of cure were similar. Furthermore, the resin viscosity followed a modified William–Landel–Ferry equation and at 120°C could maintain a viscosity below 5 Pa s for 4.1 min. These models provided valuable insight into the range of processing conditions these novel resins could experience during impregnation and molding processes.     

Fine aggregate and curing temperature effect on concrete maturity

Removal of formwork can be made in a short time by early-strength gain of concrete with heat treatment. The effects of accelerated curing temperature and fine aggregate on early strength as well as the relationships between early strength-28-day strength and strength maturity have been examined. Cube concrete specimens produced with a 10-cm constant slump value, 0.59 w/c ratio, and with two different types of fine aggregate were subjected to three-phase cure processes. These cure processes include a 1-h preheating process after having replaced concrete in the mould, the cure application process, and finally the last waiting period for 2 h that is aimed at minimizing the effects of thermal stresses. Each of the specimen groups was cured at different temperatures for different periods (6 or 18 h). At the end of curing and on the 28th day, cube compressive strengths were determined. Therefore, it was seen that it is possible to estimate 28-day strength beforehand with reasonable accuracy.     

Cure kinetics and rheology characterization of soy‐based epoxy resin system

A novel soy‐based epoxy resin system was synthesized by the process of transesterification and epoxidation of regular soy bean oil, which has the potential to be widely usable in various composite manufacturing processes. Cure kinetics and rheology are two chemical properties commonly required in process modeling. In this work, the cure kinetics and rheology of the soy‐based resin system were measured by means of differential scanning calorimetry (DSC) and viscometer. DSC was used to measure the heat flow of dynamic and isothermal curing processes. The cure kinetics models of the different formulations were thus developed. A Brookfield viscometer was used to measure the change in viscosity under isothermal conditions. A novel neural network‐based model was developed to improve modeling accuracy. The models developed for cure kinetics and rheology for soy‐based epoxy resin system can be readily applied to composite processing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3168–3180, 2006     

Development of matte finishes in electrostatic (EFB) and conventional hot dipping (CHDFB) fluidized bed coating process

This study focuses on the correlation between the thermo-rheological properties of a thermosetting powder coating system with its surface structure build-up. Epoxy powder coating systems, which displayed surface matting and surface wrinkling, were examined. Firstly, the evolution of the complex viscosity was correlated with the cure kinetic. Secondly, the structure build-up on the surface of the coatings was investigated with a combined SEM-CLA profilometry analysis at different stages of curing process for both EFB and CHDFB coating processes. Different finishes were found to characterize the films applied by using EFB and CHDFB coating processes as a result of the different way the film is heated by. Finally, a strict relationship of film morphology to the degree of conversion and to the evolution of the complex viscosity was found out for both EFB and CHDFB coating processes. The surface structure is built up after gelation point and continues to evolve after gelation with a full development of the film fine structure. Differences were observed in the surface structure build-up when different curing temperature was used, thereby indicating an influence of minimum viscosity on achievable finishing.     

Rheological,mechanical, and morphological studies of epoxy/poly(methyl methacrylate) semi‐interpenetrating polymer networks

Semi‐interpenetrating polymer networks (semi‐IPNs) of epoxy resin and poly(methyl methacrylate) (PMMA) were synthesized. Methyl methacrylate (MMA) was polymerized by free radical mechanism with azo‐bis‐isobutyronitrile in the presence of oligomeric epoxy resin (DGEBA), and hexahydrophthalic anhydride as crosslinking agent. The gelation and vitrification transitions during cure/polymerization processes have been examined using parallel‐plates rheological technique. From differential scanning calorimetry and rheological techniques, it was suggested that both curing and polymerization processes occur simultaneously. However, the gelation time was longer for the semi‐IPN than those observed for the cure of pure DGEBA or polymerization of MMA. The gelation time increased significantly when 5% of MMA was employed, suggesting a diluent effect of the monomer. Higher amount of MMA resulted in a decrease of gel time, probably because of the simultaneous polymerization of MMA during the curing process. Structural examination of the semi‐IPNs, using scanning electron microscopy, revealed phase separation in nanoscale size for semi‐IPNs containing PMMA at concentrations up to 15%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Optimal curing for thermoset matrix composites: Thermochemical considerations

A design sensitivity analysis is used to optimize the applied wall temperature vs. time in autoclave curing for thermoset matrix composites. The calculation minimizes the cure time and obeys a maximum temperature constraint in the composite. The transient, coupled thermal and cure problem is solved by a finite element method. Design sensitivity information is extracted efficiently from this primal analysis, based on an analytical, direct differentiation approach. The sensitivities are then used with gradient‐based optimization techniques to systematically improve the curing process. The optimal cure cycles for different numbers of temperature dwells may be similar (for a 2 mm thick part) or very different (for a 4 cm thick part), depending on the nature of the problem. In the latter case a large reduction of cure time is obtained when a three‐dwell cure cycle is used, and the optimizer has more flexibility to adjust the cure cycle. This systematic optimization approach provides a powerful and practical means of optimizing composite manufacturing processes.     

Incorporation of an acrylic fatty acid derivative as comonomer for oxidative cure in acrylic latex

An acrylic fatty acid derivative (AcFAD) was evaluated as comonomer for promotion of oxidative cure in waterborne latexes. AcFAD was polymerized by solvent homopolymerization and copolymerization and by emulsion copolymerization, and the final products characterized. In the two polymerization processes, NMR analyses confirmed that the reaction occurred involving both the terminal acrylic double bond and the conjugated double bonds of the aliphatic chain. Compared with a reference acrylic latex, the results obtained after AcFAD incorporation showed a time-dependent increase in gel content and in solvent resistance of dry films. These were ascribed to oxidative cure and consequent self-crosslinking of the acrylic polymer, involving the conjugated double bonds in AcFAD side chains. Oxidative cure was also confirmed by FTIR analyses. In addition, reduction in minimum film-forming temperature evidenced that AcFAD has an internal plasticization effect during film formation. Incorporation of this comonomer in acrylic paint binder formulations constitutes a promising alternative to the use of volatile coalescing agents.     

Helical flow of curing highly viscous liquids

For profile extrusion of rubber, a shear head is frequently placed at the outlet of the extruder. In the shear head, the rubber compound is heated to its cure temperature by means of internal friction between two coaxially rotating cylinders (annulus). The aim of this examination is to find suitable operating parameters for all rubber compounds. The highest possible temperatures and an even cure profile are the characteristics of suitable operations. The degree of cure should be as close as possible to the maximum cure permitted. For examination of the processes in the annulus, a coupled system of differential equations is set up and solved numerically. The cure profiles established along the annulus are of special interest. The effects of the geometry, the rotational speed of the inner cylinder, the volumetric flow, the operating temperatures, and the viscosity as a function of the shear rate and the temperature are examined. The results of the calculations show that the viscosity, which increases with increasing cure, has a strong effect on the velocity and dissipation profiles. The results of the experimental investigations on a shear head coincide well with theoretical prediction.     

Kinetics modeling and time-temperature-transformation diagram of microwave and thermal cure of epoxy resins

Stoichimetric mixtures of a diglycidyl ether of bisphenol A (DGEBA)/ diaminodiphenyl sulfone (DDS) and a DGEBA/meta phenylene diamine (mPDA) were cured using both microwave and thermal energy. Fourier transform infrared (FTIR) was used for the measurement of the extent of cure and thermal mechanical analysis (TMA) was used for the determination of the glass transition temperature (T_g). The cure kinetics of the DGEBA/mPDA and DGEBA/DDS systems were described by an autocatalytic kinetic model up to vitrification in both the microwave and thermal cure. For the DGEBA/mPDA system, the reaction rate constants of the primary amine-epoxy reaction are equal to those of the secondary amine-epoxy reaction, and the etherification reaction is negligible for both microwave and thermal cure. For the DGEBA/DDS system, the reaction rate constants of the primary amine-epoxy reaction are greater than those of the secondary amine-epoxy reaction and the etherification reaction is only negligible at low cure temperatures for both microwave and thermal cure. Microwave radiation decreases the reaction rate constant ratio of the secondary amine-epoxy reaction to the primary amine-epxy reaction and the ratio of the etherification reaction to the primary amine-epoxy reaction. T_g data were fitted to the DiBenedetto model. A master curve and a time-temperature-transformation (TTT) diagram were constructed. The vitrification time is shorter in microwave cure than in thermal cure, especially at higher isothermal cure temperatures. For the DGEBA/mPDA system, the minimum vitrification time is two to five times shorter in the microwave cure than in the thermal cure. For the DGEBA/DDS system, the minimum vitrification time is 44 times shorter in the microwave cure than in the thermal cure.     

Comparative study of continuous‐power and pulsed‐power microwave curing of epoxy resins

Three epoxy reaction systems, diglycidyl ether of bisphenol A (DGEBA) with curing agents meta phenylene diamine (mPDA), diaminodiphenyl methane (DDM), and diaminodiphenyl sulfone (DDS), were cured with both pulsed‐power and continuous‐power microwave curing systems. Isothermal curing was conducted at three different temperatures for each reaction system with both pulsed‐power and continuous‐power microwave curing systems. Extent of cure was measured with Fourier Transform Infrared Spectroscopy (FTIR). The temperature characteristics, incident and reflected power patterns, and the reaction rates were compared between the two curing approaches. The incident power and reflected power of both curing processes were observed to reveal reaction status. Continuous‐power microwave curing produced noticeably higher reaction rates than pulsed‐power microwave curing.     

Influence of cure via network structure on mechanical properties of a free-radical polymerizing thermoset

An improved understanding has been achieved regarding the relationships among cure chemistry, network structure, and final physical properties of vinyl ester (VE) resins, a thermoset polymer often used as the matrix of fiber reinforced polymers. Mechanical properties of the polymer are found to depend on both cure schedule and cure formulation. The possibilities of phase separation and micro-gel formation being the cause for these differences in mechanical properties are examined. The VE/styrene (S) system does not phase separate under the conditions studied. Though bulk properties of the resin are unaffected by the details of the cure, the microscopic morphology, in particular the type of cross-link formed (intermolecular bond or intramolecular bond), is sensitive to both cure temperature and initiation mechanism as determined by cure formulation. An analysis of cure kinetics shows that both temperature and initiation mechanism affect the apparent ‘reaction order’ of the VE/S system as determined by the autocatalytic equation. This apparent reaction order is interpreted as being an indication of the degree of heterogeneity in the resin. By controlling cure temperature and cure formulation, it is possible to minimize the apparent reaction order and thereby optimize physical properties. Finally, a theory is adapted from other non-network polymer systems to qualitatively describe how cure temperature and initiation mechanism may alter the heterogeneity in network structure via micro-gel formation and how these changes in structure affect changes in the mechanical properties.     

环氧浇铸体固化过程放热研究

本文研究了环氧树脂在不同固化剂体系时的固化放热曲线和温度差异,测定了树脂的固化度,并对填料加入的影响进行了分析。