Effects of resin storage aging on rheological property and consolidation of composite laminates

The ability to predict the viscosity of thermoset resin is important to understand the manufacturing process of composites and optimize the processing parameters. During resin or prepreg storage course, the cure reaction may happen and the degree of cure increases gradually. The storage aging effect reduces the fluidity of resin, and hence alters the processability of resin. In this article, the rheological properties of an epoxy resin and a bismaleimide resin used in composite autoclave process were measured and a viscosity model was established, which can predict the viscosity progression during cure for different aging degree of resin. Moreover, a computer simulation method was used to study the effects of aging degree on the composite consolidation and the processing operations. It is found that the viscosity model of aged resin can be obtained by modified dual Arrhenius model of fresh resin with the dynamic rheological measurement. The resin aging strongly alters the flowability, so influences composite consolidation. According to the simulated results, the processing parameters need to be adjusted to achieve cured composites with appropriate fiber content. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Chemorheology of thermosetting resins. IV. The chemorheology and curing kinetics of vinyl ester resin

The rheological properties and curing kinetics of a vinyl ester resin have been determined during isothermal cure. Both steady and oscillatory shearing flow properties were determined using a cone-and-plate rheometer, and the curing kinetics were determined using a differential scanning calorimeter (DSC). Also determined were the rheological properties and curing kinetics of the resin when it had been thickened using magnesium oxide (MgO), in the presence of calcium carbonate (CaCO₃) as filler and polyvinyl acetate (PVAc) as low-profile additive. The steady shearing flow behavior observed with the vinyl ester resin was found to be very similar to that observed with a general-purpose polyester resin, reported in Paper I of this series [C. D. Han and K. W. Lem, J. Appl. Polym. Sci., 28 , 3155 (1983)]. However, a significant difference in the oscillatory shearing flow behavior was found between the two resins. We have concluded that dynamic measurement is much more sensitive to variations in resin chemistry than steady shearing flow measurement. DSC measurement has permitted us to determine the degree of cure as a function of cure time. By combining the rheological and DSC measurements, we have constructed plots describing how the viscosity increases with the degree of cure, at various isothermal curing temperatures.     

A model for the thermal and chemorheological behavior of thermosets. I: Processing of epoxy-based composites

The rheological and thermokinetic aspects of the cure of epoxy based composite laminates are analyzed by means of a computer program developed using the heat transfer and heat generating characteristics of a polymerizable system. In particular, the temperature and degree of cure influence on the resin viscosity have been first considered, then the temperature profiles, calculated according to an appropriate kinetic and heat transfer modeling, have been used to predict the corresponding viscosity profiles. Molecular and thermocalorimetric parameters are used for the prediction of the theoretical chemorheological behavior. Commercial epoxy systems commonly used in the preparation of carbon fiber laminates have been characterized by Differential Scanning Calorimetry (DSC) and dynamic viscosity measurements and the results are compared with the theoretically predicted values.     

Viscosity modeling of a medium reactive unsaturated polyester resin used for liquid composite molding process

The development of new composite product for an application through liquid composite molding (LCM) process simulation requires submodels describing the raw material characteristics. The viscosity during resin cure is the major submodel required for the effective simulation of mold-filling phase of LCM process. The viscosity of the resin system during mold filling changes as the cure reaction progresses. Applied process temperature also affects the viscosity of the resin system. Hence, a submodel describing the resin viscosity as a function of extent of cure and process temperature is required for the LCM process simulation. In this study, a correlation for viscosity during curing of medium reactive unsaturated polyester resin, which is mostly used for the LCM process, has been proposed as a function of temperature and degree of cure. The viscosity and the degree of cure of reacting resin system at different temperatures were measured by performing isothermal rheological and isothermal differential scanning calorimetry experiments, respectively. A nonlinear-regression analysis of viscosity and degree of cure data were performed to quantify the dependence of viscosity on temperature and extent of cure reaction. Comparisons of model solutions with our experimental data showed that the proposed empirical model is capable of capturing resin viscosity as a function of extent of cure and temperature qualitatively as well as quantitatively. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Chemorheology of thermosetting resins. II. Effect of particulates on the chemorheology and curing kinetics of unsaturated polyester resin

The effect of particulates on both the rheological properties during cure and the curing kinetics of unsaturated resin has been investigated. For the investigation, a general-purpose unsaturated polyester resin was used, with calcium carbonate and clay as inorganic particulates and high-density polyethylene powder as organic particulates. It has been found that, as the particulate content increases, the resin/particulate mixture gives rise to shear-thinning behavior and the rate of cure increases. It has also been found that the CaCO₃ particles helped control shrinkage during cure when the material was subjected to steady shear deformation and that the gel time tη∞ is shorter for mixtures of resin and particulates than for the neat resin alone. Differential scanning calorimetry (DSC) is found useful for determining the curing kinetics of resin/particulate mixtures. We have combined rheological and DSC measurements to obtain a correlation between viscosity and the degree of cure during isothermal curing operations.     

Elastomer‐modified epoxy/amine systems in a resin transfer moulding process

The effect of the elastomer structure on toughening highly crosslinked epoxy systems in a resin transfer moulding process (RTM) was investigated. Two kinds of elastomers containing carboxyl functionalized groups were used: (1) a reactive liquid elastomer based on carboxyl‐terminated butadiene‐acrylonitrile copolymer (CTBN), (2) a preformed core‐shell rubber (CSR). The introduction of CTBN rubber caused the modification in the glass transition temperature due to the miscibility in the epoxy matrix, whereas CSR particles did not. During cure, these elastomers affected the morphological, rheological and dielectric behaviour of epoxy/amine systems. A blend of 5% CTBN and 5% CSR exhibited a bimodal distribution of rubber particle sizes (analyzed by transmission electron microscopy) whereas scanning electron microscopy showed the glass fibre‐matrix cohesion in fracture surfaces. A semi‐empirical model was used (developed by Castro‐Macosko for describing chemorheological behaviour of epoxy/amine systems for the RTM process). The increase in viscosity and the reduction in ion conductivity were the two key parameters to monitor the cure process. The presence of rubber affected the rheological behaviour involving initial viscosity and gel point. The investigation of temperatures, pressures and ionic conductivities in various glass fibre layers was conducted to control the front flow filling and the cure reaction. The introduction of rubber modified the inflexion area of the cured rubber–epoxy blends by changing the cure rate. Copyright © 2004 Society of Chemical Industry     

Structural Carbon/Epoxy Prepregs Properties Comparison by Thermal and Rheological Analyses

Two different carbon/epoxy prepreg materials were characterized and compared using thermal (DSC, TGA, and DMA) and rheological analyses. A prepreg system (carbon fiber preimpregnated with epoxy resin F584) that is currently used in the commercial airplane industry was compared with a prepreg system that is a prospective candidate for the same applications (carbon fiber prepreg/epoxy resin 8552). The differences in the curing kinetics mechanisms of both prepreg systems were identified through the DSC, TGA, DMA, and rheological analyses. Based on these thermal analysis techniques, it was verified that the curing of both epoxy resin systems follow a cure kinetic of n order. Even though their reaction heats were found to be slightly different, the kinetics of these systems were nevertheless very similar. The activation energies for both prepreg systems were determined by DSC analysis, using Arrhenius's method, and were found to be quite similar. DMA measurements of the cured prepregs demonstrated that they exhibited similar degrees of cure and different glass transition temperatures. Furthermore, the use of the rheological analysis revealed small differences in the gel temperatures of the two prepreg systems that were examined.     

Dielectric modeling of the curing process

Dielectric data from an epoxy resin system were used as the foundation for dielectric modeling of the curing process. This resin system (DGEBA-polyamide) was chosen as an easily processible model system. Dielectric average relaxation times, defined as the reciprocal of the angular frequency at which the loss component of the dielectric constant reaches a maximum, were determined for a 40°C isothermal cure. The changes in the average relaxation time through the cure exhibited similar behavior to those for viscosity, which inspired the correlation of the two properties. The dielectric relaxation time was modeled using a six-parameter model analogous to that used for viscosity. The model parameters were in turn associated with both intrinsic properties of the system and reaction kinetics describing the cure. The possibility of extending the relaxation time model for use with single-frequency data by means of a time-frequency correlation was also investigated. Combined, these two modeling methodologies provide a powerful constitutive approach for describing dielectric properties of thermosetting polymers during cure.     

风机叶片用环氧树脂体系流变性能研究

本文对风机叶片用环氧树脂体系的流变性能进行了研究,在粘度实验的基础上,依据双阿累尼乌斯方程建立了与实验数据较为吻合的流变模型。结果表明,两种树脂体系的粘度随温度变化情况基本一致,在23～50℃范围内,其粘度都低于300mPa.s,且低粘度保持时间大于30min,符合风机叶片真空成型对树脂低粘度的要求。所建立的粘度模型可有效预测和模拟树脂体系在不同工艺条件下的粘度行为,揭示树脂体系的优化工艺参数和低粘度平台工艺窗口,为合理拟订工艺参数和保证产品质量提供必要的科学依据。     

The relationship between dielectric and rheological behavior of epoxy resin during cure

Measurement of the frequency-dependent, vector voltage (V_c) provided an in-situ and non-destructive technique to measure continuously the rheological change of a resin due to polymerization, and can be used as the basis of real-time control. The vector voltage depends on the degree of polarization of the dipolar molecules and on the change of viscosity during cure; both result from the modified structure of the epoxy resin during cure, The initial stage of curing, represented by the former portion Of the Vc curve (divided at the minimum of the Vc curve), was caused mainly by the effects of temperature and viscosity. During the latter stage of the cure reaction, Vc alters because of the effect of the lightened matrix structure that inhibits alignment of dipoles. The duration of reaction. temperature of curing and degree of conversion all have the same effects on both vector voltage and viscosity, The minimum value of vector voltage is correlated to the minimum viscosity, and there is a nearly quantitative relationship between them, One can determine the viscosity of the epoxy resin during cure from reading of the vector voltage. Various reaction mechanisms may be explained based on the graphs of vector voltage of various types.     

Rheological behavior of polypropylene/novolac blends

The rheological behavior of polypropylene/novolac blends was investigated with special reference to the effects of the blend ratio, compatibilization, and dynamic cure. The polypropylene and all the polypropylene/novolac blends presented evidence of shear‐thinning behavior. The novolac, compatibilizer, and dynamic cure had dramatic effects on the rheological behavior of the polypropylene. Various rheological plots, including plots of the viscosity, storage modulus, loss modulus, and loss angle, Han plots, and Cole–Cole plots, were used to analyze the polypropylene/novolac blends. The results showed that the compatibilization together with the dynamic cure could increase the viscosity and modulus because of the formation of a grafting polymer between the maleic anhydride grafted polypropylene and the curing novolac resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Multiphysics simulations of cure residual stresses and springback in a thermoset resin using a viscoelastic model with cure‐temperature‐time superposition

Simulations of evolution of cure‐induced stresses in a viscoelastic thermoset resin are presented. The phenomenology involves evolution of resin modulus with degree of cure and temperature, the development of stresses due to crosslink induced shrinkage, and the viscoelastic relaxation of these stresses. For the simulations, the detailed kinetic and chemo‐thermo‐rheological models for an epoxy‐amine thermoset resin system, described in Eom et al. (Polym. Eng. Sci. 2000, 40, 1281) are employed. The implementation of this model into the simulation is facilitated by multiphysics simulation strategies. The trends in simulated cure‐induced stresses obtained using the full‐fledged viscoelastic model are compared with those obtained from two other equivalent material models, one involving a constant elastic modulus, and the other involving a cure‐dependent (but time‐invariant) elastic modulus. It is observed that the viscoelastic model not only results in lower estimates of cure‐induced stresses, but also provides subtle details of the springback behavior. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

Assessment of applicability of carreau,ellis, and cross models to the viscosity data of resin solutions

In this study, three popular rheological models, which fit adequately well to viscosity data of polymeric materials, are chosen for making a comparative assessment of their applicability to practical data. The resulting nonlinear equations of the three models are solved by using Levenberg Marquardt's algorithm. The assessment of their applicability to practical viscosity data of 66 solutions of two resins in 11 solvent systems and reported data of other polymers has been analyzed. The Carreau and Ellis models have yielded unique global estimates for various rheological parameters, whereas the Cross model yielded local solutions. However, both Carreau and Cross models yielded parameter estimates with low overall residual error. The three models are found to have good applicability to viscosity data of resin solutions in good and moderate solvents; however, some deviation is observed when they are tested for solvents in which the resin has poor solubility. © 1993 John Wiley & Sons, Inc.     

Viscoelastic behavior of thermosetting epoxy mixtures modified with syndiotactic polystyrene during network formation

The rheological behavior of thermosetting epoxy mixtures modified with thermoplastic syndiotactic polystyrene (sPS) was monitored during the curing of the epoxy resin. The selected thermosetting system was diglycidyl ether of bisphenol A cured with 4,4′‐methylene bis(3‐chloro‐2,6‐diethylaniline) in the presence of various compositions of sPS (from 2.5 to 12.5 wt %). The storage and loss shear moduli of the systems were monitored during network formation. The validity of the Winter–Chambon criterion for the accurate determination at the gelation point from rheological data was demonstrated. The influence of the sPS concentration on the dynamic rheological properties of the samples was investigated. The experimental data showed that at sPS concentrations lower than 7.5 wt %, phase separation induced a quick increase in the viscosity, which was related to a crystallization‐induced phase separation of sPS. For sPS concentrations higher than 7.5 wt %, near the phase‐inversion composition, the rheological behavior of the mixtures was characteristic of a cocontinuous structure. After the viscosity jumped at the onset of phase separation, a decrease in the viscosity was found, and later on, the viscosity increased again because of gelation. Additionally, the influence of the cure temperature on the rheological properties was studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2348–2355, 2006     

A new kinetic and viscosity model for liquid composite molding simulations in an industrial environment

Liquid composite molding is broadly used for manufacturing composite parts. Apart from the preforming of the dry fibrous material, mold filling and curing of the resin are the main steps in the manufacturing process. For process simulation numerical methods, like finite element methods are applied. Flow models describing the flow behavior through a porous medium are well established. The ability to predict and monitor the curing process in liquid composite molding is crucial for manufacturing process optimization in case of application of rapid curing resin systems. Based on differential scanning calorimetry and rheological experiments, cure kinetics and viscosity of a resin system were characterized. A new kinetic and complex viscosity model is proposed to predict epoxy resin properties in numerical modeling of liquid composite molding. The semi-empirical models are simple to use and therefore suitable for process optimization in an industrial environment. Both models were validated by a fitting to the experimental data by the Levenberg-Marquardt method. A process to determine the initial values for the fitting procedure is also proposed. The predictions of the validated models were in good agreement with the measured data, and are therefore applicable for numerical process optimization. Polym. Compos. 25:255–269, 2004. © 2004 Society of Plastics Engineers.     

Thermorheological properties of asphalt binders

The rheological properties of different types of asphalt binders were studied and compared considering their constituents and physical characteristics. The saturate, aromatic, resin, and asphaltene (SARA) analysis and differential scanning calorimetry (DSC) have shown their individual constituents and two distinct glass transition temperatures, indicating the phase changes of the two main components of the asphalt binders, namely asphaltenes and maltenes. Rheological characterization was performed over a wide range of temperatures (−10°C-60°C) showing that these materials may exhibit viscoelastic solid to viscous liquid behaviour. Master curves of complex viscosity, storage modulus, and loss modulus were constructed by applying the time-temperature superposition principle, which was found applicable over the temperature range considered. Stress relaxation and steady-shear test were applied to the samples in order to determine their rheological behaviour in the nonlinear viscoelastic regime (viscosity and nonlinear relaxation modulus). The rheological results were modelled and revealed that the Kaye-Bernstein-Kearsley-Zappas (K-BKZ) constitutive equation is suitable in representing the rheological behaviour of asphalts. The SARA analysis and rheological measurements were found to be compatible.     

Cure modeling and monitoring of epoxy/amine resin systems. II. Network formation and chemoviscosity modeling

The glass transition temperature (T_g) advancement and the chemoviscosity development under isothermal conditions have been investigated for four epoxy/amine systems, including commercial RTM6 and F934 resins. Differential scanning calorimetry (DSC) was the thermoanalytical technique used to determine the T_g advancement and rheometry the technique for the determination of the chemoviscosity profiles of these resin systems. The complex cure kinetics were correlated to the T_g advancement via an one‐to‐one relationship using Di Benedetto's formula. It was revealed that the three‐dimensional network formation follows a single activated mechanism independent of whether the cure kinetics follow a single or several activation mechanisms. The viscosity profiles showed the typical characteristics of epoxy/amine cure. A modified version of the Williams‐Landel‐Ferry equation (WLF) was adequate to model the viscosity profiles of all the resin systems, in the temperature range 130 to 170°C, with a very good degree of accuracy. The parameters of the WLF equation were found to vary in a systematic manner with cure temperature. Further correlation between T_g and viscosity showed that gelation, defined as the point where viscosity reaches 10⁴ Pas, occurs at a unique T_g value for each resin system, which is independent of the cure conditions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2178–2188, 2000     

风电叶片VIMP用环氧树脂体系流变性能研究

对两种风机叶片真空导入模塑(VIMP)工艺用环氧树脂体系的流变性能进行了研究,在黏度实验的基础上,依据双阿累尼乌斯方程建立了与实验数据较为吻合的流变模型.结果表明,两种树脂体系的黏度变化略有差异,在25～ 55℃的范围内,其黏度都低于500 mPa·s,且低黏度保持时间大于30 min,符合风机叶片VIMP工艺对树脂低...     

Modeling the chemorheological behavior of epoxy/liquid aromatic diamine for resin transfer molding applications

The analysis of the chemorheological behavior of an epoxy prepolymer based on a diglycidylether of bisphenol‐A (DGEBA) with a liquid aromatic diamine (DETDA 80) as a hardener was performed by combining the data obtained from Differential Scanning Calorimetry (DSC) with rheological measurements. The kinetics of the crosslinking reaction was analyzed at conventional injection temperatures varying from 100 to 150°C as experienced during a Resin Transfer Molding (RTM) process. A phenomenological kinetic model able to describe the cure behavior of the DGEBA/DETDA 80 system during processing is proposed. Rheological properties of this low reactive epoxy system were also measured to follow the cure evolution at the same temperatures as the mold‐filling process. An empirical model correlating the resin viscosity with temperature and the extent of reaction was obtained to carry out later a simulation of the RTM process and to prepare advanced composites. Predictions of the viscosity changes were found to be in good agreement with the experimental data at low extents of cure, i.e., in the period of time required for the mold‐filling stage in RTM process. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4228–4237, 2006