Curing cycle modification for RTM6 to reduce hydrostatic residual tensile stress in 3D woven composites

Triaxial residual tensile stresses resulting after cooling a 3D woven composite from the curing temperature cause cracking in the resin pockets for weave architectures that have high through‐the‐thickness constraint. We show how curing cycle modifications can reduce the hydrostatic tensile stress generated by thermal mismatch during cooling of Hexcel RTM6 epoxy resin constrained in a quartz tube which simulates extreme constraint in a composite. The modified curing schedule consists of a high temperature cure to just before the glass transition, a lower temperature hold that takes the resin through the glass transition thereby freezing in the zero stress state, followed by high temperature cure to bring the resin to full conversion. We show that this process is sensitive to heating rates and can reduce the zero stress state of non‐toughened RTM6 resin to a temperature similar to a commercial rubber‐toughened resin, Cycom PR520. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43373.     

Analytical estimate for curing‐induced stress and warpage in coating layers

A thermoset coating that is applied to an elastic substrate will develop residual stresses during curing because of polymerization shrinkage of the resin. This shrinkage only partly contributes to the residual stresses because, before gelation, the stresses relax completely. In this study, we developed explicit analytical expressions for the curing efficiency factor, the residual stresses, and the resulting warpage. We did this by assuming that after gelation, the material was in its rubbery state and that viscoelastic effects were absent. A difference between the free and constrained warpages during curing was made. The analytical warpage models were shown to give results comparable to those of the numerical calculations with a fully curing‐dependent viscoelastic material model. Furthermore, for the first time, accurate analytical expressions for the stress‐free temperature and stress‐free strain were obtained. With these expressions, the effect of curing shrinkage on the residual stresses could easily be incorporated into existing (numerical) stress analysis without the need for extensive curing‐dependent viscoelastic material models. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012     

Assessment of residual stresses during cure and cooling of epoxy resins

A new stress monitoring technique, a stress-tracking device, is described here. It has been used to study some important properties of epoxy resin. Residual stresses, including a curing shrinkage stress and a cooling shrinkage stress, were measured automatically and continuously during curing and cooling. Simultaneously, information such as an apparent gelation time and glass transition temperature were obtained directly during the experiment. These epoxy resin properties were related to the extent of cure. Varying cure temperature produced changes of cure behavior, which resulted in different residual stresses.     

Curing behavior and residual stresses in polymeric resins used for encapsulanting electronic packages

Polymeric encapsulants are applied in electronic packages to improve the mechanical/thermal performance and the reliability of packaged devices. During the curing process of encapsulating resin, large residual stresses are generated due to the shrinkage of polymer and the mismatches in the coefficient of thermal expansion (CTE) between various package components. In addition, the rheological properties and curing kinetics of the resin also affect the nature and distribution of residual stresses. In this work, the rheological and curing behavior of encapsulating resins are characterized using an oscillatory rheometer. The resin viscosity is closely monitored against curing temperature excursion, which is correlated to exothermic reaction and weight loss as measured from the DSC and TGA analyses. The evolution of residual stresses in encapsulating resin is evaluated in a bimaterial strip bending experiment (BMSB) in situ within a DMA chamber. The CTE values are then calculated based on the thermomechanical analysis, which are well compared with those determined from other sources. A transition temperature, apart from the glass transition temperature, is identified from the study of the changes in resin flexural modulus and residual stress profiles. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 175–182, 2005     

Optimization and numerical simulation analysis for molded thin‐walled parts fabricated using wood‐filled polypropylene composites via plastic injection molding

Plastic injection molding is discontinuous and a complicated process involving the interaction of several variables for control the quality of the molded parts. The goal of this research was to investigate the optimal parameter selection, the significant parameters, and the effect of the injection‐molding parameters during the post‐filling stage (packing pressure, packing time, mold temperature, and cooling time) with respect to in‐cavity residual stresses, volumetric shrinkage and warpage properties. The PP + 60 wt% wood material is not suitable for molded thin‐walled parts. In contrast, the PP + 50 wt% material was found to be the preferred type of lignocellulosic polymer composite for molded thin‐walled parts. The results showed the lower residual stresses approximately at 20.10 MPa and have minimum overpacking in the ranges of ?0.709% to ?0.174% with the volumetric shrinkage spread better over the part surface. The research found that the packing pressure and mold temperature are important parameters for the reduction of residual stresses and volumetric shrinkage, while for the reduction of warpage, the important processing parameters are the packing pressure, packing time, and cooling time for molded thin‐walled parts that are fabricated using lignocellulosic polymer composites. POLYM. ENG. SCI., 55:1082–1095, 2015. © 2014 Society of Plastics Engineers     

纤维增强热固性复合材料构件的固化变形研究进展

热固性复合材料的固化是一个热性能、化学性能和力学性能同时发生变化的复杂过程,也是固化变形和残余应力产生的过程。引起复合材料变形的因素主要包括构件的结构形式、树脂含量、铺层方式、基体树脂的特性、固化工艺参数及模具因素等。其中,复合材料固化过程中树脂的热收缩、化学收缩以及模具材料与复合材料间热膨胀系数的差异是引起复合材料发生固化变形的根本原因。     

In situ monitoring of residual strain development during composite cure

Internal (residual) stresses build up in a thermosetting composite as the matrix shrinks during cure, and again as the composite is cooled to ambient from its elevated processing temperature. These stresses can be significant enough to distort the dimensions and shape of a cured part as well as initiate damage in off‐axis plies, either during fabrication or under the application of relatively low mechanical loads. The magnitude of these stresses depends on a number of factors including constituent anisotropy, volume fraction and thermal expansion, ply orientation, process cycle, and matrix cure chemistry. In this study, embedded strain gauges were employed to follow, in situ, the buildup of residual strains in carbon fiber‐reinforced laminates during cure. The data were compared to those from volumetric dilatometer studies to ascertain the fraction of resin shrinkage that contributed to residual stress buildup during cure. Based on earlier studies with single‐fiber model composites, the process cycle in each case was then varied to determine if the cycles optimized to minimize residual stresses for isolated fibers in an infinite matrix were applicable to the reduction of residual stresses in conventional multifiber composites. The results of these studies are reported here.     

Resin transfer molding (RTM) process of a high performance epoxy resin. I: Kinetic studies of cure reaction

The cure kinetics of a high performance PR500 epoxy resin in the temperature range of 160–197°C for the resin transfer molding (RTM) process have been investigated. The thermal analysis of the curing kinetics of PR500 resin was carried out by differential scanning calorimetry (DSC), with the ultimate heat of reaction measured in the dynamic mode and the rate of cure reaction and the degree of cure being determined under isothermal conditions. A modified Kamal's kinetic model was adapted to describe the autocatalytic and diffusion‐controlled curing behavior of the resin. A reasonable agreement between the experimental data and the kinetic model has been obtained over the whole processing temperature range, including the mold filling and the final curing stages of the RTM process.     

The effect of the addition of a low profile additive on the curing shrinkage of an unsaturated polyester resin

Composites made of glass fibers and unsaturated polyester resins are widely applied for various products. The failure processes of such composites are insufficiently understood. Fracture of the resin often initiates bulk composite fracture. Residual stresses occur during the curing of the resin due to the resin volumetric shrinkage. These unfavorable stresses may enhance resin fracture. Moreover, resin shrinkage may decrease the surface quality of the product. The addition of Low Profile Additives (LPA) to the resin may decrease or even remove these problems. The shrinkage behavior of unsaturated polyester resin with varying amounts of LPA is investigated in this work. The emphasis is on the development of curing shrinkage occurring after the gel point of the resin and on accompanying shirnkage stresses. These stresses can be reduced and even reversed by the addition of LPA.     

Assessment of thermoset cure‐induced strains by fiber bragg grating sensor

Composites based on thermosetting resin and reinforcement fibers present generally unwanted residual internal stresses inherent to their elaboration process. In this article, different curing experiments of thermosets (isothermal and anisothermal) were monitored using optical fiber Bragg grating (FBG) sensors and thermocouples, to assess the cure‐induced strains. A thermokinetic model evaluates the degree of conversion of the resin. At the onset of stress transfer to the optical fiber, the degree of conversion ranges between 0.63 and 0.68. During curing, the FBG deforms under chemical shrinkage with an amplitude widely lower than the expected chemical strain, showing that the FBG signal is not directly related to the actual chemical shrinkage. However, once the resin is cured, the FBG sensor provides directly the coefficient of thermal expansion of the resin, as function of temperature and degree of conversion, reached in the different experiments. POLYM. ENG. SCI., 54:1585–1594, 2014. © 2013 Society of Plastics Engineers     

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     

Stress‐initiated void formation during cure of a three‐dimensionally constrained thermoset resin

During cure of epoxy resins, polymerization induces an increase in mechanical properties, which is accompanied by a volumetric shrinkage. When the resin is cured in a constrained mold to which it adheres, tensile stresses will hence develop, which may exceed the stremgth of the resin at a given curing stage. Voids will then form. The origin and governing parameters of void formation are studied using an epoxy resin cured in a three‐dimensionally constrained glass mold following isothermal cure cycles. Two types of voids are shown to appear during cure, one early in the process and a second around the gelation point. A viscoelastic analysis of the material stress state over the whole range of cure is performed. Both the viscoelastic modulus obtained from a time‐cure‐temperature superposition and the volumetric shrinkage, which was continuously measured by density change, are taken into account. A value for the critical internal stress at void initiation is thus proposed. This criterion can be used to provide guidelines for tailoring the material properties toward an increase of the critical stress for void initiation. Also, since during theprocessing of composite materials, cases may arise where the resin cures within the interstices left between consolidated fibres that do not move, this critical stress failure criterion can be of use in the eastablishment of a process window providing guidelines for the production of void free composites.     

Curing kinetics and viscosity change of a two‐part epoxy resin during mold filling in resin‐transfer molding process

The curing kinetics and the resulting viscosity change of a two‐part epoxy/amine resin during the mold‐filling process of resin‐transfer molding (RTM) of composites was investigated. The curing kinetics of the epoxy/amine resin was analyzed in both the dynamic and the isothermal modes with differential scanning calorimetry (DSC). The dynamic viscosity of the resin at the same temperature as in the mold‐filling process was measured. The curing kinetics of the resin was described by a modified Kamal kinetic model, accounting for the autocatalytic and the diffusion‐control effect. An empirical model correlated the resin viscosity with temperature and the degree of cure was obtained. Predictions of the rate of reaction and the resulting viscosity change by the modified Kamal model and by the empirical model agreed well with the experimental data, respectively, over the temperature range 50–80°C and up to the degree of cure α = 0.4, which are suitable for the mold‐filling stage in the RTM process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2139–2148, 2000     

A simplified chemorheological model of viscosity evolution for solvent containing resol resin in RTM process

The solvent content‐dependent chemorheology of the solvent containing resol resin for resin transfer molding (RTM) was investigated. The curing behavior of the resol resin was studied by in situ Fourier transform infrared spectroscopy together with rheology tests. The chemorheological behavior of resol resins with a series of solvent contents was measured under isothermal conditions. The four parameters of empirical dual‐Arrhenius equation regarding isothermal resin viscosity and reaction rate constant were found to be functions of the solvent content. A simplified chemorheological model involving only three parameters of curing temperature, time, and solvent content was first established to facilely describe the viscosity during precuring process. The simulated viscosity results during isothermal curing process agreed well with the experimental data which shows the simplified chemorheological model can be utilized to describe the viscosity evolution and offer guidance for optimizing the injection process and improving the design flexibility of RTM process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45282.     

Relation between volumetric changes of unsaturated polyester resin and surface finish quality of fiberglass/unsaturated polyester composite panels

Resin dimensional changes, including cure shrinkage and thermal expansion, highly influence the surface finish quality of composite parts. Low profile additives (LPA) are commonly incorporated in unsaturated polyester (UP) resins to compensate for resin shrinkage and obtain a high quality surface finish. In this study, the dimensional change of an UP resin with different LPA contents was characterized. Both resin cure shrinkage and resin thermal expansion were measured. A simple methodology was then developed to estimate the surface finish quality of panels, manufactured by resin transfer molding (RTM), based on the prediction of part thickness variation during the process. Results show good agreement with the experimental investigations. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Control of shrinkage and final conversion of vinyl ester resins cured in low‐temperature molding processes

Vinyl ester resin is a major thermoset polymer used in low‐temperature composite manufacturing processes such as the Seemann composite resin infusion‐molding process (SCRIMP). Volume shrinkage and residual styrene are important concerns for composites produced in such processes. A low‐shrinkage additive (LSA) is a typical agent added to control the volume shrinkage of vinyl ester resins during molding. In this study, the effects of LSA content and the temperature profile (the temperature gradient and peak temperature) on the volume shrinkage control of a vinyl ester resin were investigated. The reaction kinetics of the resin system were also studied. We achieved good volume shrinkage control if we raised the curing temperature slowly to allow sufficient time for phase separation and if the curing temperature reached a high value after phase separation to allow microvoid formation. On the basis of experimental results, we designed an improved SCRIMP to increase resin conversion, reduce resin shrinkage, and produce composites with better properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1486–1496, 2003     

Contraction stress build‐up of anisotropic conductive films (ACFs) for flip‐chip interconnection: Effect of thermal and mechanical properties of ACFs

The important mechanical mechanism for the electrical conduction of anisotropic conductive films (ACFs) is the joint clamping force after the curing and cooling processes of ACFs. In this study, the mechanism of shrinkage and contraction stress and the relationship between these mechanisms and the thermomechanical properties of ACFs were investigated in detail. Both thickness shrinkages and modulus changes of four kinds of ACFs with different thermomechanical properties were experimentally investigated with thermomechanical and dynamic mechanical analysis. Based on the incremental approach to linear elasticity, contraction stresses of ACFs developed along the thickness direction were estimated. Contraction stresses in ACFs were found to be significantly developed by the cooling process from the glass‐transition temperature to room temperature. Moreover, electrical characteristics of ACF contact during the cooling process indicate that the electrical conduction of ACF joint is robustly maintained by substantial contraction stress below T_g. The increasing rate of contraction stresses below T_g was strongly dependent on both thermal expansion coefficient (CTE) and elastic modulus (E) of ACFs. A linear relationship between the experimental increasing rate and E × CTE reveals that the build‐up behavior of contraction stress is closely correlated with the ACF material properties: thermal expansion coefficient, glassy modulus, and T_g. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2634–2641, 2004     

Toward a viscoelastic modeling of anisotropic shrinkage in injection molding of amorphous polymers

A novel approach to predict anisotropic shrinkage of amorphous polymers in injection moldings was proposed using the PVT equation of state, frozen‐in molecular orientation, and elastic recovery that was not frozen during the process. The anisotropic thermal expansion and compressibility affected by frozen‐in molecular orientation were introduced to determine the anisotropy of the length and width shrinkages. Molecular orientation calculations were based on the frozen‐in birefringence determined from frozen‐in stresses by using the stress‐optical rule. To model frozen‐in stresses during the molding process, a nonlinear viscoelastic constitutive equation was used with the temperature‐ and pressure‐dependent relaxation time and viscosity. Contribution of elastic recovery that was not frozen during the molding process and calculated from the constitutive equation was used to determine anisotropic shrinkage. Anisotropic shrinkages in moldings were measured at various packing pressures, packing times, melt temperatures, and injection speeds. The experimental results of frozen‐in birefringence and anisotropic shrinkage were compared with the simulated data. Experimental and calculated results indicate that shrinkage is highest in the thickness direction, lowest in the width direction, and intermediate in the flow direction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2300–2313, 2005     

Optimization method to reduce three-dimensional thermal gradients in resin transfer molding

Presently, the mold and resin are heated to promote resin flow and shorten curing period in order to improve manufacturing efficiency of resin transfer molding (RTM). This nonisothermal manufacturing process easily generates three-dimensional thermal gradients in the direction of resin flow and thickness of composite part. However, the existing heating systems only consider the thermal gradients along thickness direction. The thermal gradients in direction of resin flow cannot be reduced which will lead to residual stress even deformation and cracking in composite part. This article aims at reducing the three-dimensional thermal gradients in the direction of resin flow and thickness of composite part. Based on the theory of energy and fluid flow, an optimization method of heating system design by using numerical simulation is proposed. The results show this method reduces the three-dimensional thermal gradients effectively in composite part manufactured by RTM process. This study can provide powerful tools for heating system design to manufacture composites products in polymer industry. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48948.     

Synthesis and evaluation of liquid amine‐terminated polybutadiene rubber and its role in epoxy toughening

Epoxy resin is widely used for coatings, adhesives, castings, electrical insulation materials, and other applications. However, unsolved problems still remain in its applications. The main problem is low toughness: cured epoxy resin is rather brittle, with poor resistance to the propagation of cracks derived from the internal stress generated by shrinkage in the cooling process from cure temperature to room temperature. The objective of this study was to improve the flexibility and toughness of diglycidyl ether of bisphenol A based epoxy resin with a liquid rubber. For this purpose, amine‐terminated polybutadiene (ATPB) was synthesized. The product was characterized by Fourier transform infrared and NMR spectroscopy and elemental analysis. ATPB‐modified epoxy networks were made by curing with an ambient‐temperature curing agent, triethylene tetramine. We varied the epoxy/liquid rubber compositions to study the effect of toughener concentration on the impact and thermal properties. Higher mechanical properties were obtained for epoxy resins toughened with 1 phr ATPB. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2446–2453, 2005