Improvement of mechanical properties of structural thermoplastic composites using a reactive (low molecular weight) matrix component

An innovative manufacturing process for continuous fiber composites with the polymeric matrix made up of polypropylene and epoxy resin, as a model reactive low molecular weight component, was developed; variable process parameters give rise to different morphologies of matrix components surrounding the woven fabric reinforcement. Furthermore, the combination of both thermoplastic and thermosetting polymers permitted intimate fibers impregnation, typical of thermosetting matrix composites, with short process cycle time, which usually occurs in manufacturing process of thermoplastic matrix composites. Polypropylene (PP) films, glass fibers fabric, and epoxy resin film were used to produce flat composite through film‐stacking technique. The preparation process focused on control of both epoxy resin cure process and polypropylene melting. The process was able to induce the two matrix components to form either a planar (sandwich‐like) structure or a three‐dimensional (3D) network by means of controlling the process parameters such as pressure and heating rate. The strong enhancement of the mechanical properties (Young's modulus and tensile strength of the composites with the 3D structure were almost twice as high of those of the composites with sandwich‐like matrix structure) was due to the different microstructures produced by the interplanar flow of the thermoplastic polymer. POLYM. COMPOS., 31:1762–1769, 2010. © 2010 Society of Plastics Engineers.     

连续碳纤维增强热固性酚醛树脂复合材料的3D打印工艺及性能研究

针对连续碳纤维增强热固性酚醛树脂复合材料3D打印成型工艺的技术难题,本文提出了浸渍-原位预固化-后固化的3D打印成型方案,实现了连续碳纤维增强热固性酚醛树脂复合材料的3D打印成型,并研究浸渍温度对酚醛树脂接触角与表面张力,以及打印工艺对样件形貌和力学性能的影响规律。结果表明:当浸渍温度为40 ℃,预固化温度为180 ℃时,纤维-树脂界面结合效果最佳,原料具备成型条件;当打印间距为0.5 mm时,样件的弯曲强度及模量达到最大值,分别为660.00 MPa和57.99 GPa,层间剪切强度达到20.14 MPa。此连续碳纤维增强热固性酚醛树脂复合材料一体化制备工艺解决了3D打印热固性树脂原位成型难的问题,为制备具有复杂结构的连续纤维增强热固性树脂复合材料提供了参考。     

Key factors affecting permeability measurement in the vacuum infusion molding process

The composites industry, under increased environmental constraints, is seeking to shift from existing open mold manufacturing processes for composite parts. A promising manufacturing technology known as the vacuum infusion molding process is gaining acceptance among composite-parts manufacturers since it involves low tooling cost and allows complete elimination of volatile organic compounds (VOC). The process is similar to the resin transfer molding process; however, in the vacuum infusion technique, a polymeric film, often referred to as vacuum bag, replaces the stiff mold cover. The film is sealed against the lower half of the mold, at the periphery. Air expelled from the mold cavity results in the compaction of the reinforcement by the atmospheric pressure present on the outer side of the polymeric film. Finally, resin impregnates the mold cavity, usually through a resin distribution channel. The process is mainly developed for large-scale structures, where material cost is an important parameter and users cannot afford any production pitfalls. Among process parameters that affect resin flow in the vacuum infusion molding process is the permeability of the reinforcement stack, which has to be measured and evaluated taking into consideration the requirements of the process. A possible approach is the definition of a parameter that defines the maximum infused length, and this parameter will take into account the structure of the reinforcement, the resin viscosity, the fiber volume fraction and inlet geometry.     

A kinetics model for interphase formation in thermosetting matrix composites

During the cure of thermosetting polymer composites, the presence of reinforcing fibers significantly alters the resin composition in the vicinity of the fiber surface via several microscale processes, forming an interphase region with different chemical and physical properties from the bulk resin. The interphase composition is an important parameter that determines the micromechanical properties of the composite. Interphase development during processing is a result of the mass‐transport processes of adsorption, desorption, and diffusion near the fiber surface, which are accompanied by simultaneous cure reactions between the resin components. Due to complexities of the molecular‐level mechanisms near the fiber surface, few studies have been carried out on the prediction of the interphase evolution as function of the process parameters. To address this void, a kinetics model was developed in this study to describe the coupled mass‐transfer and reaction processes leading to interphase formation. The parameters of the model were determined for an aluminum fiber/diglycidyl ether of bisphenol‐A/bis(p‐aminocyclohexyl)methane resin system from available experimental data in the literature. Parametric studies are presented to show the effects of different governing mechanisms on the formation of the interphase region for a general fiber–resin system. The interphase structure obtained from the model may be used as input data for the prediction of the overall composite properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3220–3236, 2003     

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     

New porous carbon materials,Woodceramics: Development and fundamental properties

Woodceramics are new porous carbon materials obtained by carbonizing wood or woody material impregnated with thermosetting resin such as phenol resin in a vacuum furnace. During the carbonizing process, thermosetting resin changes into glassy carbon, which has superior corrosion resistance and mechanical strength, reinforces the material and suppresses the fissures and warps (caused by the porous structure specific to wood) that develop during thermoforming. The dimension, weight decrease rate, and electrical characteristics depend on the thermoforming temperature. The manufacturing method of Woodceramics is introduced in this paper and various industrial uses, such as electromagnetic shields, are discussed.     

Experimental study of flexible injection to manufacture parts of strong curvature

Flexible injection (FI) is a new process for the manufacture of high performance composites, which consists of injecting a thermosetting resin through a fibrous reinforcement contained in the lower chamber of a double cavity mold. Resin is injected in the lower cavity, which is sealed by a membrane, and then a compaction fluid is injected in the upper chamber to compress the reinforcement. This new composite manufacturing technique, which allows a limited and controlled deformation of the flexible membrane during processing, was shown to be very effective in reducing filling times in the case of planar or slightly curved geometries. In the present study, flexible injection is applied to strongly curved parts, namely here a composite rectangular panel with two 90° corners. After setting up an experimental procedure to produce the stair‐shaped components out of fiberglass and vinylester resin, longitudinal cross‐sections of the parts are analyzed to assess the quality of the final product in both the flat and curved zones. This characterization method allows detecting manufacturing defects such as thickness gradients or resin‐rich zones. Such defects are likely to induce geometrical deformations of the component and may decrease its mechanical performance. Therefore they ought to be minimized to improve the overall quality of the part. Modifications of the manufacturing procedure are proposed in this article to decrease the importance of process‐induced defaults and improve the performance of the flexible injection. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

A process for prestaging thermosetting towpreg

A method for prestaging thermosetting towpreg consisting of passing the material through a tunnel oven was developed to address the difficulties inherent in making thick-walled thermosetting composite parts: aging, moisture uptake, and low resin viscosity during lay-up; and residual stresses, warping, thermal degradation, resin gradients, and excessive void nucleation during the final cure. AS-4 carbon fiber in a 3501-6 epoxy matrix was used to test the continuous prestaging process. With prestaging, significant reductions in towpreg bulk, voids, and total enthalpy were achieved. Cure shrinkage also was achieved. The final towpreg product had good drape and greatly reduced tack. These changes addressed many of the aforementioned difficulties. A relation between residence time at 200°C (the process temperature) versus percent degree of cure (%DOC) was developed. Manufacturing characteristics such as drape, tack, and bulk were related to %DOC. A processing window of 15 to 22 %DOC yielded towpreg with optimal characteristics. Prestaged towpreg would be well suited to manufacturing with advanced fiber placement (AFP) type equipment. Initial trials in industry have been promising.     

Effect of Resin System Parameters on Resin Transfer Molding of Vinyl Ester Based Composites—A Statistically Designed Study

Although the area of composites has advanced significantly over the past three decades, there is still a lack of understanding as to the coupling between materials and processing variables, especially as related to the use of resin systems in emerging processes such as resin transfer molding (RTM). As materials are tailored through the use of additives to resin systems, intricate fiber architectures, and the use of specific processing parameters, the need for a thorough understanding of the effect of minor variations in the materials system and the ultimate need for process control techniques increases. The current investigation is aimed at developing an understanding of variation in performance in three similar vinyl ester resin based composite systems as a function of mold release agent concentration, presence of a wetting/dispersion agent, and preform tool temperature. It is seen that the concentration of mold release agent has a significant influence on performance, which can be correlated with results of dynamic mechanical analysis tests. The importance of using statistically based studies to determine optimum settings and overall variation in performance is emphasized. This approach is favored over the use of an n[sgrave] approach, which gives the user a means of controlling quality based on postproduction control rather than through the selection of settings that are insensitive to variation in the quality of incoming material process changes. The achievement of quality through control of material and process variables is important not only for the cost-efficient production of composite parts but also for the fabrication of large parts such as would be needed for civil infrastructure applications (bridge decks, piers, etc.), where postproduction rejection would result in significant losses.     

Online monitoring and analysis of resin pressure inside composite laminate during zero‐bleeding autoclave process

Resin pressure is one of the most important parameters in manufacturing composites during autoclave process. It not only greatly influences resin flow behavior, but also has effects on void formation and elimination. Online monitoring resin pressure can provide an important guidance for the optimization of the processing parameters and the control of the quality of composites. In this study, a resin pressure online measuring system for autoclave process was established based on the principle of pressure transfer in liquid, and the size of the measuring probe of the system was optimized to increase the accuracy of measured resin pressure. The results indicate that the accuracy and the dynamic response of the system can meet the requirements of resin pressure measurement during autoclave process. Furthermore, by means of this proposed resin pressure measuring system and the measurements of compaction properties of the fabric stacks, the resin pressures inside carbon fiber fabric/epoxy resin and glass fiber fabric/epoxy resin prepreg stacks during autoclave process were investigated, especially for the zero‐bleeding process which is prevailing for aircraft composite structures. It is demonstrated that during zero‐bleeding process, the resin pressures, which conform to the spring and piston model, uniformly distribute along through‐thickness and in‐plane directions. In addition, the resin pressure profile is significantly influenced by the fiber volume fraction of the prepregs, indicating that fiber content of prepreg should be optimized for achieving free defects and uniform fiber distribution. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Nondestructive Characterization of High-Performance C/SiC-Ceramics Using X-Ray-Computed Tomography

The quality control of ceramic matrix composites (CMC) has always been a challenge due to their anisotropy and inhomogeneity. Using high-resolution X-ray computed tomography, these materials can be analyzed in situ during the manufacturing process, providing a three-dimensional analysis without damaging or modifying the samples. This paper analyzes the three material states CFRP, C/C and C/SiC that occur during the processing of melt-infiltrated C/SiC composites and describes the changes in morphology occurring after each processing step. In addition, a quantitative porosity and phase-analysis of the complete volume was performed.     

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。     

Cure characterization of Cycom 977‐2A carbon/epoxy composites for quickstep processing

In this effort, Quickstep, a relatively a new technique, have been employed for manufacturing of composite materials. The cure schedule provided by a prepreg manufacturer is usually designed for autoclave or other traditional processing techniques and thermosetting resin systems are formulated for ramp rate curing 2–3 K min^?1. While in case of Quickstep processing, ramp rates of 15 K min^?1 can be achieved, thus changing the chemorheology of resin. The cure process of 977‐2A carbon/epoxy composites was evaluated for Quickstep processing using differential scanning calorimetry (DSC), dynamic mechanical and thermal analysis, and Fourier transformed infrared and results were compared with cure cycle employed for autoclave curing. Optimum hold time for Quickstep processing at upper curing temperature (180°C) was determined using DSC. The hold time of 120 min at 180°C was found to be suitable for Quickstep cure cycle, producing a panel of similar degree of cure to that achieved through autoclave processing schedule. Final degree of cure was dependent on time spent at upper cure temperature and slightly on initial steps of the cure cycle which was used to control the resin flow, fiber wetting, and void removal. Quickstep processed samples exhibited higher T_g and crosslink density and similar molecular network structure to the autoclave cured samples. POLYM. ENG. SCI., 54:887–898, 2014. © 2013 Society of Plastics Engineers     

二步法合成EP01441—310环氧树脂的研究

低分子量液态双酚Ａ型环氧树脂是一种热固性高分子材料，低分子量环氧树脂的生产工艺是通过分二次加碱进行开环反应，回收过量环氧氯丙烷后，再进行二次加碱后进行缩合反应来完成的。传统工艺中存在着产品的低质量，高消耗等缺点。     

Elevated‐temperature vacuum‐assisted resin transfer molding process for high performance aerospace composites

Vacuum‐assisted resin transfer molding (VARTM) is commonly used for general temperature applications (<150 °C) such as boat hulls and secondary aircraft structures. With growing demands for applications of composites in elevated temperature environments, significant cost savings can be achieved by employing the VARTM process. However, implementation of the VARTM process for fabricating elevated temperature composites presents unique challenges such as high porosity and low fiber volume contents. In the present work, a low cost and reliable VARTM process is developed to manufacture elevated temperature composites for aerospace applications. Modified single vacuum bagging infusion and double vacuum bagging infusion processes were evaluated. Details of the method to obtain high quality composite parts and the challenging issues related to the manufacturing process are presented. Density and fiber volume fraction testing of manufactured panels showed that high quality composite parts with void content less than 1% have been consistently manufactured. A property database of the resin system and the composites was developed. A three‐dimensional mathematical model has also been developed for flow simulation and implemented in the ABAQUS finite element package code to predict the resin flow front during the infusion process and to optimize the flow parameters. The results of the present study indicate that aircraft grade composite parts with high fiber volume fractions can be manufactured using the developed elevated temperature VARTM process. © 2013 Society of Chemical Industry     

Optimal cure cycles for the fabrication of thermosetting-matrix composites

Polymer-matrix composites using thermosetting resins as the matrix are increasingly finding use. However, a major impediment to their widespread commercial use is the high cost associated with their manufacture, arising from the long processing cycle times. This paper addresses the problem of determining cure temperature and pressure variations with time for a time-optimal manufacture of thermosetting-matrix composites subject to practical constraints. The optimal cure cycles are determined using the nonlinear programming scheme of sequential quadratic programming combined with a physical model base to simulate the process phenomena. The optimized cycles are shown to improve upon the manufacturer-recomended cycles as well as the improved cycles reported in the literature. The optimization results are reported for a wide range of resin materials, product specifications, and process constraints to illustrate their effects on the optimal cure cycles. Parametric studies are presented in terms of dimensionless groups to assess the combined effects of the product and process variables on the optimal cycles in a generalized manner.     

Void formation model and measuring method of void formation condition during hot pressing process

For resin matrix composites, voids are common defects that can seriously deteriorate the properties of the composite parts. Thus, the elimination of voids is a crucial element in controlling the manufacturing process of composite parts. This article focuses on void formation originating from hygroscopic water for resin matrix composite laminates prepared with hot pressing process. The Kardos void formation model was developed to analyze the critical resin pressure for the initiation of voids, and the influencing factors were investigated experimentally to validate the modified model. It is found that resin pressure and gel temperature are the two key parameters to control void defects and that entrapped air in prepreg stacks must be considered in the void formation model. Furthermore, a simple method was established to measure the relationship between porosity and the processing parameters, and the void formation conditions of the resin and the prepreg stack were also studied. The theoretically predicted void formation conditions and the experimental results were compatible for the studied cases. These results are valuable for eliminating void defects, optimizing processing parameters, and enhancing the performance of composite parts. POLYM. COMPOS., 31:1562–1571, 2010. © 2009 Society of Plastics Engineers     

The role of multi‐walled carbon nanotubes in epoxy nanocomposites and resin transfer molded glass fiber hybrid composites: Dispersion,local distribution,thermal, and fracture/mechanical properties

Hybrid composites containing endless glass fiber reinforcement and surface‐functionalized carbon nanotubes (CNTs) dispersed in the matrix phase were produced by resin transfer molding (RTM). An efficient surface modification of the nanotubes enhances the compatibility with the matrix system and the dispersion quality, enabling the impregnation process via liquid composite molding. We assessed the quality of the RTM process by newly developed methodologies for the quantification of the filtering of CNTs. First, we established a method to analyze the CNT length distribution before and after injection for thermosetting composites to characterize length‐dependent withholding respectively the size distribution of nanotubes in the hybrid composites. Second, the resulting test laminates were locally examined by Raman spectroscopy and compared to reference (nanocomposite) samples of known CNT content to non‐destructively quantify the local CNT concentration along the resin flow path. Moreover, the thermal and mechanical properties of the modified composites were investigated. The nanocomposites containing 0.5 wt% surface‐functionalized CNTs exhibited superior ductility and increased fracture toughness. Glass fiber hybrid composites containing 0.5 wt% functionalized CNTs in the resin phase exhibited increased fracture toughness in mode I and a slight deterioration in mode II due to the constrained formation of hackles. POLYM. COMPOS., 38:1849–1863, 2017. © 2015 Society of Plastics Engineers     

Consolidation of advanced composites having volatile generation

Processing polyimide-based thermosetting matrix composites is complicated because of gaseous volatiles produced during the polymerization and crosslinking reactions. This process involves complex interactions between part geometry, temperature and force cycles, and matrix/fiber properties. A simple model for the consolidation process that treats these composites as a three-phase system consisting of fiber, resin, and volatile has been developed. This model has been applied to compression molding process for constant thickness laminates and the predictions agree well with experiments. Further extension to handle three-dimensional parts and the required numerical techniques have also been developed.     

Electrical conductivity modeling of carbon‐filled liquid‐crystalline polymer composites

Electrically conductive resins are needed for bipolar plates used in fuel cells. Currently, the materials for these bipolar plates often contain a single type of graphite powder in a thermosetting resin. In this study, various amounts of two different types of carbon, carbon black and synthetic graphite, were added to a thermoplastic matrix. The resulting single‐filler composites were tested for electrical conductivity, and electrical conductivity models were developed. Two different models, the Mamunya and additive electrical conductivity models, were used for both material systems. It was determined how to modify these models to reduce the number of adjustable parameters. The models agreed very well with experimental data covering a large range of filler volume fractions (from 0 to 12 vol % for the carbon black filled composites and from 0 to 65 vol % for the synthetic graphite filled composites) and electrical conductivities (from 4.6 × 10^?17 S/cm for the pure polymer to 0.5 S/cm for the carbon black filled composites and to 12 S/cm for the synthetic graphite filled composites). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3293–3300, 2006