OPTIMIZED CURING OF THICK SECTION COMPOSITE LAMINATES

Conventional autoclave curing cycles for thermosetting composite laminates are generally derived from trial-and-error experimentation. Cure cycles are readily available for thin composite laminates. However, developing cure cycles for thick section laminates is time consuming and hence, costly. In addition, one cannot be sure that a selected cycle will be optimum if it is based on a conventional method. This paper shows that through numerical simulation and some minimal experimentation, optimized cure cycles can be developed for thick laminates. The heating cycles for thick laminates can be established by an iterative numerical method. Autoclave processing with conventional and optimal curing cycles for 12.5-mm-thick laminates was performed. The mechanical properties of the products were determined and shown to be comparable, with significant time saving realized in using the optimized cycle.     

固化度与固化收缩对非对称复合材料层合板固化变形的影响

采用三维有限元方法研究复合材料非对称层合板在热载荷和固化收缩载荷下的固化变形情况, 建立了材料力学特性、 固化体积收缩量和温度与固化度之间的函数关系, 考察了层合板变形曲率与温度和固化度之间的关系。数值计算结果表明: 非对称层合板变形曲率与固化终止时固化度有密切关系; 固化变形主要发生在降温阶段; 固化收缩对层合板变形曲率影响很小, 主要发生在第二个保温平台的前半段。      

热固性复合材料固化过程中温度场的三维有限元分析

根据热传导和固化动力学理论, 采用三维有限元方法, 对正交各向异性复合材料层合板固化过程的温度和固化度历程及其变化规律进行数值模拟研究。在有限元分析中节点自由度为温度和固化度, 考虑了两者之间的耦合作用。计算结果表明: 厚度越大, 温度峰值越高, 中心点开始固化越晚; 不同纤维体积含量层合板在固化初期是同步的; 中心点温度超过保温平台(85 ℃) 后, 随着环境温度继续升高, 纤维体积含量越低, 中心点温度峰值越大, 出现时间越早。      

Curing of Thick Thermoset Composite Laminates: Multiphysics Modeling and Experiments

Fiber reinforced polymer composites are used in high-performance aerospace applications as they are resistant to fatigue, corrosion free and possess high specific strength. The mechanical properties of these composite components depend on the degree of cure and residual stresses developed during the curing process. While these parameters are difficult to determine experimentally in large and complex parts, they can be simulated using numerical models in a cost-effective manner. These simulations can be used to develop cure cycles and change processing parameters to obtain high-quality parts. In the current work, a numerical model was built in Comsol MultiPhysics to simulate the cure behavior of a carbon/epoxy prepreg system (IM7/Cycom 5320–1). A thermal spike was observed in thick laminates when the recommended cure cycle was used. The cure cycle was modified to reduce the thermal spike and maintain the degree of cure at the laminate center. A parametric study was performed to evaluate the effect of air flow in the oven, post cure cycles and cure temperatures on the thermal spike and the resultant degree of cure in the laminate.     

In situ monitoring of the strain evolution and curing reaction of composite laminates to reduce the thermal residual stress using FBG sensor and dielectrometry

Generally, a large, thermal residual stress is generated during the curing process for composite laminates due to differences in the coefficients of thermal expansion of the respective layers. The thermal residual stress during fabrication greatly decreases the fatigue life and dimensional accuracy of the composite structures. In the present study, through a fiber bragg grating (FBG) sensor and dielectrometry in an autoclave, the strain evolution and curing reaction in composite laminates with a stacking sequence of [0₅/90₅]_S were monitored simultaneously during a conventional cure cycle and a modified cure cycle to reduce the thermal residual stress. From the study, it was verified that about 50% of the thermal residual stress during fabrication could be reduced in a composite laminate by adjusting the cure cycle; this improved the static strength and fatigue life by 16% and up to 614%, respectively, for a peak ratio of 0.9.     

基于多场耦合方法的厚截面复合材料固化过程的多目标优化

针对厚截面复合材料固化过程温度峰值过大所引起的材料力学性能降低及残余应力过大等问题,建立了基于多场耦合方法的复合材料固化过程多目标优化模型,用以降低固化温度峰值和缩短固化时间。首先建立包含热化学子模型、树脂黏度子模型和流动压实子模型的固化温度多场耦合模型,用以准确描述固化过程复合材料内部温度及构件厚度的演化规律。通过与文献中已有实验结果比较,证明所建立的多场耦合模型的有效性。在该多场耦合模型基础上,引入径向基(RBF)神经网络作为代理模型,利用多目标优化方法,对固化工艺参数进行最佳组合匹配。研究表明,温度峰值与保温平台温度变化呈明显非线性关联,这与复合材料固化过程的非线性特性有很大关系。在保温温度层面,为了降低温度峰值,需要提高第一阶段的保温温度,降低第二阶段的保温温度,同时在保温平台的时间上进行调整,以缩短固化时长。相比较于原有固化工艺制度,本文提出的优化方法可以显著降低厚截面复合材料层合板的固化时长和温度峰值。      

A Method for Cure Process Design of Thick Composite Components Manufactured by Closed Die Technology

During the manufacture of polymer-matrix composite components the cure degree must be uniform to have a good quality of the product. For thick composite components this condition is not often respected in fact the cure degree trend between the core and the external surface is different causing structural and geometrical/dimensional unconformities. In most cases, these problems are caused by a wrong design of cure process in terms of thermal cycle and tooling, therefore the cure cycle must be designed and optimized. The optimization of cure thermal cycle should include several performance criteria for the production system such as the targeted cure degree, the targeted maximum temperature of the part and the duration of the cure cycle as well as the production system limitations such as the maximum allowable heating rate, the maximum allowable cooling rate etc. This work aims to define by thermochemical phenomena a first step toward the definition of a method to optimize the cure degree of a thick composite components by focusing particular attention to the aspects of thermal degradations and residual stress.     

Reduction of residual stresses in thick-walled composite cylinders by smart cure cycle with cooling and reheating

The nozzle parts of solid rocket motors must endure both the internal pressure generated by high temperature exhaust gas and the mechanical load generated by steering operation. Therefore, the nozzle parts of solid rocket motors are fabricated with thick carbon fiber phenolic resin composites. When the thick-walled phenolic composite cylinder is cooled down from the curing temperature of about 155 °C to the room temperature, thermal residual stresses are created due to the anisotropic thermal deformation of the composite structure.

In this paper, a smart cure method with cooling and reheating was developed to reduce residual stresses in thick-wound composite cylinders made of carbon phenolic woven composite. The optimal cure cycle was obtained to reduce the residual stresses without increasing processing time and applied to fabrication of the thick-walled composite cylinder. From the residual stresses measured by the radial-cut-cylinder-bending method, it was found that the residual stresses were reduced 30% by using the smart cure method.     

Optimization of infrared radiation cure process parameters for glass fiber reinforced polymer composites

Elevated temperature post curing is one of the most critical step in the processing of polymer composites. It ensures that the complete cross-linking takes place to produce the targeted properties of composites. In this work infrared radiation (IR) post curing process for glass fiber reinforced polymer composite laminates is studied as an alternative to conventional thermal cure. Distance from the IR source, curing schedule and volume of the composite were selected as the IR cure parameters for optimization. Design of experiments (DOE) approach was adopted for conducting the experiments. Tensile strength and flexural strength of the composite laminate were the responses measured to select the final cure parameters. Analysis of variance (ANOVA), surface plots and contour plots clearly demonstrate that the distance from the IR source and volume of the composite contribute nearly 70% to the response functions. This establishes that polymer composites cured using IR technique can achieve the same properties using only 25% of the total time compared to that of conventional thermal curing.     

Optimization of the Temperature-Time Curve for the Curing Process of Thermoset Matrix Composites

An intelligent optimization model aiming at off-line or pre-series optimization of the thermal curing cycle of polymer matrix composites is proposed and discussed. The computational procedure is based on the coupling of a finite element thermochemical process model, dynamic artificial neural networks and genetic algorithms. Objective of the optimization routine is the maximization of the composite degree of cure by the definition of the autoclave temperature. Obtained outcomes evidenced the capability of the method as well as its efficiency with respect to hard computing or experimental procedures.     

快速固化环氧树脂及其碳纤维/环氧复合材料性能

采用双酚A型环氧树脂（DGEBA）、改性咪唑（MIM）及改性脂肪胺（MAA）研制快速固化树脂体系。分别利用DSC和流变仪测试了树脂体系的固化特性与流变行为,优选了树脂配方。采用真空辅助树脂灌注工艺（VARIM）制备了快速成型的碳纤维/环氧复合材料层板,考察了层板的成型质量和力学性能,并与常规固化的层板性能进行了对比。结果表明：采用优选的树脂配方,120 ℃下树脂在5 min内固化度达95%,碳纤维/环氧复合材料层板成型固化时间可控制在13 min以内,固化度达95%以上,并且没有明显缺陷;与常规固化相比（固化时间大于2 h）,快速固化碳纤维/环氧复合材料层板的弯曲性能和耐热性能降低幅度较小。     

基于材料性能时变特性的复合材料固化过程多场耦合数值模拟

针对热固性树脂基复合材料固化过程中各种复杂的物理化学变化之间的相互影响,建立了基于材料性能时变特性的复合材料固化过程的二维多场耦合计算模型。该模型由已知的3个经典复合材料固化过程子模型构成,包括热-化学模型、树脂黏度模型和树脂流动模型。在此基础上,将固化过程中材料性能的时变特性引入多场耦合计算模型中。通过与文献中实验结果的比较,证明了所建立的模型具有较高的可靠性。对AS4/3501-6复合材料层合平板的固化过程进行了数值模拟,重点研究了固化过程中纤维体积分数变化及材料参数的时变特性对固化过程中温度、固化度和树脂压力等参量的影响。分析结果表明:考虑纤维体积分数变化和材料性能的时变特性后,固化过程中复合材料层合板中心温度峰值明显减小,树脂压力随时间的变化将有所滞后。     

Inverse algorithm for optimal processing of composite materials

During thermoset composite materials processing, the chemical reaction is highly exothermic and because of the low thermal conductivity of the material, significant temperature and state of cure gradients can be generated in thick parts. This creates non-uniform stresses that provoke defects. We propose to control the transformation by monitoring the temperature of the mold walls. A general inverse analysis based on the conjugate gradient method of minimization associated to the adjoint equations is used. After having detailed the method, we propose two examples. The first one presents an optimal cycle to obtain uniform conversion at the end of the curing of an epoxy/glass-fiber composite. The second example is concerned with the control of the temperature variations during the curing of a polyester/glass-fiber composite. The method is experimentally validated and proves to be very powerful and flexible.     

GFRP厚板制件固化过程固化度分布

采用真空导入模塑工艺(VIMP) 制备了85 mm 厚玻璃纤维增强环氧树脂层合板, 单面刚性模具加热固化, 沿铺层厚度方向设置热电偶, 进行了实时固化温度监测, 发现固化时厚度方向存在明显的温度差异。通过DSC方法得到等温环氧树脂固化度-时间实验数据, 建立了基于自催化反应模型的等温固化反应动力学方程, 模型计算值和实验值符合良好; 提出了时间离散分步计算法, 对非等温固化条件下, 厚度方向的固化度分布进行了计算。结果表明: 固化过程中厚度方向固化度存在差异, 短时间的后固化可以消除此差异。该方法可以模拟出由温度差异导致的固化度的不均匀分布, 用于指导优化固化工艺。      

Chemical and thermal shrinkage in thermosetting prepreg

A methodology for predicting residual cure deformation and stresses in composite laminates during cure is proposed. The technique employs an unbalanced cross-ply strip denoted as a “bi-lamina” strip to measure the in situ development of chemical and thermal shrinkage deformation during a specified thermal cycle. The constitutive model of the composite material was developed based on self-consistent micro-mechanical homogenization with variable resin thermo-mechanical material properties during the cure cycle. The resin properties were determined as a function of cure and temperature using different experimental techniques, including differential scanning calorimetry, digital image correlation, rheometry and dynamic mechanical analysis. The predicted bending deflection profiles of the strip agreed closely with experimental observations. The proposed methodology can be used to validate the material model of the resin and composite during the cure cycle.     

树脂基复合材料曲面结构件固化变形数值模拟

为了研究树脂基复合材料曲面结构件的固化变形过程,首先分析了碳纤维增强树脂基复合材料在固化过程中密度、模量、热膨胀系数、比热容及热传导系数等材料物性的变化,并将这些变化引入到数值模拟当中。接着,针对复合材料复杂曲面结构件,提出了利用定常流动的流线方程构建曲线坐标系的新方法。然后,根据建立的曲线坐标系,运用有限元法计算了某轻型飞机机翼上蒙皮板在固化过程中内部温度、固化度和内应力的分布情况以及材料物性随固化度的变化情况。最后,计算了由于内部温度场和固化度场的不均匀、热膨胀系数的各向异性和固化引起的树脂体积收缩而导致的结构变形。结果表明:引入材料物性变化使固化过程的数值模拟更加合理、模拟结果更加精确,利用定常流动的流线方程构建的曲线坐标系适用于复合材料曲面结构件的有限元分析。所得结论对研究树脂基复合材料的固化变形过程和各向异性复合材料复杂曲面构件的三维实体建模均具有指导意义。     

Preparation of Microcellular Epoxy Foams through a Limited‐Foaming Process: A Contradiction with the Time–Temperature–Transformation Cure Diagram

3D cross‐linking networks are generated through chemical reactions between thermosetting epoxy resin and hardener during curing. The curing degree of epoxy material can be increased by increasing curing temperature and/or time. The epoxy material must then be fully cured through a postcuring process to optimize its material characteristics. Here, a limited‐foaming method is introduced for the preparation of microcellular epoxy foams (Lim‐foams) with improved cell morphology, high thermal expansion coefficient, and good compressive properties. Lim‐foams exhibit a lower glass transition temperature (T_g) and curing degree than epoxy foams fabricated through free‐foaming process (Fre‐foams). Surprisingly, however, the T_g of Lim‐foams is unaffected by postcuring temperature and time. This phenomenon, which is related to high gas pressure in the bubbles, contradicts that indicated by the time–temperature–transformation cure diagram. High bubble pressure promotes the movement of molecular chains under heating at low temperature and simultaneously suppresses the etherification cross‐linking reaction during post‐curing.     

Dielectric cure monitoring for glass/polyester prepreg composites

The on-line cure monitoring of fiber reinforced thermosetting resin matrix composite material has been performed for improving quality and productivity during manufacturing. Since the dissipation factor measured by dielectrometry method is dependent on the degree of cure and temperature of resin, in this study, a new method to obtain the degree of cure during on-line cure monitoring for S-glass/polyester composites without temperature effect was developed by employing a combination function of the temperature and the dissipation factor. The temperature signal was measured with a K-type thermocouple and the dissipation factor signal was measured with an interdigital dielectric sensor during curing process. Then the calculated degree of cure using the measured data from dielectrometry was compared to the measured value from differential scanning calorimetry. The developed on-line cure monitoring method was applied to a 2-step cure cycle for the verification of the developed procedure.     

Three-dimensional process cycle simulation of composite parts manufactured by resin transfer molding

A process cycle of resin transfer molding (RTM) consists of two sequential stages, i.e. filling and curing stages. These two stages are interrelated in non-isothermal processes so that the curing stage is dominated by the resin flow as well as temperature and conversion distributions during the filling stage. Therefore, it is necessary to take into account both filling and curing stages to analyze the process cycle accurately. In this paper, a full three-dimensional process cycle simulation of RTM is performed. Full three-dimensional analysis is necessary for thick parts or parts having complex shape. A computer code is developed based on the control volume/finite element method (CV/FEM). The resulting computer code can provide information regarding flow progression and pressure field during mold filling; and temperature distribution and degree of cure distribution for a process cycle. The computer code can also be used for process cycle simulation of composite structures with complex geometry and with various molding strategies including switching injection strategy, multiple gate injection strategy and variable mold wall temperature. Numerical examples provided in the present work show the capabilities of the computer code in analyzing the process cycle.     

热固性树脂基复合材料固化过程的三维数值模拟

针对热固性树脂基复合材料成型工艺的固化过程建立了数学模型,并采用有限单元法进行了三维瞬态数值分析。编制了有限元模拟程序CURESIM,通过具体数值模拟算例,表明本文中所建立的分析模型及算法具有较高的可靠性。模拟的固化过程并不特指某一成型工艺,因而模拟的数值方法具有一定的普遍性。模拟程序可以计算得到任意时刻复合材料内温度及固化度分布,通过数值模拟可以有效地优化固化加热工艺参数,提高产品质量。