一种灌封结构用环氧树脂的固化行为表征和模拟

以中高温固化的E39D环氧树脂为研究对象,基于顺序耦合热传导-固化和应力位移模块的数值仿真方法,选择合适的实验方法测试环氧树脂的固化性能,引入相关假设,推导与热传导-固化和应力位移模块相关的树脂固化性能参数和模型;然后,建立典型E39D树脂灌封结构的数值模型,模拟结构内部观测点在固化过程中的温度和应力演变,并基于FBG...     

一种碳纤维预浸料维修补片的固化工艺与性能

碳纤维预浸料作为外场胶结维修补片的主要材料，其固化工艺将直接影响补片的微观结构和力学性能。针对一种碳纤维预浸料进行差示扫描量热测试，研究预浸料的固化反应特征温度和固化动力学参数，并对不同固化工艺的维修补片进行微观形貌分析和拉伸性能测试。结果表明，不同固化保温时间得到的试样样条拉伸性能有明显差别，且拉伸强度和弹性模量随固化保温时间的增加而增大，充分的固化使得试件性能变得更为均匀，但拉伸破坏应变保持不变。保温时间越长，随着固化度的增加，树脂和碳纤结合地更加良好，因此复合材料的拉伸性能更好。该碳纤维预浸料在温度436.4K条件下固化，并保温120min制作的维修补片具有最佳拉伸力学性能。     

基于FBG应变监测的环氧树脂固化收缩及工艺参数优化

采用布拉格光纤光栅（FBG）传感器,对一种典型液态成型环氧树脂在不同固化工艺以及后固化过程中的温度及应变进行了实时在线监测。通过将树脂内部应变变化转化为树脂线性体积变化,得到不同工艺过程中树脂的固化收缩规律,以此作为依据对树脂的经验固化及后固化工艺参数进行验证和优化。结果表明:所选液态成型树脂在80℃下固化,其固化度和玻璃化转变温度分别为90%和85℃,高于75℃固化树脂,但其总固化体积收缩只比75℃固化时略为增加了约5%;树脂在120℃下进行后固化处理时,恒温180 min后FBG传感器监测到的树脂内部应变已不再变化,此时树脂已基本完全固化,无需再延长后固化时间。      

非收缩共聚环氧树脂基体固化的反应动力学

用FT—IR和DSC研究了非收缩共聚环氧树脂基体的固化过程,得到了膨胀性单体NSOC和环氧树脂E51的反应动力学参数及其共聚的表现动力学参数,并且得到了共聚树脂的固化时间与固化温度,贮存时间与贮存温度的关系曲线。这对树脂的实际应用和固化工艺的选择有重要的意义。理论处理的结果表明,固化时树脂基体的体积膨胀可能降低反应的活化能。     

基于复合材料湿法模压工艺的快速固化树脂体系研究

以适用于湿法模压工艺的快速固化环氧树脂体系为研究目标,研究了以改性胺类为主体的环氧固化体系特性。采用差示扫描量热仪(DSC)测试树脂体系的热性能,凝胶化时间测试仪确定树脂体系的固化时间,万能材料试验机表征树脂体系的力学性能,最后确定了快速固化树脂体系最佳的配比参数和浇注体性能。测试结果表明,在20%的固化剂用量和120℃的固化温度下,凝胶化时间达到48s,可以在5min左右完成固化,固化度达98%,拉伸强度达到63MPa,相比常规树脂体系和国内产品均有明显提升。     

发射箱用RTM树脂体系工艺性与固化性能研究

目的研究环氧树脂体系的黏度及固化性能,为利用树脂传递模塑(RTM)工艺制造发射箱提供理论依据。方法采用旋转黏度计测试了E-51环氧树脂体系的动态黏度和静态黏度,用非等温DSC法和平板小刀法研究了树脂体系的固化行为。结果在60~80℃下70 min,树脂体系的黏度仍小于1000 m Pa·s,符合工艺要求,并推导出了固化温度参数分别为60,125,180℃,以及凝胶时间与温度的关系方程。结论温度区间60~80℃可作为发射箱RTM工艺的操作区间,建议固化工艺制度为60,90,125℃下分别加热固化3.5,2,1 h,后处理工艺为180℃下加热固化1 h。     

非等温DSC法研究复合材料用环氧树脂的固化反应

采用非等温DSC研究了一种复合材料用环氧树脂体系的固化反应。采用n级反应模型和Malek等转化率法确定了固化反应动力学方程,通过外推法优化其固化工艺,测试优化后工艺下制备的树脂浇铸体的固化度和力学性能。结果表明,n级反应模型与实验值差别较大;采用Malek等转化率法判断固化反应按自催化反应机理进行,在2.5～15℃/min升温速率下,自催化模型计算曲线与实验曲线吻合较好;优化确定其固化工艺为70℃/2h+110℃/2h,在该工艺下制备的浇铸体固化度达98.51%,拉伸强度和弯曲强度分别为75.11MPa和128.10MPa。     

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。     

引发剂引发BMI/DP共聚双马树脂基体研究

在优选树脂组分的基础上，采用回归正交设计的实验方法优化低温固化双马树脂的配方。通过树脂体系的固化反应特性研究，确定树脂浇铸体和纤维增强复合材料的固化成型工艺，测定其主要力学性能和热性能。研究发现，固化工艺中的低温固化台阶对树脂的耐热性影响很大。引发剂引发改性使双马树脂的固化、后处理温度由２００℃、２５０℃降低到１６０℃、１８０℃，并提高了耐热性，但树脂韧性下降较大。改性树脂热变形温度３００℃，起始分解温度４１７．５℃，弯曲强度１１４ＭＰａ。     

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。      

Influence of the cure cycle upon selected physical properties of a vinyl ester resin

Detailed observations of volumetric changes which occurred during the cure of a vinyl ester resin system have led to the definition of an alternative cycle which involves the same temperatures as the original cycle but in which the recommended overall time of cure is reduced by some 75%. Flexural and tensile strengths and moduli, thermal expansion characteristics, densities and hygrothermal properties of specimens produced according to each cycle are closely similar. The mechanical properties of the same resin reinforced with glass cloth and prepared according to the two cycles were also closely similar. It is concluded that there is considerable scope for applying observations of the volumetric curing characteristics of a resin system to develop a cycle in which (i) the potential of a given formulation is fully realized and (ii) the product is manufactured as economically as possible.     

Improvement of the Compressive Strength of Carbon Fiber/Epoxy Composites via Microwave Curing

Microwave processing was used to cure the carbon fiber/epoxy composites and designed for improving the compressive strength of the materials. By controlling the power of microwave heating, vacuum bagged laminates were fabricated under one atmosphere pressure without arcing. The physical and mechanical properties of composites produced through vacuum bagging using microwave and thermal curing were compared and the multistep(2-step or 3-step) microwave curing process for improved compressive properties was established. The results indicated that microwave cured samples had somewhat differentiated molecular structure and showed slightly higher glass transition temperature. The 2-step process was found to be more conducive to the enhancement of the compressive strength than the 3-step process. A 39% cure cycle time reduction and a 22% compressive strength increment were achieved for the composites manufactured with microwave radiation. The improvement in specific compressive strength was attributed to better interfacial bonding between resin matrix and the fibers, which was also demonstrated via scanning electron microscopy analysis.     

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。      

Out-of-autoclave cure cycle study of a resin film infusion process using in situ process monitoring

Liquid resin infusion (LRI) of textile tailored reinforcements (TRs) is increasingly applied in new processing technologies for manufacturing carbon fibre composites. This work presents a cure cycle study of an out-of-autoclave toughened resin film infusion (RFI) process as part of the examination of an alternative manufacturing process for composites. To successfully produce laminates using resin film infusion in combination with a fast-curing process, the flow behaviour of the selected resin material under changed processing conditions was investigated. The effect of processing parameters, specifically heating rates and dwell times, on resin viscosity and laminate infiltration was evaluated through experimental work and supported by in situ process monitoring. A DC-resistance sensor system was applied to track the change in resin viscosity during cure. Results showed that cure cycles with a relatively short dwell time and higher heating rate compared to an autoclave cure led to enhanced flow properties of the toughened resin system. High quality laminates, comparable to autoclave panels, were manufactured with vacuum pressure only by modifying the original vacuum bagging arrangement.     

Cure cycle optimization of composites by dielectric measurements

Cure cycle monitoring by dielectric loss factor was investigated for prepreg composites based on epoxy, epoxy-phenolic, polyimide and phenolic matrices. Dielectric loss measurements were carried out to establish optimal cure conditions for the various polymer composites with respect to testing rates, curing temperature and timing for pressure application. For each polymer composite studied, initial laboratory experiments were carried out in a temperature-programmable oven to determine the onset of polymer flow, the temperature range where resin viscosity is appropriate for pressure application and the duration of the cross-linking reaction. Subsequently, autoclave processing was conducted using similar conditions accompanied by in situ dielectric loss monitoring. Dielectric cure monitoring of room temperature aged, epoxy-based prepreg indicated that curing of aged prepregs is possible provided a flow region exists. Flexural properties of specimens prepared from composite laminates processed under optimized conditions substantiated the adequacy of in situ dielectric loss measurements for cure monitoring of prepreg composites.     

海工混凝土结构用环氧树脂固化体系性能研究

随着我国海洋经济的飞速发展,对海工混凝土结构腐蚀修复补强技术的需求日益增大。现有地面以上混凝土结构修复技术非常成熟,环氧树脂固化体系对于海洋环境的适用性是其应用环境由地面拓展到海工领域的关键。本研究遴选出7种市售固化剂,通过固化剂及树脂体系黏度、水下凝胶时间对其进行初步筛选,并研究了固化环境、固化时间、固化剂用量对树脂体系的压缩性能影响。最终,通过对拉伸性能、黏结性能的研究,得到海水环境下综合性能表现最优的为810固化剂。结果表明：当环氧树脂E51与固化剂810质量比为2∶1时,在海水中养护7 d,水下凝胶时间为65 min,压缩强度为101.59 MPa,拉伸强度为32.59 MPa,断裂伸长率为4.09%,黏结强度为3.52 MPa。     

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。      

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.