高压二氧化碳强化的聚氨酯等温固化反应

采用高压差示扫描量热法研究了40～100℃,0.1～9.0 MPa的二氧化碳(CO_2)氛围中的聚醚三醇和多亚甲基多苯基多异氰酸酯合成聚氨酯的等温固化反应,并采用扩散修正后的Kamal自催化模型及等转化率法进行了动力学研究。结果表明,与相同压力的氦气中的聚氨酯固化反应相比,高压CO_2氛围中反应速率快,最终固化度高;并且随着CO_2压力的上升,反应速率和最终固化度均提高,这是因为高压CO_2的溶剂化作用降低了聚氨酯齐聚物的玻璃化转变温度和体系黏度,强化了传质;扩散修正的Kamal自催化模型所得的活化能和等转化率法计算出的不同固化度的表观活化能都随CO_2压力的升高而减小,证明了高压CO_2对聚氨酯固化反应的促进作用。     

桐马酸酐与环氧树脂的非等温固化反应动力学

采用Málek法对桐马酸酐与双酚A环氧树脂E-51体系(含有1%质量分数的DMP-30)的非等温固化反应动力学进行了研究。通过机理函数esták-Berggren方程很好地模拟了真实的固化反应过程。等转化率法求得反应活化能为69.78 kJ/mol。指前因子A的值为4.567×108 min-1,n和m的值分别为1.082和0.456。根据得到的固化动力学方程计算可知,在固化温度为137.05℃时达到98%固化度的固化时间为115 min。     

紫外红外共同固化环氧树脂的固化行为

采取先用紫外辐照引发,后改用红外辐照的方法固化添加了不同用量稀释剂的环氧树脂体系,通过凝胶转化率表征体系固化度,对不同体系的固化行为进行研究,并用Avrami方程分析体系的固化反应行为。结果表明,紫外辐照时间延长可以提高固化反应速率,而稀释剂用量的增加则会降低固化反应速率。用Avrami方程可以较好地描述终止紫外辐照后体系的固化反应行为,Avrami方程中的Avrami指数值和体系中活性反应中心有关。非平衡态热力学涨落理论分析表明,固化体系的松弛时间随着紫外辐照时间的增加而减小。     

环氧树脂非等温固化动力学及其固化工艺的研究

采用差示扫描量热法（DSC）研究了N-乙基邻对甲苯磺酰胺/环氧树脂体系的固化过程,研究了不同配比对固化反应的影晌,固化度与固化温度的关系,计算了固化反应表观活化能和反应级数,确定了N-乙基邻对甲苯磺酰胺/环氧树脂体系的固化工艺。结果表明：不同升温速率下,体系固化温度有很大差异,随着升温速率的提高,固化温度增加。通过动力学计算得到体系最佳固化温度为90℃,固化时间为4~6 h,固化体系的活化能为29.1 kJ/mol,反应级数为0.81。     

环氧树脂基预浸料热固化特征温度和固化度研究

基于固化动力学理论和有限元分析方法,建立了树脂基预浸料热固化过程中温度场研究的数学模型,数值模拟了预浸料固化过程的温度和固化度变化特征,将数值计算结果与已有文献实验结果对比,验证了计算模型和计算方法的正确性.研究了升温速率、玻璃纤维等因素对环氧树脂体系固化反应特征温度以及固化时间的影响.结果表明,升温速率增加,固化反应放热峰Tp向高温方向移动,同时固化起始温度Ti和固化终止温度Tf也相应地向高温移动,固化过程中材料内温度梯度增大,内部热应力增大.但提高升温速率可缩短固化完成所需时间.玻璃纤维的加入使树脂基预浸料各项固化反应特征温度降低,达到固化起始温度的时间延长,但对完成固化时间的影响可忽略.     

热固性乙烯基酯树脂的反应动力学研究

采用差示扫描量热法(DSC)考察了乙烯基酯树脂DERAKANE~(TM)411-350的固化反应,采用不同的升温速率,得到了乙烯基酯树脂(VER)的固化温度与升温速率的曲线,分析计算得到合理的树脂固化工艺温度:可选择85℃为凝胶温度,100℃进行固化和后处理。分别采用Kissinger法和Ozawa法求出了VER固化反应的表观活化能ΔE,其值为:71.91 kJ·mol~(-1)(Kissinger法);74.41 kJ·mol~(-1)(Ozawa法)。此外,由Crane方程还得到了固化反应的反应级数n=0.92。     

DSC法研究聚异氰酸酯/环氧树脂胶粘剂的固化反应动力学及固化工艺

采用差示扫描量热法(DSC)研究了聚异氰酸酯/环氧树脂的固化过程,研究了不同配比对固化反应的影响、固化度与固化温度的关系,计算了固化反应表观活化能和反应级数,确定了聚异氰酸酯/环氧树脂胶粘剂的固化工艺。结果表明:胶粘剂中固化剂的含量对环氧树脂的固化反应过程有显著的影响,随着聚异氰酸酯含量的增加,固化放热量增加。当聚异氰酸酯的含量达到1.2份时,固化反应放热量达到最大值;在不同升温速率下,体系固化温度有很大差异,随着升温速率的提高,固化温度升高。通过动力学计算得到体系最佳固化温度为108℃,固化时间为6—8h,固化体系的活化能为43.31kJ/mol,反应级数为1.17。     

聚氨酯柔性固化剂/环氧体系固化动力学及机理

通过不同升温速率下示差扫描量热分析(DSC)研究了自制的聚氨酯柔性固化剂ATPU/环氧树脂E-44体系的固化反应动力学及机理。通过Kissinger和Crane方程求解了表观活化能和反应级数等动力学参数,并运用该参数研究了固化反应速率常数、固化反应速率、固化度等的变化规律及影响因素。通过反应级数的研究证明了固化反应为一复杂反应,不同的固化交联反应同时发生,但主要进行的是伯氨基及仲氨基与环氧基之间的反应,该类反应使得体系得以固化。     

无损监测技术在复合材料中的应用研究

本文利用JF2107B型自动介电分析仪对环氧/玻璃纤维复合材料的固化历程进行了研究。研究了升温速率、固化剂含量对复合材料介电性能的影响。结果表明,以1.25℃/min、2.5℃/min、5℃/min三种速率进行线性升温,随升温速率增加,tgδ曲线向左移动,损耗峰出现较早,表明固化反应提前了。环氧/玻璃纤维复合材料中,固化剂含量为65%时,tgδ与固化度分别为0.0538和98.5%。树脂固化终点的tgδ值与固化剂含量呈抛物线关系,有最小极值,最小极值点的配比为最佳配比,其C点tgδ值最低,固化度最高。     

微齿轮注射成型数值模拟及正交优化

基于CAE软件采用正交试验设计方案对微注射成型工艺参数如模具温度、熔体温度、注射速率、保压压力、保压时间及冷却时间等与微齿轮制件质量的关系进行了数值模拟,并利用直观分析法和方差分析法对模拟结果进行了分析.结果表明,当模具温度为40℃、熔体温度为225℃、注射速率为10 cm3/s、保压压力为100 MPa、保压时间为1...     

Thermal analysis of thermosetting phenolic compounds for injection molding

The differential scanning calorimetry technique has been applied to investigate the curing of injection molding phenolic compounds. The data obtained include degree of cure, rate of curing, and heats and temperatures of curing as function of various heating rates, rate constants, energy of activation, and glass transition temperature. The curing temperature and heating rate were found to affect both the curing reaction kinetics and the final structure of the crosslinked network. The glass transition temperature changes continously with the extent of curing, approaching the cure temperature.     

A review of liquid silicone rubber injection molding: Process variables and process modeling

Liquid silicone rubber (LSR) is an elastomer molded into critical performance components for applications in medical, power, consumer, automotive, and aerospace applications. This article reviews process behavior, material modeling, and simulation of the (LSR) injection molding process. Each phase of the LSR injection molding process is discussed, including resin handling, plastication, injection, pack and hold, and curing; and factors affecting the molding process are reviewed. Processing behavior of LSR is marked by transient interactions between curing, shear rate, temperature, pressure, and tooling. Therefore, current LSR models for curing, viscosity, pressure, and temperature are discussed. Process dynamics and material modeling are combined in LSR injection molding simulations with applications in mold design, troubleshooting process-induced defects, and management of shear stress and non-uniform temperatures between LSR and substrates during overmolding. Finally, case studies using commercial simulation software are presented, which have shown cavity pressure and flow front advancement within 3% of experimental values. Optimization of LSR materials, data collection, model fitting, venting, and bonding remain areas of continued interest.     

Engineering analysis of reaction injection molding process of epoxy resin

An engineering analysis of reaction injection molding (RIM) process of epoxy resin was carried out through numerical simulation and actual experiment. In order to simulate the RIM process, and reaction kinetics and the viscosity function of the epoxy system were obtained from thermal analysis and rheological measurement, and the balance equations of the chemical species, momentum, and energy within a mold cavity were set up in cylindrical coordinates. As the result of the simulation, the temperature and conversion profiles within a disc type mold were obtained and a moldability analysis was made to find the optimum molding conditions. The temperature change during the curing reaction, at a fixed point within the mold cavity, was measured through the actual RIM experiment on a small scale, and was compared with the simulated results.     

Evaluation of injection‐molding simulation tools to model the cure kinetics of rubbers

Rubber injection molding is a process whereby a rubber mix is injected into a closed mold where the material is shaped to the desired geometry. Having completely filled the cavity rubber mix is vulcanized. Vulcanization is the process whereby a viscous and tacky uncured rubber is converted into an elastic material through the incorporation of chemical crosslinks between the polymer chains. The degree of cure achieved depends on the formulation recipe and the time–temperature history endured by the material during the curing process while in the mold. The aim of this study was to check the capability of commercial injection‐molding simulation tools, such as Moldflow and Cadmould, to predict the degree of cure achieved in spiral‐shaped parts when subjected to various cure cycles. To use the simulation tools, it was necessary to characterize the material in terms of their thermal properties and kinetic behavior during curing. The degrees of cure were determined with swelling techniques and by the measurement of the residual cure exotherms with differential scanning calorimetry. On comparing the experimental values of the degree of cure with those predicted by the simulation tools, we found that the initial simulations underestimated the degrees of cure. Consequently, the criteria used to calculate the cure model parameters were modified to invoke faster cures. In so doing, good agreement was achieved between the degrees of cure predicted by the simulations and those obtained experimentally.© 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

UV光固化注射成型工艺实验研究

在传统注射成型工艺的基础上,对模内“光化学制造”工艺参数进行实验研究,分析得到UV材料温度、保压压力对制品精度的影响。其中,利用成型制品平均质量评价UV光固化制品整体成型质量精度。此外,采用横截面图形比较法对制品微结构形态质量进行评价。结果表明,UV光固化注射成型具有替代热塑性材料注射成型方面的可行性。     

环氧树脂/玻璃纤维模压预浸料固化反应动力学研究

采用非等温DSC方法研究了一种模压预浸料（环氧树脂/玻璃纤维）的固化动力学,应用Kissinger和Crane方程拟合求得固化动力学参数,并建立了该预浸料固化动力学唯象模型。通过无转子硫化仪测试预浸料在不同温度下的凝胶时间,通过线性拟合得到固化温度与凝胶时间的函数关系,并对预浸料的固化工艺进行优化。结果表明,通过Kissinger和Crane方法算得该预浸料的固化反应动力学表观活化能为89.9 kJ/mol,指前因子为1.17×10¹¹ min^-1,反应级数为0.93;预浸料在模具温度为150 ℃下预热40 s,环氧树脂具有一定的流动性,并在2 MPa压力下固化300 s,可制备综合性能良好的复合材料制品。     

Moldability diagrams for the reaction injection molding of a polyurethane crosslinking system

A trial and error approach reflects the state of the art in reaction injection molding. Material and process parameters determine the “moldability” of a specific system in a particular application. The concept of “molding areas” on the critical parameters plane can be extended form thermoplastic injection molding (TIM) to reaction injection molding (RIM). In this work moldability diagrams for the filling and curing stages of a RIM process are obtained based on a simplified engineering approach. The key process parameters chosen for the filling stage are initial material temperature and filling time. In the curing stage, the critical parameters are considered to be mold wall temperature and demold time. Experimental results obtained on a laboratory-scale RIM machine on a Crosslinking polyurethane system are used to check the validity of the predicted molding areas. The agreement obtained is satisfactory considering the broad range of processing parameters used.     

聚氨酯反应注射成型固化过程数值模拟

依据反应动力学和能量守恒方程的基本理论，对聚氨酯反应注射成型的固化过程进行了合理的假设和必要的简化，建立了体系反应程度和温度的数学模型。采用显示有限差分法并结合数学软件Matlab对固化过程进行了动态模拟.结果表明：固化初始的20s内交联反应剧烈。体系迅速升至最高温度，交联度达到80％所需时间与经验值一致．约为17s。同时为优化反应注射成型工艺因素，探讨了催化剂浓度、原料初始温度和模具温度等对体系的影响。结果表明：催化剂浓度增加，使体系固化周期缩短，制品内部交联度的变化减小，但延长了制品处于高温部分的时间；模具温度主要影响制品壁面附近的反应，而物料初始温度则能影响到体系的最高温度，尤其是在低模温情况下更加明显.     

EPDM包覆层注射成型模拟及工艺参数研究

为了提高三元乙丙橡胶(EPDM)包覆层注射成型工艺的研发效率,通过数值模拟和实验验证相结合的方式研究了EPDM的流动规律并优选出合适的工艺参数。采用Carreau模型拟合EPDM的流变特性方程,使用Moldflow软件模拟EPDM包覆层的注射成型过程;模拟过程选择了合适的浇口位置,预测了气穴、熔接线位置以及前沿温度的变化,结果与实验一致,气穴易于在弧形顶部形成,同时选择侧面对称的双注射口更有助于成型;分析了温度、压力以及流动速率对填充过程的影响,得到初步的预测成型参数。基于此,进一步通过实验验证得到了合格产品的工艺参数。使用拉伸实验研究所选范围的压力和注射速率对包覆层制品质量的影响,结果表明,合适的工艺参数为:注压温度170℃,镀铬模具温度170℃,注压最大压力30MPa,注压量为148cm³,注压速率为12mm/s。     

管道连接筒注射成型数值模拟与模具设计优化

根据管道连接筒的产品要求和结构特征,运用Moldflow和UG等软件设计了注塑模具浇注系统和冷却系统,进行了注射成型数值模拟。选择熔体温度、模具温度、保压压力、保压时间和注射时间5因素设计了DOE正交试验,得到优化的注塑工艺参数及保压曲线。设计并制造出连接筒注塑模具,生产出合格的产品,验证了模拟结果的正确性。