木质素基环氧树脂固化动力学模型及固化特征

采用工业碱木质素合成环氧树脂,在空气气氛下利用非等温热失重技术研究木质素基环氧树脂(LGEP)固化特征.采用自催化反应模型计算得到了LGEP体系的固化反应动力学参数,并得到LGEP体系的固化反应动力学模型.结果表明,自催化反应模型得到的模拟曲线与实验得到的DSC曲线的一致性较好.利用外推法得到了LGEP体系的固化凝胶温度Ti0 =454.88K,固化温度Tp0=507.55K,后处理温度T80=598.77K.通过比较得出实验结果与模型计算值较一致.     

风机叶片用环氧树脂的固化动力学研究

通过动态DSC(差示扫描量热法)研究了佳发JH-239、惠利LT-5078A等两种风机叶片用环氧树脂的固化动力学特征温度,并采用Kissinger、Crane法确定它们的固化动力学参数.结果表明:佳发树脂体系的表现活化能为40.60 kJ/mol,惠利树脂体系的表现活化能为45.91kJ/mol,而二者的反应级数分别为...     

603环氧树脂体系固化动力学模型的建立与验证

采用非等温差示扫描量热法（DSC）研究了603热塑增韧环氧树脂体系的固化反应动力学。研究发现,在低升温速率测试条件下603环氧树脂体系固化反应的DSC曲线有两个重叠的放热峰,通过分离两个重叠的放热峰,研究了603环氧树脂体系固化动力学的特性。利用Kissinger方法和Kamal方程分别拟合得到603树脂体系固化反应的活化能和固化动力学参数,选择三种典型固化工艺制度下预测的树脂固化反应结果与实验数据对比,验证了所建立动力学模型的可靠性。基于不同升温速率的放热曲线,通过外推法得出该树脂占总反应比例70%的第一个反应固化温度为（177.3±2.2）℃,占总反应比例30%的第二个反应的起始温度和固化温度分别为（178.6±0.7）℃和（216.9±1.7）℃。研究结果对于多组分热固性树脂体系固化动力学的分析和复合材料成型工艺的优化具有重要的指导意义。     

Interlaminar and intralaminar durability characterization of wet layup carbon/epoxy used in external strengthening

Carbon fibers in unidirectional fabric form are increasingly being used as a means of strengthening deteriorating and understrength concrete components and systems through application as externally bonded reinforcement. The use of wet layup process under ambient conditions makes these composites susceptible to moisture and environment-related deterioration. In addition since the composite is formed in the field, often in overhead or vertical configurations, by sequential placement of fabric layers, it is critical, for the assessment of materials integrity, to characterize damage mechanisms and durability of interlaminar and intralaminar performance characteristics. It is shown that aqueous exposure, as well as freeze–thaw, results in significant fiber–matrix debonding, and this causes deterioration in short-beam-shear and in-plane shear characteristics. Changes in interlaminar properties are seen to be correlated with moisture uptake. It is also seen that fracture toughness, in the short-term, is enhanced by some of these exposures due to plasticization and flexibilizing of the matrix, which assists in the blunting of crack front progression. However, when accompanied by chemical degradation, such as with immersion in alkali solution, and embrittlement caused by low temperature exposure, G_IC values are seen to deteriorate as well. The data provides a crucial set of material characteristics for consideration side-by-side with fiber dominated characteristics (such as tensile strength and modulus, which are the only ones considered conventionally in rehabilitation design), since the matrix dominated properties will often be the critical links in determining service life.     

室温固化柔性环氧树脂固化剂的制备与性能研究

通过聚醚多元醇和甲基丙烯酸甲酯进行酯交换反应,然后利用多元胺与烯双键的加成改性,将多乙烯多胺与甲基丙烯酸酯反应,合成了含甲基丙烯酸聚醚多元醇酯柔性基目的新型环氧树脂室温固化剂.通过IR等方法对产物进行了征,探讨优化了各种反应条件,并考察了其对环氧树脂性能的影响.     

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。     

Design factors,reliability, and durability prediction of wet layup carbon/epoxy used in external strengthening

Although fiber reinforced polymer composites are increasingly used through the wet layup process for the rehabilitation of deteriorating and understrength concrete structures, there is very little validated information regarding performance over extended time periods. This has resulted in the use of excessively conservative factors in design in some cases, and unconservative estimates, or complete disregard of degradation effects on some characteristics, in others. In this paper two commonly used predictive approaches are used to provide estimates of long-term deterioration for a range of material characteristics which are compared to experimental data obtained over a 3 years period of exposure. It is shown that although predicted durability of tensile characteristics is extremely good for thin sections used conventionally, the rates of deterioration increase significantly with increase in the number of reinforcing layers used. In addition there is deterioration of other characteristics, especially related to interlaminar and intralaminar properties, that need to be considered. It is noted that both methods are unable to accurately account for effects of initial post-cure seen in ambient cured carbon/epoxy systems, although the conventional Arrhenius predictions provide good correlation with experiments once this mechanism has ceased. A methodology that is capable of accounting for temperature variation during exposure is also outlined. The predictions are compared with safety factors prescribed by ACI-440 and TR-55 and some inherent disadvantages of such approaches is highlighted. The basis for the estimation of safety factors based on a reliability approach using Weibull parameters is presented and typical results are shown, emphasizing some weaknesses in current design methodologies in the area of FRP rehabilitation of concrete.     

Acrylonitrile-capped poly(propyleneimine) dendrimer curing agent for epoxy resins: Model-free isoconversional curing kinetics,thermal decomposition and mechanical properties

Acrylonitrile-modified aliphatic amine adducts are often used as curing agents for room-temperature epoxy formulations (coatings, adhesives, sealants, castings, etc.), yet the curing reaction and properties of resultant epoxy systems still remain less fundamentally understood. Herein we systematically investigate our newly-developed acrylonitrile-modified multifunctional polyamine curing agent for bisphenol A epoxy resin (DGEBA): an acrylonitrile-capped poly(propyleneimine) dendrimer (PAN4). The impact of the molecular structure of PAN4 and a controlled poly(propyleneimine) dendrimer (1.0GPPI) on the curing reactivity, reaction mechanisms, thermal stability, viscoelastic response and mechanical properties of the epoxy systems are highlighted. Differential scanning calorimetry (DSC) confirms DGEBA/PAN4 shows markedly lower reactivity and reaction exotherm than DGEBA/1.0GPPI, and the model-free isoconversional kinetic analysis reveals that DGEBA/PAN4 has the generally lower reaction activation energy. To be quantitative, the progress of the isothermal cure is predicted from the dynamic cure by using the Vyazovkin equation. The isothermal kinetic prediction shows that DGEBA/PAN4 requires about 10 times longer time to achieve the same conversion than DGEBA/1.0GPPI, which agrees with the experimentally observed much longer gel time of DGEBA/PAN4. Subsequently, dynamic mechanical analysis shows that PAN4 results in the cured epoxy network with the lower β- and glass-relaxation temperatures, crosslink density, relaxation activation energy, enthalpy, entropy, but the higher damping near room temperature than 1.0GPPI. Finally, thermogravimetric analysis (TGA) demonstrates cured DGEBA/PAN4 is thermally stable up to 200 °C, and mechanical property tests substantiate that PAN4 endows the cured epoxy with much higher impact and adhesion strengths than 1.0GPPI. Our data can provide a deeper insight into acrylonitrile-modified aliphatic amine curing agents from the two good model compounds (PAN4 and 1.0GPPI).     

多面体低聚倍半硅氧烷/氰酸酯杂化树脂固化动力学与固化工艺研究

采用非等温差示扫描量热法测试了不同升温速率下氰酸酯及氰酸酯/多面体低聚倍半硅氧烷(POSS)复合材料的固化过程,分析了不同升温速率下,POSS对树脂体系固化行为的影响.运用Kissinger法和Flynn-Wall-Ozawa法对杂化树脂固化反应活化能进行了计算.结果表明,POSS对氰酸酯树脂固化具有催化作用,能显著降低树脂固化温度,含10%POSS的杂化体系固化温度可降至212℃;两种不同模型计算的活化能分别为83.30kJ/mol和85.68kJ/mol,与纯氰酸酯相比,杂化树脂的固化活化能和反应级数均有所增大.     

Cure kinetics characterization and monitoring of an epoxy resin using DSC,Raman spectroscopy,and DEA

The use of thick sections of fiber-reinforced polymers (FRPs) is increasing for numerous industrial applications such as wind turbine blades. In situ cure monitoring is very important to directly observe the cure process of FRPs during the manufacturing process. In this work, Raman spectroscopy and dielectric analysis (DEA) are investigated for in situ cure monitoring of an epoxy resin. The cure behavior is first characterized using differential scanning calorimetry (DSC) as a baseline comparison, and the best-fit phenomenological reaction model is determined to describe the cure behavior of the epoxy resin as well as the kinetic parameters. The relationship between T_g and degree of cure is also established. The degree of cure obtained from Raman spectroscopy and DEA under isothermal conditions is compared to that obtained from DSC. A good agreement is observed among the three methods, supporting the potential of these in situ cure monitoring methods during manufacturing. An implementation plan for in-plant monitoring is also discussed.     

新型磷硅改性双酚A型环氧树脂的制备及其固化反应动力学研究

采用羟基封端聚二甲基硅氧烷(HTPDMS)、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)与双酚A型环氧树脂合成了新型的含磷硅双酚A型环氧树脂,通过红外谱图以及核磁共振图确认了其结构,并简单讨论其反应机理;采用DSC分析方法研究其固化动力学,得到其与4,4’-二氨基二苯甲烷(DDM)固化的平均表观活化能Ea为40.74kJ/mol,反应级数n为0.90。     

纳米填料对含长链取代基液晶环氧树脂固化动力学及热性能的影响

制备了几种不同纳米粒子(SiO₂、 TiO₂、 有机化黏土10A、 有机化黏土30B)填充的液晶环氧树脂EP-6-DDM复合材料, 并用差示热分析(DSC)、 偏光显微镜(POM)、 X射线衍射(XRD)和热失重分析(TGA)等方法研究了纳米填料/EP-6-DDM复合材料体系的固化反应过程及其相结构变化和热性能。结果表明, 四种纳米填料对于EP-6-DDM体系均有催化作用, 其中SiO₂的催化能力最强, 有机化黏土30B的催化能力最弱。当黏土的质量分数为1%时, 形成了剥离型纳米复合材料, 大于3%时则剥离型和插层型共存。纳米填料的加入并未改变EP-6-DDM的液晶相织构, 但是会破坏向列相液晶纹影织构的形成和完整性。热分析结果表明, 纳米填料的加入使体系的热稳定性略有降低。      

Interactive effects of resin composition and ambient temperature of light curing on the percentage conversion,molar heat of cure and hardness of dental composite resins

The interactive effects of ambient temperature of cure and resin composition on the extent of cure are evaluated by the measurement of percentage conversion of double bonds, heat of cure and microhardness of visible light cure dental resin systems. Three bonding agents, including two BisGMA-based resins (Command Bond, Pentron Bond) and one urethane-dimethacrylate-based resin (Coe Bond), were evaluated. The results indicate a significant effect of ambient temperature of cure and resin composition on percentage conversion, molar heat of cure and microhardness. In the temperature range of 25–60 °C, thermal activation appears to be a promising approach to improve conversion and crosslinking in dental resins. At lower ambient temperatures of cure (25 °C), urethane dimethacrylate resin undergoes higher levels of conversion than BisGMA-based resins. At higher temperatures, the percentage conversion increases with temperature in all resins. However, the molar heat of cure and hardness values show a significant increase with temperature only in BisGMA-based resins, but not in the urethane dimethacrylate resin. The difference in percentage conversion and heat of cure variation with temperature and the similarity of the latter variation with that of microhardness, probably indicates that the heat of cure is a better predictor of the extent of cure in these thermoset resins. It appears that enhanced crosslinking due to thermal activation may significantly influence the extent of cure at higher ambient temperatures.     

Effect of rapid curing process on the properties of carbon fiber/epoxy composite fabricated using vacuum assisted resin infusion molding

Long processing cycle makes vacuum assisted resin infusion molding (VARIM) only suitable for low and medium volumes of production, and shortening of curing time is critical to improving the processing efficiency of automotive composite parts. In this paper, unidirectional carbon fiber reinforced composite laminates were fabricated by VARIM. Three different processes (namely quick, quick-post and preheating) were employed, in which a kind of rapid curing epoxy resin is used. The preheating of mold and fiber was conducted to shorten the filling time compared with that of quick process. Quick-post process with a post cure stage was investigated to verify the composite properties fabricated by quick process. The cycle time was 16 min for preheating process, about 30% shorter than that of quick process, simultaneously, flexural strength and interlaminar shear strength (ILSS) were respectively improved by 29% and 7% compared with those of quick process. The non-uniformity of mechanical properties at different positions along resin flow direction under preheating process was found, but the processing quality of composite was good. The preheating process is confirmed to be suitable for the improvement of processing efficiency of VARIM with good mechanical properties. In addition, the composite fabricated by quick-post process has better mechanical properties, which is attributed to the alleviation of residual stress during post curing process.     

碳纳米管-玻璃纤维/环氧层板双真空灌注工艺及性能

针对碳纳米管(CNT)-玻璃纤维/环氧树脂体系, 采用传统的真空灌注工艺(VARIM)和双真空灌注工艺(DVARIM)制备复合材料层板, 分析了不同工艺方法下层板缺陷状况, 测试了层板的弯曲性能和层间剪切性能, 并结合树脂性能和纤维/树脂界面粘结状况观察, 探讨了DVARIM对CNT分布的影响及碳管的增强机制。结果表明: 与传统的VARIM相比, DVARIM能增加纤维的间距, 提高树脂对纤维的浸润能力, 减小纤维束内的孔隙缺陷; 添加质量分数为0.05％的酸化CNT后层板性能提高, 而且采用DVARIM性能提高更明显; 不同灌注工艺对CNT的分布产生影响, 从而改变了CNT对纤维/树脂界面粘接的影响, 同时这种影响与织物结构的紧密程度有关。      

电子封装用环氧树脂固化温度与应变的三维有限元模拟

环氧树脂因具有许多优异的性能而被广泛用作电子封装材料,然而环氧树脂在固化过程中产生的内应力会对封装产品的性能产生严重影响。针对一种用于电子封装的环氧树脂,通过实验分析了其固化动力学、密度、导热系数、玻璃化转变温度、弹性模量、化学收缩应变和热应变等性能参数,建立了固化过程中的数学模型。通过ABAQUS建立三维有限元模型,采用顺序耦合分析方式,分步进行传热分析和应力应变分析,模拟环氧树脂固化过程中的温度场、固化度场和应力应变场。最后采用光纤布拉格光栅（FBG）监测环氧树脂在固化过程中内部的温度和应变变化,并与模拟进行对比,结果表明本文所建立的有限元模型具有较高的可靠性。      

Preparation and characterization of a novel microcapsule-type latent curing agent for epoxy resin

A novel spherical latent curing agent microcapsule with the diameter ranging from 6 to 30 μm has been prepared by encapsulating butyl glycidyl ether modified 2-ethyl-4-methyl imidazole (BGE-M-2E4MZ) with polyetherimide (PEI) as the shell material through emulsion/solvent evaporation method. The microcapsule-type latent curing agent was characterized by a Fourier transformation infrared spectrometer, an optical microscope, and an environmental scanning electron microscope. The optimal parameters were obtained through experiments, and the influences of different process parameters on the formation of microcapsules were studied. When the prepared microcapsule-type latent curing agent was mixed with epoxy resin, there were few curing reactions occurred after storage for 100 days at 25 °C, however this latent curing agent could be released and curing reaction of the epoxy resin could be finished within 3 h at 100 °C. In the process of curing, this agent could not be released uniformly in the resin due to the restriction of microcapsule shell, so the resin could not be cured 100%, causing a sharp decrease of mechanical properties of E-51/Mic-2E4MZ casting.     

碳纳米管的偶联剂修饰及其在环氧树脂复合材料中的应用

为了在环氧树脂( EP) 复合材料中改善碳纳米管(CNTs) 的分散性和获得优良的界面特性, 利用Fenton 试剂对CNTs 进行了羟基化处理, 然后分别利用硅烷偶联剂KH550、KH560、KH570 和钛酸酯偶联剂NDZ201对羟基化CNTs 进行表面修饰, 通过SEM、TGA、DSC 和阻抗分析仪研究偶联剂修饰对CNTs/ EP 复合材料性能的影响。实验结果表明: Fenton 试剂和4 种偶联剂修饰都能显著改善CNTs 在复合材料中的分散性, 提高EP的玻璃化温度(T_g) 和热稳定性, 其中偶联剂修饰比Fenton 试剂处理更有效; 然而这些改性却大幅度降低了复合材料的导电性能、介电常数以及介电损耗。4 种偶联剂中, KH560 对应的复合材料的T_g最高, 热稳定性和导电性能最好, 同时具有较高的介电常数和较低的介电损耗。      

高性能双组份环氧树脂固化动力学研究和TTT图绘制

用全动态DSC 研究了先进复合材料用高性能双组份环氧树脂的固化反应动力学, 获得了固化反应的动力学参数, 并建立了固化动力学的唯象模型。用恒温DSC 和动态DSC 结合DiBenedetto 方程研究了树脂玻璃化转变温度和固化度之间的关系, 并给出了玻璃化转变温度T_g和时间t 及温度T 之间的数学关系。通过DMA 研究了树脂恒温下的凝胶过程, 给出了凝胶时间tgel 和凝胶温度T 之间的关系, 回归得到凝胶时的固化度为α_gel =0.4539 , 并以此计算出了T_g ,gel = 70. 18 ℃, 为工艺选择提供了依据。并在此基础上绘制出了该树脂体系的TTT图, 提出了将TTT 图用于工艺优化的思路, 并做了初步验证。