Quantitative control of RTM6 epoxy resin polymerisation by optical index determination

RTM6 epoxy resin curing is usually characterized by the polymerisation degree. We report in this paper on a refractive index measurement technique applied on an experimental mould to control, quantitatively and in situ, the industrial RTM process. For the first time, we determined simultaneously the thermo-optical coefficient, the refractive index evolution, the specific volume and the polymerisation degree of the resin. The calculation of a “polymerisation degree optical coefficient” led to a quantification of the RTM6 epoxy resin polymerisation process. This calibration coefficient is very useful to perform a real time industrial process control. Furthermore, the optoelectronic system is connected to a data processing unit and is easy to use in an industrial environment.     

Biaxial cyclic deformation of an epoxy resin: Experiments and constitutive modeling

Biaxial (proportional and non-proportional) cyclic tests were conducted on thin-walled tubular specimens to investigate deformation behavior of an epoxy resin, Epon 826/Epi-Cure Curing Agent 9551. The focus was placed on the biaxial stress-strain response and their dependency on the load control mode, stress or strain range and loading path. Experimental results indicated that under strain-controlled equi-biaxial (proportional) cyclic loading, mean stress relaxation occurred in both axial and hoop directions, whereas under stress-controlled equi-biaxial cyclic loading, ratcheting strains accumulated in both principal directions. Under strain- or stress-controlled non-proportional cyclic loading, anisotropy in stress-strain responses was induced in both axial and hoop directions, and the axial and hoop hysteresis loops rotated in opposite directions. This was particularly evident at high stress or strain levels. The experimental results were further used to evaluate the predictive capabilities of a nonlinear viscoelastic constitutive model. Qualitative and quantitative comparison with the test data indicated a good agreement in predicting the complex stress-strain response under biaxial cyclic loading with various loading paths, applied stress or strain ranges and loading control modes.     

Mechanical fatigue of epoxy resin

In static bending fatigue tests, epoxy resins show practically no fatigue if the stress given to specimen is lower than a critical value, which is close to the bending strength of the specimen. In cyclic bending fatigue tests, on the other hand, the resins are easily fractured even though the stresses are far below the critical values. Some strain may be accumulated on the surface of specimen through cyclic deformations. However, the strain accumulated is reversible. If the specimen is allowed to rest, the strain disappears. If the strain reaches a critical value, an irreversible transition may be induced, probably in the arrangement of segments on the surface. A crack nucleus thus created may propagate and cause the final fracture of the specimen, following the fracture mechanics of elastic materials. The lifetime of epoxy resins under cyclic bending load is determined by the time required for creating a crack nucleus on surface.     

RTM快速成型环氧树脂时间-温度-转变图的构建及其碳纤维/环氧树脂复合材料评价

针对自行研制的树脂传递模塑工艺（RTM）快速成型环氧树脂,利用唯象动力学模型、DiBenedetto方程和凝胶模型研究了树脂体系的等温及非等温固化动力学,构建了时间-温度-转变（TTT）的关系图,表明树脂体系兼具较长的适用期与快速固化特性。以此设计RTM快速成型工艺,考察了树脂体系对碳纤维织物的浸润流动行为,并评价了快速成型碳纤维/环氧树脂复合材料的界面力学性能与微观形貌。结果表明,注射温度下树脂体系的浸润填充性良好,RTM快速成型碳纤维/环氧树脂复合材料的力学性能和内部成型质量较好。      

The variation in lateral and longitudinal stress gauge response within an RTM 6 epoxy resin under one-dimensional shock loading

The dynamic response of a commercially important epoxy resin (RTM 6) has been studied using plate impact experiments in the impact velocity regime of 80–960 m/s. Both longitudinal and lateral manganin stress gauges were employed to study the development of orthogonal components of stress both during and after shock arrival. In light of recent work raising doubts about the interpretation of lateral gauge data, lateral response within the RTM 6 resin was also used to investigate the physical phenomena being measured by the embedded lateral gauges. U _S–u _P and σ_X–u _P Hugoniot relationships were in good agreement with data for similar polymer materials from the literature. Derivation of shear strength behaviour both during and after shock arrival showed evidence of strengthening behind the shock front, attributed to compression of the cross-linked epoxy resin polymer chains. Comparison of the change in lateral stress behind the shock to the behaviour of an epoxy resin possessing a similar U _S–u _P Hugoniot from the literature showed a different response; likely attributable to enhanced cross-linking present in this second resin. This result suggests that the embedded lateral gauges were, at least in part, measuring a physical response behind the shock within the resin. A Hugoniot elastic limit of 0.88 ± 0.04 GPa was derived and found to be of the same order of magnitude as results found elsewhere for similar materials.     

不同秸秆增强环氧树脂复合材料的力学性能研究

秸秆具有生物降解、绿色环保等特性,且来源丰富,在绿色纺织复合材料领域受到广泛关注。本文采用真空辅助法制备了长芦苇秆、麦秆、高粱秆、稻草秆增强环氧树脂复合材料,研究了芦苇秸秆在整体和劈裂状态下复合材料的力学性能,并比较了在劈裂状态下芦苇秸秆和其他3种秸秆增强复合材料的力学性能及形态特征,分析了4种秸秆的红外光谱、表面润湿性、表面元素及微观结构。结果表明:4种秸秆均有相似的振动吸收峰位置,且它们表面微观结构差异较大,但其相同之处是表面均有硅元素、氧元素以及碳元素。同时4种秸秆都具有疏水性,芦苇秆、高粱秆、麦秆和稻草秆与水的接触角依次降低。在力学性能上,由于纤维素纤维在秸秆内合理有效分布使其出现结构物效应,秸秆增强复合材料的弯曲性能较拉伸性能具有明显的优势,同时芦苇秆劈材增强环氧树脂复合材料的拉伸强度和弯曲强度比芦苇秆复合材料高165.07%、55.72%。在4种秸秆劈材复合材料中,芦苇秆劈材复合材料的拉伸、弯曲性能最好,其次是稻草杆、高粱杆、麦秆复合材料。秸秆增强复合材料的开发有利于提高秸秆资源利用率,为复合材料的开发利用提供了新路径。     

Examination of the processes of deformation and fracture in a silica-filled epoxy resin

A series of short-term fracture tests have been undertaken on a silica-filled epoxy resin in order to examine the processes of damage initiation, development and fracture in a particulatefilled polymer. Several different types of inelastic deformation and fracture mechanisms were observed within the volume of the material. These included localized shear yielding, particlematrix debonding and micro-cracking. The relative amount of each of these was found to depend upon the test rate and temperature. At low temperatures and high rates of loading, failure was associated with one single debonding event whereas at high temperatures and low rates, debonding and yielding were found to be extensive throughout the volume of the test specimens. A detailed examination of the fractured specimens identified several distinct regions on the fracture surface. Surrounding the defect the particles were often debonded from the matrix suggesting that the crack had propagated in a sub-critical manner. Beyond this zone was a smooth zone corresponding to the region over which the crack was accelerating unstably. The smooth zone then developed into a rough three-dimensional zone in which the crack was propagating at its maximum velocity. The size of each of these zones was found to vary considerably with test temperature and cross-head speed.     

The effect of process parameters on volatile release for a benzoxazine–epoxy RTM resin

Volatile release during cure is a potential cause of void formation during the resin transfer molding of complex thermosetting resins. In this study, a blended benzoxazine–epoxy resin system is analyzed to determine the rate at which volatiles are evolved, as well as the dependence of that rate on process parameters. The evolution of thermophysical and thermochemical resin properties is characterized using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The identity and rate of evolution of the gaseous byproducts released during cure are determined at ambient pressure using a Fourier transform infrared spectrometer (FTIR) linked to a reaction cell. The results show that gas release during cure can be reduced but not eliminated by degassing at elevated temperature. Furthermore, the results indicate that the nature and rate of volatile release can be modified by judicious selection of cure cycle, as shown by a preliminary analysis of manufactured neat resin panels.     

Ultrasonic characterization of the quality of an epoxy resin polymerization

This work concerns monitoring the polymerization of an epoxy resin and its hardener. An ultrasonic pulse echo technique was used to monitor the attenuation, the phase velocity, and the acoustic impedance of the resin as a function of time. The first two parameters give information about the average state of the hardening of the resin itself. The third parameter, acoustic impedance, indicates the state of the hardening of the resin at the interface with the vessel. These parameters are determined from spectral properties of echoes extracted from the experimental echo waveforms. Experiments were made for different proportions of hardener and allowed a determination of the best mixture (10% of hardener) that corresponds to the manufacturer's recommended value. Analysis of the results shows a progressive hardening from the center of the resin toward the walls of the vessel.     

硫醇@三聚氰胺甲醛树脂/环氧树脂固化剂的制备及性能表征

采用三聚氰胺-甲醛树脂(PMF)为壁材,三羟甲基丙烷三(3-巯基丙酸酯)(TMPMP)作为芯材,原位乳液聚合法制备了硫醇@三聚氰胺甲醛树脂(TMPMP@PMF)微胶囊固化剂。研究了乳化剂种类及用量,囊壁质量比,反应温度,反应时间,pH值对合成TMPMP@PMF微胶囊粒径及稳定性等影响。结果表明:当反应乳液中芯材的质量分数达到2wt%,同时芯材与壁材的单体质量比达到2∶1时,能制备出粒径在大约100μm,粒径均匀的TMPMP@PMF微胶囊。TMPMP@PMF微胶囊的结构稳定,耐热性好,并且呈闭孔结构。采用TMPMP@PMF微胶囊为固化剂,与环氧树脂(EP)基体混合配制成压敏型TMPMP@PMF/EP固化剂,发现微胶囊结构在受到外力作用时能及时破裂,室温甚至低温下都能短时间使环氧树脂固化,并且能够很好地改善固化剂的抗冲击性能。     

纤维素纳米晶/环氧树脂复合材料的制备及性能研究

以过硫酸铵氧化微晶纤维素得到纤维素纳米晶(CNC),与二乙烯三胺在N,N-二甲基甲酰胺(DFM)中发生缩合接枝反应,制备胺化纤维素纳米晶(ACNC)。采用溶液共混法,分别将CNC和ACNC与环氧树脂复合得到纤维素纳米晶/环氧树脂复合膜,纤维素纳米晶不仅起到增强剂的作用,还起到固化交联剂的作用,进而改善环氧树脂的性能。利用万能力学试验机、动态热机械性能、环境扫描电子显微镜、热重分析等对复合材料的性能加以表征分析。结果证明,当CNC和ACNC的添加量均为0.1%时,环氧树脂复合膜的机械强度最大;纤维素纳米晶的加入不仅能够提高环氧树脂的力学性能,还能显著改善其柔韧性,ACNC对环氧树脂复合膜的增强作用高于CNC,CNC的增韧作用强于ACNC。     

新型含硅氧烷液体环氧树脂的合成与表征

以四甲基二乙烯基二硅氧烷和间氯过氧化苯甲酸为原料,通过一步氧化反应制备了1种新型含硅氧烷液体环氧树脂(SiO-EP).采用核磁、红外和质谱对该环氧树脂的结构进行了表征.采用示差扫描量热法(DSC)和热失重法(TGA)对SiO-EP/PN固化物进行了热性能分析,发现该树脂的玻璃化转变温度Tg为81℃,N2条件下700℃时燃烧残炭率高达62%.拉伸和弯曲测试表明该树脂具有良好的力学性能,其拉伸强度和弯曲强度分别为72MPa和103MPa.     

空心玻璃微珠填充环氧树脂复合材料力学性能

对不同填充质量比的改性空心玻璃微珠(HGB)/环氧树脂复合材料进行了拉伸、压缩准静态实验。研究了改性空心玻璃微珠不同填充量对复合材料密度、弹性模量、拉伸强度和压缩强度的影响, 并分析其应力松弛。实验发现, 材料的各项数据随填充比增加均有所降低。空心玻璃微珠的填入使材料表现出脆性破坏, 但破坏前有较大的变形, 破坏后回弹率大, 说明玻璃微珠的填充增强了材料的弹性。HGB/环氧树脂复合材料具有明显的应力松弛现象, 且填充比越高, 应力松弛速率越大, 可见HGB/环氧树脂复合材料具有明显的黏弹性。      

超支化聚酯基二茂铁/环氧树脂复合材料的制备及性能

以第3代环氧端基脂肪族超支化聚酯（EHBP）增韧的环氧树脂（E-51）为基体材料,超支化聚酯基二茂铁（HBPE-Fc）为吸波剂,制备具有一定力学承载及电磁性能的超支化聚酯基二茂铁/环氧树脂（HBPE-Fc/E-51）复合材料,并通过力学性能测试及扫描电镜、矢量网络分析仪等研究了该复合材料的力学及电磁性能。结果表明,添加较低含量的HBPE-Fc能较好地改善环氧树脂体系的拉伸及冲击性能,第4代HBPE-Fc质量分数为2%时,与纯环氧树脂体系相比,HBPE-Fc/E-51复合材料的拉伸强度、断裂伸长率和冲击强度分别提高了21.81%、34.32%和15.41%,对固化体系的拉伸断面分析发现引入HBPE-Fc后材料表现出韧性断裂。HBPE-Fc/E-51复合材料的玻璃化转变温度在105.29~130.27 ℃之间,具有良好的热稳定性,同时该复合材料具有一定的电磁特性。     

Multiscale molecular modeling of SWCNTs/epoxy resin composites mechanical behaviour

Atomistic and mesoscale simulations were conducted to estimate the effect of the diameter and weight fraction of single walled carbon nanotubes (SWCNTs) on mechanical behaviour and glass transition temperature (T_g) of SWCNTs reinforced epoxy resin composites. Atomistic periodic systems of epoxy resin and epoxy resin/SWCNTs were built with different weight ratios and were subject of an extensive multistage equilibration procedure. Molecular dynamics simulations were used to estimate glass transition temperature, Young modulus and solubility parameter of epoxy resin and epoxy resin/SWCNTs composites. Dissipative particle dynamics method and Flory–Huggins theory was employed to predict epoxy resin/SWCNTs morphologies. The results show that incorporation of SWCNTs with diameters ranging from 10 to 14 ? has beneficial effect on mechanical integrity and T_g. Overall, the agreement between predicted material properties and experimental data in the literature is very satisfactory.     

Multiscale molecular modeling of SWCNTs/epoxy resin composites mechanical behaviour

Atomistic and mesoscale simulations were conducted to estimate the effect of the diameter and weight fraction of single walled carbon nanotubes (SWCNTs) on mechanical behaviour and glass transition temperature (T_g) of SWCNTs reinforced epoxy resin composites. Atomistic periodic systems of epoxy resin and epoxy resin/SWCNTs were built with different weight ratios and were subject of an extensive multistage equilibration procedure. Molecular dynamics simulations were used to estimate glass transition temperature, Young modulus and solubility parameter of epoxy resin and epoxy resin/SWCNTs composites. Dissipative particle dynamics method and Flory–Huggins theory was employed to predict epoxy resin/SWCNTs morphologies. The results show that incorporation of SWCNTs with diameters ranging from 10 to 14 Ǻ has beneficial effect on mechanical integrity and T_g. Overall, the agreement between predicted material properties and experimental data in the literature is very satisfactory.