碳纳米管的表面改性对环氧树脂低温(77 K)冲击性能及热膨胀系数的影响

采用混酸氧化及表面接枝改性的方法制备了表面含不同官能团的多壁碳纳米管(MWCNTs), 并研究了不同MWCNTs对环氧树脂的低温(77 K)抗冲击性能及热膨胀系数(CTE)的影响。结果表明: 通过接枝反应将—NCO基团封端的PEO齐聚物引入MWCNTs表面, 可提高MWCNTs在环氧树脂基体中的分散性, 加强MWCNTs与环氧树脂的界面作用; 相对于纯环氧树脂, 添加质量分数为0.5%的纯MWCNTs、 氧化MWCNTs和表面接枝MWCNTs改性后的环氧树脂的低温冲击强度分别升高了10.27%、 26.13%和32.95%, 而CTE则分别降低了14.79%、 29.59%和40.29%。这表明表面接枝改性MWCNTs可明显提高环氧树脂基体的低温抗冲击性能并降低环氧树脂在玻璃化转变温度下的CTE。     

热塑性塑料对环氧树脂热膨胀系数的影响研究

环氧树脂基体的热膨胀系数(CTE)对碳纤维增强环氧树脂层状材料的性能影响巨大,如何降低环氧树脂基体的CTE是提高碳纤维增强环氧树脂复合材料低温使用性能的关键。本研究采用聚对苯二甲酸丁二醇酯(PBT)、聚碳酸酯(PC)和聚醚酰亚胺(PEI)3种热塑性塑料改性环氧树脂,研究了这3种热塑性塑料对环氧树脂基体CTE的影响。结果表明:这3种热塑性塑料分子链中的羰基在环氧树脂固化过程中可与环氧分子侧链上的羟基形成氢键作用,从而加强了热塑性塑料与环氧树脂的界面作用;采用这3种热塑性塑料改性环氧树脂均可提高环氧树脂基体的玻璃化转变温度;相对于纯环氧树脂,PBT、PEI和PC改性的环氧树脂在玻璃化转变温度下的CTE分别降低了14.99%、17.44%和23.96%,但在玻璃化转变温度上的CTE均高于纯环氧树脂。     

酸酐固化环氧树脂-有机蒙脱土纳米复合材料的制备及性能研究

以甲基四氢酸酐为固化剂,对含羟基长链烷基季铵盐改性蒙脱土-环氧树脂纳米复合材料的制备进行了研究。通过TEM、SEM、TGA和DMA等对其微观结构、热性能和动态力学性能等进行表征和分析。TEM结果表明:有机蒙脱土以纳米片层分散在环氧树脂基体中,形成了纳米复合材料;有机蒙脱土含量3wt％时,环氧树脂被同时增韧增强:冲击强度提高87.8%,拉伸强度提高20.9%。纳米片层蒙脱土的加入同时也改善了环氧树脂的热稳定性和动态力学性能;有机蒙脱土含量5wt%时,热分解温度提高24.7℃,热变形温度提高了8.7℃;在T<T_g时,环氧树脂的储能模量提高42.86%,在T>T_g时,提高229.8%;相应玻璃化转变温度T_g提高14.7℃。      

可溶性聚醚醚酮对复合环氧/DDM的改性

热熔法制备了可溶性聚醚醚酮（s-PEEK）/E-51/多官能度环氧树脂复合体系,测试了体系的冲击强度、高温拉伸剪切强度和玻璃化温度,用扫描电镜（SEM）观察体系的微观结构,并与聚醚醚酮（PEEK）改性进行对比。结果表明,复合环氧体系加入两种聚醚醚酮后冲击强度下降,但含量为5g时出现较大值;体系的玻璃化温度随着s-PEE...     

Micro-crack behavior of carbon fiber reinforced thermoplastic modified epoxy composites for cryogenic applications

Three different types of thermoplastics, poly(ether imide) (PEI), polycarbonate (PC), and poly(butylene terephthalate) (PBT) were used to modify epoxy for cryogenic applications. Carbon fiber reinforced thermoplastic modified epoxy composites were also prepared through vacuum-assisted resin transfer molding (RTM). Dynamic mechanical analysis (DMA) shows that the storage moduli of PEI, PC, and PBT modified epoxies are 30%, 21%, and 17% higher than that of the neat epoxy respectively. The impact strength of the modified epoxies at cryogenic temperature increases with increasing thermoplastic content up to 1.5 wt.% and then decreases for further loading (2.0 wt.%). The coefficient of thermal expansion (CTE) values of the PBT, PEI, and PC modified epoxies also decreased by 17.76%, 25.42%, and 30.15%, respectively, as compared with that of the neat epoxy. Optical microscopy image analysis suggests that the presence of PEI and PC in the carbon fiber reinforced epoxy composites can prevent the formation of micro-cracks. Therefore, both the PEI and PC were very effective in preventing micro-crack formation in the composites during thermal cycles at cryogenic condition due to their low CTE values and high impact strength.     

Thermal-mechanical properties of a graphitic-nanofibers reinforced epoxy

We previously developed a series of reactive graphitic nanofibers (r-GNFs) reinforced epoxy (nano-epoxy) as composite matrices, which have shown good wetting and adhesion properties with continuous fiber. In this work, the thermal-mechanical properties of the nano-epoxy system containing EponTM Resin 828 and Epi-cure Curing Agent W were characterized. Results from three-point bending tests showed that the flexural strength and flexural modulus of this system with 0.30 wt% of reactive nanofibers were increased by 16%, and 21% respectively, over pure epoxy. Fracture toughness increased by ca. 40% for specimens with 0.50 wt% of r-GNFs. By dynamic mechanical analysis (DMA) test, specimens with 0.30 wt% of r-GNFs showed a significant increase in storage modulus E' (by ca. 122%) and loss modulus E" (by ca. 111%) with respect to that of pure epoxy. Also thermo-dilatometry analysis (TDA) was used to measure dimensional change of specimens as a function of temperature, and then, coefficients of thermal expansion (CTE) before and after glass transition temperature (Tg) were obtained. Results implied that nano-epoxy materials had good dimensional stability and reduced CTE values when compared to those of pure epoxy.     

石墨烯微片表面接枝PMMA及其环氧树脂复合材料性能

利用石墨烯微片（GNPs）表面羟基与硅烷偶联剂反应,并通过原子转移自由基聚合（ATRP）方法在GNPs表面接枝了聚甲基丙烯酸甲酯（PMMA）。应用扫描电子显微镜、透射电子显微镜、红外光谱和X射线衍射方法分析了化学接枝前后GNPs的微观结构变化。将接枝PMMA的GNPs加入环氧树脂中,研究其对环氧树脂力学性能与尺寸稳定性的影响。研究结果表明,与原始GNPs相比,表面接枝PMMA的GNPs对环氧树脂力学性能的增强作用更明显。添加质量分数为0.5%的GNPs-PMMA可以使环氧树脂拉伸强度和模量分别提高17.4%和75%,弯曲强度和模量也分别增加了6%和12%,同时可以使环氧树脂在低于玻璃化转变温度的线性热膨胀系数（CTE）降低25%。     

Investigating of polysulfide and epoxy‐polysulfide copolymer curing

Polysulfide can be cured in various methods. In this work, the effect of various oxidative curing agents (manganese dioxide and para quinonedioxime) in presence of curing accelerator (Diphenylguanidine) on mechanical‐dynamical properties and cure time of polysulfide resin (G4) was investigated. Results showed that mentioned oxidative curing agents have no remarkable effect on mechanical properties and cure time. But preferred method is preparation of polysulfide‐epoxy copolymer. This copolymer is a new class of liquid polymer composition containing block copolymers, with alternating blocks of polysulfide and polyepoxide. in different epoxy/polysulfide ratio, the epoxy‐polysulfide copolymer showd different tensile strenght, elongation, hardness, gel time, viscosity and Tg, but epoxy free polysulfide approximately revealed constant mechanical and dynamical properties so that epoxidized polysulfide had excellent mechanical properties and suitable curring times in comparison with those samples which were cured in other methods. FT‐IR spectroscopy, viscometry and GPC were used to verify the formation of epoxy‐polysulfide copolymer. Results obtained from DMTA and SEM showed that phase separation of epoxy resin from the copolymer matrix took place and The glass transition temperature (Tg) of the cured copolymer was between the cured epoxy and polysulfide glass transition temperatures.     

聚乙二醇对环氧胶衣温度冲击开裂性能的影响

为开发一种满足航空环境要求的新型环氧胶衣,首先,研究了不同分子量、不同含量的聚乙二醇(PEG)改性环氧胶衣在室温下的冲击韧性及冲击断面形貌;然后,采用一种简单温度冲击试样模型,着重研究了PEG改性环氧胶衣在温度冲击(-50℃/30 min+90℃/30 min)下的开裂性能,并通过分析热膨胀及储能模量等的变化趋势对其进行了验证。结果表明:5wt% PEG-1000改性环氧胶衣的冲击强度比未改性环氧胶衣的提高了31.8%,达到最高值4.97 kJ·m-2;PEG-1000和PEG-2000改性环氧胶衣的冲击断面呈现出更明显的塑性变形形貌,胶衣的冲击韧性得到提高;15wt% PEG-400改性环氧胶衣在温度冲击下的宏观初始开裂性能达到最佳,平均初始开裂需要进行10.4次循环;改性环氧胶衣的耐开裂扩散性能基本上随着PEG分子量和含量的增加而提高,但裂纹宽度也会随PEG分子量的增加而扩大。      

Novel high performance no flow and reworkable underfills for flip-chip applications

 Flip-chip interconnect is the emerging technology for the high performance, high I/O (Inputs/Outputs) IC devices. Due to the thermal mismatch between the silicon IC (CTE=2.5 ppm/⁰ C) and the low cost organic substrate such as FR-4 printed wiring board (CTE=18–22 ppm/°C), the flip chip solder joints experience high shear stress during temperature cycling testing. Underfill encapsulant is used to couple the bilayer structure and is critical to the reliability of the flip-chip solder joint interconnects. Novel no-flow underfill encapsulant is an attractive flip-chip encapsulant due to the simplification of the no-flow underfilling process. To develop the no-flow underfill material suitable for the no-flow underfilling process of flip-chip solder joint interconnects, we have studied and developed a series of metal chelate latent catalysts for the no-flow underfill formulation. The latent catalyst has minimal reaction with the epoxy resin (cycloaliphatic type epoxy) and the crosslinker (or hardener) at the low temperature (<180° C) prior to the solder reflow and then rapid reaction takes place to form the low-cost high performance underfills. The effects of the concentration of the hardener and the catalyst on the curing profile and physical properties of the cured formulations were studied. The kinetics and exothermic heat of the curing reactions of these formulations were investigated by differential scanning calorimetry (DSC). Glass transition temperature (Tg) and coefficient of thermal expansion (CTE) of these cured resins were investigated by using thermo-mechanical analyzer (TMA). Storage moduli (G′) and crosslinking density of the cured formulations were measured by dynamic-mechanical analyzer (DMA). Weight loss of these formulations during curing was investigated by using thermo-gravimetric analyzer (TGA). Additionally, some comparison results of our successful novel generic underfills with the current commercial experimental no-flow underfills are reported. Additionally, approaches have been taken to develop the thermally reworkable underfill materials in order to address the non-reworkability problem of the commercial underfill encapsulants. These include introducing the termally cleavable blocks to thermoset resins, and adding additives to thermoset resins. For the first approach, five diepoxides containing thermally cleavable blocks were synthesized and characterized. These diepoxides were mixed with the hardener and the catalyst. Then the properties of these mixtures including Tg, onset decomposition temperature, storage modulus, CTE, and viscosity were studied and compared with those of the standard formulation based on the commercial epoxy: ERL-4221D. These mixtures all decompose at lower temperature than the standard formulation. Moreover, one mixture – Epoxy5 – showed acceptable Tg, low viscosity, and fairly good adhesion. For the latter approach, two additives were shown that after added to typical cycloaliphatic epoxy formulation, do not interfere with epoxy curing, and do not affect the typical properties of cured epoxy system, yet provide die removal capability to the epoxy. Furthermore, the combination of the two approaches showed positive results. Received: 28 September 1998 / Reviewed and accepted: 1 October 1998     

Studies of modified bismaleimide resins Part I The influence of resin composition on thermal and impact properties

The influence of the components of a modified bismaleimide (BMI) resin on the thermal properties and impact properties of these resins are investigated in this paper. Toughened BMI resin castings incorporating 0%, 5%, 10%, 15%, 20%, 30%, and 40% (by weight) thermoplastic-modified polyetherketone (PEK-C) were prepared. The modified resins were characterized and analysed using dynamic mechanical thermal analysis (DMTA), thermogravimetric (TG) analysis, free beam impact tests, and scanning electron microscope (SEM) techniques. The results indicate that a typical 4,4'-bismaleimidodiphenyl methane (MBMI)/0,0'-diallybisphenol A (DABPA) two-component system modified with 4,4'-bismaleimide diphenyl ether of biphenyl A (MEBMI), Allyl phenol epoxy (AE), and PEK-C has a high glass transition temperature (Tg), excellent thermal stability, and outstanding impact strength. This novel toughened BMI resin is expected to find use in advanced composites.     

聚硅氧烷改性环氧树脂体系的制备,形态与性能

聚胡氧烷－环氧树脂体系微相分离形态形成过程不同于一般反应性液体橡胶改性环氧树脂。此体系微相分离结构是在预反应过程中形成的，是聚硅氧烷在环氧树脂中的分散和聚结两种趋势共同作用的结果。预反应中形成的嵌段共聚物使该体系微相分散微细而且均匀，一未改性环氧树脂相比，经预反应制得的固化物弯曲杨氏模量和玻璃态线性热膨胀系数均有明显下降，因此内应力大幅度降低，抗开理解指数大为提高；而直接共混法改性环氧树脂低应力化     

液晶聚氨酯/环氧树脂复合材料的合成及应用

以对苯二酚二对苯甲酸酯(HQB)、N,N'-二(ω-羟乙基)苯均四甲酰二亚胺(BHDI)、甲苯二异氰酸酯(TDI)为单体, 利用溶液缩聚方法, 合成了一种含有亚氨基的新型液晶聚氨酯(HBLCP), 并将该液晶聚氨酯与环氧树脂(E-51)共混制备液晶聚氨酯/环氧树脂复合材料(HBLCP/E-51)。采用FTIR、DSC、POM和WAXD等方法对HBLCP的结构和液晶相转变行为进行了表征, 并利用SEM观察复合材料断裂形貌, 探讨其增韧机制。结果表明, 加入质量分数为3%的HBLCP, 可使HBLCP/E-51复合材料的冲击强度提高2.3倍, 拉伸强度和弯曲强度也有不同程度的提高, 呈现出典型的韧性断裂, 热分解温度提高12~20 ℃, 出现最大分解速率时的温度提高12~15 ℃。      

有机硅改性双酚F环氧树脂的性能

合成了脂肪族二官能度端环氧基聚二甲基硅氧烷、含酚羟基烷氧基硅烷及3,3′,3″-三羟基苯氧基硅烷三缩水甘油醚,研究了有机硅对环氧树脂力学性能的影响,并用TMA及化学分析方法研究了改性固化物的热性能和树脂/玻璃纤维复合材料的耐酸性。研究结果表明,3,3′,3″-三羟基苯氧基硅烷三缩水甘油醚可使环氧树脂的拉伸强度、弯曲强度分别提高10.4%及53.6%,线胀系数降低18.8%,抗开裂指数提高52.2%,同时保持固化物较高的玻璃化温度,提高耐酸性,是一种理想的环氧树脂新型改性剂。     

不同相对分子质量聚乙二醇增塑聚乳酸共混物的制备与性能

文中探究不同相对分子质量聚乙二醇(PEG)对聚乳酸(PLA)增塑改性的影响。采用转矩流变仪、万能试验机、差示扫描量热分析、动态力学、热重分析、旋转流变仪等测试表征方法对共混材料的增塑效果、力学性能、热行为、流变行为进行分析。实验结果表明,PEG可有效增塑PLA,PEG相对分子质量越低增塑效果越好,可以使PLA的塑化时间从250 s降低到128 s;加入PEG后,共混物的拉伸强度下降,断裂伸长率提高,PEG相对分子质量越低,拉伸强度下降越明显;PEG的加入使PLA的T_g和T_(cc)降低20℃左右,而T_m有所提高,其中低相对分子质量PEG可以更好地促进PLA结晶,但是随着PEG的加入共混体系的热分解温度降低,相对分子质量越低,热分解温度降低越明显;流变实验表明共混体系的复数黏度(η*)、储能模量(G')及损耗模量(G')的变化随PEG相对分子质量的减小下降越明显。     

稀释剂对环氧树脂电子束辐射固化性能的影响

对分别加入4 种稀释剂的双酚A 环氧树脂和酚醛环氧树脂的电子束辐射固化性能进行了研究。分析了稀释剂种类及含量对环氧树脂体系辐射产物的固化度、固化均匀性、固化区域大小及其动态力学性能的影响规律。结果表明: 电子束固化环氧树脂体系中加入稀释剂后, 辐射产物的固化度、玻璃化转变温度及储能模量有所下降, 但固化均匀性得到提高; 加入稀释剂的环氧树脂电子束固化区域的厚度均小于未加稀释剂树脂, 而底面直径却大于未加稀释剂树脂; 随着树脂中实际稀释剂含量的增加, 电子束固化环氧树脂固化度逐渐降低, 固化层厚度减小, 固化区域的底面直径先增加后减小。      

Effect of surfactant treatment on thermal stability and mechanical properties of CNT/polybenzoxazine nanocomposites

The mechanical and thermo-mechanical properties of polybenzoxazine nanocomposites containing multi-walled carbon nanotubes (MWCNTs) functionalized with surfactant are studied. The results are specifically compared with the corresponding properties of epoxy-based nanocomposites. The CNTs bring about significant improvements in flexural strength, flexural modulus, storage modulus and glass transition temperature, T_g, of CNT/polybenzoxazine nanocomposites at the expense of impact fracture toughness. The surfactant treatment has a beneficial effect on the improvement of these properties, except the impact toughness, through enhanced CNT dispersion and interfacial interaction. The former four properties are in general higher for the CNT/polybenzoxazine nanocomposites than the epoxy counterparts, and vice versa for the impact toughness. The addition of CNTs has an ameliorating effect of lowering the coefficient of thermal expansion (CTE) of polybenzoxazine nanocomposites in both the regions below and above T_g, whereas the reverse is true for the epoxy nanocomposites. This observation has a particular implication of exploiting the CNT/polybenzoxazine nanocomposites in applications requiring low shrinkage and accurate dimensional control.     

The role of carbon nanofibers on thermo-mechanical properties of polymer matrix composites and their effect on reduction of residual stresses

In this research, the effects of carbon nanofibers (CNFs) on thermo-elastic properties of carbon fiber (CF)/epoxy composite for the reduction of thermal residual stresses (TRS) using micromechanical relations were studied. In the first step, micromechanical models to calculate the coefficient of thermal expansion (CTE) and Young's modulus of CNF/epoxy and CNF/CF/epoxy nanocomposites were developed and compared with experimental results of the other researchers. The obtained results of the CTE and Young's modulus of modified Schapery and Halpin-Tsai theories have good agreement with the experimental results. In the second step, the classical lamination theory (CLT) was employed to determine the TRS for CNF/CF/epoxy laminated nanocomposites. Also, the theoretical results of the CLT were compared with experimental results. Finally, reduction of the TRS using the CLT for different lay-ups such as cross ply, angle ply, and quasi-isotropic laminates were obtained. The results demonstrated that the addition of 1% weight fraction of CNF can reduce the TRS that the most reduction occurred in the unsymmetric cross-ply laminate by up to 27%.     

废胶粉/空心玻璃微珠改性环氧树脂的结构与性能

研究了微波辐射改性废胶粉(WRP)、偶联剂改性空心玻璃微珠(HGM)对环氧树脂复合材料的结构和性能的影响.采用差示扫描量热、热重分析等方法进行测试和表征,用扫描电镜观察了复合材料的断面形态.结果表明,少量合适粒径的改性WRP可以提高环氧树脂复合材料的冲击强度,适量的改性HGM可以提高复合材料的T<,g>和弯曲强度,并改...     

两亲性嵌段共聚物增韧环氧树脂

合成了端环氧基硅油与聚醚胺(D-230)的嵌段共聚物。采用端环氧基硅油和嵌段共聚物对双酚A型环氧树脂(E-51)进行改性。结果表明,采用端环氧基硅油和D-230的嵌段共聚物改性环氧树脂(EP),效果优于端环氧基硅油改性的方式。采用4份端环氧基硅油预反应改性EP后,Tg由未改性的163.23℃提高到164.81℃。除耐热性有所提高外,其拉伸强度也几乎能保持不变,断裂伸长率由38.62%降低到30.53%,冲击强度由20.23 kJ/m2提高到32.51 kJ/m2。