Synthesis and Characterization of High Performance Polymeric Hybrid Siliconized Epoxy Composites for Aerospace Applications

Two different types of hybridized siliconized epoxy matrix systems have been developed using two commercially available (CIBA-GEIGY) epoxy resins with hydroxyl terminated polydimethyl siloxane. The percentage siloxane content in the epoxy systems have been optimized based on the physico-chemical, electrical, mechanical and thermal properties. The matrix resins are cured using aliphatic amine (HY951), aromatic amine (HT972) and polyamidoamine (HY840) from CIBA-GEIGY and γ-aminopropyltriethoxysilane (A-186, Union Carbide). The optimized siliconized epoxy materials are filled with additives like fillers (SiO₂, BaSO₄ and TiO₂), plasticizer (dioctylphthalate), flame retardant (tris (2-chloropropyl) phosphate) and reinforced with E-glass fiber and Kevlar-49 and their effect on electrical and mechanical properties are studied. Introduction of siloxane units (silicone) in to the epoxy systems enhances dielectric properties with little loss of mechanical properties. Additives alter the electrical and mechanical characteristics based on their nature and concentration. Reinforcements enhanced the electrical and mechanical behavior to an appreciable extent. Data resulted from the studies reveal that the siliconized epoxy matrix systems reinforced with E-glass fiber and Kevlar-49 can be used in the filament wound liquid pressure vessels in the field of aerospace and other high performance engineering applications.     

Manufacturing and mechanical properties of soy-based composites using pultrusion

Two primary cost driving factors for the composites industry are raw materials and labor. Inexpensive alternative epoxy resin systems based on epoxidized soyate resins are developed for fiber reinforced composite applications. This research investigated on the manufacturing and mechanical characterization of fiber/epoxy composites using chemically modified soy-based epoxy resins. Co-resin systems with up to 30 wt% soyate resins were used to manufacture composites through pultrusion. Mechanical tests show that the pultruded composites with soy based co-resin systems possess comparable or improved structural performance characteristics such as flexural strength, modulus, and impact resistance. Maximum mechanical properties enhancement is demonstrated by the enhanced epoxidized allyl soyate (EAS) formulation. Further property improvement is obtained through using a two-step prepolymer process. The EAS holds great potential as partial supplement for polymer and composites applications from renewable resources.     

Influence of the Kapitza resistance on the thermal conductivity of filled epoxies

The thermal conductivity of epoxy resins filled with copper powder was measured as a function of grain size and filler concentration between 1.5 and 20 K. In addition, the thermal boundary layer resistance (Kapitza resistance) between epoxy resin and copper was measured. As a consequence of this resistance the thermal conductivity is strongly dependent on grain size in the lower temperature range. Below a characteristic temperature dependent on grain size, thermal conductivity is reduced by adding filler. A simple formula is presented for calculation of the thermal conductivity of filled resins.     

Cure kinetics and rheology characterisation and modelling of ambient temperature curing epoxy resins for resin infusion/VARTM and wet layup applications

Ambient temperature curing epoxy resins are widely used as the matrix material in fibre reinforced plastics in the marine and wind energy sectors, where they are popular due to their relatively high mechanical performance yet low processing and tooling costs. To date, the characterisation of ambient curing epoxy resins has been limited to relatively simple measures, not suitable for use in heat transfer and flow process models. A complete cure kinetics and rheology model allows the prediction of the progression of degree of cure and viscosity for any time–temperature history. The progression of degree of cure of two epoxy resin systems was measured by differential scanning calorimeter and fitted to an nth order model incorporating vitrification effects. Viscosity was measured using an oscillatory rheometer and fitted to a model from the literature. The resulting cure kinetics and rheology model enables the improvement of resin infusion and wet layup processes by providing a thorough understanding of the interlinked relationship between time, temperature, degree of cure and viscosity.     

Investigation into the effects of modification of the passive phase for improved manufacture of 1-3 connectivity piezocomposite transducers

The 1-3 connectivity composite transducers comprise active piezoceramic pillars within a passive polymer matrix. The first stage in manufacturing the 1-3 material is to produce a bristle block (comprising a solid stock of active material with protruding pillars) by injection moulding or by dicing a piece of ceramic using precision sawing equipment. The bristle block is filled with a reactive polymer liquid that produces the passive polymer phase, and the filled block is machined to the desired dimensions. For optimum performance, the polymer phase should have complementary interaction with the ceramic phase as well as imparting dimensional stability. Epoxy-based polymers are the most usual passive materials because of their low viscosity in the uncured state and solvent resistance, coupled with their excellent adhesive, mechanical, and electrical properties. However, the curing of epoxy resins results in shrinkage of the polymer matrix and internal stress within the passive phase. This can lead to prestressing of the active ceramic material, distortion of pillars, reduction in the parallelism between the sides of pillars, acid, in certain circumstances, warpage of transducers. This is particularly evident when the solid stock in the bristle block is relatively thin. This paper reports the in situ modification of epoxy in the bristle block by UV-based low temperature polymerization of acrylate monomers within the epoxy matrix prior to polymerization of the epoxy resin. Internal stress measurements are presented to quantify the influence of this modification via a reduction of internal stress within the polymer matrix. Results from finite element analysis emphasise the conclusions of the experimental work, and examples of manufactured devices are presented. Composite transducer performance is assessed by laser measurement of surface displacement profiles, and a 50% improvement in surface displacement magnitude was observed for the modified devices.     

环氧-亚胺树脂研究进展

环氧树脂有优异的粘结性能和良好的机械性能等而被广泛应用 ,但耐热性较差、脆性大等限制了其在高性能领域的应用 ;聚酰亚胺是一类耐热性好、机械性能等优异的工程塑料。用聚酰亚胺改性环氧树脂 ,将两者的优势结合起来 ,从而成为改善环氧树脂性能的一个有潜力的途径。介绍了几种合成环氧 亚胺树脂的方法以及树脂的性能 ,指出如何同时提高环氧 亚胺树脂的耐热性和韧性 ,在保持工艺性同时降低价格 ,是今后的研究方向。     

Toughening of epoxy resin systems using core–shell rubber particles: a literature review

Journal of Materials Science - Excellent thermal and mechanical properties and high chemical resistance with low shrinkage of epoxy resins open a wide window of various industrial applications,...     

扩链增韧环氧树脂水分散乳液的制备及性能

采用聚丙二醇对高相对分子量环氧树脂E-20进行扩链增韧,即而丙烯酸类极性单体进行自由基接枝共聚合,制备了增韧改性的环氧树脂水分散乳液。利用ZETA电位分析仪、差示扫描量热法和热重分析等对其乳液的粒径与分布、稀释行为,改性树脂的玻璃化转变温度、耐热性能及力学性能进行了测定与分析。结果表明,水分散乳液粒径随着改性树脂中羧基中和程度的增加而减小,其稀释行为与溶剂分散体系明显不同;当作为固化涂膜材料时,比较改性环氧树脂与未改性树脂,其柔韧性和耐热性能均有显著提高。     

含氟对苯型酚醛环氧树脂的制备与性能研究

将三氟甲基引入到对苯型酚醛环氧树脂体系的分子结构中,制备了新型舍氟对苯型酚醛环氧树脂(FPE)和含氟对苯型酚醛树脂固化剂(FPN).系统研究了含氟基团对环氧树脂固化物的耐热性能、力学性能和阻燃性能的影响规律,并对由其制备的环氧塑封料的综合性能进行了评价.结果表明,以含氟对苯型酚醛环氧树脂体系FPE/FPN制备的塑封料不但具有突出的绝缘性能,同时表现出优异的本征阻燃性.     

环氧树脂增韧改性的研究进展

介绍了环氧树脂韧性差、脆性大的缺点和环氧树脂增韧改性的主要途径,概述了近年来利用橡胶弹性体、热塑性树脂、液晶聚合物、无机纳米填料、有机硅、超支化聚合物、柔性固化剂以及互穿网络等方法来增韧环氧树脂的原理,分析了目前各种增韧改性技术存在的问题,指出了环氧树脂增韧技术的最新研究进展,并对将来的发展趋势进行了展望。     

Nanoparticles with various surface modifications as functionalized cross-linking agents for composite resin materials

The performance of epoxy resins used for carbon fibre reinforced plastics can be significantly improved by the incorporation of nanoparticles. It is well known that the effect of material altering depends on many factors as filler material, particle distribution, particle size and shape. This paper investigates the hypothesis that particle surface modifications lead to a further improvement of the mechanical properties. Results of nanocomposites filled with four different surface modified boehmite particles are presented. The material was tested with different filler contents and analysed for chemical bonding, viscosity, thermal properties and bending performance. Surprising results show a strong influence of the surface modification on the viscosity, but no significant changes in the other material characteristics. The change of filler content in contrast has an influence on all tested performances of the nanocomposites. The results show a contrary effect of network interruption due to sterical hindrance by the particles and reinforcement due to the stiff ceramic fillers. For different filler contents these two effects have a varying influence on the material characteristics. From these results a model for the mechanism of the particle reinforcement in thermosets is concluded, which helps to understand the effectiveness of nanoparticles as reinforcement of epoxy resins.     

Engineering the coefficient of thermal expansion and thermal conductivity of polymers filled with high aspect ratio silica nanofibers

The thermomechanical properties of epoxy filled with two different types of silica nanofillers: spherical nanoparticles and nanofibers were investigated as a function of silica nanofiller aspect ratio and concentration. Results indicated that at room temperature and at 8.74% silica nanofiber concentration (by volume) the thermal conductivity of epoxy increased twofold and coefficient of thermal expansion (CET) decreased by ∼40%. Silica nanofiber filled epoxy showed 1.4 times greater CET and 1.5 times greater thermal conductivity compared to spherical nanoparticle filled epoxy. The significant changes observed in thermomechanical properties of silica nanofiber filled epoxy were attributed to its high aspect ratio by constraining the polymer matrix as well as reducing the phonon scattering due to the formation of a continuous fiber network within the matrix. In addition to being electrically insulating, the improved properties of silica nanofiber filled epoxy make it an extremely attractive material as underfill and encapsulant in advanced electronic packaging industry.     

Preparation and properties of hollow glass microsphere-filled epoxy-matrix composites

Hollow glass microsphere (HGM)–filled epoxy composites, with filler content ranging from 0 to 51.3 vol.%, were prepared in order to modify the dielectric properties of the epoxy. The results showed that the dielectric constant (D_k) and dielectric loss (D_f) of the composites decreased simultaneously with increasing HGM content, which was critical for the provision of superior high-frequency device performance. Other properties of the composite, such as the coefficient of thermal expansion (CTE) and the glass transition temperature (T_g), were also improved. The improvement in these properties was related to strong interaction between the HGM and epoxy, which was indicated by the formation of an interphase between the HGM and epoxy-matrix. It was unsatisfactory in this study that the thermal conductivity of the composites also decreased with HGM content. In order to obtain relatively high thermal conductivity and a low dielectric constant simultaneously, this paper suggests further adding other filler.     

Effects of colloidal nanosilica on the rheological properties of epoxy resins filled with organoclay

The rheological properties of epoxy resins filled with organoclay and colloidal nanosilica were investigated by employing a parallel plate rheometer in flow mode at 25 degrees C. Shear thickening and shear thinning behaviors were observed in the epoxy resins filled with a mixture of organoclay and colloidal nanosilica. Minima were observed in the relaxation time of the systems consisting of epoxy resins filled with organoclay and colloidal silica as the content of colloidal nanosilica was increased. It seems that the colloidal nanosilica increased the mobility of the filled epoxy resins and reduced the interactions between the silicate layers in the systems.     

环氧灌封材料的研究进展

环氧树脂作为当前应用最广泛的灌封材料之一,具有优异的介电绝缘性能、热学性能和粘接性能,成型工艺简单,粘度低,优良的耐化学、湿、腐蚀性能,低固化收缩率等优点.针对环氧树脂脆性大的缺点,综述了环氧灌封材料的几种增韧方法,主要包括橡胶、核-壳结构聚合物、热塑性树脂、液晶聚合物和无机刚性粒子增韧,并介绍了环氧灌封材料的应用研究进展,最后展望了环氧灌封材料的发展趋势和前景.     

Thermal,mechanical, and conductivity properties of cyanate ester composites

Cyanate ester resins have been widely proposed as replacements for epoxy resins in high temperature applications. One such application, semiconductor encapsulation, uses a large amount of inorganic filler, typically 65 wt%. The effect of filler incorporation, on the properties of cyanate ester composites, was assessed incrementally in this work.It was found that, as is the case with epoxy based encapsulants, silica filler increased cyanate ester composite thermal conductivity, Young's modulus, and dielectric constant (slightly), and decreased encapsulant thermal expansion. It was also found that silica addition resulted in a marginal decrease in strength. This indicated a high degree of interfacial adhesion between the untreated silica filler and the cyanate ester matrix, a conclusion supported by work by Possart et al. [1].     

Incorporation of silver nanoparticles coated with mercaptosuccinic acid/poly(ethylene glycol) copolymer into epoxy for enhancement of dielectric properties

A novel route to the synthesis of polymer-coated silver nanoparticles (NPs) was developed on the basis of the reduction of Tollens' reagent using mercaptosuccinic acid/poly(ethylene glycol) (MSA/PEG) copolymer as reducing agent and stabilizer simultaneously. The average size of the polymer-coated silver NPs could be controlled in a wide range from 10 to 120 nm by changing the MSA/PEG molar ratio. These surface-coated silver NPs can be uniformly dispersed in polar solvent and a homogeneous silver NPs/acetone dispersion has been prepared. Silver–epoxy nanocomposites have been developed by incorporating these silver NPs into epoxy. The nanocomposites with silver volume content of 25% showed a more than 3000% increase in dielectric constant as compared to neat matrix and a relatively low dielectric loss below 0.05, which meets the main requirement for embedded decoupling capacitors. Moreover, thermal properties of the silver–epoxy nanocomposites were also characterized by thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA). The initial decomposition temperature and glass transition temperature were elevated with the increase of silver content, which exhibit great thermal stability and facilitate electrical applications requiring higher heat-resistance.     

低介电苯并(恶)嗪树脂的研究进展

苯并(恶)嗪树脂作为一种新型的酚醛树脂,具有分子设计性强,固化过程无小分子释放,热稳定性和力学性能优异,残炭率高等优点,使其成为电子通讯行业的重要基体材料.为满足高频、高速通信技术对低介电高分子树脂的应用需要,苯并嗪树脂的低介电改性对于信号的高频、高速传播具有重要意义,这引起了材料研究者的广泛关注.文中综述了近年来对苯并嗪树脂进行低介电改性的一系列研究工作,包括新单体合成,无机-有机杂化,与其它树脂共聚等,并对低介电苯并噁嗪树脂的研究趋势进行了概述.     

电子束固化环氧树脂温度效应影响因素分析

对环氧树脂电子束辐射过程中的温度特性进行了研究。利用实时3D温度场采集系统测定了辐射过程树脂体系的温度,探讨了环氧树脂化学结构、分子量、引发剂、稀释剂及其含量对体系温度的影响。结果表明,电子束作用于体系后,体系温度随辐射剂量的加大而升高,但当剂量达到某一值后,体系温度不再升高而保持恒定;此种热效应主要是由被辐射体系吸收高能电子能量引起的。树脂分子的吸电子能力取决于环氧树脂分子的化学结构,与分子量无关。加入稀释剂之后,体系会出现温度峰,且随着稀释剂含量的增多,温度峰峰顶温度升高。      

Analysis on the thermal and electrical characteristics of impregnating materials for the bifilar winding-type superconducting fault current limiter

The resistive type high temperature superconducting fault current limiter (HTSFCL) limits the fault current with the resistance that generated by fault current. The generated resistance by fault current makes large pulse power which makes the operation of HTSFCL unstable. So, the cryogenic cooling system of the resistive type HTSFCL must diffuse and eliminate the pulse energy very quickly. Although the best way is to make wide direct contact area between HTS winding and coolant as much as possible, HTS winding also need the impregnation layer which fixes and protects it from electromagnetic force. This paper deals with thermal conductivity and dielectric strength of some epoxy compounds for the impregnation of high temperature superconducting (HTS) winding at 77 K. The measured data can be used in the optimal design of impregnation for HTS winding. Aluminar filling increased the thermal conductivity of epoxy compounds. Hardener also affected the thermal conductivity and the dielectric strength of epoxy compounds.