Carbon/carbon composites derived from phenolic resin/silica hybrid ceramers Part I Oxidation resistance and morphological properties

A novel phenolic resin/silica hybrid ceramer fabricated via the sol-gel method was prepared. Hybrid systems with different inorganic contents were used as the matrix precursors to fabricate the silica containing carbon/carbon composites. Isothermal oxidation tests at temperatures ranging between 650°C and 750°C were employed to investigate how the oxidation resistance of the derived carbon/carbon composites is improved. Furthermore, the isothermal oxidation test results between 550°C and 615°C were used to calculate the activation energy of oxidation. Experimental results demonstrate that the silica containing carbon/carbon composites have a better oxidation resistance than those derived from pure phenolic resins. Meanwhile, morphological observations indicate that the oxidation of carbon fibers is retarded in the phenolic resin/silica hybrid derived carbon/carbon composites.     

AlB2对高硅氧纤维/可瓷化酚醛树脂复合材料及其裂解产物力学性能的影响

以AlB₂和SiC颗粒填充酚醛树脂作为基体,高硅氧纤维作为增强体,制备了高硅氧纤维/可瓷化酚醛树脂复合材料。研究了不同添加量的AlB₂颗粒对高硅氧纤维/可瓷化酚醛树脂复合材料常温和1200℃裂解产物性能的影响,并分析了AlB₂颗粒对其裂解产物的增强机制。结果表明:随着AlB₂颗粒的添加,高硅氧纤维/可瓷化酚醛树脂复合材料常温下的弯曲强度逐渐减小,但其1200℃裂解产物的弯曲强度先增大后减小。当AlB₂颗粒与酚醛树脂的质量比为12%时,裂解产物的弯曲强度提高最为显著,相比未添加AlB₂颗粒的复合材料,其裂解产物的弯曲强度提高了16.4%。AlB₂颗粒在1200℃有氧环境中反应生成由B₂O₃ 、Al₂O₃和Al₂₀B₄O₃₆组成的共熔体,填充了树脂基体裂解产生的孔隙,明显减少复合材料裂解产物的结构缺陷,阻止内部材料进一步氧化,提高了裂解产物的力学性能。      

高强度—中密度纳米孔树脂基防隔热复合材料的制备与性能

针对新一代航天器长时防隔热-高气动剪切的防热需求,以杂化酚醛树脂为基体、纤维布/纤维网胎逐层针刺结构为增强体,通过溶胶-凝胶工艺,制备出一种中密度-高强度-防隔热一体化的纳米孔树脂基复合材料(IPC-90),系统研究了石英纤维(QF/IPC-90)和碳纤维(CF/IPC-90)对复合材料的微观结构、力学性能、静态隔热和烧蚀性能的影响,探讨了其在低-中-高温度下的烧蚀机制。结果表明：纤维布的引入使IPC-90具有优异的力学性能(拉伸曲强度>120 MPa,弯曲强度>90 MPa);纳米孔基体和纤维网胎的引入使IPC-90在中密度(～0.95 g/cm³)下具有较低的热导率(室温热导率依次为0.089 W/(m·K)和0.120 W/(m·K))。在1 000℃静态隔热试验中,两种材料均展现了较好的热稳定性和抗氧化性,其等效热导率分别为0.142 W/(m·K)和0.186 W/(m·K)。在2 000℃以下氧-丙烷烧蚀试验中,QF/IPC-90和CF/IPC-90的烧蚀主要由基体热解、炭化收缩引起,其1 600℃下的线烧蚀率依次为0.0208 mm/s和...     

石墨/酚醛树脂复合材料双极板的制备与性能

双极板是质子交换膜燃料电池的重要组成部分,石墨与聚合物的复合材料双极板是目前研究的重要方向。采用模压热固化二步法,以酚醛树脂为粘结剂、天然鳞片石墨为导电骨料、炭黑为添加剂制备了质子交换膜燃料电池用复合材料双极板。系统研究了不同种类石墨对石墨/酚醛树脂复合材料电性能和抗弯强度的影响。结果表明:以天然鳞片石墨为导电原料时,所制备的石墨/酚醛树脂双极板的性能最好;添加导电炭黑能有效提高石墨/酚醛树脂复合材料的电导率;在复合材料制备中加入4wt%的碳纤维,碳纤维-石墨/酚醛树脂复合材料的抗弯强度提高了29%;碳纤维表面液相氧化处理能有效提高纤维与基体间的结合强度,随着处理时间的延长与处理温度的升高,碳纤维-石墨/酚醛树脂复合材料的电导率和抗弯强度都有很大程度的提高;最终固化温度主要影响酚醛树脂的交联程度,随着最终固化温度的升高,酚醛树脂的交联程度增加,电导率增大,但抗弯强度有一定程度减小。     

含炔基酚醛树脂改性PSA及碳纤维布/PSA-EPAN复合材料性能

合成了乙炔基苯基偶氮酚醛树脂（EPAN）,通过溶液共混的方法用其对含硅芳炔树脂（PSA）进行改性,研究了PSA-EPAN树脂的热性能,并制备了PSA-EPAN的碳布预浸料,经热模压制备碳纤维布（T300CF）增强PSA-EPAN复合材料,对其力学性能进行了研究。结果表明：EPAN均匀分布于PSA树脂中,EPAN共混改性PSA树脂的固化温度提高,混入质量分数为7%的EPAN,N₂中固化PSA-EPAN树脂在800℃残留率超过90%,其玻璃化转变温度高于500℃,PSA-EPAN共混树脂浇铸体的弯曲性能高于PSA树脂,达40.7 MPa,提高了95.5%;PSA树脂经T300CF/PSA-EPAN复合材料力学性能显著提高,弯曲强度达到了423.5 MPa,提高了74%,层间剪切强度（ILSS）提高至29.53 MPa,增加了65%。     

Lightweight carbon-bonded carbon fiber composites with quasi-layered and network structure

Lightweight carbon-bonded carbon fiber (CBCF) composites were fabricated with chopped carbon fibers and dilute phenolic resin solution by pressure filtration, followed by carbonization at 1000 °C in argon. The as-prepared CBCF composites had a homogenous fiber network distribution in xy direction and quasi-layered structure in z direction. The pyrolytic carbon derived from phenolic resin was mainly accumulated at the intersections and surfaces of chopped carbon fibers. The composites possessed compressive strengths ranged from 0.93–6.63 MPa in xy direction to 0.30–2.01 MPa in z direction with a density of 0.162–0.381 g cm^− 3. The thermal conductivity increased from 0.314–0.505 to 0.139–0.368 Wm^− 1 K^− 1 in xy and z directions, respectively. The experimental results indicate that the CBCF composites prepared by this technique can significantly contribute to improve the thermal insulation and mechanical properties at high temperature.     

高刚度环氧树脂与高模碳纤维的界面相容和性能匹配

自行开发了一种高刚度环氧树脂（5182树脂）,研究了5182树脂的增刚机制、耐热性能和力学性能。结果表明,原位生成的酰亚胺刚性链段及增加的多交联位点提高了5182树脂交联网络的刚性,其玻璃化转变温度达228℃,拉伸模量达到4 375 MPa。采用高刚度5182树脂制备了国产BHM3和东丽M40J高模碳纤维增强高刚度环氧树脂复合材料,考察了高模碳纤维/高刚度环氧树脂单丝复合材料的界面黏结性能和断面微观形貌,并评价了高模碳纤维/高刚度环氧树脂单向复合材料的宏观力学性能。结果表明,由于树脂模量的提高及界面破坏区域由碳纤维表面转移到环氧树脂区,高模碳纤维/高刚度环氧树脂复合材料的界面剪切强度最高达106.8 MPa,宏观力学性能优异,尤其弯曲性能和层间剪切强度大幅提高。      

膨胀蛭石/酚醛阻燃保温复合材料的制备及性能

以膨胀蛭石为阻燃剂,采用中温发泡方法与酚醛树脂复合制备膨胀蛭石/酚醛阻燃保温复合材料。阻燃保温复合材料通过极限氧指数、锥形量热、导热系数和表观密度分析了发泡温度、固化剂含量、发泡剂含量、表面活性剂含量、固化时间以及蛭石含量对膨胀蛭石/酚醛阻燃保温复合材料阻燃及保温性能的影响。结果表明:以膨胀蛭石为阻燃剂制备的膨胀蛭石/酚醛阻燃保温复合材料的阻燃保温性能优越、表观密度低。单因素实验结果表明,膨胀蛭石/酚醛阻燃保温复合材料的最优条件为发泡温度80℃、固化剂含量10wt%、发泡剂含量10wt%、表面活性剂含量5wt%、固化时间2 h以及蛭石含量60wt%。最优条件下的膨胀蛭石/酚醛阻燃保温复合材料表观密度为190.08 kg/m3、压缩强度为0.32 MPa、导热系数为0.054 9 W/（m·K）、极限氧指数为71.1%、平均热释放速率为15 kW/m2。      

The preparation and characterization of hybrid materials composed of phenolic resin and silica

Novel organic-inorganic hybrid materials were prepared by in situ polymerization of silicon alkoxide in a phenolic resin matrix. Very uniform hybrid materials composed of a phenolic resin and silica were obtained using varying amounts of silica. The transparency of the hybrid materials could be varied depending on the size of the resulting silica particles. SEM observations revealed that the hybrid materials consist of fine silica particles embedded in a phenolic resin matrix with good interaction at the interface. Density and ²⁹Si-NMR measurements indicate that the silica incorporated in the hybrid material has a high density and mainly Q4 chemical bonding environments. The hybrid material exhibits excellent mechanical improvements in modulus, strength, strain at break and impact strength.     

农林废物生物炭/高密度聚乙烯复合材料的制备与性能

利用稻壳、杨木在600℃下制备稻壳炭、杨木炭,以稻壳、稻壳炭、杨木、杨木炭为填料填充高密度聚乙烯(HDPE)制备复合材料,并对其性能进行测试分析.结果表明,跟稻壳、杨木相比,稻壳炭、杨木炭具有较高的含碳量、较大的比表面积、发达的孔隙结构及较低的极性;稻壳炭/HDPE复合材料的弯曲强度、弯曲模量、拉伸强度、拉伸模量分别为...     

由椴木木粉和酚醛树脂制备木材陶瓷的研究

以椴木木粉和酚醛树脂为原料制成一种新的木材陶瓷.用TGA、XRlD和SEM技术分别对木材陶瓷的形成机理、物相构成和微观结构进行了表征与研究.详细讨论了碳化温度和酚醛树脂用量对木材陶瓷显气孔率、体积电阻率和弯曲强度的影响.结果表明,木材陶瓷是由酚醛树脂生成的玻璃态的硬碳和由木粉生成的无定形的软碳组成的多孔性碳复合材料;随碳化温度升高或酚醛树脂用量的增加,木材陶瓷的显气孔率和弯曲强度增大,体积电阻率下降;碳化温度升高可以使(002)衍射峰逐渐变窄,强度增大,并且向高角度移动,晶面间距d₍₀₀₂₎减小,而酚醛树脂用量的增加对(002)衍射峰和晶面间距d₍₀₀₂₎基本没有影响;当碳化温度为1350℃,酚醛树脂用量为160wt％时,木材陶瓷的显气孔率、体积电阻率和弯曲强度分别达到了50％、2.0×10^-2Ω·cm和25MPa.     

Investigation of the effect of rice husk derived Si/SiC on the morphology and thermal stability of carbon composite aerogels

Highly porous carbon aerogels were prepared by pyrolyzing the novolac–silica aerogels. The silica phase was extracted from rice husk ash (RHA). The polymer aerogel was synthesized via the novel method of sol–gel polymerization in solvent vapor-saturated atmosphere. This method removes the need for supercritical drying and reduces the shrinkage of aerogels during drying stage and also has much lower process time compared to the conventional sol–gel method. In the next step, polymer composite aerogels become carbon/silica and carbon/silica/silicon carbide composites in pyrolysis (800 °C) and carbothermal reduction (1500 °C) stages, respectively. The characterization of the prepared composite aerogels was performed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) analyses, respectively. Thermal and mechanical properties of the samples were investigated by differential scanning calorimetry (DSC) and compressive strength analysis. The resultant composite aerogels show a nanostructure with high porosity (above 82%) and low density (below 0.3 g cm^− 3). Si mapping images showed the good distribution of silica phase throughout the carbon matrix. Also the rate of oxidation for carbon composites decreased by silica incorporation and oxidation temperature increased about 20% by adding RHA silica. Compressive strength of composite samples increased about 25% by increasing RHA silica phase content.     

碳化铪含量对C/C复合材料喉衬烧蚀性能的影响

将炭毡浸渍于饱和的HfOCl2.8H2O乙醇溶液中,经600℃热处理形成HfO2/C复合材料,然后采用热梯度化学气相沉积工艺在2100℃进行致密化和石墨化处理使HfO2转化为HfC而得到碳化铪(HfC)改性、整体炭毡增强的炭/炭(HfC-C/C)复合材料整体喉衬。利用小型固体火箭发动机试车台装置,在7MPa、3200℃烧蚀3s以测定HfC含量对喉衬烧蚀性能的影响。结果表明,HfC质量分数为5.7%的HfC-C/C喉衬线烧蚀率减小了25.2%;HfC质量分数为8.7%的HfC-C/C喉衬线烧蚀率减小了49.6%。同时,当HfC质量分数为5.7%时,HfC-C/C喉衬出现了以恒定线烧蚀率为特征的稳态烧蚀阶段,且该阶段的持续时间随HfC含量的增加而增加。     

Effects of fibre surface silanisation on silica fibre/phenolics composites produced by resin transfer moulding process

Abstract

The effects of fibre surface silanisation on silica fibre/phenolics composites produced by the resin transfer moulding (RTM) solution impregnation route were investigated. Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and micro-Wilhelmy method were used to evaluate the surface properties of silanised silica fibre. The interlaminar shear strength (ILSS) measurements and morphological observations of the silica fibre/phenolics composites were also performed. The interactions occurring between silica fibre and the components of phenolic resin solution affect the dynamic adsorption behaviour of phenolic resin onto fibre reinforcement. The competitive adsorption of ethanol as solvent onto silica fibre suppresses that of phenolic resin. Fibre surface silanisation by γ-aminopropyl-triethoxysilane (γ-APS), γ-glycidoxypropyl-trimethoxysilane (γ-GPS) and γ-methacryloxypropyl-trimethoxysilane (γ-MPS) leads to the improvement of mechanical interfacial properties of silica fibre/phenolics composites on one hand and decreases the inhomogeneities of resin distribution and mechanical interfacial properties at different regions of the RTM product on the other hand.     

Effect of chopped Si–Al–C fiber addition on the mechanical properties of silicon carbide composite

Silicon carbide (SiC) composites containing 0–50 mass% of chopped Tyranno^® Si–Al–C (SA) fiber (mean length: 214 μm (SA(214)), 394 μm (SA(394)), and 706 μm (SA(706)) were fabricated using the hot-pressing technique at 1800 °C for 30 min under a uniaxial pressure of 31 MPa in Ar atmosphere. The maximum flexural strength of the SiC composite was 344 MPa for 30 mass% of SA(706) fiber addition, whilst the maximum fracture toughness was 4.7 MPa m^1/2 for 40 mass% of SA(706) fiber addition. Increasing the mean fiber length from 214 to 706 μm decreased the flexural strength from 380 to 281 MPa for 30 mass% of fiber addition, whilst the fracture toughness increased from 3.4 to 4.7 MPa m^1/2 for 40 mass% of fiber addition. Through use of a treated SA(706) fiber containing an approximately 100 nm surface layer of carbon, the fracture toughness further increased to 6.0 MPa m^1/2 for 40 mass% of fiber addition; this value was more than twice that of the monolithic SiC ceramic and is believed to be the highest so far achieved for this type of SiC/SiC composite containing chopped fibers.     

竹炭/酚醛树脂复合导电材料的制备与性能

以碳化温度为900 ℃的竹炭为导电骨料、 酚醛树脂为黏结剂、 炭黑为添加剂, 采用模压成型法制备竹炭/酚醛树脂复合导电材料。考察了竹炭的粒度、 酚醛树脂用量、 炭黑用量、 成型压力及固化温度等工艺因素对竹炭/酚醛树脂复合导电材料导电性和抗弯强度的影响。结果表明: 随着酚醛树脂用量的增加, 复合材料的抗弯强度增大, 电导率先增大后减小; 增加成型压力可同时提高复合材料的电导率和抗弯强度; 增大竹炭粉粒的粒径、 增加炭黑用量、 提高固化温度有利于改善复合材料的导电性, 但会不同程度地改变复合材料的力学性能。制备竹炭/酚醛树脂复合导电材料的最佳工艺条件为: 竹炭粒度≤75 μm, 树脂用量30%, 炭黑用量7.5%, 成型压力280 MPa, 固化温度180 ℃。      

Preparation of polybenzoxazine foam and its transformation to carbon foam

An organic foam derived from a new type of phenolic resin, namely polybenzoxazine, was successfully prepared with a noncomplex and economical foaming method by using azodicarbonamide (AZD) as a foaming agent. The influence of foam density on the physical and mechanical properties of the foams was studied. All resulting polybenzoxazine foams and carbon foams exhibit a tailorable uniform microstructure. Polybenzoxazine foams showed a density in the range of 273–407 kg/m³, and a compressive strength and a compressive modulus in the range of 5.2–12.4 MPa and 268–681 MPa, respectively. The foam density not only affects the physical and mechanical properties, but also affects the deformation response of the foam. In addition, the polybenzoxazine foam was further transformed into carbon foam by carbonization at 800 °C under an inert atmosphere, and its properties were examined.     

炭基复合材料与人骨的力学性能对比分析

选用3种炭基复合材料,分别为采用化学气相沉积（CVD）工艺和CVD/浸渍复合工艺制备的2种C/C复合材料以及采用CVD/熔融渗硅（MSI）工艺制备的C/C-SiC复合材料,通过对比分析3种炭基复合材料与人骨的微观结构和力学性能,研究了所选用的3种炭基复合材料作为新型骨折内固定材料的可行性。结果表明:3种炭基复合材料与人骨均具有纤维增强、多孔基体的微观结构形态。在力学性能方面,3种炭基复合材料的弹性模量与人骨都较为接近,其中C/C-SiC复合材料的力学性能与人骨最为接近,分别为弯曲强度213.0 MPa、剪切强度19.3 MPa、压缩强度228.1 MPa,有望成为理想的接骨板材料。CVD和CVD/浸渍工艺制备的C/C复合材料,弯曲强度分别仅为161.8 MPa和174.6 MPa,低于人骨的弯曲强度,后期可通过改进坯体结构和制备工艺等方法来使其力学性能与人骨相匹配。      

碳泡沫导热性能及力学性能研究

用微胶囊化得到的空心酚醛树脂微球制备出酚醛泡沫材料, 在Ar气的保护下进行1000℃碳化和2000℃的石墨化处理, 得到所需的泡沫材料. 研究了孔隙率、热处理温度等因素对碳泡沫导热性能的影响. 结果表明: 提高材料内部空心微球的比例可以降低材料的导热性能, 得到低热导率的泡沫材料; 而对于孔隙率接近的泡沫材料, 降低材料内部的孔径可以起到降低材料热导率的作用; 得到了密度为0.50g/cm³, 热导率为1.007W/m·K, 压缩强度为8.82MPa的碳泡沫材料.     

The manufacture and mechanical testing of thermosetting natural fibre composites

High volume fraction hemp and flax fibre composites were manufactured using low viscosity epoxy and phenolic resins. Using 80% volume fraction of flax fibres in epoxy resin, composites with a mean stiffness of 26 GPa and a mean strength of 378 MPa were produced. By reducing processing damage of the plant fibres mechanical properties could be increased by 40%. Strips of retted fibre tissue were found to be just as effective for reinforcement as fibre bundles and individual fibres. Phenolic resin and decorticated flax fibres produced very poor composites. Using 40% volume fraction of fibres the mean stiffness was 3.7 GPa and the mean strength was 27 MPa. Two fibre pre-treatments were devised to improve adhesion with resins. The first, 6 M urea was used only in natural fibre-epoxy composites where it increased the stiffness but not the strength. The second pre-treatment was a 50% PVA solution, which was cured prior to the addition of space filling resin. The PVA treatment improved the stiffness and strength of both natural fibre-epoxy composites and natural fibre-phenolic composites.