后热处理对C_f/ZrC复合材料微观结构及性能的影响

以C/C复合材料为基材、Zr_2Cu合金为渗剂,采用低温反应熔渗工艺制备得到碳纤维增强碳化锆陶瓷基复合材料(Cf/ZrC),重点研究后热处理对Cf/ZrC复合材料微观结构及性能的影响。结果表明:经1400~2200℃热处理后,材料密度下降,开孔率增大;材料在后热处理过程中会发生残余富铜熔体的流失、ZrC基体体积分数的增加以及ZrC基体结构的破坏;后热处理造成材料力学性能下降,热处理温度达到2200℃时,材料的弯曲强度保留率仅为52.3%。     

碳化锆陶瓷复合材料的制备、显微组织与性能

碳化锆(ZrC)陶瓷复合材料具有熔点高、密度低、耐烧蚀的优点, 在超硬、航天防热、新能源等领域应用前景广阔。本文概述了ZrC金属陶瓷和复相陶瓷、纤维增强ZrC复合材料的制备方法。着重介绍了粉末烧结、先驱体转化、反应浸渗等工艺的应用, 并讨论了不同制备工艺下复合材料显微组织的特点。在总结两类材料力学性能和烧蚀性能的基础上, 分析了各自的影响因素, 并指出ZrC金属陶瓷和复相陶瓷韧性低, 纤维增强ZrC复合材料烧蚀层易剥落的问题。最后总结展望了ZrC陶瓷复合材料相关研究的发展趋势。     

C/C-ZrC复合材料的微观结构和力学性能研究

采用ZrOCl₂溶液浸渍法把锆化合物引入碳纤维预制体, 经热处理、热梯度化学气相渗透致密化和高温石墨化工艺制备了C/C-ZrC复合材料。性能测试结果表明, C/C复合材料的弯曲强度和模量随ZrC含量的增加而增大, ZrC含量为12.08wt%时, 其强度和模量分别为42.5 MPa 和9.6 GPa, 比未改性试样分别提高了70.0%和43.3%。基体中结合较弱的微米级ZrC颗粒的存在不利于碳基体强度的提高, 但其对材料最终性能的影响是次要的, 碳基体中亚微米/纳米级ZrC颗粒的存在和良好的ZrC-C界面结合, 提高了碳基体的强度和模量, 进而提高了复合材料的最终性能。     

基于离心纺丝技术制备稳定的碳化锆纤维

本研究提出了一种利用离心纺丝技术制备稳定碳化锆(ZrC)纤维的有效方法。此方法使用醋酸锆和蔗糖作为锆源和碳源, 聚乙烯吡咯烷酮(PVP)作为纺丝助剂, 经过1600 ℃的裂解与碳热还原热处理后, 所纺原丝转化成由均匀纳米ZrC晶体组成的ZrC纤维。研究结果表明, 纤维中残留的少量碳可助力ZrC纤维在2000 ℃的超高温环境下仍保持较好的结构稳定性。     

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.     

化学气相沉积ZrC陶瓷涂层的微观结构和抗烧蚀性能

为了提高碳／碳（C／C）复合材料的抗烧蚀性能,在C／C基体上成功制备了碳化锆（ZrC）高温抗烧蚀涂层。用常压化学气相沉积法,前驱体选用ZrCl4＋C3H6＋H2＋Ar体系。通过调节C3H6的流量,制得3种碳锆原子比的ZrC陶瓷涂层（ZrC1.0＋C,ZrC1.0,ZrC0.7）。分析了不同锆碳比ZrC涂层的相组成和形貌差异,研究了锆碳比对ZrC陶瓷涂层的烧蚀性能的影响。结果表明,3种ZrC涂层都可有效提高C／C复合材料的抗烧蚀性能,但由于微观结构特征不同,3种涂层显示不同的烧蚀性能和烧蚀机制。其中,ZrC0.7涂层试样烧蚀后,表面形成致密的氧化物层,烧蚀性能最佳,烧蚀240s后质量烧蚀率和线烧蚀率分别为1．1×10^-4g／cm^2·s和0．3×10^-3mm／s。     

普通纸张模板纤维素碳化机理的研究与多孔木材陶瓷的制备

以普通纸张和酚醛树脂为模板制备出新型多孔碳模板,深入研究纤维素碳化的机理.碳化过程的收缩率随树脂/纸张复合体中树脂含量的增大而减小;所得多孔碳的气孔率随树脂/纸张复合体中树脂含量的增大而减小,且随碳化温度的升高而减小;多孔碳的弯曲强度随树脂/纸张复合体中树脂含量的增大而增大,并随碳化温度的升高而增大.     

基于激光选区烧结的煤系高岭土多孔陶瓷的制备及其性能

以煤系高岭土为原料,采用激光选区烧结(SLS)技术制造复杂结构的多孔陶瓷,研究SLS工艺参数和烧结温度对煤系高岭土多孔陶瓷性能的影响。利用X射线衍射仪(XRD)和扫描电子显微镜(SEM)表征煤系高岭土多孔陶瓷的物相组成和显微形貌。结果表明:煤系高岭土/环氧树脂E12复合粉末SLS成型效果良好;当激光功率为5W,扫描速率为2000mm/s,扫描间距为0.13mm,单层层厚为0.15mm时,陶瓷素坯可获得最佳的成型质量,其尺寸误差(Z方向),相对密度和抗弯强度分别为10.43%,37.89%和0.984MPa。随着烧结温度的升高,煤系高岭土多孔陶瓷的收缩率和抗弯强度逐渐增大,而显气孔率则逐渐减小;当烧结温度为1450℃时,煤系高岭土多孔陶瓷具有较高的显气孔率和抗弯强度,分别为44.55%和6.1MPa。煤系高岭土多孔陶瓷的主晶相为莫来石,具有典型的三维网络骨架结构。     

气压浸渗法制备ZrC-W-Cu复合材料的显微组织与力学性能

为提高钨渗铜材料的性能以适应先进推进技术发展的需求,以ZrC粉和W粉为原料,采用无压烧结工艺制备ZrC-W多孔骨架,进而采用气压浸渗工艺对开气孔在20％左右的ZrC-W骨架压力渗铜,制备出ZrC-W-Cu复合材料.研究ZrC含量对ZrC-W骨架开气孔率、压缩强度及ZrC-W-Cu复合材料的显微组织和力学性能的影响规律.结果表明:随着ZrC含量(体积分数,下同)的增加,ZrC-W骨架的开气孔率先升高后降低,在ZrC含量为10％时开气孔率最大,为29.77％;ZrC-W骨架的压缩强度随ZrC含量的增加而下降,且整体低于W骨架;ZrC-W-Cu复合材料维氏硬度随ZrC含量的增加逐步增大,在ZrC含量为15％时达到3.26 GPa;弹性模量基本不变;断裂韧度随着ZrC含量的增加先升高后降低,抗弯强度在ZrC含量为4％时达到最大值,为1243 MPa.     

自蔓延高温原位合成ZrC/Cu复合材料

采用自蔓延高温合成工艺,原位合成了ZrC/Cu复合材料.利用DTA、XRD、FE-SEM等手段,研究了自蔓延高温合成ZrC/Cu复合材料的反应行为.实验结果表明,随着Cu含量的增加,Cu-Zr-C体系的燃烧温度逐渐降低,且合成产物中ZrC颗粒尺寸亦随之减小,其形貌从不含Cu时的无规则的大块状转变为含30%(质量分数)Cu时的纳米级的小球状.ZrC/Cu复合材料中只有ZrC颗粒和Cu两相存在,并无Cu-Zr中间相形成.DTA热分析的结果显示反应起始于912℃时生成的Cu10Zr7中间亚稳相,然后在987℃生成CuZr2中间相,当温度达到1022℃,将会生成部分的ZrC,继续加热到1098℃,Cu开始熔化,最后温度为1232℃时,Zr与C发生剧烈反应从而合成大量的ZrC.     

孔隙率对三维针刺C/C复合材料电磁屏蔽性能的影响

通过多次重复先驱体浸渍裂解(PIP)工艺过程,改变材料的孔隙率和体密度,制备不同孔隙率的三维针刺碳/碳(C/C)复合材料,并研究了在8.2~12.4GHz频率范围内(X波段)不同孔隙率C/C复合材料的电磁屏蔽效能。结果表明:适当降低孔隙率有利于提高C/C复合材料的总电磁屏蔽效能和电磁吸收屏蔽效能,当开气孔率为33.4%时,C/C复合材料具有最大的电磁屏蔽效能(40dB),且电磁吸收屏蔽效能(30dB)远大于电磁反射屏蔽效能(12dB),是极具潜力的高吸收低反射电磁屏蔽材料。     

酚醛树脂/木粉复合材料制备木材陶瓷结构变化过程研究

酚醛树脂/椴木木粉复合材料经高温真空碳化制成了木材陶瓷。利用XRD、SEM和FTIR技术对碳化温度和酚醛树脂/木粉质量比对木材陶瓷物相、微观结构和物理化学结构变化的影响进行了表征和研究。结果表明,木材陶瓷具有拓扑均匀的连通孔的三维网络结构,是含有C C、C—O—C和C—H等基团的类石墨结构的碳/碳复合材料;随碳化温度的升高,(002)峰强度增大,晶面间距d₍₀₀₂₎降低,碳化木粉收缩,其间隙增大;酚醛树脂/木粉质量比增大,浸渍树脂的木粉成形能力改善,所得木材陶瓷结构更均匀,但其对木材陶瓷的XRD衍射花样影响不大。      

X-ray diffraction studies ofAcacia andEucalyptus wood chars

Acacia andEucalyptus wood chars, prepared at various temperatures in the range 400–1200°C, have been studied by X-ray diffractometry. The objective was to investigate the changes in structural ordering in relation to carbonization temperature and time. For both theAcacia andEucalyptus wood chars, the apparent interlayer spacing (d ₀₀₂) decreased slightly while the apparent microcrystallite diameter,L _a, increased markedly with increasing carbonization temperature. The trend was, in general, similar with increased soaking time at carbonization temperatures of 800 and 1000°C, but these X-ray properties (i.e.d ₀₀₂ andL _a) were found to be more susceptible to carbonization temperature than to time. The results also showed that both the wood species, when carbonized under identical conditions, yielded chars with practically similar diffraction profiles.     

Fabrication,properties, and cytocompatibility of ZrC film on electropolished NiTi shape memory alloy

The microstructural characteristics, mechanical properties, and cytocompatibility of ZrC films deposited on electropolished NiTi shape memory alloy (SMA) by magnetron sputtering are investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), nanoindentation, and MTT test. The deposition rate of the ZrC film is smaller than the pure Zr film. Although ZrC is the only phase in the film, the pure ZrC film with small oxygen content is non-stoichiometric. The hardness and modulus increase initially with larger nanoindentation depths, reach maximum values, and then gradually decrease afterwards as a result of the composite effects of the ZrC film and NiTi substrate. Deposition of the ZrC film promotes proliferation of fibroblasts revealing enhanced cytocompatibility compared to uncoated NiTi.     

Carbonization behavior of coal tar pitch modified with benzoquinone

A soluble fraction of coal tar pitch (CP) in tetrahydrofuran (THF) was reacted with p-benzoquinone (BQ) at 160 and 180°C and followed by carbonization and graphitization. The reaction and carbonization behavior were monitored in-situ by using differential scanning calorimeter, high-temperature ¹H NMR and high-temperature ESR. The reactions of CP and BQ resulted in an increase in molecular weight with an increase in BQ concentration. Such molecular weight increases led to the formation of a less ordered structure due to the reduced mobility of the molecules. The relative order of the carbonized materials was determined by using polarized light microscope and X-ray diffraction. The molecular size of the precursor was recognized as an important factor in determining the morphology of carbon materials.     

Laminated biomorphous SiC/Si porous ceramics made from wood veneer

Biomorphous SiC/Si porous ceramics with laminated structure are prepared from beech veneer and phenolic resin. The preparation involves carbonization under vacuum and reaction with melted silicon to obtain the biomorphous carbide template. X-ray diffraction confirms that the biomorphous SiC/Si porous ceramics are mainly composed of β-SiC, free silicon and residual carbon. Scanning election microscopy observations indicate a laminated structure and 1–10 μm microporous structures, which suggest retention of the native characteristics of the wood. This paper examines mechanical properties of the final composite in relation to the lamination, porous structure, and free silicon content. The bending strength of the ceramics decreases as the apparent porosity increases. The fracture toughness increases initially with apparent density and then decreases. The fracture toughness load–displacement curve presents a step-like pattern, which suggests that the laminated SiC/Si porous ceramics have high fracture toughness.     

Microstructure and thermal conductivity of carbon/carbon composites containing zirconium carbide

Carbon/carbon (C/C) composites containing zirconium carbide (ZrC) were prepared by a novel method. Carbon fiber felt with addition of zirconia was prepared by a microwave-hydrothermal reaction, followed by densification and graphitization. The crystalline structure of the pyrolytic carbon and morphology of the composites were investigated by X-ray diffraction, Raman spectrascope, polarized light microscope, and scanning electron microscopy. Results show that the ZrC grains with sub-micron size present a homogeneous distribution in carbon matrix. The degree of order of the pyrolytic carbon matrix is decreased due to adding ZrC into the C/C composites. Graphitization degree of the C/C composites is decreased by the addition of ZrC. ZrC grains uniformly embedded in the pyrolytic carbon matrix act as pinning particles blocking the conversion of disordered to ordered structure during graphitization. Thermal conductivity is higher in the C/C composites containing ZrC, which is attributed to the increased phonon-defect interaction produced by the thermal motion of the CO in the micropores and gaps of the composites.     

Scanning electron microscopic study of acacia and eucalyptus wood chars

SEM studies of acacia and eucalyptus wood chars, prepared under different carbonization conditions, were undertaken to provide information on what happens in the transformation of wood to chars. The material normally lost as volatiles contributes totally to the formation of pores, cracks and pyrolytic carbon. Both woods exhibited similar devolatilization behaviour in pore structure development, crack formation and pyrolytic carbon deposition, showing a decrease in pore size with an increase in carbonization temperature and cracks/voids formation during rapid carbonization at higher temperatures (i.e. 800–1050 °C). Slow carbonization led to pyrolytic carbon deposition in resulting wood char structures and did not disturb the fibrous nature and cell structures of the wood, even at a high carbonization temperature of 1200 °C. Prolonged heating at carbonization (slow) temperatures of 800 and 1000 °C caused sintering of the adjacent fibres resulting in the formation of compacted mass.     

Combustion synthesis of ZrB2-SiC composite powders ignited in air

ZrB₂-SiC composite powders have been synthesized by combustion synthesis in air, using a mixture of Zr, B₄C and Si as raw materials. It was found that the air atmosphere has played an important role in the ignition process of the SHS reaction. Three other kinds of ZrB₂-SiC-ZrC composite powders with different ZrC content were also synthesized, and the ignition time has been measured for better understanding the ignition mechanism. As a result, the composite powders with particle size smaller than 1 µm and oxygen content as low as 0.4 wt.% were obtained.