采用在SiC毡上CVD—SiC涂层提高C／C复合材料抗氧化性能

最近发展起来的SiC纤维复合涂层，也就是SiC/SiC层与化学气相沉积（CVD）SiC结合形成复合涂层，已能够在高温下提高C／C复合材料的抗氧化性。形成的SiC纤维复合涂层约300μm厚，生产时先将SiC毡覆盖在3D－C／C基体材料上，然后浸渍一种碳粉与硅粉均匀分散的料浆进行化学气要沉积。通过化学气相沉积（CVD）过程，在复合材料上形成致密的涂层。在CO2－H2O－N2组成的混合气体（CO2 9％、N273％、H2O18％），1700℃下进行5h氧化实验，结果发现有SiC毡增强复合涂层比没有SiC毡增强复合材料失重率低。SiC纤维毡复合涂层由双层结构组成，里层是多气孔的SiC/SiC纤维层，外层为致密的SiC涂层。由于SiC/SiC纤维层热膨胀系数介于C／C复合基体材料与CVD－SiC涂层之间，因此，SiC/SiC中间层在复合材料中起了重要作用，从而由于热膨胀系数不同产生的热应力致使涂层开裂降低到最低程度。涂层试样氧化后，采用缓冲冲床（MSP）测试其残余强度。MSP测试结果表明氧化后C／C复合材料强度值呈发散性，从纤维折断面看有z轴方向分布纤维存在。然而，这种方法仅适用于测试小尺寸试样。从这篇论文中，可看出涂层后的C／C复合材料有高的抗氧化性，其氧化后仍能保持高的残余强度。     

c—SiC—B4C复合材料的制备及其抗氧化性能研究

以生石油焦为炭质原料,向其中掺入定量SiC、B4CN瓷相,以改质煤焦油沥青作为粘结剂,通过模压制备出C—SiC—B4C复合材料。通过XRD、SEM、DTA—TG、EDS等分析方法研究了SiC、B4CNJ瓷相对C—SiC—B4C复合材料结构和性能的影响。研究表明,C—SiC—B4C复合材料的高温抗氧化性与氧化温度、各陶瓷相含量、本身气孔率等有关。掺入的Sic、B4C能够在一定程度上降低炭材料的气孔率,同时,高温条件下陶瓷相形成硼硅酸玻璃覆盖炭基体表面,减少材料表面活性区域数量,提高炭材料的表观活化能。     

B_4C-C复合材料抗氧化行为研究

用混合磨碎法制备了B4C－C复合材料，考查了不同B4C含量、温度、湿度以及空气流量对复合材料抗氧化行为的影响，并讨论了其影响机制。     

热处理温度对C／C复合材料摩擦磨损性能的影响

利用销一盘式摩擦磨损试验机研究了不同热处理温度制备C／C复合材料与GCrl5钢配副在油润滑务件下的摩擦磨损行为。结果表明,在油润滑条件下,材料摩擦系数低,其值在0．06～0．17范围内,磨损率在（1．03～2．56）×10^4mg／N·m范围,其中2100℃热处理的材料具有最低的摩擦系数和磨损率。在摩擦试验过程中,2000℃以上热处理的材料可以形成完整致密的摩擦膜,能起到润滑作用。结果还表明,随热处理温度的提高,材料石墨化程度提高,硬度降低,其磨损机制以磨粒磨损为主转向以疲劳磨损和粘着磨损占据主导地位。     

热压碳化硼氧化行为及其对摩擦特性的影响

研究了热压碳化硼在973－1273K的氧化行为及其对摩擦性能的影响。氧化试样用X射线衍射分析其成分。用电子显微镜观察其微观形貌。结果表明,氧化试样表面生成一层薄而透明的B2O3薄膜。由于B2O3与B4C材料的热膨胀系数相差甚远,因而冷却时发生龟裂B2O3继而与空气中的水蒸汽发生反应,生成白色的H3BO3。H3BO3是一种固体润滑剂,当其出现于碳化硼摩擦副表面,可将摩擦系数由未经氧化处理的B4C／B4C摩擦副的0．25－0．35降至0．05左右,但氧化温度达1273K时,由于表面氧化腐蚀较严重,可能造成表面颗粒剥落,不利于降低摩擦系数。     

先驱体转化-热压单向Cf/SiC复合材料的高温弯曲力学行为

研究了采用先驱体转化－热压烧结制备的单向C1／SiC复合材料室温,1573,1723,1923K温度下力学行为,并从显微结构的特征分析了单向Cf/SiC复合材料高温力学行为的变化原因,结果表明：C1/SiC复合的室温,1573,1723,1923K温度下弯曲强度分别为550,392,394,574MPa,弯曲模量分别为157,148,132,83GPa,Cf/SiC复合材料破坏时,其破坏方式将从室温和573K的分层断裂向1723K,1923K的脆性断裂转化,Cf/SiC显微结构的分析表明,在纤维周围和大晶粒间存在着大量的有一定结晶程度的玻璃相,它在高温时的软化对Cf/SiC复合材料的高温强度和弯曲模量变化规律起到重要的支配作用。     

表层SiC梯度分布Cf/C-SiC复合材料的制备与组织性能研究

为提高Cf/C复合材料的高温抗氧化性能，采用RCLD工艺技术，利用二次沉积法，沉积温度为700～1200℃，系统压力为0．1MPa，制备了表层SiC含量呈梯度分布的Cf／C复合材料。试样表层约1mm内，SiC含量由2．54wt％逐渐减少的梯度层。结果表明：新材料的耐磨性能较C1／C复合材料高20倍；同等氧化失重条件下，氧化相对质量损失是Gf／C复合材料的1／3。RCLD工艺具有操作简单，易于控制，生产成本低的突出特点。     

SiC/FexSiy复合材料抗氧化性能研究

对以铁尾矿为主要原料制备的SiC/FexSiy复合材料进行抗氧化性能实验.变温氧化实验结果表明,复合材料在1000℃下有很好的抗氧化性能,而在1180℃以上氧化明显加剧.随氧化时间的延长,扩散成为控制性环节,表现为保护性氧化.复合材料在整个变温氧化过程中,表现为先失重再增重;1210℃时,增重达到最大值;整个变温氧化过程分为三个阶段:(1)增重阶段;(2)恒重阶段;(3)失重阶段.复合材料的氧化规律服从化学反应控速-混合控速-扩散控速三段模型.通过对复合材料恒温氧化动力学推导,求出材料在不同阶段表观活化能及频率因子,进而可推导出各阶段氧化速度常数k和温度T(K)的经验关系式.     

C/C多孔体的制备及其对C/C-SiC-Si复合材料的影响

C／C—SiC—Si材料是一种新型的复合材料。本文通过反应熔渗法将液态硅渗入C／C多孔体中得到致密的C／C—SiC—Si复合材料。重点研究了制备C／C多孔体的树脂浸渍裂解法，并测定了在不同浸渍次数下得到的不同的C／C多孔体的体积密度和气孔率，用扫描电镜观察了其形貌，讨论了不同的C／C多孔体对C／C—SiC—Si复合材料最终形貌的影响。     

脉冲FCVI制备炭/炭复合材料的氧化行为

采用脉冲强制流动热梯度化学气相渗透工艺(IFCVI)制备了炭/炭复合材料(C/C复合材料),利用等温氧化实验对C/C复合材料在不同温度(673～1173 K)条件下的氧化行为进行了研究,并借助于扫描电子显微镜观察了C/C复合材料的氧化形貌.实验结果表明:C/C复合材料的基体在氧化反应中优先氧化,氧化反应速率随温度的升高而增大;在高于或低于临界温度973 K时,C/C复合材料的氧化反应分别受2种不同机制控制,其反应活化能分别为1.29×105 J/mol和2.94× 104 J/mol.     

High‐Temperature Isothermal Oxidation of Ultra‐High Temperature Ceramics Using Thermal Gravimetric Analysis

Oxidation of ZrB₂ + SiC composites is investigated using isothermal measurements to study the effects of temperature, time, and gas flow on oxidation behavior and microstructural evolution. A test method called dynamic nonequilibrium thermal gravimetric analysis (DNE‐TGA), which eliminates oxidation during the heating ramp, has been developed to monitor mass change from the onset of an isothermal hold period (15 min) as a function temperature (1000°C–1600°C) and gas flow (50 and 200 mL/min). In comparing isothermal to nonisothermal TGA measurements, the scale thicknesses from isothermal tests are up to 4 times greater, indicating that oxidation kinetics are faster for isothermal testing, where the oxide scale thickness is 110 μm after 15 min at 1600°C in air. Isothermal oxidation followed parabolic kinetics with a mass gain that is temperature dependent from 1000°C–1600°C. The mass gain increased from ~5 to 45 g/m² and parabolic rate constants increased from 0.037 to 2.2 g²/m⁴·s over this temperature range. The effect of flow velocity on oxidation is not significant under the given laminar flow environment where the gas boundary layer is calculated to be 4 mm. These values are consistent with diffusion of oxygen through the glass‐ceramic surface layer as rate limiting.     

A low-temperature prepared composite coating to protect SiC-coated C/C composites against oxidation in a wide temperature range for long-life service

To improve the oxidation resistance of carbon/carbon (C/C) composites in a wide temperature range (1173–1773 K), a composite coating containing rich B₂O₃ glass was prepared on SiC-coated C/C composites by slurry dipping-densifying at low temperature. Borosilicate and SiO₂ glasses acted as oxygen barriers at low and medium-high temperatures, respectively. Besides, Hf-oxides (HfO₂, HfSiO₄) ceramic particles improved the thermal stability of the glass and enhanced the crack resistance of glass layer. Therefore, the composite coating can effectively protect C/C composites against oxidation for 403 h at 1173 K, 723 h at 1473 K and 403 h at 1773 K with the mass gain of 3.77 g·m⁻², 21.41 g·m⁻² and 0.42 g·m⁻², respectively. After 50 times thermal cycles between room temperature and 1773 K, the mass gain of the coated sample was 3.95 g·m⁻² and the mass retention rate was up to 98.19 % during the thermos-gravimetric test from room temperature to 1773 K.     

B4C／C复合材料高温氧化过程中的结构变化模型的研究

在用混合磨碎法制备Ｂ４Ｃ／Ｃ复合材料的基础上,考察了不同条件对复合材料氧化失重速率的影响,然后讨论了上述各因素对复合材料抗氧化性能的影响机制,并对复合材料结构与其自愈合功能的性进行了分析,在此基础上建立了复合材料高温氧化过程的结构变化模型。     

Dynamic mechanical properties of oil palm fiber/phenol formaldehyde and oil palm fiber/glass hybrid phenol formaldehyde composites

The dynamic mechanical properties of oil palm fiber reinforced phenol formaldehyde (PF) composites and oil palm/glass hybrid fiber reinforced PF composites were investigated as a function of fiber content and hybrid fiber ratio. The dynamic modulus of the neat PF sample decreases with decrease in frequency. Glass transition attributed with the α relaxation of the neat PF sample was observed around 140°C. Tanδ values and storage modulus show great enhancement upon fiber addition. The value increases with increase in fiber content. The loss modulus shows a reverse trend with increase in fiber loading. Incorporation of oil palm fiber shifts the glass transition towards lower temperature value. The glass transition temperature of the hybrid composites is lower than that of the unhybridized composites. The highest value of mechanical damping is observed in hybrid composites. Storage modulus of the hybrid composites is lower than unhybridized oil palm fiber/PF composite. A similar trend is observed for loss modulus. Activation energies for the relaxation processes in different composites were calculated. Activation energy is increased upon fibrous reinforcement. Complex modulus variations and phase behavior of the composites were studied from Cole‐Cole plots. Finally, master curves for the viscoelastic properties of the composites were constructed on the basis of time‐temperature superposition principle. POLYM. COMPOS., 26:388–400, 2005. © 2005 Society of Plastics Engineers     

Oxidation behavior of oxidation protective coatings for PIP-C/SiC composites at 1500 °C

Three-dimensional carbon fiber reinforced silicon carbide (C/SiC) composites were fabricated by precursor infiltration and pyrolysis (PIP) with polycarbosilane as the matrix precursor, SiC coating prepared by chemical vapor deposition (CVD) and ZrB₂-SiC/SiC coating prepared by CVD with slurry painting were applied on C/SiC composites, respectively. The oxidation of three samples at 1500 °C was compared and their microstructures and mechanical properties were investigated. The results show that the C/SiC without coating is distorted quickly. The mass loss of SiC coating coated sample is 4.6% after 2 h oxidation and the sample with ZrB₂-SiC/SiC multilayer coating only has 0.4% mass loss even after oxidation. ZrB₂-SiC/SiC multilayer coating can provide longtime protection for C/SiC composites. The mode of the fracture behavior of C/SiC composites was also changed. When with coating, the fracture mode of C/SiC composites became brittle. When after oxidation, the fracture mode of C/SiC composites without and with coating also became brittle.     

A Si–Mo–W Coating to Protect SiC-Coated Carbon/Carbon Composites Against Oxidation

In order to protect carbon/carbon (C/C) composites against oxidation, a Si–Mo–W coating was prepared on the surface of SiC-coated C/C composites by a simple reaction method. The microstructures of the as-received coating were characterized by scanning electron microscopy, X-ray diffraction, and energy dispersive spectroscopy analyses. The results show that the SiC/Si–Mo–W coating can protect C/C composites from oxidation in air at 1673 K for 220 h with a mass loss of 0.003%, and at 1773 K for 252 h with a mass gain of 1.56%. The excellent oxidation-resistant property of the SiC/Si–Mo–W coating at 1673–1773 K is attributed to the formation of SiO₂ film on the coating surface. The mass loss of the coated C/C composites during the oxidation test at 1873 K in air primarily resulted from the reaction of C/C substrate and oxygen diffusing through the penetration cracks in the coating.     

Oxidation behavior of C–SiC composites with a Si–W coating from room temperature to 1500°C

Oxidation tests of carbon fiber reinforced silicon carbide composites with a Si–W coating were conducted in dry air from room temperature to 1500°C for 5 h. A continuous series of empirical functions relating weight change to temperature after 5 h oxidation was found to fit the test results quite well over the whole temperature range. This approach was used to interpret the different oxidation mechanisms. There were two cracking temperatures of the matrix and the coating for the C–SiC composite. Oxidation behavior of the C–SiC composite was nearly the same as that of the coated C–C composite above the coating cracking temperature, but weight loss of the C–SiC composite was half an order lower than that of the coated C–C composite below the cracking temperature. As an inhibitor, the SiC matrix increased the oxidation resistance of C–SiC composites by decreasing active sites available for oxidation. As an interfacial layer, pyrolytic carbon decreased the activation energy below 700°C. From 800°C to 1030°C, uniform oxidation took place for the C–SiC composite, but non-uniform oxidation took place for the coated C–C composite in the same temperature range. The Knudsen diffusion coefficient could be used to explain the relationship between weight loss and temperature below the coating cracking temperature and the matrix cracking temperature.     

Oxidation behavior of C/SiC-SiBCN composites at high temperature

In order to improve the anti-oxidation performance of C/SiC composites at high temperature, C/SiC composites should be modified by self-healing components. SiBCN ceramic is an ideal self-healing component because of excellent oxidation resistance and thermal stability. C/SiC composites were modified by PDC SiBCN ceramic (C/SiC-SiBCN) by using CVI combined with polymer infiltration and on-line pyrolysis (PI-OP). The oxidation behaviors of C/SiC composites fabricated by CVI method and C/SiC-SiBCN composites fabricated by CVI + PI-OP method and CVI + PIP method at different temperatures in air were compared. The results showed that the strength retention ratios of the composites fabricated by the three methods decreased with the increase of temperature. Compared with the samples fabricated by the other two methods, the weight loss of the samples fabricated by CVI + PI-OP method was greater, but the strength retention ratio was higher.     

A gradient composite coating to protect SiC-coated C/C composites against oxidation at mid and high temperature for long-life service

To improve the oxidation resistance of carbon/carbon (C/C) composites at mid and high temperature, a gradient composite coating was designed and prepared on SiC-coated C/C composites by in situ formed-SiO₂ densifying the porous SiC-ZrSi₂ pre-coating. SiO₂ gradient distribution was conducive to inhibiting the cracking of the coating. A dual-layer structure with the outer dense layer and the inner microporous layer was formed in the coating during densifying. The dense layer had excellent oxygen diffusion resistance and the microporous layer alleviated CTE mismatch between SiC inner coating and dense layer. Moreover, ZrSiO₄ particles inhibited crack propagation and stabilized SiO₂ glass. Therefore, the coating can protect the C/C composites from oxidation at 1473 K, 1573 K and 1773 K for 810 h, 815 h and 901 h, respectively. The coated samples underwent 30 thermal cycles between room temperature and 1773 K without mass loss, exhibiting good thermal shock resistance.     

Mechanical and thermal performances of epoxy resin/graphitic carbon nitride composites

In this paper, a series of graphitic carbon nitride (g-C₃N₄) was synthesized under different thermal oxidation etching temperatures and epoxy/g-C₃N₄ composites were prepared via solution blending. The morphology and structure of g-C₃N₄ were investigated by transmission electron microscope, X-ray diffraction (XRD), Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The tensile fracture morphology and structure of epoxy resin (EP) composites were demonstrated by scanning electron microscopy and XRD, respectively. Mechanical properties of EP composites were characterized by tensile testing, and the thermal performances were investigated by dynamic mechanical thermal analysis and thermal gravimetric analysis. The results revealed that the active groups on g-C₃N₄ sheets increased under thermal oxidation etching and the C to N ratio of g-C₃N₄ decreased from 0.94 to 0.76 with the increasing etching temperature. Noticeably, the tensile strength of EP composites was enhanced by 58% with the addition of C₃N₄-NS-500 and the thermal properties were also improved significantly, including T_0.5 (the decomposition temperature at the mass loss of 50%) increased by 21.5 °C and glass transition temperature improved by 8 °C. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48598.