纤维多孔陶瓷作为复合蓄热材料基体的可行性研究

混合烧结法与熔融浸渍法是目前复合蓄热材料的两种基本制备方法，自发浸渍法是无机盐／多孔基体复合蓄热材料较佳的制备工艺。结合自发浸渍工艺原理的分析，对蜂窝陶瓷、添加造孔剂制备的多孔陶瓷与纤维多孔陶瓷在孔隙率、孔结构及力学性能等方面进行了比较。纤维多孔陶瓷凶其高孔隙率（可达95%以上）、优良的连通孔结构及特殊的断裂力学性能，可用作复合蓄热材料基体。纤维多孔陶瓷用于复合蓄热材料基体可有效地解决普通多孔基体中相变材料含量低、熔融物易溢出及抗热震稳定性差等问题。     

多孔陶瓷的制备方法及研究现状

近年来,多孔陶瓷材料在保温、气体过滤、催化载体、分离膜、窑具、骨和牙齿的生物医学替代品,以及传感器材料等领域应用越来越广泛。针对多孔陶瓷制备工艺和性能的研究呈现快速发展的趋势,并取得了大量的研究成果。本文以多孔陶瓷的制备工艺为主线,综述了部分烧结法、牺牲模板法、复制模板法、直接发泡法和3D打印法等5种主要多孔陶瓷制备方法的发展现状与研究成果。同时也探讨了各种方法的优缺点以及未来的发展方向,为多孔陶瓷的进一步发展提供了指导和参考。     

SiC多孔陶瓷制备方法研究进展

碳化硅(SiC)多孔陶瓷作为一种重要的结构材料,具有高熔点、高强度、比表面积大、体积密度小、热膨胀系数小以及良好的化学稳定性等优点,被广泛应用于催化剂载体、气/液过滤装置、生物医学材料、保温材料和耐火材料等领域。SiC多孔陶瓷的微观结构、性能及服役寿命等均受其制备方法的影响,因此综述了近年来国内外在SiC多孔陶瓷制备方法方面的研究进展,总结了物理成孔法(包括颗粒堆积法、冷冻干燥法及3D打印法等)和化学成孔法(包括添加造孔剂法、有机泡沫浸渍法与生物模板法等)制备SiC多孔陶瓷的优缺点,并对其发展方向和重点进行了展望。     

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。     

多孔SiC陶瓷/石蜡复合相变材料定型封装及热性能研究

以微米级SiC粉为原料,采用冷冻干燥工艺制备具有连贯层状孔结构的SiC陶瓷。以多孔SiC陶瓷为基体,石蜡为相变芯材,通过真空浸渍法制备多孔SiC陶瓷/石蜡复合相变材料,研究了石蜡在层状多孔SiC陶瓷内的浸渗行为及复合材料的储热性能。结果表明,层片状多孔SiC陶瓷的显微形貌对石蜡的浸渗过程及储热性能有明显影响。当石蜡负载量为21.7%(质量分数)时,复合相变材料熔融温度为59.6 ℃,凝固温度为53.9 ℃,相变潜热为28.4 J/g,室温下的热导率为2.4 W·(m·K)^-1。复合相变材料吸热峰和放热峰强度随着石蜡负载量减少而降低,当温度为200 ℃时,多孔SiC陶瓷/石蜡复合相变材料失重为5%(质量分数),表明材料具有良好的热稳定性。复合相变材料在100 ℃热处理30 min后陶瓷基体未发生形变,经100次热循环后具有稳定的相变潜热和良好的定型能力。     

多孔ZrB_2–SiC–Graphite超高温陶瓷的抗热冲击性能

为了改善ZrB2基超高温陶瓷的热冲击损伤抗性,采用冷等静压–无压烧结法在ZrB2–SiC–Graphite(ZSG)材料体系中引入孔隙制备ZSG多孔陶瓷,同时利用热压法制备了ZSG致密陶瓷作为对比材料,研究了2种ZSG陶瓷材料的力学性能,并探究了孔的引入对ZSG复合陶瓷热冲击性能的影响。结果表明:孔的引入降低了ZSG陶瓷的抗弯强度(由230.04 MPa降为98.12 MPa)和断裂韧性(由4.69 MPa·m1/2降为4.27 MPa·m1/2),但孔的引入大大提升了ZSG陶瓷的临界裂纹尺寸(由132μm增长为602μm)。孔的引入明显提高了材料的残余强度保持率(由54%增长为84%),即改善了ZrB2基陶瓷的热冲击损伤抗性。与其它材料体系不同的是,孔的引入还提高了ZSG复合陶瓷的临界温差,说明孔对ZSG复合陶瓷的热冲击断裂抗性和损伤抗性具有同时增强的效果。     

多孔硼化锆–碳化硅–石墨超高温陶瓷的抗热冲击性能

为了改善ZrB_2基超高温陶瓷的热冲击损伤抗性,采用冷等静压–无压烧结法在ZrB_2–SiC–Graphite(ZSG)材料体系中引入孔隙制备ZSG多孔陶瓷,同时利用热压法制备了ZSG致密陶瓷作为对比材料,研究了2种ZSG陶瓷材料的力学性能,并探究了孔的引入对ZSG复合陶瓷热冲击性能的影响。结果表明:孔的引入降低了ZSG陶瓷的抗弯强度(由230.04 MPa降为98.12 MPa)和断裂韧性(由4.69 MPa·m1/2降为4.27 MPa·m1/2),但孔的引入大大提升了ZSG陶瓷的临界裂纹尺寸(由132μm增长为602μm)。孔的引入明显提高了材料的残余强度保持率(由54%增长为84%),即改善了ZrB_2基陶瓷的热冲击损伤抗性。与其它材料体系不同的是,孔的引入还提高了ZSG复合陶瓷的临界温差,说明孔对ZSG复合陶瓷的热冲击断裂抗性和损伤抗性具有同时增强的效果。     

新型材料对RSiC抗氧化性的影响

为了提高多孔SiC陶瓷材料的抗氧化性，研究了其氧化机理。研制的新型V-NOX材料，添加到SiC陶瓷中，可防止其氧化，有效地保护了SiC陶瓷。     

生物形态SiC陶瓷的研究

木材经1200℃高温真空碳化生成生物模板(木炭)，然后经气相Si、SiO的反应性渗入或经SiO2溶胶真空，压力浸渍工艺和碳热还原反应过程制成多孔SiC陶瓷。借助SEM、XRD和FT—IR等方法对转变为多孔SiC过程中的显微结构、物相组成和物理化学结构变化进行了表征。试验结果表明：在木炭转变为多孔SiC的高温处理过程中，木炭的显微结构很好地留在了多孔SiC陶瓷中；生成的SiC主要是β—SiC.介绍了木炭转变为SiC陶瓷的过程与机理。     

多孔陶瓷的制备和应用研究进展

由于多孔陶瓷材料在化学工业、信息通讯、生物技术、环境能源等领域的广泛应用，近年来倍受关注。综述了多孔陶瓷的几种制备方法，并将多孔陶瓷在过滤材料、催化剂载体、生物材料、吸音隔热材料、敏感材料上的应用情况作了简要说明，充分肯定了多孔陶瓷对人类社会的作用。     

Effect of technological parameters on densification of reaction bonded Si/SiC ceramics

Si/SiC composite ceramics was produced by reaction sintering method in process of molten silicon infiltration into porous C/SiC preform fabricated by powder injection molding followed by impregnation with phenolic resin and carbonization. To optimize the ceramics densification process, effect of slurry composition, debinding conditions and the key parameters of all technological stages on the Si/SiC composite characteristics was studied. At the stage of molding the value of solid loading 87.5% was achieved using bimodal SiC powder and paraffin-based binder. It was found that the optimal conditions of fast thermal debinding correspond to the heating rate of 10?°C/min in air. The porous C/SiC ceramic preform carbonized at 1200?°C contained 4% of pyrolytic carbon and ～25% of open pores. The bulk density of Si/SiC ceramics reached 3.04?g/cm³, silicon carbide content was 83–85?wt.% and residual porosity did not exceed 2%.     

Fabrication and Characterization of Near‐Net‐Shape In Situ Reaction‐Bonded Porous Cordierite/SiC Ceramics

Porous cordierite/SiC ceramics were fabricated by in situ reaction bonding using α‐SiC, α‐Al₂O_3, and MgO powders as the starting materials. During sintering, part SiC is oxidized to SiO₂ and then the latter reacts with Al₂O₃ and MgO to form cordierite. As a result, porous cordierite/SiC ceramics were obtained, and the ceramics are strengthened by the residual SiC. Due to the large volume expansion introduced by the oxidation of SiC, the ceramics exhibit small sintering‐induced dimension variations. In addition, a fine‐grained microstructure and good thermal and mechanical properties were obtained for the porous cordierite/SiC ceramics.     

Complex geometry macroporous SiC ceramics obtained by 3D-printing,polymer impregnation and pyrolysis (PIP) and chemical vapor deposition (CVD)

We present here an original route for the manufacturing of SiC ceramics based on 3D printing, polymer impregnation and pyrolysis and chemical vapor deposition (CVD). The green porous elastomer structures were first prepared by fused deposition modeling (FDM) 3D-printing with a composite polyvinyl alcohol/elastomer wire and soaking in water, then impregnated with an allylhydridopolycarbosilane preceramic polymer. After crosslinking and pyrolysis, the polymer-derived ceramics were reinforced by CVD of SiC using CH₃SiCl₃/H₂ as precursor. The multiscale structure of the SiC porous specimens was examined by X-ray tomography and scanning electron microscopy analyses. Their oxidation resistance was also studied. The pure and dense CVD-SiC coating considerably improves the oxidation resistance.     

On the oxidation kinetics and mechanisms of various SiC-coated carbon-carbon composites

SiC coatings on the surface of C-C were produced by either silicone resin impregnation/ pyrolysis or reaction sintering. Cycles of resin impregnation/pyrolysis produced an SiC coating, on the walls of fine open pores, which was effective in reducing the oxidation rate of C-C and in shifting the transition temperature to a higher value. Unless it is pre-coated with a pyrocarbon layer before sintering, plain reaction sintered SiC has oxidation behaviors similar to those of the above-mentioned SiC. The dense pyrocarbon film deposition on the surface of C-C could form a better SiC film than others. The carbon film homogenized the surface of C-C and a dense SiC film was established. The oxidation of the coated C-C can be modelled by a set of “oxidation resistors” in series and/or in parallel, with each resistor corresponding to an oxidation element. The controlling mechanism can be resolved from the activation energy. A combined resistant layer, consisting of resin impregnation, pyrocarbon film and reaction sintering SiC, showed the best oxidation resistance of any single-layer coated C-C composite.     

先驱体转化法制备多孔陶瓷的研究现状

多孔陶瓷作为重要的陶瓷材料,广泛应用于冶金、化工等众多领域,其制备工艺的改进一直是研究重点。先驱体转化法是20世纪末提出的制备多孔陶瓷新型工艺,利用陶瓷先驱体高温裂解产生气体的特性,可将其作为粘结剂、骨料、发泡剂制备多孔陶瓷,具有成型工艺简单,烧成温度低等特点,拥有广泛的应用前景。本文主要从以上几个方面简要介绍先驱体转化法制备多孔陶瓷的工艺、结构和性能的研究现状。     

泡沫碳化硅陶瓷材料的研究进展

泡沫碳化硅陶瓷材料除了孔隙率高、比表面积大,还具有相对密度小、优良的热学、力学、电学、声学性能等特性,已经广泛应用于化工、机械、生物、环保等领域。本文总结了泡沫碳化硅陶瓷材料的主要制备技术,包括粉末烧结法、固相反应烧结法、含硅树脂热解法以及气相沉积法等。阐述了泡沫碳化硅陶瓷材料的几种优良特性,包括结构特征、流体阻力、抗氧化性、吸波性等。最后举例介绍了该陶瓷在催化、过滤、生物学等领域的应用现状,重点介绍了其作为塔内件在化工领域中的应用,指出为满足对泡沫碳化硅陶瓷更高性能的需求,不仅要对现有技术进行集成创新,更要挖掘和开发泡沫碳化硅的潜在优势。     

Low-temperature preparation of porous SiC ceramics using phosphoric acid as a pore-forming agent and a binder

Porous SiC ceramics combine the properties of both SiC ceramics and porous materials. Herein, we design a facile method via pressureless sintering at relatively low temperatures for the synthesis of porous SiC ceramics. In the synthesis process, phosphoric acid was used as the sintering additive that reacted with SiO₂ on the surface of SiC to form phosphates. The formed phosphates acted as a binder to connect the SiC particles. At a fixed temperature, the phosphates were partially decomposed and released a large amount of gas. This changed the pore structure of the ceramics and greatly improved their porosity. Finally, we obtained the porous SiC ceramics with high porosity and high strength. We investigate the effects of H₃PO₄ content on the phase composition, microstructure, porosity, mechanical properties and thermal expansion coefficient of the prepared porous SiC ceramics. It was shown that at the sintering temperature of 1200 °C, the highest porosity of the samples can reach 70.42% when the H₃PO₄ content is 25 wt%, and their bending strength reaches 36.11 MPa at room temperature when the H₃PO₄ content is 15 wt%. In addition, the porous SiC ceramics show good high-temperature stability with a bending strength of 42.05 MPa at 1000 °C and the thermal expansion coefficient of 3.966 × 10⁻⁶/°C.     

Reaction Sintering of Polycarbosilane-Impregnated Compact of Silicon Carbide Hollow Particles and the Resultant Thermoelectric Properties

Porous SiC ceramics fabricated from hollow particles and polycarbosilane (PSC) are promising materials for high-temperature thermoelectric energy conversion. Reaction sintering of PCS-impregnated compacts of SiC hollow particles gave rise to porous microstructures with the hollow shape remaining. The repetition of the PCS-impregnation and sintering process resulted in only a slight increase in density but in a great improvement in thermoelectric properties.     

不同助烧结剂及造孔剂对SiC多孔陶瓷的影响

采用真空烧结方法制备了SiC多孔陶瓷，研究了不同助烧结剂Al2O3-Y2O3、Si以及不同造孔剂丙烯酰胺聚合物、羧甲基纤维素（CMC）对SiC多孔陶瓷形貌和气孔率的影响。结果表明：与Si相比较，Al2O3-Y2O3更有利于促进SiC的烧结；以Al2O3-Y2O3为助烧结剂的试样比以Si为助烧结剂的试样具有较高的气孔率。