反应熔渗法制备C/C-SiC复合材料及其反应机理和动力学的研究进展

对反应熔渗法制备C/C-SiC复合材料过程中Si的渗入行为以及Si/C的反应机理和动力学进行了综合评述.分析了高温下Si的密度、粘度、表面张力及Si/C润湿角对渗入能力的影响.概括了Washburn公式及其改进模型在液Si渗入行为方面的研究进展,给出了渗入时间、SiC生成速率与渗入高度之间的关系.对控制Si/C反应的溶解-沉淀机理和扩散机理进行了阐述,总结分析得出：不同阶段Si/C反应发生的区域不同,因而控制反应的机理也不同.最终的SiC相是由不同反应机理共同作用形成的.     

Influence of Carbon Content on Ceramic Injection Molding of Reaction‐Bonded Silicon Carbide

Reaction‐bonded silicon carbide (RBSC) was prepared by ceramic injection molding (CIM) technique with feedstocks containing silicon carbide (SiC), a wax‐based organic system and different amounts of carbon black. As a critical effect of the reaction sintering process, carbon was introduced from the carbon black and the decomposition product of the organic polymers, respectively. This study described the influence of carbon content on the mixing and injection process firstly and then emphasized the debinding process since it played a large role in the process of the pyrolysis of organic. Results indicated that the preferable thermal debinding was performed in N₂ and the optimal performance was obtained for RBSC with 7 wt.% of carbon black, with the density of 2.98 g/cm³, apparent porosity of 0.24%, bending strength of 301.59 MPa and fracture toughness of 4.18 MPa·m^1/2.     

Mechanical,structural and oxidation resistance enhancement of carbon foam by in situ grown SiC nanowires

A method for processing carbon foams containing both silicon carbide (SiC) nanowires and bulk SiC and silicon nitride (Si3N4) phases has been developed by reaction of powder mixtures containing precursors for carbon, sacrificial template, silicon (Si), short carbon fibers (SCF) and activated carbon (AC). In situ growth of Si nanowires during pyrolysis of the foam at 1000 °C under N2 changed the foam׳s microstructure by covering the porous skeleton inside and out. In situ-grown SiC nanowires were found smoothly curved with diameters ranging around two main modes at 30 and 500 nm while their lengths were up to several tens of micrometers. SCF were found effectively mixed and well-bonded to pore walls. Following density, porosity and pore size distribution analyses, the heat-treated (HT) foam was densified using a chemical vapor infiltration (CVI) process. Thereafter, density increased from 0.62 to 1.30 g/cm³ while flexural strength increased from 29.3 to 49.1 MPa. The latter increase was attributed to the densification process as well as to low surface defects, presence of SCF and coating, by SiC nanowires, of the entire SiC matrix porous structure. The foam׳s oxidation resistance improved significantly from 58 to 84 wt% residual mass of the heat treated and densified sample. The growth mechanism of Si nanowires was supported by the vapor–liquid–solid mechanism developed under pyrolysis conditions of novolac and reducing environment of coal cover.     

Studying the wettability of Si and eutectic Si-Zr alloy on carbon and silicon carbide by sessile drop experiments

The contact angles of two different systems, molten silicon and a eutectic Si-8 at. pct Zr alloy and their evolution over timeon vitreous carbon and polycrystalline silicon carbide (SiC) substrates were investigated at 1500°C under vacuum, as well as in argon using the sessile drop technique. The contact angle and microstructure of the liquid droplet/solid substrate interface were studied to understand fundamental features of reactive wetting as it pertains to the infiltration process of silicon and silicon alloys into carbon or C/SiC preforms. Both pure Si and theeutectic alloy showed good wettability onvitreous carbon and SiC characterized by equilibrium contact angles between 29° and 39°. Theeutectic alloy showed a higher initial contact angle and slower spreading as compared to that of pure Si. On vitreous carbon bothsilicon and the eutecticalloy formed SiC at the interface, while no reaction was observed on the SiC substrates.     

MCMB–SiC composites; new class high-temperature structural materials for aerospace applications

Graphite–silicon carbide (G–SiC), carbon/carbon–silicon carbide (C/C–SiC) and mesocarbon microbeads–silicon carbide (MCMB–SiC) composites were produced using liquid silicon infiltration (LSI) method and their physical and mechanical properties, including density, porosity, flexural strength and ablation resistance were investigated. In comparison with G–SiC and C/C–SiC composites, MCMB–SiC composites have the highest bending strength (210 MPa) and ablation resistance (9.1%). Moreover, scanning electron microscopy (SEM) and optical microscopy (OM) are used to analyze the reacted microstructure, pore morphology and pore distribution of carbon-based matrices. As a result, SiC network reinforcement was formed in situ via a reaction between liquid silicon and carbon. The unreacted carbon and solidified silicon are two phases present in the final microstructure and are characterized by X-ray diffraction (XRD). Based on the results obtained and the low-cost processing of pitch-based materials, the MCMB–SiC composite is a promising candidate for aerospace applications.     

Synthesis of nanosized SiC by low-temperature magnesiothermal reduction of nanocomposites of functionalized carbon nanotubes with MCM-48

Silicon carbide synthesis by a magnesiothermal method was investigated using MCM-48 as the silica source mechanically mixed with carbon nanotubes (CNTs) as the carbon source, and nanocomposites of MCM-48/functionalized CNTs (CNTF). SiC syntheses were carried out with different molar ratios of MCM-48, carbon and magnesium at 700?°C in argon. The MCM-48 and carbon nanotube starting materials and the SiC products were characterized by BET, XRD, FESEM, EDX and TEM. The effect of the carbon content and the type of CNTs (either functionalized or unfunctionalized) on the SiC synthesis was studied. The results show that an improved yield of SiC is obtained when the carbon nanotubes are functionalized, producing a better contact with the MCM-48. This improved contact between the reactants ensures a good degree of reaction in a stoichiometric mixture of silicon and carbon, with no improvement in product formation being achieved by the use of additional carbon. These findings suggest that the degree of contact between reactants is an important factor in the magnesiothermal synthesis of SiC. The SiC products from magnesiothermal synthesis of the functionalized nanocomposite precursors were shown by TEM and FESEM to have unusual nanofiber morphologies mimicking the morphology of the CNTF nanotubes.     

黄杨木制备SiC木质陶瓷的性能与表征

SiC木质陶瓷是近年来应用前景广阔的新型陶瓷材料,以绿色可再生的木材为原材料,通过反应烧结工艺制备出的陶瓷具有优良的高温力学性能。为探究影响生物质陶瓷性能的因素,将黄杨木在800 ℃氮气保护下热解形成生物质炭坯,然后在1 650 ℃和1 900 ℃两种高温下进行熔融渗硅制备SiC木质陶瓷。利用X射线衍射仪(XRD)和扫描电子显微镜(SEM)研究SiC木质陶瓷的物相组成和微观结构,采用阿基米德排水法和三点弯曲法测定陶瓷的开孔率、密度和弯曲强度,再使用维氏硬度计测定SiC木质陶瓷的显微硬度。研究结果表明:在1 650 ℃下通过熔融渗硅可以得到微观结构均匀的SiC木质陶瓷,在1 650 ℃比在1 900 ℃下熔融渗硅制备陶瓷的力学性能更优异,陶瓷的密度更大,为2.27 g/cm³,此时弯曲强度为192.45 MPa;游离Si会提高SiC木质陶瓷的密度,增强陶瓷的弯曲强度。     

Effect of Carbon and Silicon Carbide/Carbon Interlayers on the Mechanical Behavior of Tyranno-SA-Fiber-Reinforced Silicon Carbide-Matrix Composites

Several CVI-SiC/SiC composites were fabricated and the mechanical properties were investigated using unloading–reloading tensile tests. The composites were reinforced with a new Tyranno-SA fiber (2-D, plain-woven). Various carbon and SiC/C layers were deposited as fiber/matrix interlayers by the isothermal CVI process. The Tyranno-SA/SiC composites exhibited high proportional limit stress (∼120 MPa) and relatively small strain-to-failure. The tensile stress/strain curves exhibited features corresponding to strong interfacial shear and sliding resistance, and indicated failures of all the composites before matrix-cracking saturation was achieved. Fiber/matrix debonding and relatively short fiber pullouts were observed on the fracture surfaces. The ultimate tensile strength displayed an increasing trend with increasing carbon layer thickness up to 100 nm. Further improvement of the mechanical properties of Tyranno-SA/SiC composites is expected with more suitable interlayer structures.     

Fabrication of carbon-coated boron carbide particle and its role in the reaction bonding of boron carbide by silicon infiltration

To tackle the dissolution problem of boron carbide particles in silicon infiltration process, carbon-coated boron carbide particles were fabricated for the preparation of the reaction-bonded boron carbide composites. The carbon coating can effectively protect the boron carbide from reacting with liquid Si and their dissolution, thus maintaining the irregular shape of boron carbide particles and preventing the growth of boron carbide particles and reaction formed SiC regions. Furthermore, the nano-SiC particles, originated from the reaction of the carbon coating and the infiltrated Si, uniformly coated on the surfaces of boron carbide particles, thus forming a ceramic skeleton of the nano-SiC particles-coated and -bonded boron carbide particles. The Vickers hardness, flexural strength and fracture toughness of the composites can be increased by 26 %, 45 %, and 37 % respectively, by using carbon-coated boron carbide particles as raw materials.     

In-situ synthesis and textural evolution of the novel carbonaceous SiC/mullite aerogel via polymer-derived ceramics route

A novel carbonaceous SiC/mullite composite aerogel is derived from catechol-formaldehyde/silica/alumina hybrid aerogel (CF/SiO₂/AlOOH) via polymer-derived ceramics route (PDCR). The effects of the reactants concentrations on the physicochemical properties of the carbonaceous SiO₂/Al₂O₃ aerogel and SiC/mullite aerogel are investigated. The mechanism of the textural and structural evolution for the novel carbonaceous SiC/mullite is further discussed based on the experimental results. Smaller reactants concentration is favorable to formation of mullite. Reactants concentration of 25% is selected as the optimal condition in considering of the mullite formation and bulk densities of the preceramic aerogels. Spherical large silica particles are also produced during heat treatment, and amorphous silica is remained after this reaction. With further heat treatment at 1400 °C, silicon carbide and mullite coexist in the aerogel matrix. The mullite addition decreases the temperature of SiC formation, when compared with the conventional methods. However, after heat treatment at 1450 °C, the amount of mullite begins to decrease due to the further reaction between carbon and mullite, forming more silicon carbide and alumina. The carbonaceous SiC/mullite can be transferred to SiC/mullite binary aerogel after carbon combustion under air atmosphere. The carbonaceous SiC/mullite has a composition of SiC (31%), mullite (19.1%), SiO₂ (14.4%), and carbon (35%). It also possesses a 6.531 nm average pore diameter, high surface area (69.61 m²/g), and BJH desorption pore volume (0.1744 cm³/g). The oxidation resistance of the carbonaceous SiC/mullite is improved for 85 °C when compared with the carbon based aerogel.     

Synthesize and crystallization behavior of SiOC/SiC nanocomposites derived from organosilane slurry residue

A route preparing SiOC/SiC nanocomposites directly by pyrolysis of organosilane slurry residue was investigated. Organosilane slurry residue's unique composition, containing both silicon and carbon, offers an intriguing platform for developing advanced ceramic materials. The pyrolysis process is examined comprehensively, revealing the chemical reactions and structural changes leading to SiC crystals formation. The phase evolution at various annealing temperatures was revealed. Crystallization behavior in the process were studied. The results reveal that SiOC matrix was generated at annealed temperature 800°C and SiC nanoparticles were formed at 1300°C. In comparison to phase separation of SiOC, carbothermal reduction of SiO₂ was domain in SiC formation. This research advances the understanding of SiOC/SiC nanocomposites, highlighting the value of repurposing industrial byproducts for sustainable and innovative materials development.     

In-situ growth of silicon carbide nanowire (SCNW) matrices from solid precursors

In an effort to develop highly porous silicon carbide for high temperature air filtration, an alternative approach to forming silicon carbide nanowires (SCNW) was developed by blending carbon containing materials with silicon powder and heating these precursors to 1400?°C. The mixing ratio of precursor materials and processing temperature were investigated with respect to the formation of SCNWs. Results indicate that anthracite and starchy materials can yield high purity SiC ceramics, yet these combinations did not produce SiC nanowires. SCNWs were successfully grown from a combination of guar gum and silicon powder precursors at 1400?°C, when held for 4?h with an argon flow rate of 1?L/min. The produced SiC is a high purity product with nanowire diameters of approximately 40?nm and ranging in length from about 100?nm to several micrometers in length. Iron was used to catalyze the nanowire growth through vapor-liquid-solid (VLS) mechanisms by adsorbing the silicon and carbon vapor at the iron rich tip, which then led the nanowire growth. TEM analysis revealed the growth of SCNWs followed the [1,1,2] direction. A wafer comprised of the synthesized SiC nanowire matrix has much higher hardness compared with a wafer of the porous commercially available cordierite.     

Low‐Density Open Cellular Silicon Carbide Foams from Sucrose and Silicon Powder

Open cellular SiC foams with low densities were prepared by thermo‐foaming and setting (130°C–150°C) of silicon powder dispersions in molten sucrose followed by pyrolysis and reaction sintering at 1500°C. The bubbles generated in the dispersion by water vapor produced by the –OH condensation was stabilized by the adsorption of silicon particles on the air‐molten sucrose interface. The composition of a sucrose‐silicon powder mixture for producing SiC foam without considerable unreacted carbon was optimized. The sucrose in the thermo‐foamed silicon powder dispersion leaves 24 wt% carbon during the pyrolysis. The sintering additives such as alumina and yttria promoted the silicon‐carbon reaction. SiC nanowires with diameters in the range of 35–55 nm and length >10 μm observed on the cell walls as well as in the fractured strut region were grown by both vapor–liquid–solid and vapor–solid mechanisms. Large SiC foam bodies without crack could be prepared as the total shrinkage during pyrolysis and reaction sintering was only ~30 vol%. The relatively low compressive strength (0.06–0.41 MPa) and Young's modulus (14.9–24.2 MPa) observed was due to the large cell size (1.1–1.6 mm) and high porosity (93%–96%).     

A hybrid graphite powder PFC@G for reserving higher carbon content of self-lubrication graphite/SiC composites by RMI

The appropriate carbon content is indispensable for the application of self-lubricating graphite/SiC composites. However, it is a big challenge to retain high carbon content in the reaction-formed graphite/SiC composites because of drastic consumption of carbon by violent reaction with liquid silicon. In this study, a hybrid powder constructed by graphite particles (G) and glassy carbon derived from phenolic resin (PFC) was used as carbon sources, or PFC@G for short, to reserve higher content of carbon in the reaction-formed composites. The weight ratio of phenolic resin to graphite particles was adjusted to obtain an appropriate PFC@G with dense microstructure and close-grained surface. Compared with the graphite/SiC composites only using raw graphite particles as carbon sources, the carbon content of the composites fabricated with compact and large PFC@G has obviously increased (up to 172%). In particular, the carbon content of the composites fabricated with the weight ratio = 0.8 reached a high value of 44.26 vol.%, which exhibited outstanding self-lubrication properties among the four kinds of the composites. The mechanism of reserving higher content of carbon in the graphite/SiC composites by constructing PFC@G is investigated, revealing that a continuous SiC layer formed on the surface of the larger size PFC@G and most closely packed graphite particles inside of PFC@G were insulate from liquid silicon by the layer.     

残余碳对碳化硅陶瓷光学表面加工性能的影响

为深入了解碳化硅陶瓷的光学表面加工性能,采用常压固相烧结法制备了碳化硅陶瓷,在保证致密度的前提下,通过改变碳的含量,研究了残余碳对SiC陶瓷抛光面的表面质量和光学性能的影响。研究发现,C的质量含量为3%～7%时,SiC陶瓷抛光表面的RMS(root mean square)粗糙度均约为2nm。当C含量为3%～6%时,SiC陶瓷抛光表面在400～750nm波段的全反射率、漫反射率和镜面反射率无明显变化;当C含量升至7%时,全反射率稍有降低,漫反射率稍有上升,镜面反射率稍有降低。其原因可能是过多的残余碳引起SiC陶瓷的折射率下降和产生光学散射,最终造成镜面反射率降低。     

Application of a Waste Carbon Material as the Carbonaceous Reductant During Silicon Production

It is important to study the application of alternative carbon reductants for industrial silicon smelting to reduce consumption of carbonaceous reducing agents, electricity, and CO₂ emissions during silicon production. In this study, an industrial experiment was carried out in an 8 MVA submerged arc furnace using waste carbon material in place of approximately 20% partial reducing agents. The system was analyzed for silicon yield, power consumption, overall energy efficiency, CO₂ emissions, and the utilization rate of carbonaceous materials. The system improved the efficiency of carbonaceous materials and decreased power consumption using alternative carbon reductants. The results have showed that use of waste carbon materials reduced carbon emissions per ton silicon by more than 19.14% and specific CO₂ emissions decreased to 0.865 t.     

Reactive Infiltration of Si-Mo Alloyed Melt into Carbonaceous Preforms of Silicon Carbide

A MoSi₂/reaction-bonded SiC composite was prepared from a preform of petroleum coke and commercial SiC powders (in weight ratios of 0.5 and 0.6), following reactive infiltration of a Si-Mo melt (molybdenum concentration of 7–29 wt%) made from elemental powder. The resulting material had a relative density of >90% of the theoretical density and, on a microstructural scale, contained SiC and MoSi₂, in addition to unreacted carbon and silicon. The SiC and MoSi₂ boundary was smooth and sharp, with no sign of any reaction. The occasional presence of an intermediate zone between SiC and MoSi₂ was detected; this zone contained silicon, iron, and aluminum, the formation of which may be related to the presence of impurities in the silicon and SiC.     

Fabrication of C/SiC composites by combining liquid infiltration process and spark plasma sintering technique

Carbon fibre-reinforced silicon carbide composites (C-SiC) were fabricated combining, for the first time, a liquid infiltration process (LI) of a mesophase pitch doped with silicon carbide nanoparticles followed by reactive liquid silicon infiltration using Spark Plasma Sintering (SPS) technique. A graphitization step was applied in order to improve the effectiveness of the processing. Up to three different morphologies of SiC particles were identified with a noticeable influence on the preliminary oxidation tests carried out. The presence of SiC nanoparticles added to the carbon matrix affects the morphology of the SiC obtained by in situ reaction of silicon and carbon during the LI process by SPS and it leads to an improvement of the material oxidation resistance. The results show that SPS is a promising method to develop C-SiC composites in a short time and with a high efficiency in the liquid silicon infiltration process.     

Chemical Preparation and Shock Wave Compression of Carbon Nitride Precursors

Two synthetic routes have been developed to produce high-molecular-weight organic precursors containing a high weight fraction of nitrogen. One of the precursors is a pyrolysis residue of melamine-formaldehyde resin. The second precursor is the byproduct of an unusual low-temperature combustion reaction of tetrazole and its sodium salt. These precursors have been shock compressed under typical conditions for diamond and wurtzite boron nitride synthesis in an attempt to recover a new ultrahard carbon nitride. The recovered material has been analyzed by X-ray diffraction, FTIR, and Raman microprobe analysis. Diamond is present in the recovered material. This diamond is extraordinarily well ordered relative to diamond shock synthesized from carbonaceous starting materials.     

原料体系对Ti3SiC2合成过程中相组成和显微结构演变的影响

分别以粉末钛粉、硅粉、石墨和钛粉、碳化硅、石墨为原料,采用热压烧结法制备了Ti3SiC2材料,借助XRD和SEM手段研究了原料体系和烧成温度对试样相组成、致密化程度和显微结构的影响,并分析了反应烧结机理。结果表明:(1)随着温度的升高,钛粉-硅粉-石墨体系较钛粉-碳化硅-石墨体系合成出的Ti3SiC2块体材料纯度更高;(2)钛粉-硅粉-石墨体系在烧结温度低于1300℃时,主要以Ti5Si3、TiC和残余的硅粉、石墨反应生成Ti3SiC2,在烧结温度为1300～1600℃时,主要以形成的液相Ti-Si(L)与TiC反应生成了Ti3SiC2;钛粉-碳化硅-石墨体系在1485℃液相出现之后,颗粒经历重排和溶解再析出的过程,在液相中生成Ti3SiC2。