Novel application of ceramic precursors for the fabrication of composites

Preceramic polymers are enabling the development of a variety of advanced shaping methods which, in turn, make possible new and cost-effective approaches for the fabrication of composite materials. This opens new perspectives for the mass production of composites which might, for example, be used in cost-sensitive areas of application in the machine and automobile industries. In two examples it will be shown how preceramic polymers can be used to obtain both metal matrix composites (MMC) and ceramic matrix composites (CMC). Their properties will be discussed in particular with respect to the usage of a preceramic polymer.The first example shows an approach to manufacturing short-fibre-reinforced CMCs by means of a plastic forming technique which involves mixing of either carbon or SiC fibres, ceramic fillers and a viscous ceramic precursor. The precursor permits a fibre-reinforced ceramic with a low porosity to be obtained. The role of the precursor in the whole process and the resulting material properties will be discussed.The second example shows a method for fabricating porous SiC ceramic preforms which are subsequently infiltrated with aluminium to form a MMC. By using the precursor route, a machinable preform with tailored porosity can be produced. Correlations between precursor, preform and MMC properties will be drawn.     

Powder bed fusion of polyamide powders combined with different preceramic polymers infiltration and pyrolysis to produce complex-shaped ceramics

The fabrication of a wide range of polymer-derived ceramic parts with high geometric complexity through a novel hybrid additive manufacturing technique is presented in this article. The process that we introduced in a previous work uses the powder bed fusion technology to manufacture high porous polymeric preforms to be then converted into ceramics through preceramic polymer infiltration and pyrolysis. The cellular architectures of a rotated cube (strut-based) and a gyroid (sheet-based) with 25 mm diameter, 44 mm height and 67 % of geometric macroporosity were generated and used for the fabrication. The complex structures were 3D printed and polycarbosilane, polycarbosiloxane, polysilazane and furan liquid polymers were used to produce SiC, SiOC, SiCN and glassy carbon, respectively. Despite a linear shrinkage of about 24 %, the parts maintained their designed complex shape without deformations. The significant advantages of the proposed method are the maturity of powder bed fusion for polymers with respect to ceramic additive manufacturing techniques and the possibility to fabricate net-shape complex ceramic parts directly from preceramic precursors.     

Fabrication of scalable,aligned and low density carbon nanotube/silicon carbide hybrid foams by polysilazane infiltration and pyrolysis

Polymer-derived ceramic (PDC) process is an attractive technique that has high ceramic yield. This versatile method allows for fabrication of porous carbon nanotube (CNT)/ silicon carbide (SiC) hybrid materials that is important high temperature structural applications. Although several forms of CNT assemblies have been used with the PDC approach, the fabricated CNT/ceramic nanocomposites were either one or two dimensional. Herein, we report, for the first time, the fabrication of a low density, three-dimensional (3D) and scalable CNT/SiC structure using PDC technique. It was synthesized by impregnating preceramic polysilazane (PSZ) into ultralow density, anisotropic, and highly aligned CNT foams, followed by thermosetting and pyrolysis processes. The ceramic phase conformally coated the CNTs. The X-ray diffraction (XRD) diffractogram confirmed the presence of β-SiC crystalline phase. The resulting hybrid foam inherited the morphology and form factor of the original CNT foam, and possessed mechanical robustness, improved electrical properties, and extraordinary thermal stability.     

反应诱导相分离热解法制备交联互通状多孔炭单体

以酚醛树脂和乙二醇混合物经过反应诱导相分离热解后形成的多孔炭单体制备复杂形状SiC陶瓷。通过用场发射扫描电子显微镜和压汞仪对多孔炭进行表征,分别研究了乙二醇含量、催化剂含量以及预固化温度对多孔炭的孔形貌、尺寸及分布的影响。结果表明：乙二醇含量可以影响多孔炭单体的形成,以及孔的形貌、大小和分布;催化剂含量和预固化温度对多孔炭的影响不显著。     

气相硅反应性渗入法制备橡木结构SiC陶瓷

橡木经1200℃高温真空碳化转化为碳模板,再用反应性渗入方法在1500～1600℃、Ar气氛下气相渗硅0．5～8h,制成一种具有橡木显微结构的多孔SiC陶瓷。采用XRD和SEM对其物相变化和显微结构进行了表征。结果表明：随反应时间的延长,木炭的转化率增大,弯曲强度显著提高,而气孔率变化不大。在1600℃下反应8h时,木炭几乎完全转变成具有橡木显微结构的β-SiC陶瓷,其弯曲强度和气孔率分别为42．1MPa和46．4％。此外,还对气相Si在木炭中的渗入-反应机理进行了简单介绍。     

Additive manufacturing of silicon carbide by selective laser sintering of PA12 powders and polymer infiltration and pyrolysis

In this work, we propose a novel hybrid additive manufacturing technique, which combines selective laser sintering (SLS) of polyamide powders and subsequent preceramic polymer infiltration and pyrolysis to manufacture Silicon Carbide components for complex architectures. By controlling the porosity of the sintered polymeric preform we are able to control the shrinkage upon the first infiltration and pyrolysis. This enabled the manufacturing of smaller features than those achievable with other manufacturing techniques. The mechanical strength of the resulting ceramic increased with the number of reinfiltration cycles up to 24 MPa, inversely the residual porosity decreased to 10 vol%. The microstructure showed two distinct phases of SiOC and SiC. The first was attributed to the interaction between the porous polyamide and the ceramic precursor during the first infiltration. SiC derived from the pyrolysis of the preceramic precursor alone.     

Facile preparation of morph-genetic SiC/C porous ceramic at low temperature by processed bio-template

A porous morph-genetic SiC/C ceramic material was fabricated using biomass-derived C template, Si powder, and Fe(NO₃)₃·9H₂O as the starting materials. The effects of heating temperature, and catalyst/Si mole ratio on the formation of SiC/C ceramic were investigated. In addition, the pore size distribution was obtained through pore size analysis, and the determination of oxidation resistance of SiC/C ceramics and C template was carried out by thermogravimetric analysis. The results show that copious amounts of SiC nanowires, which were distributed on the surfaces and interiors of the C template holes, were formed at 1300 °C with 4 wt% Fe as catalyst. The SiC nanowires significantly affected the oxidation resistance and microporous structures of the prepared materials. Moreover, a possible formation mechanism for the porous SiC/C ceramic was determined.     

Synthesis and characterization of Si/SiC ceramics prepared using cotton fabric

A Si/SiC ceramic was prepared from cotton fabric by the reactive infiltration of liquid silicon into the carbon template. A large density difference between the samples has been observed. This may be due to the variation in the pore size and its distribution within the sample. Scanning electron microscopy with energy dispersive spectroscopy shows the presence of three distinct phases, i.e., SiC, free Si and free carbon. X-ray diffraction pattern also confirms the presence of SiC and Si phases. However, there is no peak corresponding to carbon. So, it is inferred that the carbon exists in amorphous form. Micro-hardness, fracture toughness and bending strength of the ceramics were also studied. The values are lower than commercially available SiC ceramics. This may be due to the highly porous nature of cotton fabric-based SiC, as compared to commercially available SiC.     

Preparation of ultra-high temperature SiC–TiB2 nanocomposites from a single-source polymer precursor

SiC–TiB₂ ceramic nanocomposites are valuable ultra-high temperature materials, which are rarely prepared from preceramic polymers. In this work, we synthesized SiC–TiB₂ nanocomposites from a new preceramic polymer called titanium- and boron-modified polycarbosilane (TB–PCS). The polymer structure was characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy. The structure, composition, and morphology of the resulting ceramic products were investigated by FT-IR, X-ray diffraction, and transmission electron microscopy. The elements of titanium and boron were incorporated into the preceramic polymer, and nanoscale TiB₂ and β-SiC grains generated in situ were detected in the pyrolyzed ceramic products at temperatures higher than 1400 °C. The new preceramic polymer presents a novel approach to preparing SiC–TiB₂ nanocomposites.     

Preparation of ordered mesoporous SiCN ceramics with large surface area and high thermal stability

For the first time, highly ordered two-dimensional (2-D) and three-dimensional (3-D) mesoporous SiCN ceramics with high surface area and high thermal stability were prepared by nanocasting a preceramic polymer solution into mesoporous carbon templates, CMK-3 and CMK-8, respectively. As a negative replica of CMK-3 carbon, the obtained mesoporous SiCN ceramic possessed an ordered 2-D hexagonal mesostructure, which is similar to the structure of SBA-15 silica except for the reduced dimensions. An ordered 3-D cubic mesoporous SiCN ceramic was also fabricated using CMK-8 as a template. The wall of the mesoporous SiCN replicas consisted of an amorphous SiCN ceramic phase, which possessed high thermal stability at high temperature up to 1000 °C. N₂-sorption isotherms revealed that these ordered mesoporous SiCN ceramics have high BET surface areas (up to 472 m² g⁻¹) and narrow pore-size distributions, which was preserved even after a re-treatment at 1000 °C in air. The use of carbon template played an important role in the preparation of mesoporous SiCN replicas and enhanced the thermal stability of the SiCN products. It is expected that many other types of ordered mesoporous ceramics can be prepared from nanoporous carbon by nanocasting method.     

In-Situ Chemical Vapor Growth of Carbon-Rich Silicon Carbide Fibers Upon Pyrolysis of Polyzirconosilane

Carbon-rich SiC fibers were prepared in a cost-effective way using in-situ chemical vapor growth upon pyrolysis of polyzirconosilane at 1200 °C under nitrogen atmosphere, with 0.5-1 μm in diameter and a few milimeters in length and a yield of about 30 %. The empirical formula of the fibers is Si₁C_6.6O_0.1, and both silicon and carbon atoms inside the fibers are found to be uniformly distributed, and the free carbon atoms show a turbostratic state. The carbon-rich SiC fibers show ideal thermo-oxidation resistance at 1200 °C in air. Chemical vapor growth of ceramic fibers upon preceramic pyrolysis can be used to prepare high performance ceramic fibers on a large scale cost- effectively.     

Preparation of SiC nanowires-filled cellular SiCO ceramics from polymeric precursor

SiC nanowires-filled cellular SiCO ceramics were prepared using polyurethane sponge as a porous template infiltrated with silicone resin by pyrolysis at 1400 °C under Ar atmosphere. The pyrolysis temperature was an important parameter affecting the formation of SiC nanowires. The as-prepared sample obtained at 1000 °C was composed of SiCO glasses and turbostratic carbon. The SiCO ceramic was further converted into SiO₂ crystals and amorphous carbon by pyrolysis at 1200 °C. With the increasing pyrolysis temperature, SiC nanocrystals embedded in the non-crystalline SiCO matrix were observed. Furthermore, the SiC nanowires were formed in the pores of the SiCO ceramic. The diameters of the SiC nanowires are in the range 80–150 nm and the lengths are up to several tens of micrometers. The growth mechanism of the nanowires was supported by the vapor-solid mechanism.     

Polymer derived SiC environmental barrier coatings with superwetting properties

Surfaces with superwetting capabilities can be used for corrosion protection, self-cleaning and bio-fouling protection amongst other applications. In this work, we present a method to produce a SiC coating with an almost superhydrophobic behavior exhibiting water contact angles of 145±3°. Ceramic coatings were produced by the pyrolysis of polycarbosilane as a preceramic precursor of SiC. Aluminum and carbon powders were used as active and passive fillers to compensate for the volume shrinkage of polycarbosilane during pyrolysis. The effects of particle size (Al particles ranging from 0.8 to 10 µm) and concentration 10–30% wt.) C and Al of both fillers were studied to produce defect-free ceramic coatings. We have observed that the fillers used not only affected the microstructure but also the surface roughness. We show that the addition of carbon fillers can increase the water contact angle of the ceramic from 42° up to 141°. The combination of carbon and aluminum fillers resulted in water contact angles up to 145°.     

Effects of porosity on electrical and thermal conductivities of porous SiC ceramics

The effects of porosity on the electrical and thermal conductivities of porous SiC ceramics, containing Y₂O₃–AlN additives, were investigated. The porosity of the porous SiC ceramic could be controlled in the range of 28–64 % by adjusting the sacrificial template (polymer microbead) content (0–30 wt%) and sintering temperature (1800–2000 °C). Both electrical and thermal conductivities of the porous SiC ceramics decreased, from 7.7 to 1.7 Ω⁻¹ cm⁻¹ and from 37.9 to 5.8 W/(m·K), respectively, with the increase in porosity from 30 to 63 %. The porous SiC ceramic with a coarser microstructure exhibited higher electrical and thermal conductivities than those of the ceramic with a finer microstructure at the equivalent porosity because of the smaller number of grain boundaries per unit volume. The decoupling of the electrical conductivity from the thermal conductivity was possible to some extent by adjusting the sintering temperature, i.e., microstructure, of the porous SiC ceramic.     

Fabrication of dense SiSiC ceramics by a hybrid additive manufacturing process

In this work, we report the fabrication of Silicon infiltrated Silicon Carbide (SiSiC) components by a hybrid additive manufacturing process. Selective laser sintering of polyamide powders was used to 3D print a polymeric preform with controlled relative density, which allows manufacturing geometrically complex parts with small features. Preceramic polymer infiltration with a silicon carbide precursor followed by pyrolysis (PIP) was used to convert the preform into an amorphous SiC ceramic, and five PIP cycles were performed to increase the relative density of the part. The final densification was achieved via liquid silicon infiltration (LSI) at 1500°C, obtaining a SiSiC ceramic component without change of size and shape distortion. The crystallization of the previously generated SiC phase, with associated volume change, allowed to fully infiltrate the part leading to an almost fully dense material consisting of β-SiC and Si in the volume fraction of 45% and 55% respectively. The advantage of this approach is the possibility of manufacturing SiSiC ceramics directly from the preceramic precursor, without the need of adding ceramic powder to the infiltrating solution. This can be seen as an alternative AM approach to Binder jetting and direct ink writing for the production of templates to be further processed by silicon infiltration.     

Synthesis of high-surface area mesoporous SiC with hierarchical porosity for use as catalyst support

Porous SiC with a hierarchical mesoporous structure is a promising material for high-performance catalytic systems because of its high thermal conductivity, high chemical inertness at high temperature, and oxidation resistance. Attempts to produce high-surface area hierarchical SiC have typically been made by using porous carbon as a template and reacting it with either Si or SiO₂ at high temperature under inert atmosphere. Because the reaction mechanism with Si involves a carbon dissolution step, and the reaction with SiO₂ is highly dependent on C-SiO₂ dispersion, the porous structure of the carbon template is not maintained, and the reaction yields nonporous SiC. In this work, mesoporous SiC has been synthesized using a novel hard-template methodology. SiC was prepared from hierarchical (mesoporous) silica which served as a solid template. Carbon deposition was done by Carbon Vapor Deposition (CVD) using CH₄ as carbon precursor, where different temperatures and reaction times were tested to optimize the carbon coating. The synthesized SiC retained 61 (118 m²/g) and 47% (0.3 cm³/g) of the BET surface area and the mesopore volume of the original SiO₂, which is 10 times higher than the retention reported for other template methods used to produce high surface area SiC.     

Processing of Porous Silicon Carbide Ceramics from Carbon-Filled Polysiloxane by Extrusion and Carbothermal Reduction

Porous silicon carbide (SiC) ceramics with porosities ranging from 60% to 83% were fabricated from extruded blends of carbon-filled polysiloxane using expandable microspheres as sacrificial templates. The fabrication process involved the following steps: (i) extrusion and in situ foaming of a mixture of polysiloxane, carbon black (used as a carbon source), Al₂O₃–Y₂O₃ (used as a sintering additive), expandable microspheres (used as sacrificial templates), and SiC (an optional inert filler); (ii) cross linking the polysiloxane in the extruded blends; (iii) transforming the polysiloxane by pyrolysis into silicon oxycarbide; and (iv) fabricating porous SiC ceramics by carbothermal reduction and subsequent sintering.     

Optimized preceramic polymer for 3D structured ceramics via fused deposition modeling

3D structured ceramics stemmed from preceramic polymers via additive manufacturing have attracted much attention recently. However, these polymers with high ceramic yield are so brittle that extrusion-based additive manufacturing techniques are hardly able to be utilized for assembling 3D structures. Herein, we developed a strategy to prepare feedstocks for these manufacturing techniques, i.e., utilizing a small amount of thermal-plastic polymer to optimize the preceramic polymer while good compatibility is required between the two polymers to ensure a homogeneous mixture. Polycarbosilane and polypropylene were selected as the representative materials. Polypropylene occupied a small proportion (≤5wt.%) and significantly improved the formability of the precursor. Three-dimensional SiC were obtained via fused deposition modeling combined with crosslinking and pyrolysis. The SiC ceramic filaments showed a mean tensile strength of 471 MPa. The strategy is also applicable to a large field of ceramic systems with corresponding precursor, such as sialon ceramic and multicomponent Si-based ceramics.     

Porous Silicon Carbide Ceramics Produced by a Carbon Foam Derived from Mixtures of Mesophase Pitch and Si Particles

Carbon foam templates were prepared from a mixture of mesophase pitch (MP) and Si particles, followed by foaming and carbonization. Subsequent molten Si infiltrated into the carbon foam at 1500°C for 4 h in an inert atmosphere resulted in the formation of porous SiC ceramics. Micrographs were investigated by a scanning electron microscope (SEM), and phase identification of porous SiC ceramics was performed by X-ray diffraction (XRD). The flexural strength and bulk density of porous SiC ceramics were also measured and calculated. The results revealed that the flexural strength of porous SiC ceramics increases with increasing Si content and decreasing porosity. The addition of Si in MP results in an increased densification of porous SiC struts. With 50 wt% Si, porous SiC ceramics with a high flexural strength of 23.9 MPa and a porosity of 55% were obtained.     

Electrically conductive silicon oxycarbide thin films prepared from preceramic polymers

This work focuses on silicon oxycarbide thin film preparation and characterization. The Taguchi method of experimental design was used to optimize the process of film deposition. The prepared ceramic thin films with a thickness of c. 500 nm were characterized concerning their morphology, composition, and electrical properties. The molecular structure of the preceramic polymers used for the preparation of the ceramic thin films as well as the thermomechanical properties of the resulting SiOC significantly influenced the quality of the ceramic films. Thus, an increase in the content of carbon was found beneficial for the preparation of crack-free thin films. The obtained ceramic films exhibited increased electrical conductivity as compared to monolithic SiOC of similar chemical composition. This was shown to correlate with the unique hierarchical microstructure of the SiOC films, which contain large oxygen-depleted particles, mainly consisting of highly graphitized carbon and SiC, homogeneously dispersed in an oxygen-containing amorphous matrix. The matrix was shown to also contain free carbon and to contribute to charge carrier transport between the highly conductive large particles. The ceramic thin films possess electrical conductivities in the range from 5.4 to 8.8 S/cm and may be suitable for implementation in miniaturized piezoresistive strain gauges.