Stereolithography 3D printing of SiC ceramic with potential for lightweight optical mirror

Silicon carbide (SiC) ceramic is the most prospective candidate material for space-based lightweight optical mirror. Stereolithography 3D printing has been reported to fabricate many kinds of ceramics, showing great potential for fabricating lightweight SiC ceramic optical mirror. In this paper, SiC ceramic was fabricated using stereolithography 3D printing combined with polymer burn-out, pre-sintering, and precursor infiltration and pyrolysis (PIP). The relative density, flexural strength, and microstructure during each step were investigated. The as-prepared lightweight SiC ceramic optical mirror exhibited high accuracy and high quality. Finally, it was proved that stereolithography 3D printing has a great potential for lightweight SiC ceramic optical mirror fabrication.     

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.     

Fabrication of SiC ceramic architectures using stereolithography combined with precursor infiltration and pyrolysis

Stereolithography based additive manufacturing provides a new route to produce ceramic architectures with complex geometries. In this study, 3D structured SiC ceramic architectures were fabricated by stereolithography based additive manufacturing combined with precursor infiltration and pyrolysis (PIP). Firstly, photosensitive SiC slurry was prepared. Then, stereolithography was conducted to fabricate complex-shaped green SiC parts. Polymer burn-out was subsequently performed, and porous SiC preforms were produced. After that, precursor infiltration and pyrolysis was used to improve the density and strength. Finally, 3D-structured SiC ceramic architectures with high accuracy and quality were obtained. It is believed that this study can give some fundamental understanding for the additive manufacturing of SiC ceramic structures.     

Silicon infiltrated silicon carbide from extruded thermoplastic wood polymer composites

Silicon-infiltrated silicon carbide (SiSiC) is an important technical ceramic material for several demanding applications such as heat exchangers, nozzles or mechanical seals. However, shaping and machining tools are quickly worn down, due to the application of hard abrasive silicon carbide (SiC) particles as part of the conventional starting compounds for monolithic SiSiC ceramics. Within this work, an alternative route fabricating SiSiC without primary SiC particles and with low residual carbon contents derived from thermoplastic wood polymer composites (WPC) is described. By varying the proportions of the raw materials, the phase compositions of the SiC ceramic could be modified. A reduction in the average wood particle size from 120 to 60 µm led to a homogenous SiSiC with high SiC content. SiSiC with flexural strengths up to 230 MPa and a Weibull modulus of 16 were developed. The residual carbon content could be reduced below 1 wt%.     

The fabrication and mechanical properties of SiC/SiC composites prepared by SLS combined with PIP

Traditionally, SiC components with complex shapes are very difficult or even impossible to fabricate. This paper aims to develop a new manufacturing process, combining selective laser sintering (SLS), cold isostatic pressing (CIP) and polymer infiltration pyrolysis (PIP), to manufacture complex silicon carbide parts and improve the mechanical properties of silicon carbide ceramic parts. The density and porosity of SiC/SiC composites were measured. Furthermore, the mechanical properties of the specimens with cold isostatic pressing and the specimens without cold isostatic pressing were compared. The bending strength of the specimens with cold isostatic pressing was 201?MPa, and the elastic modulus was 1.27?GPa. And, the bending strength of the specimens without cold isostatic pressing was 142?MPa, and the elastic modulus was 0.88?GPa. Increasing the density of SiC/SiC can enhance the mechanical properties of SiC/SiC composites.     

Microstructure Evolution and Reaction Mechanism of Biomorphous SiSiC Ceramics

Liquid Si infiltration (LSI) of beech wood-derived biocarbon (C_B) templates at 1550°C yields biomorphous SiSiC ceramics with the morphology of the initial biological preform. The biomorphous SiSiC ceramic consists of solidified Si in the cell lumina, polycrystalline β-SiC and residual carbon islands located at the position of former wood cell walls. The evolution of the microstructure during reactive Si melt infiltration was assessed by infiltration experiments at various times and investigated by X-ray diffraction as well as light scanning electron and transmission electron microscopy in combination with elemental analysis by energy-dispersive X-ray spectrometry. Four different stages of the reactive infiltration process could be distinguished, starting with a heterogeneous nucleation of nano-grained SiC on the pore surfaces of the C_B template by a Si vapor phase reaction below the Si melting temperature. After spontaneous Si melt infiltration, a stepwise reaction results in the simultaneous formation of a nano-grained SiC layer and a coarse-grained SiC phase on the inner pore surfaces. Further reaction proceeds slowly by diffusion of the reactants through the formed SiC layer and the microstructure evolution is dominated by dissolution and re-crystallization processes.     

Direct laser sintering of reaction bonded silicon carbide with low residual silicon content

Additive manufacturing (AM) techniques are promising manufacturing methods for the production of complex parts in small series. In this work, laser sintering (LS) was used to fabricate reaction bonded silicon carbide (RBSC) parts. First, silicon carbide (SiC) and silicon (Si) powders were mixed in order to obtain a homogeneous powder. This powder mixture was subsequently laser sintered, where the Si melts and re-solidifies to bind the primary SiC particles. Afterwards, these SiSiC preforms were impregnated with a phenolic resin. This phenolic resin was pyrolysed yielding porous carbon, which was transformed into secondary reaction formed SiC when the preforms were infiltrated with molten silicon in the final step. This resulted in fully dense RBSC parts with up to 84?vol% SiC. The optimized SiSiC combined a Vickers hardness of 2045?HV, an electrical conductivity of 5.3?×?10³?S/m, a Young's modulus of 285?GPa and a 4-point bending strength of 162?MPa.     

Bioinspired Rattan-Derived SiSiC/Zeolite Monoliths: Preparation and Characterisation

In the present article, a three-step process for the preparation of SiSiC/zeolite composites is presented. Rattan-derived SiSiC composites were obtained via a two-step biotemplating liquid silicon infiltration process (LSI). The LSI process, consisting of pyrolysis of the biotemplates (Rattan stems) followed by reactive infiltration of the carbon preforms with liquid silicon at 1550 °C, led to the formation of SiSiC ceramic composites. The SiSiC replicas (59 wt.% of SiC, 40 wt.% of solidified Si, 1 wt.% carbon) faithfully reproduced the macrostructure of Rattan and exhibited an open porosity between 20 and 40 vol.%, with unidirectional parallel microchannels in the range of 100–300 μm in diameter. In a third stage MFI-type zeolite (Silicalite-1 and ZSM-5) coatings were developed on the SiSiC ceramic supports via a partial conversion of the substrate into zeolite (support self-transformation method). The metallic Si in the support was partially dissolved under hydrothermal conditions in a reaction mixture consisting of deionised water, template (TPABr) and NaOH, but without any external Si-source. The influence of different synthesis parameters in the development of the zeolite coating is discussed in detail. The resulting products were characterised by X-ray diffraction, TGA, N₂ adsorption/desorption and SEM-EDX. The filtrates were analysed by ICP-OES. SEM and adsorption measurements revealed that biomorphic cellular SiSiC/zeolite composites possess bimodal (micro-/macro-) porosity. In the final SiSiC/zeolite composite, a maximum zeolite loading up to 40 wt.% was calculated on the basis of TGA and XRD analyses. Thermal shock tests showed that a good coating adherence to the SiSiC substrate was obtained. In addition, a SiSiC/ZSM-5 monolith was also tested as structured catalyst for n-hexane cracking.     

Friction and wear properties of C/C–SiC braking composites

Two series of C/C–SiC composites were fabricated via precursor infiltration pyrolysis (PIP) and chemical vapor infiltration (CVI) using porous C/C composites with different original densities as preforms, respectively. The tribological characteristics of C/C–SiC braking composites were investigated by means of MM-1000 type of friction testing machine. The friction and wear behaviors of the two series of composites were compared and the factors that influence the friction and wear properties of C/C–SiC composites were discussed. Results show that the friction and wear properties relate close-knit to the content of SiC and porosity. As the original preform density increasing, the content of SiC and porosity decrease, and then the friction coefficient increases obviously, the braking time and the wear rate both decrease. Preparation techniques play an important role in the tribological properties of C/C–SiC composites. Compared with PIP process, the samples from CVI have a little higher friction coefficient, shorter braking time and higher wear rate.     

Preparation and mechanical characteristics of fine-woven cloth and punctured felt preform Cf/C-SiC-ZrC composite

A 3D architecture carbon fiber preform, specifically fine-woven cloth and punctured felt preform, is used to manufacture a novel advanced C_f/C-SiC-ZrC composite. The composite matrix is produced by chemical vapor infiltration (CVI) plus precursor infiltration and pyrolysis (PIP) process and finalized by using a chemical vapor deposition (CVD) of SiC coating to make the final density of the material reach 1.95 g/cm³. The organic precursors of SiC and ZrC have a weight ratio of 4:1 in a xylene solute. The composite mechanical properties, such as tensile, compression, bending, shear, and Z-direction load bearing, are introduced under analysis to find possible applications for the composite. What is more, scanning electron microscope (SEM) images are employed to illustrate the failure behavior of the ceramic composite. The results showed that the punctured filament tows will be beneficial, not only for the composite to withstand compression force up to 308.6 MPa and shear strength to 18.14 MPa but also for the alternatively stacked weave piles and short fiber layers to support the punctured bundles, as well as to hold the composite structure under mechanical forces from different orientations, which is believed to reinforce the ceramic matrix for some high pressure and severe ablation applications.     

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.     

Preparation of low residual silicon content Si-SiC ceramics by binder jetting additive manufacturing and liquid silicon infiltration

Complex silicon carbide (SiC) ceramic components are difficult to fabricate due to their strong covalent bonds. Binder jetting (BJ) additive manufacturing has the outstanding advantages of high forming efficiency and no thermal deformation, especially suitable for printing complex structure SiC components. This study tried to obtain low silicon content silicon carbide ceramics by binder jetting followed by phenolic resin impregnation and pyrolysis (PRIP) and liquid silicon infiltration (LSI). BJ was used for the SiC green parts fabrication, and the highest compressive strength (7.7 ± 0.3 MPa) and lowest dimensional deviations (1.2–1.6 mm) were obtained with the printing layer thickness of 0.15 mm. Subsequently, PRIP treatments were introduced to increase the carbon content for the following LSI process. As the number of PRIP cycles increased, the carbon density of SiC/C preform increased and the porosity decreased. After the LSI treatment, the final Si-SiC composites processed with 2 PIRP cycles reached the highest flexural strength (257 ± 14.26 MPa) and the best wear resistance. This was attributed to the low residual silicon content (10.2 vol%) and almost no residual carbon. Furthermore, several complex structural components were fabricated using these methods. The preparation of complex components verifies the feasibility of BJ and LSI for manufacturing high-strength and high-precision SiC ceramics. Besides, this work hopes to provide technical guidance for the preparation of complex SiC composites in the future.     

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%.     

Comparison of Two Processes for Manufacturing Ceramic Matrix Composites from Organometallic Precursors

A commercial polysilazane is used as a silicon carbonitride matrix precursor for the manufacture of ceramic matrix composites using bi-directional SiC Nicalon fabrics as reinforcing material. The objective is to develop a simple and fast process leading to materials able to compete with SiC/C/SiC composites obtained by the Chemical Vapour Infiltration (CVI) route. Two processes are investigated: (1) a ‘conventional’ process using the densification of a SiC fibre preform by several cycles of impregnation of the preform with the polymer followed by pyrolysis and (2) a ‘modified’ process consisting in a powder filling of the fibre preform prior to the precursor impregnation and pyrolysis. This paper describes the different steps of both processes. The materials obtained are characterised in terms of their porosity, microstructure and mechanical properties. ©     

C/C–SiC composites derived from single-source poly(silylene–acetylene) precursors

Carbon-fiber-reinforced carbon–silicon carbide (C/C–SiC) composites were prepared by impregnating carbon fibers with ethynylphenyl-terminated poly(silylene–acetylene) (EPTSA) as a single-source precursor with subsequent hot pressing and pyrolysis. The structural evolution, crystallization behavior, and graphitization of bulk C–SiC ceramics, as well as their mechanical properties and ablation behavior, were investigated. The EPTSA precursor starts to transform into inorganic SiC ceramic materials at 800°C, which is characterized by an amorphous structure with weight loss, shrinkage, and densification between 800 and 1000°C. The formation of SiC crystals inhibited the growth of the graphitic structure between 1000 and 1200°C. As the temperature was raised, both graphite and SiC crystals continued to grow, and the crystalline forms became more complete. The carbon-fiber cloth (T300CF)-reinforced C–SiC composite (T300CF/C–SiC) prepared using polymer infiltration and pyrolysis (PIP) exhibited excellent mechanical properties. After five PIP cycles, the flexural strength, flexural modulus, and interlaminar shear strength of the T300CF/C–SiC composite reached 169 MPa, 32.5 GPa, and 9.38 MPa, respectively. In addition, the chopped-carbon-fiber-reinforced C–SiC composite fabricated using the PIP process demonstrated good oxyacetylene-torch ablation properties.     

Additive manufacturing of continuous carbon fiber reinforced high entropy ceramic matrix composites via paper laminating,direct slurry writing,and precursor infiltration and pyrolysis

In this study, continuous carbon reinforced C_f/(Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C–SiC high entropy ceramic matrix composites were additively manufactured through paper laminating (PL), direct slurry writing (DSW), and precursor infiltration and pyrolysis (PIP). (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C high entropy ceramic (HEC) powders were synthesized by pressureless sintering and ball milling. A certain proportion of HEC powder, SiC powder, water, binder, and dispersant were mixed to prepare the HEC-SiC slurry. Meanwhile, BN coating was prepared on the 2D fiber cloth surface by the boric acid-urea method and then the cloth was cut into required shape. Additive manufacturing were conducted subsequently. Firstly, one piece of the as-treated carbon fiber cloth was auto-placed on the workbench by paper laminating (PL). Then, the HEC-SiC slurry was extruded onto the surface of the cloth by direct slurry writing (DSW). PL and DSW process were repeated, and a C_f/HEC-SiC preform was obtained after 3 cycles. At last, the preform was densified by precursor infiltration and pyrolysis (PIP) and the final C_f/HEC-SiC composite was prepared. The open porosity of the C_f/HEC-SiC composites, with the HEC volume fractions of 15, 30 and 45%, were 7.7, 10.6, and 11.3%, respectively. And the density of the C_f/HEC-SiC composites, with the HEC volume fractions of 15, 30 and 45%, were 2.9, 2.7 and 2.3 g/cm³, respectively. The mechanical properties of the C_f/HEC-SiC composites increased firstly and then decreased with the HEC content increase, reaching the maximum value when the HEC volume fraction was 30%. The mechanical properties of the C_f/HEC-SiC composites containing 45, 30 and 15% HEC were as follows: flexural strength (180.4 ± 14 MPa, 183.7 ± 4 MPa, and 173.9 ± 4 MPa), fracture toughness (11.9 ± 0.17 MPa m^1/2, 14.6 ± 2.89 MPa m^1/2, and 11.3 ± 1.88 MPa m^1/2), and tensile strength (71.5 ± 4.9 MPa, 98.4 ± 12.2 MPa, and 73.4 ± 8.5 MPa). From this study, the additive manufacturing of continuous carbon fiber reinforced high entropy ceramic matrix composites was achieved, opening a new insight into the manufacturing of ceramic matrix composites.     

Interaction of fiber matrix bonding in SiC/SiC ceramic matrix composites

Non-oxide ceramic matrix composites (CMC) based on SiC fibers with SiC matrix were fabricated by polymer infiltration and pyrolysis (PIP) and characterized regarding their microstructural features and their mechanical properties. The fiber preform was made using winding technology. During the winding process, the SiC fiber roving was impregnated by a slurry containing SiC powder and sintering additives (Y₂O_3, Al₂O₃ and SiO₂). This already helped to achieve a partial matrix formation during the preform fabrication. In this way, the number of PIP cycles to achieve composites with less than 10% open porosity could be reduced significantly. Additionally, damage-tolerant properties of the composites were obtained by an optimal design of the matrix properties although only uncoated fibers were used. Finally, composites with a strength level of about 500 MPa and a damage-tolerant fracture behavior with about 0.4% strain to failure were obtained.     

SiC陶瓷基体及抗氧化涂层

介绍了5种主要SiC基体的成型方法,分别是化学气相渗透(CVI)、聚合物先驱体浸渍-裂解法(PIP)、液相硅渗透法(LSI)、反应烧结法、化学气相反应法(CVR)。阐述了各种基体的组织结构、致密效率及陶瓷基复合材料的性能,其中CVI+PIP/LSI的复合成型技术可达到优化的制备过程,提高基体的组织结构和致密化效率;C/C及C/SiC复合材料表面化学气相转换法SiC涂层及多层涂层技术是提高CMC抗氧化性能的有效途径,并已得到工程实际验证。     

Liquid metal infiltration of silicon based alloys into porous carbonaceous materials. Part I: Modelling of channel filling and reaction phase formation

A relation for an adequate pore fraction needed to obtain residual Si and C free composites via reactive Si-X alloy infiltration is presented. The volume ratio of SiC and carbonaceous phase, the composition of the infiltrating liquid and the apparent density of the preform are used as design entities. The approach allows identifying combinations of these design entities leading to desirable microstructures, e.g. those free of residual silicon or free of excess graphite. The approach gives further access to important post infiltration characteristics like propensity of the various phases.An idealising mathematical model describing the reactive flow of Si-X alloy in a single micron sized capillary channel of carbon as well as in carbonaceous preforms is presented. The model is further expanded to evaluate the infiltration depth in porous carbonaceous preform for a given composition of Si-X alloy and infiltration temperature. The model is presented for both isothermal and non-isothermal cases.The analysis is formulated in general terms and is hence applicable to a large variety of Si-C-refractory metal systems of potential interest.     

Damage development during flexural loading of a 5-directional braided C/C-SiC composite,characterized by X-ray tomography and digital volume correlation

In situ observations of damage development within 3-dimensional 5-directional braided carbon fiber reinforced carbon and silicon carbide (C/C-SiC) ceramic composites, fabricated by gaseous silicon infiltration (GSI) and precursor infiltration pyrolysis (PIP), have been obtained using laboratory X-ray computed tomography during in situ flexural tests. The GSI composite has a denser structure than that fabricated by PIP, but contains initial defects within the fiber bundles. The GSI composite ultimately failed due to fracture across the fiber bundles, while failure of the higher strength PIP composite propagated along the interface between the fiber bundle and matrix with a greater degree of fiber pullout. These differences arise from the higher process temperature and greater degree of matrix-fiber reaction of GSI compared to PIP. Digital volume correlation (DVC), applied to the tomographs, measured the 3-dimensional deformations and hence the specimen curvature. This demonstrated the significant reduction in elastic modulus caused by the development of internal cracking with tensile strain in both materials.