Investigations of the effect of Si addition on graphite elimination and the oxidation behavior of SiC joint using Inconel 625 powder filler

Graphite, whose presence is harmful to the mechanical property, is one of the main reaction products between Ni-based alloy and SiC. This paper reports a method of eliminating graphite based on thermodynamic calculations. Different amounts of Si powders are added into the Inconel 625 powder filler to adjust the interfacial reactions during the brazing process. When the Si content in the liquid reaches the theoretically calculated value, the reactions between the Inconel 625 filler and SiC substrate are suppressed, and no graphite forms on the interface. The graphite-free SiC joints show good oxidation resistance. The joint's strength maintains at 25.7 MPa while that with graphite drastically drops to 5.5 MPa after 185 h oxidation in air. The reaction products and oxidation process of the SiC joints are also carefully analyzed in this paper.     

Nickel-catalyzed preparation of self-bonded SiC refractories with improved microstructure and properties

3C-SiC was synthesized after 3?h firing of Si and expanded graphite in flowing Ar at 1300?°C with in-situ formed Ni nanoparticle (NP) catalyst. First-principles calculations suggest that Ni catalyst accelerated the formation of SiC via weakening the bonds in adsorbed CC bond, and CO and SiO molecules. Apart from this, Ni NP catalyst facilitated the epitaxial growth of SiC nanowires. Based on these findings, self-bonded SiC refractories were prepared by using black SiC grain, expanded graphite and Si powders as raw materials and Ni NP as a catalyst. Large amounts of SiC nanowires were catalytically formed in the fired refractories specimens, which resulted in significant improvements in both mechanical strength (MOR of 32.2?MPa at 1400?°C) and thermal shock resistance. The catalytic formation method investigated in this work could be readily modified and extended to develop many other types of high performance refractories.     

Liquid metal infiltration of silicon based alloys into porous carbonaceous materials Part-III: Experimental verification of conversion products and infiltration depth by infiltration of Si-Zr alloy into mixed SiC/graphite preforms

Porous carbonaceous preforms, made from graphite and silicon carbide (SiC) powders, with varying graphite powder mass fractions and particle sizes, were infiltrated at 1500 °C and 1700 °C by Si-8 at. pct Zr alloy to produce dense Si-Zr-SiC composites. The experiments were performed in a graphite chamber vacuum furnace at 10^?2 mbar. The most desirable results were obtained for preforms composed of a mixture of graphite and SiC powders, with preforms containing 15–20 % mass fraction of graphite and infiltrated at 1500 °C. The banding of the Zr-rich phase observed in the cross-sections of SiC-C pre- forms infiltrated by the Si-Zr alloy may help in decoding the reactive infiltration process with binary alloys.     

Synthesis of ZrC–SiC Powders from Hybrid Liquid Precursors with Improved Oxidation Resistance

ZrC–SiC powders are synthesized by high‐temperature pyrolysis of hybrid liquid precursors, which are prepared from organic Zr‐containing precursor (PZC) and liquid polycarbosilane (LPCS). Due to the excellent miscibility between PZC and LPCS, the hybrid liquid precursors are formed by dissolving PZC into LPCS without adding organic solvent. The viscosity and elemental content of Zr and Si of the hybrid precursors are readily adjustable by controlling the LPCS/PZC mass ratio. SEM and TEM observations reveal that the ZrC–SiC powders pyrolyzed at 1550°C exhibit spherical morphology with characteristic dimension of less than 60 nm, and the two phases are uniformly distributed in composite powders. The advantage of the ZrC–SiC powders synthesized by this novel method is demonstrated by investigating the oxidation behavior of powders with different amount of SiC and ZrC. Below 700°C, ZrC quickly oxidizes to generate an almost nonprotective ZrO₂ scale, whereas at ~ 1000°C, dense and protective SiO₂ forms that improves the oxidation resistance of the ZrC–SiC composite powders.     

ZrB2–SiC–G Composite Prepared by Spark Plasma Sintering of In‐Situ Synthesized ZrB2–SiC–C Composite Powders

To avoid introduction of milling media during ball‐milling process and ensure uniform distribution of SiC and graphite in ZrB₂ matrix, ultrafine ZrB₂–SiC–C composite powders were in‐situ synthesized using inorganic–organic hybrid precursors of Zr(OPr)₄, Si(OC₂H₅)₄, H₃BO₃, and excessive C₆H₁₄O₆ as source of zirconium, silicon, boron, and carbon, respectively. To inhabit grain growth, the ZrB₂–SiC–C composite powders were densified by spark plasma sintering (SPS) at 1950°C for 10 min with the heating rate of 100°C/min. The precursor powders were investigated by thermogravimetric analysis–differential scanning calorimetry and Fourier transform infrared spectroscopy. The ceramic powders were analyzed by X‐ray diffraction, X‐ray photoelectron spectroscopy, and scanning electron microscopy. The lamellar substance was found and determined as graphite nanosheet by scanning electron microscopy, Raman spectrum, and X‐ray diffraction. The SiC grains and graphite nanosheets distributed in ZrB₂ matrix uniformly and the grain sizes of ZrB₂ and SiC were about 5 μm and 2 μm, respectively. The carbon converted into graphite nanosheets under high temperature during the process of SPS. The presence of graphite nanosheets alters the load‐displacement curves in the fracture process of ZrB₂–SiC–G composite. A novel way was explored to prepare ZrB₂–SiC–G composite by SPS of in‐situ synthesized ZrB₂–SiC–C composite powders.     

Experimental additive manufacturing of green body of SiC/Graphite functionally graded materials by stereolithography

Ceramic stereolithography (CSL)-additive manufacturing (AM) technology is used to create a functionally graded ceramic (FGC) green body made of silicon carbide (SiC) and graphite. For the SiC/graphite FGC, the mixing parameters of ceramics powders and ultraviolet (UV) curing resin are improved, and correlations of the resultant slurry curing depth with integrated light intensity are discovered. Therefore, the SiC/graphite FGC-produced green body has no flaws, pores, or cracks on its surfaces. According to the association between cure depth and integrated light density for each slurry's composition, several interfacial collapses discovered in a cracked cross-section might be decreased.     

The graphitization of carbon nanofibers produced by catalytic decomposition of methane: Synergetic effect of the inherent Ni and Si

The catalytic effect of the inherent Ni and Si on the graphitization of carbon nanofibers produced by catalytic decomposition of methane is reported. The participation of the inherent Ni and Si metals as co-catalysts in the graphitization of the carbon nanofibers through the formation of Ni₂Si and SiC was inferred. Taking advantage of this catalytic effect, graphite materials showing structural characteristics comparable to oil-derived graphites which are employed in several industrial applications have been prepared from the carbon nanofibers. Unlike SiC which is further descomposed to graphite, the role of Ni₂Si remains unclear. At the CNFs heat treatment temperatures employed, Ni₂Si is in a liquid state where the carbon can be dissolved to form a supersaturated solution from which the SiC can be produced by segregation, thus being an intermediate stage in the catalytic graphitization of the carbon nanofibers. Further work are currently in progress to go insight this issue.     

Microstructure and ablation behaviors of a novel gradient C/C-ZrC-SiC composite fabricated by an improved reactive melt infiltration

An improved reactive melt infiltration (RMI) route using Zr, Si tablet as infiltrant was developed in order to obtain high-performance and low-cost C/C-ZrC-SiC composite with well defined structure. Two other RMI routes using Zr, Si mixed powders and alloy were also performed for comparison. Effects of different infiltration routes on the microstructure and ablation behavior were investigated. Results showed that C/C-ZrC-SiC composite prepared by Zr, Si tablets developed a dense gradient microstructure that content of ZrC ceramic increased gradually along the infiltration direction, while that of SiC ceramic decreased. Composites prepared by Zr, Si mixed powders and alloy showed a homogeneous microstructure containing more SiC ceramic. In addition, two interface patterns were observed at the carbon/ceramic interfaces: continuous SiC layer and ZrC, SiC mixed layers. It should be due to the arising of stable Si molten pool in the tablet. Among all as-prepared samples, after exposing to the oxyacetylene flame for 60 s at 2500 °C, C/C-ZrC-SiC composite infiltrated by Zr, Si tablet exhibited the best ablation property owing to its unique gradient structure.     

Ni包裹SiC对SiC(Ni)/Fe复合材料性能的影响

分别以SiC粉体和Ni包裹的SiC复合粉体为硬质相,采用热压工艺(1000°C,20°C/min,40 MPa和45 min)制备了SiC含量为1 wt%~9 wt%的SiC/Fe复合材料。采用扫描电镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)等研究了复合材料的界面反应物。研究结果表明:Ni过渡层的存在有效避免了SiC颗粒与Fe基体之间的化学反应。随着Ni包裹SiC粉体含量的增加,复合材料的相对密度和抗弯强度先增加后减小,当SiC(Ni)粉体含量为5 wt%时达到最大值。     

Interfacial reaction mechanism of SiC joints joined by pure nickel foil

To investigate the reaction mechanism of Ni/SiC system, 0.1 μm-thick pure nickel foil is used to join SiC ceramic at 1245 °C for different times. Interfacial melting is calculated to occur at 964 °C along the interface due to the low eutectic point of θ-Ni₂Si and NiSi, a periodical layered structure, consisting alternating layers of silicides/silicides+graphite, is formed along the interface due to periodical detachment of graphite from SiC reaction interface during the reactions between Ni-Si liquid phase and SiC. The reaction products of Ni/SiC are successfully predicted by CALPHAD method, based on a home-made Ni-Si-C ternary database. The reaction processes between Ni and SiC and the morphology changes of the joined seam are discussed in detail in this paper. The average shear strengths of SiC joints held for 15 min, 30 min and 60 min are tested to be 16.53 MPa, 19.32 MPa and 29.43 MPa, respectively.     

Oxidation bonding of porous silicon carbide ceramics with synergistic performance

Porous silicon carbide (SiC) ceramics were fabricated by an oxidation-bonding process, in which the powder compacts are heated in air so that SiC particles are bonded to each other by oxidation-derived SiO₂ glass. It has been shown that a high porosity can be obtained by adding a large amount of graphite into the SiC powder compacts and that the pore diameter can be controlled by the size of graphite particles and/or SiC powders. When a 0.3-μm SiC powder was used, a high strength up to 133 MPa was achieved at a porosity of 31.5%. Moreover, oxidation-bonded SiC (OBSC) ceramics were observed to exhibit an excellent resistance to oxidation and thermal shock.     

Effect of silicon/graphite ratio and temperature on oxidation protective properties of SiC/ZrB2–SiC coatings prepared by pack cementation

To investigate the silicon/graphite ratio and temperature on preparation and properties of ZrB₂–SiC coatings, ZrB₂, silicon, and graphite powders were used as pack powders to prepare ZrB₂–SiC coatings on SiC coated graphite samples at different temperatures by pack cementation method. The composition, microstructure, thermal shock, and oxidation resistance of these coatings were characterized and assessed. High silicon/graphite ratio (in this case, 2) did not guarantee higher coating density, instead could be harmful to coating formation and led to the lump of pack powders, especially at temperatures of 2100 and 2200 °C. But residual silicon in the coating is beneficial for high density and oxidation protection ability. The SiC/ZrB₂–SiC (ZS50-2) coating prepared at 2000 °C showed excellent oxidation protective ability, owing to the residual silicon in the coating and dense coating structure. The weight loss of ZS50-2 after 15 thermal shocks between 1500 °C and room temperature, and oxidation for 19 h at 1500 °C are 6.5% and 2.9%, respectively.     

Novel synthesis and characterization of silicon carbide nanowires on graphite flakes

Silicon carbide nanowires were synthesized on the surface of graphite by partially reacting with silicon powders in NaF–NaCl based salt at 1150–1400 °C in argon. The effects of temperature and time of heat treatment as well as Si/graphite ratio on synthesis of SiC nanowires were studied. The results showed that the formation of SiC nanowires started at about 1200 °C, and the amounts of SiC nanowires increased in the resultant powders with increasing temperature. Their morphologies were characterized by scanning electron microscopy and high-resolution transmission electron microscopy. It was found that β-SiC nanowires with diameter of 10–50 nm and various lengths grew along their preferred direction perpendicular to (111). The zeta potential of graphite was also increased after coating with silicon carbide nanowires. SiC nanowires that formed on the graphite surface acted as an anti-oxidant to a certain extent, and they protected the inner graphite from oxidation.     

Preparation of SiC coated graphite flake with much improved performance via a molten salt shielded method

Oxide-based castables have been used in high-temperature furnace linings, especially for steel and iron processing, however, the poor thermal shock resistance and corrosion resistance limited the further enhancement of their service life. Carbon possesses excellent performances including low wettability to slag, low thermal expansion coefficient, which can greatly improve thermal shock resistance and slag resistance of oxide-based castables. However, it has poor water-wettability and oxidation resistance, which limited its application in the castables. Many efforts have been attempted to improve water-wettability of graphite flake used for carbon-containing castables, but it is still a huge challenge. In this work, a facile method for fabricating silicon carbide (SiC) coated graphite flakes has been firstly proposed by using graphite flake and silicon powder as the precursors via a molten salt shielded synthesis technique in air atmosphere, KCl was chosen to be a salt encapsulation providing a liquid reaction medium and a shield against oxidation of air. Effects of firing temperature, holding time, and molar ratio of Si and graphite flake on the formation of SiC coatings were investigated. The results show that the as-prepared SiC coated graphite powders were loose and non-agglomerated, and the coatings with ∼5 μm in thickness were crack-free and firmly grown on the surface of graphite flake, composed of SiC nanosized particles. Compared to uncoated graphite flake, the SiC coated graphite possessed significantly improved water-wettability, dispersibility, and oxidation resistance, making it to be a prime carbon form for fabricating carbon-containing castables.     

Microstructures and mechanical properties of Cf/LAS composite and Ti60 alloy joints brazed with TiZrNiCu + Cf mixed powders

In this paper, carbon fiber reinforced lithium aluminosilicate (LAS) glass-ceramics matrix composites (C_f/LAS composites) are joined to Ti60 alloy using TiZrNiCu + C_f mixed powders by proper process parameters. The carbon fibers distribute uniformly in the brazing interlayer and react with Ti, Zr elements in the brazing alloy to form (Ti, Zr)C thin reactive layers, which are between the carbon fibers and the Ti, Zr elements. The effect of C_f content on the mechanical properties and microstructure of brazed joints are investigated. The microstructure of brazed joints varied obviously with the increasing of C_f content. The thickness of reactive layer between interlayer and C_f/LAS composites and Ti solid solution (Ti (s.s)) decrease gradually, and the volume of eutectic structure (Ti(s,s) + (Ti,Zr)₂(Ni,Cu)) decrease gradually. The obtained brazed joints exhibit a maximum shear strength of 73.5 MPa at room temperature using TiZrNiCu + 0.3 wt% C_f mixed powders. The enhanced shear strength can be attributed to the reduction in thermal stress and the reinforcing effect originated from the carbon fiber addition.     

Polymer precursor synthesis of novel ZrC–SiC ultrahigh-temperature ceramics and modulation of their molecular structure

In this study, ZrC–SiC composite ceramics were prepared with varying Zr/Si molar ratios using sol–gel method. Composites were characterized by Fourier-transform infrared spectroscopy (FT–IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman spectroscopy, and energy-dispersive X-ray spectroscopy (EDS). FT–IR analysis confirmed macromolecular network structure of composites, in which the precursor is composed of polyvinyl butyral (PVB) as main chain, silane molecules are interlinked via –OH moieties in PVB side chains, and Zr atoms are crosslinked with Si in corresponding proportion. Ceramic precursor begins to decompose at a temperature exceeding 1300 °C and is completely transformed into ZrC–SiC composite ceramics with corresponding Zr/Si molar ratio at 1600 °C. Raman spectroscopy and TEM results reveal that after annealing at 1600 °C, ZrC powder uniformly covers surface of SiC ceramics, and high-crystallinity graphite carbon covers ZrC powder.     

Effect of preparation conditions on diamond cluster formation in bulk nanoporous carbon

The structure of bulk nanoporous carbon chemically prepared from SiC powders is studied by TEM microdiffraction and HRTEM techniques. The conditions for the formation of diamond and graphite clusters in the carbonization process are analyzed. The experimental data suggest that diamond clusters can be produced near carbonization reaction front in the case of its quick propagation into the precursor. The slower the reaction front, the greater is the chance that graphite or quasi-graphite clusters are formed.     

In situ reaction synthesis of Al2O3–SiC nanostructure using different carbon sources

Abstract

The formation of Al₂O₃–SiC nanostructure was studied using three different carbon sources (charcoal activated, graphite and carbon black) mixed with colloidal silica and aluminium nitrate. All mixtures were heated at 1500°C for duration of 30, 45 and 60 min. The results showed that Al₂O₃–SiC powders with an average diameter of ～220 nm and almost equiaxial geometry with aspect ratio of 1–1·2 could only be synthesised from the mixture containing carbon black (30 wt-%) at low heating time (30 min). It was found that the intensity of SiC peaks was the highest in samples containing graphite which was attributed to the higher initial density of this sample.     

Brazing SiC ceramics and Zr with CoCrFeNiCuSn high entropy alloy

CoCrFeNiCuSn high-entropy alloy and Cu foam composite interlayer was used as a filler for the brazing of SiC ceramics and Zr. The microstructure and mechanical properties of the brazed joint at room temperature and high temperatures as well as the brazing mechanism were systematically investigated. The microstructure is adjusted by controlling the brazing temperature. The main phases in the joint were identified at different brazing temperatures to be a high-entropy alloy phase, α-Zr (s, s), Zr₂Cu, (Zr, Sn) and Zr(Cr, Fe)₂ Laves phase. The joint brazed at 1040 °C for 20 min exhibited a maximum shear strength of 221 MPa at room temperature and an average shear strength of 207 MPa at 600 °C. The room temperature and high temperature-strength obtained here are much higher than those obtained for joints brazed using a conventional filler. Owing to the high-entropy effect, the joint matrix is mainly composed of solid solution phase, which improves the strength and thermal stability of the joint. The existence of the hard Zr(Fe, Cr)₂ Laves phase and the soft α-Zr (s, s) phase in the joint significantly improves its strength and plasticity.     

石墨粉电镀法镀锌工艺研究

过电镀法使锌均匀沉积在预处理过的微米级鳞片石墨上,从而制得石墨／锌复合材料。研究了镀锌过程中镀锌工艺条件对电镀效果及镀锌石墨粉含锌量的影响。用扫描电镜对镀锌石墨粉的微观形貌进行分析,用X射线衍射仪对镀锌石墨粉850℃灼烧后的剩余物进行分析并推导出计算镀锌石墨粉含锌量的计算公式。研究结果表明：采用电镀法可在预处理过的微米级鳞片石墨粉表面成功镀覆上一层均匀致密的单质锌,镀锌石墨粉的含锌量70wt％以上。