Incorporating Zr to achieve self-protecting and enhancement of silica sol bonded SiC castables at active oxidation condition

SiC castables exhibit degraded properties in static air at 1700 °C, due to the formation of gaseous products. The efficiency of different contents of Zr in SiC castables was evaluated by considering sintered properties, mechanical performance, isothermal oxidation behavior, and microstructural analysis of the SiC castables. Specimens with more Zr exhibited enhanced mechanical behavior and anti-oxidation capability. The addition of Zr decreased the evaporation of SiO₂ by reducing its equilibrium partial pressure (g), and formed a dense ZrO₂-SiO₂ protective layer (e.g., the sample with 0.9 wt% Zr) to prevent further degradation of the SiC castable. The Zr that was preferentially oxidized to ZrO₂ reduced the partial pressure of the oxidizing gases (O₂ and CO₂) in the matrix, and increased SiO (g) content, which facilitates formation of SiC fibers, which, in turn, improves the anti-oxidation capability and mechanical behavior of SiC castables, preventing their degradation in static air at 1700 °C. The addition of Zr created a ZrO₂-SiO₂ protective layer on the surface and prevented the decrease in SiC content, by forming SiC fibers. This made the silica sol bonded SiC castable a self-protecting refractory.     

Effects of andalusite aggregate pre-fired at different temperatures on volume stability and oxidation resistance of Al2O3–SiC–C castables

In the present work, the effects of the pre-firing temperature of andalusite aggregates (5–3 mm) on the conversion of andalusite as well as the volume stability and oxidation resistance of the Al₂O₃–SiC–C castables were investigated. The phases of the andalusite aggregates were tested via X-ray diffraction, and their microstructures as well as those of the castables were characterized via scanning electron microscopy. The linear expansion of the castables decreased with increase in the pre-firing temperature of andalusite, as less residual andalusite in the pre-fired aggregates lowered its transformation in the castables during firing at high temperatures. Moreover, the higher amounts of SiO₂-rich glass produced by andalusite pre-fired at high temperatures and secondary mullite generated between andalusite and the matrixes were both favorable to the production of castables with denser structure. This prevented the diffusion of O₂ into the castables and improved their oxidation resistance.     

Carbon containing castables: current status and future prospects

Abstract

Measures to overcome the main technical di fficulties hindering the development and application of carbon containing castables are discussed. The aqueous wettability and dispersion properties of graphite can be improved by coating with materials such as carbides (SiC) and oxides (Al₂O₃, TiO₂, SiO₂, MgO, ZrO₂) or by forming micropellets / briquettes. Thick and dense crack free coatings are needed not only to improve the aqueous wettability and dispersion of graphite, but also its oxidation resistance. Small and dense micropellets or briquettes enable a homogeneous distribution of graphite in the matrix to be achieved, along with acceptable mechanical strength and corrosion resistance. Coating techniques have also been used to improve the hydration resistance of aluminium based antioxidants, but detailed studies in this area are still needed. The main binder systems are currently based on superfine silica fume and hydratable alumina as these do not form low melting phases in castables. As well as developing the existing coating and micropellet/briquette fabrication techniques, future work will continue to seek novel methods of incorporating graphite, and will begin to investigate installation methods and drying and heating schedules.     

High-temperature oxidation response of Mo–Si–B composites with TiO2W/SiCW addition

In this study, TiO_2W addition improved the oxidation resistance of the Mo–Si–B composite at 1300 °C. The TiO₂ partially dissolved in SiO₂ modified the network structure of the SiO₂ glass and improved its fluidity at the initial oxidation stage. This favored to a continuous scale cover on the surface of the Mo–Si–B composite rapidly. The residual TiO_2W promoted the formation of a passivated multilayer borosilicate scale at current temperature, which could impede the MoO₃ volatilisation and O diffusion at the stable oxidation stage. The SiC_W addition, compared to the TiO_2W, especially could ensure the Mo–Si–B–SiC composite withstand a higher temperature such as 1400 °C. Its oxidation and the more intermetallics in the composite could increase the number of active sites of the SiO₂ glass, thereby supplying the borosilicate scale with a relatively sufficient Si element. Thus, the transient oxidation stage was minimised and the initial mass loss was reduced, which indicated a continuous borosilicate scale had formed quickly at the initial stage. Finally, the improved viscosity of the borosilicate due to a lower B/Si ratio, could obviously decreased the oxygen diffusion and enabled the formation of a protective borosilicate layer at or above 1400 °C.     

Ablation resistant ZrC coating modified by polymer-derived SiC/TiC nanocomposites for ultra-high temperature application

To improve the ablation resistance of ZrC coating on SiC-coated carbon/carbon composites above 2000 °C, SiC/TiC nanocomposites (SiC/TiC-NCs) powders derived from single-source precursor were incorporated into ZrC coating, denoted as ZrC-SiC/TiC-NCs, via supersonic atmospheric plasma spraying (SAPS). After SAPS, the incorporated SiC/TiC-NCs evolved into TiC/(SiC and Zr_xTi_yC) embedded in amorphous SiC. The ablation resistance of the ZrC-SiC/TiC-NCs coating was evaluated by oxyacetylene flames with a heat flux of 4.18 MW/m². For comparison, the ZrC-SiC-NCs coating without Ti modification was seriously damaged due to rapid gas denudation. The good ablation resistance of ZrC-SiC/TiC-NCs coating is mainly attributed to the distinctive “capsule-like” multi-crystalline microstructure of SiC/TiC-NCs. During ablation, TiO₂ and Zr_xTi_yO₂, due to the oxidation of TiC and Zr_xTi_yC, contributed to the formation of Zr-Ti-Si-O glass with high viscosity and low evaporation pressure, improving the ablation resistance.     

Effect of carbon black on corrosion resistance of Al2O3–SiC–C castables to SiO2–MgO slag

Metallurgical solid waste recycling is the shape of things to come in green development of Chinese iron and steel industry. Utilization of ironworks slag for producing mineral wool at high temperature is an important approach. However, refractory lining is seriously corroded by the SiO₂–MgO based slag at 1600 °C during the production process. Different production steps need different atmospheres, the changeable service atmospheres (air and reducing atmosphere) put forward high requirements for slag resistance. The Al₂O₃–SiC–C castables containing carbon black are usually used in iron runner, which faces high-temperature service condition of 1450 °C–1500 °C. Nevertheless, the function of carbon black in the Al₂O₃–SiC–C castables at 1600 °C is till essentially unknown. In the current study, the carbon black was introduced to tabular alumina based Al₂O₃–SiC–C castables to improve corrosion resistance to SiO₂–MgO based slag at 1600 °C. The result showed that 0.4 wt% carbon black was suitable for the castables, which the slag resistance of castables was significantly improved. The carbon black had contributed to block slag by wettability resistance. By comparison with the castables without carbon black, the corrosion index and penetration index had been reduced by 20.2% and 28.0%, respectively, under air atmosphere. And there were little corrosion or penetration under reducing atmosphere for castables with 0.4 wt% carbon black. For the mechanical properties, the Al₂O₃–SiC–C castables with 0.4 wt% carbon black could serve production process although the carbon black impaired the physical properties.     

Effect of partial substitution of alumina–chromium slag for Al2O3 on microstructures and properties of Al2O3–SiC–C trough castables

Alumina–chromium slag (ACS), a cheap and abundant refractory raw material comprising aluminum–chromium oxides and β-Al₂O₃, is a byproduct of ferrochrome smelting. For this reason, we investigated the relationships between composition and mechanical properties, abrasion resistance, oxidation resistance, and resistance to iron slag erosion for Al₂O₃–SiC–C trough castables in which ACS was substituted for alumina. Due to the presence of β-Al₂O₃ in ACS, the aluminum-chromium slag reacted with SiO₂ to form a low-melting phase of albite and promoted the formation of mullite, which filled the pores at high temperatures and reduced the porosity, thereby promoting densification and strengthening of the sample. The cold mechanical properties of the sample and the normal temperature wear resistance were enhanced, but the high-temperature mechanical properties and the resistance to iron slag corrosion of the sample were impaired. According to the results of the anti-oxidation experiment, the presence of β-Al₂O₃ in the ACS reduced the porosity and made the sample more dense, which remarkably improved oxidation resistance of the sample. For industrial production requirements, ACS substitution should not exceed 48?wt% due to of thermomechanical properties and anti-slag corrosion performance in Al₂O₃–SiC–C trough castables.     

Enhancement of bonding network for silica sol bonded SiC castables by reactive micropowder

Silica sol bonded castables have obvious advantages over low cement or hydratable alumina bonded castables in drying performance and sintering properties for SiC castables. However, they are not widely used due to their weak strength at low temperature. The efficiency of bonding network for silica sol bonded SiC castable in the presence of different reactive micropowder such as SiO₂ micropowder and α-Al₂O₃ micropowder was evaluated through oscillatory tests, sintered properties and microstructural analysis. Results show that the polymerization reaction between SiO₂ micropowders enhanced the siloxane network and reinforced the bonding strength, furthermore, the addition of α-Al₂O₃ micropowder contributed to accelerating the formation of the siloxane network and hardening of the silica sol at lower temperatures and shorter time. Silica sol performed well as a binder agent for SiC castables with an addition content of 3 wt% SiO₂ micropowder and 2 wt% α-Al₂O₃ micropowder, which showed high strength and good workability at room temperature. And Silica sol bonded SiC castable with the above micropowder contents possessed the best mechanical behavior after heat treatment due to combined binding of SiC whiskers and mullite.     

Towards chrome-free of high-temperature solid waste gasifier through in-situ SiC whisker enhanced silica sol bonded SiC castable

Refractory containing Cr₂O₃ was widely used in solid waste gasifier due to its excellent slag resistance. However, hexavalent chrome compounds (formed during the preparation and the use of refractory containing Cr₂O₃) will give rise to detrimental effect on environment and human's health. In addition, the Al₂O₃-Cr₂O₃ materials acted as the lining materials. Serious exfoliation occurred after about twenty days. For the purpose of chrome-free and service longevity of lining materials for solid waste gasifier, in-situ SiC whisker enhanced SiC castable and spinel castable containing 20%wt of Cr₂O₃ were prepared. The mechanical properties and corrosion resistance after heat treatment in different temperature of the castables were determined. The strength of SiC castable rised with the increasing of the temperature. And the nano SiC/SiO₂ core-shell whiskers was formed at 1500 °C. In comparison to the spinel castable containing 20 wt% of Cr₂O₃, the better volume stability and the reinforcement of the nano whiskers led to excellent resistance to crack propagation at high temperature. In addition, SiC castable showed lower apparent porosity because of the forming of SiO₂ through the oxidation of SiC over 1300 °C, the viscosity of slag increased since that the SiO₂ dissolve into the slag, which caused excellent penetration resistance of SiC castable compared with spinel-Cr₂O₃ castable. Excellent mechanical properties and slag resistance at high temperature indicated that SiC castable had the application prospect for high-temperature solid waste gasifier.     

High‐Temperature Oxidation of ZrB2–SiC–AlN Composites at 1600°C

The effect of AlN substitution on oxidation of ZrB₂–SiC was evaluated at 1600°C up to 5 h. Replacement of ZrB₂ by AlN, with 30 vol% SiC resulted in improved oxidation resistance with a thinner scale and reduced oxygen affected area. On the other hand, substitution of AlN for SiC resulted in a deterioration of the oxidation resistance with an abnormal scale and significant recession. The effect of SiC content was also studied, and was found to be consistent with the literature for the composites without AlN additions. A similar effect was observed when AlN was added, with the higher SiC content materials showing improved oxidation resistance. X‐ray photoelectron spectroscopy showed the presence of Al₂O₃ and SiO₂ on the surface, which could possibly lead to a modification in the viscosity of the glassy oxide scale. Possibly, the oxidation behavior of ZrB₂–SiC composites can be improved with controlled AlN additions by adjusting the Al:Si ratios.     

Comparison of microstructure,toughness, mechanical properties and work hardening of titanium/TiO2 and titanium/SiC composites manufactured by accumulative roll bonding (ARB) process

In this study, the effects of TiO₂ ceramic nanoparticles and SiC microparticles on the microstructure, mechanical properties and toughness of titanium/TiO₂ nanocomposite and titanium/SiC composite were investigated. To achieve this goal, TiO₂ and SiC ceramic particles were incorporated as the reinforcement in titanium through the ARB (accumulative roll bonding) process. By adding SiC ceramic particles, the mechanical properties of the composite and the nanocomposite were enhanced, while their toughness was decreased, as compared to TiO₂ nanoparticles. After applying 8 cycles of the ARB process, UTS in Ti/5 vol% SiC composite reached to about 1200 (MPa), as compared to that in Ti/0.5 wt% TiO₂ nanocomposite, which was about 1100 (MPa). Furthermore, toughness in the Ti/5 vol% SiC composite and the Ti/0.5 wt% TiO₂ nanocomposite was 60 and 29 J/m³, respectively. Finally, SEM and TEM images showed SiC microparticles clustering in Ti/SiC composite samples and a suitable distribution of TiO₂ nanoparticles in the Ti/TiO₂ nanocomposite. By adding TiO₂ nanoparticles, mechanical properties and work hardening coefficient were found to be increased, as compared to those of the monolithic samples. TiO₂ nanoparticles, after being distributed in the titanium matrix through the ARB process, caused pin dislocations. As clearly shown in TEM images, dislocation tangles around TiO₂ nanoparticles acted as the main mechanism improving the work hardening coefficient.     

Self‐Generating High‐Temperature Oxidation‐Resistant Glass‐Ceramic Coatings for C–C Composites Using UHTCs

Carbon–carbon (C–C) composites are ideal for use as aerospace vehicle structural materials; however, they lack high‐temperature oxidation resistance requiring environmental barrier coatings for application. Ultra high‐temperature ceramics (UHTCs) form oxides that inhibit oxygen diffusion at high temperature are candidate thermal protection system materials at temperatures >1600°C. Oxidation protection for C–C composites can be achieved by duplicating the self‐generating oxide chemistry of bulk UHTCs formed by a “composite effect” upon oxidation of ZrB₂–SiC composite fillers. Dynamic Nonequilibrium Thermogravimetric Analysis (DNE‐TGA) is used to evaluate oxidation in situ mass changes, isothermally at 1600°C. Pure SiC‐based fillers are ineffective at protecting C–C from oxidation, whereas ZrB₂–SiC filled C–C composites retain up to 90% initial mass. B₂O₃ in SiO₂ scale reduces initial viscosity of self‐generating coating, allowing oxide layer to spread across C–C surface, forming a protective oxide layer. Formation of a ZrO₂–SiO₂ glass‐ceramic coating on C–C composite is believed to be responsible for enhanced oxidation protection. The glass‐ceramic coating compares to bulk monolithic ZrB₂–SiC ceramic oxide scale formed during DNE‐TGA where a comparable glass‐ceramic chemistry and surface layer forms, limiting oxygen diffusion.     

Large-scale fabrication of TiC@C powders and its effect on the properties of Al2O3-MgO-C castables

High performance carbon containing castables have always been pursued by researchers and steelmaking producers, unfortunately, poor water-wettability of graphite flakes was greatly limited their application in castables. To respond this, we proposed a large-scale and low-cost modified molten salt shielding synthesis technique for fabricating TiC coated graphite in air atmosphere using graphite flake and Ti powder as raw materials. Microstructure, wettability and oxidation resistance of TiC@C powders, and effect of TiC@C powders on the properties of Al₂O₃-MgO-C castables were investigated. The results demonstrate that TiC coated graphite was synthesized via modified molten salt shielding synthesis route in air atmosphere. A uniform and continuous TiC layer was formed on the surface of graphite, thereby significantly improving the water-wettability and oxidation resistance of graphite flakes. The castables with 5% TiC@C powders possessed lower apparent porosity, higher cold strength, good oxidation resistance, and slag resistance in comparison with the castables with graphite flakes, and slag resistance were also better than Al₂O₃-MgO castables. The as-fabricated TiC@C powders have good water-wettability and oxidation resistance, making them as a prime carbon source for producing carbon containing castables for steel ladle linings.     

Effect of temperature gradient on the erosion behavior of SiC coating for carbon/carbon composites in a combustion environment

SiC coating with a thickness of 50–70 µm was prepared on the surface of C/C composites by in-situ reaction method. The SiC coated C/C composites were then tested in a wind tunnel where a temperature gradient from 200 to 1600 °C could be obtained to investigate their erosion behavior. The results of wind tunnel test indicated that the service life of C/C composites was prolonged from 0.5 to 44 h after applying the SiC coating. After the wind tunnel test, three typical oxidation morphologies, including glassy SiO₂ layer, porous SiO₂ layer and clusters of honeycomb-like SiO₂ grains, were found on the SiC coated C/C composites. With the decrease of oxidation temperature, the amount of glassy SiO₂ declined and the thermal stress increased, which induced the cracking followed by the degradation of the SiC coating.     

Effect of SiC–graphite–Al-metal addition on low- and ultra-low cement bauxite castables

Eight batches of low- and ultra-low cement castables were prepared from calcined Chinese bauxite and high alumina cement (HAC). The effect of alumina-cement replacement by SiC, graphite and aluminum metal on the sinterability and properties of these castables was investigated. Physical properties such as bulk density and apparent porosity of hydrated and sintered castables were studied. The sintered castables were also characterized for their solid phase compositions and microstructure using X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. In the castables containing SiC, new phases such as mullite (3Al₂O₃·2SiO₂), SiC, and quartz (SiO₂) were formed at the expense of calcium aluminate phases (i.e. CA and CA₂; the main cement phases). Generally, the bulk density of the control castable sample was the highest among all prepared samples, while the batches containing graphite showed the lowest bulk density. The presence of Al-metal reduced the oxidation of SiC and consequently increased the densification of the castables compared with castables containing graphite only. Cold crushing strength (CCS) of the hydrated specimens i.e. green castables, decreased as the additives contents increased at the expense of HAC which is responsible for the bonding at room temperature. The highest CCS value of the sintered castable was obtained for the sample containing 6 wt.% SiC, 3 wt.% CA and 0.5 wt.% Al-metal.     

Single-crystalline SiC integrated onto Si-based substrates via plasma-activated direct bonding

We propose a plasma-activated direct bonding process at low temperatures (≤200 °C) to form heterostructures between single-crystalline SiC and conventional Si-based substrates (SiO₂, Si, and glass) without any interlayers. Surface activation was performed via an inductively coupled O₂ plasma for 60 s with a lower bombardment damage position. The SiC surfaces were much more hydrophilic after activation, and the generation of defect states was suppressed. Consequently, void-free and robust bonding interfaces of SiC/SiO₂, SiC/Si and SiC/glass were successfully achieved. There were no carbon-enriched layers across the bonding interfaces, which could improve the electrical properties of SiC-based devices. Additionally, the bonding interface of SiC/glass exhibited excellent optical transparency, and interfacial corrosion resistance was confirmed via immersion tests in biological solutions. This bonding method provides a feasible route towards industry-compatible heterogeneous integration of single-crystalline bulk SiC onto Si-based platforms for electronic, optical, mechanical, and biomedical applications.     

Ultra‐High‐Temperature Ceramic HfB2‐SiC Coating for Oxidation Protection of SiC‐Coated Carbon/Carbon Composites

To protect the carbon/carbon (C/C) composites from oxidation, an outer ultra‐high‐temperature ceramics (UHTCs) HfB₂‐SiC coating was prepared on SiC‐coated C/C composites by in situ reaction method. The outer HfB₂‐SiC coating consists of HfB₂ and SiC, which are synchronously obtained. During the heat treatment process, the formed fluid silicon melt is responsible for the preparation of the outer HfB₂‐SiC coating. The HfB₂‐SiC/SiC coating could protect the C/C from oxidation for 265 h with only 0.41 × 10^?2 g/cm² weight loss at 1773 K in air. During the oxidation process, SiO₂ glass and HfO₂ are generated. SiO₂ glass has a self‐sealing ability, which can cover the defects in the coating, thus blocking the penetration of oxygen and providing an effective protection for the C/C substrate. In addition, SiO₂ glass can react with the formed HfO₂, thus forming the HfSiO₄ phase. Owing to the “pinning effect” of HfSiO₄ phase, crack deflecting and crack termination are occurred, which will prevent the spread of cracks and effectively improve the oxidation resistance of the coating.     

Comprehensive oxidation mechanisms of heterogeneous laminated HfB2–SiC/Ti ceramics under oxyacetylene conditions

A laminated HfB₂–SiC/Ti ceramic prepared via tape casting and spark plasma sintering was characterized upon an oxyacetylene torch test at 2040 ℃. The volatility diagram for the binary HfB₂–SiC system was established along with the detailed ablation microstructure of the upper surface to investigate the ablation behavior of the samples. In addition, the mass (8.93 mg/s) and linear ablation rate (1.22 µm/s) of the laminate are ascribed to the strong oxidation protection of the Ti interlayer by the dense SiO₂ coating on the side surface, retarding the occurrence of oxidation weight loss and exfoliation at the interface. The corresponding oxidation behavior is proposed.     

Effects of fine reactive alumina powders on properties of alumina-magnesia castables with TiO2 additions

The design of alumina-magnesia castables was optimized based on the action mechanism of raw materials. In this study, the effects of fine reactive alumina powders on the properties of alumina-magnesia castables with TiO₂ additions were investigated. The phase composition and microstructure of castables with different contents of TiO₂ and two fine reactive alumina powders were characterized by X-ray diffraction and scanning electron microscopy. The results of these studies showed that the Na₂O/SiO₂ ratio of reactive alumina affected on the phase evolution and properties of castables. The changes in the spinel and CA₆ content and their solid solubility could account for the comprehensive effect of TiO₂ and reactive alumina on the castables. The difference in the expansion of castables with 1 wt% TiO₂ addition after calcination at 1350 °C was significant. The permanent linear changes and the apparent porosity of castables first increased and then decreased with increasing the calcination temperature. Castables containing reactive alumina with lower Na₂O/SiO₂ ratio had higher cold moduli of rupture.     

Oxidation protection of carbon/carbon composites with SiC/indialite coating for intermediate temperatures

In order to improve the oxidation resistance of carbon/carbon composites at intermediate temperatures, a novel double-layer SiC/indialite coating was prepared by a simple and low-cost method. The internal SiC transition layer was prepared by pack cementation and the external indialite glass–ceramic coating was produced by in situ crystallization of ternary MgO–Al₂O₃–SiO₂ glass. The microstructures and morphologies of coating were determined by scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS). Oxidation resistance of the as-coated C/C composites was evaluated in ambient air at temperature from 800 °C to 1200 °C. Nearly neglectable mass loss was measured after 100 h isothermal oxidation test, indicating that SiC/indialite coating possesses excellent oxidation protection ability. The as-coated samples have a good thermal shock resistance and no obvious damage was found in the coating even after suffered more than 11 thermal cycles between test temperature and room temperature. The oxidation protection mechanism of this coating was also discussed.