Sintering,high temperature strength and oxidation resistance of liquid-phase-pressureless-sintered SiC–AlN ceramics with addition of rare-earth oxides

SiC–AlN composites can be pressureless sintered with the addition of rare-earth oxides (RE = Y, Yb, Er, Lu, Ho, Sm, Ce) and without protective powder bed. Sintered bodies showed high density (≥97% T.D.) and were mainly composed by 2H SiC–AlN solid solution with additive containing grain boundary phases. The high temperature strength and oxidation resistance of the composites were also investigated and correlated with the cationic radii of the oxide additives. The flexural strength at 1500 °C increased from 269 MPa to 587 MPa as direct consequence of the rare-earth cationic radius decrease. The specific weight gain during oxidation at 1500 °C for 200 h showed the same behaviour, decreasing from 12.60 mg/cm² to 3.13 mg/cm².     

Fabrication and oxidation behavior of Al4SiC4 powders

Al₄SiC₄ powders with high purity were synthesized by heating the powder mixture of aluminum (Al), silicon (Si), and carbon (C) at 1800°C in argon. The microstructure is characterized as platelike single grain. Both the nonisothermal and isothermal oxidation behavior of Al₄SiC₄ was investigated at 800°C‐1500°C in air by means of thermogravimetry method. It is demonstrated that Al₄SiC₄ powder possesses good oxidation resistance up to 1200°C and is almost completely oxidized at 1400°C. At 800°C‐1100°C, the oxide scales consist of an Al₂O₃ outer layer and a transition layer. Al₄SiC₄ remains the main phase. At 1200°C, some spallation resulting from the increment of Al₂O₃ and the mismatch of thermal expansion coefficient between different product layers can be observed. Above 1300°C, the oxide layer is composed of two part, i.e., large‐scale Al₂O₃ crystals (outer layer) and mullite with less amount of SiO₂ (inner layer). The oxidation behavior changes due to the different oxide products. For the reaction kinetics, a new kind of real physical picture model is adopted and obtains a good agreement with the experimental data. The apparent activation energy is calculated to be 176.9 kJ/mol (800°C‐1100°C) and 267.1 kJ/mol (1300°C‐1400°C).     

Si/B/C/N/Al precursor-derived ceramics: Synthesis,high temperature behaviour and oxidation resistance

The Si/B/C/N/H polymer T2(1), [B(C₂H₄Si(CH₃)NH)₃]_n, was reacted with different amounts of H₃Al·NMe₃ to produce three organometallic precursors for Si/B/C/N/Al ceramics. These precursors were transformed into ceramic materials by thermolysis at 1400 °C. The ceramic yield varied from 63% for the Al-poor polymer (3.6 wt.% Al) to 71% for the Al-rich precursor (9.2 wt.% Al). The as-thermolysed ceramics contained nano-sized SiC crystals. Heat treatment at 1800 °C led to the formation of a microstructure composed of crystalline SiC, Si₃N₄, AlN(+SiC) and a BNC_x phase. At 2000 °C, nitrogen-containing phases (partly) decomposed in a nitrogen or argon atmosphere. The high temperature stability was not clearly related to the aluminium concentration within the samples. The oxidation behaviour was analysed at 1100, 1300, and 1500 °C. The addition of aluminium significantly improved the oxide scale quality with respect to adhesion, cracking and bubble formation compared to Al-free Si(/B)/C/N ceramics. Scale growth rates on Si/B/C/N/Al ceramics at 1500 °C were comparable with CVD–SiC and CVD–Si₃N₄, which makes these materials promising candidates for high-temperature applications in oxidizing environments.     

Preparation,microstructure and ion-irradiation damage behavior of Al4SiC4-added SiC ceramics

Single-phase Al₄SiC₄ powder with a low neutron absorption cross section was synthesized and mixed with SiC powder to fabricate highly densified SiC ceramics by hot pressing. The densification of SiC ceramics was greatly improved by the decomposition of Al₄SiC₄ and the formation of aluminosilicate liquid phase during the sintering process. The resulting SiC ceramics were composed of fine equiaxed grains with an average grain size of 2.0 μm and exhibited excellent mechanical properties in terms of a high flexure strength of 593 ± 55 MPa and a fracture toughness of 6.9 ± 0.2 MPa m^1/2. Furthermore, the ion-irradiation damage in SiC ceramics was investigated by irradiating with 1.2 MeV Si⁵⁺ ions at 650 °C using a fluence of 1.1 × 10¹⁶ ions/cm², which corresponds to 6.3 displacements per atom (dpa). The evolution of the microstructure was investigated by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The breaking of Si–C bonds and the segregation of C elements on the irradiated surface was revealed by XPS, whereas the formation of Si–Si and C–C homonuclear bonds within the Si–C network of SiC grains was detected by Raman spectroscopy.     

ZrSiO4对Si3N4结合SiC制品强度和抗氧化性的影响

研究了硅酸锆 (ZrSiO4)添加物对氮化硅结合碳化硅制品性能尤其是强度和抗氧化性能的影响 ,分析了其作用机理。研究结果表明 ,硅酸锆可显著提高氮化硅结合碳化硅制品的抗氧化性能 ,但提高制品强度的作用较小。     

In situ formation of mullite strengthened SiC porous ceramics via gelcasting with high strength and good alkali resistance

Mullite-bonded porous SiC ceramics sintered in air by gelcasting are still challenges due to the high porosity induced severe oxidation of SiC, which results in the formation of large amount of detrimental cristobalite phase. Here in this work, small amounts of Y₂O₃ and CaF₂ were added in SiC and Al(OH)₃ raw materials as sintering additives for the in situ growth of mullite reinforcement. This additive system promoted the reaction between oxidation-derived SiO₂ from SiC and Al₂O₃ decomposed from Al(OH)₃ to mullite phase. Almost no cristobalite phase was detected when sintered at 1450℃/2 h with CaF₂ addition of more than 2.0 wt%. Mullite whisker reinforcement was in situ formed due to the gas reaction mechanism caused by CaF₂ addition. Thus obtained porous SiC ceramics exhibited a flexural strength of 67.6 MPa at porosity of 41.3%, which maintained exceeding 36 MPa after 8 h corrosion in 10 wt% NaOH 80℃ solution, being the best performance up to now. This high performance of porous SiC was attributed to the additive induces proper phase control and in situ formation of whisker-like mullite reinforcement.     

Pursuing enhanced oxidation resistance of ZrB2 ceramics by SiC and WC co-doping

The oxidative degradation of ZrB₂ ceramics is the main challenge for its extensive application under high temperature condition. Here, we report an effective method for co-doping suitable compounds into ZrB₂ in order to significantly improve its anti-oxidation performance. The incorporation of SiC and WC into ZrB₂ matrix is achieved using spark plasma sintering (SPS) at 1800?°C. The oxidation behavior of ZrB₂-based ceramics is investigated in the temperature range of 1000?°C–1600?°C. The oxidation resistance of single SiC-doped ZrB₂ ceramics is improved due to the formation of silica layer on the surface of the ceramics. As for the WC-doped ZrB₂, a dense ZrO₂ layer is formed which enhances the oxidation resistance. Notably, the SiC and WC co-doped ZrB₂ ceramics with relative density of almost 100% exhibit the lowest oxidation weight gain in the process of oxidation treatment. Consequently, the co-doped ZrB₂ ceramics have the highest oxidation resistance among all the samples.     

Pressureless sintered Al4SiC4 ceramics with Y2O3 addition

Highly densified Al₄SiC₄ ceramics with a relative density of 96.1% were prepared by pressureless sintering using 2 wt% Y₂O₃ as additives. The densification mechanism, phase composition, microstructures and mechanical properties of Al₄SiC₄ ceramics were investigated. Y₂O₃ in-situ reacted with the oxygen impurities in Al₄SiC₄ powder to form a yttrium aluminate liquid phase during sintering, which promoted the densification and anisotropic grain growth. The final Al₄SiC₄ ceramics were composed of equiaxed grains and columnar grains, and presented a bimodal grain distribution. The mechanical properties of the pressureless sintered Al₄SiC₄ ceramics were better than those reported for hot pressed Al₄SiC₄, including a flexural strength of 369 ± 24 MPa, fracture toughness of 4.8 ± 0.1 MPa m^1/2 and Vickers hardness of 11.3 ± 0.2 GPa. Pressureless sintering of Al₄SiC₄ ceramics is of great significance for the development and practical application of Al₄SiC₄ ceramic parts, especially with big size and complex shape.     

Improved mechanical strength and thermal resistance of porous SiC ceramics with gradient pore sizes

Thermal insulation applications of porous SiC ceramics require low thermal conductivity and high mechanical strength. However, low thermal conductivity and high mechanical strength possess a trade-off relationship, because improving the mechanical strength requires decreasing the porosity, which increases the thermal conductivity. In this study, we established a new strategy for improving both the mechanical strengths and thermal resistances of porous SiC ceramics with micron-sized pores by applying a double-layer coating with successively decreasing pore sizes (submicron- and nano-sized pores). This resulted in a unique gradient pore structure. The double-layer coating increased the flexural strengths and decreased the thermal conductivities of the porous SiC ceramics by 24–70 % and 29–49 % depending on the porosity (48–62 %), improving both their mechanical strengths and thermal resistances. This strategy may be applicable to other porous ceramics for thermal insulation applications.     

The high temperature reaction of ammonia with carbon and SiC–C ceramics

This contribution aimed at developing a treatment under ammonia in order to eliminate free carbon from the surface of SiC-based fine ceramics like fibers or coatings. The reaction of NH₃ with graphitic and non-graphitic carbon was first investigated through kinetic measurements, in situ gas phase analysis and physicochemical investigations of the solid. The carbon etching rate is controlled by heterogeneous reactions involving active sites arising from bulk structural defects and the formation of HCN. A selection of SiC-based fibers and coatings with various carbon contents and (micro)structures was treated in ammonia in favorable conditions. The analyses of the tested SiC–C specimens revealed a reduction of the free carbon content and, simultaneously, a nitridation of the initial Si–C–(O) continuum over a reaction layer. The growth rate, composition and the volume change of this layer vary with the initial microstructure. The ammonia treatment is able to restore the adhesion of carbon-contaminated surfaces.     

Potential of SiC multilayer ceramics for high temperature applications in oxidising environment

Multilayered ceramics seem very promising for applications at very high temperatures in an oxidising environment. Actually, they present lower cost and better oxidation resistance than many conventional ceramic composites.     

Optimization of SiC–ZrC high emissivity composite flexible coating for thermal protection with high interfacial bond strength and temperature resistance

Aluminum silicate fiber fabric (ASFF) has been widely used in the outer surface of flexible insulation felt on the leeward side of aerospace vehicle. In order to improve the temperature resistance of ASFF, a kind of SiC–ZrC composite coating was prepared on the surface of fiber fabric via spraying method with SiC as emittance agent and ZrC as additive. The surface morphology and mechanical properties of the coating were studied. Compared with the single-component SiC coating, the composite coating could effectively avoid coating spalling and improve the surface integrity at high temperature. After thermal treatment at 1100 °C for 2 h, the interface bond strength of the composite coating/substrate was 52.41% higher than that of SiC coating/substrate. The tensile strength of fiber fabric with SiC–ZrC composite coating could reach 91.75 MPa, which was 101.76% higher than that of raw ASFF. Therefore, the SiC–ZrC coating could greatly improve the temperature resistance of ASFF, and has an attractive application prospect in the field of thermal protection system.     

Fracture toughness,strength and creep of transparent ceramics at high temperature

Fracture toughness, four-point bending strength of transparent spinel, Y₂O₃ and YAG ceramics in function of temperature (from room temperature up to 1500° C) were measured. Creep resistance at 1500–1550° C was studied too. Grain size distribution was determined on polished and etched surfaces of samples. Fracture surfaces after tests were examined by scanning electron microscopy. The obtained results showed that: in the case of spinel ceramics fracture toughness and strength decreased from 20 to 800° C, increased from 800 to 1200° C and decreased at higher temperature; in the case of Y₂O₃ ceramics they increased from 400 to 800° C, and next kept constant up to 1500° C; in the case of YAG ceramics they kept constant from 20 to 1200° C and then decreased. The creep strain rate was measured for spinel and YAG but not for Y₂O₃ ceramics which appeared creep resistant. The hypotheses concerning toughening and creep mechanisms were proposed.     

Advances in oxidation and ablation resistance of high and ultra-high temperature ceramics modified or coated carbon/carbon composites

Carbon/carbon (C/C) composites are considered as one of the most promising materials in structural applications owing to their excellent mechanical properties at high temperature. However, C/C composites are susceptible to high-temperature oxidation. Matrix modification and coating technology with ultra-high temperature ceramics (UHTCs) have proved to be highly effective to improve the oxidation and ablation resistance of C/C composites. In this paper, recent advances in oxidation and ablation resistance of C/C composites were firstly reviewed, with attention to oxidation and ablation properties of C/C composites coated or modified with UHTCs. Then, several new methods in improving oxidation and ablation resistance were discussed, such as by using nanostructures to toughen UHTCs coatings or carbon matrix and the combination of matrix modification and coating technology. In addition, relevant ablation tests with scaled models were also briefly introduced. Finally, some open problems and future challenges were highlighted in the development and application of these materials.     

A new approach for the net-shape fabrication of porous Si3N4 bonded SiC ceramics with high strength

In this study, Si₃N₄ bonded porous SiC ceramics with high strength had been net-shapely fabricated by a new approach. In this approach, we proposed a two-step processing route composed of freeze casting and carbothermal reduction reactions in which carbon aerogels, derived from sol infiltration and pyrolysis, involved. The phase components, microstructures and properties of the prepared ceramics were investigated. The results showed that carbon aerogels with high apparent surface area had been completely reacted and new SiC and Si₃N₄ grains had been produced. The porous ceramics with flexural strength of 164.3 MPa at 33% porosity and 80.5 MPa at 46% porosity were obtained, whose linear shrinkages were only 1.06% and 1.94% during the whole processing respectively.     

TiO2涂层耐蚀性能和抗高温氧化性能

用溶胶－凝胶法在碳钢表面制备TiO2涂层。用正交设计法对水解反应温度、涂覆次数、热处理温度和时间4因素进行了优化，并考察了上述4因素对涂层在10％（体积分数）H2SO4介质中的耐蚀性能和650℃空气气氛中的抗高温氧化性能的影响。     

MnxCo3-xO4 spinel coatings: Controlled synthesis and high temperature oxidation resistance behavior

A controllable method for the synthesis of Mn_xCo_3-xO₄ (x = 0.4, 0.8, 1.0, 1.2) spinel coatings with unique microstructures and high-temperature oxidation resistances for solid oxide fuel cells is crucially desired. Herein, we report the synthesis and analysis of synthesized coatings with different phase compositions of ferritic stainless steel interconnects. The coatings are fabricated using a sol-gel dip-coating method. Multiple experimental results confirm that the Mn_xCo_3-xO₄ coatings exhibit the advantages of having fine grains and uniform density. Furthermore, the as-prepared Mn_1.2Co_1.8O₄ coating has a low coefficient of thermal expansion (11.98 × 10^-6 K^-1), matching that of ferritic stainless steel, which effectively improves the anti-stripping property of the materials. In particular, oxidation tests illustrate that the oxidation weight gain of this coating decreased by 84.4% compared with bare ferritic stainless steel after 3600 h. The area-specific resistance (ASR) results indicate that the ASR value of the Mn_1.2Co_1.8O₄-coated sample reduced by about 70% compared with those of the ferritic stainless steel samples, which demonstrates its desirable high-temperature oxidation resistance property. It is hoped that this work stimulates new research ideas for the development of spinel oxide coating.     

Investigations of SiC aggregates oxidation: Influence on SiC castables refractories life time at high temperature

This paper reports results concerning the oxidation of silicon carbide of pure SiC powder (98% of SiC) and the oxidation of two silicon carbide castables, used in waste-to-energy plants (WTE), and containing 60% and 85% of SiC, respectively. The investigated temperature range (800-1200 °C) corresponds to typical service conditions in WTE. Thanks to thermogravimetric and thermal expansion tests, kinetics of oxidation of the powder of SiC and of the castables has been investigated. According to these tests, several important points have been underlined. Firstly, the oxidation of SiC aggregates has a high influence on the thermal expansion and on the weight gain of SiC castables. Secondly, the grain size distribution of SiC aggregates within castables plays a dominating role (especially enhanced for the fine particles) in castable expansion behaviour induced by oxidation. This is a key point according to the evolution of thermal expansion of such materials.     

Microstructure evolutions of SiC whiskers at high temperature and its effects on silicon carbide ceramics

SiC whisker with a single-crystal structure is promising in enhancing the strength and toughness of advanced structural ceramics, owing to its excellent properties. However, studies on its microstructure evolution at high temperature (>2000 °C) are scarce. Herein, SiC whiskers were calcined at 2100 °C, and XRD, SEM, and TEM were employed to analyze microstructure evolutions. Compared with raw whiskers, XRD results indicated serious annihilation of stacking faults after calcination. The annihilation led to the fracture of whiskers and the formation of β-SiC grains, and then partial grains underwent the phase transformation to form hexagonal prism and triangular prism α-SiC grains with diameters of about 10 μm, according to SEM and TEM results. Furthermore, SiC ceramics containing different whisker contents were innovatively fabricated by pressureless solid-state sintering. The flexural strength and fracture toughness of SiC ceramic containing 10 vol% whiskers were 540 MPa and 5.1 MPa m^0.5, resulting in 38% and 11% higher values than those without whiskers, respectively.