Effect of Nb–Al–SiC elements combined with pre-oxidation treatment on the pesting resistance of MoSi2

Nb, Al, SiC elements were introduced into the matrix to improve the pest phenomenon of the MoSi₂ composites. The results showed that although the oxidation rate of the composite decreased, the pest phenomena eventually occurred at the oxidation temperature of 500 °C and 750 °C. And after 120 h of oxidation, the bending strength of the composite decreased dramatically from 472 MPa to 258 MPa (500 °C) and 225 MPa (750 °C). In order to solve this problem, pre-oxidation has been adopted. During pre-oxidation at 1200 °C via exposure to air, a dense fibrous layer was in-situ formed, which had excellent adhesion to the matrix. The substrate which adjoins the interface of the oxide layer and matrix was oxidized into nano-sized grains. This layer and the nano-sized substrate played important roles in eliminating the pest phenomenon of the MoSi₂ composite.     

Enhanced performance of low-carbon MgO–C refractories with nano-sized ZrO2–Al2O3 composite powder

Low-carbon MgO–C refractories are facing great challenges with severe thermal shock and slag corrosion in service. Here, a new approach, based on the incorporation of nano-sized ZrO₂–Al₂O₃ composite powder, is proposed to enhance the thermal shock resistance and slag resistance of such refractories in this work. The results showed that addition of ZrO₂–Al₂O₃ composite powder was helpful for improving their comprehensive performances. Particularly, the thermal shock resistance of the specimen containing 0.5 wt% composite powder was enhanced significantly which was related to the transformation toughening of zirconia and in-situ formation of more spinel phases in the matrix; also, the slag resistance of the corresponding specimen was significantly improved, which was attributed to the optimization of pore structure and formation of much thicker MgO dense layer.     

陶瓷隔热瓦耐高温高辐射率涂层的制备及表征

在短切莫来石纤维隔热瓦表面采用浆料喷涂法制备了短切莫来石纤维增韧Mo Si_2-Si C-B_2O_3-SiO_2/Mo Si_2-Si C-B_2O_3-SiO_2-SiB_6梯度涂层,并利用XRD、XPS、SEM和EDS对涂层的组成、结构及形貌进行了分析,探讨了涂层的形成机理。分析表明涂层主要由MoSi_2、硼硅玻璃及少量的Mo_(4.8)Si_3C_(0.6)组成。涂层表面及截面的SEM照片表明涂层表层致密,靠近基体部分疏松多孔,部分涂层深入多孔的基体,提高了涂层与基体的结合力。     

High temperature oxidation behavior of MoSi2–Al2O3 composite coating on TZM alloy

A novel MoSi₂–Al₂O₃ composite coating was prepared on Mo-based TZM alloy by slurry sintering method. The oxidation behavior of the coating was evaluated at 1600 °C in static air. Microstructure and phase composition of the as-prepared and oxidized coatings were characterized, and the antioxidant mechanism of the coating at high temperature was discussed. A three-layer structure was observed in the as-prepared coating, consisting of a ～2 μm thick Mo₅Si₃ diffusion layer, a ～65 μm thick MoSi₂ inner layer and a ～36 μm thick outer layer of mixture of MoSi₂ and Al₂O₃. After oxidation at 1600 °C for 5 h, all MoSi₂ phases were completely converted to intermediate silicide Mo₅Si₃ by solid-state diffusion, and the formed Mo₅Si₃ phase would be transformed into Mo₃Si phase with further extending the oxidation time. Furthermore, a dense oxide layer of SiO₂-mullite was formed on the specimen surface, which can effectively protect the material to further oxidation. The MoSi₂–Al₂O₃ coating could protect the substrate effectively at 1600 °C for 20 h without failure. The enhanced oxidation resistance of MoSi₂–Al₂O₃ coating is due to the formation of multi-layer structure containing a SiO₂-mullite composite oxide outer layer with high thermal stability and low oxygen permeability.     

Thermal conductivity of binary ceramic composites made of insulating and conducting materials comprising full composition range – Applied to yttria partially stabilized zirconia and molybdenum disilicide

The thermal diffusivity and conductivity of dense and porous binary composites having an insulating and conducting phase were studied across its entire composition range. Experimental evaluation has been performed with MoSi₂ particles embedded into yttria partially stabilized zirconia (YPSZ) as prepared by spark plasma sintering (SPS). The thermal diffusivity of the composites was measured with Flash Thermography (FT) and Laser Flash Analysis (LFA) techniques. Subsequently, the thermal conductivity was determined with the measured heat capacity and density of the composites. The actual volume fraction of the conducting phase of the composites was determined with image analysis of X-ray maps recorded with scanning electron microscopy (SEM). The phases present and their density were determined with X-ray diffractometry (XRD) using Rietveld refinement. The thermal diffusivity increases with increasing volume fraction of MoSi₂. Porosity reduces the thermal diffusivity, but the effect diminishes with high volume fractions MoSi₂. The thermal diffusivity as a function of the MoSi₂ volume fraction of the YPSZ composites is captured by modelling, which includes the porosity effect and the high conductivity paths due to the percolation of the conductive phase.     

Characterisation and properties of low-conductivity microporous magnesia based aggregates with in-situ intergranular spinel phases

Development of microporous magnesia based aggregates serving as working-line refractories have great significance in reducing energy loss and saving resource. Microporous magnesia-based aggregates were fabricated at 1780 °C by in-situ decomposition of magnesite with addition of nano-sized Al₂O₃. Intergranular MgAl₂O₄ phases formed in situ decreased the closed-pore size, thermal conductivity and improved the ceramic bonding and thermal shock resistance. Furthermore, the results suggested that pore size distribution was the dominate factor affecting thermal conductivity. Thermal contact resistance owing to networks of intergranular spinel in magnesia could improve thermal insulation performance effectively. The mismatch of thermal expansion coefficient between spinel and magnesia and the micro-scale closed pores enhanced thermal shock resistance by accommodating thermal stress and suppressing crack propagation. Microporous magnesia-based aggregates with 3 wt% nano-sized Al₂O₃ presented a mean pore size of 3.42 μm, thermal conductivity of 5.76 W m^?1 k^?1 (800 °C), a cold compressive strength of ~285 MPa, and a residual strength retention rate of 65.0% after thermal shock cycles. The low-conductivity microporous magnesia-based aggregates with excellent thermal shock resistance show promise for future application in working-lining lightweight refractories.     

Effect of magnesium aluminum silicate glass on the thermal shock resistance of BN matrix composite ceramics

The effects of magnesium aluminum silicate (MAS) glass on the thermal shock resistance and the oxidation behavior of h‐BN matrix composites were systematically investigated at temperature differences from 600°C up to 1400°C. The retained strength rate of the composites rose with the increasing content of MAS showing a maximum value at the 60 wt% MAS. Compared with the original strength, the retained strength of the specimen after thermal shock increased to 77% (ΔT=1000°C). The strengthening effect of MAS and the surface microstructural evolution of composites are responsible for the improved thermal shock resistance. Surface oxidation of the composites during the thermal shock process plays a positive role in enhancing the retained strength by self‐healing cracks and the appearance of the compressive stress. The oxide layer also acted as a thermal barrier to decelerate the actual thermal stress. Furthermore, this dense layer also improved the oxidation resistance of h‐BN matrix composites by prevent diffusion of oxygen. These results indicated that short‐term surface oxidation during thermal shock process is favorable to the enhancement of the thermal shock resistance of BN‐MAS composite ceramics.     

Processing of High‐Density Magnesia Spinel Electro‐Conducting Ceramic Composite and its Oxidation at 1400°C

Dense conductive ceramic composites of MgAl₂O₄ and MoSi₂ were processed using combustion synthesis under‐load methodology. The starting reactants were blends of MoO₃, SiO₂, MgO, and Al powders. The study revealed that to obtain dense composite with homogeneous microstructure, 30 wt. % of MoSi₂, 18.5 μm Al average particle size, and 175 MPa load are required. The produced dense composite was found to have a low apparent porosity (<1.0 vol. %), moderate density 4.61 g/cm³, and low electrical resistivity 0.3 Ωcm. The dense composite exhibited excellent thermodynamic stability between its phases at 1400°C in open atmosphere.     

Cordierite ceramics from silicone resins containing nano-sized oxide particle fillers

Many silicates and alumino-silicates feature remarkable mechanical properties at high temperatures, low thermal expansion and high thermal shock resistance, optimum dielectric properties, etc. The poor interdiffusion, due to their characteristic partially covalent bonding however, greatly complicates the obtainment of dense and/or phase pure articles, by conventional sintering. The present paper concerns the realization of high-purity cordierite (2MgO·2Al₂O₃·5SiO₂) components by direct thermal treatment in air of preceramic polymers embedding suitable nano-sized oxide particles. More precisely, a selection of silicone resins allowed the obtainment of both dense and highly porous bodies.     

Preparation and high-temperature oxidation resistance of multilayer MoSi2/MoB coating by spent MoSi2-based materials

Spent MoSi₂ and MoB were used as raw materials to prepare multilayer MoSi₂/MoB coating on molybdenum by the two-step method of slurry deposition and spark plasma sintering. The results showed dense MoSi₂/MoB coating after sintering while penetrated cracks appeared in MoSi₂ coating due to coefficient of thermal expansion mismatch between the Mo substrate and coating. After the sintering of MoSi₂/MoB coatings, MoB and Mo₂B diffusion layers were formed between MoB transition layer and Mo substrate without defects, exhibiting good metallurgical bonding. The high-temperature oxidation behavior of coatings (1500°C) was also explored. After oxidation of 50 h at 1500°C, lowest mass gain (0.035 mg/cm²) was obtained for MoSi₂/MoB coating, and the oxide scale was dense and complete without voids, making the oxygen diffusion at elevated temperature inhibited. Compared with MoSi₂ coating under the same oxidation conditions, relatively thinner silica oxide scale was acquired by MoSi₂/MoB coating because of the reduction of cracks, and the multilayer coating exhibits better anti-oxidation properties at high temperature.     

Reaction synthesis of spark plasma sintered MoSi2-B4C coatings for oxidation protection of Nb alloy

MoSi₂-B₄C coatings with different B₄C contents were prepared on Nb alloy by spark plasma sintering (SPS) process. Powder mixtures of Mo, Si and B₄C were used as the coating starting materials. Besides MoSi₂ and B₄C phases, small amounts of SiC and MoB are also found in the coatings because of the reactions of Mo, Si and B₄C powders during sintering. Compared with single MoSi₂ coating, the MoSi₂-B₄C coatings show better oxidation resistance at 1450?℃, and dense B₂O₃-SiO₂ oxide scales form after 100?h oxidation. The B₄C or MoB in the MoSi₂-B₄C coatings can serve as the B donor for the formation of B₂O₃. A slight degradation in the microstructure of the MoSi₂-B₄C coatings after oxidation is observed, which can be attributed to the presence of an NbB layer in the inter-diffusion zone of the coatings that retards the inward diffusion of Si from the coating into the substrate alloy. The microstructure development and oxidation behavior of the MoSi₂-B₄C coatings have been discussed.     

Effects of SiC or MoSi2 second phase on the oxide layers structure of HfB2-based composites

Monolithic HfB₂, HfB₂-30 vol% SiC and HfB₂-10 vol% MoSi₂ composites were prepared by SPS and oxidized in stagnant air at 1500 °C for 70 min. The microstructure of the oxide layer cross-sections showed that the oxidation extents were as follow: monolithic HfB₂ > HfB₂-30 vol%SiC > HfB₂-10 vol% MoSi₂.According to the EDS Line-scan, only one porous oxide layer containing a minor amount of B₂O₃was found on the HfB₂ oxidized surface whereas a thick silicate glass layer and a porous oxide layer below that existed on the surface of HfB₂-30 vol% SiC. After oxidation, the surface of HfB₂-10 vol% MoSi₂ had a narrow silicate-oxide compact layer covered by a very thin glass layer. X-ray diffraction patterns of the oxidized surfaces showed the monolithic HfB₂,the HfB₂-30 vol% SiC and HfB₂-10 vol% MoSi₂composites contain, upon oxidation, only m-HfO₂ phase, mainly m-HfO₂ with a minor amount of HfSiO₄ and mainly HfSiO₄ with a minor amount of m-HfO₂ phases, respectively. Based on the observations in this study, it is suggested that the elimination of the porous layer and subsequent increase of the HfSiO₄ phase are the main reasons for the better oxidation resistance of HfB₂-10 vol% MoSi₂.     

Thermal shock resistance of Al2O3/SiO2 composites by sol-gel

In this paper, the SiO₂ ceramic matrix composites were reinforced by the two-dimensional (2D) braided Al₂O₃ fibers by sol-gel. To develop the high performance aeroengine with excellent resistance to thermal shock for advanced aerospace application, two different thermal shock temperatures (1100?°C and 1300?°C) and three different thermal shock cycles (10, 20 and 30 cycles) were tested and compared in this paper; besides, the thermal shock resistance of Al₂O₃/SiO₂ composites was investigated in air. Our results suggested that, the flexural strength of the untreated composites was 78.157?MPa, while the residual strength of Al₂O₃/SiO₂ composites under diverse thermal shock cycles and temperatures had accounted for about 95% and 50% of the untreated composites, respectively. Meanwhile, the density and porosity of the composites were gradually increased with the increase in test temperature. Moreover, the changes in fracture morphology and micro-structural evolution of the composites were also observed. Our observations indicated that, the fracture morphology of the composites mainly exhibited ductile fracture at the thermal shock temperature of 1100?°C, whereas brittle fracture at the thermal shock temperature of 1300?°C. Additionally, Al₂O₃/SiO₂ composites belonged to the Oxide/Oxide CMCs, so no new phase was formed after thermal shock tests. Above all, findings of this paper showed that Al₂O₃/SiO₂ composites had displayed outstanding thermal shock resistance.     

High-temperature mechanical property and thermal shock resistance of Al2O3f/Al2O3 composites

Continuous alumina fiber–reinforced alumina matrix composites (Al₂O_3f/Al₂O₃ composites) were produced via sol–gel process, then the high-temperature mechanical property and thermal shock resistance of Al₂O_3f/Al₂O₃ composites were investigated. The results showed that the composites exhibited excellent high-temperature properties. The mechanical property of the composites was affected by heat treatment (prepared at 1100°C exhibited the most desirable mechanical property). The tensile strength of the composites abruptly decreased at higher temperatures. Although the mechanical property of the composites deteriorated after the thermal shock test was conducted at high temperatures, they exhibited excellent thermal shock resistance. After 50 thermal shock tests conducted at 1300 and 1500°C, the flexural strength of the composites was found to be 124.34 and 93.04 MPa, thus showing a decrease in strength with the increasing temperature.     

The effect of different sintering additives on the electrical and oxidation properties of Si3N4–MoSi2 composites

The fabrication and properties of electrically conductive Si₃N₄–MoSi₂ composites using two different sintering additive systems were investigated (i) Y₂O₃–Al₂O₃ and (ii) Lu₂O₃. It was found that the sintering atmosphere used (N₂ or Ar) had a critical influence on the final phase composition because MoSi₂ reacted with N₂ atmosphere during sintering resulting in the formation of Mo₅Si₃. The electrical conductivity of the composites exhibited typical percolation type behaviour and the percolation concentrations depended on the type of sintering additive and atmosphere used. Metallic-like conduction was the dominant conduction mechanism in the composites with MoSi₂ content over the percolation concentrations due to the formation of a three-dimensional percolation network of the conductive MoSi₂ phase. The effect of the sintering additives on the electrical and oxidation properties of the composites at elevated temperatures was investigated. Parabolic oxidation kinetics was observed in the composites with both types of additives. However, the Lu₂O₃-doped composites had superior oxidation resistance compared to the composites containing Y₂O₃–Al₂O₃. It is attributed to the higher eutectic temperature and crystallisation of the grain boundary phase and the oxidation layer in the Lu₂O₃-doped composites.     

Combustion synthesis of MoSi2 based composite and selective laser sintering thereof

Additive manufacturing is gaining increasing attention as it provides cost-effective and waste-less production of materials with multi-axis geometries. Selective laser sintering of ceramics is very challenging in terms of poor sinterability caused by low thermal shock resistance and insufficient electron conductivity blocking absorption of laser beam energy.Here, we present a novel strategy for manufacturing dense, hierarchically structured ceramics, particularly, MoSi₂-based composites by selective laser sintering. MoSi₂-Si composite powders were prepared by combustion synthesis technique, where the ceramic grains were covered with different amount of Si. MoSi₂-Si powder was consolidated by selective laser sintering reaching 92% of density. The hardness of the manufactured samples varied with the amount of Si and applied laser current from 7.7–11.4?GPa. The maximum value of the compressive strength was determined to be 636?MPa. The manufactured MoSi₂-Si was subjected to nitridation, which resulted in the growth of Si₃N₄ fibres on the surface and pores of the samples.     

Detailed electrical and mechanical retention characteristics of MoSi2–RSiC composites exhibiting three-dimensional (3D) interpenetrated network structure during long-term high-temperature oxidation process

MoSi₂–RSiC composites were prepared via a combination of precursor impregnation pyrolysis and high-temperature melt infiltration, in which re-crystallized silicon carbide (RSiC) was used as matrix. The composition, microstructure, oxidation resistance, electrical and mechanical retention characteristics of the composites during long-term high-temperature oxidation process were studied. SEM images revealed that dense MoSi₂–RSiC composites exhibiting three-dimensional (3D) interpenetrated network structure were obtained. XRD patterns confirmed that the primary compositions of the composites were 6H-SiC and hexagonal MoSi₂, as well as a small amount of Mo_4.8Si₃C_0.6. The weight gain rate of the MoSi₂–RSiC composites was about 50% lower than that of RSiC, indicating that the MoSi₂–RSiC composites possess improved oxidation resistance, which was mainly attributed to the acute decrease in porosity of the composites and the oxidation only occurred on the surface of it. The electrical properties of the MoSi₂–RSiC composites decreased slightly and then reached a flat with the increase in oxidation time, suggesting that the MoSi₂–RSiC composites possessed an excellent electrical retention characteristic. The calculated infactor I of the modified mixture value indicated that the interface combination played a more important role than that of interpenetrated network structure on the electrical retention characteristic of the composites. The composites oxidized for 50 h achieved the maximal flexural strength and elastic modulus, and values were 132.38 MPa (flexural strength) and 335.45 GPa (elastic modulus) for MoSi₂-RSiC-2, respectively, exhibiting 31.30% and 27.7% improvement compared with their initial values. The mechanical properties of MoSi₂–RSiC composites were higher than their original values even after 100 h of oxidation. This phenomenon can be due to the dense 3D interpenetrated network structure of the composites, in which oxidation reaction only occurred on the external surface.     

Oxidation and thermal shock resistant properties of Al-modified environmental barrier coating on SiCf/SiC composites

SiC_f/SiC ceramic matrix composites (CMCs) are being widely used in the hot-sections of gas-turbines, especially for aerospace applications. These CMCs are subjected to surface recession if exposed to heat-corrosion. In this research, an alternative environmental barrier coating (EBC) is introduced to protect the SiC_f/SiC CMC from high temperature degradation that is, Al film was deposited on the surface of SiC_f/SiC CMC followed by heat-treatment in a vacuum. After that, a dense Al₂O₃ overlay was in-situ synthesized on the surface of CMC, and in this process the microstructure evolution of SiC_f/SiC CMC was analyzed. The oxidation and thermal shock resistance were characterized, showing that the Al-modified SiC_f/SiC CMC has a better oxidation resistance, because the dense Al₂O₃ overlay can hinder oxygen diffusion from environment. What is more, the water-quenching testes show that the Al-modified SiC_f/SiC CMC has a good spallation resistance.     

Oxidation behavior of ZrB2-MoSi2-SiC composites in air at 1500 °C

We investigated the oxidation behavior and the effect of the amount of SiC added on oxidation resistance in both hot-pressed ZrB₂-MoSi₂-SiC composites, 55ZrB₂-40MoSi₂-5SiC and 40ZrB₂-40MoSi₂-20SiC (vol.%), exposed to dry air at 1500 °C for up to 10 h. Quantitative electron microprobe analysis characterizations of the chemical compounds of post-oxidized composites were carried out. Parabolic oxidation behavior was observed for both composites. The addition of SiC improved the oxidation resistance of ZrB₂-MoSi₂-SiC composites, and the improvement enhanced with amount of SiC added. The microstructure of the post-oxidized composites consisted of two characteristic regions: oxidized reactive region and unreactive bulk material region. The oxidized reactive region divided into an outermost dense silica-rich scale layer and oxidized reactive mixture layer. The improvement of oxidation resistance with SiC addition is associated with the presence of a thicker dense outermost scale layer which inhibited inward diffusion of oxygen through it.     

High-temperature oxidation resistance of spent MoSi2 modified ZrB2–SiC–MoSi2 coatings prepared by spark plasma sintering

The spent MoSi₂ modified ZrB₂–SiC–MoSi₂ coatings were prepared on carbon matrixes by spark plasma sintering. A continuous metallurgical bonding was formed at the interface between the coating and matrix, and no obvious defects such as pores and cracks were observed inside. The effects of spent MoSi₂ content and trace doping in the spent powder on the oxidation behavior of the coatings in air at 1700 °C were investigated. During the active oxidation stage, the spent MoSi₂ promoted the densification of the coating and enhanced the structural oxygen barrier properties. With the increase of service time, during the inert oxidation stage, doping an appropriate amount of spent MoSi₂ helped to increase the fluidity of the rich-SiO₂ protective layer so that the Zr oxides fully dispersed in the generated Zr–B–Si–O–Al multiphase glass layer, which could impede the penetration of oxygen and enhance the oxidation protection efficiency. However, excessive spent MoSi₂ exacerbated the volatilization of gas by-products, forming pores and cracks in the glass layer and rising the oxidation loss. When the content of spent MoSi₂ was 20 vol%, the glass layer is dense and uniform, with few defects and the best oxygen resistance property. Moreover, compared with commercial powders, spent MoSi₂ contained Al₂O₃ and SiO₂. Al₂O₃ had an excellent modification effect, while SiO₂ glass can promote liquid phase sintering and seal the defects in the coatings. By adding spent MoSi₂, the modified ZrB₂–SiC–MoSi₂ composite coatings could inhibit the formation of defects and improve the dynamic stability of the coatings effectively.