MoSi2 oxidation resistance coatings for Mo5Si3/MoSi2 composites

In order to improve the oxidation resistance properties of 30 at.% Mo₅Si₃/MoSi₂ composite at high temperature in air, a molybdenum disilicide coating was prepared on its surface by a molten salt technology. XRD and SEM analysis showed that only tetragonal MoSi₂ phase existed in the coating after being siliconized for 5 h at 900°C. The oxidation film formed on the uncoated sample was not dense, so that oxygen diffused easily through it. The volatilization of MoO₃ resulted in the oxidation film separating from the substrate. The MoSi₂ coating was proved to be an effective method to prevent 30 at.% Mo₅Si₃/MoSi₂ composites from being oxidized at 1200°C. A dense glassy SiO₂ film was formed on the MoSi₂ coating surface, which acted as a barrier layer for the diffusion of oxygen atoms to the substrate. The 30at.% Mo₅Si₃/MoSi₂ composites with a MoSi₂ coating showed much better oxidation resistance at high temperature.     

Oxidation features of SiOC/MoSi2 composite at low temperatures

The oxidation behavior of SiOC containing dispersed MoSi₂ particles was studied. An SiOC/MoSi₂ composite was prepared by converting polymethylsiloxane into SiOC via pyrolysis after mixing MoSi₂ particles. The SiOC matrix phase oxidized to SiO₂, and MoSi₂ particles oxidized to SiQ and MoO₃. The composite displayed superior oxidation resistance at 110 0°C, because a thin SiO₂ layer formed on the surface deterred the formation of highly volatile MoO₃. However, accelerated oxidation occurred between 400 and 500°C owing to the concurrent formation of SiO₂ and MoO₃, which led to porous, nonprotective scale formation.     

A MoSi2/SiC oxidation protective coating for carbon/carbon composites

To protect carbon/carbon (C/C) composites against oxidation, a MoSi₂ outer coating was prepared on pack-cementation SiC coated C/C composites by a hydrothermal electrophoretic deposition. The phase composition, microstructure and oxidation resistance of the prepared MoSi₂/SiC coatings were investigated. Results show that hydrothermal electrophoretic deposition is an effective route to achieve crack-free MoSi₂ outer coatings. The MoSi₂/SiC coating can protect C/C composites from oxidation at 1773 K for 346 h with a weight loss of 2.49 mg cm⁻² and at 1903 K for 88 h with a weight loss of 5.68 mg cm⁻².     

Formation mechanism and oxidation behavior of MoSi2–SiC protective coating prepared by chemical vapor infiltration/reaction

In order to protect C/C composites from oxidation, SiC-MoSi₂ composite coating was synthesized by chemical vapor infiltration /reaction (CVI/CVR) technology. A porous Mo layer was prefabricated on SiC coated C/C composites, and then MoSi₂ and SiC were subsequently prepared in a CVI /CVR process using methyltrichlorosilane (MTS) as precursor. The deposition and reaction mechanism of the MoSi₂-SiC composite coating was investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The oxidation behavior of SiC-MoSi₂ coated specimens was tested. The results show that the porous Mo layer can be densified with SiC phase decomposed from MTS, and transformed into SiC-MoSi₂ by reacting with MTS as well. A dense composite coating was prepared with optimized deposition parameters. The coated specimen exhibits a good oxidation resistance with a little mass loss of 1.25% after oxidation at 1500 °C for 80 h.     

Microstructure Characteristics and Oxidation Behavior of Molybdenum Disilicide Coatings Prepared by Vacuum Plasma Spraying

In this study, molybdenum disilicide (MoSi₂) coatings were fabricated by vacuum plasma spraying technology. Their morphology, composition, and microstructure characteristics were intensively investigated. The oxidation behavior of MoSi₂ coatings was also explored. The results show that the MoSi₂ coatings are compact with porosity less than 5%. Their microstructure exhibits typical lamellar character and is mainly composed of tetragonal and hexagonal MoSi₂ phases. A small amount of tetragonal Mo₅Si₃ phase is randomly distributed in the MoSi₂ matrix. A rapid weight gain is found between 300 and 800 °C. The MoSi₂ coatings exhibit excellent oxidation-resistant properties at temperatures between 1300 and 1500 °C, which results from the continuous dense glassy SiO₂ film formed on their surface. A thick layer composed of Mo₅Si₃ is found to be present under the SiO₂ film for the MoSi₂ coatings treated at 1700 °C, suggesting that the phenomenon of continuous oxidation took place.     

Oxidation protection of C/SiC coated carbon/carbon composites with Si–Mo coating at high temperature

To protect carbon/carbon (C/C) composites against oxidation, a Si–Mo coating was prepared on C/SiC-coated C/C composites by a simple slurry method. The microstructure of the coating was characterized by X-ray diffraction, scanning electron microscopy and Raman spectra. Results showed that the coating was mainly composed of SiC, MoSi₂ and Si. It could protect C/C composites from oxidation at 1873 K in air for 300 h and withstand 13 thermal cycles between room temperature and 1873 K. The excellent oxidation and thermal shock resistance of the coating was attributed to the formation of dense SiO₂ glass at high temperature. The volatilization of MoO₃ and SiO₂ at 1873 K was the main reason of the weight loss of the coated C/C composites.     

Microstructures and Properties of the C/Zr-O-Si-C Composites Fabricated by Polymer Infiltration and Pyrolysis

A way to improve the ablation properties of the C/SiC composites in an oxyacetylene torch environment was investigated by the precursor infiltration and pyrolysis route using three organic precursors (zirconium butoxide, polycarbosilane, and divinylbenzene). The ceramic matrix derived from the precursors at 1200 °C was mainly a mixture of SiC, ZrO₂, and C. After annealing at 1600 °C for 1 h, ZrO₂ partly transformed to ZrC because of the carbothermic reductions and completely transformed to ZrC at 1800 °C in 1 h. The mechanical properties of the composites decreased with increasing temperature, while the ablation resistance increased due to the increasing content of ZrC. Compared with C/SiC composites, the ablation resistance of the C/Zr-O-Si-C composites overwhelms because of the oxide films which formed on the ablation surfaces. And, the films were composed of two layers: the porous surface layer (the mixture of ZrO₂ and SiO₂) and the dense underlayer (SiO₂).     

Oxidation behavior of MoSi2 and Mo(Si,Al)2 coated Mo–0.5Ti–0.1Zr–0.02C alloy

MoSi₂ and Mo(Si, Al)₂ coatings were prepared on Mo–0.5Ti–0.1Zr–0.02C alloy using pack cementation process. Oxidation studies revealed that Mo(Si, Al)₂ coating had a much superior oxidation resistance in the temperature range from 400 to 900 °C, where pest disintegration of MoSi₂ occurs due to internal oxidation. The growth kinetics of Al₂O₃ layer formed on Mo(Si, Al)₂ coating was much slower than that of SiO₂ layer formed on MoSi₂ coatings during oxidation.     

C/SiC/MoSi2–SiC–Si multilayer coating for oxidation protection of carbon/carbon composites

C/SiC/MoSi₂–SiC–Si oxidation protective multilayer coating for carbon/carbon (C/C) composites was prepared by pack cementation and slurry method. The microstructure, element distribution and phase composition of the as-received coating were analyzed by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The results show that the multilayer coating was composed of MoSi₂, SiC and Si. It could effectively protect C/C composites against oxidation for 200 h with the mass loss of 3.25% at 1873 K in static air. The mass loss of the coated C/C composites results from the volatilization of SiO₂ and the formation of cracks and bubble holes in the coating.     

Microstructure,sintering behavior and mechanical properties of SiC/MoSi2 composites by spark plasma sintering

SiC/MoSi₂ composites were synthesized at different temperatures by spark plasma sintering using Mo, Si and SiC powders as raw materials. The phase composition, microstructure and mechanical properties of the as-prepared composites were investigated and the sintering behavior was also discussed. Results show that SiC/MoSi₂ composites are composed of MoSi₂, SiC and trace amount of Mo_4.8Si₃C_0.6 phase and exhibit a fine-grain texture. During the synthesis process, there was an evolution from solid phase sintering to liquid phase sintering. When sintered at 1600 °C, the SiC/MoSi₂ composites present the most favorable mechanical properties, the Vickers hardness, bending strength and fracture toughness are 13.4 GPa, 674 MPa and 5.1 MPa·m^1/2, respectively, higher 44%, 171%, 82% than those of monolithic MoSi₂. SiC can withstand the applied stress as hard phase and retard the rapid propagation of cracks as second phase, which are beneficial to the improved mechanical properties of SiC/MoSi₂ composites.     

Establishing multilayered coating on Mo–12Si–8.5 B alloy by Si pack cementation and its oxidation behavior at 900°C–1300°C

A multilayered oxidation protection coating consisting of MoSi₂ outer layer, Mo₅Si₃ internal layer, and Mo₅SiB₂/MoB inner layer was developed on the surface of Mo–12Si–8.5B 1.0 wt% ZrB₂ alloy via Si pack cementation. The multilayered coating significantly enhanced the oxidation resistance of the alloy at 900°C, 1100°C, and 1300°C in the air by exhibiting negligible oxidation recession. MoSi₂ outer layer provided admirable oxidation protection for the alloy at high temperatures by forming a thin and protective SiO₂-rich glass scale on its surface. This was supplemented by the Mo₅Si₃ internal layer and Mo₅SiB₂/MoB inner layer that reduced the thermal expansion mismatch between the MoSi₂ outer layer and substrate, and therefore no obvious cracks were found in the MoSi₂ outer layer. More importantly, the Mo₅SiB₂/MoB layer as an in situ barriers of Si interdiffusion ensured the stable existence of MoSi₂ and Mo₅Si₃ layers without obvious thickness change during oxidation at 900°C and 1100°C. Mechanical property test indicated that the formation of the coating layers could not affect the fracture toughness of the alloy.     

Compatibility of CVD SiC and SiCf/SiC Composites with High Temperature Helium Simulating Very High Temperature Gas-Cooled Reactor Coolant Chemistry

The chemical compatibility aspects of CVD β-SiC and SiC_f/SiC composites with a VHTR specific helium coolant were examined. The specimens were exposed to helium gas containing 20 Pa H₂, 5 Pa CO, 2 Pa CH₄, and 0.02–0.1 Pa H₂O, which is an expected VHTR coolant chemistry. Oxidation tests were carried out at 900 and 950 °C for up to 250 h. β-SiC and SiC_f/SiC composites had an excellent compatibility with the expected VHTR helium coolant environment. The oxidation of β-SiC as a matrix material of the SiC_f/SiC composite reacted in a passive oxidation regime owing to the presence of water vapor. A condensed version of the oxide SiO₂ formed at an early stage of oxidation and the growth of this oxide layer was very limited as the oxidation time increased up to 250 h. The recession of the pyrolytic carbon interphase of SiC_f/SiC composite could not be observed in the test range.     

Oxidation behaviour of particle reinforced MoSi2 composites at temperatures up to 1700°C. Part I: Literature review

In the first part of this paper the results of a literature review are presented. An overview of the oxidation behaviour in air and in combustion environments of both pure MoSi₂ and MoSi₂ composites in the temperature range from 400 to 1650°C is given. The second part of this paper reports about our results from oxidation tests with selected MoSi₂ composites (containing 15 vol.‐% Al₂O₃, Y₂O₃, ZrO₂, HfO₂, SiC, TiB₂, ZrB₂, or HfB₂, respectively) from different development stages at temperatures in the pest region as well as up to 1700°C. The third part describes the oxidation behaviour of the optimised MoSi₂ composites developed on the basis of the results from part II.     

Oxidation behaviour of particle reinforced MoSi2 composites at temperatures up to 1700°C.

Part III: Oxidation behaviour of optimised MoSi₂ composites The topic “Oxidation behaviour of particle reinforced MoSi₂ composites at temperatures up to 1700°C” is discussed in a three part publication. In the first part of this paper a literature survey on the oxidation behaviour of MoSi₂ and MoSi₂ composites has been given. In the second part an initial screening at 1600°C revealed those composites which may be suitable for high temperature applications. The low temperature oxidation behaviour of selected composites in the “pest” region was examined as well. Additionally, the effect of iron impurities on the high temperature behaviour of the composites was explained. The present part deals with a detailed investigation of an optimised MoSi₂/HfO₂ composite. These investigations include high temperature oxidation at 1500 to 1700°C and low temperature oxidation at 400 and 500°C.     

SiC nanowire-toughened MoSi2-SiC coating to protect carbon/carbon composites against oxidation

To protect carbon/carbon (C/C) composites against oxidation, a SiC nanowire-toughened MoSi₂-SiC coating was prepared on them using a two-step technique of chemical vapor deposition and pack cementation. SiC nanowires obtained by chemical vapor deposition were distributed random-orientedly on C/C substrates and MoSi₂-SiC was filled in the holes of SiC nanowire layer to form a dense coating. After introduction of SiC nanowires, the size of the cracks in MoSi₂-SiC coating decreased from 18 ± 2.3 to 6 ± 1.7 μm, and the weight loss of the coated C/C samples decreased from 4.53% to 1.78% after oxidation in air at 1500 °C for 110 h.     

Oxidation behaviour of particle reinforced MoSi2 composites at temperatures up to 1700°C. Part II: Initial screening of the oxidation behaviour of MoSi2 composites

In the first part of this paper a literature survey on the oxidation behaviour of MoSi₂ and MoSi₂ composites has been given. The present second part reports about the experimental results from oxidation tests with several MoSi₂ composites containing 15 vol.‐% Al₂O₃, Y₂O₃, ZrO₂, HfO₂, SiC, TiB₂, ZrB₂, or HfB₂, respectively, from different development stages. The tests were conducted at 1600°C in air for 100 hours. It was shown that the production route of the powders has a significant influence on the performance of the materials at high temperatures. This was attributed to contaminations. Additionally, the results indicated that only the composites with SiC, ZrO₂ or HfO₂, respectively, are suitable for application above 1500°C. A more detailed report about the optimised material will follow in the third part of this paper.     

Microstructure Evolution of Plasma-Sprayed MoSi<Subscript>2</Subscript> Coating at RT-1200 °C in Air

In this work, the phase composition and microstructure evolution of vacuum plasma-sprayed MoSi₂ coating between room temperature and 1200 °C in air was evaluated and characterized. The results showed that hexagonal MoSi₂ (h-MoSi₂) became the main phase in the deposited coating, which remained even after 50 h oxidation at 500 °C, exhibiting excellent thermal stability. MoO₃ bundles and SiO₂ clusters were generated by consuming tetragonal MoSi₂ (t-MoSi₂) after 1 h, and white powders formed on the coating’s surface after 10-h exposure to air at 500 °C. Most h-MoSi₂ transformed to t-MoSi₂ at 800 °C; moreover, a protective silica layer formed on the coating surface. Similar phenomenon was observed for the coating exposed to 1000 °C where grain growth also occurred. Vacuum heat treatment at 900 °C effectively improved the thermal stability of the MoSi₂ coating. The formation of silica layer alleviated negative effects of structural defects and helped the MoSi₂ coating serve as a protective coating for varied substrates.     

Fabrication and mechanical properties of SiCw/MoSi2–SiC composites by liquid Si infiltration of pyrolyzed rice husk preforms with Mo additions

Dense SiC ceramic matrix composites containing SiC whiskers (SiC_w) and MoSi₂ phase (SiC_w/MoSi₂–SiC) are fabricated by a liquid Si infiltration (LSI) method. Pyrolyzed rice husks (RHs) containing SiC whiskers, particles and amorphous carbon are mixed with different amounts of Mo powder to form preforms for the infiltration. Microstructure and mechanical properties of the composites are studied. Fracture mode of the composites is discussed. Results show that the SiC whiskers and fine particles in the pyrolyzed RHs were preserved in the composites after the LSI process. The amorphous carbon and Mo powder in the preforms reacted with molten Si, forming SiC and MoSi₂ in the composites. The presence of MoSi₂ in the composite increases the elastic modulus but lowers the flexure strength. Content of MoSi₂ of ca. 20 wt.% provides an enhanced fracture toughness of 4.1 MPa m^1/2 for the composite. But too large amount of MoSi₂ caused crack formation in the composite. The compressive residual stress introduced by the formation of MoSi₂ and SiC, and the de-bonding of the fine SiC particles and SiC whiskers from the residual Si phase are considered to favor the fracture toughness of the composites.     

Effect of SiC Addition on Oxidation Behavior of ZrB<Subscript>2</Subscript> at 1273 K and 1473 K

The oxidation behavior of ZrB₂–SiC composites with different contents of SiC addition was investigated at 1273 and 1473 K in air for 12 h in this study. The SiC addition contents ranged from 0 to 30 wt%. The results showed that when ZrB₂–SiC composites were oxidized at 1273 K in air, a two-oxide layer-structure forms: a continuous glassy layer and a ZrO₂ layer contained unoxidized SiC. When SiC content is 5 and 10 wt%, the glassy layer is mainly composed by B₂O₃. When SiC content is 20 and 30 wt%, a borosilicate glass could be formed on the top layer, which could improve the oxidation resistance of ZrB₂. When ZrB₂–SiC composites were oxidized at 1473 K in air, the oxide layer was composed of ZrO₂ and SiO₂ and unreacted SiC. Additionally, when SiC addition content was higher than 10 wt%, a continuous borosilicate glass layer could be formed on the top of the oxide layer at 1473 K. With the increase of SiC content in ZrB₂, the oxide layer thickness decreased at both 1273 and 1473 K.     

The Ablation and Oxidation Behaviors of SiC Coatings on Graphite Prepared by Slurry Sintering and Pack Cementation

SiC coatings were generated on graphite using slurry sintering (SS) and pack cementation (PC). The samples’ ablation features were assessed by an oxyacetylene torch. The rates of mass ablation of the PC–SiC and SS–SiC coatings were approximated 2.17?×?10^?3 and 9.52?×?10^?3 g s^?1, respectively, decreased by 84.1 and 29.6% compared to the uncoated samples. It was mainly attributed to the formation of a SiO₂ layer on the surface. The continuous SiO₂ molten film formed via the PC–SiC oxidation generates a sealing mechanism which can be an obstacle against the oxygen diffusion and hinder more ablation. This is while discontinuous SiO₂ film formed from the thin SS–SiC cannot protect the graphite effectively. The non-isothermal oxidation test shows that without the SiC coating, the sample weight is lost largely from 25 to 1500 °C, and its weight loss was 2.2% after the TGA. However, after coating, the samples possessed excellent oxidation protection and weight losses of SS–SiC and PC–SiC coatings are down to 1.3 and 0.6%, respectively. The more oxidation of the graphite substrate occurred due to the formation of macrocracks in the coating during the TGA and also the formation of holes on SiO₂ glass layer owing to release of CO or CO₂.