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 disili-tide coating was prepared on its surface by a molten salt technology. XRD and SEM analysis showed that only tetragonal MoSi2 phase ex-isted in the coating after being siliconized for 5 h at 900℃. 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 MoSi2coating was proved to be an effective method to prevent 30 at.% MosSi3/MoSi2 composites from being oxidized at 1200℃. 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.     

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.     

双峰结构Mo-Si-B基体表面多层硅化物涂层的表征和抗氧化性能

由于在细晶Mo-Si-B合金中制备双峰分布的α-Mo晶粒能够在不显著降低合金强度的前提下大幅提高其断裂韧性,为了加强双峰结构合金的表面防护,同时保持其优异的力学性能,通过包埋渗在合金表面上制备了一个具有多层结构（MoSi₂,Mo₅Si₃和Mo₅SiB₂/MoB）的涂层。研究结果表明,相比在细晶结构基体上制备的涂层,双峰结构基体上的涂层表面较为粗糙,并且也表现出双峰分布的微观组织。此外,覆盖涂层后的双峰结构合金的断裂韧性依然良好,并且分布在涂层中的La₂O₃颗粒能够增韧涂层。具有涂层的双峰结构合金在1100~1300 ℃下展现出了卓越的抗氧化性,这是由于氧化过程中在涂层表面快速形成了一个薄且能自愈合的SiO₂-B₂O₃膜。随着氧化温度升高,SiO₂-B₂O₃膜的粘度降低,使得SiO₂-B₂O₃膜的厚度和氧化产物Mo₅Si₃均增加。并且,升高温度促进了Si和B的互扩散,加速了Mo₅Si₃和Mo₅SiB₂/MoB层的增长。在1300 ℃下,由于单峰结构的MoSi₂涂层拥有更多的晶界,使得含涂层的细晶合金相比含涂层的双峰结构合金表现出更多的氧化增重。     

Mo5Si3-B and MoSi2 deposits fabricated by radio frequency induction plasma spraying

Induction plasma-spray processing was used to produce free-standing parts of Mo₅Si₃-B composite and MoSi₂ materials. The oxidation resistance, up to 1210 °C, of the Mo₅Si₃-B composite was compared with MoSi₂, which is known to be resistant to high-temperature oxidation. The deposits were oxidized isothermally in air at atmospheric pressure. The structural performance of these materials under high-temperature oxidation conditions was found to depend on the boron content in the specimens. In particular, the composite containing 2 wt.% boron exhibited excellent resistance to oxidation, as indicated by the specimen mass change, which was found to be near zero after the 24 h oxidation test.     

钼表面包埋渗法制备(Ti, Mo)Si2/MoSi2 涂层及其在1200 ℃周期性氧化环境下的氧化行为

利用连续沉积的包埋渗法,在钼表面制备了(Ti,Mo)Si₂/MoSi₂复合涂层。利用X射线衍射、扫描电子显微镜、能谱仪和热力学计算对涂层进行了表征与反应机理分析。结果表明,共沉积法无法实现Ti的有效沉积。先渗Ti、再渗Si的两步沉积工艺能有效制备Ti改性硅化物涂层。涂层分为3层,最外层为(Ti,Mo)Si₂三元化合物层,次外层为MoSi₂层,次外层与基体间为Mo₅Si₃过渡层。渗硅温度对涂层结构无明显影响。Ti改性硅化物涂层的生长速率略低于单一渗硅涂层的生长速率。(Ti,Mo)Si₂/MoSi₂复合涂层的形成由Ti、Si内扩散控制。Ti元素集中在涂层表层,Si元素通过(Ti,Mo)Si₂化合物层与基体作用形成MoSi₂层和Mo₅Si₃过渡层。渗Ti过程中,埋渗料间反应会引入游离态铝氟化物AlF₃。在随后的渗硅过程中,游离态Al以Al₃Mo的形式在(Ti,Mo)Si₂层中靠近MoSi₂层的上界面处析出。在1200 ℃周期性氧化过程中,(Ti,Mo)Si₂/MoSi₂复合涂层持续循环氧化180 h后未出现明显失重。(Ti,Mo)Si₂层氧化形成的SiO₂与TiO₂致密复合氧化层能填充涂层表面裂纹,持续阻碍氧扩散,因此其在周期性氧化环境下的抗氧化性能显著优于单一渗硅涂层。     

High temperature oxidation and microstructure of MoSi2/MoB composite coating for Mo substrate

The two-layer MoSi₂/MoB composite coatings were developed using the halide activated pack cementation (HAPC) method on Mo substrate. Oxidation resistance property and microstructural evolution of the coatings at high temperatures were investigated. During oxidation exposure, the coatings exhibited a good oxidation resistance property. The mass gains of the coated specimens oxidized at 1200 °C for 100 h and at 1300 °C for 80 h were 0.270 and 0.499 mg/cm², respectively. Compared with the monolithic MoSi₂ coatings, the transformation of MoSi₂ phase in the MoSi₂/MoB composite coatings was more sluggish at elevated temperatures. The growth rate constant of the Mo₅Si₃ layer in the composite coatings was two orders of magnitude lower than that of the Mo₅Si₃ layer in the monolithic coatings at 1300 °C. The microstructural degradation of MoSi₂ in the composite coatings at high temperatures was slowed by the introduced MoB layer. The MoB layer in the composite coatings is useful to prolong the service life of MoSi₂ coatings at high temperatures.     

Reaction diffusion of MoSi2 and Mo5SiB2

To establish quantitative basis for oxidation-protective coating of Mo–Si–B ternary alloys by MoSi₂, phase transformations in MoSi₂ vs. Mo₅SiB₂ diffusion couples have been studied. Two layers are formed on reaction diffusion at temperatures between 1400 and 1600 °C: a single-phase layer of Mo₅Si₃ and a two-phase layer consisting of Mo₅Si₃ and MoB. The growth obeys the parabolic low for both the layers, and the rate constants of the two layers are found to be approximately equal. The interdiffusion coefficient in the T₁ layer has also been evaluated. The microstructural evolution in the diffusion zone is modeled in terms of mass conservation, as well as that of a Mo–9Si–18B two-phase alloy coated with MoSi₂ reported previously [Intermetallics 12 (2004) 407].     

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.     

Growth kinetics and pesting resistance of MoSi2 and germanium-doped MoSi2 diffusion coatings grown by the pack cementation method

The rapid, destructive low-temperature oxidation (pesting) of MoSi₂ is an important limitation to its practical use. The growth of molybdenum silicide diffusion coatings by a halide-activated pack cementation method results in an adherent superficial, salt by-product, whose composition depends on the halide activator used to grow the coating. As a consequence of the residual salt deposit, coatings grown by a NaF-activated pack did not pest after 2500 hours of isothermal oxidation or after cyclic oxidation for 600 1 hour cycles in air at 500°C. An additional minor improvement in the pesting resistance was observed for the germanium-doped MoSi₂ Coatings. The growth kinetics for a three-layer Ge-doped Mo(Si, Ge)₂/Mo₅(Si, Ge)₃/Mo₃(Si, Ge) coating are compared with rates calculated for the diffusion-controlled growth of an undoped three-layer silicide and for three-layer germanide coatings. The activation energy for the solid-state diffusional growth of MoSi₂ is the same as that for Mo(Si, Ge)₂, but the growth rates for Mo(Si, Ge)₂ are faster. The activation energies for the solid state diffusional growth of the inner Mo₅(Si, Ge)₃ and Mo₃(Si, Ge) layers are similar to Mo₅Ge₃ and Mo₃Ge, but the rates are slower. The chemical demixing of Mo(Si, Ge)₂ under a chemical potential gradient creates a maximum in the Ge concentration at the Mo(Si, Ge)₂/Mo₅(Si, Ge)₃ interface, which produces unusual growth kinetics for the Mo₅(Si, Ge)₃ and Mo₃(Si, Ge) layers.     

Materials for temperatures above 1500°C in oxidizing atmospheres. Part II: Experimental results on the oxidation of MoSi2 composites and coated RSiC

The topic “Materials for temperatures above 1500°C in oxidizing atmospheres” is discussed in a 3 part publication. In the first part a literature survey had been performed leading to the conclusion that either particle or fiber reinforced MoSi₂‐based materials or RSiC coated with a MoSi₂‐based layer are suitable for applications at such high temperatures. In the present part such material systems are investigated experimentally at 1500 and 1600°C with respect to their oxidation resistance in air. Particular interest was given to the influence of the Mo₅Si₃ content in MoSi₂ and the influence of second phase particles in MoSi₂ consisting of ZrB₂ and SiC. Furthermore, the oxidation resistance of several dip‐coatings on RSiC which were manufactured from a polysiloxane precursor by subsequent pyrolysis were also investigated. Part III which reports about “contact corrosion” between different materials at these temperatures will follow in the next issue.     

Growth Kinetics and Microstructure Evolution of Intermediate Phases in MoSi<Subscript>2</Subscript>-Si<Subscript>3</Subscript>N<Subscript>4</Subscript>-WSi<Subscript>2</Subscript>/Mo Diffusion Couples

The growth kinetics and silicon diffusion coefficients of intermediate silicide phases in MoSi₂-3.5 vol.% Si₃N₄-5.0 vol.% WSi₂/Mo diffusion couple prepared by spark plasma sintering were investigated in temperatures ranging from 1200 to 1500 °C. The intermediate silicide phases were characterized by x-ray diffraction. The microstructures and components of the MoSi₂-Si₃N₄-WSi₂/Mo composites were investigated using scanning electron microscope with energy-dispersive spectroscopy. A special microstructure with MoSi₂ core surrounded by a thin layer of (Mo,W)Si₂ ring was found in the MoSi₂-Si₃N₄-WSi₂ composites. The intermediate layers of Mo₅Si₃ and (Mo,W)₅Si₃ in the MoSi₂-Si₃N₄-WSi₂/Mo diffusion couples were formed at different diffusion stages, which grew parabolically. Activation energy of the growth of intermediate layers in MoSi₂-3.5 vol.% Si₃N₄-5.0 vol.% WSi₂/Mo diffusion couple was calculated to be 316 ± 23 kJ/mol. Besides, the hindering effect of WSi₂ addition on the growth of intermediate layers was illustrated by comparing the silicon diffusion coefficients in MoSi₂-3.5 vol.% Si₃N₄-5.0 vol.% WSi₂/Mo and MoSi₂-3.5 vol.% Si₃N₄/Mo diffusion couples. MoSi₂-3.5 vol.% Si₃N₄-5.0 vol.% WSi₂ coating on Mo substrate exhibited a better high-temperature oxidation resistance in air than that of MoSi₂-3.5 vol.% Si₃N₄ coating.     

Effects of ternary additions on the microstructure and thermal stability of directionally-solidified MoSi2/Mo5Si3 eutectic composites

Effects of ternary additions on the microstructure and thermal stability of directionally-solidified MoSi₂/Mo₅Si₃ eutectic composites have been studied for twelve different elements (Ti, V, Cr, Fe, Co, Ni, Nb, Ta, W, Ir, B and C) paying special attention to the variation of lattice misfits and interface segregation behavior with ternary additions. Among six elements (type-1: Ti, V, Cr, Nb, Ta and W) with a relatively high solubility in MoSi₂ and Mo₅Si₃, Ta and W are found to be beneficial to microstructure refinement. All other six ternary elements (type-2: Fe, Co, Ni, Ir, B and C) with a negligibly low solubility in MoSi₂ and Mo₅Si₃ exhibit a strong tendency to segregate on MoSi₂/Mo₅Si₃ interfaces, resulting in both microstructure refinement and the modification of the interface morphology.     

Microstructure ofin situ MoSi2/SiC nanocomposite coating formed on Mo substrate by displacement reaction

The microstructure of an in-situ Mosi₂/β-SiC nanocomposite coating formed by the solid-state displacement reactions of Si deposited by chemical vapor deposition (CVD) with Mo-carbide layers at 1100°C, which had previously been formed on the surface of a Mo substrate by a CVD process, was investigated. The Mo-carbide layers formed by the simultaneous CVD of Mo and carbon at 900°C for 5 h using a gas mixture of C₂H₄−MoCl₅−Ar consisted of two layers, an inner layer of Mo₂C and an outer layer of MoC. While the monolithic MoSi₂ coating showed a typical colummar microstructure perpendicular to the Mo substrate, the MoSi₂/β-SiC nanocomposite coating formed by the solid-state displacement reactions between the Mo-carbide layers and Si was composed of equiaxed MoSi₂ grains with an average size of 150–500 nm and β-SiC particles with an average size of 80–105 nm. The β-SiC particles exhibited an oblate-spheroidal shape and were located mostly at the grain boundaries of MoSi₂. The volume percentage of β-SiC particles ranged from 18.5 to 29.2% with respect to the carbon concentration in Mo-carbide layers.     

钼基体表面二硅化钼涂层的制备及其高温抗氧化性能

以工业废弃硅化钼棒为原料,采用浆料涂刷法在钼表面制备MoSi2基抗氧化涂层.研究涂层的显微组织、相组成及在1500℃的高温氧化行为.结果表明,以废弃硅化钼棒和纯MoSi2粉末为原料制备的涂层和基体之间形成明显的连接层.纯MoSi2制备的涂层(PM)在烧结后出现少量裂纹,而以废弃硅钼棒为原料制备的涂层(SM)在烧结后没有...     

Morphology, structure and formation mechanism of silicide coating by pack cementation process

The MoSi2 coating on C 103 niobium based alloy was prepared by pack cementation method. The formative mechanism, morphology and structure of coating were investigated. The silicide coating was formed by reactive diffusion obeying parabolic rule during pack cementation process. It is found that the composite structural coating is composed of three inferior layers as follows. The main layer is composed of MoSi2, the two phases＇ transitional layer consists of NbSi2 and a few NbsSi3 and the diffuse layer is composed of NbsSi3. The dense amorphous glass layer formed on the surface at high temperature oxidation circumstance can effectively prevent the diffusion of oxygen into coating.     

Oxidation of SiOC/MoSi2/SiC Composites Prepared by Polymer Pyrolysis

From the pre-ceramic polymer of polymethylsiloxane (PMS) and powders of MoSi₂, SiC and Si, new ceramic composites that consisted primarily of an amorphous SiOC matrix containing dispersed particles of MoSi₂ and SiC were synthesized. The composites displayed superior oxidation resistance at both high and low temperatures by forming SiO₂ on the surface. The thin, amorphous SiO₂ layer that formed initially gradually to crystallized during oxidation between 1000 and 1300°C. An outer highly porous and an inner superficial SiO₂ layer that formed from the initial stage of oxidation between 400 and 500°C protected the composites from pesting.     

Influence of siliconizing on the oxidation behavior of plasma sprayed MoSi2 coating for niobium based alloy

Plasma spraying combined with halide activated pack cementation (HAPC) was used to deposit silicide coating on Nb-based alloy. X-ray diffraction (XRD) and energy disperse spectrum (EDS) indicate the formation of the siliconized NbSi₂ transition layer and the sprayed MoSi₂ outer layer. NbSi₂ layer prepared with HAPC exhibits relatively uneven surface which could promote the deposition of the sprayed MoSi₂. The coating specimen with 5 h siliconizing presented the best oxidation resistance with only 0.18% mass gain after 25 h oxidation at 1200 °C in air. The synergistic protection effect, depending on the continuous silica layer formed on the coating surface and the dispersal silica within the coating and interface, is responsible for the excellent oxidation resistance of the coating.     

Oxidation behavior of molybdenum silicides and their composites

A key materials issue associated with the future of high-temperature structural silicides is the resistance of these materials to oxidation at low temperatures. Oxidation tests were conducted on Mo-based silicides over a wide temperature range to evaluate the effects of alloy composition and temperature on the protective scaling characteristics and pesting regime for the materials. The study included Mo₅Si₃ alloys that contained several concentrations of B. In addition, oxidation characteristics of MoSi₂–Si₃N₄ composites that contained 20–80 vol.% Si₃N₄ were evaluated at 500–1400°C.     

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.     

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

To protect carbon/carbon (C/C) composites from oxidation, a dense coating has been produced by a two-step pack cementation technique. XRD and SEM analysis shows that the as-obtained coating was composed of MoSi₂, SiC and Si with a thickness of 80-100 μm. The MoSi₂-SiC-Si coating has excellent anti-oxidation property, which can protect C/C composites from oxidation at 1773 K in air for 200 h and the corresponding weight loss is only 1.04%. The weight loss of the coated C/C composites is primarily due to the reaction of C/C substrate and oxygen diffusing through the penetration cracks in the coating.