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。     

Characterization of silicide phases formed during pack siliconizing coating on the Nb-1Zr-0.1C alloy

The present paper describes the morphology, chemistry and crystallography of the phases observed in the silicide coatings produced by pack cementation technique on Nb based alloys. Cross-sectional microstructures examined by transmission electron microscopy and scanning electron microscopy techniques have shown that the coating has two silicide layers: NbSi₂ and Nb₅Si₃. NbSi₂ formed at the surface of the sample and Nb₅Si₃ formed in between the substrate (Nb alloy) and NbSi₂ coating layer. Electron diffraction analyses revealed that NbSi₂ has hexagonal crystal structure with lattice parameters as a = 0.48 nm and c = 0.66 nm and Nb₅Si₃ has tetragonal crystal structure with lattice parameters as a = 0.65 nm and c = 1.19 nm. Nb₅Si₃ showed fine equiaxed grains, whereas, NbSi₂ exhibited duplex morphology having columnar grain morphology near to the Nb₅Si₃ layer and large equiaxed grains at the surface of the coating sample. The presence of duplex morphology was explained by estimating diffusion of various species and it was shown that columnar morphology of grains could be attributed to outward diffusion of Nb and equiaxed grains to inward diffusion of Si. In the case of Nb₅Si₃, growth takes place due to single element Si diffusion, leading to development of single equiaxed grain morphology of the Nb₅Si₃ phase.     

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.     

Structure of Al-modified silicide coatings on an Nb-based ultrahigh temperature alloy prepared by pack cementation techniques

In order to prepare Al-modified silicide coatings on an Nb-based ultrahigh temperature alloy, both a two-stage pack cementation technique and a co-deposition pack cementation technique were employed. The two-stage process included siliconizing a specimen at 1150 °C for 4 h followed by aluminizing it at 800-1000 °C for 4 h. The coating prepared by pack siliconization was composed of a thick (Nb,X)Si₂ (X represents Ti, Cr and Hf elements) outer layer and a thin (Nb,X)₅Si₃ transitional layer; after the siliconized specimens were aluminized at or above 860 °C, a (Nb,Ti)₃Si₅Al₂ phase developed at the surface of the coating, and furthermore, when aluminizing was carried out at 860 °C, a new (Nb,Ti)₂Al layer formed in the coating between the (Nb,X)₅Si₃ layer and the substrate, but when aluminizing was performed at 900-1000 °C, the new layer formed was (Nb,Ti)Al₃. The co-deposition process was carried out by co-depositing Si and Al on specimens at 1000-1150 °C for 8 h under different pack compositions, and it was found that the structure of co-deposition coatings was more evidently affected by co-deposition temperature than pack composition. An Al-modified silicide coating with an outer layer composed of (Nb,Ti)₃Si₅Al₂, (Nb,X)Si₂ and (Nb,Ti)Al₃ was obtained by co-depositing Si and Al at 1050 °C.     

Oxidation Resistant Ce-modified Silicide Coatings Prepared on Ti–6Al–4V Alloy by Pack Cementation Process

Cerium-modified silicide coatings were prepared on Ti–6Al–4V by pack cementation. The effects of different kinds of activators (NaCl, AlF₃, AlCl_3, and NH₄Cl) and pack CeO₂ concentrations (1, 3, and 5 wt%) on the coating structures were studied. The results show that the coatings were mainly composed of a TiSi₂ outer layer, a TiSi middle layer, a Ti₅Si₄ inner layer and a 1–2 μm thick Ti₅Si₃ interdiffusion zone. NH₄Cl was a more suitable activator for preparing the Ce-modified silicide coating on Ti–6Al–4V, based on the coating microstructure and growth rate. The coating thickness decreased with increasing CeO₂ concentration in the pack. Oxidation tests at 800 °C in air showed that the Ce-modified silicide coating showed improved oxidation resistance compared to both the uncoated alloy and the pure silicide coating. A dense, but thick oxide scale formed that was composed of a TiO₂ outer layer and a SiO₂ inner layer.     

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.     

Microstructure and High Temperature Oxidation Performance of Silicide Coating on Nb-Based Alloy C-103

The microstructure and oxidation resistance of NbSi₂ coating formed on Nb-based alloy C-103 by a pack siliconization process have been studied. The as-formed coating consists of an outer NbSi₂ layer and an inner Nb₅Si₃ layer. A NbSi₂–Nb₅Si₃ two-phase zone is also present between the above two layers. Weight-change data obtained under isothermal and cyclic oxidation in air at 1100 and 1300°C, suggests that the coating gives oxidation protection up to about 4 h. The oxide scale that formed on the coating during oxidation exposure consists of an outer glassy silica layer and an inner Nb₂O₅-silica mixed layer. Nb₂O₅ phase is also present in the outer silica scale in the form of elongated particles. Oxidation protection is achieved primarily by the presence of the glassy silica layer on the surface. Spallation of this layer during thermal cycling causes significant reduction in the protective life of the coating.     

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.     

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 resistance coatings of Mo−Si−B alloys via a pack cementation process

Oxidation behavior of Si pack cementation coatings on a three-phase Mo−Si−B alloy was examined. During Si pack cementation of a three-phase Mo−Si−B alloy, a MoSi₂ outer layer was synthesized on the exterior layer. Following oxidation in air of the pack-coated alloys at 1200°C, the MoSi₂ phase layer was consumed and replaced by the Mo₅Si₃ (or T₁) phase. The synthesized T₁ phase provided excellent oxidation resistance when exposed to high temperatures. The silicide-coated alloys exhibit higher oxidation resistance compared with uncoated Mo−Si−B alloys. The enhanced oxidation behavior and its mechanism are discussed in terms of the thicknesses of the oxide layers under exposure to high temperatures.     

Preventing the accelerated low-temperature oxidation of MoSi2 (pesting) by the application of superficial alkali-salt layers

Previous work showed that MoSi₂ diffusion coatings formed by a NaF-activated pack cementation process did not pest. A Na–Al-oxide by-product layer resulting from the NaF activator formed a Na-silicate layer to passivate MoSi₂. Superficial NaF layers were then used to prevent the pesting of MoSi₂ diffusion coating that were otherwise susceptible to pest disintegration. In this study, the use of superficial alkali-salt layers to prevent the accelerated oxidation of bulk MoSi₂ at 500°C is investigated more broadly. The application of Na-halide, KF, LiF, Na₂B₄O₇, or Na-silicate layers prior to oxidation prevented accelerated oxidation and pesting for at least 2000 hr at 500°C in air. The formation of a fast-growing, Na-silicate layer passivates MoSi₂. The MoO₃ that forms during oxidation absorbs sodium by intercolation to form stable Na-molybdate precipitates. Na₂B₄O₇, Na-silicate, LiF, and KF prevented accelerated oxidation at 500°C by a similar mechanism. The application of alkali-halide salts is a simple, effective solution to prevent the accelerated oxidation and pesting of MoSi₂.     

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.     

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].     

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。     

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.     

B2O3 modified SiC–MoSi2 oxidation resistant coating for carbon/carbon composites by a two-step pack cementation

To protect carbon/carbon (C/C) composites against oxidation, a B₂O₃ modified SiC–MoSi₂ coating was prepared by a two-step pack cementation. The microstructure and the oxidation resistant property of the coating were studied. The results show that, the as-received coating is a dense structure, and is composed of α-SiC, β-SiC and MoSi₂. The B₂O₃ modified SiC–MoSi₂ coating has excellent oxidation resistant property, and can protect C/C composites from oxidation at 1773 K in air for more than 242 h. The failure of the coating was considered to arise from the existence of the penetration cracks in the coating during the slow cooling from 1873 to 673 K.     

Formation of MoSi2 and Al doped MoSi2 coatings on molybdenum base TZM (Mo–0.5Ti–0.1Zr–0.02C) alloy

Formation of aluminium (Al) doped molybdenum di-silicide (MoSi₂) coatings was studied to improve the high temperature oxidation behavior of TZM (Mo–0.5Ti–0.1Zr–0.02C) alloy. The pack composition of the halide activated pack cementation process was successfully optimized to form silicide and Al doped silicide coatings on the TZM alloy substrates. Mo(Si, Al)₂ phase was found to form at the outer layer of the coating prepared by doping Al in MoSi₂. A change in composition of the phases with increase in coating temperature was detected with Al doping, whereas un-doped silicide coating process was dominated by the formation and growth of MoSi₂ phase. Oxidation test and the characterization studies using SEM, EDS, XRD, and micro-hardness measurements indicated the improved performance of Al doped silicide coating during high temperature oxidation in dry air due to the formation of the protective alumina scale.     

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.     

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.     

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.