Glass-ceramic oxidation protection of higher manganese silicide thermoelectrics

A higher manganese silicide (HMS) thermoelectric, with composition MnSi1.74, densified by spark plasma sintering, was successfully coated with a glass-ceramic, in order to be used at temperatures higher than 500 °C. Compositional changes in both the HMS substrate and the glass-ceramic coating are reviewed and discussed with respect to the electrical properties of the uncoated and coated HMS before and after thermal cycles from RT to 600 °C in air. The formation of a Si-deficient layer (MnSi) on the uncoated HMS surface is due to the reaction between the HMS and oxygen at 600 °C, thus contributing to a lower power factor in comparison with the as-sintered HMS. Coated HMS samples (after thermal cycles RT-600 °C) show a lower electrical resistivity and a significantly higher power factor in comparison with the uncoated ones. The glass-ceramic coating is self-reparable at 600 °C, as demonstrated by the complete sealing of an induced scratch on its surface.     

Oxidation behavior of SiC/glaze-precursor coating on carbon/carbon composites

In order to improve the oxidation behavior of carbon/carbon composites in a wide range of temperature, a new SiC/glaze-precursor coating was developed.The SiC layer was produced by slurry and sintering, while the glaze precursor layer was prepared by slurry and drying. The microstructures and phase compositions of the coating were analyzed by SEM and XRD, respectively. The oxidation resistance of the coated composites was investigated using both isothermal and temperature-programmed thermogravimetric analysis in the temperature range from room temperature to 1600 °C. The results showed that the oxidation behavior of the coating was mainly controlled by the diffusion of oxygen during the test.The coating showed excellent oxidation resistance and self-healing ability in a wide range of temperature.     

Microstructure and oxidation behaviors at 800°C and 1250°C of MoSi2/ReSi2/NbSi2 compound coating prepared by electrodeposition and then pack cementation

MoRe duplex film has been electrodeposited from aqueous solution innovatively and then applied to fabricate protective silicide coating for the NbTiSi based alloy successively. The XRD, SEM and EDS results indicated the formation of MoSi₂/ReSi₂/NbSi₂ compound coating after halide reactivated pack cementation (HAPC) treatment. Pesting oxidation of MoSi₂ layer was suppressed and the NbTiSi based alloy was effectively protected at 800?°C with a mass gain of 0.48?mg?cm^?2 after oxidation for 100?h. At 1250?°C, continuous mass gain was observed with a mass gain of 2.6?mg?cm^?2 after exposure of 10?h. The synergistic combination of MoSi₂ and NbSi₂ layer enabled admirable protection of the substrate, in which MoSi₂ layer worked as the major anti-oxidation coating and the NbSi₂ layer could be a reservoir for Si. The contrast experiments indicate that ReSi₂ layer could improve the integrity and adherence of MoSi₂ layer, reduce the outward diffusion of alloying elements and oxidation of NbSi₂ layer, and then improve oxidation resistance of the compound coating ultimately.     

Oxidation behavior of ytterbium silicide

Si-rich ytterbium silicide was fabricated by through an arc-melting technique for applying use as a bond coat material in an environmental barrier coating system. Evaluation of its potential was accomplished through oxidation tests in dry air and an inert atmosphere. The experimental results showed that the changes in weight and morphologies of ytterbium silicide observed after the tests depended on the oxygen partial pressure. Extensive oxidation and weight gain occurred after oxidation in air. In order to apply this material for hot structures, improvement of the oxidation resistance is needed.     

Thermophysical behavior of thermal sprayed yttria stabilized zirconia based composite coatings

The effective thermal conductivity of a composite coating depends on intrinsic thermal conductivity of the constituent phases, its characteristics (size, shape) and volume fraction of porosities. The present study concerns studying the effect of CoNiCrAlY and Al₂O₃ content on the coefficient of thermal expansion and thermal conductivity of the YSZ (YSZ-CoNiCrAlY and YSZ-Al₂O₃) based composite coatings developed by thermal spray deposition technique. The coefficient of thermal expansion and thermal conductivity of the composite coatings were measured by push rod dilatometer and laser flash techniques, respectively, from room temperature to 1000 °C. Variation in density, porosity, coefficient of thermal expansion, and thermal conductivity was observed in the composite coatings with the addition of different volume fraction of CoNiCrAlY and Al₂O₃ powders in YSZ-CoNiCrAlY and YSZ-Al₂O₃ composites, respectively. Comparison between the theoretical and experimental thermal conductivities showed a mismatch varying from 4% to 58% for YSZ-CoNiCrAlY composite coatings and from 58% to 80% for YSZ-Al₂O₃ composite coatings. Model based analyses were used to understand the mechanism of thermal conductivity reduction in the composite coatings. It was concluded that the morphology of porosities varied with composition.     

Phase transformation mechanism of the APS yttria partially stabilized hafnia coating undergoing thermal exposure

8 mol.% Y₂O₃ partially stabilized HfO₂ (YSH8) free-standing coating was prepared by air plasma spraying (APS) method, and the crystal structure and phase transformation under 1300 °C were studied using Rietveld method of XRD, SEM and TEM. Results show that the as-sprayed YSH8 coating is mainly composed of tetragonal structure (T phase). The phase transformation of YSH8 coating is controlled by the diffusion of Y element. As the thermal exposure time prolongs, the weight fraction of monoclinic phase (M phase) quickly increases and reaches 68.1 % after 24 h. The Y content at the interface between the M phase and the original microstructure increases to 9 %–17 % after 24 h, and is in cubic phase. After exposure for 24, the T phase completely transforms to C + M phase.     

滑板工作面用耐火涂料的研制

介绍了涂料中复合填料、防氧化剂、悬浮剂、表面活性剂的选择过程及涂料密度与涂层厚度、渗透性的关系。该耐火涂料经过数千套滑板工作面上的喷涂应用,证明具有快干、耐磨蚀、防氧化等特性,提高了滑板的工作性能。     

Synthesis of nanocrystalline 8 mol% yttria stabilized zirconia powder from sucrose derived organic precursors

An organic precursor synthesis of 8 mol% yttria stabilized zirconia (YSZ) powder from Zr–Y composite nitrate solution and sucrose has been studied. Oxidation of sucrose in Zr–Y composite nitrate solution containing excess nitric acid in situ generates hydroxy carboxylic acids that forms a white sol which showed peaks at 1640 cm⁻¹ and 1363 cm⁻¹ in IR spectrum corresponding to hydroxy carboxylic acid complexes of Zr and Y. Precursor mass obtained by drying the sol on calcinations at 600 °C produced loosely agglomerated particles of cubic YSZ. Deagglomerated YSZ contain submicron particles with D₅₀ value of 0.5 μm and the particles are aggregates of nanocrystallites of nearly 10 nm size. Compacts prepared by pressing the YSZ powder sintered to 96.7% TD at 1450 °C. The sintered YSZ ceramic showed an average grain size of 2.2 μm.     

Thermo-oxidative aging of epoxy coating systems

The thermo-oxidative behavior of unformulated (unfilled) samples of epoxy coatings has been studied at five temperatures ranging from 70 °C to 150 °C. Two epoxy networks based on diglycidyl ether of bisphenol A (DGEBA), respectively, cured by jeffamine (POPA) or polyamidoamine (PAA) were compared. Infrared spectrophotometry (IR), differential scanning (DSC) and sol–gel analysis (SGA) were used to monitor structural changes.     

Damage behavior of atomic oxygen on zirconium carbide coating modified carbon/carbon composite

Zirconium carbide (ZrC) components were induced as coating modification on carbon/carbon (C/C). These ZrC–C/C specimens were investigated after atomic oxygen (AO) exposure for different assessment times, low earth orbit (LEO) ground-based environmental simulator was employed. The results indicate that ZrO₂ is the major production generated by the AO chemical reaction with the ZrC coating. Upon further exposure to AO, the production of ZrO₂ would drop off, then exfoliate easily, due to the mechanical impacting effect. Then the exposed graphite matrix and carbon fiber get corroded. Amorphous diamond-like carbon (DLC) is detected by X-ray photoelectron spectroscopy during AO exposure. Bending strength performance increased by 25% under AO exposure at first 10 h, then dropped by 52.1% from 10 h to 30 h of AO exposure. The AO damage mechanisms of ZrC–C/C composites are revealed.     

Ultra-high temperature oxidation resistance of a novel (Mo,Hf, W,Ti)Si2 ceramic coating with Nb interlayer on Ta substrate

In order to solve the challenge of recyclability of tantalum substrates in high temperature oxidation environments, a novel MoSi₂-WSi₂-HfSi₂-TiSi₂ composite ceramic coating containing an Nb interlayer was prepared on the surface of tantalum substrate by a three-step method. The mix ceramic silicide coating exhibited superior performance and effective protection for 10.2 h at 1800 °C, possibly due to the formation of an outer SiO₂-HfO₂-HfSiO₄ composite oxide film with low oxygen permeability, moderate viscosity and thermal expansion coefficient, as well as good self-healing ability. Furthermore, the coating successfully passed 537 thermal cycles from room temperature to 1800 °C. The presence of Nb interlayer significantly mitigated the thermal mismatch between the ceramic coating and the tantalum substrate, and the bidirectional diffusion of Nb element during the high temperature oxidation and thermal shock process further reduced the tendency of the coating to crack.     

A MoSi2-SiOC-Si3N4/SiC anti-oxidation coating for C/C composites prepared at relatively low temperature

In this study, SiC coating for C/C composites was prepared by pack cementation method at 1773 K, and MoSi₂-SiOC-Si₃N₄ as an outer coating was successfully fabricated on the SiC coated samples by slurry method at 1273 K. The microstructure and phase composition of the coatings were analyzed. Results showed that a porous β-SiC inner coating and a crack-free MoSi₂-SiOC-Si₃N₄ coating are formed. Effect of Si₃N₄ content on the oxidation resistance of the coated C/C composites at 1773 K in air was also investigated. The weight loss curves revealed that introducing the appropriate proportion of Si₃N₄ could improve the oxidation resistance of coating. The MoSi₂-SiOC/SiC coated C/C sample had an accelerated weight loss after oxidation in air for 20 h. However, the coating containing 45% Si₃N₄ could protect C/C composition from oxidation for 100 h with a minute weight loss of 0.63%.     

Evolution of microstructure and anti-oxidation ability of ZrB2 improved by a unique inert glass phase

Zirconium Boride is widely used as thermal protection materials. However, the characteristics of poor oxidation resistance of ZrB₂ at high temperatures limits its applications. In order to improve the anti-oxidation performance of ZrB₂, a novel method of doping LaF₃ is adopted in present study. In the synthesis process of ZrB₂ via carbothermal reduction method, LaF₃ was introduced to the initial materials. Motivated by the slightly higher formation temperature of ZrB₂ than the melting point of LaF₃, a liquid glass phase composed of F and La was deposited on the surface of ZrB₂, which naturally brought in oxygen starvation and contributed to improved oxidation resistance performance. The crystal lattice parameters and the anti-oxidation ability of ZrB₂ are closely dependent on the added LaF₃ content, which can ascribe to La³⁺/Zr²⁺ substitution and the amount of glass phase on the surface of ZrB₂.     

Anti-coking and anti-carburizing behavior of amorphous AlPO4 coating

The aim of the present study was to examine the anti-coking and anti-carburizing behavior of amorphous AlPO₄ coating. So, aluminum phosphate composition was synthesized by sol-gel process and applied on the AISI 304 stainless steel by dip coating technique. Anti-coking performance was examined in a tube furnace at 1000 °C for 30 min under Ethane (C₂H₆) atmosphere. Carburizing test was performed in a sealed charcoal medium at 1100 °C for a total of 30 h exposure time. Phase composition of the samples was analyzed by X-Ray Diffraction (XRD) after coking and carburizing tests. Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray Spectroscopy (EDS) were employed to study the morphology and elemental analysis of the samples after coke and carbon formation experiments. Microhardness indenter was applied on the cross section of the carbon-exposed specimens to plot the hardness profile through the carburizing zone. The results of the coking experiment revealed catalytic coke formed on the uncoated surface, while irregular spherical coke with no trace of catalytic coke was formed on the coated surface, indicating the great anti-coking performance of the amorphous AlPO₄ coating. The results of pack-carburizing test demonstrated that the thickness of the carbide layer formed on the bare surface was ～10 times greater than that of the coated sample. Hardness measurement for the amorphous AlPO₄ coated sample detected lower values compared to those for the uncoated one at all distances from the surface, indicating less carbon diffusion occurred beneath the coated surface. In overall, the results declared that the amorphous AlPO₄ coating could be a good candidate for surface protection of stainless steel against catalytic coke formation and carbon diffusion.     

Oxidation and defect control of CVD SiC coating on three-dimensional C/SiC composites

Two kinds of multi-layer CVD SiC coatings were prepared on a three-dimensional C/SiC composite. Oxidation behavior of the coating and the composite were studied and the effect of defects in the coating on its oxidation protection property were investigated. Above 1200 °C, thickness of the oxide film formed on the coating was related to oxidation time by the Fick’s first law X(t)²=Bt, the diffusion rate constant increased with oxidation temperature according to the Arrhenius’ relation ln B=−32?483/T+1.4048. Morphology of the interface between the CVD SiC and its oxide film was different after oxidation at temperatures from 1200 to 1500 °C. It was interpreted by consideration of the interfacial stress produced by thermal expansion mismatch and the CO gas pressure produced by interfacial reaction.     

Oxidation behavior of C–SiC composites with a Si–W coating from room temperature to 1500°C

Oxidation tests of carbon fiber reinforced silicon carbide composites with a Si–W coating were conducted in dry air from room temperature to 1500°C for 5 h. A continuous series of empirical functions relating weight change to temperature after 5 h oxidation was found to fit the test results quite well over the whole temperature range. This approach was used to interpret the different oxidation mechanisms. There were two cracking temperatures of the matrix and the coating for the C–SiC composite. Oxidation behavior of the C–SiC composite was nearly the same as that of the coated C–C composite above the coating cracking temperature, but weight loss of the C–SiC composite was half an order lower than that of the coated C–C composite below the cracking temperature. As an inhibitor, the SiC matrix increased the oxidation resistance of C–SiC composites by decreasing active sites available for oxidation. As an interfacial layer, pyrolytic carbon decreased the activation energy below 700°C. From 800°C to 1030°C, uniform oxidation took place for the C–SiC composite, but non-uniform oxidation took place for the coated C–C composite in the same temperature range. The Knudsen diffusion coefficient could be used to explain the relationship between weight loss and temperature below the coating cracking temperature and the matrix cracking temperature.     

Research on microstructure and oxidation resistant property of ZrSi2-SiC/SiC coating on HTR graphite spheres

ZrSi₂-SiC/SiC coating was prepared on the surface of high temperature gas-cooled reactor (HTR) matrix graphite spheres by two-step pack cementation and sintering process. The microstructure, oxidation resistance and thermal shock resistance properties of the as-prepared coatings with different original powder mixtures were investigated. Results show that dense microstructure of the ZrSi₂-SiC/SiC coating and continuous ZrSiO₄-SiO₂-ZrO₂ glass phase generated during the oxidation process were the key factors for the outstanding thermal properties. When the mole ratio of Zr:Si:C reaches 1:7:3 in the second pack cementation powders, the coated graphite spheres have optimum oxidation resistant ability. The weight gain is only 0.6 wt% after 15 times thermal shock tests and 0.12 wt% after isothermal oxidation test at 1500 °C for 20 h in air. The oxidation resistant mechanism of the coating was also discussed. The dense inner SiC layer and the outer glass layer generated during the oxidation process could protect the ZrSi₂-SiC/SiC coating from further oxidation.     

Influence of different coating structures on the oxidation resistance of MoSi2 coatings

Two different structures of MoSi₂ coatings were prepared on Niobium based alloys by using a two step process. The as-deposited type(a) MoSi₂ coating structure consists of a MoSi₂ layer on the surface and a NbSi₂ layer underneath, while the type(b) MoSi₂ coating consists of an outer MoSi₂ layer and an inner unsiliconized Mo layer. The oxidation behaviors of the two different types MoSi₂ coatings were examined at 1200 °C for 100 h in air, and the mass gains of type(a) and type(b) MoSi₂ coated specimens were 0.64 mg/cm² and 0.59 mg/cm² respectively. The excellent oxidation resistance of both type(a) and type(b) MoSi₂ coated samples at 1200 °C was due to the formation of a dense and continuous SiO₂ scale during oxidation. As the CTE mismatch between the outer MoSi₂ coating and the inner layer, cracks distributed within both type(a) and type(b) MoSi₂ coating structures.     

Densification and high-temperature oxidation behavior of SiC sintered with multicomponent rare-earth additives

This study examined the effects of rare-earth (RE) elements such as Sc, Y, Ce, and Yb on the densification and oxidation of SiC. After adding binary or ternary RE nitrates in liquid form to β-SiC, hot pressing was performed at 1750 °C for 2 h under 20 MPa. RE nitrate was transformed into RE oxide and formed a liquid phase during sintering by a reaction with SiO₂ present on the SiC surface, where the total amount of RE oxide was fixed at 5 wt%. RE-based silicate melts acted as sintering additives without decomposing SiC at high sintering temperatures. SiC containing Sc–Y as an additive showed a much higher density (≥ 99%) than SiC containing the conventional Al–Y additive (∼95%). The multicomponent RE additive with a melting point (T_m) < 1550 °C had a relatively lower density than that with a higher T_m, owing to the evaporation of the additive at 1750 °C. The density of SiC also depended on the additive composition. The oxidation test, conducted at 1300 °C for up to 168 h in air, exhibited a parabolic weight gain. The SiC sample sintered with the Sc–Yb additive achieved the highest resistance of 3.23 × 10⁻⁵ mg/cm⁴·s.     

Nanomechanical behavior of yttria stabilized zirconia (YSZ) based thermal barrier coating

In the present study, the detailed evaluation of nanomechanical properties in terms of hardness and Young׳s modulus of duplex and compositionally graded YSZ based thermal barrier coating (TBC) have been evaluated by nanoindentation technique. Duplex and compositionally graded TBCs have been fabricated by thermal spray deposition technique. As TBCs are commonly applied for high temperature protection, effect of isothermal treatment in air (at 900 °C and 1000 °C) on nanomechanical properties has also been evaluated. Finally, the mechanical properties have been correlated with characteristics of the coating. The hardness and Young׳s modulus of the TBCs are found to increase with increased duration of thermal exposure. Modulus of resilience and resistance to plastic deformation of the duplex and compositionally graded TBC have also been evaluated at room temperature and with thermal exposure and discussed in detail.