High-temperature oxidation behaviour of Ti<Subscript>3</Subscript>Si<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>C<Subscript>2</Subscript> in air

The oxidation behaviours of bulk Ti₃Si_(1−x)Al _x C₂ prepared by hot pressing were investigated. The results showed that the isothermal oxidation behaviour of Ti₃SiC₂ obeyed a parabolic law between 900 and 1100°C, and followed a two-step parabolic rate law between 1200°C and 1300°C. The cyclic oxidation behaviour of material is assumed to obey a three-step parabolic rate law at 1100°C and 1200°C. The calculated activation energy of isothermal oxidation is 101·43 kJ·mol⁻¹. The oxide layers consisted of a mass of α-Al₂O₃ and little TiO₂ and SiO₂ are observed on Ti₃SiC₂ as a dense and adhesive protect scale. The oxidation mechanism varies with the additive aluminum that greatly improves the oxidation resistance of Ti₃SiC₂.     

Microstructure and oxidation behaviour of Fe–Cr–silicide coating on a niobium alloy

The cyclic oxidation performance of a Fe–Cr-modified silicide coating on Nb-alloy C-103 was evaluated in air at temperatures between 1100 and 1500°C and the microstructural changes examined. The coating was oxidation resistant and the duration of protection increased from 60 minutes at 1100°C to 255 minutes at 1500°C. The formation of the surface glassy silica layer and its ability to heal the cracks in the coating enhanced the oxidation performance at high temperatures. The outer NbSi₂ layer served as a reservoir of Si and sustained the formation of the protective silica scale. Spallation of the silica scale and the concomitant depletion of the NbSi₂ layer towards the regeneration of the silica scale limit the oxidation life of the coating.     

Synthesis and some properties of Ti3SiC2 by hot pressing of Ti,Si and C powders Part 2 – Mechanical and other properties of Ti3SiC2

Abstract

Some properties of the remarkable Ti₃SiC₂ based ceramic synthesised by hot pressing of elemental Ti, Si, and C powders have been investigated. Its flexural strength by using three point bending tests and fracture toughness by using single edge notched beam tests were measured at room temperature to be in the range 310–427 MPa and about 7·MPa m^1/2, respectively. This material is a relative 'soft' ceramic with a low hardness of 4 GPa. Ti₃SiC₂ is similar to the soft metals and is a damage tolerant material that is able to contain the extent of microdamage. An oxidation test has been performed in the temperature range 1000–1400°C in air for 20 h. The oxidation resistance below 1100°C was good. Two oxidized layers were formed, the outer layer consisting of pure rutile-type TiO₂, and the inner layer a mixture of SiO₂ and TiO₂. The average coefficient of thermal expansion (CTE) of Ti₃SiC₂ was measured to be 9·29 × 10^?6 K^?1 in the temperature range 25–1400°C. The thermal shock resistance of Ti₃SiC₂ was evaluated by quenching the samples from 800°C, 1200°C, and 1400°C, respectively. The retained flexural strength drops dramatically at quenching temperature, but shows a slight increase after quenching from 1400°C compared with quenching from 800°C and 1200°C.     

In situ chemical vapour co-deposition of Al and Si to form diffusion coatings on TZM

Multilayer alumino-silicide and silicide coatings were formed by in situ chemical vapour co-deposition of Al and Si on TZM (Mo–0.5Ti–0.1Zr–0.02C) alloy for improving its high-temperature oxidation resistance. MoSi₂ and Mo (Si, Al)₂ layers were formed in the inner and the outer layers, respectively in the case of alumino-silicide coating. Whereas silicide coating consisted of Mo₅Si₃ and MoSi₂ phases in the inner and the outer layers, respectively. 24–100-μm thick coatings were formed by optimizing the pack mixture of Al and or Si, NH₄F and Al₂O₃ powders and conducting the experiments at 1000 °C for 8–36 h. MoSi₂ layer showed a faster growth rate and presence of columnar grains. A small weight gain at the initial stages was observed during the oxidation tests of the coated samples under continuous or cyclic heating at 1300 °C in air. Neither cracks nor peeling of the coating layers were noticed after oxidation tests.     

Facile and scalable synthesis of Ti<Subscript>5</Subscript>Si<Subscript>3</Subscript> nanoparticles via solid-state route in an autoclave

A novel method of the synthesis of titanium silicide nanoparticles via solid-state route in an autoclave at 700°C is reported. The reaction of titanium silicide could be described briefly as: 5TiO₂ + 3Si + 20Li = Ti₅Si₃ + 10Li₂O. XRD pattern indicated that the product was hexagonal Ti₅Si₃. The Ti₅Si₃particle size (about 20–40 nm) is confirmed by the TEM images. Furthermore, the thermal stability and oxidation resistance of the titanium silicide nanoparticles were also investigated.     

A new synthesis reaction of Ti3SiC2 from Ti/TiSi2/TiC powder mixtures through pulse discharge sintering (PDS) technique

Ti/TiSi₂/TiC powder mixtures with molar ratios of 1:1:4 (M1) and 1:1:3 (M2) were first employed for the synthesis of Ti₃SiC₂ through pulse discharge sintering (PDS) technique in a temperature range of 1100–1325 °C. It was found that Ti₃SiC₂ phase began to form at the temperature above 1200 °C and its purity did not show obvious dependence on the sintering temperature at 1225–1325 °C. The TiC contents in M2 samples is always lower than that of the M1 samples, and the lowest TiC contents in the M1 and M2 samples were calculated to be about 7 wt% and 5 wt% when the sintering was conducted at the temperature near 1300 °C for 15 minutes. The relative density of the M1 samples is always higher than 99% at sintering temperature above 1225 °C, indicating a good densification effect produced by the PDS technique. A solid-liquid reaction mechanism between Ti-Si liquid phase and TiC particles was proposed to explain the rapid formation of Ti₃SiC₂. Furthermore, it is suggested that Ti/TiSi₂/TiC powder can be regarded as a new mixture to fabricate ternary carbide Ti₃SiC₂. Received: 5 September 2001 / Accepted: 11 September 2001     

Effect of the La<Subscript>2</Subscript>O<Subscript>3</Subscript> sol–gel coating on the alumina scale adherence on a model Fe–20Cr–5Al alloy at 1100 °C

The effect of lanthanum sol–gel coatings was studied in order to improve the alumina scale adherence during the model Fe–20Cr–5Al alloy oxidation, at 1100 °C, in air. Various sol–gel coating procedures were applied. Argon annealing of the lanthanum sol–gel coating was tested at temperatures ranging between 600 and 1000 °C. The coating crystallographic nature was characterized by X-ray diffraction (XRD) depending on the annealing temperature. The oxidation process has been examined at 1100 °C by in situ XRD on blank Fe–20Cr–5Al, sol–gel coated and argon-annealed specimens. This study shows that the coating argon annealing at 1000 °C leads to the preferential formation of LaAlO₃ instead of La₂O₃. This coating procedure leads to an alumina scale formation showing the best adherence under thermal cycling conditions at 1100 °C.     

Improvement of high-temperature oxidation resistance of titanium-based alloy by sol–gel method

Sol–gel dip coating of SiO₂ was applied on a TiAl-based alloy, and subsequent heat treatment was performed. XRD and SEM/EDS analysis revealed that an amorphous silica coating was formed on the alloy. Isothermal oxidation and cyclic oxidation at 600 and 700 °C in static air of the specimens with or without coating were performed to investigate the effect of the SiO₂ coating on the oxidation behavior of the alloy by thermogravimetry. The average parabolic rate constants of the coated specimens were greatly reduced due to the presence of the coating. Severe cracks and spallation of the scales were observed on the blank specimens, but not on the coated ones. The oxide scales formed on the uncoated specimens were stratified. For the coated samples, a mixture layer of rutile TiO₂ and Al₂O₃ occurred beneath the applied film.     

Wettability of Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript> by Ag–Cu and Ag–Cu–Ti melts

Recently, the ternary carbide Ti₃SiC₂ has gained much attention due to its unique characteristics combining the properties of metals and ceramics (i.e., a low density, decent thermal and electrical conductivities, an excellent thermal shock resistance, a good machinability, damage tolerance, low friction, and so on). This study describes an investigation of the wettability in high vacuum of bulk Ti₃SiC₂ by a classical braze alloy based on the Ag–Cu–Ti system. Two techniques, i.e., the sessile drop and dispensed drop methods, were utilized. The results indicated that spreading kinetics is controlled by deoxidation kinetics of Ti₃SiC₂ surface under vacuum. The final contact angle on clean Ti₃SiC₂ is very small (~10°), testifying the development of strong, metallic interactions across the liquid–solid interface. The reactivity between the ternary carbide and the liquid phase during isothermal heating at 800 °C was also considered.     

Role of rare earth oxide coatings on oxidation resistance of chromia-forming alloys

Rare earths (RE) have been used to increase high temperature oxidation resistance of chromia and alumina forming alloys. The RE can be added as elements (or oxides) to the alloys or applied as oxide coatings to the alloy surface. This paper presents the effect of different RE oxide coatings and lanthanum chromite coatings on the high temperature oxidation behavior of Fe20Cr and Fe20Cr4Al alloys. The oxidation resistance of the Fe20Cr alloy increased with increase in ionic radius of the RE element in the coating. The RE oxides decreased chromia growth rate more than alumina growth rate. In extended cyclic oxidation tests that were carried out from peak temperatures of 900 °C, 1,000 °C and 1,100 °C to room temperature at cooling rates of 300 °C/s and 1,000 °C/s, the La₂O₃ coating increased cyclic oxidation resistance of the Fe20Cr alloy significantly more than the Pr₂O₃ coating. The role of RE in increasing overall oxidation resistance of chromia forming alloys is discussed.     

Effect of Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript> addition on microwave absorption property of plasma sprayed Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript>/NASICON coatings

The work attempted to develop a kind of high temperature microwave absorption coating. The Ti₃SiC₂/NASICON composite coatings with different Ti₃SiC₂ concentrations were fabricated by atmospheric plasma spraying. The effect of Ti₃SiC₂ addition on phase, density, microstructure, dielectric property and microwave absorption property of as-sprayed coatings was investigated. Results show that the complex permittivity increases with increasing the content of Ti₃SiC₂ due to the enhanced space charge polarization, decreased porosity and increased conduction loss. When the content of Ti₃SiC₂ increases to 30 wt%, the coating exhibits the optimal microwave absorption property with a bandwidth (below ??5 dB) of 4.01 GHz and lowest reflection loss of ??12.4 dB at 9.63 GHz in 1.4 mm thickness. It indicates that the Ti₃SiC₂/NASICON composite coating can be a potential candidate for microwave absorption.     

Low temperature synthesis of Ti3 SiC2 from Ti/SiC/C powders

Abstract

Ternary carbide Ti₃ SiC₂ was first synthesised through a pulse discharge sintering (PDS) technique from mixtures of Ti, SiC, and C with different molar ratios. Sintering processes were conducted at 1200 – 1400°C for 15 – 60 min at a pressure of 50 MPa. The phase constituents and microstructures of the synthesised samples were analysed by X-ray diffraction (XRD) technique and observed by scanning electron microscopy (SEM). The results showed that, for samples sintered from 3Ti/SiC/C powder at 1200 – 1400°C, TiC is always the main phase and only little Ti₃ SiC₂ phase is formed. When the molar ratios Ti : SiC : C were adjusted to 3 : 1.1 : 2 and 5 : 2 : 1, the purity of Ti₃ SiC₂ in the synthesised samples was improved to about 93 wt-%. The optimum sintering temperature for Ti₃ SiC₂ samples was found to be in the range 1250 – 1300°C and all the synthesised samples contain platelike grains. The relative density of Ti₃ SiC₂ samples was measured to be higher than 99% at sintering temperatures above 1300?C. It is suggested that the PDS technique can rapidly synthesise ternary carbide Ti₃ SiC₂ with good densification at lower sintering temperature.     

Coatings for protecting nickel-base TaC eutectics against oxidation

A class of very high strength eutectic superalloys consisting of TaC fibers in a γ- Ni/γ'-Ni₃Al matrix is being critically evaluated as a potential turbine blade material. However, the strongest alloys in this system lack the inherent oxidation resistance needed for extended use at 1100°C and above. The present study describes a program aimed at improving oxidation resistance and coating-substrate compatibility for a substrate of a γ/γ'-TaC which has been designated NiTaC- 13.A preliminary study considered seven different electron beam vapor-deposited coating systems of the MCrAlY type (M≡Ni, Co or Fe). The most promising coating was a NiCrAlY composition which showed excellent oxidation resistance; however, during high temperature exposure of all of these coated materials, a region with complete absence of carbide fibers developed in the substrate at the coating-substrate interface.The mechanism of carbide denudation was investigated using samples coated with Ni-20Cr-10Al-lY. It was concluded that a primary cause of fiber denudation was diffusion and dissolution of C in the C-free coating rather than carbon diffusion through the coating with resulting oxidation at the coating-atmosphere interface.NiCrAlY coatings containing C were deposited by several techniques to determine whether C additions would be useful in improving coating-substrate compatibility. The most promising coating was a duplex coating; the first layer of Ni-20Cr-5Al-0.1Y-0.1C was deposited by flame spraying and this was subsequently overcoated with Al. This coating withstood 2000 h of cyclic oxidation with little loss of coating thickness and absence of fiber denudation.Sequential metallographic examinations were made through the 2000 h of testing to show the development of the coating-substrate interactions. Microstructural and phase changes are described and are compared with macrostructural changes and the change in sample weight indicative of oxidation and spallation.     

Oxidation behaviour of three-dimensional woven C/SiC composites

Abstract

The oxidation behaviour of a three-dimensional woven C/SiC composite protected with an SiC seal coating and with an SiC coating combined with an SiO₂–B₂O₃ glassy coating have been respectively investigated through an experimental approach based on mass and flexural strength changes. Three main temperature domains exist for C/SiC composites protected with an SiC seal coating. At low temperatures (<700°C), the mechanisms of reaction between carbon and oxygen control the oxidation kinetics. At an intermediate temperatures (between 700 and 1100°C), the oxidation kinetics are controlled by gas phase diffusion through a network of microcracks in the SiC matrix and coating. At high temperatures (>1100°C), the oxidation kinetics are controlled by oxygen diffusion through the SiO₂ scale formed on the SiC coating. Composites of C/SiC with an SiC/(SiO₂–B₂O₃) coating exhibit better oxidation resistance. The filling of the pores and the microcracks and the flow of the glassy coating at higher temperatures result in a global decrease of mass loss in the composites. By researching the relationship between the residual flexural strength and the mass variation in different temperature ranges, it is shown that the change in the residual flexural strength is dominated by the degradation of carbon phase.     

Modification of NiCoCrAlY with Pt: Part I. Effect of Pt depositing location and cyclic oxidation performance

Pt layers of 5?μm in thickness were electroplated before or after depositing NiCoCrAlY coating by arc ion plating (AIP) aiming for identifying the effect of Pt enriching position on microstructure and cyclic oxidation behavior of Pt modified NiCoCrAlY coatings. Al-rich zones formed at the same position of Pt-rich zones for both modified coatings due to uphill diffusion of Al driven by Pt. Cyclic oxidation tests at 1000 and 1100?°C indicated that oxidation resistance of NiCoCrAlY was improved by Pt modification via different mechanisms: at surface, Pt-rich zone promoted selective oxidation of Al to form α-Al₂O₃, whilst at coating/substrate interface Pt-rich zone acted as effective diffusion barrier for titanium. Roles of Pt played in enhancing the oxidation performance of various Pt-modified NiCoCrAlY coating were investigated.     

Optimization of the Carbosilicothermic Synthesis of the Ti<Subscript>4</Subscript>SiC<Subscript>3</Subscript> MAX Phase

We have studied the formation of the Ti4SiC3 MAX phase during the vacuum carbosilicothermic reduction of TiO₂ with a combined reducing agent consisting of SiC and elemental Si and analyzed the effects of the synthesis temperature, heat treatment time, and percentage of elemental silicon in the starting mixture on the Ti₄SiC₃ yield. Optimal Ti₄SiC₃ synthesis conditions are as follows: temperature from 1550 to 1650°C, isothermal holding time of 360 min, and the starting-mixture composition TiO₂ + 1.2SiC + 0.6Si. The Ti₄SiC₃ yield then reaches 92 wt %.     

Synthesis and phases evolution of Si–C–Ti from polycarbosilane (PCS) and metal Ti

Si–C–Ti ceramics were synthesized by reactive pyrolysis of polycarbosilane (PCS) precursor filled with metal Ti powder. Pyrolysis of mixture with atomic ratio of Ti:Si through 3:1–3:2 was carried out in argon atmosphere at given temperature up to 1500 °C. The metal–precursor reactions, and phase evolution were studied using X-ray diffraction and scanning electron microscopy with EDX. The Ti₃SiC₂ phase was obtained firstly from reaction of PCS and Ti. Ti₃SiC₂ formation starts at 1300 °C and its amount increases significantly in a narrow temperature range between 1400 °C and 1500 °C. In addition, addition of CaF₂ can promote the formation of Ti₃SiC₂ phase.     

Fluctuation synthesis and characterization of Ti3SiC2 powders

 A novel fluctuation method for the synthesis of Ti₃SiC₂ powders was developed. The raw materials used in this process are Ti, Si, and graphite powders. Fluctuation synthesis utilized Si as in-situ liquid forming phase (additive), which was formed by heating the powder mixtures to 1300°C and using the heat released from the exothermic reaction for Ti₃SiC₂ formation. The result demonstrated that the reaction time for the formation of Ti₃SiC₂ was dramatically shortened using fluctuation method and the powders produced using this method contained more than twice amount of Ti₃SiC₂ compared to the solid reaction synthesized powders. The powders prepared by fluctuation method are fiber-like in morphology with dimensions of 0.8–2 μm in width and 5–10 μm in length. The growth direction of the fiber-like Ti₃SiC₂ particulate is {101^–1}*. The lattice parameters for Ti₃SiC₂ were determined by a trial-and-error method and are a=3.067 ? and c=17.645 ?. Received: 28 September 1998 / Reviewed and accepted: 1 October 1998     

Oxidation behavior and electrochemical corrosion performance of Ti<Subscript>3</Subscript>Al alloy with TiAl coating

Magnetron-sputter deposition was used to produce a Ti–48Al–8Cr–2Ag (at. %) coating on a Ti–24Al– 17Nb–0.5Mo (at. %) alloy substrate. Oxidation behavior was studied in air at 900–1000°C. The results indicated that the oxidation rate of sputtered Ti–48Al–8Cr–2Ag nanocrystalline coating was lower than that of the Ti₃Al alloy at 900°C. The former formed a scale of merely Al₂O₃, and the latter formed a scale of TiO₂. However, the Ti–48Al–8Cr–2Ag nanocrystalline coating showed a little bit higher oxidation rate than Ti₃Al alloy at 1000°C because the outer TiO₂ scale formed and columnar boundaries of the coating gave a larger actual oxidation area than the original alloy. The electrochemical corrosion behavior was investigated in a 3.5% NaCl solution at room temperature. The coating showed excellent electrochemical corrosion resistance in 3.5% NaCl solution because it exhibited stable passive polarization behavior without any overpassivation phenomena.     

Effect of ZrB2 and Polyvinyl Butyral Content on the Oxidation Resistance of ZrB2–SiC Coatings Produced by Slurry Brushing Method

ZrB₂–SiC coatings are prepared on the surface of graphite by slurry brushing method to improve the oxidation resistance. Effects of ZrB₂ content and polyvinyl butyral (PVB)–ethanol solution concentration on microstructure and static oxidation behavior of the ZrB₂–SiC coatings are investigated at 1200 °C in air. The results indicate that increasing ZrB₂ content improves the oxidation resistance of the coatings. When ZrB₂ content increases from 30 to 45 wt%, weight loss rates of the coated samples after oxidation at 1200 °C for 120 min decrease from −0.92% to −1.67%. Increasing binder solution concentration raises component content in the coatings. As PVB–ethanol binder concentration increases from 0.025 to 0.075 g mL⁻¹, weight loss rates of the coated samples after oxidation at 1200 °C for 120 min decrease from 0.32% to −0.38%. Excellent oxidation resistance of ZrB₂–SiC coating is attributed to self-sealing ability of B₂O₃ and borosilicate glass. The composite glass can inhibit oxygen diffusion by filling defects in the coating promptly. The borosilicate glass phase can enhance the fluidity of the composite glass. ZrO₂ and ZrSiO₄ particles restrict the growth of the microcrack, which improves the oxidation resistance of ZrB₂–SiC coating.