Thermal stability of γ-Al2O3 coatings for challenging cutting operations

Crystalline PVD Al₂O₃ coatings offer great potential for their use in cutting operations. They promise high hot hardness and high oxidation resistance at elevated temperatures. Alumina exists in different crystallographic phases. α-Al₂O₃ appears to be the only thermodynamically stable phase at all common temperatures and pressures. Today there are many efforts to generate α-Al₂O₃ by means of physical vapour deposition. In this regard one problem is the high deposition temperature, which does not allow the deposition on temperature-sensitive materials.Another promising candidate is γ-Al₂O₃ which is more fine-grained than α-Al₂O₃ and can be deposited at lower temperatures. At high temperatures γ-Al₂O₃ might be transformed into α-Al₂O₃, which could limit the application temperature. But until now it is not clearly proved, up to which temperatures γ-Al₂O₃ thin films are stable and which mechanisms influence the stability. In the present work different (Ti,Al)N/γ-Al₂O₃ coatings are deposited on cemented carbides by means of Magnetron Sputter Ion Plating (MSIP). The (Ti,Al)N bond coat was employed to improve adhesion of γ-Al₂O₃ on the substrate. It could be shown that the γ-phase is stable in vacuum up to 1200 °C. In the atmosphere the formation of α-Al₂O₃ begins at 900 °C and it is influenced by the choice of transition zone between the (Ti,Al)N interlayer and γ-Al₂O₃. The results show that the thermal stability of the γ-phase and therefore the application temperature of the coating can be enhanced by the choice of interlayer.     

TEM and DFT investigation of CVD TiN/κ-Al2O3 multilayer coatings

This paper investigates the interfacial structure in hot-wall CVD TiN/κ-Al₂O₃ multilayer coatings using both HREM and DFT modeling. Two multilayers with different thicknesses of the TiN layers (50 and 600 nm) separating the κ-Al₂O₃ layers are analyzed. The general microstructure of the two multilayers is relatively similar. The TiN layer in the thicker TiN/κ-Al₂O₃ coating is thick enough to be several TiN grains high. This means that epitaxial columns, which are often found in the thinner TiN/κ-Al₂O₃ coatings, are not present. However, the orientation relationships at the TiN/κ-Al₂O₃ interfaces are the same in both multilayers. The HREM investigations show that κ-Al₂O₃ (001) planes can grow directly on flat (111) TiN faces, without any other phases or detectable amounts of impurities, such as sulphur, present. Where the TiN layers are more curved, γ-Al₂O₃ can be grown, at least partly stabilized by the cube-on-cube orientation relationship between γ-Al₂O₃ and the underlying TiN. The DFT calculations show very similar adsorption strengths for an O monolayer positioned on Ti-terminated TiC(111) and TiN(111) surfaces, with preferred adsorption in the fcc site. O adsorption on N-terminated TiN(111) is much weaker, with preferred adsorption in the top site. Calculated elastic-energy contributions yield a higher stability for κ-Al₂O₃ on TiN(111) than on TiC(111) and a higher stability for κ-Al₂O₃ than for α-Al₂O₃ on both TiC and TiN. This indicates that the observed higher stability of κ-Al₂O₃ on TiC(111) than on TiN(111) is not due to the lattice mismatch, while the preferred epitaxial growth of κ-Al₂O₃ over α-Al₂O₃ can be partly attributed to the mismatch.     

Effect of α-Al2O3 on in situ synthesis low density O′-sialon multiphase ceramics

In this paper, the effect of α-Al₂O₃ on in situ synthesis low density O′-sialon multiphase ceramics was investigated. Thermodynamics analysis was used to illustrate the feasibility of synthesizing O′-sialon at a low temperature of 1420 °C. The crystalline phase and microstructure were investigated by X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. The actual substitution parameter x value of O′-sialon was estimated via lattice correction. The results showed that, O′-sialon multiphase ceramics with different x values could be synthesized successfully through varying α-Al₂O₃ content. Bulk densities of samples ranging from 1.64 to 2.11 g cm⁻³ were adjusted with the percentage of α-Al₂O₃ increasing from 5.21 wt.% to 15.62 wt.%. Formation of nearly single-phase O′-sialon was obtained in the sample containing 10.42 wt.% α-Al₂O₃. The actual substitution parameter x increased with the increase of α-Al₂O₃, whereas it was lower than the original designation, and the O′-sialon with a low x value was achieved.     

Effect of H2 flow rate and stand-off distance on the formation of phases in plasma-sprayed Al2O3 coatings

Plasma-sprayed Al₂O₃ coatings contain both metastable and stable phases of Al₂O₃. The formation of these phases is influenced by various process parameters, such as stand-off distance (SOD), gas flow rates, nozzle diameter and is also dependent on the melting and solidification behaviour of feedstock particles, as these help in controlling the weight fraction of different phases formed in the coating. The present work reports the investigation on the effect of two major plasma spray parameters, namely secondary gas (H₂) flow rate and SOD, on the formation of phases in plasma-sprayed Al₂O₃ coating. The phases were identified by X-ray diffraction analysis and to quantify those phases, the Rietveld refinement method was used. The influence of α-phase on the mechanical properties of the Al₂O₃ coatings was evaluated, and it has been observed that α-phase content decreases with the increase in secondary gas flow rate. With the increase in SOD, the α-Al₂O₃ phase content first decreases and then increases.     

Oxidation behaviour of Ti-46.7Al-1.9W-0.5Si in air and Ar-20%O2 between 750 and 950 °C

The oxidation behaviour of an intermetallic alloy, Ti-46.7Al-1.9W-0.5Si, was studied in air and Ar-20%O₂ atmospheres at 750, 850 and 950 °C. Oxidation of the alloy followed a parabolic rate law at low temperature (750 °C) in both environments. The alloy oxidised parabolically in air and at a slower rate in Ar-20%O₂ at 850 °C. Following a parabolic oxidation for a relatively short exposure period (72 h) at 950 °C, the oxidation rate was reduced after prolonged exposure (up to 240 h) in air. The alloy oxidised in a slower manner in the Ar-20%O₂ atmosphere at 950 °C. Higher oxidation rates were observed in air than in Ar-20%O₂ at all three experimental temperatures. Multi-layered scales developed in both environments. The scale formed in air consisted of TiO₂/Al₂O₃/TiO₂/TiN/TiAl₂ layers, ranging from the surface to the substrate—whilst the scale developed in the Ar-20%O₂ atmosphere comprised of the sequence TiO₂/Al₂O₃/TiO₂/Al₂O₃/Ti₃Al/substrate. The two layers of Al₂O₃ in Ar-20%O₂ were more effective in providing protection of the substrate against high temperature corrosion than the single layer of Al₂O₃ formed in air.     

Catalyst-free shape controlled synthesis of In2O3 pyramids and octahedron: Structural properties and growth mechanism

In₂O₃ pyramids and octahedrons were synthesized on a silicon substrate by catalyst-free and improved chemical vapor deposition in order to reduce the influence of undesired doping or impurities on the observed properties, directly from metallic indium by controlled oxidation. These single crystalline In₂O₃ structures have potential use in ultra-sensitive gas and chemical sensors.     

Microstructure and characterization of La2O3 and CeO2 doped diamond-like carbon nanofilms

Seven kinds of hydrogen-free La₂O₃ and CeO₂ doped DLC films with thickness of 220-280 nm were deposited on Si (100) substrates by unbalanced magnetron sputtering. Nanoparticles with diameter of 20-30 nm are formed on the surface of films. The surface roughness Ra of films is in the range of 1.5-2.0 nm. C, La, Ce and O elements distribute uniformly along the depth direction, and C, La, and Ce elements diffuse into the Si substrate at the interface. X-ray photoelectron spectroscopy confirms that the La₂O₃ and CeO₂ form within the DLC amorphous films, and Raman spectra indicate the obvious amorphous characteristics of DLC films. High-resolution transmission electron microscopy shows the nanocrystallines structure with diameter of 2-3 nm of 16% La₂O₃ and 10% CeO₂ doped DLC films, and Fourier transformation spectroscopy also exhibits the obvious crystalline characteristics. In this work, the microstructure of two kinds of rare earth oxides doped DLC composite films is measured and analyzed.     

The effect of fe on high temperature oxidation of NiAl

A study was conducted to observe the oxidation of NiAl+3.5at.%Fe alloy inβ-NiAl phase field at air temperatures of 1000, 1200 and 1400°C, and these results were compared with those of pure NiAl alloys. The primary effects of the Fe-addition in NiAl were found to be: 1) decrease in oxidation resistance and adherence of scales during both isothermal and cyclic oxidation tests, 2) enhancement of phase transformation rate from θ toα-AL₂O₃, 3) more rapid formation of characteristically ridgedα-A1₂O₃ scales during initial oxidation stages, and 4) partial sealing of voids formed at the scale-substrate interface and dissolution of Fe inside the alumina scale by the outward diffusion of Fe from the substrate alloy.     

Synthesis of crystalline γ-Al2O3 with high purity

Crystalline γ-AlO(OH) was synthesized by the precipitation of sodium aluminate and oxalic acids in aqueous solution. And then γ-AlO(OH) was successfully transferred to γ-Al₂O₃ after subsequent high temperature heat treatment. The effects of reaction conditions on formation of γ-AlO(OH) and γ-Al₂O₃ were further investigated in detail. The XRD analysis shows that the complete formation of crystalline γ-Al₂O₃ is at pH 8–9, reaction temperature of 93–96 °C and calcination temperature of higher than 400 °C. The product of γ-Al₂O₃ contains impurity, including iron, calcium and silicon ion with a low content of about 0.01% and has large specific surface area and high pore volume of 269.9 m²/g and 0.57 mL/g, which can be applied in catalysts and catalyst supports.     

The combined effect of refractory coatings containing reactive elements on high temperature oxidation behavior of chromia-forming alloys

The high temperature oxidation behaviors of chromia-forming alloys (F17Ti and Fe-30Cr alloys) have been studied at 1273 K under isothermal conditions and at 1223 K under cyclic conditions, in air under the atmospheric pressure. To extend the oxidation lifetime, coatings have been applied onto the alloy surfaces. Al₂O₃ and Cr₂O₃ films doped with Sm₂O₃ or Nd₂O₃ were prepared via the metal-organic chemical vapor deposition technique. Single Cr₂O₃, Al₂O₃, Nd₂O₃ and codeposited Cr₂O₃-Nd₂O₃, Al₂O₃-Nd₂O₃, Al₂O₃-Sm₂O₃ coatings drastically improved the chromia-forming alloy high temperature oxidation behavior, since they decreased the oxidation rate and enhanced the oxide scale adhesion. Results showed that a critical amount of reactive element (Nd or Sm) in chromia or alumina coatings (11-18 at.%) was needed to observe the most effective effect. The fast precipitation of NdCrO₃ or NdTi₂₁O₃₈ and the segregation of reactive elements at the chromia grain boundaries slowing down outward cation transport and consequently blocking the chromia grain growth, was supposed to be the main reasons of the beneficial effect ascribed to the reactive elements in chromia scales.     

Densification and mechanical properties of fine-grained Al2O3-ZrO2 composites consolidated by spark plasma sintering

Alumina matrix composites containing 5 and 10 wt% of ZrO₂ were sintered under 100 MPa pressure by spark plasma sintering process. Alumina powder with an average particle size of 600 nm and yttria-stabilized zirconia with 16 at% of Y₂O₃ and with a particle size of 40 nm were used as starting materials. The influence of ZrO₂ content and sintering temperature on microstructures and mechanical properties of the composites were investigated. All samples could be fully densified at a temperature lower than 1400 °C. The microstructure analysis indicated that the alumina grains had no significant growth (alumina size controlled in submicron level 0.66-0.79 μm), indicating that the zirconia particles provided a hindering effect on the grain growth of alumina. Vickers hardness and fracture toughness of composites increased with increasing ZrO₂ content, and the samples containing 10 wt% of ZrO₂ had the highest Vickers hardness of 18 GPa (5 kg load) and fracture toughness of 5.1 MPa m^1/2.     

用于钯催化载体的P改性高孔隙率 γ-Al2O3/α-Al2O3 泡沫

提出了一种新方法来制备用于钯催化剂的P-γ-Al₂O₃涂层改性的α-Al₂O₃泡沫。采用聚氨酯模板法,通过优化工艺参数,使陶瓷泡沫的显气孔率达到90.28%,体积密度达到0.45 g·cm^-3,且该泡沫具有可使用强度。将掺有P元素的γ-Al₂O₃涂层涂覆在α-Al₂O₃泡沫上,然后通过超声波辅助浸渍法来装载活性催化相(Pd)。结果表明,含P涂层增加了惰性泡沫的比表面积和弱酸性位点,同时减少了强酸性位点的占比。与无涂层的泡沫相比,改性的泡沫更容易装载活性相,且装载的金属Pd不容易被氧化,CO的催化转化温度(T₅₀,T₉₀)降低了50℃左右。该研究证明了低成本改性α-Al₂O₃陶瓷泡沫在钯催化剂生产中具有极大的应用潜力。     

Investigations on synthesis of HfB2 and development of a new composite with TiSi2

This paper presents the results of investigation carried out on synthesis and densification of monolithic HfB₂ and the effect of TiSi₂ as sinter additive. Pure phase HfB₂ was prepared by boron carbide reduction of HfO₂ and hot pressed to full density with the addition of TiSi₂. Isothermal oxidation study of this composite was carried out at 850 °C up to 64 h. Formation of HfB₂ was seen at 1200 °C but pure HfB₂ was formed at a much higher temperature of 1875 °C in vacuum. Hot pressing of HfB₂ at 1850 °C and 35 MPa pressure gave a compact of 80% TD. Addition of TiSi₂ helped in achieving a much higher density at a lower temperature of 1600 °C and a pressure of 20 MPa. A fully dense composite of HfB₂ and TiSi₂ was obtained with 15% TiSi₂. Hardness and fracture toughness of this composite were 27.4 ± 1.9 GPa and 6.6 ± 0.2 MPa m^1/2, respectively. Considerable deflection was observed in the crack propagation in composites. Oxidation studies indicated the formation of HfO₂, SiO₂, TiO₂ and HfSiO₄ with some glassy phase and the composite with 15% TiSi₂ was seen to be completely covered with a protective glassy layer.     

Characterisation and oxidation of LVOF sprayed Al2O3–40%TiO2 coating on superni 601 and superni 718 superalloys at 800 and 900°C

Failure of components due to high temperature oxidation is the major degradation mechanism in boiler and gas turbine industries. Superalloys having superior mechanical properties and creep resistance are used in these applications but lack resistance to oxidation under aggressive environments. Protective coatings are used to improve their oxidation resistance in such applications. In the present investigation, Al₂O₃–40%TiO₂ coating was deposited on superni 718 and superni 601 superalloys by low velocity oxy fuel process. The as sprayed coating was characterised for microhardness, surface roughness, scanning electron microscopy and X-ray diffraction analysis. High temperature oxidation behaviour of Al₂O₃–40%TiO₂ coated and uncoated superni 718 and superni 601 superalloys has been evaluated at the elevated temperatures of 800 and 900°C for total duration of 50 cycles under cyclic conditions. Each cycle consisted of keeping the samples for 1 h at the elevated temperature followed by 20 min cooling in ambient air. Al₂O₃–40TiO₂ coating in the as sprayed condition showed the presence of Al₂O₃–TiO₂, α-Al₂O₃, TiO₂ as the main phases. Al₂O₃–40%TiO₂ coating on superni 718 and superni 601 superalloys has shown a lower oxidation rate as compared to those of uncoated superalloys. However, the oxidation rate of the coating was not steady due to the occurrence of spallation/sputtering at various stages. The coating was found adherent on the substrate superalloys throughout the study.     

La2O3含量对Al2O3/Cu基复合材料组织与性能的影响

以La2O3粉、Al粉、CuO粉为反应物原料,纯铜为基体,采用原位合成技术和近熔点铸造法制备颗粒增强Cu基复合材料,研究La2O3对Al-CuO体系制备的Cu基复合材料组织及性能的影响.结果表明:添加La2O3可获得纳米Al2O3颗粒,且弥散分布于Cu基体中,制备的材料组织更加细小、均匀,其材料的电导率及耐摩擦磨损性能...     

Influence of micro-blasting on the microstructure and residual stresses of CVD κ-Al2O3 coatings

Cemented carbides coated with CVD multilayers are commonly used in metal cutting turning and milling operations. For many applications, a micro-blasting finishing procedure based on an impact treatment of the surfaces is carried out in order to smooth the coated surface and reduce sharp cutting edges. In this work, micro-blasting with corundum in aqueous solution at pressures between 0.05 and 0.3 MPa was applied to CVD TiN/Ti(C,N)/κ-Al₂O₃ multilayer coatings deposited onto cemented carbides in order to investigate its influence on the micro-topography, microstructure and residual stresses. The results showed that the micro-blasting reduces the surface roughness and affects the coating thickness. TEM investigations revealed no significant changes on the microstructure of the κ-Al₂O₃ top layer. Synchrotron X-ray investigations showed that the residual stress state of the as-deposited κ-Al₂O₃ top layer is not affected by the micro-blasting treatment under the conditions investigated.     

纳米 α-Al2O3添加剂对铝合金微弧氧化膜层性能的影响

目的探究微弧氧化电解液中纳米α-Al2O3的浓度对铝合金微弧氧化膜层组织和性能的影响。方法在硅酸盐体系电解液中加入1~5 g/L纳米α-Al2O3,微弧氧化获得不同的陶瓷膜层,对膜层的微观结构、厚度、硬度和耐腐蚀性能进行分析。结果膜层的主要组成相为α-Al2O3、γ-Al2O3和SiO2。当纳米α-Al2O3添加量为3 g/L时,膜层表面微裂纹少,孔隙率小,厚度达70μm,硬度为513HV,耐腐蚀性能好。结论硅酸盐电解液中加入纳米α-Al2O3,能够改善铝合金微弧氧化膜层的综合性能。     

Synthesis and characterization of titanium doped sodium beta″-alumina

High dense Na-β″-Al₂O₃ electrolyte materials have been synthesized by solid state reaction with boehmite, magnesia, sodium carbonate and titania as the starting materials. The effects of TiO₂ doping percentage on the properties and microstructures of the prepared samples were investigated by X-ray diffraction (XRD), scan electron microscope (SEM), three point bending and ionic conductivity tests. The results indicated that both the relative densities and the phase purities of the samples could effectively improved after doping with TiO₂. The proper doping amount of TiO₂ was to form the transient liquid phase during the sintering process, which would reduce the steric effect and accelerate the diffusivity. Moreover, the mechanical performance of the obtained sample increased to the value above 280 MPa as the doping amount of TiO₂ was larger than 1 wt%. As to the electric properties, if the doping amount was less than 1 wt%, the grain boundary resistivity reduced as the density increased, so the ionic conductivity of the Na-β″-Al₂O₃ was enhanced obviously. However, when the doping amount was above 1 wt%, the ionic conductivity was deteriorated because of the increased resistivity caused by the broadening grain size.