Interfacial reactions and oxidation behavior of Al2O3 and Al2O3/Al coatings on an orthorhombic Ti2AlNb alloy

The uniform and dense Al₂O₃ and Al₂O₃/Al coatings were deposited on an orthorhombic Ti₂AlNb alloy by filtered arc ion plating. The interfacial reactions of the Al₂O₃/Ti₂AlNb and Al₂O₃/Al/Ti₂AlNb specimens after vacuum annealing at 750 °C were studied. In the Al₂O₃/Ti₂AlNb specimens, the Al₂O₃ coating decomposed significantly due to reaction between the Al₂O₃ coating and the O-Ti₂AlNb substrate. In the Al₂O₃/Al/Ti₂AlNb specimens, a γ-TiAl layer and an Nb-rich zone came into being by interdiffusion between the Al layer and the O-Ti₂AlNb substrate. The γ-TiAl layer is chemically compatible with Al₂O₃, with no decomposition of Al₂O₃ being detected. No internal oxidation or oxygen and nitrogen dissolution zone was observed in the O-Ti₂AlNb alloy. The Al₂O₃/Al/Ti₂AlNb specimens exhibited excellent oxidation resistance at 750 °C.     

Ab-initio study of long-period superstructures and anti-phase boundaries in Al-rich γ-TiAl (L10)-based alloys

In this work, we report first-principles investigation of structural stability of all experimentally observed ordered long-period superstructures (LPSs), viz., r-Al₂Ti, h-Al₂Ti, Al₅Ti₃ along with Al₅Ti₃′, Al₁₁Ti₇ and Al₃Ti₂ LPSs, which are observed only as short-range ordered clusters at nanoscale level in Al-rich TiAl-based alloys. We adopt a procedure based on space-filling tiling arrangement of ordered Ti₂Al, Ti₃Al, Ti₄Al motifs and their combination along with a symmetry analysis programme to determine the unit cell and the crystallographic information of Al₅Ti₃′, Al₁₁Ti₇ and Al₃Ti₂ LPSs in terms of L1₀ fcc unit cell. First-principles calculations are performed to further refine these crystallographic parameters (Wyckoff positions and lattice parameters) obtained from the above procedure. Moreover, it is found that the family of five LPSs have subgroup–supergroup relationships with γ-TiAl (Sp. gr. P4/mmm) and among themselves. Further, we find the inherent stability of r-Al₂Ti?+?γ-TiAl and 2Al₅Ti₃?+?γ-TiAl phase mixtures at 0?K compared to isomolecular Al₃Ti₂ and Al₁₁Ti₇ LPSs at their respective concentrations. The calculations of single-crystal elastic constants of Al₅Ti₃, Al₁₁Ti₇, Al₃Ti₂ and Al₅Ti₃′ LPSs show all these four structures are mechanically stable. We also calculate antiphase boundary (APB) formation energies for two types of APBs, viz., type-A and type-C in ordered Al₅Ti₃ LPS using the supercell approach. The relaxed APB energies for type-A and type-C APBs are 15.44 and 124.16?mJ/m², respectively.     

Ab initio electronic structure,bonding and optical properties of two relatively new ceramics Hf2Al3C4 and Hf3Al3C5: A comparative study

The structural, electronic and optical properties of the ternary carbides Hf₂Al₃C₄ and Hf₃Al₃C₅ are studied via first principles orthogonalized linear combination of atomic orbitals (OLCAO) method. Results on crystal structure, interatomic bonding, band structure, total and partial density of states (DOS), localization index (LI), effective charge (Q*), bond order (BO), dielectric function (ε), optical conductivity (σ) and electron energy loss function are presented and discussed in detail. The band structure plots show the conducting nature of Hf₂Al₃C₄ and Hf₃Al₃C₅ carbides. DOS results disclose that the total number of states at Fermi level N(E_F) are 1.89 and 2.38 states/(eV unit cell) for Hf₂Al₃C₄ and Hf₃Al₃C₅ respectively. The Q* calculations show an average charge transfer of 0.723 and 0.711 electrons from Hf and 0.809 and 0.807 electrons from Al to C sites in Hf₂Al₃C₄ and Hf₃Al₃C₅ respectively. The BO results provide the dominating role of Al–C bonds with BO value of 6.62 (BO%?=?59%) and 6.66 (BO%?=?49%) for Hf₂Al₃C₄ and Hf₃Al₃C₅ respectively and are considered responsible for the crystals cohesion. The LI results reflect the presence of highly delocalized states in the vicinity of the Fermi level. The dielectric function plots of the real (?₁(?ω)) and imaginary (?₂(?ω)) parts show the anisotropic behavior of Hf₂Al₃C₄ and Hf₃Al₃C₅. The results on optical conductivity (σ) support the trends observed in dielectric functions. The electron energy loss functions reveal the presence of sharp peaks both in ab-plane and along c-axis around 20?eV in Hf₂Al₃C₄ and Hf₃Al₃C₅ ternary carbides.     

The ab initio calculations of the doping Zr's influence on the electronic structure of AlCo2Ti

The electronic structures of the ternary (Hume-Rothery) L2₁-phase compound AlCo₂Ti are calculated by first-principles using full potential linearized augmented plane wave (FLAPW) method with the generalized gradient approximation (GGA). The ab initio results are analyzed with a simplified model for Al-based compounds containing transition metal (TM) atoms. The results show that the total DOS depends strongly on the positions of TM atoms, and the TM d DOS plays a crucial role in hybridization with other element valence electrons. However, the Al 3s states are repelled far away from the Fermi energy in studied sample, and the Al 3d states are far more extended-like in the character than the d states. Furthermore, the total DOS_s are modulated by Al 3p states and the Al 3p states are more sensitive than d states to change in the electronic interactions. Then, the Al 3p is also important for the ternary stability of the intermetallic compound. The Co-Ti interaction becomes stronger by the doping element Zr in the Al₄Co₈Ti₃Zr structure. Especially, the doping Al₄Co₈Ti₃Zr alloy has a larger value DOS at the Fermi level and makes the total DOS gap smaller than the AlCo₂Ti.     

First-principles studies on Ti3Si0.5Ge0.5C2 under pressure

The structural, electronic and elastic properties of Ti₃Si_0.5Ge_0.5C₂ have been investigated by using the pseudopotential plane-wave method within the density-functional theory. Our calculated equation of state (EOS) is consistent with the experimental results. The density of states (DOS) indicates that Ti₃Si_xGe_1−xC₂ (x=0, 0.5, 1.0) are metallic, and these compounds have nearly the same electrical conductivity. The elastic constants for Ti₃Si_0.5Ge_0.5C₂ are obtained at zero pressure, which is compared to Ti₃SiC₂ and Ti₃GeC₂. We can conclude that Ti₃Si_0.5Ge_0.5C₂ is brittle in nature by analyzing the ratio between bulk and shear moduli. There appears to be little effect on the electronic and elastic properties with the Ge substitution to Si atoms in Ti₃SiC₂.     

Lanthanum-doped Bi4Ti3O12 ceramics prepared by high-pressure technique

We present an effective way in this paper to increase the density of lanthanum doped bismuth titanate ceramics, Bi4-xLaxTi3O12 (BLT), thereby significantly improving the performance of the BLT ceramics. Dense BLT ceramicses, Bi4-xLaxTi3O12 (x = 0.25, 0.5, 0.75, 1.0), are prepared by using nanocrystalline powders fabricated by a-gel method and high-pressure technique. The microstructures of the BLT ceramicses prepared separately by conventional-pressure and high-pressure techniques are investigated by using x-ray diffraction and transmission electron microscope. The influence of La-doping on the densification of bismuth titanate ceramics is investigated. The experimental results indicate that the phase compositions of all samples with various lanthanum dopings sintered at 900°C possess layer-structure of Bi4Ti3O12 . The green compacts are pressed under 2.5 GPa, 3.0 GPa, 3.5 GPa and 4.0 GPa, separately. It is found that the density of BLT ceramics is significantly increased due to the decreasing of porosity in the green compacts by high-pressure process.     

Effect of Si addition on the stability of Al-10Ti-5Cu-xSi alloy/SiC interface

The effect of Si addition on the interfacial stability of Al-10Ti-5Cu-xSi (x = 0, 5, 10, 15) alloy/SiC is investigated. SiC and the Al-10Ti-5Cu-xSi alloys were compacted to obtain a stable interface with 10 wt% Si. Analysis of the processing conditions and the microstructures indicated that an excellent Ti₃SiC₂ phase had been formed and the deleterious Al₄C₃ phase had been eliminated successfully by the addition of 10 wt% Si to the Al-10Ti-5Cu alloy. Formation of Ti₃SiC₂ increased at first and then decreased, while the formation of Al₄C₃ was gradually inhibited with increasing Si content. Ti₃SiC₂ possesses good chemical stability, and flexibility. However, Al₄C₃ degrades within few days, in composites exposed to ambient conditions. The presence of Ti₃SiC₂ at the interface and the elimination of Al₄C₃ together ameliorate the bonding of Al-10Ti-5Cu-xSi alloy to SiC, thereby improving the interfacial stability of Al-10Ti-5Cu-xSi/SiC.     

Micro- and nanocomposite Ti-Al-N/Ni-Cr-B-Si-Fe-based protective coatings: Structure and properties

A new type of nanocomposite Ti-Al-N/Ni-Cr-B-Si-Fe-based coatings 70–90 μm thick produced by combined magnetron sputtering and a plasma detonation technology is created and studied. Phases Ti₃AlN + Ti₃Al₂N₂ and the phases caused by the interaction of plasma with a thick Al₃Ti + Ni₃Ti coating are detected in the coatings. The TiAlN phase has a grain size of 18–24 nm, and other phases has a grain size of 35–90 nm. The elastic modulus of the Ti-Al-N coating is E = 342 ± 1 GPa and its average hardness is H = 20.8 ± 1.8 GPa. The corrosion rate of this coating is very low, 4.8 μg/year, which is about three orders of magnitude lower than that of stainless steel (substrate). Wear tests performed according to the cylinder-surface scheme demonstrate high wear resistance and high adhesion between the thick and thin coatings.     

Structural, elastic and electronic properties and formation energies for hexagonal (W0.5Al0.5)C in comparison with binary carbides WC and Al4C3 from first-principles calculations

First principle calculations have been performed with the purpose to understand the peculiarities of the structural, elastic parameters and electronic properties and interatomic bonding for novel hexagonal carbide (W_0.5Al_0.5)C in comparison with binary phases WC and Al₄C₃. The geometries of all phases were optimized and their structural, elastic parameters and theoretical density were established. Besides, we have evaluated the formation energies (E_form) of W_0.5Al_0.5C for different possible preparation routes (namely for the reactions with the participation of simple substances (metallic W, Al and graphite, binary W or Al carbides and metallic Al and W, or binary W and Al carbides). The results show that the synthesis of the ternary carbide from simple substances is more favorable in comparison with the reactions with participation of W and Al carbides. Moreover, band structures, total and partial densities of states were obtained and analyzed systematically for (W_0.5Al_0.5)C, WC and Al₄C₃ phases in comparison with available theoretical and experimental data. The bonding picture in W_0.5Al_0.5C was described as a mixture of metallic, ionic and covalent contributions with the high anisotropy for the covalent W-C and Al-C bonds, where p-p like Al-C bonds become weaker than p-d like W-C bonds.     

The leakage current mechanisms in the Schottky diode with a thin Al layer insertion between Al0.245Ga0.755N/GaN heterostructure and Ni/Au Schottky contact

This paper investigates the behaviour of the reverse-bias leakage current of the Schottky diode with a thin Al inserting layer inserted between Al0.245Ga0.755 N/GaN heterostructure and Ni/Au Schottky contact in the temperature range of 25-350°C. It compares with the Schottky diode without Aluminium inserting layer. The experimental results show that in the Schottky diode with Al layer the minimum point of I-V curve drifts to the minus voltage, and with the increase of temperature increasing, the minimum point of I-V curve returns the 0 point. The temperature dependence of gate-leakage currents in the novelty diode and the traditional diode are studied. The results show that the Al inserting layer introduces interface states between metal and Al0.245Ga0.755N. Aluminium reacted with oxygen formed Al2O3 insulator layer which suppresses the trap tunnelling current and the trend of thermionic field emission current. The reliability of the diode at the high temperature is improved by inserting a thin Al layer.     

Investigations on structural,elastic, thermodynamic and electronic properties of TiN,Ti2N and Ti3N2 under high pressure by first-principles

The lattice parameters, cell volume, elastic constants, bulk modulus, shear modulus, Young's modulus and Poisson's ratio are calculated at zero pressure, and their values are in excellent agreement with the available data, for TiN, Ti₂N and Ti₃N₂. By using the elastic stability criteria, it is shown that the three structures are all stable. The brittle/ductile behaviors are assessed in the pressures from 0 GPa to 50 GPa. Our calculations present that the performances for TiN, Ti₂N and Ti₃N₂ become from brittle to ductile with pressure rise. The Debye temperature rises as pressure increase. With increasing N content, the enhancement of covalent interactions and decline of metallicity lead to the increase of the micro-hardness. Their constant volume heat capacities increase rapidly in the lower temperature, at a given pressure. At higher temperature, the heat capacities are close to the Dulong–Petit limit, and the heat capacities of TiN and Ti₂N are larger than that of c-BN. The thermal expansion coefficients of titanium nitrides are slightly larger than that of c-BN. The band structure and the total Density of States (DOS) are calculated at 0 GPa and 50 GPa. The results show that TiN and Ti₂N present metallic character. Ti₃N₂ present semiconducting character. The band structures have some discrepancies between 0 GPa and 50 GPa. The extent of energy dispersion increases slightly at 50 GPa, which means that the itinerant character of electrons becomes stronger at 50 GPa. The main bonding peaks of TiN, Ti₂N and Ti₃N₂ locate in the range from −10 to 10 eV, which originate from the contribution of valance electron numbers of Ti s, Ti p, Ti d, N s and N p orbits. We can also find that the pressure makes that the total DOS decrease at the Fermi level for Ti₂N. The bonding behavior of N–Ti compounds is a combination of covalent and ionic nature. As N content increases, valence band broadens, valence electron concentration increases, and covalent interactions become stronger. This is reflected in shortening of Ti–N bonds.     

Comparative Raman study of the Ti complex Cp2Ti(η2-C60) · C6H5CH3 and TixC60 films

Raman spectra from the first Ti fullerene complex Cp ₂Ti(η²-C₆₀) · C₆H₅CH₃ are presented. Compared to spectra of pure C₆₀, the spectra of the Ti complex exhibit a number of new peaks due to the symmetry lowering for C₆₀. The A _g(2) mode is downshifted by 12 cm⁻¹ compared to C₆₀, which corresponds to a charge transfer of one electron per Ti-C₆₀ bond. This value (6 cm⁻¹ for one transferred electron) is identical to the downshift of the A _g(2) mode in alkali metal fullerides with ionic bonding. The spectra of Cp ₂Ti(η²-C₆₀) · C₆H₅CH₃ were compared to the spectra of evaporated Ti_xC₆₀ films. The A _g(2) mode in Ti₄C₆₀ showed a downshift of about 25 cm⁻¹ compared to pure C₆₀, which corresponds to a charge transfer of one electron per Ti atom; this is similar to the ionic alkali metal fullerides and different from η²-C₆₀-type bonding. From Fizika Tverdogo Tela, Vol. 44, No. 3, 2002, pp. 483–485. Original English Text Copyright ? 2002 by Talyzin, Jansson, Usatov, Burlakov, Shur, Novikov. This article was submitted by the authors in English.     

Planar nano-block structures Tin+1Al0.5Cn and Tin+1Cn (n = 1, and 2) from MAX phases: Structural,electronic properties and relative stability from first principles calculations

Structural, electronic properties and relative stability of quasi-two-dimensional (2D) free-standing planar nano-block (NBs) structures Ti_n+1Al_0.5C_n and Ti_n+1C_n (n = 1 and 2), which can be prepared using the recently developed procedure of exfoliation of corresponding NBs from MAX phases, were examined within first principles calculations in comparison with parent MAX phases Ti₃AlC₂ and Ti₂AlC. We found that in general Ti_n+1C_n and Ti_n+1Al_0.5C_n NBs retain the atomic geometries of the corresponding blocks of the MAX phases, but some structural distortions for the NBs occur owing to the lowering of the coordination number for atoms in the external Ti sheets of the nano-block structures. Our analysis based on their cohesive and formation energies reveals that the stability of the nano-block structures increases with index n (or, in other words, with a growth of the number of Ti–C bonds), the Al-containing NBs becoming more stable than the “pure” Ti–C NBs. Our data show that the magnetization of the simulated planar nano-block structures can be expected; so, for the Ti₃C₂ nano-block the most stable will be the spin configuration, where within each external Ti sheet the spins are coupled ferromagnetically together with antiferromagnetic ordering between opposite external titanium sheets of this nano-block.     

Al2O3X(X=H,D, T)的电子振动近似理论方法研究

用密度泛函理论(DFT)方法在6-311++G(d,p)水平上对Al₂O₃X(X=H, D, T)分子较低能量的几何构型进行了优化. 计算结果表明该分子有两个可能基态, 即Al₂O₃X(X=H,D,T)(²A′)C_s和Al₂O₃X 关键词： 2O₃X(X=H;D;T)分子团簇')" href="#">Al₂O₃X(X=H;D;T)分子团簇 热力学函数 氢同位素效应 吉布斯自由能改变     

Equation of state of aluminum carbide Al4C3

Quasi-hydrostatic compression of aluminum carbide, Al₄C₃ has been studied to 6 GPa at room temperature using energy-dispersive X-ray powder diffraction with synchrotron radiation. A fit of the experimental p-V data to the Birch equation of state yields the values of the bulk modulus, B₀, of 130(5) GPa and the first pressure derivative of the bulk modulus, B′₀, of 4.6(9). The compression is found to be anisotropic, with the a-axis being more compressible than the c-axis.     

Deactivation of TiO2 photocatalytic films loaded on aluminium: XPS and AFM analyses

TiO₂ films were loaded on aluminium substrates by dip-coating method. Based on cyclic photocatalytic degradation experiments using benzamide as model molecule, XPS and AFM tests, the deactivating behaviour of the samples was studied. Experiment results show that the samples with less coating times (one to four times) deactivated very quickly, while the samples coated more than five times did not lose activity. Al element was proved to segregate from substrate and diffuse into TiO₂ films during calcination and annealing treatment, existing as mixture of Al₂O₃ and Al(OH)₃ at the boundaries among TiO₂ particles. During photocatalytic reactions in aqueous phase, the transformation of Al from Al₂O₃ to Al(OH)₃ and the leaching of the latter brought out serious alternation of surface morphology to the samples coated one to three times, on whose surface Ti³⁺ and Ti²⁺ centers were also detected after six cycles of photocatalytic reactions, while fresh films and the tested films which did not deactivate possess unique +4 valence Ti. The alteration of surface morphology, together with the change of valence of surface Ti element, resulted in the deactivation encountered in this research.     

Equation of state and thermal stability of Al3BC

The lattice parameters of Al₃BC have been measured up to 5 GPa at ambient temperature using energy-dispersive X-ray powder diffraction with synchrotron radiation. A fit to the experimental p-V data using Birch-Murnaghan equation of state gives values of the Al₃BC bulk modulus 116(4) GPa and its first pressure derivative 9(2). In the 1.6-4.8 GPa range at temperatures above 1700 K Al₃BC undergoes incongruent melting that results in the formation of Al₃BC₃, AlB₂ and liquid aluminum.     

Effect of Al doping on the magnetic and electrical properties of layered perovskite La1.3Sr1.7Mn2−xAlxO7

The effect of Al substitution for Mn site in layered manganese oxides La_1.3Sr_1.7Mn_2−xAl_xO₇ on the magnetic and electrical properties has been investigated. It is interesting that all the samples undergo a similar and complex transition with lowing temperature; they transform from the two-dimensional short-range ferromagnetic order at T*, then enter the three-dimensional long-range ferromagnetic state at T_C, at last they display the canted antiferromagnetic state below T_N. T*, T_C and T_N are all reduced with Al content. Resistivity increases sharply with increasing Al concentration, and the metal-insulator transition disappears when x reaches 10%. Additionally, magnetoresistance (MR) effect is weakened. Al substitution dilutes the magnetic active Mn-O-Mn network and weakens the double exchange interaction, and further suppresses FM ordering and metallic conduction. Owing to the anisotropic interaction in the layered perovskite, the magnetic and electrical properties are more sensitive to Al doping level than those in ABO₃-type perovskite.     

冲击加载下Zr51Ti5Ni10Cu25Al9金属玻璃的塑性行为

进行了10—27 GPa应力范围内Zr₅₁Ti₅Ni₁₀Cu₂₅Al₉金属玻璃的平面冲击实验以研究其高压-高应变率加载下的塑性行为.由样品自由面粒子速度剖面的分析获得了冲击加载过程的轴向应力,并通过轴向应力与静水压线的比较获得剪应力.实验结果表明,尽管存在明显的松弛效应,但Zr基金属玻璃的Hugoniot弹性极限随着冲击应力的增加而增加.然而,塑性波阵面上的剪应力则显示先硬化而后软化现象,而且软化的幅度随冲击应力的增加而增加.冲击加载下Zr基金属玻璃的上述剪应力变化特征与分子动力学模拟结果比较一致,但与压剪实验结果和一维应力冲击实验结果明显不同.     

STUDY OF THE Al/GRAPHITE INTERFACE

Thin Al films with a thickness of 20－30nm were prepared by ultra-high vacuum deposition of Al onto a graphite surface parallel to a (0001) basal plane. The samples were annealed up to 1070K. X-ray photoelectron spectroscopy analysis has shown that for temperatures just higher than 770K, a little carbide occurs in the Al film and only an Al－C phase is present at the Al/graphite interface. After annealing at 970K, the Al₄C₃ phase can be observed, and the binding energy of the Al2p electrons increases continuously from 72.7 to 74.2eV with increasing temperature up to 1070K. Auger electron spectroscopy depth profiles are measured to investigate the phases existing in the Al film as well as at the Al/graphite interface. It is found that the Al₄C₃ phase at the interface is the final product of a series of Al carbides from the interfacial reaction between Al and graphite.