Structural and dielectric properties of Bi2Zn2/3Nb4/3O7 thin films prepared by pulsed laser deposition at low temperature for embedded capacitor applications

Bi₂Zn_2/3Nb_4/3O₇ thin films were deposited on Pt/TiO₂/SiO₂/Si(1 0 0) substrates at a room temperature under the oxygen pressure of 1-10 Pa by pulsed laser deposition. Bi₂Zn_2/3Nb_4/3O₇ thin films were then post-annealed below 200 °C in a rapid thermal process furnace in air for 20 min. The dielectric and leakage current properties of Bi₂Zn_2/3Nb_4/3O₇ thin films are strongly influenced by the oxygen pressure during deposition and the post-annealing temperature. Bi₂Zn_2/3Nb_4/3O₇ thin films deposited under 1 Pa oxygen pressure and then post-annealed at a temperature of 150 °C show uniform surface morphologies. Dielectric constant and loss tangent are 57 and 0.005 at 10 kHz, respectively. The high resolution TEM image and the electron diffraction pattern show that nano crystallites exist in the amorphous thin film, which may be the origin of high dielectric constant in the Bi₂Zn_2/3Nb_4/3O₇ thin films deposited at low temperatures. Moreover, Bi₂Zn_2/3Nb_4/3O₇ thin film exhibits the excellent leakage current characteristics with a high breakdown strength and the leakage current density is approximately 1 × 10⁻⁷ A/cm² at an applied bias field of 300 kV/cm. Bi₂Zn_2/3Nb_4/3O₇ thin films are potential materials for embedded capacitor applications.     

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.     

Deposition, microstructure and properties of texture-controlled CVD α-Al2O3 coatings

The influence of nucleation on the microstructure and properties of CVD Al₂O₃ was investigated. The experimental α-Al₂O₃ layers were deposited (a) without nucleation control and (b) with nucleation steps resulting in pronounced , and growth textures. The experimental layers were characterised using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Wear properties of the textured coatings were evaluated in turning. The chemistry of the nucleation surface appeared to be an important factor in pre-determining the phase content and growth textures of the Al₂O₃ layers. Optimised nucleation resulted in substantially improved wear properties and these kinds of α-Al₂O₃ layers were typically composed of relatively small, defect-free grains exhibiting no porosity. The textured α-Al₂O₃ layer showed the best wear resistance.     

Growth and microstructural stability of epitaxial Al films on (0001) α-Al2O3 substrates

Al films were grown epitaxially on single-crystal α-Al₂O₃ substrates by magnetron sputtering and molecular beam epitaxy, respectively. The microstructure and thermal stability of these films were analysed in detail using X-ray diffraction methods and electron microscopy techniques. The films consist of two twin-related growth variants, related by a 180° rotation around the <111> film normal resulting in a {111} Al || (0001) α-Al₂O₃, and ± < > Al || < > α-Al₂O₃ orientation relationship. The Al variants are separated by Σ3 { } Al twin boundaries possessing a rigid body translation of the {111} Al planes across the boundary plane in order to reduce their energy. Motion of the twin boundaries was observed by annealing plan-view samples in situ in a transmission electron microscope. The twin boundaries advance in jerky motion at velocities of several μm/s at temperatures of ˜400 °C, resulting in grain coarsening. In all cases, heat treatments resulted in increased area fraction of one twin variant, which finally will result in single-crystal films upon further annealing.     

Preparation, microstructure and properties of molybdenum alloys reinforced by in-situ Al2O3 particles

The conventional molybdenum alloys, lacking of hard particles enhancing wear property, have relative poor wear resistance though they are widely used in wear parts. To resolve the above question, Mo alloys reinforced by in-situ Al₂O₃ particles are developed using powder metallurgy method. The in-situ α-Al₂O₃ particles in molybdenum matrix are obtained by the decomposition of aluminum nitrate after liquid-solid incorporation of MoO₂ and Al(NO₃)₃ aqueous solution. The α-Al₂O₃ particles well bonded with molybdenum distribute evenly in matrix of Mo alloys, which refine grains of alloys and increase hardness of alloys. The absolute density of alloy increases firstly and then decreases with the increase of Al₂O₃ content, while the relative density rises continuously. The friction coefficient of alloy, fluctuating around 0.5, is slightly influenced by Al₂O₃. However, the wear resistance of alloy obviously affected by the Al₂O₃ particles rises remarkably with the increasing of Al₂O₃ content. The Al₂O₃ particles can efficiently resist micro-cutting to protect molybdenum matrix, and therefore enhances the wear resistance of Mo alloy.     

Cyclic oxidation behavior and thermal barrier effect of YSZ-(Al2O3/YAG) double-layer TBCs prepared by the composite sol-gel method

Novel YSZ (6 wt.% yttria partially stabilized zirconia)-(Al₂O₃/YAG) (alumina-yttrium aluminum garnet, Y₃Al₅O₁₂) double-layer ceramic coatings were fabricated using the composite sol-gel and pressure filtration microwave sintering (PFMS) technologies. The thin Al₂O₃/YAG layer had good adherence with substrate and thick YSZ top layer, which presented the structure of micro-sized YAG particles embedded in nano-sized α-Al₂O₃ film. Cyclic oxidation tests at 1000 °C indicated that they possessed superior properties to resist oxidation of alloy and improve the spallation resistance. The thermal insulation capability tests at 1000 °C and 1100 °C indicate that the 250 μm coating had better thermal barrier effect than that of the 150 μm coating at different cooling gas rates. These beneficial effects should be mainly attributed to that, the oxidation rate of thermal grown oxides (TGO) scale is decreased by the “sealing effect” of α-Al₂O₃, the “reactive element effect”, and the reduced thermal stresses by means of nano/micro composite structure. This double-layer coating can be considered as a promising TBC.     

Synthesis and characterization of Al2O3-Ce0.5Zr0.5O2 powders prepared by chemical coprecipitation method

Al₂O₃-Ce_0.5Zr_0.5O₂ catalytic powders were synthesized by the coprecipitation (ACZ-C) and mechanical mixing (ACZ-M) methods, respectively. As-synthesized powders were characterized by XRD, Raman spectroscopy, surface area and thermogravimetric analyses. It was found that the mixing extent of Al³⁺ ions affected the phase development, texture and oxygen storage capacity (OSC) of the Ce_0.5Zr_0.5O₂ powder. Single phase of ACZ-C could be maintained without phase separation and inhibit α-Al₂O₃ formation up to 1200 °C. The specific surface area value of ACZ-C (81.5 m²/g) was larger than that of ACZ-M (62.1 m²/g) and Ce_0.5Zr_0.5O₂ (17.1 m²/g) powders, which were calcined at 1000 °C. In comparison with ACZ-C and Al₂O₃, which were calcined at high temperature (900–1200 °C), it was found that the degradation rate of specific surface area of ACZ-C was lower than that of Al₂O₃. ACZ-C sample showed a higher thermal stability to resist phase separation and crystallite growth, which enhanced the oxygen storage capacity property for Ce_0.5Zr_0.5O₂ powders.     

Examination of wire electrical discharge machining of Al2O3p/6061Al composites

Alumina particle reinforced 6061 aluminum matrix composites (Al₂O₃p/6061Al) have excellent physical and chemical properties than those of a traditional metal; however, their poor machinability lead to worse surface quality and serious cutting tool wear. In this study, wire electrical discharge machining (WEDM) is adopted in machining Al₂O₃p/6061Al composite. In the experiments, machining parameters of pulse-on time were changed to explore their effects on machining performance, including the cutting speed, the width of slit and surface roughness. Moreover, the wire electrode is easily broken during the machining Al₂O₃p/6061Al composite, so this work comprehensively investigates into the locations of the broken wire and the reason of wire breaking.The experimental results indicate that the cutting speed (material removal rate), the surface roughness and the width of the slit of cutting test material significantly depend on volume fraction of reinforcement (Al₂O₃ particles). Furthermore, bands on the machined surface for cutting 20 vol.% Al₂O₃p/6061Al composite are easily formed, basically due to some embedded reinforcing Al₂O₃ particles on the surface of 6061 aluminum matrix, interrupt the machining process. Test results reveal that in machining Al₂O₃p/6061Al composites a very low wire tension, a high flushing rate and a high wire speed are required to prevent wire breakage; an appropriate servo voltage, a short pulse-on time, and a short pulse-off time, which are normally associated with a high cutting speed, have little effect on the surface roughness.     

High-temperature oxidation of Fe3Al-based iron aluminides in oxygen

The isothermal high-temperature oxidation behavior of Fe₃Al-based iron aluminides in oxygen has been studied. Fe–25Al was oxidized at 1225, 1330, 1425 and 1530 K, while Fe–28Al, Fe–24Al–5Cr, Fe–24Al–5Ti, Fe–28Al–2Cr and Fe–30Al–4Cr (all compositions in atom percent) were oxidized at 1330 K. The weight gain data were analyzed and rate constants (k_p) determined by assuming a parabolic rate law. The variations of instantaneous parabolic rate constant with time reflected the complexity of the oxidation behavior. These have been attributed to the changes taking place in the nature and properties of the scale as a function of time. The values of k_p for oxidation of Fe₃Al were one to two orders of magnitude lower than those for Ti₃Al-based intermetallics. As revealed by X-ray diffraction, the scale formed on Fe–25Al was predominantly α-Al₂O₃ at higher temperatures, while θ-Al₂O₃ was observed after oxidation at lower temperatures. The observed kinetics matched with α-Al₂O₃-formation kinetics at higher temperatures and θ-Al₂O₃-formation kinetics at lower temperatures. For all the other intermetallics, only α-Al₂O₃ was identified at 1330 K. The whisker morphology of θ-Al₂O₃ and the ridged morphology of α-Al₂O₃ were confirmed by scanning electron microscopy. Alloying with Cr or Ti increased the oxidation rate of iron aluminides, especially during the initial stages. Addition of Ti changed the nature, color, and morphology of the scale, leading to improved adherence.     

The high-temperature corrosion behavior of Nb-Al alloys in a H2/H2S/H2O gas mixture

The corrosion behavior of pure Nb and three Nb Al alloys containing 12.5, 25, and 75 at.% Al was studied over the temperature range of 800–1000°C in a H₂/H₂S/H₂O gas mixture. Except for the Nb-12.5Al alloy consisting of a two phase structure of -Nb and Nb₃Al, other alloys studied were single phase. The corrosion kinetics followed the parabolic rate law in all cases, regardless of temperature and alloy composition. The parabolic rate constants increased with increasing temperature, but fluctuated with increasing Al content. The Nb-75Al alloy exhibited the best corrosion resistance among all alloys studied, whose corrosion rates are 1.6–2.2 orders of magnitude lower than those of pure-Nb (depending on temperature). An exclusive NbO₂ layer was formed on pure Nb, while heterophasic scales were observed on Nb-Al alloys whose compositions and amounts strongly depended on Al content and temperature. The scales formed on Nb-12.5Al consisted of mostly NbO₂ and minor amounts of Nb₂O₅, NbS2, and -Al₂O₃, while the scales formed on Nb-25Al consisted of mostly Nb₂O₅ and some -Al₂O₃. The scales formed on Nb-75Al consisted of mostly -Al₂O₃ and Nb₃S₄ atT 900°C, and mostly -Al₂O₃ , Nb₃S₄ and some AlNbO₄ at 1000°C. The formation of -Al₂O₃ and Nb₃S₄ resulted in a significant reduction of the corrosion rates.     

Mechanical properties of La2O3 doped diamond-like carbon films

Twelve La₂O₃ doped diamond-like carbon (DLC) nanofilms were deposited using unbalanced dual-magnetron sputtering. AFM, XRD, Raman spectroscopy, AES, XPS, TEM, contact surface profiler and nanoindenter were employed to investigate the structure and tribological properties of deposited films. The results show that the La₂O₃ doped DLC films are amorphous. La₂O₃ doping obviously decreases internal stress, and effectively increases the elastic modulus. This results from the dissolving and dissolution of La₂O₃ within the amorphous DLC matrix. Furthermore, the friction coefficient of the doped DLC films decreases, and adhesion strength increases. These are attributed to the lubrication function of La₂O₃ and the formation of transition layer at interface, respectively.     

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.     

Effect of Ag-doping on crystal structure and high temperature thermoelectric properties of c-axis oriented Ca3Co4O9 thin films by pulsed laser deposition

Ag-doped Ca₃Co₄O₉ thin films with nominal composition of Ca_3−xAg_xCo₄O₉ (x = 0∼0.4) have been prepared on sapphire (0 0 0 1) substrates by pulsed laser deposition (PLD). Structural characterizations and surface chemical states analysis have shown that Ag substitution for Ca in the thin films can be achieved with doping amount of x ≤ 0.15; while x > 0.15, excessive Ag was found as isolated and metallic species, resulting in composite structure. Based on the perfect c-axis orientation of the thin films, Ag-doping has been found to facilitate a remarkable decrease in the in-plane electrical resistivity. However, if doped beyond the substitution limit, excessive Ag was observed to severely reduce the Seebeck coefficient. Through carrier concentration adjustment by Ag-substitution, power factor of the Ag-Ca₃Co₄O₉ thin films could reach 0.73 mW m⁻¹ K⁻² at around 700 K, which was about 16% higher than that of the pure Ca₃Co₄O₉ thin film.     

Oxidation of Cr2AlC coatings in the temperature range of 1230 to 1410 °C

The isothermal oxidation behavior of Cr₂AlC coatings on alumina substrates was investigated in the temperature range of 1230 to 1410 °C. The structure, surface morphology, microstructure evolution and chemistry of the reaction products have been investigated. In the investigated temperature range, the Cr₂AlC films form a dense continuous oxide scale consisting of α-Al₂O₃ on Cr carbides. The oxidation rates determined by thermo gravimetric analysis (TGA) were parabolic, indicating that diffusion through the scale is the rate limiting mechanism. The activation energy for oxidation was determined to be 348 kJ mol^− 1 and the parabolic rate constant at 1230 °C was 7.1 × 10^− 10 kg² m^− 4 s^− 1. Hence, the oxidation behavior is comparable to NiAl in the temperature range and time intervals investigated. With increasing oxidation time voids form at the interface between oxide and Cr carbides and the amount of Cr₇C₃ increases at the expense of Cr₃C₂. Based on our thermodynamic calculations the oxygen partial pressure below the oxide scale increases as Al is depleted and Cr carbides oxidize, resulting in CO gas- and Cr₂O₃-formation. The formation of gas may together with the depletion of Al and Cr lead to the significant void formation observed in the Cr carbide interlayer. Observation of both Cr carbide precipitates and the formation of (Al,Cr)₂O₃ solid solution support this notion. For comparison bulk Cr₂AlC was oxidized. It is argued that the absence of pores in oxidized bulk Cr₂AlC is due to the considerably larger amount of Al available.     

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.     

Conductivity of a new pyrophosphate Sn0.9Sc0.1(P2O7)1−δ prepared by an aqueous solution method

New pyrophosphate Sn_0.9Sc_0.1(P₂O₇)_1−δ was prepared by an aqueous solution method. The structure and conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ have been investigated. XRD analysis indicates that Sn_0.9Sc_0.1(P₂O₇)_1−δ exhibits a 3 × 3 × 3 super structure. It was found that Sn_0.9Sc_0.1(P₂O₇)_1−δ prepared by an aqueous method is not conductive. The total conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ in open air is 2.35 × 10⁻⁶ and 2.82 × 10⁻⁹ S/cm at 900 and 400 °C respectively. In wet air, the total conductivity is about two orders of magnitude higher (8.1 × 10⁻⁷ S/cm at 400 °C) than in open air indicating some proton conduction. SnP₂O₇ and Sn_0.92In_0.08(P₂O₇)_1−δ prepared by an acidic method were reported fairly conductive but prepared by similar solution methods are not conductive. Therefore, the conductivity of SnP₂O₇-based materials might be related to the synthetic history. The possible conduction mechanism of SnP₂O₇-based materials has been discussed in detail.     

Microstructural changes in particles detected during the transformation from β-FeOOH to α-Fe2O3 in dense aqueous suspensions

The hydrothermal transformation from β-FeOOH to α-Fe₂O₃ in dense aqueous suspensions, obtained by partial neutralization of concentrated FeCl₃ solution with concentrated NaOH solution, was investigated. Mössbauer spectroscopy was used for the phase analysis of samples, as well as the complementary techniques XRD and FT-IR. The size and morphology of the particles were inspected with FE-SEM. At the beginning of the crystallization process very fine β-FeOOH particles were formed, which transformed to α-Fe₂O₃ (end-product) with a prolonged time of heating. A small amount or traces of α-FeOOH as an intermediate phase were detected by FT-IR and FE-SEM. Gradual formation of α-Fe₂O₃ double spheres with ring was monitored. Double spheres with ring were formed by the aggregation mechanism. The orientation effect of α-Fe₂O₃ subunits in double spheres with ring was observed. α-Fe₂O₃ double spheres with ring also showed two narrow particle size distributions.     

Mechanochemical synthesis of Al2O3-TiB2 nanocomposite powder from Al-TiO2-H3BO3 mixture

Alumina-titanium diboride nanocomposite (Al₂O₃-TiB₂) was produced using mixtures of titanium dioxide, acid boric and pure aluminum as raw materials via mechanochemical process. The phase transformation and structural characterization during mechanochemical process were utilized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analyses (TG-DTA) techniques. A thermodynamic appraisal showed that the reaction between TiO₂, B₂O₃ and Al is highly exothermic and should be self-sustaining. XRD analyses exhibited that the Al₂O₃-TiB₂ nanocomposite was formed after 1.5 h milling time. The results indicate that increasing milling time up to 40 h had no significant effect other than refining the crystallite size.     

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.     

Enhanced thermoelectric properties of n-type Bi2Te3-based nanocomposite fabricated by spark plasma sintering

Highly dense n-type Bi₂Te₃-based thermoelectric materials dispersed with x vol.% γ-Al₂O₃ nanoparticles (x = 0, 0.4, 1.0, 1.5) were fabricated by spark plasma sintering method. The effects of γ-Al₂O₃ addition on microstructure and the thermoelectric properties were studied. It was found that γ-Al₂O₃ nanoparticles locate both at grain boundaries and inside Bi₂Se_0.3Te_2.7 grains. The nanoparticles induce both potential barrier scattering effect and additional phonon scattering effect, which simultaneously enhance the Seebeck coefficient and reduce the lattice thermal conductivity of the nanocomposites in the measured temperature range of 300-500 K, respectively. The maximum dimensionless figure of merit (ZT_max) reaches up to 0.99 for the sample with x = 1.0 at 400 K, which is 35% improvement over the Bi₂Te₃-based matrix. More importantly, the average ZT value of the sample increases from 0.65 to 0.91 in the temperature range 300-500 K, making the nanocomposites much more applicable in cooling and power generation.