Formation and stability of small well-defined Cu- and Ni oxide particles

Well-defined and -structured Cu/Cu₂O and Ni/NiO composite nanoparticles have been prepared by physical-vapor deposition on vacuum-cleaved NaCl(001) single crystal facets. Epitaxial growth has been observed due to the close crystallographic matching of the respective cubic crystal lattices. Distinct particle morphologies have only been obtained for the Ni/NiO particles, comprising truncated half-octahedral, rhombohedral- and pentagonal-shaped outlines. Oxidation of the particles in the temperature range 473–673 K in both cases led to the formation of well-defined CuO and NiO particles with distinct morphologies. Whereas CuO possibly adopts its thermodynamical equilibrium shape, NiO formation is accompanied by entering a Kirkendall-like state, that is, a hollow core–shell structure is obtained. The difference in the formation of the oxides is also reflected by their stability under reducing conditions. CuO transforms back to a polycrystalline mixture of Cu metal, Cu₂O and CuO after reduction in hydrogen at 673 K. In contrast, as expected from theoretical stability considerations, the formation of the hollow NiO structure is reversed upon annealing in hydrogen at 673 K and moreover results in the formation of a Ni-rich silicide structure Ni₃Si₂. The discussed systems present a convenient way to tackle and investigate various problems in nanotechnology or catalysis, including phase transformations, establishing structure/activity relationships or monitoring intermetallic particles, starting from well-defined and simple models.     

Microstructure and oxidation-resistant of ZrO2/Ni coatings applied by high-speed jet electroplating

ZrO₂/Ni composite coatings with different contents of ZrO₂ particles were deposited on superalloy K17 substrate using high-speed jet electroplating process. The microhardness and microstructure of composite coatings were studied. The oxidation kinetic curves of uncoated and coated K17 alloys were obtained. The results indicated that ZrO₂/Ni composite coatings exhibit higher microhardness than that of pure nickel coatings under the same high-speed jet electrodeposition conditions. ZrO₂/Ni composite coatings exposure to air at 1000 °C for 5 h formed scale containing NiO and Cr₂O₃; after exposure to air at 1000 °C for 100 h the scale was comprised NiO, NiCr₂O₄, and Cr₂O₃. The formation of Cr₂O₃ scales on the ZrO₂/Ni composite coating directly improved the oxidation resistance of superalloy K17.     

NiO/SiO2 nanostructure and the magnetic moment of NiO nanoparticles

We report on the synthesis, morphology and magnetic properties of a novel NiO/SiO₂ nanostructure. The NiO/SiO₂ nanostructure was synthesized by a method based on the contribution of sol-gel and combustion processes. X-ray powder diffraction (XRPD) showed the formation of the nanocrystalline NiO phase. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) revealed perfectly spherical NiO nanoparticles with diameter of about 5 nm. Amorphous silica shell around the NiO nanoparticles was also observed by HRTEM showing NiO/SiO₂ core-shell nanostructure. Magnetic measurements show hysteretic behavior at 2 K with coercivity H_C = 700 Oe, remanent magnetization M_r = 3.9 emu/g, saturation magnetization M_S = 28.2 emu/g and huge magnetic moment m_p ≈ 1300 μ_B of the nanoparticles.     

Simple synthesis of ZrO2/SiOx core/shell nanofibers using ZrSi2 with gallium

ZrO₂/SiO_x core/shell nanofibers with diameter ~ 50 nm were synthesized by the thermal oxidation of ZrSi₂ substrates with gallium. The crystalline ZrO₂ cores were grown with amorphous SiO_x shells. It is proposed that the growth of crystalline ZrO₂ core was guided by the prior supersaturation of Zr species in the molten gallium film, whereas the amorphous SiO_x shell could be attributed to the deposition of SiO vapor on the surface of ZrO₂ core. In addition, the ZrO₂/SiO_x core/shell nanofibers show a wide visible photoluminescence (PL) emission at 480 nm, which should originate from the SiO_x shells.     

Sol-gel coatings in the ZrO2-SiO2 system for protection of historical works of glass

Different kinds of protective treatments based on sol-gel coatings have been designed and prepared. Final application of these coatings would be used for protection and preventive conservation of a wide variety of historical glasses from several times and provenance. Historical glasses show a superficial deterioration depending on the exhibition conditions submitted by the ancient objects since their origin.The coatings effectiveness was confirmed by means of accelerated ageing tests under simulated atmospheric polluted conditions by using SO₂ as a pollutant and different kind of glasses as reference substrates.Coatings with compositions 100SiO₂ and 10ZrO₂·90SiO₂ (mol%) proved to be highly protective when they were densified up to 250 and 400 °C for 1 h. Those coatings densified at lower temperature (for instance, 60 °C for 3 days) appeared partially cracked and detached after the ageing tests. For compositions 50ZrO₂·50SiO₂ and 100ZrO₂ the major problem was concerned to the high surface reflectance provided by the zirconium oxide, which modifies very much the appearance of the substrate glasses.     

Dielectric and non-Ohmic properties of CaCu3Ti4O12 ceramics modified with NiO, SnO2, SiO2, and Al2O3 additives

In order to conciliate dielectric and non-Ohmic properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics, NiO, SnO₂, SiO₂, and Al₂O₃ were added as sintering aids to promote the grain growth of CCTO ceramics. Microstructure, dielectric properties, and non-Ohmic behavior of the CCTO ceramics were investigated. Among them, NiO-modified CCTO exhibits good dielectric and non-Ohmic properties (ε = 69833, tanδ = 0.073, α = 3.66 and E _B = 296.7 V/cm), due to NiO is also one of giant dielectric materials. Therefore, it is suitable for applying semiconductor circuits. The relationship between electrical current density (J) and electrical field (E) demonstrated that Schottky barrier should exist at grain boundaries. Non-linear coefficient α was directly proportional to the height of barrier. Depressing barrier width would improve significantly dielectric permittivity but decrease breakdown voltage.     

Electrodeposition PbO2-TiO2 and PbO2-ZrO2 and its physicochemical properties

Composite materials based on PbO₂ containing TiO₂ or ZrO₂ were prepared from electrolytes containing a suspension of TiO₂ or ZrO₂. The contents of foreign oxides in the composite depend on the electrolyte composition and conditions of deposition. When a dispersed phase is incorporated into the composite coating, the dimensions of lead dioxide crystals decrease to submicro- and nano-size. Physico-chemical properties of composite materials are mainly determined by their chemical composition.     

Characterization of Al2O3/ZrO2 nano multilayer thin films prepared by pulsed laser deposition

Microstructural characterization of pulsed laser deposited Al₂O₃/ZrO₂ multilayers on Si (1 0 0) substrates at an optimized oxygen partial pressure of 3 × 10⁻² mbar and at room temperature (298 K) has been carried out. A nanolaminate structure consisting of alternate layers of ZrO₂ and Al₂O₃ with 40 bi-layers was fabricated at different zirconia layer thicknesses (20, 15 and 10 nm). The objective of the work is to study the effect of ZrO₂ layer thickness on the stabilization of tetragonal ZrO₂ phase for a constant Al₂O₃ layer thickness of 5 nm. The Al₂O₃/ZrO₂ multilayer films were characterized using high temperature X-ray diffraction (HTXRD) in the temperature range 298–1473 K. The studies showed that the thickness of the zirconia layer has a profound influence on the crystallization temperature for the formation of tetragonal zirconia phase. The tetragonal phase content increased with the decrease of ZrO₂ layer thickness. The cross-sectional transmission electron microscope (XTEM) investigations were carried out on a multilayer thin films deposited at room temperature. The XTEM studies showed the formation of uniform thickness layers with higher fraction of monoclinic and small fraction of tetragonal phases of zirconia and amorphous alumina.     

A new synthesis process and characterization of three-dimensionally ordered macroporous ZrO2

A three-dimensionally ordered macroporous (3DOM) material ZrO₂ has been successfully synthesized by using ZrOC1₂·8H₂O as precursor and polystyrene beads with diameters of 480 nm as template. The merit of this process is that ZrOC1₂·8H₂O is cheaper and has a high melting point. SEM images show that precursor concentration has an important effect in fabricating 3DOM ZrO₂. The sample prepared by using the precursor solution with a concentration of 1.6 M displays a well long-ranged ordered structure and uniform pore sizes. Precursor concentration between 1.3 M and 2.0 M is considered to be the most favorable to fabricate 3DOM ZrO₂. XRD analysis indicates that the crystallinity of 3DOM ZrO₂ is monoclinic phase. Nitrogen adsorption and desorption measurements at 77.4 K show detailed pore structures of 3DOM ZrO₂.     

Thin film model systems of ZrO2 and Y2O3 as templates for potential industrial applications investigated by means of electron microscopy

An analytical high-resolution electron microscopy study of Y₂O₃ and ZrO₂ thin films, being relevant oxide model systems for a range of industrial applications, is reported. Both films were deposited on vacuum-cleaved NaCl(001) single crystal planes at varying substrate temperatures. A transition from an amorphous to a well-defined and -ordered structure, exhibiting almost single-crystalline ordering of either body-centered cubic Y₂O₃ or tetragonal ZrO₂, both with uniform electronic structure, has been observed upon raising the substrate temperature from 300 to 573 K. Pronounced crystallographic relationships between the face-centered cubic NaCl structure and the structures of the deposited oxides have been held responsible for the observed epitaxial growth. In summary, the chosen preparation pathway represents an easy and reproducible method to yield well-defined oxide structures at surprisingly low substrate temperatures being at the same time promising model candidates for materials-related (e.g. solid-oxide fuel cell) research. With respect to solid-oxide fuel cell technology, monitoring carbon deposition and reactivity following high-temperature treatments in hydrocarbon-containing gas feeds or the use as templates or supports for model systems of realistic anode materials on metallic or bimetallic basis are envisioned application areas.     

Enhanced thermoelectric properties of NaCo2O4 by adding ZnO

The primary phase present in the as-sintered Na(Co_1 − xZn_x)₂O₄ (0 ≤ x ≤ 0.1) bodies was the solid solution of the constituent oxides with a bronze-type layered structure. The electrical conductivity of the Na(Co_1 − xZn_x)₂O₄ samples significantly increased with an increase in ZnO content. The sign of the Seebeck coefficient for all samples was positive over the whole temperature range (723-1073 K), i.e., p-type conduction. The power factor of Na(Co_0.95Zn_0.05)₂O₄ showed an outstanding power factor (1.7 × 10^− 3Wm^− 1 K^− 2) at 1073 K. The power factor was above four times superior to that of ZnO-free NaCo₂O₄ (0.4 × 10^− 3Wm^− 1 K^− 2). This originates from an unusually large Seebeck coefficient (415 μVK^− 1) accompanied with high conductivity (127Ω^− 1 cm^− 1) at 1073 K.     

Influence of substrate and selenization temperatures on the growth of Cu2SnSe3 films

The effects of substrate temperature and selenization temperature on the structure, composition, electrical and optical properties of Cu₂SnSe₃ films were studied systematically. Cu₂SnSe₃ films deposited at various substrate temperatures (303–573 K) by the flash evaporation method are found to be non-stoichiometric. To compensate the selenium deficiency and obtain a single-phase, an annealing Cu₂SnSe₃ films deposited at 573 K was performed in selenium atmosphere. Cu₂SnSe₃ films deposited at a substrate temperature of 573 K and then selenized at 673 K were single phase and polycrystalline exhibiting monoclinic structure. The films showed p-type conductivity with a direct band gap of 0.84 eV.     

Influence of SiO2 interlayer on the hydrophilicity of TiO2/SiO2/glass produced by RF-magnetron sputtering

The effect of silicon dioxide (SiO₂) on the hydrophilicity of the TiO₂ thin film is investigated. SiO₂ and TiO₂ films were deposited on the glass by RF-magnetron sputtering. Heat-treatment for 15 h at 573 K on TiO₂/glass and TiO₂/SiO₂/glass is carried out to make Na⁺-ion diffused from the glass to the TiO₂ thin film, which results in no band-gap change but instead the enhanced crystallinity of the anatase phase-TiO₂. This in turn leads to the improvement in hydrophilicity. Irrespective of the SiO₂ interlayer, the anatase phase-TiO₂ thin film with enhanced crystallinity shows outstanding super-hydrophilicity. Consequently, under the heat-treatment condition, the SiO₂ interlayer played an important role in improving the crystallinity of the anatase phase-TiO₂ rather than preventing Na⁺-ion diffusion.     

UV Raman spectroscopic study on the surface phase of ZrO2 modified with Nd2O3

The Nd₂O₃ modified ZrO₂ was synthesized using two methods of co-precipitation (Nd-ZrO₂) and wet impregnation (Nd/ZrO₂). The surface and bulk crystalline phases of Nd₂O₃ modified ZrO₂ were investigated by using UV Raman spectroscopy, visible Raman spectroscopy, and X-ray diffraction (XRD). It is observed that the tetragonal phase in the surface region of Nd-ZrO₂ was not effectively stabilized by Nd₂O₃, as Nd₂O₃ is mainly present in the bulk of Nd-ZrO₂. However, in Nd/ZrO₂, it is found that with the impregnation of 0.5 mol% Nd₂O₃ on ZrO₂, the surface tetragonal phase of Nd/ZrO₂ can be stabilized even after calcination at 700 °C. The UV Raman results indicate that a disordered structure, or intermediate structure, which is involved in the transition from the tetragonal to the cubic phase, is formed at the surface region of Nd/ZrO₂. The formation of the aforementioned intermediate structure inhibits the phase transition from tetragonal to monoclinic in the surface region of Nd/ZrO₂. Furthermore, it is observed that the mixed tetragonal and monoclinic phases in the surface region of ZrO₂ which has been impregnated with Nd₂O₃ can also be stabilized after calcination at 700 °C. This work provides a simple method for controlling the surface phase of ZrO₂ at high temperatures.     

Pressureless sintering of negative thermal expansion ZrW2O8/Zr2WP2O12 composites

Negative thermal expansion material ZrW₂O₈/Zr₂WP₂O₁₂ composite was prepared by liquid phase sintering. The apparent density of ZrW₂O₈ without any sintering additive was about 3.7 g/cm³, corresponding to about 73% of its theoretical density. However, the relative density of the samples, sintered with more than 5 mol% P₂O₅ was about 90%. The identified phases were mainly ZrW₂O₈ with small amounts of WO₃, ZrO₂ and Zr₂WP₂O₁₂ by XRD. The intensity of Zr₂WP₂O₁₂ peaks increased with increasing P₂O₅ content. It was surmised that the melting of ZrO₂-P₂O₅ resulted in liquid phase formation, which is then converted to Zr₂WP₂O₁₂ on the final stage of sintering. Therefore, Zr₂WP₂O₁₂ phase was observed at the gap between the ZrW₂O₈ grains and at the triple junctions. The ceramics sintered with 20 mol% P₂O₅ showed a negative thermal expansion coefficient of − 4.0 × 10^− 6 °C^− 1.     

Synthesis and characterization of CuO/ZnO-Al2O3 catalyst washcoat thin films with ZrO2 sols for steam reforming of methanol in a microreactor

Inner surface and the fine structure of the microchannel reactor using porous alumina support CuO/ZnO mixed with ZrO₂ sol washcoat catalyst for autothermal reforming of methanol have been synthesized and characterized. Experimentally, catalyst slurries have been dried at 298 K for 5 h and then calcined at 623 K for 2 h to increase the surface area and specific pore structures of washcoat catalysts. Intensities of Cu content from XRD patterns indicate that Al₂O₃ assign with Cu(0) to from CuAl₂O₄. The EXAFS data reveals that the Cu species in washcoat have a Cu-O bonding with a bond distance of 1.96 Å and a coordination number of 2.95, respectively.     

Crystallization of CaHf1? x Zr x Ti2O7 (0?≤ x ≤?1) zirconolite in SiO2–Al2O3–CaO–Na2O–TiO2–HfO2–ZrO2–Nd2O3 glasses

Glass-ceramics containing (Hf,Zr)-zirconolite crystals (nominally CaHf_1−x Zr _x Ti₂O₇ with 0 ≤ x ≤ 1) were envisaged to immobilize minor actinides and plutonium. Such materials were prepared in this study by controlled crystallization of glasses belonging to the SiO₂–Al₂O₃–CaO–Na₂O–TiO₂–HfO₂–ZrO₂–Nd₂O₃ system. Neodymium was used as trivalent actinides surrogate. The effect of total or partial substitution of ZrO₂ by HfO₂ (neutron poison for fission reactions) on glass crystallization in the bulk and near the surface is presented. It appeared that Hf/Zr substitution had not significant effect on nature, structure, and composition of crystals formed both on glass surface (titanite + anorthite) and in the bulk (zirconolite). This result can be explained by the close properties of Zr⁴⁺ and Hf⁴⁺ ions and by their similar structural role in glass structure. However, strong differences were observed between the nucleation rate I_Z of zirconolite crystals in glasses containing only HfO₂ and in glasses containing only ZrO₂. Hf-zirconolite (CaHfTi₂O₇) crystals were shown to nucleate only very slowly in comparison with Zr-zirconolite (CaZrTi₂O₇) crystals. Composition changes - by increasing either HfO₂ or Al₂O₃ concentration or by introducing ZrO₂ in parent glass - were performed to increase I_Z in hafnium-rich glasses. The proportion of Nd³⁺ ions incorporated in the zirconolite phase was estimated using ESR.     

Development of NiO-based thin film structures as efficient H2 gas sensors operating at room temperatures

P-type NiO thin films have been developed on high resistivity Si and SiO₂ substrates by a pulsed laser deposition technique using an ArF^? 193 nm excimer laser at deposition temperature of 300 °C and in 40 Pa partial oxygen pressure. Structures based on such NiO films as host material in the form of Au-NiO Schottky diodes have been subsequently developed under vacuum. In a different procedure, an n-SnO₂ layer has been deposited by a CVD technique on a NiO film to produce a p/n heterojunction. The sensing properties of all above structures have been tested upon exposure to a H₂ flow in air ambient gas at various operating temperature ranging from 30 to 180 °C. For the NiO films, the optimum temperature was about 150 °C exhibiting a sensitivity of 94%. After surface sensitization of NiO by Au the NiO films showed an H₂ response at operating temperature of 30 °C. The sensitivity of p-NiO/n-SnO₂ heterojunction devices was extracted from I-V measurements in air and under H₂ flow mixed in air. In this case a dramatic increase of the sensitivity was achieved at operating temperature of 30 °C for a forward bias of 0,2 V.     

Structure and property changes of ZrO2/Al2O3/ZrO2 laminate induced by low-temperature NH3 annealing applicable to metal-insulator-metal capacitor

Phase transformation and morphology evolution of ZrO₂/Al₂O₃/ZrO₂ laminate induced by the post-deposition NH₃ annealing at 480 °C were studied and the effect on the electrical property of the TiN/ZrO₂/Al₂O₃/ZrO₂/TiN capacitor module was evaluated in dynamic random access memory cell. Experimental results indicated N could indeed be incorporated into the dielectric laminate by the low-temperature NH₃ annealing, resulting in tetragonal-to-cubic phase transformation and small crystallites in the ZrO₂ layers. The C residue and Cl impurity in the ZrO₂/Al₂O₃/ZrO₂ laminate, which derived from the dielectric film formation and capping TiN layer deposition, respectively, could also be reduced by the nitridation process. As a result of the better surface morphology and less impurity content, lower dielectric leakage current and longer reliability lifetime were observed for the nitrided ZrO₂/Al₂O₃/ZrO₂ capacitor. This study demonstrates the low-temperature NH₃ annealing on ZrO₂/Al₂O₃/ZrO₂ dielectric can be applicable to the metal-insulator-metal capacitor structure with nitride-based electrode, which brings advantages over mass production-wise property improvements and extends the practical applicability of the ZrO₂/Al₂O₃/ZrO₂ dielectric.     

Hysteresis in metal insulator semiconductor structures with high temperature annealed ZrO2/SiOx layers

Hysteresis behaviour in sandwich structure — zirconium oxide/chemical silicon oxide, annealed at temperature of 850 °C in oxygen ambient, was studied. Formation of thin ZrSi_xO_y layer due to the high temperature annealing was found. Metal-insulator-semiconductor (MIS) capacitors using ZrO₂/ZrSi_xO_y/SiO_x insulator were studied. High-frequency capacitance-voltage (HF C-V), current-voltage (I-V) and current-time (I-t) measurements were carried out on the Al/ZrO₂/ZrSi_xO_y/SiO_x/Si capacitors.Two leakage current components were identified — tunneling current component at high electric fields and transient current component at low fields. The transient leakage currents are due to charge trapping phenomena. The measured I-t characteristics are related with charging/discharging and dielectric relaxation phenomena. A counter-clockwise HF C-V hysteresis, larger than 2 V at thickness of the stack structure of about 50 nm was observed.Metal-insulator-semiconductor field effect transistors (MISFETs) using ZrO₂/ZrSi_xO_y/SiO_x-gate insulator were studied. P-channel MISFETs with aluminum gate electrode were fabricated on standard n-type silicon substrates. Due to charging/discharging phenomena in the gate dielectric the transistors can be switched between On- and Off-state with the polarity of applied stress voltage.