Phase composition, microstructure and electrical properties of alumina-zirconia eutectic composites

Oxide eutectic composites prepared by a directional solidification are noticeable for their good mechanical properties and high temperature stability in oxidizing environments. In this paper we study the influence of stabilizers (Y, Sc) on the phase composition, microstructure and electrical properties of Al₂O₃ - ZrO₂ eutectic composites. At a hypereutectic composition of the melt, we have prepared the composites with tetragonal ZrO₂, which possesses conductivities comparable to those of the composites containing cubic ZrO₂. An addition of Sc₂O₃ improves the ionic conductivity of the Al₂O₃ - (Y₂O₃)ZrO₂ eutectic composite at high temperatures. Both the microstructure and ionic conductivity do not change along the composite (grown at a constant growth rate). Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Impedance spectroscopy analysis of percolation in (yttria-stabilized zirconia)-yttria ceramic composites

(ZrO₂:8 mol% Y₂O₃)+m mol% Y₂O₃ ceramic composites with nominal yttria concentration varying from 0 to70 mol% (0–82.9 vol.%) were prepared by evaporation of a suspension of ZrO₂:8 mol% Y₂O₃ and Y₂O₃ in ethanol followed by pressing and sintering. The samples were analyzed by X-ray diffractometry and scanning electron microscopy for microstructural characterization. The electrical properties were studied by impedance spectroscopy (IS) allowing for the separation of the inter- and intragranular components of the electrical conductivity. The percolative behavior of these components was analyzed using the general effective media (GEM) equation and the percolation thresholds found were ∼28 vol.%. The results indicate that impedance spectroscopy provides useful information in addition to the dc techniques concerning the electrical characterization of composite materials.     

Permeation barrier properties of an Al2O3/ZrO2 multilayer deposited by remote plasma atomic layer deposition

We report the permeation barrier properties of Al₂O₃/ZrO₂ multi-layers deposited by remote plasma atomic layer deposition. Electrical Ca degradation tests were performed to derive the water vapor transmission rate (WVTR) of Al₂O₃, ZrO₂ and Al₂O₃/ZrO₂ multi-layers at 50 °C and 50% relative humidity (RH). Al₂O₃/ZrO₂ multi-layers exhibit better barrier properties than Al₂O₃ and ZrO₂ layers, and when more individual layers were deposited in the same total thickness, the WVTR value was reduced further, indicating a better barrier property. The WVTR of the Al₂O₃ and ZrO₂ layers were 9.5 × 10⁻³ and 1.6 × 10⁻² g/m² day, respectively, but when deposited alternatively with 1 cycle of each layer, the WVTR decreased to 9.9 × 10⁻⁴ g/m² day. X-ray diffraction results indicated that ZrO₂ has a monoclinic structure but Al₂O₃ and Al₂O₃/ZrO₂ multi-layers show an amorphous structure. Cross sectional Al₂O₃/ZrO₂ multi-layer structures and the formation of a ZrAl_xO_y phase are observed by transmission electron microscopy (TEM). X-ray photoelectron spectrometry (XPS) results indicate that Al₂O₃ and ZrO₂ contain 33.7% and 37.8%, respectively, Al–OH and Zr–OH bonding. However, the ZrAl_xO_y phase contained 30.5% Al–OH and Zr–OH bonding. The results of transmittance measurement indicate that overall, Al₂O₃, ZrO₂ and Al₂O₃/ZrO₂ multi-layers show high transmittance greater than 80% in the visible region.     

Synthesis and luminescent characterization of sol-gel derived zirconia–alumina

Luminescence and sintering characteristics of α-Al₂O₃-tetragonal zirconia [t-ZrO₂(Y₂O₃)] mixtures have been investigated. The pseudoboehmite is one of the main precursors of the α-alumina. In this investigation pseudoboehmite has been synthesized through a desulphatation of the commercial Al₂(SO₄)₃ using an ammonia solution. Tetragonal zirconia powders were added in adequate proportion for each composition. The mixture constituted by Al₂O₃ (pseudoboehmite) and t-ZrO₂ has been annealed at different temperatures to obtain the crystalline phases. XRD and SEM techniques measurements have been used to structural characterization. Photoluminescence (PL) emission spectra of Al₂O₃–ZrO₂ composites were performed at room temperature. Thermoluminescent emission spectrum of the samples was obtained and analyzed.     

The effect of ferrimagnetic ordering in insulating component of composites HTSC+Yttrium Iron Garnet on its transport properties

Composites Y_3/4Lu_1/4Ba₂Cu₃O₇+Y₃Fe₅O₁₂ modeling random network superconductor-ferrimagnetic-superconductor have been prepared and their transport properties (temperature dependences of resistivity ρ and critical current density j_c, current-voltage characteristics) have been studied. Below the superconducting transition temperature T_c, the ρ(T) dependences exhibit a kink at some temperature T_m. The crossover of current-voltage characteristics from ohmic-like behavior in range T_m/T_c to non-linear one below T_m is observed. Transport properties of the ‘benchmark’ composites Y_3/4Lu_1/4Ba₂Cu₃O₇+Y₃Al₅O₁₂ are typical for network superconductor-insulator-superconductor Josephson junction. The behavior observed for Y_3/4Lu_1/4Ba₂Cu₃O₇+Y₃Fe₅O₁₂ composites is attributed to peculiarities of supercurrent carriers tunnelling through ferrimagnetic barriers.     

Preparation and characterization of Y1−xPrxBa2Cu3O7−δ single crystals

We present a reliable method for growing single crystals of Y_1−xPr_xBa₂Cu₃O_7−δ high-T_c superconductors in ZrO₂ crucibles. This method results in crystals with greatly improved superconducting properties compared to crystals grown with the previously reported methods which use Al₂O₃ crucibles. We describe techniques for crystal growth in both Al₂O₃ and ZrO₂ crucibles using an excess of BaCo₃ and CuO as the flux. The crystals were characterized by means of DC magnetic-susceptibility measurements, electrical-resistivity measurements, and electron microprobe analysis. The effects of Al contamination on the conditions for crystal growth and on the superconducting properties of the crystals are found to be quite significant.     

Thin film solid oxide fuel cells

We have investigated the deposition of 91% ZrO₂ − 9% Y₂O₃ thin films by a variety of sputtering techniques for the application as electrolytes in thin film solid oxide fuel cells. The deposition by RF sputtering was accomplished by using an oxide target of the desired composition. The deposition rate in these initial tests was limited to 0.5 μm/hr and the morphology of the film was substantially modified by deposition rate and substrate temperature. Using DC magnetron sputtering we deposited metallic films from a metallic target with the desired chemical composition. We introduced oxygen into the sputtering chamber to reactively deposit the desired 91% ZrO₂ − 9% Y₂O₃ thin films; however, we encountered problems with target oxidation and growth rate reproducibility. We subsequently demonstrated that controlled oxidation of the metallic films could result in adhering, non porous yttria stabilized zirconia films. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Defects in Ce-doped LuAG and YAG scintillation layers grown by liquid phase epitaxy

The single crystalline Lu₃Al₅O₁₂ (LuAG) and Y₃Al₅O₁₂ (YAG) garnet layers doped by Ce³⁺ ions were grown by the liquid phase epitaxy from the flux. The effect of the flux composition, growth conditions, and substrate polishing on the layer morphology, creation of defects, and on optical and emission properties of layers was studied. The defects typical of the epitaxial growth are discussed.     

Photoluminescence of zinc oxide modified by nanopowders

The modifying effect of Al₂O₃, Al₂O₃ · CeO₂, ZrO₂, ZrO₂ · Y₂O₃ nanopowders on the photoluminescence spectra of ZnO powder in the 360–660 nm range is investigated. It is found that the introduction of nanoparticles causes a decrease in the ultraviolet band intensity and an increase in the visual spectral band intensity. The change in the intensity of elementary components of the visible range band during modification seems to be explained by the emergence of oxygen and zinc vacancies (V _O⁺ and V _Zn⁻) and interstitial oxygen ions (O _i ⁻).     

Development of ceria-doped zirconia electrolytes with high toughness and ionic conductivity

Development of Y₂O₃ stabilized ZrO₂ electrolytes for solid oxide fuel cell with better mechanical properties was attempted. 3 mol% Y₂O₃ stabilized ZrO₂ doped with 3–15 mol% CeO₂ was investigated in the present work. The results reveal that the toughness and the bending strength of 3–6 mol% CeO₂ doped 3 mol% Y₂O₃–ZrO₂ are much higher than that of 8 mol% Y₂O₃–ZrO₂. The best ionic conductivity observed in 6 mol% ceria-doped 3 mol% Y₂O₃–ZrO₂ electrolyte is better than that of 8 mol% Y₂O₃–ZrO₂ at 800 °C, which indicates the possibility of developing ZrO₂-based electrolyte with enhanced toughness.     

The synthesis of polycrystalline H3O+β″βAl2O3 ceramics from conventional precursor NaKβ″/βAl2O3 powders

H₃O⁺β″Al₂O₃, H₃O⁺/βAl₂O₃ and H₃O⁺β″/βAl₂O₃ /ZrO₂ ceramics of equiaxed, fine-grained microstructure were prepared by conventional synthesis techniques, gas-phase and vapour-phase ion exchange to the potassium form and field-assisted ion exchange in dilute HCl vapour to the hydronium form. The bend strength of the polycrystalline H₃O⁺β″Al₂O₃ and H₃O⁺β″/βAl₂O₃ was > 200 MPa. The conductivity of H₃O⁺β″Al₂O₃, H₃O⁺β″/βAl₂O₃ ZrO₂ was 8×10⁻⁶, 2×10⁻⁶ and 9×10⁻⁷ (Ω cm)⁻¹, respectively, at 25°C. The materials were demonstrated to perform in steam electrolysis cells at 100°C.     

The effect of alumina addition on the conductivity, microstructure and mechanical strength of zirconia — yttria electrolytes

The effect of alumina additions on the ionic conductivity and mechanical properties of 3 and 8 mol% Y₂O₃ - ZrO₂ compositions has been investigated. Such materials are of interest for use in fuel cells and other similar applications. Sintered specimens were characterised by XRD, SEM, impedance spectroscopy, four — probe DC conductivity and mechanical strength measurements. Alumina additions had no affect on the conductivity degradation behaviour at 1000 °C and the activation energy but resulted in an increase in the strength of 8 mol% Y₂O₃ - ZrO₂ composition by about 25%. However, a significant drop in the ionic conductivity well above what could be accounted for by the decrease in the volume fraction of the conducting phase, was observed.     

Y2O3 stabilized ZrO2 thin films deposited by electron beam evaporation: Structural, morphological characterization and laser induced damage threshold

Four kinds of Y₂O₃ stabilized ZrO₂ (YSZ) thin films with different Y₂O₃ content have been prepared on BK7 substrates by electron-beam evaporation method. Structural properties and surface morphology of thin films were investigated by X-ray diffraction (XRD) spectra and scanning probe microscope. Laser induced damage threshold (LIDT) was determined. It was found that crystalline phase and microstructure of YSZ thin films was dependent on Y₂O₃ molar content. YSZ thin films changed from monoclinic phase to high temperature phase (tetragonal and cubic) with the increase of Y₂O₃ content. The LIDT of stabilized thin film is more than that of unstabilized thin films. The reason is that ZrO₂ material undergoes phase transition during the course of e-beam evaporation resulting in more numbers of defects compared to that of YSZ thin films. These defects act as absorptive center and the original breakdown points.     

Preparation and properties of composite ceramic coating containing Al2O3–ZrO2–Y2O3 on AZ91D magnesium alloy by plasma electrolytic oxidation

A composite ceramic coating containing Al₂O₃–ZrO₂–Y₂O₃ was successfully prepared on AZ91D magnesium alloy by plasma electrolytic oxidation (PEO) technique in an alkaline aluminate electrolyte. The morphology, elemental and phase composition, corrosion behavior and thermal stability of the uncoated and coated samples were studied by environmental scanning electron microscopy (ESEM), energy dispersive X-ray spectrometer (EDS), X-ray diffractometer (XRD), electrochemical corrosion test, high temperature oxidation test and thermal shock test. The results showed that the composite ceramic coating was composed of Al₂O₃, c-ZrO₂, t-ZrO₂, Y₂O₃ and some magnesium compounds, such as MgO, MgF₂ and MgAl₂O₄. After PEO treatment, the corrosion potential of AZ91D alloy was increased and the corrosion current density was significantly reduced. Besides, the coated magnesium alloys also showed excellent high temperature oxidation resistance and thermal shock resistance at 500 °C environment.     

Study of directionally solidified ceramics by neutron diffraction methods

The effect of the growth rate of directionally solidified Al₂O₃-Y₃Al₅O₁₂ ceramics on the structural perfection of the two-phase material is studied by low-angle neutron scattering, as well as by constant-wavelength and time-of-flight neutron diffraction methods. When the growth rate is high, the orientation and size of Y₃Al₅O₁₂ needles remain unchanged, while the Al₂O₃ matrix phase decomposes into crystallites. Neutron diffraction methods are viewed as an effective tool for flexible crystal growth control.     

Microstructure and oxidation behaviour of SiC fibre-reinforced Si3N4-AlN-Al2O3-Y2O3 matrix composites

A series of SiC fibre-reinforced Si₃N₄-AlN-Al₂O₃-Y₂O₃ matrix composites with different matrix compositions are fabricated by slurry infiltration followed by hot pressing at 1600°C for 30 min. The diffusion of yttrium and aluminium into fibres is apparent during the high temperature processing. All the as-processed composites show fracture with fibre pull-out. After heat treatment in air at 1000°C for 60 min, composites with minimal Y₂O₃ and Al₂O₃ in the matrix composition demonstrate the fracture behaviour with most extensive fibre pull-out. Composites with the highest aluminium and yttrium oxide content form an yttrium–aluminium–garnet phase and an aluminosilicate glassy phase. The latter phase provides an oxygen diffusion path, resulting in the removal of the carbon-rich interphase by oxidation. This results in catastrophic fracture without fibre pull-out after heat treatment of the composite in air.     

Al2O3-Y2O3-ZrO2三相复合陶瓷的介电谱研究

采用传统的固相反应法,在1400–1500 ℃下烧结,制备得到Al₂O₃-Y₂O₃-ZrO₂三相复合陶瓷.样品的结构、形貌和电性能分别用X射线衍射(XRD)、扫描电子显微镜(SEM)及介电谱表征.XRD表明此三相复合体系无其他杂相,加入Y₂O₃及ZrO₂后使得Al₂O₃成瓷温度降低;SEM表明此体系晶粒直径为200–500 nm,并且样品随烧结温度的升高而变得更加致密,晶界更加清晰;介电损耗谱中出现峰值弛豫现象,根据Cole-Cole复阻抗谱得出其为非德拜弛豫. 关键词： 2O₃-Y₂O₃-ZrO₂三相陶瓷')" href="#">Al₂O₃-Y₂O₃-ZrO₂三相陶瓷 介电弛豫 阻抗谱 热导率     

Integrated chemical process for exothermic wave synthesis of high luminance YAG:Ce phosphors

In this paper, high-luminance yellow-emitting Y₃Al₅O₁₂:Ce³⁺ phosphor (YAG:Ce) microparticles were prepared in a solid flame using a 1.425Y₂O₃+2.5Al₂O₃+0.15CeO₂+k(KClO₃+urea)+mNH₄F precursor mixture (here k is the number of moles of the KClO₃+urea red-ox mixture, and m is the number of moles of NH₄F). The self-sustaining combustion process for the entire reaction sample was provided by the heat generated from the KClO₃+urea mixture. Parametric studies demonstrated that the maximum temperature in the combustion wave varied from 885 to 1200 °C for k=2.0-3.0 mole and m=0-1.5 mole. X-ray analysis results showed that the product obtained in the solid flame consisted of Y₃Al₅O₁₂:Ce³⁺ and KCl phases. Therefore, after dissolving potassium chloride in distillated water, pure-phase YAG:Ce phosphor powder was obtained. The as-prepared YAG:Ce phosphor particles had diameters of 10-25 μm and good dispersity and exhibited luminescence properties comparable to those of YAG:Ce phosphor powders prepared by conventional high-temperature processing.     

Magneto-transport and magnetic properties of (1-x)La0.7Ca0.3MnO3+xAl2O3 composites

We report magneto-transport and magnetic properties of (1-x)La_0.7Ca_0.3MnO₃+xAl₂O₃ composites synthesized through a solid-state reaction method combined with a high energy milling method. Most interestingly, the effective magnetic anisotropy is found to decrease with increase in the non-magnetic insulating Al₂O₃ phase fraction in the composites. In addition, we observed that the magnitude of low-field magnetoresistance arising from spin-polarized tunneling of conduction electrons, as well as that of high-field magnetoresistance, displays a Curie-Weiss law-like behavior. Finally, we found that the temperature dependence of low and high-field magnetoresistance is controlled predominantly by the nature of temperature response of surface magnetization of the particles.     

Phase composition and the structure of (1–<Emphasis Type="Italic">x</Emphasis>)KNO<Subscript>3</Subscript> + <Emphasis Type="Italic">x</Emphasis>Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposites by X-ray diffraction

The phase composition and the structural properties of potassium nitrate KNO₃ and its heterogeneous composites with nanometer-sized powder of aluminum oxide Al₂O₃ have been studied by X-ray diffraction at various concentrations of an Al₂O₃ nanopowder. It is found that, in the (1–x)KNO₃ + xAl₂O₃ nanocomposites, additional high-temperature rhombohedral phase of potassium nitrate (phase III) with lattice parameters a = 5.4644 Å and c = 9.0842 Å. With increasing concentration of Al₂O₃ nanopowder, the content of the main potassium nitrate phase (phase II) is found to significantly decrease, and the relative fraction of the phase III in the total content of the nitrate in the composite composition increases. This phase is assumed to be “frozen” in the nanocomposite at the KNO₃–Al₂O₃ interface. The estimated size of KNO₃ crystallites in the phase III is more than 20 nm.