Zirconia‐Alumina Nanoparticles Prepared by Laser Evaporation: Powder Characterisation by TEM and 27Al MAS NMR

Contrary to predictions of the ZrO₂‐Al₂O₃ phase diagram powders of solid solutions of alumina in zirconia with up to 40 mol% Al₂O₃ are described in the recent literature. Up to now the interpretations of the microstructure of these materials are still inconsistent. Therefore we reinvestigated nanopowders prepared by laser evaporation starting from a mixture of 55 mol% ZrO₂ and 45 mol% Al₂O₃ by analytical high resolution transmission electron microscopy (TEM) and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR). The results reveal that in case of this preparation route a heterogeneous powder system is formed consisting dominantly of nanocrystallites of zirconia with an incorporation of, obviously, only a very small amount of alumina, and that the crystallites are surrounded by an amorphous layer of predominantly alumina. No indication was found that Al³⁺ ions occupy seven‐ or eight‐fold co‐ordinated sites of Zr⁴⁺ ions. A simple kinetic model for the formation of the nanoparticles' microstructure is given.     

First-principles study of the α-Al2O3(0001)/Cu(111) interface

Adhesive energetics and interfacial electronic structures have been computed from first principles for the Cu/Al₂O₃ interface. Recent transmission electron microscopy results of Cu grown by molecular beam epitaxy on Al₂O₃(0001) were helpful in modelling the interfacial atomic structure. We found that Al₂O₃(0001) relaxation effects can lower the work of adhesion W _ad by over a factor of 3. Our computed W _ad value is in reasonably good agreement with experiment, being somewhat larger, as expected from our assumption of a coherent interface. One might begin to understand this metal/ceramic adhesion as a competition between Cu and Al for oxide formation, which is easily won by Al. However this simple picture is complicated by several indications of a significant metallic/covalent component to the Cu/Al₂O₃ adhesive bond.     

Interfacial structure of sub-micron Al2O3 particles in aluminum matrix

The surfaces of ellipsoidal Al₂O₃ particles with average size of 0.15 μm and the interfaces between the Al₂O₃ particles and 1070Al were investigated by transmission electron microscopy (TEM) and high resolution electron microscopy (HREM).The results show that the surfaces of Al₂O₃ particles appear to be polyhedrons consisting of crystal planes with small angle, while every plane of the polyhedrons could be considered as a stepped structure composed of close-packed planes along the close-packed direction. The interfaces of the 0.15 μm Al₂O₃p/1070Al composite bond well, without any interfacial reaction products. It is proposed that there are several kinds of crystallographic orientation relationships between the aluminum matrix and Al₂O₃particles due to the polyhedral structure. In our study, such orientation relationships are found to be {110} _Al ||{1100} _Al2O3 and ?110? _Al ||?1126? _Al2O3 .     

Microstructure and mechanical properties of Al2O3-Al composite coatings deposited by plasma spraying

Al₂O₃ and Al₂O₃-Al composite coatings were prepared by plasma spraying. Phase composition of powders and as-sprayed coatings was determined by X-ray diffraction (XRD), while optical microscopy (OM) and scanning electron microscopy (SEM) were employed to investigate the morphology of impacted droplets, polished and fractured surface, and the element distribution in terms of wavelength-dispersive spectrometer (WDS). Mechanical properties including microhardness, adhesion and bending strength, fracture toughness and sliding wear rate were evaluated. The results indicated that the addition of Al into Al₂O₃ was beneficial to decrease the splashing of impinging droplets and to increase the deposition efficiency. The Al₂O₃-Al composite coating exhibited homogeneously dispersed pores and the co-sprayed Al particles were considered to be distributed in the splat boundary. Compared with Al₂O₃ coating, the composite coating showed slightly lower hardness, whereas the coexistence of metal Al phase and Al₂O₃ ceramic phase effectively improved the toughness, strength and wear resistance of coatings.     

Fabrication of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al structure by nitric acid oxidation at room temperature

A thick Al₂O₃/aluminum (Al) structure has been fabricated by oxidation of Al with 68wt% and 98wt% nitric acid (HNO₃) aqueous solutions at room temperature. Measurements of the Al₂O₃ thickness vs. the oxidation time show that reaction and diffusion are the rate-determining steps for oxidation with 68wt% and 98wt% HNO₃ solutions, respectively. Observation of transmission electron micrographs shows that the Al₂O₃ layer formed with 68wt% HNO₃ has a structure with cylindrically shaped pores vertically aligned from the Al₂O₃ surface to the Al₂O₃/Al interface. Due to the porous structure, diffusion of HNO₃ proceeds easily, resulting in the reaction-limited oxidation mechanism. In this case, the Al₂O₃/Al structure is considerably rough. The Al₂O₃ layer formed with 98wt% HNO₃ solutions, on the other hand, possesses a denser structure without pores, and the Al₂O₃/Al interface is much smoother, but the thickness of the Al₂O₃ layer formed on crystalline Al regions is much smaller than that on amorphous Al regions. Due to the relatively uniform Al₂O₃ thickness, the leakage current density flowing through the Al₂O₃ layer formed with 68wt% HNO₃ is lower than that formed with 98wt% HNO₃.     

Nanocomposites of Poly(vinyl alcohol) Reinforced with Chemically Modified AL2O3: Synthesis and Characterization

The surface of α-alumina (Al₂O₃) nanoparticles was first modified with γ-aminopropyltriethoxy silane as a coupling agent. Then a series of poly(vinyl alcohol)/ surface modified Al₂O₃ nanocomposite suspensions were prepared in ethanol by a simple ultrasonic irradiation process. Composite films with 5, 10, and 15 wt % of inorganic Al₂O₃ nanoparticles were achieved after solvent evaporation. The formation of the composite materials were confirmed by Fourier transform infrared spectroscopy, X-ray diffraction, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and optical transparencies. The FE-SEM and TEM results showed a homogenous dispersion of nanoscale inorganic particles in the poly(vinyl alcohol) matrix. TGA thermographs showed that the thermal stability of the prepared Al₂O₃-reinforced nanocomposites was improved, increasing with increasing content of the nanoparticles. According to the optical transparencies, the optical clarity of poly(vinyl alcohol)/Al₂O₃ nanocomposite films was only slightly affected by the presence of the Al₂O₃ content.     

Shock-wave and conventional deformation of Al and dispersion-hardened Al alloy containing different concentrations of alumina particles

Summary The structure and substructure changes in Al and dispersion-hardened Al alloy are studied after rapid deformation by explosion and slow conventional deformation (cross-rolling and compression) using X-ray diffraction analysis and transmission electron microscopy. Shock wave deformation generates a small dislocation density which does not produce any significant change in the microstructure as well as in the texture of Al and Al alloy containing a different concentration of Al₂O₃ particles (4 and 7%). After slow conventional deformation, in particular after cross-rolling, significant variations are observed due to the nonuniformly distributed high dislocation densities.     

Surface‐enhanced Raman scattering investigations on silver nanoparticles deposited on alumina and titania nanotubes: influence of the substrate material on surface‐enhanced Raman scattering activity of Ag nanoparticles

Silver nanoparticles deposited on various ‘inert’ porous materials (mainly Al₂O₃ and TiO₂) are often used as substrates for surface‐enhanced Raman scattering (SERS) measurements. In this study, we used the sputter deposition technique to cover tubular arrays of Al₂O₃ and TiO₂ with Ag nanoparticles. Raman spectra of pyridine (as a probe molecule) and of two selected dyes (5‐(4‐dimethylaminobenzylidene)rhodanine and 5‐(4‐(dimethylamino)benzylidene)‐3‐(3‐methoxypropyl)rhodanine) adsorbed on fabricated Ag/TiO₂‐n/Ti and Ag/Al₂O₃‐n/Al substrates were measured. We found that the SERS spectra of pyridine adsorbed on Ag nanoparticles deposited on an Al₂O₃‐n/Al substrate are distinctly different from those measured for an Ag/TiO₂‐n/Ti composite. Similar effects were observed for dyes adsorbed on the surface of both composites. The spectral differences between two kinds of composites (Ag/TiO₂‐n/Ti and Ag/Al₂O₃‐n/Al) are discussed in terms of (1) the modified electronic structure of the Ag nanoparticles due to their interaction with different substrate materials and (2) the different atomic topology of the metal particles thus deposited on the surfaces of the substrates. Composite samples were also studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to reveal their characteristic morphological and chemical features. Copyright © 2012 John Wiley & Sons, Ltd.     

Electron microscopy study of Hispanic Terra Sigillata

Two Hispanic Terra Sigillata pottery samples from different workshops – Tricio and Andújar – have been characterized by means of electron microscopy and associated techniques and X-ray diffraction data. The combined information from transmission electron microscopy images, electron diffraction patterns and microchemical analysis has revealed the nature and distribution of the precipitates of the ceramic piece slip, which is a very important part in the characterization of these kind of ceramic wares. Both samples present homogeneously dispersed α-Fe_2-xAl_xO₃ (corundum-type structure) particles embedded in a glassy matrix of SiO₂-Al₂O₃. The Si : Al ratio of the matrix is different in each case, with a higher Al content in the Andújar ceramic sample. Crystallites of spinel – Mg(Al,Fe)₂O₄ – and Al_2-xFe_xO₃ are also detected in both cases. In addition, ilmenite phase (FeTiO₃) and TiO₂ (rutile-type) were observed less frequently. PACS  68.37.Lp; 79.20.Uv; 61.10.Nz     

Fluorination of Al2O3 blocking layer for improving the performance of metal‐oxide‐nitride‐oxide‐silicon flash memory

The characteristics of Al₂O₃ film grown by atomic‐layer deposition as blocking layer with and without fluorine plasma treatment were investigated based on a capacitor structure of Al/Al₂O₃/TaON/SiO₂/Si. The physical structure was studied by transmission electron microscopy, and the chemical composition of the blocking layer was analyzed by X‐ray photoelectron spectroscopy and secondary ion mass spectroscopy. Moreover, the surface roughness of the blocking layer was investigated by atomic force microscopy. Compared with a capacitor with Al₂O₃ blocking layer, the one with fluorinated Al₂O₃ displayed higher programming/erasing speeds, better endurance property and better charge retention characteristic because the fluorination could reduce excess oxygen and traps in the blocking layer, thus forming a larger barrier height at the interface between the charge‐trapping layer and the blocking layer. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electronic structure of Al2O3 from electron energy loss spectroscopy

The electronic structure of Al₂O₃ has been studied by electron energy loss spectroscopy (ELS), and an energy level model of both filled and empty states has been constructed from the ELS and available optical data. For the high temperature pyrolytic α-polycrystalline Al₂O₃ films, the transitions are assumed to originate at the two principal peaks in the valence band density of states and the O(2s) core state, and to terminate on two peaks within the conduction band density of states. We also report energy loss spectra due to excitations out of the deeper Al(2p), Al(2s), Al(1s), and O(1s) core levels. The excitations originating at the Al(2p), Al(2s), and Al(1s) core levels terminate on levels in the conduction band and on an exciton lying about 1 eV below the conduction-band edge.     

X-ray emission study of the electronic structure of nanocrystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Valence states of metal ions and the phase composition of nanocrystalline Al₂O₃ (of the original oxide and the oxide irradiated by high-energy Fe⁺ ions) are studied by using x-ray emission Al L_{2, 3} and O Kα spectra. It is established that the shape of the Al L_{2, 3} spectra strongly changes as one goes from the original (bulk) Al₂O₃ to nanocrystalline oxide, while the O Kα spectra remain practically unchanged. Moreover, irradiation by high-energy Fe⁺ ions results in slight additional changes in the x-ray spectral characteristics of the aluminum oxides under study. The obtained experimental data are compared with the results of theoretical calculations of the electronic structure of α and γ phases of Al₂O₃ performed using the LDA formalism. Using the results of x-ray spectral studies, electronic structure calculations, and x-ray diffraction analysis, it is shown that the revealed spectral differences between the nanocrystalline state of aluminum oxide and the bulk material can be interpreted as a phase transition from the α phase to the γ phase of Al₂O₃ with an addition of bayerite.     

Reaction mechanisms between Al and Fe3O4 powders in the formation of an Al-based metal matrix composite

The reaction mechanisms between Al and Fe₃O₄ powders were investigated. Differential thermal analysis revealed that a two-step displacement reaction between Al and Fe₃O₄ took place during sintering. Initially, the Fe₃O₄ was converted to amorphous FeO at ～720°C and some of the Al was oxidized to amorphous Al₂O₃. In the final stage, when the temperature reached ～840°C, crystalline Al₂O₃ particles were produced in the molten Al–Fe liquid. The effects of cooling rate on the microstructures were studied. When the Al–Fe liquid was furnace-cooled to room temperature, proeutectic Al₃Fe plates, plate-like divorced eutectic Al₃Fe and Al₂O₃ particles were in situ formed in the Al(Fe) matrix. While quenching from 700°C, nanometer-sized Al dendrites and Al–Al₆Fe eutectic lamellae were produced in the Al matrix. However, when it was rapidly quenched from 900°C, the size of the proeutectic Al₃Fe phases was further reduced and Al₆Fe nanorods were found in the Al–Al₆Fe eutectics. A model was proposed to describe the transformation of the Al–Fe intermetallics during solidification.     

Phase transformations in γ-Al(OH)<Subscript>3</Subscript> under heat treatment in air and water vapor

The kinetics and mechanism of phase transitions (PTs) in gibbsite (γ-Al(OH)₃) under heat treatment in air and water vapor (170–550°C) have been investigated by iso-and nonisothermal thermogravimetry, X-ray phase analysis, transmission electron microscopy, ²⁷Al nuclear magnetic resonance, and chemical analysis. It is shown that (i) the gibbsite PT in air involves two interrelated transformations occurring simultaneously: (1) gibbsite → boehmite (γ-AlOOH) and (2) gibbsite → X-ray-amorphous alumina (Al₂O₃); both are implemented through the topochemical mechanism; and (ii) in water vapor only transformation of gibbsite into boehmite occurs (PT-3), which is implemented through the dissolution-precipitation mechanism. The apparent activation energies of the PTs under consideration have been determined.     

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.     

Electronic excitations and defects in nanostructural Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

A time-resolved cathodo-and photoluminescence study of nanostructural modifications of Al₂O₃ (powders and ceramics) excited by heavy-current electron beams, as well as by pulsed synchrotron radiation, is reported. It was found that Al₂O₃ nanopowders probed before and after Fe⁺ ion irradiation have the same phase composition (the γ-phase/δ-phase ratio is equal to 1), an average grain size equal to ～17 nm, and practically the same set of broad cathodoluminescence (CL) bands peaking at 2.4, 3.2, and 3.8 eV. It was established that Al₂O₃ nanopowders exhibit fast photoluminescence (PL) (a band at 3.2 eV), whose decay kinetics is described by two exponential stages (τ₁ = 0.5 ns, τ₂ = 5.5 ns). Three bands, at 5.24, 6.13, and 7.44 eV, were isolated in the excitation spectrum of the fast PL. Two alternate models of PL centers were considered, according to which the 3.2-eV luminescence either originates from radiative relaxation of the P^? centers (anion-cation vacancy pairs) or is due to the formation of surface analogs of the F⁺ center (F _S ⁺ -type centers). In addition to the fast luminescence, nano-Al₂O₃ was found to produce slow luminescence in the form of a broad band peaking at 3.5 eV. The excitation spectrum of the 3.5-eV luminescence obtained at T = 13 K exhibits two doublet bands with maxima at 7.8 and 8.3 eV. An analysis of the luminescent properties of nanostructural and single-crystal Al₂O₃ suggests that the slow luminescence of nanopowders at 3.5 eV is due to radiative annihilation of excitons localized near structural defects.     

Investigation on densification of Al2O3/B4C ceramic by ab initio calculation and experiment

Compared to experiment, the adsorption energies, bonding properties, and electronic structure of two different Al₂O₃/B₄C bridge sites with seven different Al₂O₃ surfaces are investigated by ab initio periodic density functional theory. The Al₂O₃/B₄C ceramic sintered in Ar is synthesized and measured by XRD and TEM. The calculated results reveal that the densification of O_bridge site of Al₂O₃/B₄C surface is better than that of Al_bridge. The Al₂O₃ (1 1 3)/B₄C with O_bridge is the most favorable and stable. The electronic structure shows that the electron hybridization exists between Al, O atoms and C, B atoms. The results indicate that the calculated results are in good agreement with the experiment.     

Characterization of laser-induced plasma plume: Comparison between Al and Al2O3 targets

Characterization of the plasma plume produced by laser ablation from Al and Al₂O₃ targets was carried out on the basis of the line profile analysis of Al(I) (²P°–²S) emission. The spatial distribution and density parameters of electrons and Al atoms in the plume were obtained by comparing observed spectral line profiles with a theoretical calculation. The results showed different behavior for the Al and Al₂O₃ targets. The Al atoms from the Al₂O₃ target were populated in a smaller region than those from the Al target. PACS 52.38.MF; 52.70.Kz; 52.25.Os     

Formation of an encapsulated Fe2O3 nanostructure during mechanochemical interaction of iron oxide and excess alumina

The reasons for an abrupt deceleration of the mechanical synthesis of the composite (Al₂O₃ nanoceramics with inclusions of iron intermetallides) from the (Fe₂O₃ + Al) source mixture at Al excess are explained using Mossbauer spectroscopy and electron microscopy. Dependence of the morphology of the obtained composites on the initial concentrations of the mixture components is considered.     

Structure of Al2O3 thin layers synthesized on the silicon surface by atomic layer deposition

The distribution of the phase and chemical composition at an Al₂O₃/Si interface is studied by depth-resolved ultrasoft x-ray emission spectroscopy. The interface is formed by atomic layer deposition of Al₂O₃ films of various thicknesses (from several to several nanometers to several hundreds of nanometers) on the Si(100) surface (c-Si) or on a 50-nm-thick SiO₂ buffer layer on Si. L _2,3 bands of Al and Si are used for analysis. It is found that the properties of coatings and Al₂O₃/Si interfaces substantially depend on the thickness of the Al₂O₃ layer, which is explained by the complicated character of the process kinetics. At a small thickness of coatings (up to 10–30 nm), the Al₂O₃ layer contains inclusions of oxidized Si atoms, whose concentration increases as the interface is approached. As the thickness increases, a layer containing inclusions of metallic Al clusters forms. A thin interlayer of Si atoms occurring in an unconventional chemical state is found. When the SiO₂ buffer layer is used (Al₂O₃/SiO₂/Si), the structure of the interface and the coating becomes more perfect. The Al₂O₃ layer does not contain inclusions of metallic aluminum, does not vary with the sample thickness, and has a distinguished boundary with silicon.