Formation and mechanical properties of alumina ceramics based on Al<Subscript>2</Subscript>O<Subscript>3</Subscript> micro- and nanoparticles

Alumina micro- and nanopowders with the particle size from 200 μm to 40 nm synthesized by the sol-gel method are studied. The particle size dependence of γ-Al₂O₃→α-Al₂O₃ phase transformation is studied by differential thermal analysis, X-ray diffraction method, and transmission electron microscopy. X-ray diffraction data show that for alumina nanoparticles γ-Al₂O₃→θ-Al₂O₃ phase transformation occurs at 900°C, and for micro-particles it occurs in the temperature range 1150–1200°C. The alumina ceramics produced of alumina nanoparticles is shown to have higher flexural strength under three-point bending than the ceramics produced of micro-particles. The obtained results demonstrate that alumina particle size reduction stabilizes the formation of α-Al₂O₃ at lower temperatures, due to which the grain growth rate decreases and the flexural strength of monolithic oxide ceramics increases.     

EPR study of ordered Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-based aerogel

Samples of oriented aerogel based on aluminum oxide are studied by the electron paramagnetic resonance (EPR) technique under steady-state and pulse conditions. At least two types of paramagnetic centers interacting with Al nuclei on the surface of aerogel are revealed. Their spectra are characterized by the presence or absence of superhyperfine structure in the EPR spectra, respectively. The X-ray irradiation at room temperature gives rise to the formation of additional long-lived paramagnetic centers of the second kind. Their characteristic decay times for the “fast” and “slow” processes are determined. The interaction of induced paramagnetic centers with protons located on the surface of aerogel is revealed.     

Properties of an Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Si interface

The phase chemical composition of an Al₂O₃/Si interface formed upon molecular deposition of a 100-nm-thick Al₂O₃ layer on the Si(100) (c-Si) surface is investigated by depth-resolved ultrasoft x-ray emission spectroscopy. Analysis is performed using Al and Si L_{2, 3} emission bands. It is found that the thickness of the interface separating the c-Si substrate and the Al₂O₃ layer is approximately equal to 60 nm and the interface has a complex structure. The upper layer of the interface contains Al₂O₃ molecules and Al atoms, whose coordination is characteristic of metallic aluminum (most likely, these atoms form sufficiently large-sized Al clusters). The shape of the Si bands indicates that the interface layer (no more than 10-nm thick) adjacent to the substrate involves Si atoms in an unusual chemical state. This state is not typical of amorphous Si, c-Si, SiO₂, or SiO_x (it is assumed that these Si atoms form small-sized Si clusters). It is revealed that SiO₂ is contained in the vicinity of the substrate. The properties of thicker coatings are similar to those of the 100-nm-thick Al₂O₃ layer and differ significantly from the properties of the interfaces of Al₂O₃ thin layers.     

Luminescence properties of transparent ceramics Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Yb

We present the results of studying the luminescence properties of transparent ceramics Y₃Al₅O₁₂:Yb obtained by the vacuum sintering and nanocrystalline technology. In the course of research, we measured the luminescence and luminescence excitation spectra, as well as the temperature and kinetic behavior of luminescence. Our results are analyzed in comparison with the characteristics of corresponding single crystals. We revealed that processes of generation and relaxation of electronic excitations that occur in ceramics, in particular, in the charge transfer state, are similar to processes occurring in crystals. The behavior of two charge-transfer luminescence bands at 340 and 490 nm is studied. In the range 300–600 nm, we revealed a broad emission band of radiation of other type, which is also observed in spectra of undoped ceramics. This broad band is attributed to F⁺ centers. Emission and excitation spectra of charge transfer luminescence at a maximum of the temperature dependence of 100 K are measured for the first time. We found that, upon excitation in the charge transfer band, luminescence in ceramics is more intense than in single crystals with similar concentrations of Yb and has a higher quenching temperature.     

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.     

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.     

Thermal hysteresis of a simulated Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Thermal hysteresis in a simulated Al₂O₃ system has been investigated using a Molecular Dynamics (MD) method. Simulations were done in the basic cube under periodic boundary conditions containing 3000 ions with Born-Mayer type pair potentials. The system was cooled down from 7000 K to 0 K and heated up from 0 K to 7000 K by the same cooling/heating rate of 1.7178×10¹⁴ K/s. The temperature dependence of the system density upon cooling and heating shows thermal hysteresis. The differences between structure and dynamics of the models obtained by cooling (MOBC) and heating (MOBH) at three different temperatures of 2100 K, 3500 K and 5600 K have been detected. Calculations show that the differences in the dynamics of the systems are more pronounced than those in the structure. Furthermore, dynamical heterogeneities in MOBC and MOBH at the temperature of 2100 K have been studied through a non-Gaussian parameter and comparison of partial radial distribution functions (PRDFs) for the 10% most mobile or immobile particles with their corresponding mean ones. Cluster size distributions of the 10% most mobile or immobile particles in MOBC and MOBH at the temperature of 2100 K have been obtained. Calculations show that differences in dynamical heterogeneities are pronounced.     

Al<Subscript>2</Subscript>O<Subscript>3</Subscript> plasma production during pulsed laser deposition

A Nd:YAG laser operating in second harmonic (532 nm), 3 ns pulse duration, 150 mJ pulse energy, and 10 Hz repetition rate, is employed to irradiate Al₂O₃ target placed in high vacuum. The produced plasma is investigated by an ion collector used in time-of-flight configuration and by a mass quadrupole spectrometer, in order to determine the equivalent plasma temperature and the atomic and molecular composition. Pulsed laser deposition technique has been used to produce thin films on different substrates placed close to the target. Different surface analyses, such as energy dispersive X-ray fluorescence (EDXRF), X-ray photoelectron spectroscopy (XPS) and surface profilometry are employed to characterize the produced films. Measurements of ablation yield, plasma equivalent temperature, acceleration voltage and characterization of grown thin films are presented and discussed.     

Synthesis and magnetic properties of FeNi<Subscript>3</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> core-shell nanocomposites

In this study, FeNi₃/Al₂O₃ core-shell nanocomposites, where individual FeNi₃ nanoparticles were coated with a thin layer of alumina, were fabricated by a modified sol-gel method. Several physical characterizations were performed on the samples of FeNi₃/Al₂O₃ nanocomposites with different thickness of Al₂O₃ shell. The encapsulation of FeNi₃ nanoparticles with alumina stops FeNi₃ agglomeration during heat treatment, and prevents interaction among the closely spaced magnetic FeNi₃ nanoparticles. The Al₂O₃ insulating shell improves the soft magnetic properties of FeNi₃. The study of the complex permeability of the samples shows that the real part μ’ of the permeability of the sample with Al molar content of 20% (Al/(Fe+Ni)) is as high as 12, and independent of frequency up to at least 1 GHz. The tunneling magnetoresistance arising from the presence of the Al₂O₃ shell have also been studied.     

Metallic liquid hydrogen and likely Al<Subscript>2</Subscript>O<Subscript>3</Subscript> metallic glass

Dynamic compression has been used to synthesize liquid metallic hydrogen at 140 GPa (1.4 million bar) and experimental data and theory predict Al₂O₃ might be a metallic glass at ∼ 300 GPa. The mechanism of metallization in both cases is probably a Mott-like transition. The strength of sapphire causes shock dissipation to be split differently in the strong solid and soft fluid. Once the 4.5-eV H-H and Al-O bonds are broken at sufficiently high pressures in liquid H₂ and in sapphire (single-crystal Al₂O₃), electrons are delocalized, which leads to formation of energy bands in fluid H and probably in amorphous Al₂O₃. The high strength of sapphire causes shock dissipation to be absorbed primarily in entropy up to ∼400 GPa, which also causes the 300-K isotherm and Hugoniot to be virtually coincident in this pressure range. Above ∼400 GPa shock dissipation must go primarily into temperature, which is observed experimentally as a rapid increase in shock pressure above ∼400 GPa. The metallization of glassy Al₂O₃, if verified, is expected to be general in strong oxide insulators. Implications for Super Earths are discussed.     

Theoretical study of ZnO adsorption and bonding on Al<Subscript>2</Subscript>O<Subscript>3</Subscript> (0001) surface

ZnO adsorption on sapphire (0001) surface is theoretically calculated by using a plane wave ultrasoft pseudo-potential method based onab initio molecular dynamics. The results reveal that the surface relaxation in the first layer Al-O is reduced, even eliminated after the surface adsorption of ZnO, and the chemical bonding energy is 434.3(±38.6) kJ · mol⁻¹. The chemical bond of ZnO (0.185 ± 0.01 nm) has a 30° angle away from the adjacent, Al-O bond, and the stable chemical adsorption position of the Zn is deflected from the surface O-hexagonal symmetry with an angle of about 30°. The analysis of the atomic populations, density of state and bonding electronic density before and after the adsorption indicates that the chemical bond formed by the O²⁻ of the ZnO and the surface Al³⁺ has a strong ionic bonding characteristic, while the chemical bond formed by the Zn²⁺ and the surface O²⁻ has an obvious covalent characteristic, which comes mainly from the hybridization of the Zn 4s and the O 2p and partially from that of the Zn 3d and the O 2p.     

Investigation of luminescence spectra of the Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> and Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce single-crystal films

The luminescence spectra of single-crystal films and bulk crystals of yttrium-aluminum garnet Y₃Al₅O₁₂ and Ce³⁺-activated Y₃Al₅O₁₂ were investigated. It was shown that the room-temperature luminescence intensity of the Ce³⁺-free single-crystal Y₃Al₅O₁₂ film was considerably lower than that of the bulk crystals, while the luminescence intensity of the Ce³⁺ ions in the Y₃Al₅O₁₂:Ce films was considerably higher than that one for the corresponding bulk crystal.     

Experimental study of antiferromagnetic resonance in noncollinear antiferromagnetic Mn<Subscript>3</Subscript>Al<Subscript>2</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript>

The structural and magnetic properties of the mesoporous systems based on silicon dioxide with a regular hexagonal arrangement of pores several microns in length and several nanometers in diameter, which are filled with iron compound nanofilaments in various chemical states, are studied in detail. The studies are performed using the following mutually complementary methods: transmission electron microscopy, SQUID magnetometry, electron spin resonance, Mössbauer spectroscopy, polarized neutron small-angle diffraction, and synchrotron radiation diffraction. It is shown that the iron nanoparticles in pores are mainly in the γ phase of Fe₂O₃ with a small addition of the α phase and atomic iron clusters. The effective magnetic field acting on a nanofilament from other nanofilaments is 11 mT and has a dipole nature, the ferromagnetic–paramagnetic transition temperature is in the range 76–94 K depending on the annealing temperature of the samples, and the temperature that corresponds to the change in the magnetic state of the iron oxide nanofilaments is T ≈ 50–60 K at H = 0 and T ≈ 80 K at H = 300 mT. It is also shown that the magnetization reversal of an array of nanofilaments is caused by the magnetostatic interaction between nanofilaments at the fields that are lower than the saturation field.     

Metastable superconductivity of the Al/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> interface

Superconductivity in the interface region between metallic Al and its oxide, Al₂O₃, has been detected at about 45 K in the measured dynamic magnetic susceptibility.     

Modification of the Al<Subscript>2</Subscript>O<Subscript>3</Subscript> surface by high-energy bismuth ions

This paper reports on an atomic-force microscopy study of the surface of α-Al₂O₃ single crystals irradiated by Bi ions with energies of 710, 557, 269, and 151 MeV. The shape of the radiation defects produced by single ions was established to depend on the ionization energy loss. The threshold ionization density above which the surface topography is observed to change lies in the 27–35 keV/nm interval. Possible mechanisms of defect formation in the thermal-spike model, namely, a phase transition and the creation of thermoelastic stresses in the high-energy ion track, are considered.     

Silver conductor fabrication by laser direct writing on Al<Subscript>2</Subscript>O<Subscript>3</Subscript> substrate

A novel technology for manufacturing circuitry, differing from conventional methods, called laser micro-cladding electronic pastes is presented. In this article, high-quality silver conductors were made on an Al₂O₃ substrate by this method. The process and corresponding mechanisms are described in detail. The experimental results show that the conductive lines produced have a minimum line width of 20 m, which is much smaller than the current limitations of conventional processes. The resistivity can reach the order of 10^-6 cm, which is the same level for pure bulk silver. Optical micrographs and SEM morphology observations were also carried out. PACS 81.15.Fg; 42.70.Hj; 42.62.-b; 42.62.Cf; 61.80.Ba     

Spalling uniaxial strength of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> at high strain rates

In this article research into the uniaxial tensile strength of Al₂O₃ monolithic ceramic is presented. The experimental procedure of the spalling of long bars is investigated from different approaches. This method is used to obtain the tensile strength at high strain rates under uniaxial conditions. Different methodologies proposed by several authors are used to obtain the tensile strength. The hypotheses needed for the experimental set-up are also checked, and the requirements of the set-up and the variables are also studied by means of numerical simulations. The research shows that the shape of the projectile is crucial to achieve successfully tests results. An experimental campaign has been carried out including high speed video and a digital image correlation system to obtain the tensile strength of alumina. Finally, a comparison of the test results provided by three different methods proposed by different authors is presented. The tensile strength obtained from the three such methods on the same specimens provides contrasting results. Mean values vary from one method to another but the trends are similar for two of the methods. The third method gives less scatter, though the mean values obtained are lower and do not follow the same trend as the other methods for the different specimens.     

Effect of annealing temperature on the structural reorganization of Eu<Superscript>3+</Superscript> optical centers in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>-BiOF gel films

The dependence of the structural reorganization of Eu³⁺ optical centers in Al₂O₃-Eu₂O₃-BiOF films on the annealing temperature has been investigated. It is shown by the methods of crystal field theory and computer simulation that the increase in the annealing temperature from 700 to 1100 °C leads to removal of bismuth from Eu-O-Bi complex centers with the C _3V symmetry in the Al₂O₃ structure and the change in symmetry from D ₃ to O _h for a large fraction of EuAlO₃ centers.     

Luminescence in collisions of low-energy ions with graphite and Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Excitation of H⁺, H₂ ⁺, H₃ ⁺, He⁺, and Ar⁺ ions by impact on graphite and Al₂O₃ was investigated by means of emission spectroscopy in the 50–1000 eV energy range of the projectiles. Emission of Balmer series from excited neutral hydrogen is observed for both targets. In addition, for the Al₂O₃ target a continuum emission is observed. The continuum probably originates from excited M_nO_m molecules produced in the collision cascade, when surface atoms bound by ionic bonds are released after the bond breaking caused by neutralization. The spectra obtained under Ar⁺ -bombardment show Ar II lines emitted by backscattered ions.