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     

X-ray diffraction and calorimetric studies of powder nanocrystalline systems based on ZrO<Subscript>2</Subscript>(Y) and Al<Subscript>2</Subscript>O<Subscript>3</Subscript> with second insoluble component

Four nanocrystalline ZrO₂(Y)- and Al₂O₃-based powders synthesized by plasma spray pyrolysis have been studied. It has been shown that the ZrO₂(3Y)-based system with second component Al₂O₃ forms a nonequilibrium solid solution ZrO₂(3Y, Al) with the tetragonal structure. It has been found that the existence of an component (ZrO₂(Y)) insoluble in the coarse-grained state in Al₂O₃-based systems causes the delay of the γ → α transformation and decreases the size of the coherently scattering domains of formed nanosized modifications of Al₂O₃.     

Infrared-to-visible up-conversion emissions and thermometric applications of Er 3+-doped Al 2 O 3

Er³⁺-doped Al₂O₃ has been prepared by a sol–gel method, using aluminium isopropoxide [Al(OC₃H₇)₃]-derived Al₂O₃ sols with addition of erbium nitrate [Er(NO₃)₃·5H₂O]. The phase structure of θ-(Al,Er)₂O₃ phase was obtained for the 0.1 mol. % Er³⁺-doped Al₂O₃ at the sintering temperature of 1273 K. The green and red up-conversion emissions centered at about 523, 545 and 660 nm, corresponding respectively to the ² H _11/2, ⁴ S _3/2→⁴ I _15/2 and ⁴ F _9/2→⁴ I _15/2 transitions of Er³⁺, were detected by a 978-nm semiconductor laser diode excitation. The temperature dependence of green up-conversion emissions was studied over a wide temperature range of 295–725 K, and reasonable agreement between the calculated temperatures obtained by the fluorescence intensity ratio theory and the measured temperature was obtained, which proved that Er³⁺-doped Al₂O₃ has a good potential for the development of high-temperature sensors. It has some advantages compared to glasses due to its higher thermal and mechanical resistance and allows measurements in a large temperature range. PACS 78.55.Hx; 81.40.Tv     

Angular dependence of surface acoustic wave characteristics in AlN thin films on a-plane sapphire substrates

AlN thin films have been grown on a-plane sapphire (Al₂O₃(112̄0)) substrates. X-ray diffraction measurements indicate the films are fully c-plane (0001) oriented with a full width at half maximum of the AlN(0002) rocking curves of 0.92. The epitaxial growth relationships have been determined by the reflection high energy electron diffraction analysis as AlN[11̄00]//Al₂O₃[0001] and AlN[112̄0]//Al₂O₃[11̄00]. Angular dependence of important surface acoustic wave (SAW) characteristics, such as the phase velocity and electromechanical coupling coefficient, has been investigated on the AlN(0001)/Al₂O₃(112̄0) structure. While the SAW is excited at all propagation angles with an angular dispersion of the phase velocity in the range of 5503–6045 m/s, a higher velocity shear-horizontal (SH) mode is observed only at 0°, 105° and 180° off the reference Al₂O₃[11̄00] over a 180° angular period. The phase velocity of the SH mode shows dispersion (6089–6132 m/s) as a function of the SAW wavelength. Temperature coefficients of frequency are also demonstrated for both modes. PACS 81.15.Hi; 77.84.-s; 77.65.Dq     

Electrochemical fabrication of arrayed alumina nanowires showing strong blue emission

Arrayed alumina nanowires having controlled uniform diameters of 30–90 nm and lengths of 2–10 μm have been fabricated electrochemically with a high yield using two-step anodized aluminum oxide membranes as templates. The observed photoluminescence of the arrayed alumina nanowires arising from the emission of F⁺ and F centers is strong and blue-shifted compared with that of porous alumina membranes due to the structural difference of Al₂O₃. Our synthesized alumina nanowires are also found to be chemically more stable than the templates.     

Electrical properties of Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>-based composite systems

Composite electrolytes are well-known multiphase systems and exhibit maxima in the conductivity at certain second-phase concentration. An attempt has been made to investigate a number of sodium sulfate (Na₂SO₄)-based composite systems. The dispersoids that have been used are MgO, Al₂O₃, and SiO₂. The samples have been characterized using impedance spectroscopy, X-ray diffraction, and differential scanning calorimetry. The maximum conductivity has been observed for MgO dispersed system, and the percolation threshold has been observed at 30-mol% dispersoid, MgO concentration. Interestingly, two maxima have been observed in case of the Na₂SO₄–SiO₂ and Na₂SO₄–Al₂O₃ composite systems. In the Na₂SO₄–SiO₂ system, the first maximum occurs at lower concentration, i.e., in the range between 10 and 20 mol%, whereas the second occurs at the 40-mol% dispersoid concentration. For the Na₂SO₄–Al₂O₃ system, although slightly indistinguishable, two peaks in the conductivity vs composition plot have been observed around 12- and 30-mol% Al₂O₃ concentrations.     

Interface interaction and wetting of Sc<Subscript>2</Subscript>O<Subscript>3</Subscript> exposed to Cu–Al and Cu–Ti melts

Scandia is a thermodynamically stable oxide and could be used as a structural material for a crucible in order to avoid a melt contamination. In the present study wetting experiments of Cu–Al and Cu–Ti melts on Scandia substrate were preformed at 1423 K by a sessile drop method. It was established that Al and Ti additions lead to the improved wetting and that the final contact angle decreases with increasing the additives concentration. For Al containing melts, the contact angle changes gradually with time, and a relatively thick interaction layer, which consists of Al₂O₃, Sc₂O₃, and metallic channels, was formed at the Sc₂O₃/Cu–Al interface. For Ti containing melts, the final contact angle is achieved already during heating, and an extremely thin layer based on a Ti–Sc–O compound was detected by AES at the Sc₂O₃/Cu–Ti interface. The results of a thermodynamic analysis, which takes into account the formation free energy of the oxides, involved in the systems, and the thermodynamic properties of the liquid solutions are in a good agreement with the experimental observations.     

A study of the optical absorption induced in vacuum thermolysis of aluminum trihydroxide

The diffuse reflection spectroscopy technique was used to investigate the color centers (CC) in the products of thermolysis and photolysis of disperse Al(OH)₃ in a vacuum. The spectra were recorded in situ in the region of 2.5–6.0 eV and 4000–12,000 cm⁻¹. It was found that in thermolysis of Al(OH₃) production of Al is accompanied, by transformation of the IR spectra of the compound and overtone vibrations of OH groups and by the appearance of an absorption band (AB) at 4.0 eV with a shoulder at 4.4 eV. A similar AB is induced by UV irradiation of Al(OH)₃ in a vacuum. In the position of the maximum and shape, the AB at 4.0 eV in aluminum oxide produced by thermolysis of Al(OH)₃ coincides with the AB of CC responsible for light- and temperature-stimulated degradation of white anode oxide coatings on Al(Al-AOC). This suggests that in Al-AOC, CC are formed in decay of structural O_mH_n groups. In Al oxide and in Al-AOC, their nature is discussed with the use of data on optical absorption of radiation-induced defects in Al₂O₃. Research Institute of Physics at St. Petersburg State University, St. Petersburg 1, Ul’yanovskaya St., Petrodvorets St. Petersburg, 198904, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 400–404, May–June, 1998.     

The production of nickel–alumina composite coating via electroplating

A series of electroplating works have been conducted to investigate the best condition for the coelectrodeposition of nickel–alumina (Ni/α–Al₂O₃) composite coating. Co-electrodeposition was done onto mild steel as cathode at ambient temperature (27°C) with current density of 30 mA/cm² under α-Al₂O₃ concentration of 2 g/l and various agitation speeds of 50, 100, 150, 200, and 250 rpms. The cross-section of the composite coatings portrayed α-Al₂O₃ particles was co-deposited. Under field emission scanning electron microscopy analysis, the coating shows a coarse surface morphology, while cross-sectional microstructures shows a compact embedding of α-Al₂O₃ particle in the Ni matrix. Elemental analysis by EDX detected the presence of Ni and α-Al₂O₃. Vickers microhardness testing shows that the coating hardness increases almost 60% at the highest agitation speed, i.e., 250 rpm.     

Preparation and characterization of ferroelectric SrBi2Ta2O9 thin films on Si using Al2O3 buffer layers

SrBi₂Ta₂O₉ (SBT) thin films were prepared on p-type Si(100) substrates with Al₂O₃ buffer layers. Both the SBT films and the Al₂O₃ buffer layers were deposited by a pulsed laser deposition technique using a KrF excimer laser. An Al prelayer was used to prevent Si surface oxidization in the initial growth stage. It is shown that Al₂O₃ buffer layers effectively prevented interdiffusion between SBT and Si substrates. Furthermore, the capacitance–voltage (C-V) characteristics of the SBT/Al₂O₃/Si heterostructures show a hysteresis loop with a clockwise trace, demonstrating the ferroelectric switching properties of SBT films and showing a memory window of 1.6 V at 1 MHz. Received: 17 July 2000 / Accepted: 16 August 2000 / Published online: 30 November 2000     

Structural and catalytic properties of ZnO and Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanostructures loaded with metal nanoparticles

Nanostructured zinc oxide (ZnO) nanobelts and aluminum oxide (Al₂O₃) nanoribbons have been grown successfully from the vapor phase. XRD results confirmed the purity and the high quality of the formed crystalline materials. TEM images showed that ZnO nanostructures grew in the commonly known tetrapod structure with nanobelts separated from the tetrapods with an average width range of 10–30 nm and a length of about 500 nm. Al₂O₃ nanostructures grew in the form of nanoribbons with an average width range of 20–30 nm and a length of up to 1 μm. The catalytic oxidation of CO gas into CO₂ gas over the synthesized nanostructures is also reported. Higher catalytic activity was observed for Pd nanoparticles loaded on the ZnO nanobelts (100% conversion at 270 °C) and Al₂O₃ nanoribbons (100% conversion at 250 °C). The catalytic activity increased in the order Cu < Co < Au < Pd for the metal-loaded nanostructures. The preparation methods could be applied for the synthesis of novel nanostructures of various materials with novel properties resulting from the different shapes and morphologies.     

Phase composition and structure of nanocrystalline powders based on ZrO<Subscript>2</Subscript>(Y) and Al<Subscript>2</Subscript>O<Subscript>3</Subscript> obtained by plasma spray pyrolysis

It is shown that a nonequilibrium solid solution ZrO₂(3Y, Al) with tetragonal structure is formed in systems based on ZrO₂(3Y) with Al₂O₃ as a second component. A delay in the γ → α Al₂O₃ transformation and a reduction in the size of the coherently scattering domain of modifications are observed in systems based on Al₂O₃ with ZrO₂(Y) as a second component.     

Al2O3 thin films by plasma-enhanced chemical vapour deposition using trimethyl-amine alane (TMAA) as the Al precursor

2 O₃ thin films by plasma-enhanced chemical vapour deposition (PECVD) using trimethyl-amine alane (TMAA) as the Al precursor. The thin films were deposited on both Si and quartz silica (SiO₂) substrates. Deposition rates were typically 60 Å min^-1 keeping the TMAA temperature constant at 45 °C. The deposited Al₂O₃ thin films were stoichiometric alumina with low carbon contamination (0.7–1.3 At%). The refractive index ranged from 1.54 to 1.62 depending on the deposition conditions. The deposition rate was studied as a function of both the RF power and the substrate temperature. The structure and the surface of the deposited Al₂O₃ thin films were studied using X-ray diffraction, atomic force microscopy (AFM) and scanning electron microscopy (SEM). Received: 20 May 1997/Accepted: 12 June 1997     

Optical and spectroscopic characterization of Nd-doped aluminosilicate fiber preforms made by the MCVD method using chelate delivery

4 F_3/2 level of Nd³⁺ in aluminosilicate optical fiber preforms after 807-nm excitation are reported in the temperature range from 15 °C to 500 °C for Nd₂O₃ concentrations in the range from 0.2 to [%wt]0.9 and Al₂O₃ concentrations of between [%wt]3.8 and [%wt]8. At room temperature it is observed that for concentrations of less than [%wt]0.6 Nd₂O₃ the fluorescence decay is approximately exponential; for the higher Nd₂O₃ concentrations the decay is increasingly bi-exponential. We have identified a “slow” (≈500 μs) and a “fast” (≈100 μs) decay time; the slow decay is attributed to isolated ions and the faster decay to energy transfer between homogeneously dispersed ions. The measured 1/e folding fluorescence decay time τ decreases slowly at a constant rate of -0.08±0.007 μs/K for [%wt]0.9 Nd₂O₃. It is shown that increasing the Al₂O₃ concentration tends to suppress this temperature quenching effect. A radiative decay time of 640 μs is obtained by Judd–Ofelt analysis. Received: 24 October 1997/Revised version: 2 February 1998     

Adsorption of titanium,chromium, and copper atoms on thin aluminum and magnesium oxide film surfaces

Methods of Auger electron spectroscopy (AES), spectroscopy of characteristic electron energy losses (SCEEL), slow electron diffraction (SED), and contact potential difference (CPD) in ultrahigh vacuum are used to investigate the adsorption-emission properties and stability of two-component film systems formed by putting of Ti, Cr, and Cu atoms on MgO–Mo(011) and Al₂O₃–Mo(011) surfaces. All atoms have the properties of electronegative adsorbates. Continuous adatom monolayers are formed on the Al₂O₃–Mo(011) system surface, and three-dimensional islands are formed on the MgO–Mo(011) surface. The properties of monoatomic films on the oxide layer surface are close to those observed for bulk materials. No radical changes of the system properties are detected with increasing dielectric layer thickness. The thermal stability of the newly formed structures decreases in the order Ti, Cr, Cu, Al₂O₃(MgO), and Mo(011).     

Tunable optical parametric oscillator based on a KTP crystal,pumped by a pulsed Ti<Superscript>3+</Superscript>:Al<Subscript>2</Subscript>O<Subscript>3</Subscript> laser

We present the characteristics of an optical parametric oscillator based on a KTP crystal, pumped with noncritical phase matching by a pulsed Ti³⁺:Al₂O₃ laser, tunable in the range 677–970 nm. Tunable generation of signal and idler waves is obtained in the ranges 1030–1390 nm and 2690–3050 nm respectively. The efficiency of conversion of the pump to the signal wave is ≈23%, which for pulses of duration ≈8 nsec ensures an energy in the range 1.0–11.5 mJ. The width of the emission spectrum for the signal wave is within the range 0.8–1.8 nm and is predominantly determined by the linewidth of the Ti³⁺:Al₂O₃ pump laser. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 3, pp. 351–356, May–June, 2007.     

Magnetic properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.47</Subscript>Al<Subscript>0.03</Subscript>O<Subscript>2</Subscript> as positive electrode for Li-ion batteries

The layered LiNi_0.5Mn_0.47Al_0.03O₂ was synthesized by wet chemical method and characterized by X-ray diffraction and analysis of magnetic measurements. The powders adopted the α-NaFeO₂ structure. This substitution of Al for Mn promotes the formation of Li(Ni_0.47²⁺Ni_0.03³⁺Mn_0.47⁴⁺Al_0.03³⁺)O₂ structures and induces an increase in the average oxidation state of Ni, thereby leading to the shrinkage of the lattice unit cell. The concentration of antisite defects in which Ni²⁺ occupies the (3a) Li lattice sites in the Wyckoff notation has been estimated from the ferromagnetic Ni²⁺(3a)–Mn⁴⁺(3b) pairing observed below 140 K. The substitution of 3% Al for Mn reduces the amount of antisite defects from 7% to 6.4–6.5%. The analysis of the magnetic properties in the paramagnetic phase in the framework of the Curie–Weiss law agrees well with the combination of Ni²⁺ (S = 1), Ni³⁺ (S = 1/2) and Mn⁴⁺ (S = 3/2) spin-only values. Delithiation has been made by the use of K₂S₂O₈. According to this process, known to be softer than the electrochemical one, the nickel ions in the (3b) sites are converted into Ni⁴⁺ in the high spin configuration, while Ni²⁺(3a)–Mn⁴⁺(3b) ferromagnetic pairs remain, as the Li⁺(3b) ions linked to the Ni²⁺(3a) ions in the antisite defects are not removed. The results show that the antisite defect is surrounded by Mn⁴⁺ ions, implying the nonuniform distribution of the cations in agreement with previous NMR and neutron experiments.     

Preparation and reactivity of aluminum nanopowders coated by hydroxyl-terminated polybutadiene (HTPB)

HTPB-coated aluminum (Al) nanopowders were prepared by laser-induction complex heating. The characterization of the nanopowders was revealed using transmission electronic microscopy (TEM), high-resolution transmission electronic microscopy (HRTEM), X-ray diffraction analysis (XRD) and Fourier transform infrared (FTIR) spectrometry. Results showed that HTPB-coated Al nanopowders have a core-shell structure with size ranging from 30 to 100 nm and organic HTPB exists in HTPB-coated Al nanopowders. Differential scanning calorimeter (DSC) and thermal gravimeter (TG) analysis of the HTPB-coated Al nanopowders and Al₂O₃-passivated Al nanopowders stored for 2 years in ambient environment indicated that the reactivity and stability of HTPB-coated Al nanopowders outperform Al₂O₃-passivated Al nanopowders. These findings demonstrate that HTPB is a suitable surface coating material for Al nanopowders.     

Permittivity and conductivity of triglycine sulfate films on Al/SiO2 and α-Al2O3 substrates

Triglycine sulfate (TGS) films have been prepared by evaporation from a saturated aqueous solution on substrates of fused quartz coated by a layer of thermally deposited aluminum (Al/SiO₂) and white sapphire (α-Al₂O₃) on whose surface interdigital electrodes have been deposited by photolithography. The TGS films have a polycrystalline structure made up of blocks measuring 0.1–0.3 mm (Al/SiO₂) and 0.1 × 1.0 mm (α-Al₂O₃). The polar axis in the blocks is mostly confined to the substrate plane. The temperature dependences of the capacitance and dielectric losses normal to and in the film plane have maxima at the temperature coinciding with that of the ferroelectric phase transition in a bulk crystal, T _c . The low-frequency conductivity G in TGS/Al/SiO₂ structures displays a frequency dispersion described by the relation G ∼ ω ^s (s ≈ 0.82). The conduction can be tentatively ascribed to the hopping mechanism involving localized carriers with a ground state energy of 0.8–0.9 eV. At temperatures above and below T _c , the low-frequency conductivity in TGS/α-Al₂O₃ films operates through a thermally-activated mechanism with an activation energy of 0.9–1.0 eV. At the phase transition, an additional contribution to conductivity appears in TGS/α-Al₂O₃ films with a dispersion G ∼ ω^0.5, which can be associated with domain-wall relaxation.     

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