Simple identification of Al2O3 and MgO·Al2O3 spinel inclusions in steel using X-ray-excited optical luminescence

Nonmetallic inclusions in steel cause problems in steel products and steel production. In particular, an analysis of Al₂O₃ and MgO·Al₂O₃ spinel inclusions is important since they are one of the most harmful inclusions. A rapid and simple analysis of nonmetallic inclusions is required as the conventional analytical methods for nonmetallic inclusions are time-consuming. In this study, we propose a simple method to identify Al₂O₃ and MgO·Al₂O₃ spinel inclusions in steels. X-ray-excited optical luminescence (XEOL) analysis was selected as a promising method because it can rapidly identify sizes, shapes, and compositions of nonmetallic inclusions and can be performed in air. A model steel sample prepared by heating a mixture of Fe, Al, and MgO powders at 1550°C in argon atmosphere was used. XEOL images of the model steel sample showed that Al₂O₃ inclusions emitted blue and red luminescences. Using a filter attached to the camera, blocking light in the wavelength region above 650 nm, only the blue luminescence of the Al₂O₃ inclusions was observed. This was implemented as the luminescences of the Al₂O₃ inclusions appeared in both blue and red regions at wavelengths of 350, 485, 695, and 750 nm; consequently, the luminescences at 695 nm and 750 nm were blocked by the filter. In contrast, MgO·Al₂O₃ spinel inclusions emitted green luminescence (peak at 520 nm), unaffected by the filter. This indicates that we can simply identify Al₂O₃ and MgO·Al₂O₃ spinel inclusions by an XEOL image in the wavelength range of 420–650 nm.     

Cr3+ doped Al2O3 nanoparticles: Effect of Cr3+ content in intensifying red emission

Cr³⁺-doped α-Al₂O₃ nanoparticles (Al_2−xCr_xO₃, 0.005 ≤ x ≤ 0.05) were synthesized by co-precipitation method. X-ray diffraction (XRD) patterns of Cr³⁺:Al₂O₃ nanoparticles revealed the crystallite size of ∼53 nm and electron microscopy (SEM & TEM) confirmed the spherical nanoparticle formation. Diffuse reflectance spectra (DRS) displayed peaks at 406 and 558 nm corresponding to the Cr³⁺ transitions which became prominent with the increase in Cr³⁺ concentration which was also evidenced by the gradually increasing pink coloration of the samples. Photoluminescence (PL) studies showed the sharp red emission at 694 nm (ruby line) which was observed for all samples. The Dq/B value for all samples was found to be greater than 2.3 confirming the presence of Cr³⁺ ions in the octahedral sites. Chromaticity diagrams displayed the maximum red appearance for the sample with x = 0.01 and a lifetime of 4 ms. The synthesized Cr³⁺:Al₂O₃ nanoparticles with smaller crystallite sizes and narrow near monochromatic emission can be used in various applications including sensing, lasing, and bioimaging applications.     

Characteristics of LiAlO2 – Radioluminescence and optically stimulated luminescence

Radioluminescence (RL) and optically stimulated luminescence (OSL) results of LiAlO₂ were compared with Al₂O₃:C. For blue (470 nm) optical stimulation, RL + OSL signal in LiAlO₂ exhibited a sharp initial increase followed by a decay within the first 20 s of continuous wave (CW)-OSL and a very slow increase thereafter. The RL + OSL signal was about 1.25 times of its RL signal in LiAlO₂ as compared to 2.5 times in Al₂O₃:C. With the continued beta irradiation, the RL signal exhibited a faster growth in LiAlO₂ than that in Al₂O₃:C. Emission spectrum of LiAlO₂ exhibited multiple emission peaks in the range from 320 to 380 nm as against 410 nm of Al₂O₃:C. RL and OSL emission spectra were similar in both LiAlO₂ and Al₂O₃:C. The intense RL in LiAlO₂ (about 300 times of that of its background signal) for a beta ray dose rate of 4.6 mGy/s appears attractive for radiation dosimetry including real time/online dosimetry and dose mapping.     

Effects of Zr impurity on microscopic behavior of Hf metal

Hf metal with ∼ 3 wt% Zr impurity has been reinvestigated by perturbed angular correlation (PAC) spectroscopy using a LaBr₃(Ce)–BaF₂ detector set up to understand the microscopic behavior of this metal with temperature. From present measurements, five quadrupole interaction frequencies have been found at room temperature where both pure hcp fraction (∼33%) with 12 nearest neighbor Hf surrounding the probe ¹⁸¹Hf atom and the probe–impurity fraction (∼33%) corresponding to 11 nearest neighbor Hf plus one dissimilar Zr atom are clearly distinguished. At room temperature, the results for quadrupole frequency and asymmetry parameter are found to be ω_Q=51.6(4) Mrad/s, η=0.20(4) for the impurity fraction and ω_Q=46.8(2) Mrad/s, η=0 for the pure fraction with values of frequency distribution width δ=0 for both components. At 77 K, only 1 NN Zr impurity (∼93%) and pure hcp (∼7%) components have been found with a value of δ ∼ 10% for the impurity fraction. A drastic change in microstructural configuration of Hf metal is observed at 473 K where the impurity fraction increases to ∼ 50% and the pure hcp fraction reduces to ∼ 15% with abrupt changes in quadrupole frequencies for both components. The pure fraction then increases with temperature and enhances to ∼50% at 973 K. In the temperature range 473–973 K, quadrupole frequencies for both components are found to decrease slowly with temperature. Using the Arrhenius relation, binding energy (B) for the probe–impurity pair and the entropy of formation are measured from temperature dependent fractions of probe–impurity and pure hcp in the temperature range 473–773 K. The three other minor components found at different temperatures are attributed to crystalline defects.     

Luminescence behaviour and Raman characterization of dendritic agate in the Dereyalak village (Eski?ehir), Turkey

Results are presented for the cathodoluminescence (CL), X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and simultaneously two thermal analyses of (DTA/TGA) spectroscopy of dendritic agate which occurs in the Pliocene polymictic conglomerates of the Höyüklü Formation, North West of the Dereyalak village (Eskisehir, Turkey). Micro-Raman measurements were performed on dendritic agate and then strong quartz and moganite peaks were identified at 465 and 501 cm⁻¹, respectively. Thermal analysis shows the loss of water and hydroxyl units occurs in 2 distinct stages; at 796 and 808 °C. Spatially resolved CL results at room temperature were recorded for chosen 3 different areas. Grey area (100% SiO₂) displays the lowest CL emission. Brown area (99.7% SiO₂ and 0.3% Fe₂O₃) contains exsolved non-detected ironed phases such as goethite-lepidochrocite to explain the brown colour and the iron point substitutional defects attributed to the 643 nm CL emission. White outer (98.7% SiO₂ and 1.3% Al₂O₃) would be strongly disordered as observed in the “amorphous” Raman spectrum containing as inferred from the spectrum CL on the outer areas, particularly non-bridging oxygen hole centres (NBOHC) (317 nm) and [AlO₄]°/H⁺ (380 nm) centres produced by large amounts of aluminium in the lattice (1.33% Al₂O₃). When it comes to collect the data in the time resolved CL spectrum, at least three broad emission bands were detected in: a green band of low intensity at about 496 nm, intense orange band at about 600 nm, and a red band at 670 nm. The CL emission at 670 nm shows some relationships between the hydroxyl or alkali content and the abundance of O₂ (super 3-) centres and E′₁ centres. Another conspicuous observed feature in the CL spectra of agates is the existence of an orange emission band centred at around 600 nm. The predominance of the yellow CL emission band and the high concentration of E′₁ centres are typical for agates formed by acidic volcanism processes.     

Luminescent vacuum ultraviolet spectroscopy of Cr3+ ions in nanostructured aluminum oxide

Impurity Cr³⁺ centers in submicron and nanostructured Al₂O₃ crystals of different phase compositions at temperatures of 300 and 7.5 K were studied by a luminescent vacuum ultraviolet (VUV) spectroscopy method. Photoluminescence (PL) spectra and the energies of ²E, ⁴T₂, and ⁴T₁ excited states of Cr³⁺ ion depend on the type of crystalline samples phase. The PL excitation spectrum of R-line in α-Al₂O₃ nanoscale crystals is formed by intracenter transitions (2.5–5.5 eV region), by charge transfer band (6.9 eV) and by effective formation of impurity-bound excitons (9.0 eV region). Such impurity-bound excitons correspond to O₂p→Al₃s electron transition in surroundings of an impurity Cr³⁺ center. The efficiency of impurity-bound excitons formation decreases with the increase of the grain size above 100 nm. The size dependence is noticeably shown in PL excitation spectra in VUV region. Excitons bound to impurity centers do not appear in nanostructured δ+θ-Al₂O₃ crystals. The effect of the electron excitation multiplication is observed distinctly in nanostrucured α-Al₂O₃ at an excitation energy above 19 eV (more than 2E_g).     

Orange emissive Sr3Al2O5Cl2:Eu2+ phosphor for warm-white light-emitting diodes

Orange-emitting Sr₃Al₂O₅Cl₂:Eu²⁺ phosphors were synthesized by a high-temperature solid-state reaction. The excitation spectrum shows a broad band from the UV region to the blue region. The emission spectrum shows strong orange emission peaking at 610 nm, attributed to the d–f transition of the Eu²⁺ ion. By combining the Sr₃Al₂O₅Cl₂:Eu²⁺ phosphor with 420 nm and 460 nm chips, three white light-emitting diodes (LEDs) were fabricated. The warm-white LEDs show color rendering indexes of 76, 66 and 90 with color temperatures of 2447, 3546 and 4300 K, respectively. This new phosphor exhibits the potential to act as a single host doped with Eu²⁺ phosphor for UV or blue chip excited white LEDs.     

Optical properties of Ag–Al2O3 nano-array composite structure

Ag/Al₂O₃ nano-array composite structures were obtained by alternating current (AC) electrodeposition of Ag into the pores of anodic alumina membrane (AAM). The ordered wire-grid structure of Ag nanowires formed along a preferential direction, typically 20 nm in diameter, was fabricated. XRD revealed that Ag₂O is also preserved in the pores of AAM. Optical properties of Ag/Al₂O₃ prepared at different annealing temperatures were measured by using spectrometer. Transmission spectra indicate that the transmittance of Ag/Al₂O₃ increases obviously with the increasing of annealing temperature. Polarization spectra indicate that Ag/Al₂O₃ has good polarization in the range of 900–2000 nm, and the extinction ratio increases with the increasing of the annealing temperature or incident angle.     

Development of a 2D dosimetry system based on the optically stimulated luminescence of Al2O3

A laser-scanning 2D dosimetry system based on the Optically Stimulated Luminescence (OSL) signal from Al₂O₃ films was built and demonstrated. The main challenge of using the OSL from Al₂O₃ for 2D dosimetry by laser scanning is the long lifetime (∼35 ms) of the main luminescence centers in this material (F-centers). In this work, we demonstrated the possibility of performing 2D dosimetry by laser scanning using a combination of the fast UV emission of F⁺-centers (lifetime <7 ns) and the slow F-center emission of Al₂O₃:C, and an algorithm to correct for the slow F-center luminescence lifetime. We also investigated the possibility of using Al₂O₃:C,Mg, to take advantage of its greater F⁺-center emission compared to Al₂O₃:C. Results from 6 MV photon beam irradiations from a clinical linear accelerator were compared to radiographic and radiochromic film profiles showing a good qualitative agreement.     

Photoluminescence and radioluminescence study of NaMgF3:Eu nanoparticles

Photoluminescence (PL) and radioluminescence (RL) measurements were made on small (∼25 nm) NaMgF₃ nanoparticles doped with Eu concentrations ranging from 0.1% to 5%. We find that they contained Eu³⁺, Eu²⁺, and an additional unidentified defect with a broad PL emission ∼470 nm. Similar to previous measurements on larger (57 nm–77 nm) NaMgF₃:Eu nanoparticles with 1% Eu and 5% Eu, we find that the PL lifetime decreases with increasing Eu concentration that can be attributed to Eu energy transfer to non-radiative recombination sites. However, there is no change in the fraction of Eu³⁺ distorted sites. The ∼470 nm PL defect peak was also reported for larger nanoparticles, which suggests that this peak arises from similar unidentified point defects. However, the activated non-radiative decay for the small nanoparticles has a significantly lower activation energy. The Eu³⁺ RL decreases by only 2.3% at 10 kGy for low Eu concentrations.     

Effect of alumina addition on the microstructure and grain boundary resistance of magnesia partially-stabilized zirconia

The electrical properties of 9 mol% MgO–ZrO₂ (Mg-PSZ) with 1 mol% Al₂O₃ and the mechanisms for electrical degradation were investigated using structural, morphological, and electrochemical analyses. The addition of Al₂O₃ caused an increase in both the monoclinic and the Mg-rich phases at the grain boundaries in the Mg-PSZ. Coarse grains larger than 20 μm and an intergranular layer composed of the Mg-rich phase were identified in a specimen sintered at 1600 °C. This specimen exhibited a minimum of ionic conductivity (4.98 × 10⁻⁴ S cm⁻¹ at 700 °C) due to the grain boundary resistance (245 Ω cm²), which dominated the overall resistance. A similar trend was observed over the entire temperature range (600–1500 °C). An intergranular siliceous impurity (SiO₂) was present in conjunction with the Mg-rich phase. This impurity and the Mg-rich phase acted as a barrier layer for oxygen ion diffusion. The presence of the intergranular phases (i.e. the monoclinic and Mg-rich phases) contributed to the degradation of the ionic conductivity in Mg-PSZ with an Al₂O₃ addition.     

Preparation of ZnO–Al2O3 Particles in a Premixed Flame

Zinc oxide (ZnO) and alumina (Al₂O₃) particles are synthesized by the combustion of their volatilized acetylacetonate precursors in a premixed air–methane flame reactor. The particles are characterized by XRD, transmission electron microscopy, scanning mobility particle sizing and by measurement of the BET specific surface area. Pure (-)alumina particles appear as dendritic aggregates with average mobile diameter 43–93 nm consisting of partly sintered, crystalline primary particles with diameter 7.1–8.8 nm and specific surface area 184–229 m²/g. Pure zinc oxide yields compact, crystalline particles with diameter 25–40 nm and specific surface area 27–43 m²/g. The crystallite size for both oxides, estimated from the XRD line broadening, is comparable to or slightly smaller than the primary particle diameter. The specific surface area increases and the primary particle size decreases with a decreasing flame temperature and a decreasing precursor vapour pressure. The combustion of precursor mixtures leads to composite particles consisting of zinc aluminate ZnAl₂O₄ intermixed with either ZnO or Al₂O₃ phases. The zinc aluminate particles are dendritic aggregates, resembling the alumina particles, and are evidently synthesized to the full extent allowed by the overall precursor composition. The addition of even small amounts of alumina to ZnO increases the specific surface area of the composites significantly, for example, zinc aluminate particles increases to approximately 150 m²/g. The gas-to-particle conversion is initiated by the fast nucleation of Al₂O₃ or ZnAl₂O₃, succeeded by a more gradual condensation of the excess ZnO with a rate probably controlled by the cooling rate for the flame.     

Infrared spectra of catalysts and adsorbed molecules

The infrared absorption spectra of water adsorbed on Al₂O₃ and NiO-Al₂O₃ catalysts have been studied in the range 4000–1200 cm^–1. For all the catalysts, broad bands are observed at 3400 and 1640 cm^–1, characteristic of the stretching and bending vibrations of the OH groups in liquid water. The bands observed in the spectrum of alumina prepared from suspension in isopropyl alcohol are produced by water molecules and isopropyl alcohol molecules absorbed on the catalyst surface. The influence of treatment with heavy water and thermal treatment on the position of the infrared absorption bands in the spectrum of alumina is discussed.     

Investigation of magnetic properties of interacting Fe2O3 nanoparticles

The magnetic properties of Fe₂O₃ nanoparticles (average diameter ∅≅3 nm) in alumina (68% Fe₂O₃ in weight) have been investigated by magnetization measurements. The results indicate a superparamagnetic behavior of interacting particles, which block with decreasing temperature (the zero-field-cooled susceptibility shows a maximum at T≅145 K) with a distribution of relaxation times. A change of magnetic regime is observed below ∼60 K, due to the increasing interparticle interactions and local surface anisotropy.     

Sonochemical synthesis of supersaturated Ga–Al liquid-alloy fine particles and Al3+-doped γ-Ga2O3 nanoparticles by direct oxidation at near room temperature

In this study, we investigated the fabrication of supersaturated gallium (Ga)–aluminum (Al) liquid alloy and Al³⁺-doped γ-Ga₂O₃ nanoparticles (NPs) at near room temperature (60 °C) using sonochemical and sonophysical effects. Supersaturated Ga–Al liquid alloy microparticles (D_av = 1.72 µm) were formed and stabilized at 60 °C by the thermal nonequilibrium field provided by sonochemical hot spots. Compared with liquid Ga, supersaturated Ga–Al liquid alloy was rapidly oxidized to a uniform oxide without Al₂O₃ or Al deposition. Thus, ultrafine Al³⁺-doped γ-Ga₂O₃ NPs were obtained after only 1 h of ultrasonic irradiation at 60 °C. The oxidation of liquid Ga was remarkably accelerated by alloying with metallic Al and ultrasonic irradiation, and the time was shortened. The average diameter and surface area of the γ-Ga₂O₃-based NPs were 59 nm and 181 m²/g, respectively. Compared with γ-Ga₂O₃, the optical bandgap of the Al³⁺-doped γ-Ga₂O₃ NPs was broadened, and the thermal stability improved, indicating Al³⁺-doping into the γ-Ga₂O₃ lattice. However, the lattice constant of γ-Ga₂O₃ was almost unchanged with or without Al³⁺-doping. Al³⁺ was introduced into the defect sites of Ga³⁺, which were massively induced in the defective spinel structure during ultrasonic processing. Therefore, sonochemical processing, which provides nonequilibrium reaction fields, is suitable for the synthesis of supersaturated and metastable materials in metals and ceramics fields.     

Crystallization and conductivity of 2CaO–La2O3–5P2O5 glass–ceramic with Al2O3 addition

Al₂O₃ was added to a 2CaO–La₂O₃–5P₂O₅ metaphosphate, to replace 10% of the Ca²⁺ ions by Al³⁺, forming a phosphate with the nominal composition 1.8CaO–0.1Al₂O₃–La₂O₃–5P₂O₅. The effect of Al₂O₃ addition and heat treatment on the microstructure and conductivity of the resulting glass–ceramics was investigated by XRD, SEM, TEM, and AC impedance spectroscopy. Upon transformation from glass to glass–ceramic, conductivities increased significantly. The glasses were isochronally transformed at 700 and at 800 °C for 1 h or 5 h, in air, following heating at 3 or 10 °C/min. With Al₂O₃ addition, after a heat treatment at 700 °C, 100–300 nm nano-domains of LaP₃O₉ crystallized from the glass matrix. Annealing at 800 °C produced a further order of magnitude conductivity increase for the Al-free glass, but less so for the Al-containing glass.     

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.     

Fabrication and luminescent properties of Al2O3:Cr3 + microspheres via a microwave solvothermal route followed by heat treatment

AlOOH:Cr^3 + powders were synthesized via a microwave solvothermal route at 433 K for 30 min and were used as the precursor and template for the preparation of γ-Al₂O₃:Cr^3 + by thermal transformation at 773 K for 2 h in air. The obtained γ-Al₂O₃ based powders were microspheres with an average diameter about 1.9 μm. Photoluminescence (PL) spectra showed that the Al₂O₃:Cr^3 + particles presented a symmetric broad R band at 696 nm without appreciable splitting when excited at 462 nm. It is shown that the 0.04 mol% of doping concentration of Cr^3 + ions in γ-Al₂O₃:Cr^3 + is optimum. According to Dexter's theory, the critical distance between Cr^3 + ions for energy transfer was determined to be 47.54 Å. Based on the corresponding PL spectrum, full width at half maximum (FWHM) of Al₂O₃:Cr^3 + (0.04 mol%) was calculated to be 3.35 nm.     

High coercivity and superparamagnetic behavior of nanocrystalline iron particles in alumina matrix

Single-domain nanoscale magnetic iron particles have been embedded uniformly in an amorphous matrix of alumina using a pulsed laser deposition technique. Structural characterization by transmission electron microscopy (TEM) reveals the presence of a crystalline iron and an amorphous alumina phase. Fine particle magnetism have been investigated by carrying out field and temperature dependence of magnetization measurements using superconducting quantum interference device magnetometer. The particle size of Fe in Al₂O₃ matrices prepared by changing the deposition time of Fe, have been found to be 9, 7 and 5 nm from TEM studies. At 10 K, the coercivities of these samples are found be 450, 350 and 150 Oe, respectively. At 300 K, the coercivity of Fe–Al₂O₃ sample decreases from 100 to 50 Oe as the particle size decreases from 9 to 7 nm and finally the sample turns superparamagnetic when the Fe particle size becomes around 5 nm. Based on the calculated value of blocking temperature, T_B, (481 K), magnetic anisotropy K (4.8×10⁵ erg/cm³) for Fe, and the Boltzmann constant k_B (1.38×10⁻¹⁶ erg/K) from T_B=KV/25k_B, the mean radius of Fe particles is found to be 9.3 nm. in one of the samples. This is in good agreement with the particle size measured using TEM studies.     

Luminescent and scintillation properties of the Pr3+ doped single crystalline films of Lu3Al5−xGaxO12 garnet

The Pr³⁺ d–f luminescence was investigated in the single crystalline films (SCF) of Lu₃Al_5−xGa_xO₁₂:Pr garnet solid solution at x = 1–3, grown by the liquid phase epitaxy (LPE) method from the melt-solution based on the PbO–B₂O₃ flux. The shape of CL spectra and decay kinetics of Pr³⁺ ions in Lu₃Al_5−xGa_xO₁₂ SCFs strongly depend on the total gallium concentration x and distribution of Ga³⁺ ions between the tetrahedral and octahedral position of the garnet host. The best scintillation properties of Lu₃Al_5−xGa_xO₁₂:Pr SCF are achieved at the nominal Ga content in melt-solution in the x = 2–2.5 range.