


Volume 59, Nº 4 (2023)
Articles
Structural Characteristics and Photoelectric Properties of Iodine-Doped PbS Films Produced by Chemical Deposition
Resumo
Ammonium iodide (NH4I) has been shown to have an inhibiting effect on the growth kinetics of lead sulfide films at initial NH4I concentrations in solution from 0.05 M to 0.40 M. The addition of the inhibitor leads to a decrease in grain size, an increase in the fraction of nanoparticles in the PbS films to ~13%, and an increase in the iodine content of the films to 3.7 at %, depending on growth conditions. X-ray diffraction characterization has shown that the films have a B1 cubic structure (sp. gr.
). Increasing the inhibitor concentration in solution leads to an increase in the lattice parameter of the lead sulfide from 0.59315(1) to 0.59442(3) nm, due to iodine substitution for sulfur in the PbS crystal lattice. The spectral sensitivity peak and the long-wavelength edge of the photoresponse of the PbS films shift to shorter wavelengths from 2.5 to 2.2 and from 3.0 to 2.8 μm, respectively, which is attributable to the formation of the wide-band-gap phase PbI2. Using low-temperature measurements, the thermal band gap of the films grown in the presence of 0.15 and 0.25 mol/L NH4I has been determined to be 0.46 and 0.51 eV. The respective activation energies for acceptor impurity levels are 0.135 and 0.153 eV. The iodine-doped PbS films offer a relatively high voltage responsivity in the IR spectral region owing to an n- to p-type conversion, in combination with an anomalously short response time.



Structure and Phase Formation in the Ti–Al–Mo–N and Ti–Al–Mo–Ni–N Systems during the Arc PVD Coating Process
Resumo
Nanostructured Ti–Al–Mo–N and Ti–Al–Mo–Ni–N coatings with a layered architecture have been grown by arc PVD. We have determined deposition parameters (reaction gas (nitrogen) pressure and negative bias voltage applied to the substrate and determining the energy of incident particles) that enable the formation of a two-phase nitride (TiN + Mo2N) coating in the Ti–Al–Mo–N system and a nitride–metal (TiN + Mo2N + Ni) coating in the Ti–Al–Mo–Ni–N system. The addition of Ni to the composition of Ti–Al–Mo–N coatings leads to a decrease in the average grain size of the nitride phases from 35 to 12 nm and reduces the modulation period from 50 to 35 nm by limiting the growth of nitride nuclei. This is accompanied by a decrease in biaxial macrostress: from σ = –2.51 GPa in the Ti–Al–Mo–N coating to σ = –0.67 GPa in the Ti–Al–Mo–Ni–N coating.



Growth of Aluminum Molybdenum Oxide Films by Atomic Layer Deposition with Using Trimethylaluminum, Molybdenum Oxytetrachloride, and Water
Resumo
In this paper, we report on the growth of aluminum molybdenum oxide (AlxMoyOz) films via atomic layer deposition (ALD) with the use of trimethylaluminum (TMA) (Al(CH3)3), molybdenum oxytetrachloride (MoOCl4), and water. The film growth process was studied in situ using a quartz crystal microbalance and ex situ using various X-ray techniques. AlxMoyOz ALD was performed using supercycles consisting of TMA/H2O and MoOCl4/H2O subcycles. We obtained two types of films, with the subcycles in the ratio 1 : 1 (1Al1MoO) and 1 : 7 (1Al7MoO). Film growth at 150°C was shown to be a linear process, with growth rate of 3.0 and 5.7 Å/supercycle for 1Al1MoO and 1Al7MoO, respectively. The density of the 1Al1MoO and 1Al7MoO films were 3.7 and 3.9 g/cm3, respectively, and their surface roughness did not exceed 20 Å. The oxidation state of the molybdenum in the films found to be 6+, 5+, and 4+. X-ray diffraction characterization showed that the films had an amorphous structure.



Synthesis and Luminescence Spectra of Copper-Containing Monoclinic PbCd2B6O12-Based Materials
Resumo
New copper-containing borates with the general formula PbCd2–xB6O12:xCu2+ have been prepared by solid-state reactions and characterized by X-ray diffraction and IR spectroscopy. A continuous series of substitutional solid solutions isostructural with monoclinic PbCd2B6O12 (sp. gr. P21/n) has been shown to exist in the range 0 < x ≤ 0.08. Replacing cadmium atoms by copper atoms, which are smaller in size, leads to a linear decrease in unit-cell parameters across the solid solution series. The IR spectroscopy and X-ray diffraction data suggest the presence of BO3 and BO4 anions in the structure of the borates. The thermoluminescence intensity has been measured as a function of activator content in the range 25–400°C. The thermoluminescence intensity in the borates increases with activator content, reaching a maximum at x = 0.06, and decreases at higher doping levels. The powder borates studied here can be used as a key component of new luminescence materials.



Effect of Isomorphous Substitutions in Calcium Triphosphate, Ca3(PO4)2, on the Microstructural and Chemical Properties of Phosphate Cements Prepared from It
Resumo
This paper reports on the preparation and properties of phosphate materials for medical applications: brushite (CaHPO4·2H2O) or monetite (CaHPO4) based cements prepared from β- and α-Ca3(PO4)2 (TCP) via isomorphous substitutions of Na+ or K+ for Ca2+ and of SiO4-4 or SO42- for
. The mixing liquid used to prepare phosphate cements from substituted TCP was orthophosphoric acid or H2O, and TCP was mixed with dry Ca(H2PO4)2·H2O. Isomorphous substitutions of Na+ and K+ for Ca2+ ions and PO43- and PO42- for SiO44-, SO42 were confirmed by scanning electron microscopy, X-ray microanalysis, and X-ray diffraction. It has been shown that, as a result of hardening of cement pastes with the use of different mixing liquids, one can obtain materials differing in microstructure, in which brushite or monetite prevails, depending on the TCP phase used in the preparation of the cement. In addition, we have studied interaction of the cements with water for a long time (16 days). The pH of the aqueous medium has been shown to vary from 5 to 7.5. This pH range is favorable for medical applications of the phosphate materials studied.



Thermal Stability and Luminescence Properties of Cerium-Containing Tricalcium Phosphate
Resumo
Cerium-containing tricalcium phosphate (TCP, Ca3(PO4)2) nanopowders with the whitlockite structure have been prepared via precipitation from solution. After heat treatment at 1300°C, the materials contained 0, 0.07, 0.18, and 0.39 wt % cerium, which corresponded to х = 0, 0.0025, 0.006, and 0.013 in the general formula Ca3 – хCe2х/3(PO4)2. The thermal stability of β-TCP has been shown to increase with increasing cerium content. The synthesized cerium-containing TCP powders show luminescence properties under excitation at wavelengths from 270 to 320 nm, with a peak emission wavelength from 360 to 390 nm, characteristic of Ce3+ luminescence. Varying the percentage of cerium in the materials and heat treatment temperature causes the emission spectrum to shift.



Laser Amorphization of a Crystalline Phase in the Bulk of a Thermally Stable Lithium Aluminosilicate Glass-Ceramic
Resumo
This paper presents results of femtosecond laser micromachining of a transparent glass-ceramic in the Li2O–Al2O3–SiO2 system with a near-zero linear thermal expansion coefficient in the thermal and athermal regimes. Electron microscopy and electron diffraction data confirm complete amorphization of nanocrystals of β-eucryptite-like solid solutions under the effect of laser pulses. Using quantitative phase microscopy, we have evaluated refractive index changes in individual laser-written tracks. In the athermal regime at a pulse repetition rate of 10 kHz, complete glass-ceramic amorphization leads to a decrease in the refractive index of the material (Δn = −0.0035) in the laser treatment region, which opens up the possibility of using direct laser writing of channel waveguides in a thermally stable glass-ceramic matrix.



Effect of Erbium Complexes on the Anti-Stokes Luminescence of Y2O2S:Er Ceramics
Resumo
Emission spectra of Y2O2S:Er (1 at %) ceramics and decay times of their visible photoluminescence have been studied at different pulsed IR excitation wavelengths. The results demonstrate that the visible anti-Stokes luminescence of the erbium-doped material is due to isolated Er3+ ions or complexes of erbium ions. We have obtained characteristic emission centers of the complexes and isolated erbium centers. A method has been proposed for selective delayed luminescence measurements in order to separate the contributions of various erbium centers to anti-Stokes emission of Y2O2S:Er.



Synthesis of ZrN-Based Composites via Nitridation of Zircon + Aluminum Mixtures in Combustion Mode
Resumo
Self-propagating high-temperature synthesis has been used to nitride zircon with aluminum additions (5–30%). We have examined the influence of the key process parameters (composition of the starting mixture, gas pressure, and sample diameter) on the combustion speed, nitrogen content, and phase composition of the synthesis products and found critical parameters at which combustion was impossible: less than 20% aluminum, nitrogen pressure under 2 MPa, and sample diameter less than 35 mm. The addition of 20–30% aluminum has been shown to change the phase composition of the synthesis products. On the addition of 20–25% Al, the phase composition was ZrN, Al2O3, Si3Al3O3N5, ZrO2, and ZrSi2; at 30% Al, it was ZrN, Al2O3, ZrSi2, Al3O3N5. The combustion products have been shown to contain aluminum oxynitride (Al3O3N5) forming from the gas phase. We have identified the mechanism underlying nitridation of a ZrSiO4 + Al mixture in combustion mode. A composite powder with the composition ZrN–Al2O3–ZrSi2–Al3O3N was tested as a material for producing coatings by nonvacuum electron-beam cladding.



Ternary Intermetallic Compounds R26(RuxIn1 – x)17 (R = Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Lu), Pr21Ru8.2In5 and Gd6Ru2In with High Content of Rare Earth Elements
Resumo
In the R–Ru–In (R—rare earth element) systems in the area with a high content of rare-earth elements (>60 at %), a number of isostructural compounds R26(RuxIn1 – x)17 (R = Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Lu) were found, which crystallize in a tetragonal cell (P4/mbm) with the Sm26(Co0.65Ga0.35)17 structure type, as well as Pr21Ru8.2In5 compounds in a tetragonal cell (I4/mcm) with the Y3Rh2 structure type and Gd6Ru2In in a rhombic cell (Immm) with the Ho6Co2Ga structure type. The samples were prepared by arc-melting the stoichiometric quantities of elementary components. The structures were determined by single-crystal X-ray diffraction and refined by the Rietveld method using powder patterns. Compounds R26(RuxIn1–x)17 (R = Dy, Ho, Er, Tm, Lu) exist in the homogeneity range 0.28 < x < 0.47. All crystal structures of the obtaining compounds are based on a frame from atoms of rare earth elements, inside which are smaller in size atoms of ruthenium and indium. A general fragment of all the considered structures are columns of various lengths from InR8 tetragonal prisms and RuR8 tetragonal antiprisms conjugated by mutual bases. The new compounds have a congruent melting pattern.



Microstructure and Impact Toughness of Acicular Ferrite in Low Alloy Steel Weld Joints from Results of Multiple Impact Bending Tests
Resumo
Analysis of impact bending test results for a large number of specimens is used to investigate fracture of a weld metal consisting predominantly of acicular ferrite. The metal has a very broad ductile-to-brittle transition interval: from +20 to below –60°C. In the temperature range studied, we observe three stable impact toughness levels. Transitions between them with decreasing temperature determine the scatter in the work done to fracture the specimen. According to fractography results, the ductile-to-brittle transition is due to a single-step change from a ductile fracture mechanism to cleavage. Cleavage cracks nucleate at large acicular ferrite grains. Their different arrangements on a cleavage site determine the impact toughness level. Comparison of dynamic fracture curves and the macroscopic structure of fracture surfaces demonstrates that cleavage cracks nucleate at the tip of a stably growing ductile crack. Examination of fracture surfaces makes it possible to identify individual cleavage events observed in the corresponding dynamic curve.



Calculation of the Heat Capacity Baseline in a Model of a Two-Phase Region in the Absence of Phase Transformations and Other Transitions
Resumo
This paper presents calculations of the heat capacity baseline in a model of a two-phase locally equilibrium region for various inorganic substances undergoing no phase transformations or other transitions. Experimental data obtained in limited temperature ranges are used to calculate model parameters. Theoretical relations are shown to adequately describe experimental data in the range from absolute zero to the melting point of the substance.


