Growth of nano-particles of Al2O3, AlN and iron oxide with different crystalline phases in a thermal plasma reactor

The paper presents the experimental results showing that the crystalline phase of the nano-particles, synthesized in a DC transferred arc thermal plasma reactor, critically depend on the operating pressure in the reaction zone. The paper reports about the changes in crystalline phases of three different compounds namely: aluminium oxide (Al₂O₃), aluminium nitride (AlN) and iron oxide (Fe_xO_y) synthesized at 760 Torr and 500 Torr of operating pressures. The major outcome of the present work is that the phases having higher defect densities are more probable to form at the sub-atmospheric operating pressures. The variations in the crystalline structures are discussed on the basis of the change in the temperature during the nucleation process, prevailing at the boundary of the plasma, on account of the ambient pressures. The as-synthesized nano-particles were examined by X-ray diffraction analysis and transmission electron microscopy. In addition, the confirmatory analysis of the crystalline phases of iron oxides was carried out with the help of Mössbauer spectroscopy.     

Solvothermal synthesis of the complex fluorides KMgF3 and KZnF3 with the Perovskite structures

The complex fluorides KMgF₃ and KZnF₃ with Perovskite structures were solvothermally synthesised at 150-180°C and characterised by means of X-ray powder diffraction, scanning electron microscopy, thermogravimetric analysis and infrared spectroscopy.     

Y2O3:Eu microstructures: Hydrothermal synthesis and photoluminescence properties

Hexagonal microprisms of yttrium hydroxide (Y(OH)₃) with tuned diameter and height have been successfully prepared for the first time via a facile hydrothermal process using sodium citrate as the shape modifying agent. Y(OH)₃ microspheres with diameter of ca. 2.5 μm and microtubes with an average length about 13 μm, outer diameter about 3 μm and tube thickness about 800 nm were also obtained in current reaction systems. The possible formation mechanism for the Y(OH)₃ microstructures was briefly proposed. Y₂O₃:Eu³⁺ (5%) microstructures with similar morphologies was obtained after thermal treatment of the as-prepared Y(OH)₃:Eu³⁺ microstructures at 700 °C for 4 h. Results show that the relative emission intensity of the Y₂O₃:Eu³⁺ microprisms is about 8 times as those of the Y₂O₃:Eu³⁺ microtubes and microspheres under excitation of 259 nm ultraviolet light. The products were characterized by XRD, SEM, and EDS.     

Electrophoretic technique for hydrothermal synthesis of NaA zeolite membranes on porous α-Al2O3 supports

Uniform and dense NaA zeolite membranes were prepared on the α-Al₂O₃ support by electrophoretic technique. The membrane morphology and membrane thickness were investigated by XRD, SEM and pervaporation properties for dehydration of 95 wt.% isopropanol/water mixture at 343 K, respectively. Under the action of the applied electric field, the negatively charged zeolite particles could migrate to the support surface homogenously and rapidly, forming uniform and dense membranes in a short time. High quality NaA zeolite membrane, with a separation factor (water/isopropanol) of 3281 and a flux of 1.24 kg/m² h, could be prepared by electrophoretic technique with the electrical potential of 1 V. The formation mechanism of zeolite membrane in the electric field is discussed.     

Preparation of In2O3 octahedrons by heating InCl3 aqueous solution on the Si substrate

In₂O₃ octahedrons have been synthesized by heating InCl₃ aqueous solution on the Si substrate at 400-900 °C for 2 h. The average size of In₂O₃ octahedrons is decreased by increasing the heating temperature. The In₂O₃ octahedrons are single-crystalline with the body-centered cubic structure and have controllable sizes in the range of 0.7-1.0 μm. A possible mechanism was also proposed to account for the formation of In₂O₃ octahedrons. A strong photoluminescence with a peak at 458 nm was observed from the In₂O₃ octahedrons at room temperature. This emission can be attributed to oxygen vacancies and indium-oxygen vacancy centers.     

Synthesis and upconversion emission of rare earth-doped olive-like YF3 micro-particles

The olive-like YF₃ micro-particles were fabricated via a two-step route. The precursor NH₄Y₃F₁₀ nano-cages sized 8 nm with hollow interiors were first synthesized in a solid reaction at room temperature. In the course of subsequent hydrothermal treating, the unstable NH₄Y₃F₁₀ nano-cages were decomposed, resulted in the formation of Y(OH)_1.63F_1.37 micro-tubes. Prolonging the hydrothermal reaction induced the further decomposition of Y(OH)_1.63F_1.37 to produce YF₃ nano-crystals, which then aggregated together forming the final olive-like YF₃ micro-particles. For the Er³⁺/Yb³⁺ co-doped olive-like YF₃ micro-particles, intense visible upconversion emissions were measured under 976 nm excitation owing to the partition of rare earth ions in the lattice, indicating this material a promising luminescent host.     

GexNbSe2 and GexNbS2 intercalation compounds

The structures of two intercalation compounds, Ge_∼0.2NbSe₂ and Ge_∼0.3NbS₂ were investigated by single crystal X-ray diffraction and electron microscopy (selected area electron diffraction (SAED), high resolution electron microscopy (HRTEM) and X-ray microanalysis by energy dispersive spectroscopy (XEDS)). Crystal structure determinations of the average structure of the intercalation compounds 2H-Ge_0.217NbSe₂ and 4H-Ge_0.288NbS₂ are reported: the selenide compound crystallizes in the space group P6₃/mmc with a = 3.4560(9) Å and c = 12.966(3) Å and adopts the 2H-NbSe₂ structure-type, while the sulfide compound crystallizes in the P6₃mc space group, with a = 3.3392(9) Å and c = 25.404(7) Å with a structure-type 4H_c-NbS₂ which it is known for TaSe₂. In both structures the germanium atoms are located in the empty octahedral positions of the van der Waals gap between the NbX₂ (X = S, Se) layers. Electron diffraction patterns from several Ge_xNbSe₂ crystal flakes show different superstructures and exhibit diffracted diffuse intensity: weak satellites corresponding to and 2a₀ × 2a₀ superstructures were observed for x ∼ 0.15 (a₀ is the basal lattice parameter of the host structure). For x ∼ 0.25-0.33, the same type of satellite is observed with a stronger intensity. For x ∼ 0.5 only satellites corresponding to the superstructure were present. In the case of Ge_xNbS₂, with 0.10 < x < 0.25, the germanium atoms are ordered in domains with an superstructure. In some crystals disorder along the c-axis has been observed.     

Mechanochemical synthesis of NaNbO3

The mechanochemical synthesis of NaNbO₃ is studied. It is shown that NaNbO₃ can be prepared by milling the constituents, i.e. Na₂CO₃ and Nb₂O₅ in the planetary mill. After 40 h of mechanochemical treatment NaNbO₃ nanoparticles in the range of 10-20 nm are obtained. Furthermore, the high-energy milling leads to the mechanochemically-triggered carbonate decomposition, which has been observed for a few cases in the open literature.     

Structural study by X-ray diffraction and transmission electron microscopy of the misfit compound (SbS1−xSex)1.16(Nb1.036S2)2

In the Sb-Nb-S-Se system, a new misfit layer compound (MSL) has been synthesized and its structure was determined by combining single crystal X-ray diffraction (XRD) and transmission electron microscopy (TEM) techniques. It presents a composite crystal structure formed by (SbS_1−xSe_x) slabs stacking alternately with double NbS₂ layers and both can be treated as separate monoclinic subsystems. The (SbS_1−xSe_x) slabs comprise a distorted, two-atom-thick layer with NaCl-type structure formed by an array of {SbX₅} square pyramids joined by edges (X: S, Se); the NbS₂ layers consist of {NbS₆} trigonal prisms linked through edge-sharing to form sheets, just as in the 2H-NbS₂ structure type. Both sublattices have the same lattice parameters a = 5.7672(19) Å, c = 17.618(6) Å and β = 96.18(3)°, with incommensurability occurring along the b direction: b₁ = 3.3442(13) Å for the NbS₂ subsystem and b₂ = 2.8755(13) Å for the (SbS_1−xSe_x) subsystem. The occurrence of diffuse scattering intensity streaked along c^* indicates that the (SbS_1−xSe_x) subsystem is subjected to extended defects along the stacking direction.     

Large-scale synthesis of ultralong Sb2S3 sub-microwires via a hydrothermal process

This paper describes an ethylene glycol (EG)-assisted approach to the large-scale ultralong Sb₂S₃ sub-microwires, formed by a simple hydrothermal reaction between SbCl₃ and Na₂S in the presence of distilled water. Transmission electron microscopy and scanning electron microscopy studies indicate that these Sb₂S₃ sub-microwires possess a diameter around 200 nm and length up to 100 μm. High-resolution transmission electron microscopy and selected area electron diffraction studies reveal that each Sb₂S₃ sub-microwire is a single-crystal along the [0 0 1] direction. The possible formation mechanism of the sub-microwires was discussed. The effects of volume ratio of EG/water, reaction temperature and the concentration of CO(NH₂)₂ on the morphology of Sb₂S₃ sub-microwires were also investigated.     

Structure study of Bi4Ti3O12 produced via mechanochemically assisted synthesis

Nanosized bismuth titanate was prepared via high-energy ball milling process through mechanically assisted synthesis directly from their oxide mixture of Bi₂O₃ and TiO₂. Only Bi₄Ti₃O₁₂ phase was formed after 3 h of milling time. The excess of 3 wt% Bi₂O₃ added in the initial mixture before milling does not improve significantly the formation of Bi₄Ti₃O₁₂ phase comparing to stoichiometric mixture. The formed phase was amorphized independently of the milling time. The Rietveld analysis was adopted to determine the crystal structure symmetry, amount of amorphous phase, crystallite size and microstrains. With increasing the milling time from 3 to 12 h, the particle size of formed Bi₄Ti₃O₁₂ did not reduced significantly. That was confirmed by SEM and TEM analysis. The particle size was less than 20 nm and show strong tendency to agglomeration. The electron diffraction pattern indicates that Bi₄Ti₃O₁₂ crystalline powder is embedded in an amorphous phase of bismuth titanate. Phase composition and atom ratio in BIT ceramics were determined by X-ray diffraction and EDS analysis.     

Fabrication of β-Si3N4 whiskers by combustion synthesis with MgSiN2 as additives

β-Si₃N₄ whiskers with diameter of 0.5–2 μm and aspect ratio of 10–15 have been successfully prepared by combustion synthesis under 30–50 atm nitrogen pressure. The addition of MgSiN₂ powder plays a significant role in the growth of β-Si₃N₄ whiskers. The as-prepared products were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM).     

Size and morphology-controlled Ni2[Fe(CN)6]·xH2O Prussian Blue analogue fabricated via a hydrothermal route

Nanocrystalline Prussian Blue analogue Ni₂[Fe(CN)₆]·xH₂O was synthesized through hydrothermal process at 180 °C for 24 h with NiSO₄·6H₂O and K₄[Fe(CN)₆]·3H₂O as precursors. The effects of reactant concentration and protective matrix (Polyethylene glycol 400, PEG-400) on the size and morphology of nanoparticles were investigated. The as-synthesized products were identified as face-centered cubic structure by powder X-ray diffraction. Field-emission scanning electron microscopy and transmission electron microscopy images showed that well dispersed nanoparticles with fairly narrow size distribution were successfully prepared.     

Polyol method synthesis and characterization of nanoscale Sb2Se3 wires

Sb₂Se₃ nanowires ([0 0 1] orientation) with diameter of ∼100 nm and high aspect ratio were successfully synthesized in large scale by a facile nonaqueous polyol method, where home-prepared NaHSe alcohol solution is used as selenium source and PEG-400 serves as an excellent solvent and structure director. The product was characterized by XRD, TEM, SAED, HRTEM, EDS and diffuses reflectance spectroscopy, respectively. The effects of the experimental conditions on the final morphologies were also investigated. The method is promising to be extended to synthesize other V₂VI₃ compound semiconductor 1D nanostructure.     

Chemical synthesis of α-iron in aqueous FeCl3

Iron-aluminium composite and α-iron powder have been prepared by chemical reduction of aqueous FeCl₃ with aluminium at different conditions. Experiments showed that the concentration of FeCl₃ and aluminium particle size are the main factors to influence the reaction. XRD, SEM and potentiometric titration were employed to characterize the products. SEM showed that as iron particles grow they tend to form spherical seed on the surface of aluminium. XRD revealed that the α-iron was single phase after deposit treatment by NaOH solution. The purity of as-prepared α-iron was 99.5%, as determined from the X-ray fluorescence spectroscopy. The possible formation mechanism is a two-stage red-ox-process: Fe³⁺→Fe²⁺→α-Fe.     

Molten salt solvent synthesis of La2Mo2O9 nano-wires by controlling the subsequent calcinations process

Large amounts of La₂Mo₂O₉ nano-wires have been produced using molten-salt synthesis method. The powder X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy are used to investigate structure and morphological features of the obtained products. The formed nano-wires have an average diameter of about 100 nm and a length in the range from ten to several tens of micrometers. The analyses of the high resolution transmission electron microscopy and the selected area electron diffraction results show that the nano-wires are single crystalline and grow along the [0 0 1] direction. A growth mechanism of La₂Mo₂O₉ nano-wires is also proposed in this report. It implies that the temperature, chloride ions and cation lattice in β-La₂Mo₂O₉ might be related to the particles morphologies transition.     

Large-scale synthesis of ear-like Si3N4 dendrites from SiO2/Fe composites and Si powders

Large-scale ear-like Si₃N₄ dendrites were prepared by the reaction of SiO₂/Fe composites and Si powders in N₂ atmosphere. The product was characterized by field emission scanning electron microscopy, X-ray diffraction, and transmission electron microscopy. The results reveal that the product mainly consists of ear-like Si₃N₄ dendrites with crystal structures, which have a length of several microns and a diameter of 100-200 nm. Nanosized ladder-like Si₃N₄ was also obtained when changing the Fe content in the SiO₂/Fe composites. The Si₃N₄ nanoladders have a length of hundreds nanometers to several microns and a width of 100-300 nm. The ear-like Si₃N₄ dendrites are formed from a two-step growth process, the formation of inner stem structures followed by the epitaxial growth of secondary branches.     

SrF2 hierarchical flowerlike structures: Solvothermal synthesis, formation mechanism, and optical properties

We present a solvothermal route to the synthesis of SrF₂ hierarchical flowerlike structures based on thermal decomposition of single source precursor (SSP) of strontium trifluoroacetate in benzylamine solvent. These flowerlike superstructures are actually composed of numerous aggregated nanoplates, and the growth process involves the initial formation of spherical nanoparticles and subsequent transformation into nanoplates, which aggregated together to form microdisks and finally flowerlike superstructures. The results demonstrate the important role of benzylamine in the formation of well-defined SrF₂ superstructures, not only providing size and shape control to form nanoplates but also contributing to the self-assembly behavior of nanoplates to build into flower-like superstructures. Additionally, the photoluminescence properties of the obtained SrF₂ superstructures are studied.     

Hydrothermal synthesis and optical properties of Eu doped NaREF4 (RE = Y, Gd), LnF3 (Ln = Y, La), and YF3·1.5NH3 micro/nanocrystals

5 mol% Eu³⁺ doped NaYF₄ (α-, β-), YF₃, YF₃·1.5NH₃, NaGdF₄, and LaF₃ micro/nanocrystals have been synthesized by a hydrothermal method. The final products are characterized by X-ray diffraction, field emission scanning electron microscopy, photoluminescence excitation and emission spectra, and luminescent dynamic decay curves. Due to its sensitivity to local symmetry, Eu³⁺ shows different optical properties in the above samples. It has stronger luminescent intensity in β-NaYF₄ than that in α-NaYF₄ while it exhibits different higher energy ⁵D_1,2 to lower ⁷F_J emissions as well as the asymmetric ratios and the splits of ⁵D₀ → ⁷F₁, ⁷F₄. YF₃, LaF₃, and β-NaGdF₄ have analogous optical intensities to those of β-NaYF₄. However, β-NaGdF₄ has the similar spectral profile to that of β-NaYF₄ while YF₃ and LaF₃ have the opposite cases in the ⁵D₀ → ⁷F₂, ⁷F₁ emissions. Further, Judd-Ofelt calculation has been used to analyze the experimental phenomena.     

Structural properties of Al2O3-La2O3 binary oxides prepared by sol-gel

The structural properties of La₂O₃ and Al₂O₃-La₂O₃ binary oxides prepared by sol-gel were studied by XRD, HRTEM and UV-vis. The binary oxides with high lanthana contents show an amorphous structure after calcination at 650 °C. At calcination temperatures higher than 1000 °C there is a phase transformation from the amorphous state to the crystalline LaAlO₃ with a perovskite structure. The structure of La₂O₃ is consistent with the hexagonal system; however, some crystalline microdomains with a monoclinic structure were detected by HRTEM. Islands of La₂O₃ and LaAl₁₁O₁₈ phases were detected at high lanthana concentration in the binary oxide. The modification in the coordination shell of the Al³⁺ cations due to the interaction with La³⁺ cations confirms the formation of phases with a perovskite structure and the presence of islands of the LaAl₁₁O₁₈ phase.