Phase and morphology controllable synthesis of Sb2O3 microcrystals

A simple and facile solution route has been developed for phase and morphology controllable synthesis of antimony trioxide (Sb₂O₃) microcrystals. Orthorhombic phase and cubic phase Sb₂O₃ microcrystals have been selectively synthesized in high yield. The products were characterized by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The as-obtained microcrystals exhibited a variety of morphologies and structures, such as microspindles, nanoplates, and octahedra. Several experimental parameters have been investigated to gain morphology control of Sb₂O₃ microcrystals. Based on the time-dependent experimental results, an aggregation, and recrystallization mechanism was proposed to describe the formation process of these novel microstructures.     

Crystallization behavior of (GeS2)0.1(Sb2S3)0.9 glass

The crystal growth kinetics of antimony trisulfide in (GeS₂)_0.1(Sb₂S₃)_0.9 glass has been studied by microscopy and DSC. The linear crystal growth kinetics has been confirmed in the temperature range 492 ? T ? 515 K (E_G = 405 ± 7 kJ mol⁻¹). The applicability of standard growth models has been assessed. From the crystal growth rate corrected for viscosity plotted as a function of undercooling it has been found that the most probable mechanism is interface controlled 2D nucleated growth. The non-isothermal DSC data, corresponding to the bulk sample, can be described by the Johnson-Mehl-Avrami equation.     

Synthesis,characterization and growing mechanism of monodisperse Fe3O4 microspheres

Monodisperse Fe₃O₄ microspheres assembled by a number of nanosize tetrahedron subunits have been selectively synthesized through the hydrothermal process. The synthesized Fe₃O₄ microspheres have good dispersibility. The subunits made up of microspheres were uniform in size and like-tetrahedron in shape. The average diameter of each Fe₃O₄ microsphere is about 50–55 μm. The length of each edge of tetrahedron is about 100 nm. A series of experiments had been carried out to investigate the effect of reductant, precipitator and reaction time on the formation of Fe₃O₄ microsphere and tetrahedron subunits. The results show that ascorbic acid as reductant and urea as precipitator supplied a relatively steady environment during the synthesis process and led to the formations of Fe₃O₄ tetrahedron subunit and monodisperse Fe₃O₄ microspheres. As the reaction time increased from 3 to 24 h, the Fe₃O₄ microspheres tended towards dispersion and becoming large in size from 10–20 to 50–55 μm, and the subunits formed Fe₃O₄ microspheres that varied from spheroid to tetrahedron and from a small nanoparticle (20–30 nm) to a large one (90–110 nm). A reasonable explanation for the formations of the Fe₃O₄ microsphere and the tetrahedron subunit was proposed through Ostwald ripening and the attachment growth mechanism, respectively.     

An electron microscopy study of the crystal growth of schwertmannite needles through oriented aggregation of goethite nanocrystals

The formation of the iron oxyhydroxide schwertmannite has been monitored by time-resolved transmission electron microscopy (TEM) studies. Schwertmannite aggregates are found to form initially as spherical agglomerates of ferrihydrite crystallites, which then begin to grow characteristic needles on their surfaces. High-resolution images of the needles show that they are initially comprised of aligned goethite nanocrystals, which subsequently coarsen to form crystallographically coherent needles of goethite. Thus, needle formation on schwertmannite aggregates can be considered as the first stage in the phase transformation from schwertmannite to goethite. The results of this study suggest that schwertmannite is not a distinct mineral phase, but may be a mixture of ferrihydrite and poorly crystalline goethite with a distinctive morphology directed by the presence of surface-adsorbed sulfate anions.     

Synthesis and characterization of single-crystalline PrCO3OH dodecahedral microrods and its thermal conversion to Pr6O11

Single-crystalline PrCO₃OH dodecahedral microrods with an orthorhombic structure have been successfully synthesized by the hydrothermal method used urea as the precipitator. Pr₆O₁₁ dodecahedral microrods have been obtained by thermal conversion of PrCO₃OH dodecahedral microrods at 600 °C in air for 6 h. The as-synthesized products were characterized by X-ray powder diffraction, field-emission scanning electron microscope, transmission electron microscopy, high-resolution transmission electron microscopy, selected-area electron diffraction, X-ray photoelectron spectra, fourier transform infrared spectroscopy and thermogravimetry–differential thermal analysis. The effect of the reaction parameters on the morphology of the product has been investigated. The dodecahedral microrods with larger size and better crystallinity can be obtained under the higher reaction temperature. The possible formation mechanism of PrCO₃OH microrods was discussed.     

Influence of La/Ce-doping on phase transformation and crystal growth in TiO2-15 wt% ZnO gels

Titania based ceramic is a good candidate for environmental sensing materials. Ion doping is an effective method to improve the properties by modifying their microstructure and phase composition. By using differential thermal analysis and X-ray diffraction methods, the transformation behaviors of La³⁺/Ce³⁺-doped TiO₂-15  wt% ZnO gels were studied so as to modify the phase transformation and decrease the granularity of crystals. Experimental results show that, anatase, rutile and ZnTiO₃ nanocrystals can be tailored by varying La³⁺/Ce³⁺ contents and sintering temperatures. La³⁺/Ce³⁺ doping decreases the transformation temperature of gel to anatase and the forming temperature of ZnTiO₃ phase, enhances the transformation temperature of anatase to rutile and results in appearance of Zn₂Ti₃O₈ interphase. With the increases of La³⁺/Ce³⁺ contents, the transformation rates of ZnTiO₃, gel to anatase and anatase to rutile, as well as the granularity of the crystals are reduced. Ultimately, the action mechanism of La³⁺/Ce³⁺ doping was discussed.     

Compositional analysis of a polymer-induced liquid-precursor (PILP) amorphous CaCO3 phase

Amorphous calcium carbonate (ACC) has been of keen interest in the biomimetics field because of recent evidence which suggests it plays an important role in biomineralization. In this report, an in vitro model system is used to examine the composition of an amorphous phase generated by polyanionic process-directing agents, such as the sodium salt of polyaspartic acid (Pasp), which is considered a simple mimic to the proteins associated with calcific biominerals. This additive leads to the formation of a highly hydrated, amorphous mineral precursor to calcium carbonate (CaCO₃), referred to as a polymer-induced liquid-precursor (PILP) phase. The precursor phase was collected by centrifugation, and the quantity of precursor phase and the water content were determined. It was found that Pasp promotes and stabilizes the amorphous precursor, which has a composition that steadily changes with time as the polymer and water are excluded. Elemental analysis was used to investigate the role of the polymer in influencing the calcium/carbonate ratio, the water content, and the amount of precursor phase. Raman and ATR-FTIR spectroscopy were used to compare the compositions of the precursor phases generated with different polymeric concentrations. The role of Pasp in generating and stabilizing the ACC precursor phase is discussed.     

Ring- and single-crystal-like superstructures of Fe-doped PbTiO3 nanocrystals

Ring- and single-crystal-like superstructures of Fe-doped PbTiO₃ nanocrystals have been prepared by a simple hydrothermal method using (poly ethylene glycol) (PEG) as a surfactant. Two oriented-attachment forms of the nanocrystals favor the formation of the rings in view of geometry. Magnetism measurement shows that Fe-doped PbTiO₃ sample is ferromagnetic even at room temperature. It is proposed that the magnetic dipole interactions and the presence of PEG molecules could together contribute to the formation of ring- and single-crystal-like superstructures composed of Fe-doped PbTiO₃ nanocrystals.     

A facile route to prepare boron nitride hollow particles at 450 °C

Hexagonal boron nitride (h-BN) particles including hollow spheres (with a proportion of ~30–40%) and nanotubes (10%) have been synthesized by using sodium fluoroborate and sodium azide at 450 °C for 20 h. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) studies show that the as-obtained BN hollow particles are crystalline. The total specific surface area of the product calculated from Brunauer–Emmentt–Teller (BET) absorption measurement is 89.79 m²/g, indicating that it may be utilized as a promising candidate for hydrogen storage container or catalyst. Thermal gravimetric analysis (TGA) result reveals its excellent thermal stability below 800 °C. Its possible growth mechanism and the effects of reaction parameters were also briefly discussed.     

Synthesis and ammonia sensing property of Ag3CuS2 nanocages obtained from Cu7S4 18-facet hollow nanopolyhedra

Ag₃CuS₂ nanocages were successfully fabricated for the first time via a convenient ion-exchange route by Ag⁺ reacting with Cu₇S₄ 18-facet hollow nanopolyhedra. The average size and shell thickness of Ag₃CuS₂ nanocages were around 400 and 30 nm, respectively. Room-temperature response of Ag₃CuS₂ nanocages to ammonia was investigated by photoluminescence-type sensor. Sensing results suggested that these hollow-structured Ag₃CuS₂ exhibited better performances including higher sensitivity, shorter response and recovery time than their rod-shape counterparts. A possible hole trapping mechanism was proposed.     

Single crystals growth and absorption spectra of Cr-doped Al2−xInx(WO4)3 solid solutions

The growth conditions of pure and Cr³⁺-doped Al_2−xIn_x(WO₄)₃ single crystals, using top-seeded solution growth (TSSG) technique, have been studied. A series of experiments have been performed at different In concentrations, x=0.0, 0.3, 0.6 and 1.0, as well as at different concentrations of Cr³⁺ (0.0, 0.1, 0.2, 0.5 and 1.0) in at% with respect to the initial total concentration of Al and In in the starting solutions. The basic parameters of the crystal growth are varied over a wide range: seed orientation, speed of rotation, axial and radial temperature differences in the solution and the solution cooling rate. The investigated relations between the basic defects in the crystals and these parameters result in determination of the optimal conditions for growth of defect-free crystals. Distribution coefficients of Al, In and Cr have been determined, so the growth of crystals with given compositions is possible. Values of Dq/B (crystal field strength) for the various crystal compositions are calculated from the optical absorption spectra. The calculated values show that the discussed solid solutions have weak crystal field and are suitable for media with broadband emission spectra.     

Growth,thermal and optical properties of a new nonlinear optical crystal: ZnBi2B2O7

Single crystals of ZnBi₂B₂O₇ (ZBBO) have been successfully grown by the top-seeded growth method from a high-temperature melt. The crystal was colorless and transparent with size of 15×10×5 mm³. The orientation of ZBBO crystal has been discussed. The melting point, molar enthalpy of fusion, and molar entropy of fusion of the crystal were determined to be 964.02 K, 110680.36 J mol⁻¹, and 113.92 J K⁻¹ mol⁻¹, respectively. The transparency range of the crystal extends from 370 to 2100 nm.     

Green synthesis of metal sulfide nanocrystals through a general composite-surfactants-aided-solvothermal process

In this paper, we developed a generalized and greener composite-surfactants-assisted-solvothermal process (CSSP) to produce colloidal nanoparticles of metal sulfides. X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectra (XPS) revealed that single-molecular-layer type of MoS₂ nanoparticles with diameter 6–10 nm were successfully synthesized. The molecular structure model of the capped MoS₂ nanoparticles was suggested through further examination by infrared spectra. Hexagonal CdS nanocrystals with spherical, triangle, and hollow sphere shapes were controllably synthesized by varying the experimental conditions. A possible in-situ reduction–sulfidation mechanism was proposed for the formation of Ag₂S nanocrystals, where the metal ions were reduced to metallic nanoparticles before the generation of sulfides. The obtained nanocrystals through this CSSP approach could provide the building blocks for the bottom-up approach to nanoscale fabrication in nanoscience and nanotechnology.     

Study on the growth and interfacial strain of CoFe2O4/BaTiO3 bilayer films

CoFe₂O₄/BaTiO₃ bilayer films were epitaxially deposited on SrTiO₃ substrates by laser molecular beam epitaxy (LMBE). The growth process of the bilayer films was in-situ monitored by reflection high-energy electron diffraction (RHEED). Sixty nanometer thick-BTO layer was firstly fabricated in a layer-by-layer growth mode with an atomic smooth surface. CFO films with a varying thickness ranging from 5 to 60 nm were subsequently deposited on BTO-coated STO substrates. The different growth behaviors of CFO films were observed due to the lattice mismatch strain. Between two short stages of the growth mode transforming, a long duration with Stransky and Krastonov growth mode was maintained. Strainfully relaxed CFO film in the island growth mode was finally formed. High-resolution X-ray diffraction (HRXRD) was used to further analyze the strain effect. It was found that the tensile stress imposed on BTO by CFO was strengthened with increasing the thickness of CFO films, which could lessen the distortion of BTO by counteracting the compressive stress caused by STO substrates. The strengthened tensile stress weakened the ferroelectric property of BTO films by reducing structural tetragonality, which was demonstrated by polarization-electric (P-E) measurement.     

Effects of Li replacement on the nucleation, crystallization and microstructure of Li2O-Al2O3-SiO2 glass

The Li replacement including the Li₂O replaced by other oxides and the expensive Li₂CO₃ replaced by low-cost spodumene mineral was studied to lower the product cost of (Li₂O-Al₂O₃-SiO₂, LAS) glass ceramic, and the effects of Li replacement on the nucleation, crystallization and microstructure of LAS glass were investigated by the differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that Li₂O replacement increases the crystallization activation energy, lowers the crystal growth, and increases the nucleation and crystallization temperature by restraining the formation of crystalline phases. The Li₂CO₃ replacement decreases the crystallization activation energy, promotes the crystal growth, without affecting the nucleation, and lowers the crystallization temperature by adding some beneficial compositions with mixed alkali effect.     

Crystal growth and characterization of K2B4O11H8

Single crystals of K₂B₄O₁₁H₈, a non-centrosymmetric borate material, have been prepared by slow evaporation of water solution at room temperature. The crystals were colorless and transparent with smooth faces. The single-crystal X-ray diffraction analysis showed that K₂B₄O₁₁H₈ crystallized in the orthorhombic space group P2₁2₁2₁ with a=6.8556(6) Å, b=11.7787(12) Å, c=12.8949(14) Å, Z=4, R₁=0.0188, and wR₂=0.0464. The powder X-ray diffractometry (PXRD), infrared spectrum, transmittance spectrum, TG–DTA curves and second harmonic generation properties of title compound have been determined.     

Size-controlled synthesis of LaAlO3 by reverse micelle method: Investigation of the effect of water-to-surfactant ratio on the particle size

Lanthanum monoaluminate (LaAlO₃) nanoparticles have been synthesized using microreactors made of poly(oxyethylene) nonylphenyl ether (Igepal CO-520)/water/cyclohexane microemulsions. The control of particle size was achieved by varying the water-to-surfactant molar ratio. The synthesized and calcined powders were characterized by thermogravimetry–differential thermal analysis (TGA-DTA), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR). Differential thermal analysis showed that LaAlO₃ phase transformation decreases with increase in water/surfactant (R) value. Pure LaAlO₃ phase was synthesized by annealing at 800 °C for 2 h in air directly from amorphous precursors, without formation of intermediate phase. The average particle size was found to increase with increase in water-to-surfactant ratio (R). FTIR analysis was carried to monitor the elimination of residual oil and surfactant phases from the microemulsion-derived precursor and calcined powder.     

Numerical description for the recalescence of bulk-undercooled Cu70Ni30 alloy

Assuming thermal balance and solute conservation, a numerical model has been proposed to describe the recalescence behavior of bulk-undercooled Cu–Ni melts. Applying a finite-difference scheme, the transformed solid fraction upon recalescence is given as a function of the liquid temperature, while the average liquid concentration can be tracked by calculation of the liquid/solid (L/S) Gibbs energy difference, in combination with a dendrite growth model. Accordingly, a transition from non-equilibrium to equilibrium process has been described from the evolution of L/S Gibbs energy difference. Applying the present model, the experimentally observed maximum recalescence temperature can be well predicted.     

Glasses and glass-ceramics in the oxyfluoride ternary system Pb(PO3)2-WO3-PbF2

Glasses were prepared by the melt-quenching method in the ternary system Pb(PO₃)₂-WO₃-PbF₂ and doped with Er³⁺ in order to prepare luminescent transparent glass-ceramics. This work focused on thermal and structural characterization of tungsten lead-phosphate glasses and crystallization study for preparing transparent glass-ceramics. Thermal properties such as thermal stability and crystallization behavior upon heating were investigated by DSC in function of PbF₂ content. For low PbF₂ concentrations, only one crystallization peak due to Pb₃(PO₄)₂ is observed whereas samples containing more than 15% of PbF₂ present another exothermic event at lower temperatures related with precipitation of PbF₂, Pb₂P₂O₇ and Pb₂OF₂. Structural investigations by Raman spectroscopy suggest that PbF₂ modifies the tungsten-phosphate network through the formation of P―F and P―O―Pb bonds but the average network connectivity remains almost constant. A crystallization study has been performed by DSC to investigate the dominant crystallization mechanisms in these glasses and it has been established that Pb₃(PO₄)₂ is nucleated on the surface whereas PbF₂, Pb₂P₂O₇ and Pb₂OF₂ crystallize dominantly from the glassy bulk. Transparent glass-ceramics containing nanosized PbF₂ crystallites were also prepared by suitable heat-treatment on the glass sample containing 20% of PbF₂ and Raman microscopy of these glass-ceramics supports the crystallization mechanisms determined by DSC.     

Dynamic process of crystallization of Sb2Se3 from Sb50Se50 amorphous film

Dynamics of crystallization of amorphous antimony-selenium film deposited on carbon substrate have been studied by the high-resolution transmission electron microscopy. The amorphous film was suddenly crystallized at 200°C by heating in vacuum. By the electron beam irradiation crystallization occurred at the focused electron beam region in the amorphous film. The growth process of crystallization by electron beam irradiation was recorded on a video image at the atomic resolution mode. The growth front of crystallization showed nano-concave and -convex shapes. The recrystallization with the different orientation at the first grown crystal have been found, and discussed as the influence of remaining antimony crystallites at the first crystallized film region.