The ternary system: H2O–Fe(NO3)3–Co(NO3)2 isotherms −15 and −25 °C

The binary system H₂O–Fe(NO₃)₃ has been investigated at temperature ranging between –25 and 47 °C.The solid–liquid equilibria of the ternary system H₂O–Fe(NO₃)₃–Co(NO₃)₂ were studied at −15 and −25 °C by using a synthetic method based on conductivity measurements which allows all the characteristic points of the isotherms to be determined, and the stable solid phases which appear are respectively: ice, Fe(NO₃)₃·9H₂O, Fe(NO₃)₃·6H₂O, Co(NO₃)₂·9H₂O, Co(NO₃)₂·6H₂O and Co(NO₃)₂·3H₂O.     

Effects of additives on synthesis of vanadium carbide (V8C7) nanopowders by thermal processing of the precursor

Vanadium carbide (V₈C₇) nanopowders can be synthesized by thermal processing of the precursor of ammonium vanadate (NH₄VO₃) and nanometer carbon black. Effects of additives (CaF₂, CeCl₃·7H₂O and LaCl₃·7H₂O) on the phase composition and microstructure of the synthesized powders were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that additives (CaF₂, CeCl₃·7H₂O and LaCl₃·7H₂O) can accelerate the solid state reaction during synthesis of V₈C₇, and these additives play a vital role in determining the phase composition and microstructure. V₈C₇ powders with basically single phase can be synthesized at 1100 °C for 0.5 h with the addition of additives (CaF₂, CeCl₃·7H₂O and LaCl₃·7H₂O), and the powders show good dispersion and are mainly composed of uniformly-sized spherical particles with a mean diameter of 50 nm. Further experiment shows that V₈C₇ powders can be prepared at 950 °C for 1 h with 1.0 wt% CaF₂ as additive.     

Synthesis and performance of Li3V2(PO4)3/C composites as cathode materials

Carbon-coated Li₃V₂(PO₄)₃ cathode materials for lithium-ion batteries were prepared by a carbon-thermal reduction (CTR) method using sucrose as carbon source. The Li₃V₂(PO₄)₃/C composite cathode materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical measurement. The results show that the Li₃V₂(PO₄)₃ samples synthesized using sucrose as carbon source have the same monoclinic structure as the Li₃V₂(PO₄)₃ sample synthesized using acetylene black as carbon source. SEM image exhibits that the particle size is about 1 μm together with homogenous distribution. Electrochemical test shows that the initial discharge capacity of Li₃V₂(PO₄)₃ powders is 122 mAh·g⁻¹ at the rate of 0.2C, and the capacity retains 111 mAh−g⁻¹ after 50 cycles.     

X-ray scattering from Co0.83[Pt(C2O4]2]·6H2O: A system with two coupled order parameters

X-ray studies of the quasi-one-dimensional conductor Co_0.83 [Pt(C₂O₄)₂]·6H₂O, Co(def)OP, show both a Peierls distortion with a period of 2k_F = 1.70·2π/c and a separate (earlier reported) three-dimensional superlattice. The two distortions couple, so that the drastic decrease in electrical conductivity is accompanied by the occurence of the superlattice spots with a common critical temperature, T = (297 ± 4)K. The striking differences between Co(def)OP and Mg(def)OP are discussed and explained in terms of the different atomic structures of the cations.     

Self-healing mechanism of a protective film prepared on a Ce(NO3)3-pretreated zinc electrode by modification with Zn(NO3)2 and Na3PO4

Self-healing mechanism of a protective film against corrosion of zinc at scratches in an aerated 0.5 M NaCl solution was investigated by polarization measurements, X-ray photoelectron spectroscopy (XPS) and electron-probe microanalysis (EPMA). The film was prepared on a zinc electrode by treatment in a Ce(NO₃)₃ solution and addition of aqueous solutions containing 9.98 or 19.9 μg/cm² of Zn(NO₃)₂ · 6H₂O and 55.2 μg/cm² of Na₃PO₄ · 12H₂O. After the coated electrode was scratched with a knife-edge crosswise and immersed in the NaCl solution for many hours, polarization measurements, observation of pit formation at the scratches, XPS and EPMA were carried out. This film was remarkably protective and self-healing against zinc corrosion on the scratched electrode. The cathodic and anodic processes of zinc corrosion were markedly suppressed by coverage of the surface except for scratches with a thin Ce₂O₃ layer containing a small amount of Ce⁴⁺ and the surface of scratches with a layer composed of Zn₃(PO₄)₂ · 4H₂O, Zn(OH)₂ and ZnO mostly.     

Fabrication of V3O7·H2O@C core-shell nanostructured composites and the effect of V3O7·H2O and V3O7·H2O@C on decomposition of ammonium perchlorate

V₃O₇·H₂O@C core-shell materials have been synthesized using V₃O₇·H₂O nanobelts as the cores and glucose as the source of carbon via an environmental hydrothermal method. The as-obtained V₃O₇·H₂O@C core-shell materials were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), elemental analysis (EA), Fourier transform infrared spectroscopy (FT-IR) and Raman spectrum. The influences of the reaction temperature, concentration of glucose and reaction time on the morphologies of the samples were respectively discussed in detail. The possible formation mechanism of V₃O₇·H₂O@C was proposed according to our experimental results. Furthermore, the effect of V₃O₇·H₂O and V₃O₇·H₂O@C on the thermal decomposition of ammonium perchlorate (AP) were investigated by thermal gravimetric analyzer (TG) and differential thermal analysis (DTA). The thermal decomposition temperatures of AP in the presence of V₃O₇·H₂O and V₃O₇·H₂O@C were reduced by 70 and 89 °C, respectively, which indicates that V₃O₇·H₂O@C core-shell composites have higher activity than V₃O₇·H₂O.     

Preparation and characteristic of spherical Li3V2(PO4)3

Spherical Li₃V₂(PO₄)₃ was synthesized by using N₂H₄ as reducer. The products were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that single-phase, spherical and well-dispersed Li₃V₂(PO₄)₃ has been successfully synthesized in our experimental process. Electrochemical behaviors have been characterized by charge/discharge measurements. The initial discharge capacities of Li₃V₂(PO₄)₃ were 123 mAh g⁻¹ in the voltage range of 3.0–4.3 V and 132 mAh g⁻¹ in the voltage range of 3.0–4.8 V.     

Synthesis of CeO2/TiO2 nanoparticles by laser ablation of Ti target in cerium (III) nitrate hexahydrate (Ce(NO3)3·6H2O) aqueous solution

A new synthesis process, laser ablation in an aqueous solution of target material, was applied to synthesize nanostructured CeO₂/TiO₂ catalyst particles. Reactivity within the laser plume (plasma) can be used to synthesize CeO₂ from an aqueous solution, 2 M cerium (III) nitrate hexahydrate (Ce(NO₃)₃·6H₂O) aqueous solution, and to fabricate TiO₂ from Ti target. CeO₂/TiO₂ nanoparticles were successfully synthesized by the laser ablation of Ti target in 2 M cerium (III) nitrate hexahydrate (Ce(NO₃)₃·6H₂O) aqueous solution. Laser ablation of Ti in a liquid environment and chemical reactions of the solution within a plasma plume are discussed.     

Microstructure and electrical properties of Y(NO3)3·6H2O-doped ZnO-Bi2O3-based varistor ceramics

Y(NO₃)₃·6H₂O-doped ZnO-Bi₂O₃-based varistor ceramics were prepared using a solid reaction route. The microstructure, electrical properties, degradation coefficient (D_V), and dielectric characteristics of varistor ceramics were studied in this paper. With increasing amounts of Y(NO₃)₃·6H₂O in the starting composition, Y-containing Bi-rich, Y₂O₃, and Sb₂O₄ phases were formed, and the average grain size decreased. Results also showed that with the addition of 0.16 mol% Y(NO₃)₃·6H₂O, Y(NO₃)₃·6H₂O -doped ZnO-based varistor ceramics exhibit comparatively better comprehensive electrical properties, such as a threshold voltage of 425 V/mm, a nonlinear coefficient of 73.9, a leakage current of 1.78 μA, and a degradation coefficient of 1.7. The dielectric characteristics and lightning surge test also received the same additional content of Y(NO₃)₃·6H₂O. The results confirmed that doping with rare earth nitrates instead of rare earth oxides is very promising route in preparing high-performance ZnO-Bi₂O₃-based varistor ceramics.     

Phase equilibria in the system La2O3-BaO-P2O5: The partial system LaPO4-Ba2P2O7-Ba(PO3)2

The LaPO₄-Ba₂P₂O₇-Ba(PO₃)₂ portion of the oxide La₂O₃-BaO-P₂O₅ system has been investigated. Important parts of this investigation were the determination of equilibria in the LaPO₄-Ba(PO₃)₂ subsystem and the addition of liquidus data to the partially known LaPO₄-Ba(PO₃)₂-Ba₂P₂O₇ subsystem. These data were combined with known data from the LaPO₄-Ba₂P₂O₇ subsystem and with measurements of the equilibria within the LaPO₄-Ba₃P₄O₁₃ isopleth to determine the nature of the phase equilibria in the quasi-ternary LaPO₄-Ba₂P₂O₇-Ba(PO₃)₂ system.     

Analysis of the electrochemical reaction behavior of alloy AZ91 by EIS technique in H3PO4/KOH buffered K2SO4 solutions

The EIS technique was used to analyze the electrochemical reaction behavior of Alloy AZ91 in H₃PO₄/KOH buffered K₂SO₄ solution at pH 7. The corrosion resistance of Alloy AZ91 was directly related with the stability of Al₂O₃ · xH₂O rich part of the composite oxide/hydroxide layer on the alloy surface. The break down of the oxide layer was estimated to occur mainly on the matrix solid solution phase in Alloy AZ91. The mf capacitive loop arose from the relaxation of mass transport in the solid oxide phase in the presence of Al₂O₃ · xH₂O rich part and from Mg⁺ ion concentration within the broken area in the absence of Al₂O₃ · xH₂O rich part in the composite oxide structure on the alloy surface. The lf inductive loop had tendency of disappear when the dissolution rate of the alloy decreased as a result of the formation of the protective oxide layer.     

The influence of methylcellulose (MC) on solubility of calcium hydroxyapatite (HA) crystals in HA/MC nanocomposites

The influence of methylcellulose ([C₆H₇O₂(OH)_3–x(OCH₃)_x]_n, MC) on the morphology and solubility of calcium hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, GA) nanocrystals (NCs) in GA/MC organomineral nanocomposites (OMCs) is studied. GA/MC OMCs with the MC content of 0.5, 1, 2, 5, 10 and 20 wt % are synthesized in the Ca(OH)₂–H₃PO₄–[C₆H₇O₂(OH)_3–x(OCH₃)_x]_n–H₂O system under biomimetic conditions (37°C). The composition and structural features of OMCs, as well as crystallographic characteristics, size, and morphology of GA NC in OMCs, are determined via chemical analysis, X-ray diffraction (XRD), infrared spectroscopy (IRS), thermal analysis (DTA and DTG), scanning (SEM) and transmission (TEM) electron microscopy, and electron diffraction (ED). It is shown that the growth in the MC concentration in OMCs leads to the change in the GA NC morphology and the increase in their solubility (for Ca²⁺ and PO₄^3- ions).     

Conductivity of a new pyrophosphate Sn0.9Sc0.1(P2O7)1−δ prepared by an aqueous solution method

New pyrophosphate Sn_0.9Sc_0.1(P₂O₇)_1−δ was prepared by an aqueous solution method. The structure and conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ have been investigated. XRD analysis indicates that Sn_0.9Sc_0.1(P₂O₇)_1−δ exhibits a 3 × 3 × 3 super structure. It was found that Sn_0.9Sc_0.1(P₂O₇)_1−δ prepared by an aqueous method is not conductive. The total conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ in open air is 2.35 × 10⁻⁶ and 2.82 × 10⁻⁹ S/cm at 900 and 400 °C respectively. In wet air, the total conductivity is about two orders of magnitude higher (8.1 × 10⁻⁷ S/cm at 400 °C) than in open air indicating some proton conduction. SnP₂O₇ and Sn_0.92In_0.08(P₂O₇)_1−δ prepared by an acidic method were reported fairly conductive but prepared by similar solution methods are not conductive. Therefore, the conductivity of SnP₂O₇-based materials might be related to the synthetic history. The possible conduction mechanism of SnP₂O₇-based materials has been discussed in detail.     

Synthesis and Preliminary Tests of Suspension Plasma Spraying of Fine Hydroxyapatite Powder

The synthetic hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) is a very useful biomaterial for numerous applications in medicine, such as e.g., fine powder for suspension plasma spraying. The powder was synthesized using aqueous solution of ammonium phosphate (H₂(PO₄)NH₄) and calcium nitrate (Ca(NO₃) · 4H₂O) in the carefully controlled experiments. The synthesized fine powder was characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The powder was formulated into water and alcohol based suspension and used to carry out the initial tests of plasma spraying onto titanium substrate. The phase analysis of sprayed coating was made with the XRD.     

Phase relations and flux research for zinc oxide crystal growth in the ZnO–K2O–P2O5 system

The subsolidus phase relations of the ternary system ZnO–K₂O–P₂O₅ were investigated by means of X-ray diffraction (XRD). There are 7 binary compounds, 6 ternary compounds and 20 three-phase regions in this system. The phase diagram of the pseudo-binary system KZn₄(PO₄)₃–ZnO was also investigated by means of XRD and differential thermal analysis (DTA) methods. KZn₄(PO₄)₃–ZnO is a eutectic system with eutectic temperature about 952 °C and eutectic point at about 2 mol% ZnO. Only narrow composition range in the KZn₄(PO₄)₃–ZnO system is suitable for the growth of ZnO crystals.     

Luminescence properties of Ca10K(PO4)7:RE (RE = Ce, Tb, Dy, Tm and Sm) under vacuum ultraviolet excitation

A series of RE³⁺ (RE = Ce, Tb, Dy, Tm and Sm) activated Ca₁₀K(PO₄)₇ were synthesized by conventional state reaction and their photoluminescence properties under vacuum ultraviolet excitation were investigated. The PO₄³⁻ absorption lies within the range from 125 to 180 nm in all the excitation spectra of Ca₁₀K(PO₄)₇:RE³⁺. The first f-d transition of Ce³⁺ is observed at 316 nm, and the Ce³⁺ emission is located at about 350 nm. Both the first spin-allowed and spin-forbidden f-d transitions of Tb³⁺ are situated at 232 and 263 nm, respectively. The emission spectrum of Ca₁₀K(PO₄)₇:Tb³⁺ exhibits typical Tb³⁺ emissions with the predominant peak at 544 nm. The O²⁻-Dy³⁺ charge transition band was calculated and identified around 173 nm, the CIE chromaticity coordinates of Dy³⁺ were calculated to be 0.364 and 0.392. The Ca₁₀K(PO₄)₇:Tm³⁺ demonstrates the strongest excitation at about 182 nm assigned to O²⁻-Tm³⁺, and gives the predominant emission at 453 nm. The ⁴G_5/2-⁶H_7/2 transition of Sm³⁺ at 601 nm is the most intensive in the emission spectrum.     

Improved high-Q microwave dielectric resonator using ZnO-doped La(Co1/2Ti1/2)O3 ceramics

The microwave dielectric properties and the microstructures of ZnO-doped La(Co_1/2Ti_1/2)O₃ ceramics prepared by conventional solid-state route have been studied. Doped with ZnO (up to 0.75 wt%) can effectively promote the densification of La(Co_1/2Ti_1/2)O₃ ceramics with low sintering temperature. At 1320 °C, La(Co_1/2Ti_1/2)O₃ ceramics with 0.75 wt% ZnO addition possesses a dielectric constant (_r) of 30.2, a Q × f value of 73,000 GHz (at 8 GHz) and a temperature coefficient of resonant frequency (τ_f) of −35 ppm/°C.     

The first-class reciprocal quaternary system H3PO4-K2SO4-K3PO4-H2SO4-H2O application to fertilizer fabrication problems

The first-class reciprocal quaternary system H₃PO₄-K₂SO₄-K_3PO₄-H₂SO₄-H₂O has been carefully investigated at 25 and 75°C. Representations have been given using the J?necke coordinates. Using the established diagrams as a base, a procedure is proposed for preparing specific fertilizers containing potassium and phosphate ions by reacting phosphate rock with aqueous solutions of KHSO₄, addition of calculated amounts of water to the reaction mixture, elimination of an insoluble products, and programmed water evaporation.     

One-step synthesis of MFe2O4 (M = Fe, Co) hollow spheres by template-free solvothermal method

Monodispersed magnetic MFe₂O₄ (M = Fe, Co) hollow spheres were synthesized by simple template free solvothermal method in ethylene glycol (EG) solution. The hollow spheres were in the same size with an average diameter of about 360 nm and the shells of these spheres were about 80 nm, consisted of closely packed nanocrystallines due to Ostwald ripening. EG plays the key role in the synthesis of hollow spheres in contrast with octahedral crystals synthesized in aqueous solution. The products synthesized in aqueous solution were calcined at 800 °C and 1000 °C. The amount of spinel ferrite products increased monotonically with the increase of temperature and appeared as a single phase at 1000 °C. The saturation magnetization (M_s), remanent magnetization (M_r) and coercivity (H_c) for Fe₃O₄ hollow spheres was 74.47 emu/g, 2.59 emu/g and 32.503 Oe respectively whereas the reading of the same indicators for CoFe₂O₄ hollow spheres was 69.07 emu/g, 14.46 emu/g and 242.79 Oe, respectively. The magnetic variation between Fe₃O₄ and CoFe₂O₄ hollow spheres was caused by the radius difference of Fe²⁺ (3d⁶) and Co²⁺ (3d⁷) ions and it was also relevant with nanocrystal sizes of the spin disorder of crystal surface.     

Corrosion characteristics of LiBH4 film exposed to a CO2/H2O/O2/N2 mixture

LiBH₄ films were prepared by pulsed laser deposition using a LiB target in a background pressure of hydrogen. The corrosion characteristics of LiBH₄ films were measured by exposing them to a gas mixture of CO₂/H₂O/O₂/N₂ at ambient temperature for 1–24 h. Scanning electron microscopy images show some cracks on the surface of corrosion films, which could act as easy paths for H₂O and CO₂ to further react with Li⁺ and B³⁺. The X-ray photoelectron spectroscopy results and theoretical analysis show that LiBH₄ tends to react with H₂O and CO₂ to form Li₂B₄O₇, Li₂CO₃ and LiOH during the corrosion process.