Electrolytic deposition of amorphous and crystalline zinc–calcium phosphates

Amorphous Zn–Ca phosphates and crystalline Zn3(PO4)2·4H2O conversion layers on cathode substrates were prepared by electrolysis of mixtures of acidic solutions saturated with metal phosphates. The solutions contained tricalcium phosphate (Ca3(PO4)2) and/or zinc phosphate dihydrate (Zn3(PO4)2·2H2O). The depositions was carried out with constant or pulsating cathode current densities in the range 20–70 mA cm-2 at 20–70 °C. The deposition of the uniform crystalline Zn3(PO4)2·4H2O was performed at a pulsating cathode current density of 70 mA cm-2 at 70 °C for periods up to 10 min. Amorphous deposits of Zn–Ca phosphates containing 20 wt% H2O with variable Zn-to-Ca ratios were deposited at a constant cathodic current of 30 mA cm-2 at 20 °C for 3 min. Surface areas of the amorphous deposits were of the order of 28 m2 g-1. X-ray diffraction, differential thermal analysis and thermogravimetry were used to investigate phase formation and transitions at increasing temperatures. The amorphous Zn–Ca phosphate deposit was after calcination at 900 °C transformed to crystalline phosphates containing the -Ca3(PO4)2 or Ca3-xZnx(PO4)2 and -CaZn2(PO4) phases. © 1998 Kluwer Academic Publishers     

Fibrous growth of tricalcium phosphate ceramics

Structural transformation and sintering processes of tricalcium phosphate (TCP) ceramics prepared from defective hydroxyapatite (Ca9HPO4(PO4)5OH) were studied by X-ray diffraction (XRD) and atomic force microscopy (AFM). Starting powders with Ca/P ratio 1.5 were obtained by adding 0.5 l of 0.3 M H3PO4 solution to an equal volume of 0.45 M Ca(OH)2. In the prepared ceramics, the onset temperature for transformation of defective hydroxyapatite into TCP (witlokite) agrees with the onset temperature for sintering (800 °C). Sintering occurs through the formation of a fibrous structure, which resembles biological hard tissue. In the 1000–1200°C range, these fibres coalesce into grains of up to 0.6 m in size with a fibrous-laminar morphology. At the end of this sintering stage witlokite transforms into TCP. At about 1450°C, partial decomposition of TCP into Ca2P2O7+Ca4P2O9 is observed. AFM observations suggest that Ca2P2O7 is segregated in the liquid state and increases the velocity of grain growth (up to 12 m).     

Novel aqueous sol–gel preparation and characterization of barium M ferrite, BaFe12O19 fibres

Gel fibres of barium M ferrite, BaFe12O19, were blow spun from an aqueous inorganic sol and calcined at temperatures up to 1200°C. The ceramic fibres were shown by X-ray diffraction to be single phase crystalline M ferrite at 1000°C, and surface area and porosity measurements indicated an unusually high degree of sintering at this temperature. The fibres also demonstrated a favourable grain structure of less than 0.1 m at this temperature and maintained a small grain size of less than 4 m even up to 1200°C, an important factor in the magnetic properties of this material.     

Phase transformation in the Al2O3–ZrO2 system

Co-precipitation methods have been used to produce 20 mol% Al2O3–80 mol% ZrO2 mixed oxides, from aqueous solutions of zirconium oxychloride and aluminium chloride, followed by precipitation with ammonia. The resulting gel was calcined at increasing temperatures, and X-ray diffraction confirmed that the structure remained amorphous up to 750°C and then crystallized as a single-phase cubic zirconia solid solution, but with a reduced unit-cell dimension. At higher temperatures, the unit-cell dimension increased and, above 950°C, this phase started to transform to a tetragonal zirconia (t-ZrO2) phase, again of reduced cell dimensions compared with t-ZrO2, with simultaneous appearance of small amounts of -Al2O3. Above 1100°C, the tetragonal phase transformed to monoclinic zirconia on cooling, and the amount of -Al2O3 increased. Above 1200°C, the -Al2O3 transformed to the stable -Al2O3. These results confirm that aluminium acts as a stabilizing cation for zirconia up to temperatures of about 1100°C. © 1998 Chapman & Hall     

γ-Alumina composite membranes modified with microporous silica for CO2 separation

-Al2O3 composite membranes have been modified with microporous silica layers to improve the separation factor of CO2 to N2. From the analysis of micropore volume fraction and CO2 adsorption behaviour of SiO2 unsupported membranes, it was found that the SiO2 membrane layer feasible to separate CO2 could be obtained from a sol prepared by hydrolysis of tetraethyl orthosilicate in aqueous nitric acid solution (acid concentration of 0.001 M and sol pH of 2.0). The unsupported membrane prepared from this optimum sol had a micropore volume fraction of 0.85 and CO2 adsorption amount of 27 cm3(STP)g–1 at 0.1 MPa and 25°C. Defect-free silica modified -Al2O3 membranes could besynthesized by dipcoating or pressurized coating from outside the support. The CO2/N2 separation factor of these membranes varied severely with the separation process parameters, such as transmembrane pressure, stage cut and CO2 concentration in feed gas. -Al2O3 membranes modified by dipcoating and pressurized coating had a CO2/N2 separation factor of 2.4 and 1.45, respectively, at P = 0.3 MPa, stage cut = 0.1, and 25°C for a CO2 feed gas mole fraction of 0.5. The CO2/N2 separation factor at 25°C decreased with increasing heat-treatment temperature. The main mechanisms of CO2 permeation through silica modified membranes were surface diffusion and Knudsen diffusion.     

(ZnO)3In2O3 fine powder prepared by combustion reaction of nitrates-glycine mixture

Conducting fine powder was obtained in the ZnInO system by combustion of the gel prepared from an aqueous solution of mixed zinc and indium nitrates in the presence of glycine. Glycine worked as a fuel as well as a gelling agent in the combustion under the strong oxidizing power of the nitrates. In spite of the low furnace temperature of 350 °C, the product was (ZnO)₃In₂O₃ which has been obtained above 1260 °C in a solid state reaction of a mixture of ZnO and In₂O₃. The combustion synthesis led to an aggregated fine powder of hexagonal platelets of about 40 nm in diameter. Its compacted mass showed an electrical resistivity of about 700 Ω cm. The agglomeration was improved by dispersing the fine powder in an acetic acid aqueous solution.     

Coating of CaTiO3 on titanium substrates by hydrothermal reactions using calcium-ethylene diamine tetra acetic acid chelate

Titanium plates were treated in [Ti(O₂)EDTA]^2-– -Ca(EDTA)^2- mixed solutions and/or Ca(EDTA)^2- solutions (where EDTA is ethylene diamine tetra acetic acid) at pH 9–13 and 150–250 °C for 0.5–12 h. The film, about 50 m thick, and consisting of mixtures of CaTiO₃ and TiO₂ was formed in 0.01 M [Ti(O₂)EDTA]^2- – 0.01 M Ca(EDTA)^2- mixed solution at pH 13 and 250 °C for 6 h. The film consisted of large icosahedral and hexagonal particles, of about 10 m diameter, and small aggregated particles, of about 1 m diameter. On the other hand, the film, about 20 m thick, consisted of hexagonal plate-like CaTiO₃ particles, of about 1 m diameter, was formed in 0.01 M Ca(EDTA)^2- solution at pH 13 and 250 °C for 6 h. The thickness of both films increased with time, where the film formation rate in 0.01 M [Ti(O₂)EDTA]^2- – 0.01 M Ca(EDTA)^2- mixed solution was much faster. The CaTiO₃ film formed on the surface of titanium promoted the precipitation of hydroxyapatite on the substrate by the hydrothermal reactions in Ca(EDTA)^2-–PO ₄ ^3- mixed solutions.     

Preparation of nanocrystalline SrBi2Ta2O9 powders using sucrose-PVA as the polymeric matrix

Nanocrystalline powders of SrBi₂Ta₂O₉ (Strontium Bismuth Tantalate) have been prepared through evaporation of a polymer-based aqueous precursor solution. The precursor solution was obtained by homogeneous dispersion of the water-soluble metal salts (i.e., strontium nitrate, bismuth nitrate and tartarate complex of tantalum) in a polymeric matrix created by an aqueous solution mixture of sucrose and polyvinyl alcohol. Complete evaporation of the precursor solution (at 200°C) resulted in a fluffy, porous, carbonaceous mass, which on calcination at 750°C/2 h yield the single-phase SrBi₂Ta₂O₉ powders with average particle size 35 nm. The compacted powders, after sintering at 1000°C/4 h, show density of 96.8% of its theoretical value and dielectric constant value of 862 with Curie temperature (T _c) at 287°C, when measured at 100 KHz.     

Magnetic Co2Y ferrite, Ba2Co2Fe12O22 fibres produced by a blow spun process

Gel fibres of Co2Y,Ba2Co2Fe12O22, were blow spun from an aqueous inorganic sol and calcined at temperatures of up to 1200°C. The ceramic fibres were shown by X-ray diffraction to form crystalline Co2Y at 1000°C, and surface area and porosity measurements indicated an unusually high degree of sintering at this temperature. The fibres also demonstrated a small grain size of 1–3 m across the hexagonal plane and 0.1–0.3 m thickness at 1000°C. This only increased to 3 m in diameter and 1 m thickness even at temperature up to 1200°C. The fibrous nature combined with the improved microstructures could be an important factor in improving the magnetic properties of this material.     

The synthesis and thermal behaviour of zinc diphosphates

Zinc diphosphates (Zn₂P₂O₇ · 5H₂O, Zn₂P₂O₇ · 3H₂O, 5K_1.4Zn_1.3P₂O₇ · 16H₂O, and 5K_0.8Zn_1.6P₂O₇ · 9H₂O) were made by the wet process. The composition of the products was dependent on the conditions (concentration, pH, and dropping rate of the solution) of the process. When the products were heated, decomposition of the diphosphates to orthophosphate took place below about 150 ·C. Polymerization of the phosphates to phosphates with longer chains was observed in the temperature range 150 to 400 ° C. The amorphous phosphates thermally produced by heating diphosphates other than 5K_1.4Zn_1.3P₂O₇ · 16H₂O, showed reorganization to diphosphate above 400 ° C according to the reaction M₂O₃PO[P(O₂M)O] _n PO₃M₂ +nM₃PO₄(n + 1)M₄P₂O₇ where M represents K and/or 1/2Zn.     

Electrical properties of MREGeO<Subscript>4</Subscript> (M = Li,Na, K; RE = rare earth) ceramics

Fourteen kinds of alkali-metal rare earth germanate ceramics, MREGeO₄ (M = Li, Na, K; RE = rare earth), were synthesized and their electrical properties were investigated. The crystal structures of the major phases of MREGeO₄ could be classified into four groups; hexagonal (apatite type), tetragonal, orthorhombic (olivine type) and orthorhombic (-K₂SO₄ type). The tetragonal group exhibited higher ionic conductivity than the other groups in the range 300 to 700°C. The highest conductivity was achieved for the LiNdGeO₄ having a tetragonal structure (2.95 × 10^–2 S cm^–1 at 700°C). Analyses on the basis of the Nernsts equation indicated that the two electron reaction associated with carbon dioxide molecule takes place at the detection electrode above 400°C regardless of the kind of electrolyte. The electromotive force, EMF, of the potentiometric CO₂ gas sensors designed using MLaGeO₄ (M = Li, Na, K) increased linearly with an increase in the logarithmic value of CO₂ partial pressure, in accordance with the Nernst equation.     

X-ray diffraction and Ir-absorption characteristics of lanthanide orthophosphates obtained by crystallisation from phosphoric acid solution

Powders of LnPO₄ · H₂O (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) prepared by crystallisation from boiling phosphoric acid (2 M H₃PO₄/1) solution were characterised by X-ray diffraction and FTIR-spectroscopy. Hexagonal LnPO₄ · H₂O (La Tb), tetragonal (Ho Lu and Y) and orthorombic DyPO₄ · H₂O crystalline modifications were identified. Ir-spectra of the hydrated hexagonal, anhydrous tetragonal LnPO₄ · H₂O (Dy, Ho, Er, Tm, Yb, Lu and Y) and anhydrous monoclinic (La Tb) are consistent with those reported in the literature. However, the hydrated tetragonal LnPO₄ · H₂O (Ho, Er, Tm, Yb, Lu and Y) display a surplus band (625 cm^–1) in the region of ₄, which was not reported in the literature. The band disappears after ignition at 950°C, while the tetragonal structure is still maintained, which may imply that it is attributed to hydrogen bonding of H₂O molecules to the phosphate oxygen in hydrated salts. Some of the phosphates, after ignition at 950°C, display additional P₂O₇ ^4– band at 1265–1267 cm^–1. That may be resulted from HPO₄ ^2– for PO₄ ^3– substitution in the phosphates crystallised in acidic (2 M H₃PO₄/1) solution.     

Synthesis and thermal behaviour of sodium monoimidocyclotriphosphate

Trisodium monoimidocyclotriphosphate dihydrate, Na₃P₃O₈NH·2H₂O, was made by hydrolysing triimidocyclotriphosphate in an aqueous acetic acid solution at 70 °C. The monoimidocyclotriphosphate was converted to cyclotriphosphate by heating in air according to the reaction Na₃P₃O₈NH + H₂O (NaPO₃)₃ + NH₃     

Influence of temperature and additives on the microstructure and sintering behaviour of hydroxyapatites with different Ca/P ratios

Sintering of two hydroxyapatite (HA) samples with different Ca/P ratios was studied as a function of thermal pretreatments, sintering temperature and additives (0–0.6 ion % Li+ or 0–5 ion % Mg2+). The samples were sintered in air and characterized by density measurements, scanning electron microscopy, differential thermal analysis, X-ray diffraction and dilatometry. Upon sintering, samples with Ca/P ratio of 1.51 (HA C) transformed to -Ca3(PO4)2 and Ca10(PO4)6(OH)2, resulting in materials with low densities and containing agglomerated -Ca3(PO4)2 when sintered above 1200°C. Samples with a Ca/P ratio of 1.77 (HA S), without -Ca3(PO4)2, showed better sinterability and homogeneous microstructures. Li+ additions favoured liquied-phase sintering and reduced the -Ca3(PO4)2 content in sintered materials. Mg2+ additions did not result in higher densities, but inhibited the hydroxyapatite grain growth rate. A significant percentage of the added Mg2+ was incorporated into the -Ca3(PO4)2 structure.     

The effects of temperature on the behaviour of an apatitic calcium phosphate cement

An apatitic calcium phosphate cement is obtained by mixing -tricalcium phosphate (-TCP) and precipitated hydroxyapatite into a cement powder, and by then mixing this powder with an aqueous solution of Na₂HPO₄ as an accelerator. Setting times were reduced by about 30% by increasing the temperature from 22 to 37°C. Compressive strength reached higher intermediate and final values at 37 °C. Degrees of transformation of the -TCP in the resulting calcium-deficient hydroxyapatite (CDHA) were much higher at 37 °C after 24 h of storage in Ringer's solution according to X-ray diffraction. Differential scanning calorimetry indicated that the rate of reaction increased by a factor of about 5 when the temperature was increased from 25 to 37 °C. Scanning electron microscopy showed that the microstructure was more homogeneous and that a more tight entanglement of the precipitated CDHA crystals occurred after storage at 37 °C than at room temperature.     

The hydrolysis product of ferric nitrate in sodium hydroxide

The hydrolysis product of ferric nitrate is obtained by adding ferric nitrate solution to a boiling solution of 2.5 N sodium hydroxide. The sample is amorphous to X-rays when heated below 600° C, but it shows X-ray lines of -Fe₂O₃ at 650° C. Thermal analysis of the sample gives an endothermic peak at 80° C and two small exothermic peaks at 280° C and 700° C. Transmission electron microscopy and infrared spectroscopy confirm the primary particles as a defect form of FeOOH · H₂O. The defect FeOOH form of the sample converts to the disordered form of Fe₂O₃ on further heating around 700° C. The drastic fall in the surface area of the sample beyond 600° C suggests sudden growth of particle size, which is confirmed by a small endothermic peak at 700° C.     

Synthesis and formation mechanism of submicrometre spherical cordierite powders by ultrasonic spray pyrolysis

Cordierite powders containing very pure submicrometre spherical particles have been synthesized by the ultrasonic spray pyrolysis. Aqueous solutions of silicic acid, Al(NO3)3·9H2O and MgCl2·6H2O were used as precursors. Scanning electron micrographs have shown that particle surfaces were smooth and the mean particle diameter was 0.834 m. For the estimation of chemical and phase composition and phase transformation temperatures, differential thermal analysis, thermogravimetric analysis, X-ray diffraction, energy dispersive spectroscopy and infrared analysis have been applied. It was found that during spray pyrolysis, the condensation of silicic acid mostly occurred while aluminium and magnesium ion remained incorported between Si–O–Si chains. By subsequent heating to over 800°C, Si–O–M bonds (M=Al, Mg) were formed. The synthesis of cordierite occurred by the crystallization of -cordierite from the amorphous phase at 900°C followed by the phase transformation of - into -cordierite in the temperature range 1100–1200°C.     

Amorphous phase formation of the pseudo-binary Al2O3–ZrO2 alloy during plasma spray processing

Thick deposits of the Al2O3–ZrO2 with near eutectic compositions were prepared by plasma-spray deposition and subjected to heat treatment to investigate the crystallization and phase transformation behaviors. The structures of as-sprayed deposits are mostly amorphous and a small amount of t-ZrO2 and -Al2O3 particles with a diameter of approximately 20 nm are also present. Simultaneous crystallization of t-ZrO2 and -Al2O3 from the glass occurs at 945 °C, followed by - and -Al2O3 above 1000 °C, and only -Al2O3 are observed above 1200 °C. Phase transformation of t-ZrO2 to m-ZrO2 occurs at 1213 °C. There is no appreciable difference in amorphous formation and subsequent crystallization and phase transformation behaviors with two different feedstock powder sizes. It is shown that it is feasible to produce the thick amorphous Al2O3–ZrO2 materials with proper control of plasma spraying process parameters.     

Characteristics of translucent alumina produced by slip casting method using gypsum mold

Translucent Al₂O₃ ceramics were successfully produced by slip casting using a gypsum mold, provided that CaSO₄ impurities, which had penetrated into the green bodies from the gypsum mold, were removed by the wash of HCl aqueous solution. Some of the calcined Al₂O₃ compacts were washed with HCl aqueous solution before sintering the compacts and the others were not washed with HCl aqueous solution. The relative densities of the sintered Al₂O₃ ceramics with HCl treatment were higher than those of the untreated samples. Grains in the HCl-treated samples, which sintered at 1350°C, grew homogeneously with about 1 m in diameter. When the sintering temperature was higher, the grains grew homogeneously. The sintered Al₂O₃ ceramics with the HCl treatment were translucent. The transmittance value increased from 0 to 12% with increasing wavelength from 300 to 900 nm. The Al₂O₃ ceramics with the HCl treatment did not have the transmittance when the solid contents of slurry were low. The transmittance was influenced by the solid contents of slurry. On the other hand, grains in the HCl-untreated samples, which sintered at 1350°C, grew heterogeneously with the range from 0.2 to 2 m. The Al₂O₃ ceramics did not have the transmittance.     

Influence of the high temperature treatment of zinc phosphate conversion coatings on the corrosion protection of steel

An anhydrous -Zn₃(PO₄)₂ phase converted by the dehydration of hydrous zinc phosphate, Zn₃(PO₄)₂·2H₂O, crystal coatings in air at a temperature of approximately 300 °C, significantly enhances the corrosion resistance of steel, and also reduces the susceptibility of the crystals to alkaline dissolution. A subsequent phase transition at approximately 500 °C results in a poor protection behaviour, because of the formation of numerous microcracks on the crystal faces.