Preparation of ferroelectric Pb(Zr0.52 Ti0.48)O3 thin films by sol-gel processing

Ferroelectric Pb(Zr_0.52 Ti_0.48)O₃ thin films were prepared by sol-gel processing on the Pt/Ti/SiO₂/Si(100) substrates. Effects of the concentration (0.2–0.8 M) of the starting solution (Pb/Zr/Ti= 1.1/0.52/0.48) and the sintering temperature (500–700 ‡C) on crystallinity, microstructure and electrical properties of PZT thin films were investigated. For the thin film prepared at 0.4 M starting solution, the highest crystallinity appeared at a sintering temperature of 650 ‡C. The average grain size of the PZT thin films was about 0.17 Μm. The film thickness was about 0.2 Μm. The relative dielectric constant and the dissipation factor of the film measured at 1 kHz were about 750 and 4.3%, respectively. The remnant polarization (Pr) and coercive field (Ec) of the film measured at the applied voltage of 5 V were about 49 ΜC/cm² and 134 kV/cm, respectively.     

Sealing effects of anodic oxide films formed on Mg-Al alloys

Mg alloys were anodized in alkaline NaOH solutions with various additives as a non-chromate method. Specimen AZ91 was anodized at a potential that produced a strong surface dissolution reaction and generated a large amount of Mg(OH)₂. The effect of sealing after anodizing was investigated, focusing on the effects of sealing time, temperature and solution conditions. The current density decreased with increasing A1(OH)₃ concentration in 1 M NaOH solution during anodizing; sparking occurred at potentials above 80 V. The best corrosion resistance with anodizing in 1 M NaOH solution occurred at a potential of 4 V, which caused the strongest active dissolution reaction. The sealing effect improved with increasing time and temperature, and corrosion resistance was proportional to the relative ratio of Mg(OH)₂. If the oxygen thickness observed by EDX equaled the film thickness, the film formed at 4 V in 1 M NaOH was 10–15 Μm thickness. The optimum corrosion resistance in sealing at various solutions after anodizing was 1M-NaOH solution.     

Chemical treatment of sabkha in Saudi Arabia

There are large bodies of saline marsh water along the coast of the Red Sea in Saudi Arabia. This type of salinewater body (sabkha) was chemically processed to produce partially desalted water. Typical sabkha consists mainly of Na⁺, Mg⁺² and Ca⁺² salts. The salts are put in contact first with ammonia (NH₃) and then carbon dioxide in an attempt to convert them into chemicals such as sodium bicarbonate (NaHCO₃) and ammonium chloride (NH₄Cl). The conversions depend on the initial ammonia concentration (2.5-7.5 M), sabkha concentration (1.6-3.9 M), length of carbonation time (up to 3 h) and the NH₃/NaCl ratio. The partially desalted water obtained could be further processed for industrial and other uses.     

Preparation of microporous silica membranes for gas separation

Microporous silica membranes for hydrogen separation were prepared on a γ-alumina coated α-alumina tube by sol-gel method. The reactants of sol-gel chemistry were tetraethoxysilane (TEOS) and methacryloxypropyl-trimethoxysilane (MOTMS). The silane coupling agent, MOTMS, was added as a template in order to control the pore structure to the silicon alkoxide, TEOS. In particular, the microporous membranes were prepared by changing the molar ratio of MOTMS with respect to other substances, and their pore characteristics were analyzed. Then, the effects of thermal treatment on the micropore structure of the resulting silica membranes were investigated. The pore size of the silica membrane prepared after calcination at 400–700 ‡C was in the range of 0.6–0.7 nm. In addition, permeation rates through the membranes were measured in the range of 100–300 dgC using H₂, CO₂, N₂, CH₄, C₂H₆, C₃H₆ and SF₆. The membrane calcined at 600 ‡C showed a H₂ permeance of 2×10^-7-7×10^-7 molm^-2s^-1Pa^-1 at permeation temperature 300 ‡C, and the separation factors for equimolar gas mixtures were 11 and 36 for a H₂/CO₂ mixture and 54 and 132 for a H₂/CH₄ mixture at permeation temperatures of 100 ‡C and 300 ‡C, respectively.     

Friedel–Crafts catalysis using supported reagents. Synthesis, characterization and catalytic application of ZnCl2 supported on fluoride‐modified sol–gel‐derived aluminosilicates

ZnCl₂–aluminosilicate catalysts were prepared via a sol–gel route involving fluoride‐catalyzed hydrolysis of aluminum and silicon alkoxides in the presence of NaF, KF, NH₄F and ZnF₂. The catalysts were characterized by employing ²⁹Si, ²⁷Al and ¹⁹F solid‐state MAS NMR. The dependence of the activities of the catalysts on the nature and amount of fluoride present in the catalysts were investigated using Friedel–Crafts alkylation reaction of benzene with benzyl chloride. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thiophene hydrodesulfurization over modified alumina-supported molybdenum sulfide catalysts

Methanethiol has been synthesized by one‐step catalytic reaction from H₂S‐content syngas on K₂MoS₄/SiO₂ catalyst with selectivity over 95% under the optimum reaction conditions of 563 K, 2.0–3.0 MPa and 5–6% H₂S content in the feed syngas. The results of XRD and XPS showed that Mo–S–K phase on the surface of the catalyst K₂MoS₄/SiO₂ was responsible for the high activity and selectivity to methanethiol, and which may be restrained by the existence of (S–S)^2- species. This revised version was published online in July 2006 with corrections to the Cover Date.     

Barium titanate thin films prepared on MgO (100) substrates by coating-pyrolysis process

Barium titanate (BaTiO₃) thin films were prepared on MgO (100) substrates using metal naphthenate solution by a coating-pyrolysis process. Amorphous films pyrolyzed at 470‡C were crystallized to BaTiO₃ phase by heat treatment at higher temperatures. The crystallinity and alignment of the films depended on temperature and on atmosphere during heat treatment. Epitaxial BaTiO₃ film having (100)-orientation was obtained by heat treatment at 900‡C under oxygen partial pressure of 2x 10^-4 atm. The epitaxial BaTiO₃ film had a lattice constant of 0.401₆ nm and displayed a smooth surface with some pores dispersed on the surface. By heat treatment in air, amorphous BaTiO₃ film was obtained at 900‡C or below, and textured film with less strong (100) orientation was obtained at 1,200‡C and consisted of grains with diameter about 0.3 Μ.     

Dissolution of serpentine using recyclable ammonium salts for CO2 mineral carbonation

Low efficiency of mineral dissolution and unrecyclable use of additives are two barriers for the development of CO₂ mineral carbonation. A new pH-swing CO₂ mineralisation process using recyclable ammonium salts is proposed to overcome these barriers. This paper presents the studies of mineral dissolution with ammonium salts. In this study, dissolution of a serpentine sample was performed using a series of aqueous solutions, which include (NH₄)₂SO₄, NH₄Cl, NH₄HSO₄ and H₂SO₄. NH₄HSO₄ is the most efficient in terms of extracting Mg extraction from the serpentine sample. At 100 °C 1.4 M NH₄HSO₄ extracted 100% of Mg from serpentine in 3 h, as well as 98% of Fe and 17.6% of Si. The rate limiting mechanism of serpentine dissolution with NH₄HSO₄ is a chemical reaction with product layer diffusion control and the activation energy of this dissolution was 40.9 kJ mol⁻¹.     

Study on Selective Dimerization of α-Methylstyrenes Promoted by Ionic Liquids

The catalytic systems composed of ionic liquids containing BF₄⁻ anion and HBF₄ showed high catalytic activity to produce 4-methyl-2,4-diphenyl-1-pentene (MDP-1) or 1,1,3-trimethyl-3-phenylindan (TPI) under different temperature conditions. Up to 90.8% selectivity to MDP-1 with a 98.7% conversion of α-methylstyrene was obtained at 60 °C in the presence of [HexMIm]BF₄–HBF₄, while exclusive TPI was yielded when the reaction temperature increased to 120 °C. Further studies showed that another ionic liquid, [BMIm]Cl · 2AlCl₃, could act as an excellent catalyst and solvent for the dimerization of α-methylstyrene to produce TPI. The dimerization of α-methylstyrene catalyzed by [HexMIm]BF₄–HBF₄ and [BMIm]Cl · 2AlCl₃ performed the same reaction mechanism and the proton was the active species.     

Electrochemical treatment of ammonia in wastewater by RuO<Subscript>2</Subscript>–IrO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>/Ti electrodes

This study investigated the removal of ammonia in wastewater by an electrochemical method using titanium electrodes coated with ruthenium and iridium (RuO₂–IrO₂–TiO₂/Ti) with low chlorine evolution over-voltage. The effects of operating parameters, including chloride ion concentration, current density and initial pH, were also investigated. The results were evaluated primarily by considering the efficiency of the elimination of NH₄⁺-N. The removal of ammonia by electrochemical oxidation mainly resulted from the indirect oxidation effect of chlorine/hypochlorite produced during electrolysis. The direct anodic oxidation efficiency of ammonia was less than 5%, and the current efficiency was less than 10%. The ammonia removal followed pseudo-first-order kinetics. The electrochemical process can be applied successfully as a final polishing step, or as an alternative method to biological nitrification. The process seems to be most beneficial for small coastal cities     

Hydrothermal synthesis of LA-MN-Hexaaluminates for the catalytic combustion of methane

Hydrothermal synthesis by using urea hydrolysis at 1.0-3.0 MPa and 120-130 ‡C was employed to prepare Mn-substituted hexaaluminate catalysts for methane combustion. The results from DTA-MS demonstrated that CO_3- and Off anions co-exist in the hydrothermal reaction. XRD reveals that the components of carbonates and hydroxides in the hydrothermal reaction are more favorable than those in the (NH₄)₂CO₃ co-precipitation for the formation of the Mn-substituted hexaaluminate phase. After calcination at 1,200 ‡C for 2 h, LaMnAl₁₁O₁₉ is the major phase of the catalyst prepared by the hydrothermal synthesis method while LaAlO₃ is the major one of the catalysts prepared by NH₄OH and (NH₄)₂CO₃ co-precipitation. The catalyst prepared by hydrothermal synthesis has higher activity than that prepared by NH₄OH and (NH₄)₂CO₃ co-precipitation. The major reason is that more Mn²⁺ ions have incorporated into the hexaaluminate lattice. The effect of drying methods on the formation of hexaaluminate phase was also discussed.     

Water Denitration over a Pd–Sn/Al2O3 Catalyst

Bimetallic Pd–Sn catalysts were synthesized by incipient-wetness impregnation of the metals on alumina and employed for the reduction of nitrates from aqueous solutions. The catalysts were characterized by FTIR spectroscopy of adsorbed CO, X-ray diffraction (XRD), transmission electron microscopy (TEM), and H₂ chemisorption. The influence of the metal ratio was evaluated in reaction measurements. The bimetallic Pd–Sn catalysts exhibited high selectivity for nitrate removal forming less NO₂⁻ and NH₄⁺ than the Pd–Cu catalysts.     

Leaching kinetics of ulexite in sodium hydrogen sulphate solutions

The aim of this study was to investigate the dissolution kinetics of ulexite in sodium hydrogen sulphate solutions in a mechanical agitation system and to declare an alternative reactant to produce boric acid. Reaction temperature, concentration of sodium hydrogen sulphate solutions, stirring speed, solid/liquid ratio and ulexite particle size were selected as parameters of the dissolution rate of ulexite. The experimental results were successfully correlated by linear regression using Statistica program. Dissolution curves were evaluated in order to test shrinking core models for solid-fluid systems. It was observed that increase in the reaction temperature and decrease in the solid/liquid ratio cause an increase in the dissolution rate of ulexite. The dissolution extent is highly increased with increase in the stirring speed rate between 100 and 700 rpm experimental conditions. The activation energy was found to be 36.4 kJ/mol. The leaching of ulexite was controlled by diffusion through the ash or product layer. The rate expression associated with the dissolution rate of ulexite depending on the parameters chosen may be summarized as: 1–3(1 − X)^2/3 + 2(1 − X) = 6.17 × C^0.97 × W^1.17 × D^−1.72 × (S/L)^−0.66 × e^(−36.4/RT)·t.     

Separation of perillyl alcohol from the peel of citrus unshiu by supercritical CO2 and preparative high-performance liquid chromatography

To separate perillyl alcohol (POH), a potential anti-cancer agent, the peel of citrus unshiu was extracted by supercritical CO₂ extraction (SCE) system at 50 ‡C, 200 bar and 6 kg CO₂/hr/kg sample. The extracts were partitioned by acetonitrile/hexane (90/10, vol%). POH was eluted in the acetonitrile phase. An open-tubular chromatography with silica gel (40–63 Μm) was used to purify POH from the acetonitrile phase. Mobile phase was hexane/ethyl acetate (90/10, vol%). To obtain POH in a pure form, finally preparative high-performance liquid chromatography was applied. The collection of POH from citrus unshiu peel was achieved on a laboratory-prepared Chromatographic column (300x3.9 mm) packed with 15 Μm C₁₈ preparative packings. The composition of mobile phase was water/acetonitrile (50/50, vol%). The flow rate of the mobile phase was 1 ml/min and UV wavelength was fixed at 205 nm. It was found that the total yield of POH was 1.6xl0^-3 (wt%) as the dry powder of citrus unshiu peel.     

Pyrolysis kinetics and characteristics of the mixtures of waste ship lubricating oil and waste fishing rope

Kinetic investigations on the pyrolysis of a mixture of waste ship lubricating oil (WSLO) and waste fishing rope (WFR) were carried out using a thermogravimetric analyzer (TGA) at a heating rate of 0.5 ‡C/min, 1.0 ‡C/min and 2.0 ‡C/min. WSLO and WFR were mainly decomposed at the temperature of range of 400 ‡C to 455 ‡C and 370 ‡C to 410 ‡C, respectively. The WSLO/WFR mixture was mainly decomposed at the temperature range of 300 ‡C and 450 ‡C, which is a lower temperature than that for the WSLO or the WFR alone at each heating rate. The ranges of apparent activation energies of the WALO/WFR mixture were between 137 kJ mol^-1 and 197 kJ mol^-1 at conversions in the range of 10–95%. The mixture of WSLO and WFR was pyrolyzed in a micro-scale tubing reactor at 440 ‡C for 60 min and 80 min. The yield of pyrolyzed gases increased from 2.13 wt% to2.29 wt% with reaction time. The selectivity to C₇ hydrocarbons was shown in the pyrolyzed oil of the mixture.     

Nonoxidative dehydrogenation and aromatization of methane over W/HZSM‐5‐based catalysts

Highly active and heat‐resisting W/HZSM‐5‐based catalysts for nonoxidative dehydro‐aromatization of methane (DHAM) have been developed and studied. It was found from the experiments that the W−H₂SO₄/HZSM−5 catalyst prepared from a H₂SO₄‐acidified solution of ammonium tungstate (with a pH value at 2–3) displayed rather high DHAM activity at 973–1023 K, whereas the W/HZSM‐5 catalyst prepared from an alkaline or neutral solution of (NH₄)₂WO₄ showed very little DHAM activity at the same temperatures. Laser Raman spectra provided evidence for existence of (WO₆)^n- groups constructing polytungstate ions in the acidified solution of ammonium tungstate. The H₂‐TPR results showed that the reduction of precursor of the 3% W–H₂SO₄/HZSM‐5 catalyst may occur at temperatures below 900 K, producing W species with mixed valence states, W⁵⁺ and W⁴⁺, whereas the reduction of the 3% W/HZSM‐5 occurred mainly at temperatures above 1023 K, producing only one type of dominant W species, W⁵⁺. The results seem to imply that the observed high DHAM activity on the W–H₂SO₄/HZSM‐5 catalyst was closely correlated with (WO₆)^n- groups with octahedral coordination as the precursor of catalytically active species. Incorporation of Zn (or La) into the W–H₂SO₄/HZSM‐5 catalyst has been found to pronouncedly improve the activity and stability of the catalyst for DHAM reaction. Over a 2.5% W–1.5% Zn–H₂SO₄/HZSM‐5 catalyst and under reaction conditions of 1123 K, 0.1 MPa, and GHSV=1500 ml/(h g−cat.), methane conversion (XCH₄) reached 23% with the selectivity to benzene at ∼96% and an amount of coke for 3 h of operation at 0.02% of the catalyst weight used. This revised version was published online in July 2006 with corrections to the Cover Date.     

Purification and characterization of thermophilic and alkalophilic tributyrin esterase fromBacillus strain A30-1 (ATCC 53841)

An extracellular esterase (EC 3.1.1.1) from a thermophilicBacillus A30-1 (ATCC 53841) was purified 139-fold to homogeneity by sodium chloride (6 M) treatment, ammonium sulfate fractionation (30–80%) and phenyl-Sepharose CL-6B column chromatography. The native enzyme was a single polypeptide chain with a molecular weight of about 65,000 and an isoelectric point at pH 4.8. The optimum pH for esterase activity was 9.0, and its pH stability range was 5.0–10.5. The optimum temperature for its activity was 60°C. The esterase had a half-life of 28 h at 50°C, 20 h at 60°C and 16 h at 65°C. It showed the highest activity on tributyrin, with little or no activity toward long-chain (12–20 carbon) fatty acid esters. The enzyme displayed K_m and K_cat values of 0.357 mM and 8365/min, respectively, for tributyrin hydrolysis at pH 9.0 and 60°C. Cyclodextrin (α, β, and γ), Ca²⁺, Co²⁺, Mg²⁺ and Mn²⁺ enhanced the esterase activity, and Zn²⁺ and Fe²⁺ acted as inhibitors of the enzyme activity. The enzyme activity was not affected by ethylenediaminetetraacetic acid, p-chloromercuribenzoate andN-bromosuccinimide. This paper was presented in part at the 82nd Annual Meeting and Exposition of the American Oil Chemists’ Society, held May 12–15, 1991, in Chicago, Illinois.     

Assessment of CH4 and N2O fluxes in a Danish beech (Fagus sylvatica) forest and an adjacent N-fertilised barley (Hordeum vulgare) field: effects of sewage sludge amendments

Fluxes of CH₄ and N₂O were measured regularly in an agricultural field treated with 280 g m⁻² of sewage sludge. In a nearby beech forest N₂O and CH₄ fluxes were measured in a well-drained (dry) area and in a wet area adjacent to a drainage canal. We observed brief increases of both CH₄ and N₂O emissions immediately following soil applications of digested sewage sludge. Cumulated values for CH₄ emissions over the course of 328 days after sludge applications indicated a small net source in sludge treated plots (7.6 mg C m⁻²) whereas sludge-free soil constituted a small sink (-0.9 mg C m⁻²). The CH₄ emission amounted 0.01% of the sludge-C. Extrapolated to current rates of sludge applications in Danish agriculture this amounts to 0.1% of the total agricultural derived CH₄. Sludge applications did not affect cumulated fluxes of N₂O showing 312 mg N₂O–N m⁻² and 304 mg N m⁻² with and without sludge, respectively. Four months after the sludge applications a significant effect on CO₂ and NO emissions was still obvious in the field, the latter perhaps due to elevated nitrification. Nitrous oxide emission in the beech forest was about six times smaller (45 mg N m⁻²) than in the field and independent of drainage status. Methane oxidation was observed all-year round in the forest cumulating to -225 mg C m⁻² and -84 mg C m⁻² in dry and wet areas. In a model experiment with incubated soil cores, nitrogen amendment (NH₄Cl) and perturbation significantly reduced CH₄ oxidation in the forest soil, presumably as a result of increased nitrification activity. Sludge also induced net CH₄ production in the otherwise strong CH₄ oxidising forest soil. This emphasises the potential for CH₄ emissions from sewage sludge applications onto land. The study shows, however, that emissions of N₂O and CH₄ induced by sewage sludge in the field is of minor importance and that factors such as land use (agriculture versus forest) is a much stronger controller on the source/sink strengths of CH₄ and N₂O. This revised version was published online in August 2006 with corrections to the Cover Date.     

General aspects of ethylene polymerization by d0 and d0f n transition metals

We present a generalized view of d⁰and d⁰f ⁿ metal complexes as olefin polymerization catalysts from computational studies of the {L}M–C₂H₅ ^(0,+,2+)-fragments (M = Sc(III), Y(III), La(III), Lu(III), Ti(IV), Zr(IV), Hf(IV), Ce(IV), Th(IV) and V(V); L = NH–(CH)₂–NH^2- {1}, N(BH₂)–(CH)₂–(BH₂)N^2- {2}, O–(CH)₃–O^- {3}, Cp₂ ^2- {4}, NH–Si(H₂)–C₅H₄ ^2- {5}, {(oxo)(O–(CH)₃–O)}^3- {6}, (NH₂)₂ ^2- {7}, (OH)₂ ^2- {8}, (CH₃)₂ ^2- {9}, NH–(CH₂)₃–NH^2- {10} and O–(CH₂)₃–O^2- {11}). This revised version was published online in June 2006 with corrections to the Cover Date.     

Phase transformation in CeO2–Co3O4 binary oxide under reduction and calcination pretreatments

The CeO₂–Co₃O₄ binary oxide was prepared by impregnation of the high surface area Co₃O₄ support (S.A. = 100m² g⁻¹) with cerium nitrate (20 wt% cerium loading on Co₃O₄). Pretreatment of CeO₂–Co₃O₄ binary oxide was divided both methods: reduction (under 200 and 400 °C, assigned as CeO₂–Co₃O₄–R200 and CeO₂–Co₃O₄–R400 and calcination (under 350 and 550 °C, assigned as CeO₂–Co₃O₄–C350 and CeO₂–Co₃O₄–C550). The binary oxides were investigated by means of X-ray diffraction (XRD), nitrogen adsorption at −196 °C, infrared (IR), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS) and temperature programmed reduction (TPR). The results showed that the binary oxides pretreatment under low-temperatures possessed larger surface area. The cobalt phase of binary oxides also was transferred upon the treating temperature, i.e., the CeO₂–Co₃O₄–R200 binary oxide exhibited higher surface area (S.A. = 109m² g⁻¹) and the main phase was CeO₂,Co₃O₄ and CoO. While, the CeO₂–Co₃O₄–R400 binary oxide exhibited lower surface area (S.A. = 40m² g⁻¹) and the main phase was CeO₂, CoO and Co. Apparently, the optimized pretreatment of CeO₂–Co₃O₄ binary oxide can control both the phases and surface area.