Thermal transitions and state of water in binary mixtures of water andn-decanephosphonic acid or its sodium salts

The state of water and several transitions were examined in the systemsn-decanephosphonic acid (DPA)—water and the sodium salts of DPA—water. Temperature — composition phase diagrams are reported. The results show that several liquid crystalline phases plus isotropic liquid, and two solid phases (a waxy solid phase and a crystalline phase) are formed. Several types of water were detected: bulk-like water, interfacial water and hydration water. This work was supported by the Consejo Nacional de Ciencia y Technología de México (grant # 3319-E) and by the Consejo Nacional de Investigaciones Científicas y Técnicas de la República de Argentina.     

Simultaneous determination of Co,Mo, Ni,W and moisture content in hydrodesulfurization catalysts by neutron capture gamma-ray spectrometry

Neutron capture γ-ray spectrometry has been applied for the simultaneous determination of Co, Mo, Ni, W and moisture in hydrodesulfurization catalysts. The Co, Mo and water content are determined in a 10 min irradiation using a 500–2500 keV calibration. Ni and W, if present, require, and additional 30 min irradiation, using a 5000–9000 keV calibration. In both cases TiO₂ is used as internal standard. Results are in good agreement with those obtained by NAA for metals and by TGA for moisture. This work was supported by Grant N⁰ 31.26-Sl-0304 from the Consejo Nacional de Investigaciones Científicas y Technológicas.     

The simultaneous determinations of cobalt,nickel and molybdenum in hydrodesulfurization catalysts by photon induced X-ray fluorescence

A rapid radioisotope induced energy-dispersive X-ray fluorescence procedure for the simultaneous determinations of Cobalt, Nickel and Molybdenum in hydrodesulfurization catalysts is presented. A¹⁰⁹Cd (7 mCi) source is used as the excitation system coupled to a high resolution Si(Li) detector. A PDP-11/05 processor is employed as a multichannel analyzer and also to automatically control the complete system by means of a prewritten computer program. The relative standard deviations for the three determinations (CoO, NiO and MoO₃) are less than 5% for 300 seconds of fluorescent time for a typical sample. Finally a comparison of results by different methods is given to check the accuracy since no standard reference materials are available for catalytic material. This project was funded by Consejo Nacional de Investigaciones Científicas y Tecnológicas (CONICIT).     

Application of radioisotope excited energy dispersive X-ray fluorescence determination of palladium in catalysts and doped venezuelan laterites

A rapid procedure for determining palladium in catalysts and geoiogical materials is presented. This method involves the use of an²⁴¹Am (100 mC) source for excitation and employs a PDP-11/05 processor for the data acquisition and analysis by energy-dispersive X-ray fluorescence. The relative standard deviation for 5 independent determinations is less than 3% for 100 seconds of fluorescent time. The calculated and measured values agreed well for both, the prepared standards and the doped Venezuelan laterites. Finally, data on the different sources of error is given including counting time, sample preparation, and total error. This investigation was funded in parts by CONICIT (Consejo Nacional de Investigaciones Científicas y Technológicas).     

Thermal Behaviour of a TiO2—ZrO2 Microcomposite Prepared by Chemical Coating

A microcomposite powder in the system TiO₂—ZrO₂ as a precursor of zirconium titanate (ZT) materials has been studied by thermal methods (DTA-TG) and X-ray diffraction (XRD). The microcomposite powder has been prepared by chemical processing of crystalline TiO₂ (rutile, 10 mass% anatase),as inner core, coated with in situ precipitated amorphous hydrated zirconia gel, asouter core. The morphology and chemical composition of the resultant powders has been examined by SEM-EDX (Scanning electron microscopy-energy dispersive X-ray spectroscopy). Thermal behaviour of the microcomposite powder was reported, showing the dehydration and dehydroxylation of the zirconia gel, the crystallization into metastable cubic/tetragonal zirconia at temperatures 400—470°C, and the feasibility of preparing ZT powder materials by progressive reaction of TiO₂ and ZrO₂ at higher temperatures (1400°C).This revised version was published online in November 2005 with corrections to the Cover Date.     

Structural study of perovskite-type fine particles by synchrotron radiation powder diffraction

The crystal structures of BaTiO₃ and PbTiO₃ fine particles have been investigated by powder diffraction using synchrotron radiation high energy X-rays. It is revealed that a BaTiO₃ fine particle essentially consists of tetragonal and cubic structure components at 300 K, whereas a PbTiO₃ fine particle consists of a tetragonal structure. Adopting a structure model for the BaTiO₃ particle that a cubic shell covers a tetragonal core, the thickness of cubic BaTiO₃ shell is estimated at almost constant irrespective of particle sizes. Successive phase transitions are detected in 100 nm particles of BaTiO₃ near the phase-transition temperatures of a bulk crystal. The changes in diffraction profiles are small, but they are apparent for a most up-to-date powder diffractometry. This revised version was published online in August 2006 with corrections to the Cover Date.     

Time‐Resolved Phase Transitions of the Nanocrystalline Cubic to Submicron Monoclinic Phase in Mn2O3‐ZrO2

The nanocrystalline cubic phase of zirconia was found to be thermally stabilized by the addition of 3 to 40 mol % manganese. The nanocrystalline cubic, tetragonal and monoclinic phases of zirconia stabilized with manganese (III)oxide (Mn‐Stabilized Zirconia) were prepared by thermal decomposition of carbonate and hydroxide precursors. Both the crystallization and isothermal phase transitions associated with Mn‐SZ were studied using high temperature x‐ray diffraction and x‐ray diffraction of quenched samples. Cubic Mn‐SZ initially crystallized and progressively transformed to tetragonal, and monoclinic structures above 700°C. The nanocrystalline cubic Mn‐SZ containing 25 mol % Mn was found to have the greatest thermal stability, retaining its cubic form at temperatures as high as 800°C for periods up to 25 hours. Higher than 40 mol %, cubic Mn₂O₃ was found to coexist with cubic Mn‐SZ. The crystallite sizes observed for the cubic, tetragonal and monoclinic Mn‐SZ phases ranged from 50 to 137, 130 to 220, and 195 to 450 Å respectively, indicating, for ZrO₂, that particle size was a primary factor in determining its polymorphs. The classical Avrami equation for nucleation and growth was applied to the observed phase transformations.     

Comparison of analytical methods for the determination of trace amounts of strontium and yttrium by photon induced X-ray fluorescence techniques in lateritic materials

Three different analytical methods for the determination of strontium and yttrium in Venezuelan latterites by radioisotope induced X-ray fluorescence are compared, also with results from conventional wavelength dispersive X-ray fluorescence. The samples analyzed were from Cerro Impacto, Venezuela. The photon-induced energy dispersive X-ray fluorescence system consisted of a¹⁰⁹Cd (7 mCi) source for excitation of the characteristic K X-rays for strontium and yttrium. The detection system employed a high resolution Si(Li) detector and was completely controlled by a PDP-11/05 processor. Of the three analytical methods described, the internal standard-thin film technique was shown to be slightly superior to the conventional standard calibration curve method and the standard additon/dilution procedure. This can be explained by considering the effectiveness of the compensation of the sources of errors by these methods. It should also be noted that in the case of wavelength dispersive X-ray fluorescence, an about 5–10 times greater sample is needed, which is a limitation compared to energy dispersive X-ray fluorescence in some cases. Finally, typical relative standard deviations of the energy dispersive X-ray fluorescence methods were about 10–15% for the range of about 100–100 ppm of strontium and yttrium; these values are acceptable considering the large degree of heterogeneity in this type of geological material. This project was funded by Consejo Nacional de Investigaciones Científicas y Technológicas (CONICIT) and performed as part of UNESCO's IGCP-129 “Lateritization Processes” project.     

Phase relationships in the pseudo-binary 2(ZnTe)-CuInTe2 system

Subsolidus phase relationships in the 2(ZnTe)_x(CuInTe₂)_1−x system were investigated by TEM experiments combined with EDX analysis. The samples were prepared by the solid-state reaction of the elements during long annealing times, followed by either quenching in ice-cold water, or by controlled cooling at different rates. Using the chemical compositions of single and coexisting phases at various temperatures, the boundaries of the two-phase region have been determined. At room temperature, the two-phase region extends from x=0.10 to 0.31. For x<0.10 only mixed crystals with tetragonal structure exist. Between x=0.31 and 1 alloys with the cubic structure are stable.The morphology of the tetragonal domains and their orientation relationship to the cubic matrix were determined by SAD, TEM and HRTEM experiments. The tetragonal phase embedded within the cubic matrix has a flat ellipsoidal shape, whose short axis coincides with the tetragonal c-axis. The three topotaxial orientation relationships between the tetragonal domains and the surrounding cubic matrix were found to be: [001]_tetr.∥[100]_cub., [001]_tetr.∥[010]_cub. and [001]_tetr.∥[001]_cub.. There is an indication that the nucleation starts from small regions displaying cation ordering according to the CuPt-type structure. Reaching the two-phase equilibrium, the tetragonal domains as well as the surrounding cubic phase are free of this cation ordering.     

Thermal studies of isoxazolylnaphthoquinones by simultaneous DTA-TG-DTG

The tautomeric binary system consisting of N-(3,4-dimethyl-5-isoxazolyl)-4-amino-1,2-naphthoquinone (1),m.p. 156C, and 2-hydroxy-N-(3,4-dimethyl-5-isoxazolyl)-1,4-naphthoquinon-4-imine (2),m.p. 218C, was studied by DTA-TG-DTG and IR spectrometry. Crystals of 1, left in contact with their mother liquor during 4 months, exhibited thermal behaviour similar to that of physical mixtures of 1 and 2, which reveal the presence of a eutectic at about 146C.The effects of light, heat and humidity on the stabilities of 1 and 2 were also studied. Heat (up to 110C) did not induce any change observable by DTA-TG-DTG in either 1 or 2. Moisture and daylight affected only 1. Upon melting, interconversion of the isomers was not observed.The authors thank the Consejo National de Investigaciones Científicas y Técnicas de la RepÚblica Argentina (CONICET) and the Consejo de Investigaciones Cientificas y Tecnológicas de la provincia de Córdoba (CONICOR) for financial support. They also thank Eng. Martín Portela (C.I.M.M., INTI, Córdoba) for recording the DTA-TG-DTG curves and for helpful discussions.     

Composition-induced structural phase transitions in the (Ba1−xLax)2In2O5+x (0?x?0.6) system

Composition-induced structural phase changes across the high temperature, fast oxide ion conducting (Ba_1−xLa_x)₂In₂O_5+x, 0?x?0.6, system have been carefully analysed using hard mode infrared (IR) powder absorption spectroscopy, X-ray powder diffraction and electron diffraction. An orthorhombic brownmillerite to three-dimensionally disordered cubic perovskite phase transition in this system is signalled by a drastic change in slope of both wavenumber and average line widths of IR spectra as a function of composition. Some evidence is found for the existence of an intermediate tetragonal phase (previously reported to exist from electron diffraction data) around x∼0.2. The new spectroscopic data have been used to compare microscopic and macroscopic strain parameters arising from variation in composition. The strain and spectroscopic data are consistent with first-order character for the tetragonal→orthorhombic transition, while the cubic→tetragonal transition could be continuous. Differences between the variation with composition of spectral parameters and of macroscopic strain parameters are consistent with a substantial order/disorder component for the transitions. There is also evidence for precursor effects within the cubic structure before symmetry is broken.     

Time‐Resolved High and Low Temperature Phase Transitions of the Nanocrystalline Cubic Phase in the Y2O3‐ZrO2 and Fe2O3‐ZrO2 System

The nanocrystalline cubic Phase of zirconia was found to be thermally stabilized by the addition of 2.56 to 17.65 mol % Y₂O₃ (5.0 to 30.0 mol % Y, 95.0 to 70.0 mol % Zr cation content). The cubic phase of yttria stabilized zirconia was prepared by thermal decomposition of the hydroxides at 400°C for 1 hr. 2.56 mol % Y₂O₃‐ZrO₂ was stable up to 800°C in an argon atmosphere. The samples with 4.17 to 17.65 mol % Y₂O₃ were stable to 1200°C and higher. All samples at temperatures between 1450°C to 1700°C were cubic except the sample with 2.56 mol % Y₂O₃ which was tetragonal. The crystallite sizes observed for the cubic phase ranged from 50 to 150 Å at temperatures below 900°C and varied from 600 to 800 nm between 1450°C and 1700°C. Control of furnace atmosphere is the main factor for obtaining the cubic phase of Y‐SZ at higher temperature. Nanocrystalline cubic Fe‐SZ (Iron Stabilized Zirconia) with crystallite sizes from 70 to 137 Å was also prepared at 400°C. It transformed isothermally at temperatures above 800°C to the tetragonal Fe‐SZ and ultimately to the monoclinic phase at 900°C. The addition of up to 30 mol % Fe(III) thermally stabilized the cubic phase above 800°C in argon. Higher mol % resulted in a separation of Fe₂O₃. The nanocrystalline cubic Fe‐SZ containing a minimum 20 mol % Fe (III) was found to have the greatest thermal stability. The particle size was a primary factor in determining cubic or tetragonal formation. The oxidation state of Fe in zirconia remained Fe³⁺. Fe‐SZ lattice parameters and rate of particle growth were observed to decrease with higher iron content. The thermal stability of Fe‐SZ is comparable with that of Ca‐SZ, Mg‐SZ and Mn‐SZ prepared by this method.     

Structure,magnetic, and electrical properties of bismuth niobates doped with d-elements: VIII. Phase transitions and electrophysical properties of bismuth niobate

Reversible phase transitions of bismuth niobate Bi₃NbO₇ have been observed: from the lowtemperature cubic modification to the tetragonal one at 860°C and from the tetragonal modification to the hightemperature cubic one at 950–980°C. With increasing temperature of the cubic modification preparation, the unit cell parameter has been decreasing. Electrophysical properties of the cubic phases have matched at the frequencies below 1 kHz (up to 650 K). The specific conductivity of the tetragonal phase exceeds that of the cubic phase by no more than an order of magnitude (below 1000 K).     

A theoretical study of the relative stability of the isomeric forms of N2O3

The electronic structure, geometrical parameters and relative stability of the isomeric forms of N₂O₃ are analysed by means of ab initio calculations. Total energies of the different isomers are given. The energy difference between the most stable conformers of the symmetric N₂O₃ is 4.31 Kcal mol^–1 as provided by 6–31G basis set. The height of the rotational barrier determined by the ab initio technique is 7.12 kcal mol^–1.Member of the Carrera del Investigador CICPBA, R. Argentina.Member of the Carrera del Investigador CONICET, R. Argentina.Predoctoral fellow of CONICET, R. Argentina.     

Powder neutron diffraction of SrNbO2N at room temperature and 1.5 K

The structure of strontium niobium dioxygen nitride, SrNbO₂N, has been solved by powder neutron diffraction at room temperature and 1.5 K. SrNbO₂N crystallizes in the tetragonal space group I4/mcm, with a = 5.7056 (4) and c = 8.1002 (9) Å at room temperature, and a = 5.6938 (4) and c = 8.0974 (8) Å at 1.5 K. The crystal structure is derived from the cubic perovskite archetype by a slight rotation of the Nb(O,N)₆ octahedra with respect to the tetragonal axis. A partially ordered distribution of oxygen and nitrogen on the anionic sites was found.     

Fabrication and Characterization of Sol-Gel Derived Potassium Sodium Strontium Barium Niobate

Potassium sodium strontium barium niobate (K_0.2Na_0.2Sr_0.48Ba_0.32Nb₂O₆, KNSBN) powder and thin films dip coated onto Si(100) substrates have been prepared by sol-gel route. The thermal evolution of these sol-gel derived KNSBN was studied by differential thermal analysis (DTA) and thermogravimetry (TG). Their structural changes at different annealing temperatures were examined by X-ray diffraction (XRD) and Raman spectroscopy. Our results suggest that the KNSBN tetragonal tungsten bronze (TTB) phase is formed via an intermediate orthorhombic phase. Pure TTB phase KNSBN was obtained at annealing temperatures of 1200°C and 600°C for powder and films respectively.     

An order-disorder transition in Sr2IrD5: Evidence for square pyramidal IrD5 units from powder neutron diffraction data

Neutron diffraction data have been collected on a powdered sample of Sr₂IrD₅ over a range of temperatures. The compound, which is cubic at room temperature, has been found to exhibit a gradual transformation to a tetragonal phase in the temperature range 200-140 K. As a result of the transition, deuterium atoms which randomly occupy sixfold positions in the cubic phase, become tetragonally ordered. A small fraction of the cubic phase remained untransformed at 4.2 K. Both the cubic and tetragonal structures are consistent with square pyramidal IrD₅ units with average Ir---D distances of 1.714 and 1.718 Å, respectively. Agreement factors, R₁, for the two structural analyses are 3.44 and 4.94%.     

The use of partially restricted molecular orbitals to investigate transmission mechanisms of spin-spin coupling constants. I. Theσ andπ contributions within the FPT INDO method

Partially restricted INDO MO Calculations have been carried out to separate the -electron contributions to spin-spin coupling constants in ethylene, butadiene, benzene and toluene. Results reproduce very well known trends such as the pathway invariance, the alternation in sign and the methyl group replacement rule.Comisión de Investigaciones Científicas (CIC, Pcia.Bs.As.) fellow.     

Sonochemical synthesis and characterization of nano-sized zirconium(IV) complex: new precursor for the preparation of pure monoclinic and tetragonal zirconia nanoparticles

In this study, synthesis and characterization of two polymorphs of a new nano-sized zirconium(IV) complex, [ZrO(dmph)I₂] (1), {dmph = 2,9-dimethyl-1,10-phenanthroline (neocuproine)}, have been investigated in two different solvents. The reaction between zirconyl nitrate pentahydrate and potassium iodide with dmph as a ligand under ultrasonic irradiation in methanol and mono-ethylene glycol (MEG) leads to the formation of the nano-sized Zr(IV) complex. Characterization of the Zr(IV) complex has been performed using scanning electron microscopy (SEM), X-ray powder diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and elemental analysis. The thermal stability of the compound 1 has been studied by thermal gravimetric and differential thermal analyses. Particle sizes of the compound 1 have been decreased after thermal treatments in an autoclave. Pure monoclinic (m) and tetragonal (t) zirconia (ZrO₂) nanoparticles were readily synthesized from thermal decomposition of the Zr(IV) complex as a new precursor in presence of methanol and MEG as solvents, respectively. Zirconium oxide was characterized by FT-IR, XRD, and SEM to depict the phase and morphology. The results showed that, pure zirconia was produced with particle size about 59 nm and crystal system was monoclinic when methanol was used as a solvent during complexation process. On the other hand, particle sizes of zirconia with tetragonal structure were significantly reduced to about 39 nm, when MEG was used as solvent.