High Temperature Behavior of a Gel-Derived SiOC Glass: Elasticity and Viscosity

The high temperature behavior of a sol-gel derived silicon oxycarbide glass containing 12 at.% carbon has been characterized by means of creep and in-situ ultrasonic echography measurements. Temperature induced changes include structural relaxation and densification from 1000 to 1200°C, and crystallization to form a fine and homogeneous -SiC/glass-matrix nanocomposite with 2.5 nm large crystals above 1200°C. Young's modulus measurements clearly reveal a consolidation of the material upon annealing below 1200°C. Crystallization is almost complete after few hours at 1300°C and results in a significant increase in Young's modulus. The viscosity of the oxycarbide glass is much higher than that of fused silica, with two orders of magnitude difference at 1200°C, and the glass transition temperature ranges from 1320 to 1370°C.     

Trace determination of iron on a silicon wafer surface by silicon direct bonding and neutron activation analysis

In order to determine iron on silicon wafer surface at a level of 10¹⁴ atoms·m^–2 the efficiency of a well-type Ge detector for⁵⁹Fe -ray emissions was measured and a low temperature silicon direct bonding technique was developed. With silicon direct bonding at a temperature of 350 to 650°C iron remains near the interface of the bound silicon. The iron contamination of the interface escaped from the interface can be ignored with this technique. The value of iron obtained was (2.7 to 5.9)·10¹⁴ atoms · m^–2 in the surface on silicon wafers.     

Nucleation of Titania Nanocrystals in Silica Titania Waveguides

SiO_{2(1 – x)}-TiO_2(x) monomode waveguides at 632.8 nm, with x in the range 0.07–0.2 and thickness of about 0.4 m, were deposited on silica substrates by a dip-coating technique. Nucleation of TiO₂ nanocrystals and the growth of their size by thermal annealing up to 1300°C were studied by waveguided Raman scattering in the SiO_2(0.8)-TiO_2(0.2) composition. In the low frequency region (5–50 cm^–1) of the VV and HV polarized Raman spectra the symmetric and quadrupolar acoustic vibrations are observed. The mean size of the titania particles are obtained from the frequencies of the Raman peaks. The results are compared with those obtained from the measure of the linewidths in the X-ray diffraction spectra. Nanocrystals with a mean size in the range 4–20 nm are obtained by thermal annealing in a corresponding range of 700–1300°C.     

Preparation and Characterization of Sol-Gel Derived Y2O3 Thin Films

Sol-gel derived Y2O3 thin films have been prepared on platinum coated silicon wafers and fired to temperatures ranging from 400°C to 750°C. Multiple coats were used to obtain films up to 0.5 m thick with an intermediate firing of 400°C between coatings. Top Pt electrodes were sputtered to form monolithic capacitors. These films exhibited a dielectric constant of 18 and a leakage current of 10–11–10–7 A/cm2, making them attractive candidates for high dielectric constant dielectric films in high density DRAMs.     

Characterization of iron-silicon thin films by means of electron diffraction and X-ray spectroscopy

Iron-silicon thin films have been characterized by means of analytical transmission electron microscopic methods. Under certain conditions — composition and annealing temperature — these films exhibit thermoelectric behavior. In particular, the morphology and phase formation which results from annealing of these films, and doping with oxygen and nitrogen, are of interest. The thermoelectric phase -FeSi₂ is formed at temperatures above 500°C. This phase is transformed into electrically conducting phases at about 1000°C. A small oxygen content does not influence this crystallization process. If the oxygen content is higher than 15 atom-% the electrically conducting phases exist even at 500°C. The presence of a small nitrogen content inhibits the formation of the -FeSi₂ phase. The development of silicon and iron nitrides is possible.     

Electrical conductivity measurements of aqueous sodium chloride solutions to 600°C and 300 MPa

Electrical conductance measurements of dilute (<0.1>^–1) aqueous NaCl solutions were made primarily to quantify the degree of ion association which increases with increasing temperature and decreasing solvent density. These measurements were carried out at temperatures from 100 to 600°C and pressures up to 300 MPa with a modified version of the apparatus used previously in the high temperature study in this laboratory. Particular emphasis was placed on conditions close to the critical temperaturelpressure region of water, i.e., at 5° intervals from 370 to 400°C. The results verify previous findings that the limiting equivalent conductance A_o of NaCl increases linearly with decreasing density from 0.75 to 0.3 g-cm^–1 and also with increasing temperature from 100 to 350°C. Above 350°C. A_o is virtually temperature independent. The logarithm of the molal association constant as calculated exclusively from the data400°C is represented as a function of temperature (Kelvin) and the logarithm of the density of water (g-cm^–3) as follows:

Röntgenstrahlenbeugung bei hohen Temperaturen zur Untersuchung der thermischen Ausdehnung von MnSe und MnSe2

Zusammenfassung Durch Röntgenstrahlenbeugung mit Hilfe einer 190 mm Unicam-Hochtemperaturkamera wurde die thermische Ausdehnung von MnSe und MnSe₂ von Zimmertemperatur bis 710° bzw. 522° C untersucht. Der thermische Ausdehnungskoeffizient wurde aus den Meßdaten nach der Methode der kleinsten Fehlerquadrate erhalten und beträgt für MnSe: =24,5·10^–6°C^–1 (94–450° C) und =14,3·10^–6°C^–1 (450–710° C). Die Ausdehnung von MnSe₂ verläuft bis zum Bereich, in dem Zersetzung eintritt, linear. Die Methode der kleinsten Fehlerquadrate ergibt den Wert =20,0·10^–6°C^–1 (73–522° C).

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High temperature X-ray studies of the thermal expansion ofMnSe andMnSe ₂

The thermal expansion of MnSe and MnSe₂ has been studied above room temperature up to 710° and 522° C, resp., by X-ray diffraction techniques using a 190 mm Unicam high temperature camera. The thermal expansion coefficients, , obtained from a linear least-squares analysis of the data are for MnSe: =24.5·10^–6°C^–1 (94–450° C) and =14.3·10^–6°C^–1 (450–710° C). The expansion of MnSe₂ is linear up to the temperature range of decomposition. A least-squares analysis yields a value for of 20.0·10^–6°C^–1 (73–522° C).

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Mit 2 Abbildungen

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Herrn Prof.H. Nowotny gewidmet.     

Investigation of high concentration effects of Sb and P in silicon by combination of SIMS and TEM

Summary The combination of SIMS, electrical resistance measurements and TEM was used for investigation of high concentration effects of Sb and P in silicon. For antimony implantation and annealing combined with and without preannealing were studied. The distributions and the precipitated fraction were determined by SIMS. TEM investigations showed that by preannealing at a temperature of 1150°C no dislocations but only precipitates are formed. Thus the precipitation kinetics for an isothermal case (1000°C) could be studied. The size distributions of precipitates were determined by image processing of plan view TEM micrographs. The kinetics of the precipitation process was simulated for the distribution function by a computer model and compared with experiments. A good agreement between experiment and simulation was obtained.For phosphorus, specimens implanted with medium and high doses were investigated. With medium doses small extrinsic dislocation loops (size 20–40 nm) were observed near the amorphous/cristalline boundary. The dislocation loops are formed by agglomeration of interstitial silicon atoms which are supersatured in the long range of the implantation profile.The coupled diffusion of high doses of P and low doses of Sb and B was studied. In the SIMS distributions enrichments of boron were observed. TEM measurements showed that they were correlating to a severe band of defects.SiP precipitates and large perfect dislocation half loops [mean radius (195±112) nm] were observed after annealing at 900°C for 120 min of implants with a dose of 5×10¹⁶ cm^–2 P. Because precipitation is occurring, simulation of phosphorus diffusion is at present not possible.

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Untersuchung von Hochkonzentrationseffekten von Sb und P in Silicium durch Kombination von SIMS und TEM

     

Studies on recrystallised aluminium trihydroxide precipitates: The energetics of dissolution by sodium hydroxide solutions

Summary Aluminium hydroxide gels were recrystallised in high pH solution for 2–1000 hr to give a series of gibbsite powders of different surface areas, 1`11/2, P11/8, P11/48, P11/360 and P11/X; their average platelet lengths were 30, 60, 130, 260 and 450 nm. The dissolution equilibria of these powders in sodium hydroxide solutions of C=1-8 M were studied at 20° to 80°C.The equilibrium constants (for formation of diaquo-tetrahydroxoaluminate anion) increased with temperature and with increasing surface area; the K value for P11/2 was about four times that of P 11/X at 20 °C and about three times (that for P 11/X) at 80 °C. The dissolutions were endothermic; however, the value over this temperature range increased from –29.5 kJ mol<sup>–1</sup> (for P11/X) to –24.7 kJ (for P 11/2). This increase was related to the appreciable surface energies of the high surface-area materials.The (– G°) values increased with increasing temperature and in turn with increasing surface area; the (– G°) values for 1`11/2 dissolution at any temperature were about 4 kJ mol^–1 higher than those for P11/X dissolution.With 1 figure and 1 table     

Development of an Improved Liquid Chromatographic Method for the Analysis of Doxycycline

Summary An improved LC method is described for the separation of doxycycline and its impurities. The separation of 2-acetyl-2-decarboxamidodoxycycline from the main peak doxycycline is much better than that obtained with official pharmacopoeia methods. The method is robust and shows good selectivity, repeatability, linearity and sensitivity. Eight commercial samples were examined using the method developed. The method uses an XTerra RP-18, 5 m (25 cm × 4.6 mm I. D.) column kept at a temperature of 35 °C. UV detection is performed at 280 nm. The mobile phase consists of acetonitrile – 0.2 M tetrabutylammonium hydrogen sulphate pH 7.0 – 0.3 M ethylenediaminetetraacetate pH 7.0 – water (130:350:350:170, v/v/v/v).     

Crystalline Inclusions Formed in C+N+BF2 Coimplanted on Silicon (111)

In the present work, high-doses (10¹⁷–10¹⁸cm^–2) of carbon, nitrogen, and boron (BF₂⁺) ions were coimplanted on silicon (111) substrates at 21, 25 and 77keV, respectively. Two series of samples have been implanted (series A and B) and subsequently annealed. Series A samples have been implanted at room temperature and treated one minute by rapid thermal annealing (RTA) and 3 hours at 1200°C. Series B samples have been implanted at 600°C and subsequently annealed at 1200°C during 3 hours. The annealing in both series has been carried out in N₂ at atmospheric pressures.The structure of the buried layers has been determined by conventional and high resolution transmission electron microscopy (CTEM and HRTEM). Polycrystalline silicon and new crystalline phases are observed by electron diffraction patterns. The polycrystalline silicon inclusions have been confirmed from analysis of HRTEM images.     

Carbocyclic and nitrogen-containing fused CH-acids with an annelated indenyl fragment. Thermogravimetric and X-ray structural analysis of 6H-indeno[1,2-b]quinoline

Based on thermogravimetric characteristics first obtained for the model 6H-indeno [1,2-b]quinoline, the scheme of thermal conversions of this compound in the temperature range 20–700 °C has been proposed, and the limit of its thermal stability (300 °C) has been determined. This temperature is recommended as the optimum for synthesizing fused benzoaza(diaza)fluorenes. Based on the results of X-ray structural analysis, the molecules of the studied indenoquinoline form centrosymmetric pairs, which are arranged in (110) layers. The molecules are orientationally disordered. The observed self-association of these molecules is similar to the - association of fused heterocyclic systems with-excessive and ****- deficient fragments. It has been suggested that interferon-inducing and antitumor compounds with an annelated indenyl fragment have a common mechanism of action according to the intercalation model of stacking structures.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 703–709, April, 1995.     

Effects of SiO2 Barrier and N2 Annealing on Sb-Doped SnO2 Transparent Conducting Film Prepared by Sol-Gel Dip Coating

Oxyfluoride glass-ceramic thin films of nominal 90SiO₂10(Ba_1–xEu_x)MgF₄ compositions were prepared by sol–gel method starting from mixtures of metal trifluoroacetates and silicon alkoxide precursor solutions. Films were deposited on silica glass substrates by spin-coating and heating at 750°C. Eu²⁺ ions were preferentially incorporated into BaMgF₄ nanoparticles, which were dispersed in the silica glass matrix. The films exhibited broad-band blue photoluminescence (PL) in response to the ultraviolet light excitation. Addition of N,N-dimethylformamide to starting coating solutions resulted in a porous microstructure of the heat-treated films. Efficient UV excitation was promoted due to the Rayleigh scattering in the porous films; thereby the PL emissions could be strongly enhanced.     

Synthesis and Electrical Properties of Lithium Metazirconate

Lithium metazirconate Li₂ZrO₃ with a monoclinic lattice is synthesized; the lattice parameters are: a = 0.5432 nm, b = 0.5427 nm, c = 0.903 nm, = 112.72°, and Z = 4. The conductivity of both the stoichiometric compound and samples rich or deficient in Li₂O near this composition is determined. The conductivity of the synthesized compound reaches 0.029 S cm^–1 at 600°C. The activation energy for the high-temperature segment is 13.8 kJ mol^–1. An abnormal behavior (abrupt jump) of the temperature dependence of the conductivity at 430°C is discovered and attributed to a phase transition. The change in the structure in this temperature domain (400 to 500°C) is corroborated by the high-temperature X-ray analysis.     

Formation of small rhodium metal particles on the surface of a carbon support

A rhodium catalyst supported on a Sibunit graphitized carbon carrier was studied by in situ XAFS spectroscopy. A comparative study of the reduction of rhodium was performed for the following two samples: Rh/C(120) dried at 120°C and Rh/C(350) calcined at 350°C. EXAFS data showed an absence of carbon atoms within the nearest environment of rhodium atoms in the Rh/C(120) uncalcined sample, which implies the absence of direct interaction between rhodium and the carbon support. In the course of the reduction of this sample (200°C), coarse particles with small metal cores were initially formed. These metal particles rapidly agglomerated upon the complete reduction of rhodium (350°C). These reduction of the Rh/C(350) calcined sample at 100–500°C resulted in the formation of small metal particles early in the reduction (100°C). The high dispersity of these particles was retained as the temperature of treatment in hydrogen was increased to 500°C due to metal-support interaction. The conversion of benzene into cyclohexane on the Rh/C(350) catalyst containing small rhodium particles was much higher at the same temperature of hydrogenation.Translated from Kinetika i Kataliz, Vol. 46, No. 1, 2005, pp. 122–130. Original Russian Text Copyright © 2005 by Stakheev, Tkachenko, Klementev, Grünert, Bragina, Mashkovskii, Kustov.     

Temperature-dependent dry etching characteristics of III–V semiconductors in HBr- and HI-based discharges

Microwave discharges of HBr/H₂/Ar and H/H₂/Ar with additional do biasing of the sample were used to etch InP, GaAs, and AlGaAs at temperatures between 50–250°C. The etch rates increase by factors of 3–50 and 5–9, respectively, for HBr-and HI-based discharges over this temperature range, but display non-Arrhenius behavior. The etched surfaces became very rough above 100°C for InP with either discharge chemistry due to preferential loss of P, while GaAs and AlGaAs are more tolerant of the elevated temperature etching. The near-surface electrical properties of InP are severely degraded by etch temperatures above 100°C, while extensive hydrogen in-diffusion occurs in GaAs and AlGaAs under these conditions, leading to dopant passivation which can be reversed by annealing at 400°C.     

Reactions of 1-vinyl-4,5,6,7-tetrahydroindole and its mixtures with 4,5,6,7-tetrahydroindole in the presence of Cr- and Pd-coated catalysts

In the presence of Cr- and Pd-coated -alumina catalysts, 1-vinyl-4,5,6,7-tetrahydroindole (VTHI) and its mixtures with 4,5,6,7-tetrahydroindole (THI) are converted into 1-ethyl-4,5,6,7-tetrahydroindole (1-ETHI), indole, and 2-ethylindole, in proportions dependent on the reaction conditions and the catalyst. Over a sulfided 1% Pd--alumina catalyst in the presence of hydrogen at 200°C, VTHI is converted into 1-ETHI and THI. When the temperature is raised to 300–350°C, indole is formed in addition to these products. A 11 mixture of VTHI and THI over 1% Pd--alumina at 300°C gives indole and 2-ethylindole, over a sulfided 1% Pd --alumina catalyst at 200°C, 1-ETHI, and over a Cr oxide catalyst at 500°C, indole.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1417–1422, June, 1991.     

Alkaloids ofRhinopetalum bucharicum. The structure of rhinolinine

The combined alkaloids of the epigeal part ofRhinopetalum bucharicum have yielded solanidine, rhinoline, imperialine, a base with mp 272–274°C, and the new alkaloid rhinolinine with mp 301–302°C (methanol), []_D — 36.5° (c 1.7, ethanol), C₄₀H₆₇NO₁₂. On the basis of a study of IR and NMR spectra, and also passage to the known alkaloids rhinoline and rhinolidine, the structure of rhinolidine 3-O-[O--D-glucopyranosyl-(14)--D-glucopyranoside] has been established for rhinolinine.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 350–353, May–June, 1979.     

Thermal and radiation annealing in131I−-doped periodate crystals

Isothermal annealing at temperatures between 90 and 250°C and radiation annealing at 40, –76 and –196°C were studied in sodium periodate crystals doped by rapid crystallization and by spray techniques. The results showed the occurrence of transfer annealing because the dopant was converted to the oxidized forms of iodate and periodate depending on the treatment conditions. Similarities with the annealing behaviour of recoil species in neutron irradiated periodate systems are established and the Bellido and Wiles stepwise oxidation model is used to explain the mechanism of the processes.