Facetting of Fe-15% Cr-N, Fe-3% V-C and Fe-3% V-C,N (111) surfaces

Summary Auger electron spectroscopy (AES), low energy electron diffraction (LEED) and scanning electron microscopy (SEM) have been used to study the surface chemistry of crystallographically open bcc (111) surfaces of Fe-15% Cr-N, Fe-3% V-C and Fe-3% V-C,N alloys. The binary and ternary surface phases CrN, VC and V(C,N) were formed at temperatures ranging from 450 to 750°C depending on the alloy. On Fe-15% Cr-30ppmN (111) two-dimensional surface compounds CrN were formed at temperatures above 600°C according to the bulk phase diagram of the Fe-Cr-N system, whereas on Fe-15% Cr-N samples with nitrogen contents of more than about 100 ppm the precipitation of three-dimensional CrN took place at temperatures below 600°C. Optical and SEM micrographs as well as oxidation experiments at room temperature indicated that the substrate surfaces are inhomogeneously covered by the surface phases. Facetting of the bcc (111) surfaces induced both by cosegregation of the solutes and by surface precipitation was observed in real space (SEM) as well as in reciprocal space (LEED). It is shown that the surface phases are epitaxially arranged on (100) facets of the substrate.     

Surface cosegregation on Fe-3%V-C, Fe-3%V-C,N and Fe-15%Cr-N (110) single crystals

Surface cosegregation has been studied on (110) oriented Fe-3%V-C, Fe-3%V-C,N and Fe-15%Cr-N single crystals applying AES and LEED. The surface compounds VC,V(C,N) and CrN are formed upon annealing in the temperature range from 450 to 750° C depending on the alloy. The stoichiometries of the binary surface compounds correspond to VC_1.2 and approximately CrN_0.8 as determined by quantitative evaluation of Auger peak height ratios. The composition of the V(C,N) surface compound varies between V(C_0.6N_0.6) at 450° C and V(C_0.2N_1.0) at 640° C. Three-dimensional precipitates are not formed as indicated by Ar⁺ depth profiling. After short annealing times streaking LEED patterns are observed indicating partial disorder in one direction of the direct space. Upon sufficient annihilation of surface defects sharp (4 × 1) patterns appear. A missing and added row model is proposed for the surface compounds on bcc(110) substrate surfaces.     

Atomic Force Microscopy Analysis of Statistical Roughness of GaAs Surfaces Originated by Thermal Oxidation

We have determined the important statistical quantities of the rough boundary between a GaAs single crystal and its oxide film formed by thermal oxidation. Thermal oxidation of the GaAs surfaces was performed at the temperature of 500°C. Using mathematical procedures developed for treating AFM data consisting of a family of the values of the heights of the irregularities of this roughness the values of the important statistical quantities of roughness were determined for 11 samples of the GaAs surfaces created by dissolution of the thermal oxide films originated during thermal oxidation of the smooth GaAs samples (the times of oxidation of these 11 samples were within interval of 20min–8 hours). From the AFM analysis of the roughness of GaAs surfaces it was found that the roughnening of these surfaces was the most pronounced for shorter oxidation times, i.e. for times smaller than about 2 hours.     

Preparation of octadecyl modified column gels using heat-treated silicas and their retention behaviour in high-performance liquid chromatography

Summary The effect of silanol groups on three types of octadecylmodified column gels using heat-treated silicas by calcination has been studied by high-performance liquid chromatography. After heat-treating at 180°C, 500°C and 950°C, the silicas treated with octadecyldimethylchlorosilane were used for the measurement of physical and chemical analysis. From elemental carbon analysis data, the reactive silanol group concentrations, _OH(s), were determined to be 2.0 in the 180°C treated silica, 2.1 in the 500°C treated silica and 1.6 in the 950°C treated silica, respectively (original silica: mean pore diameter 116 Å, specific surface area 298 m²/g, pore volume 1.22 ml/g, particle size 5.0 m). The separation factors, , of pyridine versus phenol were measured to be 0.79 on 180°C treated silica, 0.91 on 500°C treated silica and 1.98 on 950°C treated silica, using acetonitrile-water mixtures as the eluent. And then, on the basis of the physico-chemical and chromatographic data, the three types of octadecyl modified column gels using heat-treated silicas by calcination have been compared.     

AES- and LEED-investigations of the oxidation behaviour of Fe-19,5 Cr-4,5 Al single crystals

Summary The oxidation behaviour of Fe-19,5 Cr-4,5 Al single crystals (110), (111) has been investigated to obtain reference data for further oxidation experiments on materials of the same composition but doped with yttrium. The oxidation of annealed specimens showing Al surface segregation and unannealed (without Al-enrichment) samples was carried out at different temperatures in an UHV-chamber at an oxygen pressure of about 10^–7 mbar. During oxidation Auger spectra (20...70 eV) were taken and LEED-patterns were photographed before and after oxidation if detectable. It has been shown that the type of oxide formed was dependent on the chemical composition of the surface and the oxidation temperature.This poster was awarded the First Prize in Poster Section B by the Deutscher Arbeitskreis für Spektroskopie (DASP)     

Temperature-induced changes in the composition of floatglass surfaces

Floatglass is an important kind of commercial glass, comprising the main body of modern flat glass used in buildings and vehicles. The stoichiometry of the surface layer differs from that of the bulk and will usually change due to subsequent high-temperature process steps or attack by water or humidity. Glass samples have been investigated by means of ion beam analysis. Using resonant nuclear reaction analysis (¹⁵N technique), hydrogen concentration profiles have been determined. Profiles of the heavier glass constituents, especially sodium and tin, have been obtained by RBS. Changes in the composition of the floatglass surfaces caused by subsequent temperature treatment (up to 700^°C) and by controlled hydration treatment are reported. Possible mechanisms of hydrogen uptake and release are discussed.     

Study of silica supported PtxNi1-x catalysts by ion scattering spectroscopy

As supported Pt_xNi_1–x catalysts are used for hydrogenation reactions, it seemed necessary to assess the surface composition of the reduced samples. To approach the usual reduction conditions we applied in situ reduction in a reaction chamber (1 mbar H₂ up to 500 °C) placed in ultra high vacuum recipient (UHV: 10^–9 to 2.10^–10mbar). All ion scattering spectroscopy measurements were performed in UHV. Charging of the samples was avoided by electron bombardment (5 eV). The variation of the surface composition was determined after subsequent sputtering, thermal treatment at 500 °C and during oxygen adsorption. A comparison with previous results of surface compositions of binary alloys (polycrystalline foils [1, 2] and single crystals Pt_xNi_1–x [3]) is given.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday     

The Iron Behaviour in Aluminosilicate Gel-Derived Materials

Electron spin resonance (ESR) measurements have been carried out on a 10Fe₂O₃ · 10Al₂O₃ · 80SiO₂ gel heat-treated at different temperatures in air and under reducing conditions. ESR spectra were obtained at 300, 50 and 5 K. The effective g value (g = h/H), linewidth (H_pp) and ESR amplitude (A) depend on heat-treatment temperature of the gel-derived samples. ESR spectra exhibit different magnetic characteristics as a function of heat-treatment temperature and atmosphere. X-ray diffraction (XRD), scanning electron microscopy (SEM) and a.c. susceptibility (_a.c.) analyses were used to better understand the ESR results. The results show that in the samples heat-treated in air, up to 700°C, Fe³⁺ ions are incorporated in the glass network in tetrahedral and/or octahedral co-ordinations. In the samples heat-treated between 250 and 700°C was not detected, by ESR, the presence of iron oxide aggregates. However, the formation of hematite particles was observed by XRD and SEM. The presence of iron oxide aggregates was detected (by ESR) in the samples heat-treated at temperatures higher than 700°C. These aggregates are formed, at 1200 and 1300°C, by hematite and magnetite particles as proved by XRD. The ESR spectra and a.c. susceptibility, of the samples heat-treated at 250°C (under reducing conditions), show a behaviour characteristic of small magnetite particles presence. The sample heat-treated at 500°C (under reducing conditios) contains magnetite particles (XRD). In the ESR spectra of the sample heat-treated at 1000°C, under reducing conditions, was not detected any resonance signal.     

The relation between the molecular weight and intrinsic viscosity of polyvinyl alcohol

Summary A series of unfractionated and fractionated samples of polyvinyl acetate were prepared by homogeneous solution polymerization of vinyl acetate in N,N-dimethylformamide at 90 °C. in presence of , -azo-(-cyano-n-valeric acid) as initiator under a variety of conditions. A portion of each sample was hydrolysed to polyvinyl alcohol. The number average molecular weights have been determined by end-group titrations. The following molecular weight-intrinsic viscosity relationships for polyvinyl alcohol have been obtained. [] = 33.88 X 10^–5 M ^0.716 — for unfractionated samples in water at 30 °C. [] = 29.51 X 10^–5 M ^0.716 — for fractionated samples in water at 30 °C.With 1 figure and 2 tables     

Mössbauer and related studies on the formation of some mixed oxide catalysts of iron and cobalt

A series of mixed oxides and ferrites of iron and cobalt has been prepared by taking iron and cobalt in the atomic ratio 10.50, 11.33 and 13.00, respectively. These samples were prepared by calcination of the stoichiometric amount of their respective nitrate salts for 6 h in air at 500±10°C. Characterization of the samples has been carried out using Mössbauer spectroscopy. Percentage formation of -Fe₂O₃ and CoFe₂O₄ has been determined using the same technique. These results have been supplemented by X-ray diffraction studies. The particle size has been calculated using Scanning Electron Microscopy. the decomposition of 0.5% w/v hydrogen peroxide at 40°C over the catalyst has also been studied.     

UV-Visible Absorption Characteristics of TEOS-Derived and Cr-Doped Silica Sonogels Aged in Different pH Solutions and Heat Treated up to 600°C

Cr-doped xerogels were obtained by sol-gel process from the acid-catalyzed and ultrasound-stimulated hydrolysis of tetraethoxysilane (TEOS) with addition of CrCl₃6H₂O in water solution during the liquid step of the process. The gels were aged immersed in different pH solutions for about 30 days, after that they were allowed to dry. The samples were annealed at temperatures ranging from 40 to 600°C and analyzed by UV-visible absorption spectroscopy. Cr³⁺ is the preferable oxidation state of the chromium ion in the gels annealed up to 250–300°C, in the case of aging in solutions of pH = 5 and 11. A high UV absorption below 320 nm, due to the host gel, and different absorption bands, depending on the temperature, due to the chromium ion were observed in the xerogels at temperatures below 250°C, in the case of aging in solutions of pH = 1 and 2. These absorption bands have not been assigned. Above 300°C up to 600°C, Cr⁵⁺, and possibly Cr⁶⁺, are the preferable oxidation states of the chromium ion independent of the pH of the aging solution, so the xerogels turn to a yellowish appearance in all cases.     

The kinetic of the oxidation of InSn48

The oxidation of InSn48 has been investigated at partial pressures between 10^-8 Pa and 10⁺⁴ Pa over a temperature range from 22^°C to 250^°C with different analytical methods. The oxide film contains a mixture of several oxides, although indium oxide forms preferentially. Below the melting point a logarithmic growth, and above this, a parabolic growth of the oxide film has been observed. The oxide film formed in air at 250^°C does not become thicker than 50 nm in the first 5 min of oxidation.     

Activity concentrations of238U and226Ra in agricultural samples

Distributions of²³⁸U and²²⁶Ra in agricultural samples and cultivated soils have been studied over ten years. The crops are rice, spinach and Chinese cabbage. Two investigated areas have been selected (35° 18 N, 113° 35 E). The agricultural samples and soils were collected annually from May 1982 through October 1991. The activity concentrations of²²⁶Ra in agricultural samples are greater than those of²³⁸U. The transfer factors of²³⁸U,²²⁶Ra are from 0.06·10^–3 to 1.2·10^–3. The²²⁶Ra/²³⁸U ratios for three agricultural samples have their characteristic values.     

Fine Patterning of Transparent, Conductive SnO2 Thin Films by UV-Irradiation

Finely patterned transparent, conductive SnO₂ thin films have been prepared. UV-light from a high-pressure mercury lamp was irradiated through a mask on the precursor films prepared from SnCl₂ with acetyl acetone in the ambient atmosphere, and this irradiation led to the change of solubility of the films in alkaline solution. Patterns with a width of about 3 to 50 m and thickness of about 0.1 m were formed with a pitch of about 2 to 20 m. The resistivity of the films heat-treated at 500°C after UV irradiation was about 1 × 10^–2 cm, which was almost the same resisitivity for the films heat-treated at 500°C without UV irradiation.     

Preparation of Transparent, Partially-Crystallized BaTiO3 Monolithic Xerogels by Sol-Gel Processing

Transparent, partially-crystallized nanostructured barium titanate (BaTiO3) monolithic xerogels (dried at 90°C) have been successfully synthesized via hydrolysis of Ba, Ti alkoxide precursor solutions in a concentration range of 1.0 mol/l with addition of water with a molar ratio of H2O/Ba 6.3. Transparent monolithic xerogels obtained from a precursor solution of 1.0 mol/l remained transparent even after firing at 500°C in oxygen, although the degree of their transparency was considerably decreased. Firing at temperatures above 500°C yielded translucent ceramics of BaTiO3, and ultimately, firing above 600°C resulted in normal opaque ceramic bodies. Those obtained from a more concentrated precursor solution of 1.2 mol/l were, on the other hand, still transparent after firing at 600°C in oxygen, and turned opaque at 700°C. The results demonstrate that the materials retained their transparency even after pyrolysis of organic compounds involving exothermic oxidation at temperatures in the range of 200 to 400°C. The densification behavior of transparent BaTiO3 monolithic xerogels obtained was found to be excellent; for example, those derived from a 1.0 mol/l precursor solution could be sintered to form monolithic BaTiO3 ceramics with a relative sintered density of about 94% and an average grain size of 1 m by firing at 1100°C for 2 h in oxygen.     

Oxygen diffusion in SrCe<Subscript>0.95</Subscript>Yb<Subscript>0.05</Subscript>O<Subscript>3−δ</Subscript>

¹⁸O/¹⁶O isotope exchange depth profiling (IEDP) combined with secondary ion mass spectrometry (SIMS) has been used to measure the oxygen tracer diffusivity of SrCe_0.95Yb_0.05O_3– between 800 °C and 500 °C at a nominal pressure of 200 mbar. The values of D* (oxygen tracer diffusion coefficient) and k (surface exchange coefficient) increase steadily with increasing temperature, and the activation energies are 1.13 eV and 0.96 eV, respectively. Oxygen ion conductivities have been calculated using the Nernst–Einstein equation. The transport number for oxide ions at 769 °C, the highest temperature studied, is only ~0.05. Moreover, SrCe_0.95Yb_0.05O_3– has been studied using impedance spectroscopy under dry O₂, wet O₂ and wet H₂ (N₂/10% H₂) atmospheres, over the range 850–300 °C. Above ~550 °C, SrCe_0.95Yb_0.05O_3– shows higher conductivity in dry O₂ than in wet O₂ or wet H₂; below that temperature the results obtained for the three atmospheres are comparable. Dry O₂ shows the highest activation energy (0.77 eV); the activation energies for wet O₂ and wet H₂ are identical (0.62 eV).Abbreviations HTPC high-temperature proton conductor - IEDP isotope exchange depth profiling - SIMS secondary ion mass spectrometryPresented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003     

Trace analysis of triazines and organophosphorus pesticides in water

A method for the determination of trace levels of triazines and organophosphorus pesticides in water is presented. The extraction method is based on a solid-phase extraction on C-18 bound silica SPE cartridges. A precolumn filled with Merck C-18 bound silica and home-made C-18 bound silica have been tested at a flow-rate of 3 ml/min with comparable preconcentration yields. A SIM-MS method using a ¹⁵N labelled internal standard has been developed for the organophosphorus pesticides. Detection limits lower than 1 g/L have been obtained. Separations have been carried out on a conventional GC column OV 17 (1 m) and a capillary column OV 17 (25 m) with a temperature program from 150° C (2 min) to 300° C (rate of 6° C/min).     

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.     

Thermal decomposition of silver cyano complex and characterization its decomposition products by ETA,DSC, DTA and TG

It was found by DTA and TG that [Phenyl₂I][Ag(CN)₂] in the solid state is chemically stable on heating in argon up to 160°C. During heating to higher temperatures it decomposes, forming volatile products such as [Phenyl]I, [Phenyl]NC and (CN)₂ [1]. After heating the sample to 500°C metallic silver resulted. The volatile and intermediate solid products were analysed by IR-spectroscopy.It was found by means of DTA and ETA that an isophase reversible transition takes place when the sample is heated and cooled, not higher than 100°C. At heating higher than 100°C the sample melts (melting pointT _m=135°C). The enthalpy melting was determined by means of DSC (H=–28 kJ·mol^–1).By means of ETA the disorder degree of the final decomposition product was estimated. The value of the activation energy of radon diffusion in the temperature range 720°–500°C equals 32.6 kJ·mol^–1.Dedicated to Prof. I. N. Bekman Moscow State University at the occasion of his 50th birthday