Effect of annealing on structure and magnetic properties of Fe-N and Fe-Ti-N thin films

The structure and magnetic properties of Fe-N and Fe-Ti-N films have been studied as a function of annealing temperature T_a with a transmission electron microscope and a vibrating sample magnetometer. The as-prepared Fe-N films consist of the γ^′-Fe₄N and α^′′-Fe₁₆N₂ phases, and the Fe-Ti-N films are composed of the γ^′-Fe₄N, α^′′-Fe₁₆N₂, and TiN phases. The structural changes with annealing temperature in the Fe-N films are distinct. The α^′′-Fe₁₆N₂ decomposes into α+γ^′ phases in the Fe-N film annealed at about 300 °C, and it disappears in the film annealed at 350 °C. Annealing of the Fe-Ti-N films shows no structural changes between room temperature (RT) and 500 °C. The saturation magnetization 4πM_S and coercivity H_c of the Fe-N films change drastically with the annealing temperature T_a, whereas those of the Fe-Ti-N films do not change with T_a up to 500 °C. These results indicate that the additon of Ti may improve the thermal stability of Fe-N films. Recieved: 6 Juli 1998 / Accepted: 19 Oktober 1998 / Published online: 10 March 1999     

On the direct formation of HO2 radicals after 248 nm irradiation of benzene C6H6 in the presence of O2

We present in this work the direct observation of HO₂ radicals after irradiation of benzene C₆H₆ at 248 nm in the presence of O₂. HO₂ radicals have been unambiguously identified using the very selective and sensitive detection of continuous wave cavity ring-down spectroscopy (cw-CRDS) coupled to a laser photolysis reactor. HO₂ radicals were detected in the first vibrational overtone of the OH stretch at 6638.20 cm^-1, using a DFB diode laser. This reaction might be important because 248 nm photolysis of H₂O₂ has often been used in the past for studying the OH^•-initiated degradation of C₆H₆, often using a large excess of C₆H₆ over H₂O₂. The possible importance of the title reaction with respect to these former laboratory studies has been quantified through comparison with HO₂ ^• signals obtained from 248 nm photolysis of H₂O₂: one obtains under our conditions (excess O₂ and total pressure of 6.6 kPa helium) from the 248 nm irradiation of identical initial concentrations [C₆H₆]=[H₂O₂] the following relative initial radical concentrations: [HO₂ ^•]=(0.28±0.05)×[OH^•]. Experiments with various O₂ concentrations have revealed that the origin of the HO₂ radicals is not the reaction of H-atoms with O₂, but must originate from the reaction of O₂ with excited C₆H₆ ^*. The quantum yield of C₆H₆ ^* formation has been deduced to ϕ=0.2±0.1. PACS  42.62.Fi; 82.20.Pm; 82.33.Tb     

Measurement of vibrational energy transfer of OH (A2Σ+,v′=1→0) in low-pressure flames

2 Σ⁺) was measured in a low-pressure H₂/O₂ flame for three rotational levels of OH (v^′=1). Rate coefficients for collisions with H₂O and N₂ were determined. At 1600 K, k_VET (N₂) is (in 10^-11 cm³s^-1) 10.1±2, 6.1±1.8, and 3.8±1.3 for N^′=0, 5, and 13, respectively. The k_VET (H₂O) is <1.1±1.8. The k_Q (N₂) is <2.4±8 for both vibrational levels. The k_Q (H₂O) in v^′=1 is 59.1±6.5, 54.7±6.4, and 54.9±6.6 for N^′=0, 5, and 13, respectively, and, determined indirectly, 74.6±10.4, 70.6±10.3, and 63.4±7.3 for N^′=0, 5, and 13 in v^′=0. A multi-level model of OH population dynamics, which is being developed for the quantitative simulation of experimental LIF spectra, was extended to include VET. It was attempted to simulate state-to-state-specific VET coefficients for N₂ collisions. From these simulations it appears that angular momentum conservation does not determine the N dependence of the vibrational relaxation step. Received: 9 September 1996/Revised version: 6 January 1997     

A new polymeric material for optical switching

′ -(2^′′,4^′′,6^′′-trichlorophenazoamino)-phenazo-4-nitrobenzene, was studied. Large nonresonant optical nonlinearity (χ⁽³⁾≥10^-28 C⁴m/J³ or 10^-9 esu) and fast response time (t<20 ps) were measured by forward degenerate four-wave mixing experiment. Optical bistable behavior in a quasi-waveguide interferometer with the thin film of the material was observed. The potential of the material for optical switching was evaluated. Received: 20 July 1998/Revised version: 11 September 1998     

LIF diagnostics of C2 radical behaviour in a laser CVD environment

A laser-induced fluorescence (LIF) system was developed to diagnose the reaction and transport of radicals in the ArF-laser-assisted CVD environment. The C₂(a ³ II _u) radicals were produced by the multi-photon dissociation of C₂H₂. The transport of the radical was directly measured by LIF. The disappearance rate of the radical in C₂H₂ was also determined. By using the values determined, the in-flux of the C₂ radicals onto a substrate was investigated, based on a diffusion model.     

Stoichiometrically controlled direct solid-state synthesis of C60H2

The direct solid-state synthesis of C₆₀H₂ has been demonstrated by controlling the amount of hydrogen introduced into the reaction with C₆₀. Palladium hydride has been used as the source of hydrogen. The main product 1,2-C₆₀ is the isomer predicted to have the lowest energy of the possible 23 isomers; in addition, small amounts of the thermodynamically most stable isomer of C₆₀H₄, 1,2,3,4-C₆₀H₄, have also been obtained.     

Tunable KrF laser-induced fluorescence of C2 in a sooting flame

2 in a flame, excited by a tunable KrF laser near 248 nm. The first comprises several P and R lines of the (1,0) band of the e ³Π_g-a ³Π_u Fox–Herzberg system, with fluorescence bands extending past 350 nm. The second is the band head region of the (7,1) band of the D ¹Σ_u ⁺←B^′ 1Σ_g ⁺ system, with fluorescence at 232 nm from D to the X ¹Σ_g ⁺ ground state. Neither band has been previously observed in any environment. The flame in these experiments is highly sooting, and the C₂ seen here is likely produced by laser vaporization of the soot with subsequent laser photolysis of a C₂ precursor. In a rich flame, this fluorescence could cause interferences in other studies such as KrF laser Raman scattering. Moreover, signal level calculations suggest native C₂ near 10 ppm could be readily observed using the Fox–Herzberg excitation. Raman measurements of major species (X≥0.01) in the same flame, using the KrF laser, are in good agreement with a model prediction. Received: 2 April 1998/Revised version: 8 June 1998     

Laser deposition of amorphous diamond films from liquid aromatic hydrocarbons

6 H₅CH₃, C₆H₆, and C₆H₅CH(CH₃)₂) to pulsed visible laser radiation of a copper vapor laser (λ=510.6 nm). The X-ray Auger electron spectroscopy (XAES), reflection high energy electron diffraction (RHEED), and Raman analysis are employed to characterize the deposited films. The sp³ fraction in deposited films amounts to 60–70% and depends on the precursor. The average film thickness on a glass substrate is about 100 nm. The films show excellent adherence, are transparent in the visible and have microhardness of 50–70 GPa, as measured by nanoindentor. Received: 28 September 1998 / Accepted: 13 January 1999     

Determination of parameters of Cu surface mass transport on sapphire from morphological changes of beaded films caused by evaporation

s , the surface diffusion coefficient, D_s ^′, and the surface reaction rate coefficient, β_s ^′, of Cu on alumina are determined in the temperature range 1048–1198 K. Measuring simultaneously the time dependence of the effective thickness, H_eff(t), the lateral shift of the boundary, y(t) of beaded films (BF) and using vapour pressure data we concluded that the process is controlled by surface reaction at the perimeters of beads. Supposing Arrhenius-type temperature dependence for D_s ^′, β_s ^′ and λ_s the activation energies and preexponential factors have been calculated. Received: 2 October 1996/Accepted: 27 November 1996     

CO2 laser-induced plasma CVD synthesis of diamond

2 laser maintenance of a stationary optical discharge in a gas stream, exhausting over a substrate into the air (laser plasmatron). Nano- and polycrystalline-diamond films were deposited on tungsten substrates from atmospheric-pressure Xe(Ar):H₂:CH₄ gas mixtures at flow rates of 2 ?/min. A 2.5-kW CO₂ laser focused beam produced plasma. The deposition area was about 1 cm² and growth rates were up to 30–50 μm/h. Peculiarities and advantages of laser plasmatrons are discussed. Received: 15 January 1998/Accepted: 16 January 1998     

Synergistic effects in mixed wormlike micelles of dimeric and single-chain cationic surfactants at high ionic strength

The mixed micellization between the cationic gemini surfactant [ C₁₂H₂₅( CH₃)₂N⁺( C₂H₄) N⁺( CH₃)₂ C₁₂H₂₅•2Br^-] and the cationic cetyltrimethylammonium bromide (CTAB) in 150 mM KBr solutions has been investigated. The variation of the cmc of the mixtures, measured by surface tension experiments, with composition revealed synergism in micelle formation. T-Jump and light scattering experiments performed in the vicinity of the crossover volume fraction showed the existence of two micellar populations, possibly linear and toroidal micelles. Rheological and dynamic light scattering experiments allowed to fully characterize the linear viscoelasticity of the mixtures. These measurements revealed synergistic gains in viscoelastic properties with a maximum of the stress-relaxation time around the equimolar composition. These effects are ascribed to a progressive intermicellar crosslinking resulting from a continuous increase of the end-cap energy with the 12-2-12 content in the mixture. Received: 18 November 2002 / Accepted: 8 April 2003 / Published online: 27 May 2003 RID="a" ID="a"e-mail: candau@fresnel.u-strasbg.fr     

Analysis of newly synthesized disulfides of aryldithiocarbonates and vanadium(V) and niobium(V) complexes of aryldithiocarbonates based on spectroscopic,thermogravimetric, SEM and DFT studies

ABSTRACT

Oxidation of the sodium salt of 2-methyl, 3-methyl, 4-methyl and 4-chloro-3-methylphenyldithiocarbonic acid by I₂ affords the disulfides of respective dithiocarbonates [(ArOCS₂)₂] (Ar?=?2-CH₃C₆H₄, 3-CH₃C₆H₄, 4-CH₃C₆H₄ and 4-Cl-3-CH₃C₆H₃. Vanadium(V) and Niobium(V) complexes of 2-methyl, 3-methyl, 4-methyl and 4-chloro-3-methylphenyldithiocarbonates have also been synthesised by one-step synthetic route. The metal salt (VOCl₃ and NbCl₅) were reacted with 2-CH₃C₆H₄, 3-CH₃C₆H₄, 4-CH₃C₆H₄ and 4-Cl-3-CH₃C₆H₃OCS₂Na in 1:2 stoichiometric molar ratio yielding the complexes corresponding to the molecular formula [(ArOCS₂)₂VO(Cl)] and [(ArOCS₂)₂NbCl₃] [Ar?=?2-CH₃C₆H₄, 3-CH₃C₆H₄, 4-CH₃C₆H₄ and 4-Cl-3-CH₃C₆H₃OCS₂)]. The compounds were characterised by elemental analyses, infrared, mass and heteronuclear NMR (¹H and ¹³C) spectroscopic studies. Thermogravimetric analysis and scanning electron microscopic analyses were also carried out for deeper investigation of the structural features. Comprehensive theoretical investigation was performed by applying density functional theory (DFT) calculations on vanadium and niobium complexes by the DFT/B3LYP/LANL2DZ method to obtain the optimised molecular geometry, vibrational frequencies, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), thermodynamic properties and various other quantum-mechanical parameters.     

Hydroxyl tagging velocimetry (HTV) in experimental air flows

 The new nonintrusive instantaneous molecular flow tagging method, hydroxyl tagging velocimetry (HTV), previously demonstrated only for high-temperature reacting flows, is now demonstrated in low-temperature (300 K) ambient air flowfields. Single-photon photodissociation of ground-state H₂O by a ∼193-nm ArF excimer laser ‘writes’ very long grid lines (>50 mm) of superequilibrium OH and H photoproducts in a room air flowfield due to the presence of ambient H₂O vapor. After displacement, the positions of the OH tag lines are revealed through fluorescence caused by A²Σ⁺ (ν^′=0)?X²Π_i (ν^′′=0) OH excitation using a pulsed frequency-doubled dye laser with an operating output wavelength of ∼308 nm. The dye ‘read’ laser accesses the strong Q₁(1) line, compensating for the relatively weak 193-nm absorption of room-temperature H₂O. The weak absorption of ground vibrational state H₂O has previously precluded the use of HTV at low temperatures, since previous HTV systems relied on a KrF excimer ‘read’ laser that could only access a weak (3?0) OH transition. The instantaneous velocity field is determined by time-of-flight analysis. HTV tag lifetime comparisons between experimental results and theoretical predictions are discussed. Multiple-line tag grids are shown displaced due to an experimental air flowfield, thus providing 2-D multipoint velocity information. Due to the instantaneous nature of the HTV tag formation, HTV is particularly suitable for, but not limited to, a variety of fast flowfield applications including nonreacting base flows for high-speed projectiles and low-temperature hypersonic external or internal flows. Received: 3 July 2001 / Revised version: 6 November 2001 / Published online: 17 January 2002     

A tunable ultrafast spectrometer based on hollow waveguides: Demonstration in violet–blue

′ -hydroxy-5^′-methylphenyl)-benzotriazole. Received: 2 June 1998/Revised version: 31 July 1998     

Tuning of the emission color of organic electroluminescent devices by exciplex formation at the organic solid interface

′ ,4^′′-tris(3-methylphenylphenylamino)triphenylamine, 1,3,5-tris[(4-diphenylaminophenyl)phenylamino]benzene, N, N^′-bis(3-methylphenyl)-N, N^′-diphenyl-[1,1^′-biphenyl]-4,4^′-diamine, and 4,4^′,4^′′-tri(N-carbazolyl)triphenylamine, emitted bright light resulting from the exciplex formed at the solid interface between TPOB and the hole-transporting material. The exciplex formation was evidenced by the measurements of the photoluminescence spectra and lifetimes of the mixture of an equimolar amount of TPOB and each of the hole-transporting materials. Tuning of the emission color from greenish blue to orange was attained by varying the ionization potential of the hole-transporting material for the fixed electron-transporting material of TPOB. Received: 27 July 1998/Accepted: 28 July 1998     

Surface characterization study of a Pd/Co3O4 methane oxidation catalyst

A surface characterization study using X-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS) has been performed on a 5 wt.% Pd/Co₃O₄ methane oxidation catalyst before and after exposure to a mixture of CH₄ and O₂ in N₂ at 250 °C for a period of 6 days. The primary peaks observed in the XPS survey spectra are the Co 2p, Pd 3d, O 1s and C 1s, along with Co, Pd and O Auger peaks. High-resolution Pd 3d spectra reveal that Pd exists on the surface predominantly as PdO, with no apparent change in chemical state during reaction. High-resolution XPS Co 2p and O 1s spectra reveal an accumulation of CoOOH and a depletion of CoO in the near-surface region during reaction. ISS analysis with intermittent 1-keV Ar⁺ sputtering was used to obtain depth profiles from the catalyst before and after reaction. The results indicate that the Pd/Co concentration ratio decreases with sputtering and that this ratio is larger for the as-prepared catalyst indicating that morphological changes occur during reaction. The ISS depth profile spectra obtained from the catalyst after reaction indicates the presence of an oxyhydroxide layer throughout the near-surface region. This observation is consistent with the XPS data indicating accumulation of hydroxide and oxyhydroxide species at the surface during reaction.Based on these data and the results of related studies, a reaction mechanism is proposed. In this mechanism, methane dissociatively chemisorbs to form a surface methoxy species and CoOOH. The remaining hydrogen atoms are stripped from the methoxy species leaving an active adsorbed C species which reacts with surface oxygen and a hydroxyl group to form an adsorbed bicarbonate ion which then decomposes to form CO₂ and a surface hydroxyl group. These hydroxyl groups also react to form H₂O and then more O₂ adsorbs dissociatively at the vacant sites.     

Exchange interactions and spin dynamics in a [CuNd2(C4O4)4(H2O)16]·2H2O crystal

Crystalline [CuNd₂(C₄O₄)₄(H₂O)₁₆]·2H₂O constructed of complexes of trivalent neodymium and divalent copper, has been synthesized and studied by EPR. The square anion groups (C₄O₄) enter as bridge ligands, forming chains of neodymium ions interconnected by (C₄O₄)Cu(C₄O₄) fragments. It is found that the relaxation rate of the neodymium subsystem at room temperature significantly exceeds the exchange interaction rate between copper and neodymium ions. Under these conditions the magnetic properties of the crystal are determined by two magnetically nonequivalent chains of copper ions, which do not interact. The intrachain exchange interaction via hydrogen bonds is estimated to be ∼0.1 cm⁻¹. As one proceeds from the high-temperature (250<T<300 K) to the low-temperature region (T<40 K), a substantial change in the nature of the interaction is revealed. An unusual magnetic structure given in a crystal is observed at low temperatures, which is determined by the presence of two magnetically nonequivalent “ribbons,” formed by the interacting copper and neodymium ions: chains of copper ions are framed on two sides by chains of neodymium ions. The magnitude of the parameter of the exchange interaction between the copper and neodymium ions is estimated as J ^Cu-Nd⩾0.2 cm⁻¹. An exchange interaction between magnetically nonequivalent neodymium ions is not revealed in the EPR spectra. Fiz. Tverd. Tela (St. Petersburg) 39, 2057–2061 (November 1997)     

Growth and characterization of oriented cadmium sulphide nanocrystals under Langmuir-Blodgett monolayer of arachidic acid

Cadmium sulphide nanocrystals were grown at room temperature (20 °C) under arachidic acid monolayers floating over an aqueous solution of CdCl₂ inside an enclosed Langmuir-Blodgett set-up, through slow infusion of H₂S gas. X-ray diffraction spectra suggest an oriented growth of the crystallites. The particle sizes were found to increase with duration of exposure to the H₂S gas. Atomic force microscopy indicated that the particles were nearly circular pellets with uniform morphology throughout. In Raman spectra, the FWHM of the LO phonon was found to be large (≈20 cm^-1) for all the films grown with different exposure times in H₂S gas, and was found to reduce to 8 cm^-1 after annealing a typical sample at 500 °C for 45 min. Received: 30 September 1998 / Accepted: 29 March 1999 / Published online: 11 August 1999     

Wavelength-agile fiber laser using group-velocity dispersion of pulsed super-continua and application to broadband absorption spectroscopy

A swept-wavelength source is created by connecting four elements in series: a femtosecond fiber laser at 1.56 μm, a non-linear fiber, a dispersive fiber and a tunable spectral bandpass filter. The 1.56-μm pulses are converted to super-continuum (1.1–2.2 μm) pulses by the non-linear fiber, and these broadband pulses are stretched and arranged into wavelength scans by the dispersive fiber. The tunable bandpass filter is used to select a portion of the super-continuum as a scan-wavelength output. A variety of scan characteristics are possible using this approach. As an example, an output with an effective linewidth of approximately 1 cm^-1 is scanned from 1350–1550 nm every 20 ns. Compared to previous scanning benchmarks of approximately 1 nm/μs, such broad, rapid scans offer new capabilities: a gas sensing application is demonstrated by monitoring absorption bands of H₂O, CO₂, C₂H₂ and C₂H₆O at a pressure of 10 bar. Received: 5 August 2002 / Revised version: 23 September 2002 / Published online: 22 November 2002 RID="*" ID="*"Corresponding author. Fax: +1-608/265-2316, E-mail: ssanders@engr.wisc.edu     

In situ investigation of the catalytic reaction H2+< ![IGNORE[O2→H2 O with second-harmonic generation

2 +O₂→H₂ O in the pressure range 0.2 Torr≤p_tot≤10 Torr on Pt(111) surface. At a catalyst temperature of T=700 K the equilibrium oxygen coverage θ_o is determined as a function of hydrogen partial pressure α. The experimentally obtained θ_o is modelled in a two step process considering the mass transport in the gas phase as well as the catalytic reaction on the surface. In this pressure range the mass transport in the gas phase changes from molecular flow conditions to laminar flow, inducing a strong modification of the gas phase present at the catalyst through different diffusivities of the reactants as well as through desorbing reaction products from the catalyst. It is shown that these gas phase alterations have to be taken into account for a proper modelling of the surface mechanism. Simulation calculations allow one to identify the sequential hydrogen addition reaction as the main reaction path for water production in this parameter range. Excellent agreement with previous investigations is obtained for the determined activation energies of the water-producing reaction steps equal to E^f _H2O≥0.7 eV. Received: 20 September 1998 / Revised version: 15 December 1998