In situ Raman spectroscopy of phase transformation in CrOx-Y2O3 system at elevated temperatures

A CrO_x-Y₂O₃ sample was prepared by a deposition-precipitation method and phase transformation of the sample under N₂ and air atmospheres was characterized by in situ Raman spectroscopy and X-ray diffraction (XRD) techniques. It was found that when the CrO_x-Y₂O₃ sample was heated, CrO₃ transformed to YCrO₄ and then to YCrO₃ and Cr₂O₃. Also, the transformation started from the surface region of the sample and then extended to the bulk, due to the fact that the phase transformation was detected by Raman spectroscopy at lower temperature compared to that by XRD. In addition, both atmosphere and temperature had influence on the phase transformation in the surface region, while the phase transformation in the bulk was merely dependent on the temperature. It was also found that low oxidation state Cr(III) species on the surface could be re-oxidized to high oxidation state Cr(V) or Cr(VI) species when the thermal treated sample was exposed to ambient air.     

Characterization of Cr/SiO2 catalysts and ethylene polymerization by XPS

Cr/SiO₂ catalysts with 1 or 3 wt.% Cr loadings and different chromium precursors were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). A method to determine chromium species in the sample was developed through the decomposition of the Cr 2p XPS spectrum in Cr⁶⁺ and Cr³⁺ standard spectra. The results of the binding energy from the Cr 2p region and of the distribution of chromium species allowed to evaluate the dynamic photo-reduction of the surface chromium species during XPS analysis. Photo-reduction of surface Cr⁶⁺ to Cr³⁺ species was verified for all samples supported in silica, depending on the precursor and chromium content. Bulk CrO₃ and Cr₂O₃ standards did not reveal variation in the binding energy of Cr 2p_3/2, but a physical mixture of CrO₃ with SiO₂ presented photo-reduction. The behavior of this mixture resembled to the catalysts and suggests the participation of the surface hydroxyls of silica in the photo-reduction process. XPS intensity measurements for assessing dispersion of chromium oxide were used to compare the calcined and reduced catalysts to different chromium precursors. Polyethylene chains were detected by in situ XPS, while oligomerization products were not observed.     

Spectrométrie électronique (ESCA) appliquée à la caractérisation de dérivés oxygénés de chrome et de sodium,NaxCryOz.

A series of compounds of chromium and sodium (Na₂CrO₄, Na₃CrO₄, Na₄CrO₄, NaCrO₂) and for comparison Cr₂O₃ and chromium metal were examined by ESCA. The binding energy values for Cr 2p, Cr 3s, Cr 3p levels increase with the oxidation number of chromium for the Na_xCr_yO_z derivatives. The separation, Δ, between Cr 2p $\text{1}\text{2}$ and Cr 2p $\text{3}\text{2}$ increases with the number of unpaired 3d electrons. The splitting of the Cr 3s peak is observed for NaCrO₂ and Cr₂O₃. For the O 1s, Na 2s and Na 2p levels, the binding energies vary little in the series. Chromium is in a tetrahedral environment of oxygens in all the compounds Na_xCrO₄ (x = 2, 3, 4), as shown by IR absorption spectroscopy.     

Solid state reduction of chromium (VI) pollution for Al2O3–Cr metal ceramics application

Reduction of chromium (VI) from Na₂CrO₄ through aluminothermic reaction and fabrication of metal-ceramic materials from the reduction products have been investigated in this study. Na₂CrO₄ could be successfully reduced into micrometer-sized Cr particles in a flowing Ar atmosphere in presence of Al powder. The conversion ratio of Na₂CrO₄ to metallic Cr attained 96.16% efficiency. Al₂O₃–Cr metal-ceramic with different Cr content (5 wt%, 10 wt%, 15 wt%, 20 wt%) were further prepared from the reduction product Al₂O₃–Cr composite powder, and aluminum oxide nanopowder via pressure-less sintering. The phase composition, microstructure and mechanical properties of metal-ceramic composites were characterized to ensure the potential of the Al₂O₃–Cr composite powder to form ceramic materials. The highest relative density and bending strength can reach 93.4% and 205 MP, respectively. The results indicated that aluminothermic reduction of chromium (VI) for metal-ceramics application is a potential approach to remove chromium (VI) pollutant from the environment.     

Site–site potential function and second virial coefficients for linear molecules

The second virial coefficients for several linear molecules were calculated using the 2CLJ potential including the electrostatic and induction effects with modified mixing rules for unlike pairs. Least squares fits of experimental values for B(T) were used to calculate the energy parameters σ and ε in the LJ core potential for N₂, O₂, Cl₂, F₂, CO, CO₂, NO, N₂O, C₂H₆, C₂F₆ and the strongly polar molecules CH₃Cl, CH₃F, CH₃CF₃, CH₃CHF₂, and CF₃CH₂F. The analysis takes into account rotation of the dipole out of the molecular axis. The calculated results for the second virial coefficient agree well with experimental data. In addition, the effect of the induction terms on the potential for calculating the second virial coefficient is shown to be important only for the molecules with strong dipole or quadrupole moments.     

Magnetic pigments for recording media

CrO₂ doped with 1--2 wt% Fe³⁺ on Cr⁴⁺ positions is one of the most important materials for magnetic recording in audio, data and video tapes. ⁵⁷Fe Mössbauer spectroscopy was applied to determine the level of iron doping in newly developed high coercivity CrO₂ particles. It was found that, compared with the conventional preparation process, the new particles contain increased amounts of Fe³⁺ ions in the CrO₂ crystal lattice giving rise to higher magnetocrystalline anisotropy. This is reflected in coercivities of up to over 900 Oe. All samples contain as a secondary iron-containing phase α-(Cr_1-xFe_x)₂O₃, the amount of which is higher in samples of the conventional preparation process than in those of the new BASF process. Details about the mechanism of the development of doped CrO₂ particles in both types of processes were obtained by means of Mössbauer, XRD and wet chemical investigations making possible an optimization of the new BASF process.     

Characterization of water exposed plasma sprayed oxide coating materials using XPS

The surface compositions and oxidation states of non-exposed and water exposed plasma sprayed oxide coatings were studied using X-ray photoelectron spectroscopy (XPS). Coating materials were TiO₂, Al₂O₃ and Cr₂O₃ and their mixtures. Water exposures were performed for free standing coating disks at mild electrolyte (1 mmol NaCl solution) at pH 4, 7 and 9. The exposure time was two weeks.It was observed that pure plasma sprayed TiO₂ material was chemically stable over whole experiment pH range and only slight surface hydroxylation was observed for this material.In case of plasma sprayed Al₂O₃ materials the surface O/Al ratio increased considerably during water exposure especially at exposure pH 7. This was probably result of surface conversion to hydrous form. No surface oxidation state changes were observed for this material.The non-exposed Cr₂O₃ materials contained both Cr(III) and Cr(VI) oxides. The water exposures increased the surface oxygen and Cr(VI) contents at the expense of Cr(III). The most probable reason for that was the dissolution of surface Cr(VI) oxide phase during water exposures and the (re)adsorption of dissolved Cr(VI) species back to the surface.     

Transmission of polar substituent effects across the cubane ring system: 19F substituent chemical shifts (SCS) of 4‐substituted (X) cub‐1‐yl fluorides revisited

¹⁹F NMR shieldings of 4‐substituted (X) cub‐1‐yl fluorides ( 4 ) for a set of substituents (X?H, NO₂, CN, NC, CF₃, COOH, F, Cl, HO, NH₂, CH₃, Si(CH₃)₃, Li, O^? and NH) covering a wide range of electronic substituent effects were calculated using the DFT‐GIAO theoretical model. The level of theory, B3LYP/6‐311+G(2d,p), provided ¹⁹F substituent chemical shifts (SCS) in good agreement with experimental values where known. By means of NBO analysis, various molecular parameters were obtained from the optimized geometries. Linear regression analysis was employed to explore the relationship between the calculated ¹⁹F SCS and polar field, resonance and group electronegativity substituent constants (σ_F, σ_R and σ_x, respectively) and also the NBO derived molecular parameters (fluorine natural charges (Q_n), electron occupancies on fluorine of lone pairs (n_F) and occupation number of the C? F antibonding orbital (σ_CF*)). The key determining parameters appear to be n_F and σ_CF*(occup). Both factors are a function of the electrostatic field influence of the substituent (σ_F effect) but are counteractive in their influence on the shifts. No evidence for a significant resonance effect influence on the shifts could be identified. Copyright © 2009 John Wiley & Sons, Ltd.     

Electron spectroscopy with excited atoms and photons.: X. Halogen-substituted methanes and methyl amines

Electron binding energy spectra have been measured for CH₃Cl, CH₃Br, CH₃I, CFCl₃, CF₂Cl₂, CF₃Cl, CF₄, CH₃NH₂, (CH₃)₂ NH and (CH₃)₃N. Measurements have been made using 584 Å (21.22 eV) photons as well as with 2³S(19.82 eV) and 2¹S(20.62 eV) metastable helium atoms. Relative spectral intensities are compared for photoionization and Penning ionization.     

Micro‐Raman characterization of laser‐induced local thermo‐oxidation of thin chromium films

Micro‐Raman spectroscopy was applied to the characterization of the chemical composition and topography of protective oxide layers formed under atmospheric conditions on the surface of thin chromium films. Strips of the layers were produced by local thermal heating using focused sub‐picosecond pulsed laser radiation. It is shown that a CrO₂ layer is initially formed on the chromium surface at low light exposures. Increasing the exposure results in the transformation of the CrO₂ layer to Cr₂O₃. The influence of the etching conditions on the composition and thickness of the oxide layers is investigated. The topography of the CrO₂ and Cr₂O₃ oxide layers in transverse sections of the strips is demonstrated by the Raman mapping. Copyright © 2011 John Wiley & Sons, Ltd.     

Temperature dependent induced spin polarization in Cr2O3 overlayers on epitaxial CrO2 films

Spin-resolved inverse photoemission investigations show that the native Cr₂O₃ surface is antiferromagnetically coupled to the CrO₂ thin film substrate, with a temperature dependent induced polarization. The Cr₂O₃ exhibits the characteristic behavior of a rigid band/spin mixing behavior (non-Stoner) of a local moment paramagnet. The strong shifts of the conduction band edge from room temperature to low temperature suggests that the extent of the induced polarization of the Cr₂O₃ oxide surface, by the CrO₂ substrate, may be partly related to Coulomb blockade effects identified in CrO₂/Cr₂O₃/CrO₂ junctions.     

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Preliminary results on the determination of Cr₂O₃ in chrome-tanned leather by measuring the content of Cr by means of radionuclide-excited XRF analysis are reported. For excitation a 3.7 G Bq²³⁸Pu source was used and the characteristic K X-rays of Cr were detected with a planar Si(Li) detector. Both smooth and rough sides of the leather were analyzed directly or with a pair of V/Ti balanced filters. A fairly good correlation was found between Cr Kx counts of the rough side and the Cr₂O₃ concentrations determined chemically in the range of 3.5 … 6.0% Cr₂O₃. The method enables a rapid and non-destructive determination of Cr₂O₃ in various leather samples.

Es werden vorläufige Ergebnisse dcr Bestimmung von Cr₂O₃ in chromgegerbtem Leder durch Messung des Cr-Gehaltes mit Hilfe der Röntgenfluoreszenzanalyse mitgeteilt. Zur Anregung der Strahlung diente eine ²³³Pu-Quelle mit 3,7 GBq und die charakteristische K-Röntgenstrahlung wurde mit einem planaren Si(Li)-Detektor registricrt. Dabei wurden beide Seiten der Lederproben – die rauhe und die glatte Seite – entweder direkt oder unter Zwischenschaltung eines V/Ti- Ausgleichsfilters gemessen. Es konnte eine gute Korrelation zwischen der Cr-K-Röntgenstrahlung dcr rauhen Seite und dem chemische ermittelten Cr₂O₃-Gehalt im Konzentrationsbereich von 3,5 … 6,0% Cr₂O₃ festgestellt werden. Die vorgeschlagene Methode erlaubt eine schnelle, zerslörungsfreie Bestimmung des Cr₂O₃-Gehaltes in verschiedenen Lederproben.     

Magnetic anisotropy of textured CrO2 thin films investigated by X-ray magnetic circular dichroism

Highly a-axis-textured CrO₂ films have been deposited on Al₂O₃ (0001) substrates by chemical vapor deposition. CrO₂ has been found to have highly a-axis (010)-oriented columnar growth on a Cr₂O₃ (0001) initial layer. The six-fold surface symmetry of the Cr₂O₃ initial layer leads to three equivalent in-plane orientations of the a-axis-oriented CrO₂ unit cell. We report Cr L_2,3 X-ray magnetic circular dichroism data along the surface normal and at 60° off-normal sample orientation. For a 60° sample alignment, a strong increase of the projected orbital moment could be observed for unoccupied majority t_2g states using moment analysis. Therefore, the c axis is identified as the intrinsic magnetic easy axis of CrO₂. In addition, a small spin moment and a very strong magnetic dipole term T_z have been found. Received: 8 January 2002 / Accepted: 8 January 2002     

Isotopically selective infrared multiphoton dissociation of 2-chloro-1,1,1-trifluoroethane: 13C selectivity and mechanism

13 C-selective infrared multiphoton dissociation of CF₃CH₂Cl has been studied by analyzing the distribution of ¹³C concentrations of the main products CF₂=CHCl, CF₂=CH₂, CF₂=CHF, C₂F₆, and the trace products CF₃CH₂CF₃ and CF₃CH=CHF₃. The mechanism mainly concerns the dissociation of energized CF₃CH₂Cl, the collisional stabilization of excited CF₃CH and CF₃CH₂ and the recombination of the nascent radicals. No significant radical–molecule reactions degrade the intrinsic ¹³C dissociation selectivity. High ¹³C production yield and ¹³C concentration can be attained at a laser fluence of 1.6 J/cm². Such low fluence can be used to improve focus condition and enhance photon utilization efficiency for practicable ¹³C separation. Received: 10 March 1998/Revised version: 17 September 1998     

Magnetic and structural studies of Cr2O5 and Cr3O8

The infrared spectra, indexed X-ray powder diffraction patterns, magnetic susceptibilities between 80 and 300 K, and electron paramagnetic resonance spectra at 80 and 300 K are reported for Cr₂O₅ and Cr₃O₈. The results indicate that both oxides are Cr³⁺/Cr⁶⁺ mixed-valence compounds which contain CrO₆ octahedra and CrO₄ tetrahedra in different ratios. The valence formula for Cr₂O₅ is Cr³⁺₂Cr⁶⁺₄O₁₅ and that of Cr₃O₈ is Cr³⁺₂Cr⁶⁺₇O₂₄. The X-ray powder data for Cr₂O₅ and Cr₃O₈ could be indexed on the basis of a monoclinic unit cell $\text{(a = 12.01(2), b = 8.52(1), c = 9.39(1)}\text{A}\text{?}\text{β = 92.0(1)°)}$ and an orthorhombic unit cell $\text{(a = 12.01(7), b = 36.60(7) and c = 3.82(1)}\text{A}\text{?}\text{)}$, respectively.     

Theoretical study on the electronic structures and phosphorescent properties of four Ir(III) complexes with different substituents on the ancillary ligand

The geometry structures, electronic structures, absorption and phosphorescent properties of four Ir(III) complexes {[(F₂-ppy)₂Ir(pta-X)], where F₂-ppy = (2,4-difluoro)phenylpyridine; pta = pyridine-1,2,4-triazole; X = –CF₃; –H; –CH₃; –N(CH₃)₂}, are investigated using the density functional method. The results reveal that the electron-accepting group –CF₃ has no obvious effect on absorption and emission properties, while the substitutive group –N(CH₃)₂ with strong electron-donating ability has obvious effect on the emission properties. The mobility of hole and electron were studied computationally based on the Marcus–Hush theory. Calculations of ionisation potential and electron affinity were used to evaluate the injection abilities of holes and electrons into these complexes. We hope that this theoretical work can provide a suitable guide to the future design and synthesis of novel phosphorescent materials for use in the organic light-emitting diodes.     

KZnF3:Cr3+和KMgF3:Cr3+四角对称电子顺磁共振参量与晶格缺陷的研究

用Newman叠加模型研究了KZnF₃:Cr³⁺四角对称基态的零场分裂,证实了Zn²⁺空位和畸变的存在;并指出,空位对晶场的贡献不可忽略。计算得到:KZnF₃:cr³⁺晶体[0,01]方向的一个F^-配体向Cr³⁺移动Δ(KZnF₃)=0.0029-0.0043nm。还研究了KMgF₃:Cr^{3+关键词：}     

Chemical shifts of Cr Kα and Kβ1, 3 lines by WDXRF spectrometry

Chemical shift and full widths at half maximum (FWHM) intensity of chromium Kα and Kβ_{1, 3} lines were examined for 12 kinds of materials containing chromium (CH₃CO₂)₇Cr₃(OH)₂, CrK(SO₄)₂.12H₂O, Cr(NO3)₃.9H₂O, Cr₂O₃, CrF₂, CrF₃.4H₂O, CrCl₂, CrCl₃, CrCl₃.6H₂O, [CrCl₂(H₂O)₄]Cl.2H₂O, Cr₂(SO₄)₃.15H₂O, CrO and Cr metal by wavelength‐dispersive X‐ray fluorescence (WDXRF) spectrometry. The chemical shifts, asymmetry index and the half‐widths of both the X‐ray emission lines show interesting trends with the oxidation state of chromium. It was observed that the chemical shifts for F compounds are higher than Cl compounds. It was also found larger chemical shifts and FWHM for Kβ_{1, 3} lines than Kα ones. It should be noted that the magnitude of chemical shifts increases with increase in the number of ligand atoms. Copyright © 2009 John Wiley & Sons, Ltd.     

Diode laser slit-jet spectra and analysis of the fundamental of 1-chloro-1,1-difluoroethane (HCFC-142b)

High resolution infrared spectra (0.001 cm^-1) have been measured for mixtures of 1-chloro-1,1-difluoroethane in Ne, expanded in a supersonic planar jet. The ν ₇ fundamental has been analyzed for both isotopic species, CH₃CF₂ ³⁵Cl and CH₃CF₂ ³⁷Cl. A weak b-type component has been observed for the first time. Received 20 May 2002 / Received in final form 10 July 2002 Published online 24 September 2002 RID="a" ID="a"Also: Dipartimento di Scienze Fisiche Universitá di Napoli “Federico II” Complesso Universitario di M.S. Angelo, 80126 Napoli, Italy. e-mail: m.snels@isac.cnr.it     

Synthesis and characterization of Cr8O21 as cathode material for rechargeable lithium batteries

Pure phase Cr₈O₂₁ with excellent electrochemical properties has been synthesized by sintering anhydrous chromium trioxide (CrO₃) at low temperature in flowing oxygen. Cyclic voltammetry (CV) and X-ray diffraction (XRD) characterizations indicate that the inner tetra-chromate groups of Cr₈O₂₁ are damaged and Cr₈O₂₁ is changed to another layer-structured material when lithium is inserted into the host.