Fe3O4(111) termination of α-Fe2O3(0001)

Scanning tunnelling microscopy (STM) has been used to investigate the structure formed on an α-Fe₂O₃(0001) substrate after argon ion bombardment and annealing in 1 × 10⁻⁶ mbar of O₂ at 1000 K. The STM images recorded at positive sample bias reveal an hexagonal array, with a distance between (Fe) atoms of 6.0 ± 0.1 rA and steps in multiples of 4.8 Å. These results are consistent with formation of an Fe₃O₄(111) epitaxial layer terminating in a monolayer of Fe atoms.     

Surface structures of in (√3 × √3 )R30° and (5√3 × 2) phases studied by surface extended X-ray absorption fine structure spectroscopy

The local surface structures of in the ( √3 × √3) R30° and (5√3 × 2) phases have been investigated by means of polarization-dependent sulfur K-edge surface EXAFS. In the (√3 × √3 ) R30° phase, sulfur adatoms are found to occupy threefold hollow sites with a S---Ni distance of 2.13 Å and an inclination angle ω of the Sz.sbnd;Ni bonds at 44° from the surface plane. In contrast, in the (5√3 × 2) phase, it is determined that the Sz.sbnd;Ni bond is longer, 2.18 Å, more inclined, ω = 31°, and that the coordination number is not 3 but 4. These results strongly support a picture involving reconstruction of the top nickel layer to form a rectangular structure. Consideration of several models proposed for the (5√3 × 2) phase leads to one which is compatible with both the present results and results recently reported using STM.     

Transformation of organic and inorganic sulphur in a lignite during pyrolysis: Influence of inherent and added inorganic matter

The transformation of organic and inorganic sulphur during pyrolysis of a Western Australian lignite has been studied using several complimentary techniques. The lignite contains high moisture, oxygen, volatile matter, organic sulphur and inherent inorganic matter. FTIR and solid state ¹³C TOSS NMR spectroscopic studies revealed that the high oxygen content is attributed to the oxygenated functional groups, which is saturated with organically bonded inherent inorganic matter. Sodium and chlorine are the dominant inorganic matter and present in the form of sodium chloride. TGA-MS studies of the raw lignite showed that SO₂ is the dominant sulphur-bearing gases evolved during the pyrolysis of the raw lignite. The effect of inherent and added inorganics was studied by comparing the amounts of various forms of sulphur retained in the chars of the raw lignite, the acid washed lignite and the acid washed lignite doped with sodium and kaolinite following pyrolysis in a fixed-bed reactor in nitrogen. Inherent inorganic matter was shown to reduce the decomposition of organic sulphur but has little effect on the decomposition of inorganic sulphur. Sodium helps the retention of sulphur in the chars between 400 and 500 °C while kaolinite has a better ability to retain sulphur above 600 °C.     

Doppler-limited dye laser excitation spectroscopy of DCF

The dye laser excitation spectrum of the vibronic transition of DCF was observed between 17 200 and 17 400 cm⁻¹ with the Doppler-limited resolution. DCF was produced by the reaction of microwave-discharged CF₄ with CD₃F. The observed spectra, which were found to be nearly free of perturbations, were assigned to 858 transitions of the K′_a − K″_a = 4−5, 3−4, 2−3, 1−2, 0−1, 1−0, 2−1, 3−2, 3−3, 2−2, 1−1, 0−0, 2−0, and 0−2 subbands, and were analyzed to determine the rotational constants and centrifugal distortion constants for both the and à states. The rotational constants of DCF thus determined were combined with those of HCF to calculate the structural parameters for this molecule: r(C---H) = 1.138 Å, r(C---F) = 1.305 Å, and HCF = 104.1° for the ground state, and r(C---H) = 1.063 Å, r(C---F) = 1.308 Å, and HCF = 123.8° for the excited à state.     

Electrical and mechanical properties of proton conducting SrCe0.95Yb0.05O3 − α

Yb³⁺-doped ceramic strontium cerate of exactly the composition SrCe_0.95Yb_0.05O_{3 − α} was prepared, having a relative density of 99.0 (± 0.3%). Great care was taken to obtain homogeneous, carbonate free material. Analysis are made of the X-ray powder diffraction pattern of the as-prepared dense ceramic, resulting in the orthorhombic unit cell parameters a = 6.997(2) Å, b = 12.296(3) Å, c = 8.588(2) Å, Z = 8 and d_x = 5.806(2) g cm⁻³. Bending strength values of the ceramic in non-proton and proton conducting state are found to be 177 and 194 MPa respectively. The ceramic kept under proton conducting conditions for 500 h at 300 °C to 800 °C in a N₂ flow containing 155 mbar water vapour and 245 mbar H₂, have shown to remain chemically and structurally stable. Impedance spectroscopy measurements of the bulk conductivity of the proton conducting ceramic revealed an activation energy of 53.2 kJ mol⁻¹ and a preexponential factor of 359.1 (Ω cm)⁻¹ K. In the non-proton conducting state the ceramic is mainly oxygen ion vacancy conducting, which indicates that charge compensation on substituting Yb⁺³ in SrCeO₃ takes place by oxygen ion vacancies.     

The microwave spectrum of phosphabutadiyne, H---CC---CP

A detailed rotational analysis of the microwave spectrum between 26.5 and 40 GHz of phosphaethene, CH₂=PH, has been carried out. This molecule is the simplest member of a new class of unstable molecules—the phosphaalkenes. The species can be produced by pyrolysis of (CH₃)₂PH, CH₃PH₂ and also somewhat more efficiently from Si(CH₃)₃CH₂PH₂. Full first-order centrifugal distortion analyses have been carried out for both ¹²CH₂³¹PH and ¹²CH₂³¹PD yielding: A₀ = 138 503.20(21), B₀ = 16 418.105(26), and C₀ = 14 649.084(28) MHz for ¹²CH₂³¹PH. The 1₀₁-0₀₀ μ_A lines have also been detected for ¹³CH₂PH, cis-CDHPH and trans-CHDPH. These data have enabled an accurate structure determination to be carried out which indicates: r(H_cC) = 1.09 ± 0.015 Å, (H_cCP) = 124.4 ± 0.8°; r(H_tC) = 1.09 ± 0.015 Å, (H_tCP) = 118.4 ± 1.2°; r(CP) = 1.673 ± 0.002 Å, (HCH) = 117.2 ± 1.2°; r(PH) = 1.420 ± 0.006 Å, (CPH) = 97.4 ± 0.4°. The dipole moment components have been determined as μ_A = 0.731 (2), μ_B = 0.470 (3), μ = 0.869 (3) D for CH₂PH; μ_A = 0.710 (2), μ_B = 0.509 (10), μ = 0.874 (7) D for CH₂PD.     

The harmonic force field and ground-state average structure of difluoroborane

An improved harmonic force field of difluoroborane has been calculated using the vibrational wavenumbers and quartic centrifugal distortion constants of four isotopic species. The unidentified vibrational mode ν₅ is predicted at 1049 ± 50 and 775 ± 50 cm⁻¹ for HBF₂ and DBF₂, respectively. The ground-state average structure of HBF₂ has been found to be r_z(BH) = 1.195 ± 0.003 Å; r_z(BF) = 1.315 ± 0.001 Å; (FBF) = 118.0 ± 0.1°.     

Microwave spectrum and structure of ethylene ozonide: Effects of large axes rotations in structure calculations

Rotational spectra for 14 isotopic species of ethylene ozonide have now been assigned. The consistency of the Kraitchman substitution structure was checked by calculating the O_p---O_p bond distance six ways; the values ranged from 1.458 to 1.502 Å. This variation was attributed to an amplification of residual vibrational effects by large axes rotations upon isotopic substitution. Estimates of errors produced from this effect were made and a procedure was developed for choosing r_s parameters in which the effect is minimized. This gave the following ring parameters: d(CO_e) = 1.416 Å, d(CO_p) = 1.412 Å, d(OO) = 1.461 Å, <CO_eC = 104.8°, <O_eCO_p = 105.5°, <CO_pO_p = 99.3°.     

Latent tracks generated in micro-crystalline α-L-alanine and standard bone powder by Co ion beams as investigated by EPR-method

Latent tracks created by ⁵⁹Co ions in l-α-alanine and standard bone powder were examinated by EPR-method. For 3.4 MeV/amu cobalt ions the mean radius of tracks (considered as the distance from the ion path on which a detectable concentration of paramagnetic centers exists) was estimated as (190±30) Å for l-α-alanine and (220±30) Å for bone powder.     

Two-Photon Laser-Induced Fluorescence Spectra of Argon in a Grimm-Style Glow Discharge Tube

Two-photon excited laser-induced fluorescence (LIF) spectra of argon atom were successfully observed in a Grimm-style glow discharge tube, which has widely been applied to depth profiling of the elemental composition on various film-like samples by emission spectrometry. The LIF signal of an argon atomic line at 641.63 nm was observed when the glow discharge argon plasma was illuminated by a pulsed Ti:sapphire laser radiation of 7–10 mJ/pulse at 753.39 or 795.66 nm without focusing of the laser beam.     

The microwave spectrum, structure, chlorine nuclear quadrupole coupling constants, dipole moment, and centrifugal distortion constants of dichlorosilane

The microwave spectra of three isotopic species of dichlorosilane, SiH₂Cl₂, in its ground vibrational state, have been measured in the frequency region 8–40 GHz. The spectra have yielded values for the rotational constants, centrifugal distortion constants, and chlorine nuclear quadrupole coupling constants, as well as the molecular dipole moment, 1.13 ± 0.02 D. The molecule has C_2v symmetry, and the bond lengths and angles r(Si---Cl=2.033±Å, r(Si---H)=1.480±0.015Å, (Cl---Si---Cl)=109°43′±20±, (H---Si---H)=111°18′±40′ The centrifugal distortion constants have been compared with those calculated using a published force field.     

Analysis of lead molybdate and lead tungstate synthesized by a sonochemical method

Lead molybdate and lead tungstate nanoparticles were successfully synthesized by a sonochemical method for 1 h. XRD patterns showed the body-centered tetragonal structures of PbMoO₄ and PbWO₄, and were in accordance with those of the simulation and JCPDS software. Calculated lattice parameters are a = b = 5.4233 Å and c = 12.1253 Å for PbMoO₄, and 5.4570 Å and 12.0995 Å for PbWO₄. They are in accordance with those of the corresponding JCPDS software. TEM images show that the particles were 29.09 ± 5.22 nm and 21.05 ± 2.68 nm for PbMoO₄ and PbWO₄, respectively. Raman and FTIR vibrations were investigated to identify a definite existence of the structures.     

One-step fastest method of nanocrystalline CuAlS<Subscript>2</Subscript> chalcopyrite synthesis,and its nanostructure characterization

Nanocrystalline CuAlS₂ chalcopyrite has been mechanosynthesized at room temperature for the first time by ball milling the stoichiometric mixture of elemental of Cu, Al, and S powders under argon atmosphere. Initially, the CuAlS₂ phase is formed by solid state reaction of elemental powders within 15 min of milling and in the course of milling crystallite size decreases slowly to ~5 nm within 10 h of milling. Microstructure characterization and phase transformation kinetics of the elemental powders toward the chalcopyrite phase formation has been made by employing the Rietveld analysis using X-ray diffraction data of unmilled and ball-milled samples.     

Laser-induced breakdown spectroscopy: A versatile tool for monitoring traces in materials

Laser-induced breakdown spectroscopy (LIBS) is an emerging technique for simultaneous multi-elemental analysis of solids, liquids and gases with minute or no sample preparation and thus revolutionized the area of on-line analysis technologies. The foundation for LIBS is a solid state, short-pulsed laser that is focused on a sample to generate a high-temperature plasma, and the emitted radiation from the excited atomic and ionic fragments produced within the plasma is characteristic of the elemental composition of the sample that can be detected and analyzed using a suitable optical spectrograph. In the present paper, the applicability of LIBS for different solid samples having homogeneous (silver ornament, aluminum plate) or heterogeneous composition (soil) using nanosecond laser pulses is discussed. Nanosecond pulse laser makes plasma at the sample surface even at very low pulse energies and also allows for precise ablation of the substrate material with little damage to the surrounding area. We have also studied the penetration of different heavy metals inside the soil surface.      

The adsorption geometry of the (2 × 1)-2O oxygen phase formed on the Co(10 0) surface

The bond geometry of the (2 × 1)-2O-p2mg overlayer on Co(10 0) was determined by analyzing low-energy electron diffraction (LEED) intensity data. Oxygen occupies the three-fold coordinated hcp site along the densely packed rows on the unreconstructed surface. The O atoms are attached to two atoms in the first Co layer and to one Co atom in the second layer. The strong interaction between O and Co is indicated by the bond lengths of 1.83 ± 0.10 Å and 1.99 ± 0.10 Å to the top-layer Co and the Co atoms in the second layer, respectively. The most striking result of our work is that oxygen adsorption causes a marked expansion (by 25%) of the first Co layer spacing (0.90 Å) with respect to the bulk value of 0.72 Å. This strong expansion might offer diffusion channels for O atoms to penetrate further into the subsurface region.     

The ZnO non-polar (10 0) surface: an X-ray structural investigation

We performed a structural analysis of the non-polar ZnO (10 0) surface by means of grazing incidence X-ray diffraction. The analysis was conducted on ten rods, smooth surface domains, though of small coherent width, having been obtained after several Ar⁺ sputtering–annealing cycles. The surface derived from the bulk structure exposes one ZnO dimer per unit cell, parallel to the [001] axis. All the existing models, derived from ab initio calculations or low-energy electron diffraction (LEED) analyses, consist in a surface dimer whose O and Zn atoms are shifted inwards, with the O pointing outwards with respect to Zn. Whereas the LEED studies conclude on a dimer distance greater than in the bulk, the theoretical studies agree on a dimer contracted by amounts ranging from 5.5 to 7.5%. This contraction is interpreted as a result of the strong ionicity of ZnO, and is associated with a moderate dimer rotation. The latter, however, is found between 2.3 and 11.4°. Despite the discrepancies between the models, the Zn atom is always found shifted downwards by more than 0.25 Å. This is unambiguously rejected by our data, which show that the Zn atom keeps very close to its bulk position. It is displaced downwards by ΔZ_Zn=−0.06±0.02 Å, and it moves along [001] towards O by ΔX_Zn=0.05±0.02 Å. We denote a trend for the O atom to be displaced downwards too, with a concomitant displacement towards Zn. The faint X-ray scattering of O prevents us from assessing its position with accuracy. Depending on the choice of position for Zn in the error bar range, the buckling is evaluated as between −6.5 and 3°, or between −4 and 0.5°. The dimer distance is evaluated equal to 1.90 Å, with a deviation equal either to 0.06 or 0.11 Å.     

Combined laser/sol-gel synthesis of calcium silicate coating on Ti-6Al-4V substrates for improved cell integration

New studies have shown that tricalcium silicate powder is a bioactive material and can encourage bone-implant integration. This paper reports the synthesis of Ca₂SiO₄ coating on Ti-6Al-4V samples by laser irradiation under submerged conditions. The results of using a 160-1500 LDL 1.5 kW diode laser (rectangular spot = 2.5 mm × 3.5 mm, λ = 808 and 940 nm with equal intensities) is reported. A number of experiments were carried out varying laser parameters, such as scanning speed and laser power. Coatings are evaluated in terms of microstructure, elemental composition (XRD), SEM and wettability. The in vitro biocompatibility of the samples is investigated by monitoring 2T3 osteoblast cell growth on the samples.     

Argon laser induced changes to the carbonate content of enamel

Argon laser irradiation can be used to cure orthodontic brackets onto teeth in significantly less time than conventional curing lights. In addition, it has been shown that the argon laser seems to impart a demineralization resistance to the enamel. The purpose of this study was to use surface science techniques to ascertain if this demineralization resistance is possibly a result of a decrease in the carbonate content of enamel. Eleven mandibular third molars previously scheduled for extraction were collected and used in the present study. The teeth were sectioned in two and randomly assigned to either the argon laser (457-502 nm; 250 mW cm⁻²) or the control (no treatment) group. The sections assigned to the argon laser group were cured for 10 s and analyzed. To exaggerate any potential changes the experimental sections were then exposed to a further 110 s of argon laser irradiation. Surface analysis was performed using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The results showed no statistically significant change in the carbonate content of enamel after argon laser irradiation (p > 0.05). Thus, it is suggested that any demineralization resistance imparted to the enamel surface by argon laser irradiation is not due to alterations in carbonate content.     

Lorentz-mikroskopie von Bloch- und Néelwänden in Ni-Fe-kristallen

We prepared thin single crystal foils of 50 Ni 50 Fe for observation in a 100 kV electron microscope. Due to its high saturation induction and low anisotropy, magnetic domain walls can be easily observed in this material. The effective anisotropy which governs the wall angles consists of crystal anisotropy and superimposed random stress anistropies so that wall angles of any magnitude are found.In accordance with theory three distinct wall types are identified for film thickness between 500 Å and 2000 Å as a function of wall angle θ: (i) the asymmetric Bloch wall for 180° θ #62; 140°, (ii) the asymmetric Néel wall for 140° #62; θ #62; θ_s, and (iii) the symmetric Néel wall for θ_s #62; θ, where θ_s is an angle which decreases with increasing film thickness.     

Detection and Characterization of Boric Acid and Borate Ion Binding to Cytochrome c Using Multiple Quantum Filtered NMR

The application of multiple quantum filtered (MQF) NMR to the identification and characterization of the binding of ligands containing quadrupolar nuclei to proteins is demonstrated. Using relaxation times measured by MQF NMR multiple binding of boric acid and borate ion to ferri and ferrocytochrome c was detected. Borate ion was found to have two different binding sites. One of them was in slow exchange, k_diss = 20 ± 3 s⁻¹ at 5°C and D₂O solution, in agreement with previous findings by ¹H NMR (G. Taler et al., 1998, Inorg. Chim. Acta 273, 388–392). The triple quantum relaxation of the borate in this site was found to be governed by dipolar interaction corresponding to an average B–H distance of 2.06 ± 0.07 Å. Other, fast exchanging sites for borate and boric acid could be detected only by MQF NMR. The binding equilibrium constants at these sites at pH 9.7 were found to be 1800 ± 200 M⁻¹ and 2.6 ± 1.5 M⁻¹ for the borate ion and boric acid, respectively. Thus, detection of binding by MQF NMR proved to be sensitive to fast exchanging ligands as well as to very weak binding that could not be detected using conventional methods.