Mössbauer studies of illites and heat-treated illite as related to coal-conversion processes

Mossbauer spectra of iron species in the following illites were studied: Grundite, Fithian, Minerva, and New Albany. Spectra of samples of Fithian illite heated at temperatures of 225, 700, and 1000 °C were also obtained. Analyses of these spectra provide Mössbauer parameter values of iron species in the illites and heat-transformed illite for comparison with similar species found in coals containing illites and in coal process residues derived from them. The illites contain both ferric and ferrous species. Mössbauer parameters for one of the ferric species, designated M(2), are virtually the same as those of pyrite. The two species are therefore difficult to distinguish from one another. Values of the concentration of pyrite in coals and shales may be inflated if the pyrite concentration is measured by Mössbauer spectroscopy. Mössbauer spectra of the heat-treated illite samples reveal changes in iron distribution, principally at the 700 and 1000 °C levels, where there are found three and six different iron species respectively. These changes are accompanied by reduction of ferric to ferrous iron. This process should be integrated into any assessment of the iron chemistry which accompanies coal-conversion processes.     

Morphology, optical, and photoelectrochemical properties of electrodeposited nanocrystalline ZnO films sensitized with Cd x Zn1−x S nanoparticles

Nanocrystalline ITO/ZnO films formed by porous zinc oxide microplatelets 1–3 μm in size and 100–200 nm in thickness, which consist of 30–50 nm ZnO crystallites, were sensitized to visible light by Cd _x Zn_1?x S nanocrystals deposited using the method of successive ionic layer adsorption and reaction (SILAR). The composition of Cd _x Zn_1?x S nanocrystals as well as the dependence between molar Cd(II) fraction in the films and the ratio of cadmium and zinc nitrate concentrations in solutions used for the SILAR procedure were determined by a combination of electron, Raman, and energy-dispersive X-ray spectroscopies. The photovoltage observed at illumination of the ITO/ZnO/Cd _x Zn_1?x S heterostructures by white light (λ >400 nm) in aqueous Na₂S solution increases with a decrease of Cd(II) content proportionally to an increment in the conduction band potential of the Cd _x Zn_1?x S nanocrystals. The photocurrent density normalized to the light absorbance of the ITO/ZnO/Cd _x Zn_1?x S films increases by a factor of around four when the conduction band potential of Cd _x Zn_1?x S nanocrystals grows by 220 mV as a result of Cd(II) fraction changing from 1.0 to 0.62–0.67. The results show that Cd _x Zn_1?x S solid solutions are more advantageous sensitizers for the short-wavelength part of the sensitivity window of the liquid-junction solar cells (400–450 nm) than conventionally used cadmium sulfide.     

High-Temperature Oxidation of Bismuth- and Antimony-Based Sulfosalts

In this article, oxidation processes of Ag-Bi-Sb-based phases were investigated. Synthesized AgBiS₂ and AgSbS₂-Sb₂S₃-Sb samples were thermally analyzed in synthetic air by applying the simultaneous DSC-TGA analysis technique. The oxidation processes at P_O?=0.2 atm and T<1173 K were observed to take place in many-step sequence of various reactions with an overall reaction 2AgMeS₂ + 5.5O₂(g) ? 2Ag + Me₂O₃ + 4SO₂(g), where Me=(Bi,Sb). Oxidations of AgBiS₂, Sb₂S₃, and AgSbS₂ were observed to begin above 549±2K, 610±2K, and 733±2K, respectively. Furthermore, oxidation processes of AgBi₃S₅ and Ag₃SbS₃ were estimated, and thermodynamic functions for the overall oxidation reactions were calculated and discussed.     

Thermodynamic Properties of Superionic Phase Ag<Subscript>4</Subscript>HgSe<Subscript>2</Subscript>I<Subscript>2</Subscript> Determined by the EMF Method

Triangulation of the Ag-Hg-Se-I system in the vicinity of quaternary phase Ag₄HgSe₂I₂ was performed by differential thermal analysis, X-ray diffraction and electromotive force (EMF) methods. The spatial position of the phase region Ag₄HgSe₂I₂-Se-HgI₂ regarding the figurative point of silver was used to write the chemical reaction of formation of Ag₄HgSe₂I₂. The EMF measurements were carried out by applying an electrochemical cell: (–) C|Ag|Ag₂GeS₃ glass|Ag₄HgSe₂I₂, HgI₂, Se|C (+), where C is graphite and Ag₂GeS₃ glass is the fast purely Ag⁺ ions conducting electrolyte. The linear dependence of the EMF of the electrochemical cell on temperature was used to determine the standard thermodynamic values of Ag₄HgSe₂I₂ for the first time.     

基于BP神经网络算法的Ti-6Al-4V激光NiAl-VC合金化的工艺研究

为了进一步提高Ti-6Al-4V的性能,以满足其在工程中更广泛的运用,研究了在Ti-6Al-4V激光NiAl-VC合金化的工艺。以改变激光功率、激光扫描速度和粉末质量含量比例进行了工艺实验,采用BP神经网络(BP-NN)算法,建立了合金化层性能与工艺参数之间的关系模型,并通过验证实验表明预测效果良好,具有可行性。采用BP-NN算法进行了模拟实验,分析了不同工艺参数条件对合金化层深度、宽度、平均硬度、最高硬度的影响规律。本研究对Ti-6Al-4V激光NiAl-VC合金化的实践应用具有指导意义和参考价值。     

Photoelastic and acousto-optical properties of Cs2HgCl4 crystals

We use a Mach-Zehdner interferometric technique to study the piezo-optical properties of Cs2HgCl4 crystals at room temperature. All piezo-optical (pi(mn)) and photoelastic (p(in)) tensor constants are obtained. A substantial photoelastic effect and low ultrasonic velocities in these crystals determine a relatively high figure of merit M2 for isotropic diffraction (for a certain geometry of acousto-optical interactions, M2 approximately 110 x 10(-15) s3/kg). The new material may be considered, therefore, a candidate for applications in acousto-optical devices. The dependence of the acoustic walk-off angle on the direction of sound propagation is calculated for the principal crystallographic planes.     

Structural evolution of La-Cr-O thin film: Part II. Elasto-plastic properties by nanoindentation

The goal of this research is to study the elasto-plastic properties of La-Cr-O thin films deposited by RF-magnetron sputtering on stainless steel interconnect materials after annealing at high temperatures in air. Elastic modulus, hardness and yield pressure derived from nanoindentation data are reported for thin films in different structural states. The amorphous film has an estimated elastic modulus of 174 GPa. The moduli of annealed films are calculated to be 150, 185 and 120 GPa after annealing at 500 °C, 600 °C and 800 °C, respectively. The film annealed at 800 °C has the lowest hardness and is dramatically different from the other structural states due to formation of the nanoporosity. The amorphous film and the films annealed at 500 °C and 600 °C both have hardness of 14 GPa, which is close to the value estimated by modeling.     

Effects of rolling and hot pressing on mechanical properties of boron carbide-based ceramics

A study of hot pressed B₄C-based laminates, after rolling and without rolling, has been performed to elucidate the existence of fracture resistance/crack length anisotropy induced by this processing technique. While the crack lengths/fracture resistance was affected significantly by the presence of the residual stresses in B₄C/B₄C–ZrB₂ laminates, no differences in Vickers crack lengths were observed in B₄C/B₄C laminates prepared by rolling and hot pressing, as compared to the crack lengths seen in pure B₄C ceramics prepared by hot pressing without rolling. X-ray diffraction analysis confirmed that no texture has been formed during the rolling and hot pressing of B₄C ceramics.     

On thermal and vibrational properties of LaGaO3 single crystals

The thermal expansion and vibrational properties of [1 0 0] and [0 0 1] LaGaO₃ single crystals have been studied by thermal mechanical analysis and micro-Raman spectroscopy. A first-order orthorhombic to rhombohedral phase transition has been confirmed by both techniques, as well as by in situ heating using optical microscopy. The appearance of a metastable intermediate phase, tentatively assigned as monoclinic, has been detected both by optical microscopy and Raman spectroscopy upon heating of the [1 0 0] and [0 0 1] LaGaO₃ single crystals. Not only temperature, but the stress-induced orthorhombic to rhombohedral phase transition has also been detected by Raman mapping of the residual impression made by Vickers indentation. The position map of bands belonging to the lower-temperature/pressure orthorhombic and the higher-temperature/pressure rhombohedral phase show that the rhombohedral phase is located inside the impression, where the applied indentation stresses are the highest, whereas no rhombohedral phase is detected outside the impression, where the surface has not been altered by contact stresses.     

Role of microporosity and surface chemistry in adsorption of 4,6-dimethyldibenzothiophene on polymer-derived activated carbons

Two carbon samples derived from poly(4-styrenesulfonic acid-co-maleic acid) based polymer by carbonization between 700 and 800 °C were oxidized to two different levels of surface acidity. The surfaces of resulting adsorbents were characterized by potentiometric titration, adsorption of nitrogen, FTIR, SEM/EDAX and thermal analysis. The materials were used as adsorbents of 4,6-dimethyldibenzothiophene (4,6-DMDBT) from hexadecane with initial concentration of sulfur between 10-150 ppmw. Although it was found that pores with diameter less than 10 Å govern the amount of 4,6-DMDBT adsorbed, that amount is enhanced when acidic groups are present in the larger pores owing to the contributions of specific interactions. Surface chemistry plays an important role in reactive adsorption and deposition of the products of surface reactions in the pore system.