Soils from the Jabal Al‐Akhdar region of North East Libya: Characterisation of the iron using chemical methods and Mössbauer spectroscopy

Soils from North East Libya have been investigated by X‐ray diffraction, chemical analysis and Mössbauer spectroscopy. Quartz, kaolinite and illite were the main components identified by XRD in all specimens. Total and poorly ordered iron oxides were estimated using dithionite–citrate–bicarbonate (DCB) and oxalate extraction methods, respectively; in all cases, the oxalate‐extractable iron represents a relatively minor fraction. Mössbauer spectroscopy showed the presence of substantial quantities of haematite and goethite, both in microcrystalline forms, but there was no systematic relationship between the relative proportions of these phases and the geographical origins of the soils.     

Deformation behavior of tetramethyl-p-silphenylenesiloxane (TMPS)-dimethylsiloxane (DMS) block copolymer spherulitic films

A study of the morphology of uniaxially drawn spherulites of TMPS-DMS block copolymers with TMPS contents ranging from 90 to 30 wt % was made especially by electron and optical microscopy. For the entire range of polymer compositions, the copolymers, like the TMPS homopolymer, form negatively birefringent spherulites when crystallized from solution, or from the supercooled melt. A banded spherulitic morphology is observed. The deformability of copolymer spherulites increases as the DMS amorphous component increases. The DMS component coexists with, but is physically excluded from the ordered TMPS “crystalline” phase. In samples having the higher TMPS compositions, deformation occurs through crack formation, mechanical slip, tilting and/or twisting of the lamellae that help comprise the spherulites. At high DMS contents this “soft” component is undoubtedly responsible for the flexible character of these copolymers. Sample clarity also increases with DMS content as the crystallinity decreases.     

Preparation of stable porous nickel and cobalt oxides using simple inorganic precursor, instead of alkoxides, by a sonochemical technique

Porous nickel and cobalt oxides were prepared using NiSO4.6H2O and anhydrous Co(CH3COO)2, a precursor other than alkoxides and cetyltrimethylammonium bromide as organic surfactant. The sonication method has been used for such synthesis. The surfactants were removed by calcination, as well as by solvent extraction and it is extent was examined by IR spectroscopy. The trend of removal of surfactant was followed by TGA studies and the change in phases by DSC. The products were identified by XRD. Peak in low angle XRD indicates the porous nature of the oxides. The morphology of the pores was studied by transmission electron microscopy. The pores were found less ordered, having an average size of 4-6 nm. The Brunauer-Emmet-Teller surface areas of the as-prepared, as well as the treated samples are reported having H2 and H4 type hysteresis for Ni and Co, respectively.     

Nanoparticles in mesoporous films,a happy marriage for materials science

Mesoporous ordered materials, whose porosity is within the 2–50-nm range, are an ideal host for functional nanoparticles. Mesoporous thin films, in particular, offer a large variety of options for the fabrication of advanced materials and devices based on the host-guest combination of matrix nanoparticles. Nanocomposite mesoporous films embedding metal, oxide, and semiconductor nanoparticles have been prepared using as matrix oxides, mixed oxides, and organic-inorganic hybrids. The organization of the pores is an important peculiar property of mesoporous ordered films and allows producing nanocomposites whose nanoparticles follow a very specific array within the material. The main synthesis methods to obtain mesostructured films containing nanoparticles, together with their applications, are briefly introduced in the present review.     

Direct experimental confirmation of the critical behaviour of antiphase domain boundaries at the second order phase transition of Al-Fe binary alloys

The present work reports, for the first time, a direct experimental observation of the critical phenomenon associated with the B2-A2 order-disorder transition of Al-Fe binary alloys. Transmission electron microscopy and energy dispersion spectroscopy are employed to span the morphological changes through the transition line from the ordered B2 phase to the disordered A2 phase. Dark field images of the microstructure around the transition line for samples aged at 973 and 1073 K for various times show an interface roughening for the {100} antiphase domain boundaries in body-centered cubic binary alloys having the B2 structure. This observation confirms theory about the instability of the second-order transition in such alloys. This behaviour occurs for compositions with Al-content slightly higher (by ∼4 at.% Al) than that of the critical point of the equilibrium order-disorder transition. In addition, roughness-induced wetting transition is also observed for alloys having compositions ranging from 1.3 to 1.5 at.% Al above the transition line. The interface roughening transition is thought to be unstable second-order while the wetting transition is suggested to be a stable first-order one.     

Hyperfine field and ordering in bcc CoFe bulk alloys studied by 59Co NMR and Monte-Carlo simulation

Bcc CoFe alloys and ordered compounds with Fe concentrations of 50 at.%, 40 at.% and 30 at.% have been studied by ⁵⁹Co NMR. Spectra with regularly spaced satellites are observed and interpreted as resulting from a step increase of the resonance frequency with each additional Fe impurity in the first coordination shell. The influence of the second-neighbour shell is also demonstrated. Satellite position analysis leads to the relationship between the hyperfine field and the first- and secondneighbour shell composition, which is found valid for the three compositions both in ordered compounds and disordered alloys. This relationship is used to determine the chemical short range order ruling the compound structure. The analysis reveals that the probability for Co to be found in perfectly ordered stoichiometric regions is higher than expected from a random distribution of the excess Co in off-stoichiometric compounds. Monte-Carlo simulations indicate that such short range order would result not only from first-neighbour interactions but also from rather large second- and/or third-neighbour interactions. However, the observations made during isothermal annealing show that the phase transformation takes place through a nucleation and growth process and not by way of homogeneous ordering. Therefore, the final short range order is also discussed in terms of kinetics of the phase transformation.     

Interrelation of intrinsic and extrinsic defects – congruent, stoichiometric, and regularly ordered lithium niobate

A new approach to the intrinsic and extrinsic defect subsystems, considering them as one integrated functional system, is developed for complex oxides. The strong interrelation of these subsystems becomes especially apparent when concentrations of both defect classes are comparable. A new parameter, reflecting the total intrinsic defect concentration, is introduced to determine the degree of crystal imperfection. The necessity of at least two calibrated samples – congruent and regularly ordered crystals – is substantiated. The accuracy by which the parameter can be determined can serve as a criterion in comparison of different methods of crystal characterisation. A procedure for crystal calibration by several physical characteristics is illustrated. Such a heuristic generalisation of the concept of mutual correlation of the whole defect system and the material only became possible on the basis of experimental and theoretical study of large numbers of LiNbO₃ crystals. The spectra of EPR, NMR, ENDOR, and other properties of crystals with different compositions, diverse modifiers (K, Mg,...), and various probe impurities have been analysed. It is found that crystals with vanishingly small concentration of intrinsic defects offer extraordinary informative opportunities. Their micro- and macroscopic properties are discussed. The developed ideas have a general character; therefore they should also be valid for other non-stoichiometric complex oxides. Received: 3 December 1998 / Revised version: 15 February 1999 / Published online: 12 April 1999     

New phases in the barium-rich region of the BaO-BaCuO2 system

The phase relations have been studied in the BaO-CuO _x system in the range of 25.0–45.0 mol % CuO at P(O₂) = 21 kPa by visual polythermal analysis (VPA), X-ray phase analysis (XPA), differential thermal analysis (DTA), thermogravimetric analysis (TGA), chemical analysis (CA), X-ray microprobe analysis (XMEA), and electron diffraction (ED), with simultaneous elemental analysis (EA) by a transmission electron microscope (TEM). A discrete deviation of the 2.10, 2.08, 2.04, 2.02 (Ba/Cu) compositions from stoichiometry in the known Ba₂CuO_{3 + δ} oxides is found. New oxides of the 2.00, l.75, 1.66, 1.15 (Ba/Cu) compositions are revealed and their unit-cell parameters are determined. The phase diagram of the BaO-CuO _x system is constructed, whose structure is considered as the total projection of phase states of the system at T = f(x) in CuO _x .     

High temperature superconductivity in Y-Ba-Cu-O and Y-Ba-Sr-Cu-O systems

Mixed metal oxides Y-Ba-Cu-O and Y-Ba-Sr-Cu-O have been prepared in varying compositions and by changing process parameters. Superconductivity with critical temperatures in the range of 70 to 100 K is reported.     

Universal properties of relaxation and diffusion in condensed matter

By and large the research communities today are not fully aware of the remarkable universality in the dynamic properties of many-body relaxation/diffusion processes manifested in experiments and simulations on condensed matter with diverse chemical compositions and physical structures. I shall demonstrate the universality first from the dynamic processes in glass-forming systems. This is reinforced by strikingly similar properties of different processes in contrasting interacting systems all having nothing to do with glass transition. The examples given here include glass-forming systems of diverse chemical compositions and physical structures, conductivity relaxation of ionic conductors(liquid, glassy, and crystalline),translation and orientation ordered phase of rigid molecule, and polymer chain dynamics. Universality is also found in the change of dynamics when dimension is reduced to nanometer size in widely different systems. The remarkable universality indicates that many-body relaxation/diffusion is governed by fundamental physics to be unveiled. One candidate is classical chaos on which the coupling model is based, Universal properties predicted by this model are in accord with diverse experiments and simulations.     

Transformations of mixed molybdenum-vanadium oxides in the oxidation of hydrocarbons by molecular oxygen

Structural-morphological transformations of molybdenum-vanadium mixed oxide catalysts of varying composition in the oxidation of hydrocarbons are studied by X-ray diffraction analysis, electron microscopy, electron paramagnetic resonance technique, and Raman scattering spectroscopy. It is shown that the catalytic reactions, which are analyzed in detail for oxides of various compositions, cause a considerable restructuring of the mixed oxides.     

Optical characteristics of highly ordered gallium oxide nano-islands on GaAs

A periodic array of Ga oxide islands was obtained by annealing the highly ordered Ga nano-droplets on GaAs surface at 400°C under an oxygen atmosphere for 7 hours. These Ga oxides are a mixture of α-Ga₂O₃ and β-Ga₂O₃ confirmed by Raman spectroscopy study. Enhanced optical transmission of GaAs with such ordered Ga oxide nano-islands was obtained. Both dielectric and dimensional confinement effects were considered in analysis of the electromagnetic characteristics of the nanostructured materials. Finite-difference time-domain method was used to numerically study the light transmission through the patterned Ga oxide on GaAs surface. Based on the calculated results, the light transmission enhancement is attributed to the formation of the ordered nano Ga oxides.     

α- and β-Mn precipitates in the spinodal Fe30Ni20Mn25Al25 alloy

Precipitates in the spinodal alloy Fe₃₀Ni₂₀Mn₂₅Al₂₅, produced by drop-casting followed by hot extrusion, have been investigated using transmission electron microscopy. The as-extruded microstructure consisted of alternating, coherent body-centred cubic and B2 (ordered body-centred cubic) rods aligned along ?100? directions with a wavelength of ～60?nm. Upon annealing at 550°C, precipitates were formed having two distinct morphologies: relatively spherical precipitates with the α-Mn crystal structure and more elongated precipitates with the β-Mn crystal structure. Both precipitates existed simultaneously after annealing at this temperature for up to at least 99?h. The compositions of the precipitates and the orientation relationships between the precipitates and the spinodal matrix were determined.     

Effect of vacancies on the resistivity of ordered alloys

An analysis is made of the effect of lattice vacancies in a binary ordered substitutional alloy with a bcc lattice on the residual resistivity. A calculation shows that the concentration dependence of the resistivity loses its symmetric form. At certain compositions vacancies can reduce the residual resistivity, and at other compositions they can increase it. An experimental study of the asymmetry of the curve will yield information about the atomic interaction energies in an alloy.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 81–87, September, 1970.     

Application of transmission electron microscopy for studying phase relations in the bismuth-rich region of the Ba-Bi-O system

The crystal structure and cation composition of oxides of the Ba-Bi-O system in the composition range 80–100 mol % BiO_1.5 have been investigated by the methods of transmission electron microscopy. Ordered phases of the compositions Ba: Bi = 2: 9, 1: 6, and 1: 15 with a rhombohedral structure have been revealed. In the range of the compositions Ba: Bi from 1: 36 to 1: 46, phases with triclinic, monoclinic, and cubic structures have been found. The monoclinic and cubic phases have structures similar to the structures of the α and γ modifications of bismuth oxide Bi₂O₃, respectively. Phase formation was found to be dependent on the following parameters: annealing temperature, partial oxygen pressure, oxygen content in the initial pairs of reacting components (BaO₂-Bi₂O₃, Ba(NO₃)₂-Bi₂O₃, BaCO₃-Bi₂O₃), and crucible material (alundum or platinum).     

Clays and clay minerals: What can Mössbauer spectroscopy do to help understand them?

Mössbauer spectroscopy is a powerful technique for the characterization of materials formed in the weathering environment. Mössbauer studies of clay-sized phyllosilicates, however, are burdened with several problems: the samples are rarely monomineralic, they may be poor in iron, and only few iron-rich species order magnetically above 4.2 K. Site occupancies are difficult to determine, and cis and trans octahedral-OH site assignments are normally not possible. Unequivocal information that can be gained from such work thus is often restricted to the determination of the oxidation state of iron and average structural site distortions. Mössbauer data on iron oxides are generally more straightforward to interpret because these can be studied in the magnetically ordered state. A further asset of Mössbauer spectroscopy when studying iron oxides lies in its high sensitivity for magnetically ordered phases. Adverse effects ensuing from small particle size, interparticle interactions, non-stoichiometry and foreign-element substitution that often affect the Mössbauer parameters of iron oxides occurring in clays and soils can be at least partly offset by taking spectra at low temperatures.     

High-entropy equiatomic AlCrFeCoNiCu alloy: Hypotheses and experimental data

Experimental data for the structural and phase transformations taking place in cast equiatomic AlCrFeCoNiCu alloy under slow cooling, melt quenching, and a number of thermal treatments are presented. Investigations are carried out by analytical transmission electron microscopy and scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray structural analysis, and X-ray diffraction analysis with the involvement of 3D atom probe tomography data, and nanohardness and elasticity modulus measurements. It is found that the as-cast alloy having a dendritic microstructure decomposes with the separation of at least six nanodimensional phases with different morphologies, structures (of type A2, B2, L1₂), and chemical compositions. It is also found that a homogeneous ultrafine-grained B2 structure arises in the alloy obtained by melt quenching. This structure decomposes into nanodimensional mainly equiaxial bcc phases, atomically ordered phases (B2), and atomically disordered ones (A2), all being highlighted by subsequent annealing.     

复方乙酰水杨酸片中有效成分的DOSY技术分析

复方乙酰水杨酸片是临床常用的解热镇痛消炎药物,目前其有效成分的分析方法存在操作繁琐而分析速度慢等不足.该文利用二甲基硅油(PDMS)辅助的扩散排序(DOSY)技术以及扩散排序-同核相关(DOSY-COSY)联用技术,成功地对复方乙酰水杨酸片中三种有效成分的分子结构进行了快速定性分析,并且利用核磁共振氢谱(~1H NMR)技术进行了相对定量分析.该方法具有方便、快捷等特点,可作为借鉴和参考用于药物的质量评价.     

Surface study of cerium oxide based coatings obtained by cathodic electrodeposition on zinc

A surface study of electrodeposited cerium oxide based coatings is presented. Different surface analytical techniques were used in order to obtain complementary information to fully characterize such complex systems. X-ray Photoelectron Spectroscopy was used as the main technique to determine the surface composition of the coating. The analysis of the core level peaks of the elements provides additional information about the functional groups present on the surface. A mixture of Ce (III) and Ce (IV) was found in the coating and their proportion was calculated at different depths. The analysis of the O 1s core level peak revealed a triple structure whose origin will be discussed. To support the results obtained, electron stimulated desorption was performed. The study was completed with Auger electron spectroscopy and Raman spectroscopy, both techniques having different surface sensitivities. From all these results, it is derived that incomplete electrochemical reactions occurred during the growth of the coatings. This led to rather complex compositions, in which defective cerium oxides are the major species. In addition, hydroxides, carbonates and nitrates are also present, together with adsorbed water.     

基质辅助 NMR 中色谱技术的研究进展

被誉为“ NMR 中色谱技术”的二维扩散排序 NMR 谱(DOSY)技术是检测混合物溶液中不同分子组分的一种有效手段．但是当面对自扩散系数差别较小的不同分子时, DOSY技术便无法对上述混合物进行基线分离． 在 NMR 魔角旋转转子或 NMR 样品管中添加一些色谱填料或高分子等基质（或称为虚拟“色谱固定相”）是一种行之有效的手段．这些虚拟“色谱固定相”与混合物组分发生相互作用并改变其自扩散系数,从而对混合物实现基线分离．该文综述了近年来基质辅助 NMR中色谱技术的研究进展．