New transition metal fluoride glasses isolated in the PbF2MtIIF2MtIIIF3 systems

New glasses have been prepared in the PbF₂M_t^IIF₂M_t^IIIF₃ systems (m_t^II = Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺; M_t^III = Fe³⁺, V³⁺, Cr³⁺, Ga³⁺). The extent of the vitreous area is shown in a PbF₂MnF₂FeF₃ diagram. Thermal properties have been measured for all samples. Some of these glasses are very transparent over a wide range of wavelengths (from 250–12 000 nm). The sixfold coordination of transition metal ions has been established by spectroscopic investigations. The structure of the glasses is discussed on the basis of a random corner-sharing of MF₆ octahedra.     

Gaseous complexes — Their role in chemical transport

The literature about gaseous complexes consisting of two different metals and one halide is reviewed. With respect to chemical transport the most important properties of gaseous complexes are their appreciable thermodynamic stability and their volatility. This is clearly illustrated in the case of RbSnCl₃, whose vapour in equilibrium with the melt at 980 °K contains around 25 mole% of RbSnCl₃ (g) and whose vapour pressure is around 20 times higher than that of RbCl. Gaseous complexes of the type Mⁿ⁺L₂Cl_n+6 (M = Mg²⁺, Ca²⁺, Mn²⁺, Co²⁺, Ni²⁺, Nd³⁺, Cr³⁺; L = Fe³⁺, Al³⁺) can, in an atmosphere of L₂Cl₆(g), have vapour pressures up to 10⁷ times higher than the vapour pressure of MCl_n. The importance of such gaseous complexes for the chemical transport of MCl_n and of compounds containing Mⁿ⁺ will be discussed.     

Über die Kristallstrukturdifferenzen der MeSO4 · nH2O-Salztypen

On the basis of the systematized data on the crystal structure of salts of the MeSO₄ · nH₂O type, where Me = Mg²⁺, Ni²⁺, Zn²⁺, Co²⁺, Fe²⁺, Cu²⁺ and n = 0–7, it is established that the differences in the structures of given chemical type metal sulphate crystal hydrates are determined by the nature of the metal ion. The differences in the crystal structure of the heptahydrate, as well as the existence or non-existence of crystal hydrates of some of the ions considered are explained with the electron configuration of the metal ions. The deformation trend of the octahedral coordination of the metal ions considered increases in the following way:      

A square-wave voltammetric study on the diffusivities of polyvalent elements in CaO/BaO/Al2O3/SiO2 glass melts

Diffusion coefficients of various polyvalent ions (Sn²⁺, As³⁺, As⁵⁺, Sb³⁺, Sb⁵⁺, Cr³⁺, Ti⁴⁺, V⁴⁺, V⁵⁺ and Fe³⁺) were measured in melts with the basic compositions of 10CaO·10 BaO·10Al₂O₃·70SiO₂ and 10CaO·10BaO·15Al₂O₃·65SiO₂ by means of square-wave voltammetry. At temperatures in the range of 1300-1600 °C, linear correlations between logD and 1/T were observed. At 1400 °C, the diffusion coefficients obtained are compared with those obtained from other glass melt compositions.     

Comparative characterization of defects formed by di-and trivalent metal dopants in KDP crystals and the structural mechanism of influence of impurities on face morphology

The structure of KDP crystals doped with trivalent (Al³⁺, Fe³⁺, Mn³⁺, V³⁺, and La³⁺) and divalent (Ni²⁺, Co²⁺, Fe²⁺, Mn²⁺, Ca²⁺, Sr²⁺, and Ba²⁺) cations was simulated by minimizing the energy of atomic interactions. Three types of defects were revealed: isolated defect centers formed by M ³⁺ and Ni²⁺ ions, cluster chain centers formed by M ²⁺ ions with ionic radii exceeding 0.9 Å, and complex centers formed via the replacement of potassium ions by large Ba²⁺ dopants with the simultaneous replacement of some of the phosphorus atoms by silicon ones. The corresponding energies of defect formation are calculated. The surface morphology of the crystal faces is studied. The changes in morphology in the presence of M ³⁺ dopants are caused by their adsorption, whereas for M ²⁺ dopants, these changes are caused mainly by their incorporation into the crystal structure.     

XPS characterization of corrosion films formed on the crystalline, amorphous and nanocrystalline states of the alloy Ti60Ni40

X-ray photoelectron spectroscopy investigations were carried out on the crystalline, amorphous and nanocrystalline states of the alloy Ti₆₀Ni₄₀ after corrosion test in 1 M HNO₃ aqueous medium using potentiodynamic polarization method. Polarization plots revealed that the nanocrystalline state is more corrosion resistant than the amorphous and crystalline states of the alloy Ti₆₀Ni₄₀. The XPS characterization of the oxide film formed after corrosion tests revealed that a multiple phase oxide film is formed on the crystalline and amorphous specimens of the alloy Ti₆₀Ni₄₀ consisting of Ti²⁺, Ti³⁺ and Ti⁴⁺ species along with some unoxidized Ti in metallic form (Ti⁰) in the case of crystalline specimen whereas the oxide film formed on nanocrystalline specimen consists of only Ti²⁺ and Ti⁴⁺ species. The high corrosion resistance of nanocrystalline state is attributed to the presence of fewer oxide species in the oxide film than that of the amorphous and crystalline states of the alloy Ti₆₀Ni₄₀.     

Synthesis and crystal chemical characteristics of the structure of <Emphasis Type="Italic">M</Emphasis><Subscript>0.5</Subscript>Zr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> phosphates

Double phosphates of zirconium and metals with an oxidation degree of +2 of the composition M_0.5Zr₂(PO₄)₃ (M = Mg, Ca, Mn, Co, Ni, Cu, Zn, Sr, Cd, and Ba) are synthesized and characterized by X-ray diffraction methods and IR spectroscopy. The crystal structures of all the compounds are based on three-dimensional frameworks of corner-sharing PO₄-tetrahedra and ZrO₆-octahedra. Phosphates with large Cd²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ cations octahedrally coordinated with oxygen atoms form rhombohedral structures (space group R3), whereas phosphates with small tetrahedrally coordinated Mg²⁺, Ni²⁺, Cu²⁺, Co²⁺, Zn ²⁺, and Mn²⁺-cations are monoclinic (space group P2₁/n). The effect of various structure-forming factors on the M_0.5Zr₂(PO₄)₃ compounds with a common structural motif but different symmetries are discussed.     

Neutron and X-ray diffraction study of superstructure and localized magnetic moments in Cu0.5Fe0.5Cr2S4 and Cu0.5In0.5Cr2S4 compounds

The superstructure parameters for the Cu_0.5Fe_0.5Cr₂S₄ and Cu_0.5In_0.5Cr₂S₄ compounds have been determined by neutron and X-ray diffraction. The localized magnetic moments in different sublattices measured for Cu_0.5Fe_0.5Cr₂S₄ are equal to 3.06 ± 0.17 μB for Fe³⁺ ions in the A-site and 2.76 ± 0.22 μB for Cr³⁺ ions in the B-site (Cu⁺ possess no magnetic moment), which are much less than the magnetic moments for the ions in the purely ionic state.     

Change in the crystal structure of zink(II) sulphate heptahydrate and magnesium(II) sulphate heptahydrate due to isodimorphous substitution by copper(II), iron(II), and cobalt(II) ions

The physico-chemical analytical data on the systems ZnSO₄(MgSO₄)–CuSO₄(FeSO₄, CoSO₄ resp.)–H₂O at 25.0°C have shown that due to isodimorphous substitution of Zn²⁺, Mg²⁺ resp., in the orthorhombic crystals of ZnSO₄ · 7 H₂O MgSO₄ · 7 H₂O, resp. for Cu²⁺, Fe²⁺ or Co²⁺ above a specific degree of ionic substitution, the orthorhombic crystals are converted into monoclinic mixed crystals. The crystal phases are characterized by X-ray diffraction, microscopic and optical studies. The dominant effect of the admixed Cu²⁺, Fe²⁺, Co²⁺ ions is explained in terms of their electronic configurations, for which, owing to the operation of the Jahn-Teller effect, a deformation of the regular octahedral arrangement of the water ligands about the metal ion is found to occur. The strongest deforming effect is that of Cu²⁺ ions followed by the Fe²⁺ ions, the weakest deforming effect being that of Co²⁺ ions.     

Fluorescence of copper, manganese and antimony ions in phosphate glass host

The paper presents a study based on luminescence characteristics of phosphate glasses containing Cu²⁺, Mn⁴⁺ and Sb³⁺. The glass samples obtained by a wet chemical route belong to Li₂O–BaO–Al₂O₃–La₂O₃–P₂O₅ oxide system. The oxide composition of the glass samples is calculated to obtain a vitreous network composed of metaphosphate chains bonded by modifier ions (Li⁺, Ba²⁺ and La³⁺) and fluorescent ions. The absorption spectra of the samples were acquired in the UV domain in order to establish the excitation wavelength for each fluorescent ion. The absorption peaks of Sb³⁺ ion are ranged at 285 nm and 250 nm, Mn²⁺ ion at 280 nm and 365 nm, Cu²⁺ ion at 295 nm and 313 nm. The luminescence peaks of Cu²⁺, Mn⁴⁺ and Sb³⁺ ions are found in the visible domain at different wavelengths, depending on the oxidation state and coordination symmetry of each fluorescent ion. The fluorescence of Sb³⁺ ion has a strong signal at 450 nm and a weak one at 465 nm, Mn²⁺ ion shows a fluorescence peak at 600 nm and the pair Cu²⁺/Cu⁺ ions reveals a fluorescence emission at 460 nm.     

Equilibrium coefficients of co‐crystallization of M2+ ions with MgSeO4·6H2O and their dependences on various physicochemical factors

Equilibrium co‐crystallization coefficients of low amounts of M²⁺ions (M²⁺ = {Ni²⁺, Cu²⁺, Co²⁺, Zn²⁺, Mn²⁺, Cd²⁺}) with MgSeO₄·6H₂O at 25 °C have been determined. Their values are comprised in the range: 0.058 (for Cd) < k_eq < 1.57 (for Co) and depend on some physicochemical and crystal chemical properties of both: co‐crystallizing salts (MSeO₄·nH₂O) and co‐crystallizing ions (M²⁺). These dependences are sometimes such strong, that they make it possible to derive simple formulae permitting estimation of k_eq coefficients at average error not exceeding 17%. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Refinement of the crystal structures of synthetic nickel- and cobalt-bearing tourmalines

The crystal structures of synthetic tourmalines with a unique composition containing 3d elements (Ni, Fe, and Co) have been refined: (Ca_0.12?_0.88)(Al_1.69Ni _0.81 ²⁺ Fe _0.50 ²⁺ )(Al_5.40Fe _0.60 ³⁺ )(Si_5.82Al_0.18O₁₈)(BO₃)₃(OH)_3.25O_0.75 I, a = 15.897(5), c = 7.145(2) Å, V = 1564(1) Å; Na_0.91(Ni _1.20 ²⁺ Cr _0.96 ³⁺ Al_0.63Fe _0.18 ²⁺ Mg_0.03)(Al_4.26Ni _1.20 ²⁺ Cr _0.48 ³⁺ Ti_0.06)(Si_5.82Al_0.18)O₁₈(BO₃)₃(OH)_3.73O_0.27 II, a = 15.945(5), c = 7.208(2) Å, V = 1587(1) ų and Na_0.35(Al_1.80Co _1.20 ²⁺ )(Al_5.28Co _0.66 ²⁺ Ti_0.06)(Si_5.64B_0.36)O₁₈(BO₃)₃(OH)_3.81O_0.19 III, a = 15.753(8), c = 7.053(3) Å, V = 1516(2) ų. The reliability factors are R ₁ = 0.038?0.057 and wR ₂ = 0.041–0.060. It is found that 3d elements occupy both Y- and Z positions in all structures. The excess positive charge is compensated for due to the incorporation of divalent oxygen anions into the O3(V)+O1(W) positions.     

Structural features of compounds of the sillenite family

It is shown that the real composition and structure of phases belonging to the sillenite family can be determined using a complex of techniques (diffraction methods, vibrational and X-ray absorption spectroscopy, and electron probe X-ray microanalysis) with a subsequent crystal-chemical analysis of the data. Refined compositions are presented for phases of nominal composition Bi₂₄ M ₂O₄₀ with M = Zn²⁺, Al³⁺, Ga³⁺, Fe³⁺, Si⁴⁺, Ti⁴⁺, Mn⁴⁺, and P⁵⁺, which demonstrate types and concentrations of point defects as functions of the M type.     

Electrochemical behavior of different structural states of the alloy Ti60Ni40

Potentiodynamic polarization studies were carried out on nanocrystalline I, nanocrystalline II and nanocrystalline III states having crystallite size 35 ± 5 nm, 18 ± 2 nm and 10 ± 2 nm of the alloy Ti₆₀Ni₄₀ in 1 M H₂SO₄ aqueous medium. It was observed that the nanocrystalline III state exhibits superior corrosion resistance as compared to the nanocrystalline II and nanocrystalline I states of the alloy Ti₆₀Ni₄₀. XPS studies were also performed after corrosion test and it was observed that nanocrystalline III state contains only Ti²⁺ and Ti⁴⁺ species whereas nanocrystalline I and nanocrystalline II state contains Ti²⁺, Ti³⁺and Ti⁴⁺ along with some unoxidized metallic Ti⁰ in the case of nanocrystalline I state. Thus the small crystallite size and the presence of only Ti²⁺ and Ti⁴⁺ species in the form of TiO and TiO₂ leads to the formation of a protective oxide film which is adherent, stable and improves the corrosion resistance of the nanocrystalline III state of the alloy Ti₆₀Ni₄₀.     

Redox freezing temperature and Bartenev equation in a 25Na2O-15B2O3-60SiO2 glass doped with chromium and manganese

In a melt with the base mol% composition 25Na₂O-15B₂O₃-60SiO₂, doped with chromium and manganese, a redox reaction takes place during cooling the melt. This reaction was studied using high temperature UV-vis spectroscopy. Above 600 °C, the reaction is in equilibrium and shifted during cooling to the Cr³⁺ and Mn³⁺ species. At temperatures between 500 and 600 °C, the kinetics of the redox reaction is decisive and the cooling rate plays an important part. At temperatures < 500 °C, the reaction is frozen in. The smaller the cooling rate, the smaller is the Cr⁶⁺ concentration and the lower is the fictive redox temperature.The kinetics of the reaction was described by a differential equation assuming Arrhenian behaviour. The equation was numerically solved and fictive temperatures were calculated. These temperatures depended on cooling rate similar to Bartenev equation. Activation energies calculated hereof were around 38 kJ?mol⁻¹ larger than those inserted into the kinetic equation. The experimentally determined activation energy is 565 kJ?mol⁻¹, a value much larger than the activation energies of diffusion of the polyvalent elements. The rate determining step in the case of the Cr³⁺/Cr⁶⁺/Mn²⁺/Mn³⁺ system is the electron transfer reaction, because a notable structural rearrangement is necessary during the course of the electron transfer reaction (Cr³⁺ and Cr⁶⁺ occur in octahedral and tetrahedral coordination, respectively). The latter leads to a large inner reorganisation energy and to an activation energy similar to that of the viscous flow. In the case of the redox reaction between copper and arsenic, the activation energy is much smaller (210 kJ?mol⁻¹), because here the coordination numbers do not change during the course of the redox reaction.     

Vanadium contribution in different glasses in view of the ligand field theory

Spectrophotometric and magnetic studies were carried out on different glasses containing known amounts of V₂O₅ in order to throw some light on the valence states and coordination of vanadium in such glasses (in view of the ligand field theory).The results obtained were found to be in agreement with those of aqueous solutions, e.g. [V(H₂O)₆]³⁺, [VO(H₂O)₅]²⁺, and VO²⁺ which showed a slight difference in band positions due to the distortion as well as the difference between the ligand field strength of glass and water. Generally it may be concluded that vanadium is present in borate and silicate glasses in three possible valencies, V⁵⁺, V⁴⁺ and V³⁺, while in phosphate glasses it is generally present in two valencies V⁴⁺ and V³⁺.     

Structure and morphology of [icosahedral Al62Cu25.5Fe12.5]100−x[decagonal Al70Co15Ni15]x alloys, for x=10(03 and 510)

Alloys made from mixtures of Al₆₂Cu_25.5Fe_12.5 icosahedral quasicrystal (IQC) and Al₇₀Co₁₅Ni₁₅ decagonal quasicrystal (DQC) were studied by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The transition from IQC to DQC was thus discussed by studying the evolution of their constituent phases in each alloy. Three approximant phases were found as common phases in most of the pseudo-binary alloys: λ-Al₁₃Fe₄, β-AlFe and τ3-Al₃Ni₂. It is found that, with the increment of the DQC content in the alloy, the λ phase changes from Al₁₃Fe₄ to Al₁₃Co₄ and the τ3 phase changes from Al₃Cu₂ to Al₃Ni₂. The formation of these phases were found also to follow the evolution of their corresponding e/a-constant lines in the Al–(Cu,Ni)–(Fe,Co) pseudo-ternary phase diagram. Under this framework, the roles played by the related approximants in the transition process are briefly discussed.     

Intensities of circular dichroism and absorption bands and the states of <Emphasis Type="Italic">d</Emphasis> ions in absorbing media: II. Tetrahedrally coordinated positions of <Emphasis Type="Italic">d</Emphasis> ions

The factors affecting the band intensity in the circular dichroism (CD) and absorption spectra of tetrahedrally coordinated d ions in an absorbing medium (symmetry selection rules, structural position, and bond covalence) are analyzed. It is shown by the examples of the Cr⁴⁺ ion in Ca₃Ga₂Ge₄O₁₄ crystal and the Fe²⁺ and Fe³⁺ ions in SiO₄ crystal that the symmetry forbiddenness of the transitions from orbitally degenerate states and the covalence of the d-ion-ligand bond lead to changes in the intensity of the corresponding CD bands in a wide range, beginning from zero. It is shown by the example of Ca₃Ga₂Ge₄O₁₄, LiAlGeO₄, LiGaGeO₄, and LiGaSiO₄ crystals activated with Cr⁴⁺ ions that the preferred ion localization position corresponds to a higher effective symmetry.     

Physical properties of lead iron phosphate glasses containing Cr2O3

The influence of Cr₂O₃ on glass forming characteristics and physical properties of PbO-Fe₂O₃-P₂O₅ glasses has been investigated by Raman and Mössbauer spectroscopies, X-ray diffraction analysis (XRD), Differential Thermal Analysis (DTA), Scanning Electron Microscopy (SEM) and impedance spectroscopy. Glasses of the general composition xCr₂O₃-(28.3-x)PbO-28.7Fe₂O₃-43.0P₂O₅, 0 ≤ × ≤ 10, (mol%) were prepared by conventional melt-quenching technique. The compositions containing up to 4 mol% Cr₂O₃ formed fully amorphous samples and their Raman spectra show systematic increase in the fraction of orthophosphate Q⁰ units with increasing Cr₂O₃ content and O/P ratio.On the other hand, compositions containing 8 and 10 mol% Cr₂O₃ partially crystallized during cooling and annealing to Fe₇(PO₄)₆, Fe₂Pb₃(PO₄)₄ and Cr₂Pb₃(PO₄)₄. A high tendency for crystallization of these melts is related to the high O/P (> 4) and Fe²⁺/Fe_tot (≈ 0.60) ratios.Electrical conductivity of xCr₂O₃-(28.3-x)PbO-28.7Fe₂O₃-43.0P₂O₅, 0 ≤ × ≤ 10, (mol%) compositions is independent of Cr₂O₃ and controlled entirely by the polaron transfer between Fe²⁺ and Fe³⁺ ions.     

Mechanism of growth of ZnO single crystals from hydrothermal alkali solutions

The results obtained in experiments on the growth of zinc oxide, ZnO, under hydrothermal conditions are generalized. The polar growth and nonstoichiometry of ZnO crystals are analyzed in terms of crystal chemistry with due regard for the physicochemical conditions of the growth medium. The effect of the Li⁺ and of di-and trivalent metal (Co²⁺, Fe²⁺, Mn²⁺, Fe³⁺, Mn³⁺, Sc³⁺, In³⁺) impurities on the kinetics and some physical characteristics of ZnO crystals are studied, and the chemical reactions occurring on the surfaces of the (0001) and \((000\bar 1)\) faces are considered.