Dependence of nanocrystalline SnO2 particle size on synthesis route

Very fine SnO₂ powders were produced by (a) slow and (b) forced hydrolysis of aqueous SnCl₄ solutions and (c) hydrolysis of tin(IV)-isopropoxide dissolved in isopropanol (sol-gel route) and then characterized by X-ray powder diffraction, Fourier transform infrared and laser Raman spectroscopies, TEM and BET. The XRD patterns showed the presence of the cassiterite structure. As found from XRD line broadening the crystallite sizes of all powders were in the nanometric range. TEM results also showed that the sizes of SnO₂ particles in all powders are in nanometric range. Very fine SnO₂ powders showed different features in the FT-IR spectra, depending on the route of their synthesis. The reference Raman spectrum of SnO₂ showed four bands at 773, 630, 472 and 86 (shoulder) cm⁻¹, as predicted by group theory. Very fine SnO₂ powders showed additional Raman bands, in dependence on their synthesis. The broad Raman band at 571 cm⁻¹ was ascribed to amorphous tin(IV)-hydrous oxide. The additional Raman bands at 500, 435 and 327 cm⁻¹ were recorded for nanosized SnO₂ particles produced by forced hydrolysis of SnCl₄ solutions. However, these additional Raman bands were not observed for nanosized SnO₂ particles produced by slow hydrolysis of SnCl₄ solution or the sol-gel route. The aggregation effects of nanosized particles were considered in the interpretation of the Raman band at 327 cm⁻¹. The method of low frequency Raman scattering was applied for SnO₂ particle size determination. On the basis of these measurements it was concluded that the size of SnO₂ particles was also in the nanometric range and that, the sol-gel particles heated to 400 °C consisted of several SnO₂ crystallites.     

Glass formation through hydrolysis of Si(OC2H5)4 with NH4OH and HCl solution

Monolithic silica glass was obtained by heating the gels prepared by hydrolyzing Si(OC₂H₅)₄ with NH₄OH and HCl solution. The effect of the condition of hydrolysis of Si(OC₂H₅)₄ on glass formation was examined by measuring the bulk density, the infrared spectra and the thermal shrinkage of the gel on heating. The gel prepared by hydrolysis with NH₄OH solution consisted of numerous spherical particles, the bulk density being about 0.8. This gel abruptly shrank at about 1050°C, being converted to the pore free material similar to fused silica. The conversion of the gel to glass followed the sintering model in which the viscous flow controlled the sintering process. The viscosity and the activation energy for viscous flow were calculated on the basis of the Frenkel equation. On the other hand, the spherical particles were not observed in the gel prepared by hydrolysis with HCl solution. The bulk density of the gel was about 1.8. This gel was converted to glass at about 700°C, which was lower than the temperature of glass formation for the gel obtained by hydrolysis with NH₄OH solution.     

Structure and properties of glasses in ZnO-P2O5-TeO2 system

Glasses in the ternary ZnO-P₂O₅-TeO₂ system were prepared and studied in two compositional series (100 − x)[0.5ZnO-0.5P₂O₅]-xTeO₂ (X-series) and 50ZnO-(50 − y)P₂O₅-yTeO₂ (Y-series) within the concentration range of x = 0-60 and y = 0-40 mol% TeO₂. Their structure was studied by Raman and ³¹P MAS NMR spectroscopies. The incorporation of TeO_x units into the structural network is associated with the depolymerisation of phosphate chain structure as revealed by both methods. At a high TeO₂ content isolated PO₄ tetrahedra are formed in the structure of glass series Y, while diphosphate O₃P-O-PO₃ groups are present in the structure of the glass series X. In the structure of glass series Y tellurium atoms form predominantly TeO₃ trigonal pyramids, whereas in the X glass series TeO₄ trigonal bipyramids prevail in the glass structure. The addition of TeO₂ to the parent zinc metaphosphate glass results in a decrease of glass transition temperature in both compositional series associated with the replacement of stronger P―O bonds by weaker Te―O bonds.     

New TiO2 precursor for TiO2:poly(N-vinylcarbazole) (PVK) thin film: Synthesis and reactivity to hydrolysis of titanium tetrakis (9H-carbazole-9-yl-ethyl-oxy)

The chemical reactivity of the ligand initially coordinated on the TiO₂ precursor plays a decisive role in the morphology of TiO₂:poly(N-vinylcarbazole) (PVK) thin film elaborated by in situ generation of the inorganic phase in the polymer matrix. The final aim of this study is to prepare a new nanocomposite TiO₂:poly(N-vinylcarbazole) (PVK) thin film from hydrolysis-condensation of titanium alkoxide in polymer thin film. In this context, we synthesized a new TiO₂ precursor, the tetrakis (9H-carbazole-9-yl-ethyl-oxy) [Ti(OeCarb)₄], bearing ligands close to the repetitive unit structure of the PVK to improve the interaction between both materials. In this study, the synthesis and reactivity to hydrolysis of Ti(OeCarb)₄ is presented. Ti(OeCarb)₄ was elaborated from alcoholysis reaction between titanium isopropoxide [Ti(ⁱOPr)₄] and 9H-carbazole-9-ethanol (ECOH) and identified by ¹H and ¹³C NMR spectroscopy. The reactivity to hydrolysis-oxolation of Ti(OeCarb)₄ was evaluated first in aqueous media by in situ ¹H NMR spectroscopy analysis. Moreover, reactivity of Ti(OeCarb)₄ to surrounding humidity was evaluated in thin film by X-ray photoelectron spectroscopy (XPS). Results show that steric hindrance of 9H-carbazole-9-yl-ethyl-oxide ligands do not influence the hydrolysis-condensation process in aqueous media in our experimental conditions when compared to [Ti(ⁱOPr)₄] but decrease the reactivity when the precursor is simply exposed to air humidity.     

O nuclear magnetic resonance study of Na2O-P2O5 glasses

The preparation and structural investigation of ¹⁷O-enriched xNa₂O-(100−x)P₂O₅ glasses (46.5?x?62.8) by nuclear magnetic resonance (NMR) is described. Enriched phosphoric acid was prepared by hydrolysis of PCl₅ with ¹⁷O-enriched water and neutralized with sodium carbonate. The sodium metaphosphate was then melted at 800 °C for 15 h and quenched. Polyphosphate and ultraphosphate glass compositions were prepared by remelting the metaphosphate with sodium carbonate and phosphorus pentoxide, respectively. ³¹P magic angle sample spinning (MAS) NMR was used to determine the Na₂O/P₂O₅ content in the glasses. ¹⁷O NMR spectra (quadrupole echo for non-rotating samples and multiple-quantum excitation for rotating samples (MQMAS)) show two oxygen sites in the samples with large quadrupolar coupling constants (4.7 and 7.7 MHz), in accordance with the high phosphorus electronegativity. According to the correlation of ¹⁷O quadrupolar constants with bond ionicity, these two components are attributed to bridging P-O-P and non-bridging P-O?Na oxygens. The average P-O-P bond angle is estimated with the quadrupolar asymmetry derived from the fit of the static echo spectra. The MQMAS spectrum shows a distribution of non-bridging oxygen chemical shifts, attributed to a variation of bond length and angle.     

Structural and optical properties of 6CaO·6SrO·7Al2O3 thin films derived by sol-gel dip coating process

The nanostructured 6CaO·6SrO·7Al₂O₃ (C6S6A7) thin films with cubic structure using calcium, strontium metals, aluminium isopropoxide and ethylene glycol monomethyl ether as stating materials has been fabricated via sol-gel route. Based on hydrolysis of Ca²⁺, Sr²⁺ and Al³⁺ in the sol-gel processing using ethylene glycol monomethyl ether as solvent have been employed as the precursor material. The films were coated on soda lime float glass by the dip coating technique and annealed at 450 °C in air atmosphere. The structure, morphology and composition of the films were investigated by Fourier transformed infrared spectroscopy, X-ray powder diffraction, scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectroscopy indicating that the films were composed of C6S6A7 nanoparticles with cubic structure. The spectral transmittance of the films was measured in the wavelength range of 200-1100 nm using an UV-visible spectrometer. It has been found that the optical properties of the films significantly affected by precursor chemistry and annealing temperature due to the improvement of the crystallinity of the films with increasing annealing temperature and became stable when the annealing temperature is higher than 450 °C. The C6S6A7 films annealed at 450 °C had high transparency about 80% in wide visible range.     

Gel-glass transformation in the SiO2Fe2O3 system

Gel-glass transformation has been studied by Mössbauer spectroscopy, DTA-TG analyses and X-ray diffractometry for four compositions in the SiO₂Fe₂O₃ system (A: 5 wt% Fe₂O₃, B: 10 wt% Fe₂O₃, C: 20 wt% Fe₂O₃, D: 40 wt% Fe₂O₃).The gels were prepared by the hydrolysis of silicon tetraethoxide and iron triethoxide and successively dried and heated in oxygen in the temperature range 40–1000°C.Samples A and B gave typical amorphous X-ray patterns up to 700°C; heating at higher temperature yielded the precipitation of quartz, cristobalite and hematite in sample A, cristobalite and hematite in sample B. Crystallization was also detected by DTA in sample A for which X-ray diffraction exhibited a larger effect.In samples C and D crystallization took place starting from 300°C with the precipitation of hematite, which remained the only crystalline phase up to 1000°C.The presence of hematite was confirmed by the obtained Mössbauer spectra which showed the characteristic sextet. The apportion of iron ions in the Fe³⁺ and Fe²⁺ oxidation states was also determined, together with the attribution of the probable coordination states for Fe³⁺ ions.Complex magnetic structure appeared in samples treated above 800°C.     

Formation and characterization of a SnO2-Al2O3 system derived from a sol-gel process based on different tin precursors

A series of SnO₂-Al₂O₃ samples with SnO₂ to Al₂O₃ molar ratio of 1:1, 0.5:1, 0.25:1 and 0.1:1, have been synthesized by the sol-gel technique using Al(C₃H₇O)₃ and tin (IV) dihydroxy 2,4-pentanedione acetate as precursors. Samples of the above series were characterized by thermal analysis, X-ray diffraction, Fourier transform infrared spectroscopy and nitrogen adsorption to establish their porous structure. The structures of the binary gel systems obtained were found to differ from those of the analogous series in which Sn(ac)₄ (acetic series) was used as precursor. The tin component introduced into the samples of both series was responsible for the narrowing of the range of diameters of the pores (contributing to the highest extent to the cumulative pore volume) relative to their range in pure aluminum gel. The range of the dominant pore diameters was at the same time shifted towards smaller values, but these changes were more pronounced for (ac) series. The use of β-diketonate complexes of tin instead of Sn(ac)₄, leads also to changes in the character of OH group on the surface of the binary gel samples. For this series (acac) of binary gels in the whole range of concentrations of the tin component only one type of hydroxyl groups appears, not present in the monocomponent aluminum gel and in the binary gels of (ac) series.     

Synthesis, Crystal Structure and Properties of the Binuclear Complex [Sm2(C10H9N2O4)2(C10H8N2O4)2(H2O)4]

Abstract  A novel binuclear Smarium (III) complex with N-(2-propionic acid)-salicyloyl hydrazone (C₁₀H₁₀N₂O₄, H₃L) was prepared and characterized. The crystal structure of [Sm₂(H₂L)₂(HL)₂(H₂O)₄] (1) was determined by X-ray single crystal diffractometry. 1 crystallizes in the monoclinic systerm, space group P2(1)/c, with a = 0.10229(2), c = 31.549(7), b = 0.70599(15) nm, and Z = 4. In the structure, Sm(III) is nine-coordinated by carboxyl O and acyl O atoms and imido N atoms of two ligands (H₂L and HL forms) and O atoms from two water molecules. H₂L and HL act as tridentate ligands which form two stable five-numbered chelating rings sharing one edge in the keto form for each ligand, and the carboxyl groups of two ligands were coordinated via bidentated bridging form. The coordination polyhedron around Sm (III) was described as a monocapped square antiprism. The inter- and intramolecular hydrogen bonds resulted in a three-dimensional network and provided extra stability for the structure. The complex was researched the interaction with calf thymus DNA by electronic absorption titration and emission titration. The results show that the complex is bound to calf thymus DNA mainly by intercalation .The complex also shows good fluorescence property. Index Abstract  The title compound, [Sm₂(H₂L)₂(HL)₂(H₂O)₄] was synthesized by the treatment of N-(2-propionic acid)-salicyloyl hydrazone (C₁₀H₁₀N₂O₄, H₃L) and Sm(NO₃) · 4H₂O and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that Sm (III) is nine-coordinated by carboxyl O and acyl O atoms and imido N atoms of two ligands (H₂L and HL forms) and O atoms from two water molecules. The carboxyl groups of two ligands were coordinated via bidentated bridging form. The coordination polyhedron around Sm (III) was described as a monocapped square antiprism. The inter- and intramolecular hydrogen bonds resulted in a three-dimensional network and provided extra stability for the structure.      

Structural and physical properties of a novel TeO2-BaO-SrO-Ta2O5 glass system for photonic device applications

A detailed study on a novel TeO₂-BaO-SrO-Ta₂O₅ glass system developed for photonic device applications is reported in this paper. The glass transition and crystallization temperatures could be selected by varying the Ta₂O₅ content in this glass system. This glass system is found to have good thermal stability among tellurite glasses. Raman spectroscopy has been used as a tool to analyze the structural details of this technologically important glass system. In addition to the TeO₄ trigonal bipyramid and TeO₃ trigonal pyramid structural units, glasses in this system revealed the presence of an additional Raman band attributed to TaO₆ octahedra. The Raman bandwidth of the present glasses are broader compared to the conventional tellurite glasses by 35%. The influence of a gradual addition of the modifier oxides on the coordination geometry of tellurium atoms has been elucidated. Unlike the other tellurite glasses, even at higher modifier concentrations the TeO₄ structural units dominate in the glass network compared to TeO₃ trigonal pyramids. The ratio of TeO₄/TeO₃ structural units was discussed for different series of glass compositions.     

The coordination state and valence state of selected transition metal ions in SiO2-B2O3 xerogels

A series of SiO₂-B₂O₃ xerogels with changing SiO₂/B₂O₃ mol% and doped with selected transition metal ions was prepared. These mixed oxide materials contained copper, nickel, cobalt, manganese, chromium and vanadium ions coordinated to oxygen donor atoms in water and OH groups. Extensive studies of the transition metal complexes in the xerogels by such spectral techniques as diffuse reflectance (UV-vis), electron paramagnetic resonance and fluorescence spectroscopies show that there exist Cu(II) in the coordination environment of D_4h symmetry, Ni(II) in octahedral coordination sphere, Co(II) in both tetrahedral and octahedral environments, Mn(II) preferably in the O_h coordination and Mn(III) in pseudo-octahedral sphere; then octahedrally coordinated Cr(III) ions occur in coupled pairs or clusters and V(IV) as VO²⁺ ions exist in distorted (C_4v) octahedral surrounding.     

Investigation of the structure evolution process in sol-gel derived CaO-B2O3-SiO2 glass ceramics

A sol-gel method was used to prepare CaO-B₂O₃-SiO₂ (CBS) glass powder for making low-temperature cofired ceramics. This paper was focused on the mechanism of hydrolysis and polymerization and also on the structural evolution of xerogel at various temperatures. The xerogel was transformed into glass ceramics containing CaSiO₃ and CaB₂O₄ crystalline phases through nucleation and crystallization processes. The results indicated that the xerogel exhibits [BO₄] or [SiO₄] based three-dimensional network structure whose interstices Ca ions fill in, which becomes more orderly and stable after heat treatments. The CBS glass ceramics through controlled crystallization have a potential as electronic packaging materials.     

Optical properties and structure of thin films from the system GeSe2-Sb2Se3-AgI

Chalcohalide glasses from the GeSe₂-Sb₂Se₃-AgI system were synthesized by taking preliminary prepared GeSe₂, Sb₂Se₃ and AgI in their molecular percentages and melting them in an evacuated quartz ampoule. Thin films from the above system were deposited using vacuum thermal evaporation at different conditions on optical glass substrates BK-7. Using X-ray microanalysis it was found that the film composition differs in a certain degree from the bulk composition. Optical transmission and reflection measurements were carried out in the spectral range 400-2500 nm. The optical constants of films thicker than 400 nm (refractive index, n, and absorption coefficient, k) and the film thickness (d) were calculated using a method developed by Konstantinov. The values of n change from 2.38 for thin GeSe₂ films up to 3.48 for thin Sb₂Se₃ films while the optical band gap decreased from 1.92 eV to 1.29 eV, respectively. After exposure to light the photo-induced changes in the optical parameters were negligible for GeSe₂ and Sb₂Se₃ films and increase for some of the ternary samples. Using IR spectroscopy some conclusions about changes in the film structure were drawn.     

Variation of optical basicity with probe ion,for Cs2O + B2O3 and Li2O + B2O3 glasses

Optical basicities (Γ) for Cs₂O + B₂O₃ and Li₂O + B₂O₃ glasses have been measured as a function of glass composition, using Tl⁺, Pb²⁺ and Bi³⁺ probe ions. The three probe ions register different values of Γ for glasses of given composition (and also for pure B₂O₃ glass and water). The divergence decreases as the alkali metal ion size decreases.For the Li₂O + B₂O₃ glasses, ideal (calculated) optical basicities agree within experimental precision with experimental values registered by Pb²⁺ (Γ_Pb²⁺) up to about 15 mol% Li₂O. For higher Li₂O contents, and for the Cs₂O + B₂O₃ glasses, ideal optical basicities agree less well with Γ_Pb²⁺, but show similar trends with composition to those shown by Γ_Pb²⁺.     

Crystallization kinetics in Cu46Zr45Al7Y2 bulk metallic glass by differential scanning calorimetry (DSC)

Crystallization transformation kinetics in isothermal and non-isothermal (continuous heating) modes were investigated in Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass by differential scanning calorimetry (DSC). In isochronal heating process, activation energy for crystallization at different crystallized volume fraction is analyzed by Kissinger method. Average value for crystallization in Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass is 361 kJ/mol in isochronal process. Isothermal transformation kinetics was described by the Johnson-Mehl-Avrami (JMA) model. Avrami exponent n ranges from 2.4 to 2.8. The average value, around 2.5, indicates that crystallization mechanism is mainly three-dimensional diffusion-controlled. Activation energy is 484 kJ/mol in isothermal transformation for Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass. These different results were discussed using kinetic models. In addition, average activation energy of Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass calculated using Arrhenius equation is larger than the value calculated by the Kissinger method in non-isothermal conditions. The reason lies in the nucleation determinant in the non-isothermal mode, since crystallization begins at low temperature. Moreover, both nucleation and growth are involved with the same significance during isothermal crystallization. Therefore, the energy barrier in isothermal annealing mode is higher than that of isochronal conditions.     

The structure analysis liquid Sb2Se3 by neutron diffraction

The radial distribution analysis of liquid Sb₂Se₃ at 670, 720 and 770°C is carried out by the neutron diffraction method. A small but apparent maximum is found at $\text{K = 1.2}\text{A}\text{?}{}^{\mathrm{?1}}$ in the structure factor. The interatomic distance and the coordination number are 2.74 Å and 2.84 respectively, at 670°C. These results suggest that intramolecular bonds in the crystalline Sb₂Se₃ remain unbroken in the liquid state. The general feature of the structure factor and the distribution function for liquid Sb₂Se₃ is similar to that for the amorphous state. However, it is clear that the liquid phase tends to have a similar atomic arrangement to that of liquid tellurium.     

Calculation and analysis of vibrational spectra of PbCl2-Sb2O3-TeO2 glass from first principles

Ternary PbCl₂-Sb₂O₃-TeO₂ system provides promising materials for photonic applications. Glasses in this system are thermally stable, their refraction index is about 2.2 and they are transparent from 400 nm up to 6 μm. The ab initio molecular dynamics (MD) simulations of xPbCl₂-10SbO_3/2−(90-x)TeO₂ glasses (x = 10, 20, 30, 40, and 50) were carried out using density functionals, the plane-wave basis set expansion, and the projector-augment waves (PAW). The resulting glassy structures were analyzed with the help of partial radial distribution functions (RDF) and partial coordination numbers. Good agreement with the available experimental data was confirmed. The axial and equatorial oxygen atoms of TeO₄ trigonal bi-pyramids were distinguished. Vibrational frequencies and their corresponding eigen-modes were found by diagonalization of the dynamical matrix. The simulated vibrational spectra were decomposed to determine the contributions from individual atomic species and some more complex structural features and compared with experimental Raman spectra. The spectral decomposition was carried out by projecting vibrational displacement vectors onto various normal modes of typical symmetric structural units. The method proved to be able to successfully interpret the experimental Raman spectra.     

Study of the structural insertion of Al in the Al2O3-SiO2 and Nd2O3-Al2O3-SiO2 glass systems

Glasses in the Al₂O₃-SiO₂ and Nd₂O₃-Al₂O₃-SiO₂ systems were prepared by the sol-gel method. The gel-glass evolution was studied using near-infrared (NIR) and ultraviolet-visible (UV-VIS) spectrophotometry, X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR). The results obtained indicate a relationship between the sample compositions, the treatment temperature and the Al coordination. In the samples of the Nd₂O₃-Al₂O₃-SiO₂ system the densification of the structure, when the treatment temperature increases, leads to the segregation of neodymium oxide particles.     

GeO2/SiO2-glasses from gels to increase the oxidation resistance of porous silicon containing ceramics

GeO₂/SiO₂-glasses with relatively high expansion coefficients (between 5 and 7.3 × 10^?6 °C^?1) were prepared by hydrolysis of metal alkoxides (tetramethoxy silane+tetraethoxy germane as well as mixtures of the silane with GeO₂-powder) with subsequent heat treatment up to 1000°C. It is shown that the preparation of thin films on glasses and ceramics is possible but also that this technique can be used for liquid infiltration of porous SiC- and Si₃N₄-materials to increase the oxidation behaviour in the temperature range 1000 to 1400°C. In the case of molybdenumdisilicide as a ceramic material it is shown that the catastrophic inner oxidation in the low temperature range (600 to 800°C) of porous specimens (tested with plasma-sprayed MoSi₂-layers on refractory metals) can be hindered if these materials are infiltrated and heat treated.     

Structural analysis of Na2OGa2O3SiO2 glasses by the X-ray diffraction method

The structure of Na₂OGa₂O₃SiO₂ glasses of four different compositions containing up to 45 mol. % Ga₂O₃ has been determined by the X-ray diffraction method. The radial distribution function D(r) obtained indicates that Ga³⁺ ions are in fourfold coordination and GaO₄ tetrahedra are formed in these glasses. The reduced intensity function S·i(S) and radial distribution function D(r) which were calculated based on a structural model for A-25, 0.25(Ga₂O₃)·0.75(Na₂O·2SiO₂)/3 glass agreed well with the observed ones.