Strontium environment transition in tin silicate glasses by neutron and X-ray diffraction

The effect of Sr modifier atoms on the structure of stannosilicate glasses of composition (Sr0)_x(SnO)_0.5−x(SiO₂)_0.5, with 0 ⩽ x ⩽ 0.15, has been studied using Mössbauer spectroscopy and neutron and X-ray diffraction. The tin is mostly in the Sn²⁺ state. The Sr–O bond length undergoes a step decrease from (2.640 ± 0.005) Å to (2.585 ± 0.005) Å as x increases from 0.10 to 0.15, indicating a decrease in co-ordination number from 8 to 7. A Sn–Sn distance of 3.507 ± 0.005 Å is revealed by a first-order difference calculation from the x = 0 sample. This is too short to be consistent with significant edge sharing of [SnO₃] trigonal pyramids.     

Neutron diffraction study of sodium borosilicate waste glasses containing uranium

The effect of uranium oxide on the structure of sodium borosilicate host glasses has been studied by neutron diffraction. The samples were prepared by quenching the melted mixtures of composition 70 wt% [(65 − x)SiO₂ · xB₂O₃ · 25Na₂O · 5BaO · 5ZrO₂] + 30 wt% UO₃ with x = 5, 10 and 15 mol%. It was found, that the U-loaded glasses posses good glass and hydrolytic stability. An enhanced probability for inter-mediate atomic correlations at around 4.8 Å has been established. The RMC simulation of the neutron diffraction data is consistent with a model where the uranium ions are incorporated into interstitial voids in the essentially unmodified network structure of the starting host glass. The U–O atomic pair correlation functions show a sharp peak at around 1.7 Å, and several farther distinct peaks are at 2.8, 3.6 and 4.1 Å. The uranium ions are coordinated by six oxygen atoms in the 1.6–3.4 Å interval.     

Crystallization of human low density lipoprotein (LDL), a large lipid–protein complex: Collection of X-ray data at very low resolution

Human LDL subfractions LDL-2 (d=1.031–1.034 g/ml) and LDL-5 (d=1.040–1.044 g/ml) were crystallized in different crystal forms using polyethylene glycol as a precipitant. Both fractions were from one donor. Crystals of LDL-5 were yellow, hexagonal, and showed no dichroism. Of LDL-2 two dichroitic crystal forms were obtained. One had a rod-like shape with deep notches at both ends (form A), the other was a more compact form with plain surfaces (form B). To be able to measure low order reflections down to 300 Å a special experimental setup was developed. One single crystal was used to obtain a complete native data set of LDL-2 (form A) with an overall internal R-factor of 4.5% for reflections from 100 to 28 Å. Data were collected under cryogenic conditions using synchrotron radiation. The space group is most probably C2 with unit cell dimensions of a=183 Å, b=421 Å, c=385 Å, α=γ=90°, β≈90°. Further optimization of the crystallization conditions and the search for heavy metal derivatives are in progress.     

In vitro changes in the structure of a bioactive calcia–silica sol–gel glass explored using isotopic substitution in neutron diffraction

Bioactive sol–gel derived glass scaffolds bond to bone and their dissolution products stimulate new bone growth in vitro and in vivo; they may therefore be used to regenerate diseased or damaged bone to its original state and function in bone tissue engineering applications. We seek herein to cast light upon these reaction mechanisms by attempting to quantify changes in the atomic-scale structure of the glass scaffold as a result of in vitro reaction with simulated body fluid (SBF). We report the results of a study using neutron diffraction with isotopic substitution (NDIS) to gain new insights into the nature of the atomic scale calcium environment in bioactive sol–gel glasses. This is augmented by high-energy X-ray total diffraction. We have thereby begun to explore the nature of the principal stages to the generation of hydroxyapatite (i.e. the mineral ‘building block’ of bone) on the bioactive glass surface. The data are examined in light of our complementary solid-state NMR and computer modelling studies. The results reveal that the Ca–O environment in an SBF exposed (CaO)_0.3(SiO₂)_0.7 sol–gel glass, which initially comprises three distinct but partially overlapping correlation shells centered at 2.3 Å, 2.5 Å and 2.75 Å, preferentially loses the shortest length correlation. A Ca⋯H correlation appears at 2.95 Å. The surface deposited Ca⋯P environment consists of three partially overlapping, but nonetheless distinct, correlation shells, at 3.15 Å, 3.40 Å and 3.70 Å.     

Vibrational behavior of a realistic amorphous-silicon model

The vibrational properties of a high-quality realistic model of amorphous silicon are examined. The longitudinal and transverse dynamical structure factors are calculated, and fitted to a damped harmonic oscillator (DHO) function. The width Γ of the best-fit DHO to the longitudinal dynamical structure factor scales approximately as k² for wavevectors k ≲ 0.55 Å⁻¹, which is above the Ioffe–Regel crossover frequency separating the propagating and diffusing regimes, occurring at k = 0.38 ± 0.03 Å⁻¹. Using the DHO function as a fitting function for the transverse dynamical structure factor (without theoretical justification), gives a dependence of Γ ∝ k^α with α ∼ 2.5 for wavevectors k ≲ 0.7 Å⁻¹. There was no evidence for Γ ∝ k⁴ behavior for either polarization.     

Ag-doped antibacterial porous materials with slow release of silver ions

The inorganic–organic hybrids of polyethyleneglycol (PEG), tetraethoxysilane (TEOS) and triethylphosphate (TEP) doped by silver ions were prepared by sol–gel method. After molding and heating at 600 °C to remove organic components, porous Ag–P₂O₅–SiO₂ monoliths were obtained. Thermogravimetry (TG), differential thermal analysis (DTA), infrared spectra, ultraviolet–visible (UV–vis) spectra and pore structure of the samples were measured to show that organic components and residual water could be removed by a heat-treatment up to 600 °C and the mesopores with 6 nm pore diameter were formed. Specific surface area and pore volume of the samples were adjusted with different contents of TEP in the starting composition. Ag⁺ ions could be stably released into water at 30 °C up to 28 days. Antibacterial experiment showed that such materials treated at 600 °C could restrain Escherichia coli effectively.     

Direct observation of the R ⋯ R separation in rare-earth phosphate glasses

Rare-earth phosphate glasses exhibit exotic optical and magnetic properties, which are dictated by their structure, principally the nature of the closest R ⋯ R separation. Conventional structural characterization tools have enabled the comprehensive determination of the radial distribution from the rare-earth ion out to ∼4 Å. At or beyond this distance, however, lies the crucially important minimum R ⋯ R separation. This study illustrates three types of non-conventional diffraction experiments that overcome the radial limitations of regular structural probes. The results from such investigations are compiled with all other known estimates of R ⋯ R separations in rare-earth phosphate glasses, (R₂O₃)_x(P₂O₅)_1−x, in the range 0.167 < x < 0.25, both from experimental and computational means. Coupled with tabulations of all known minimum R ⋯ R separations in analogous meta- and ultra-phosphate crystal structures, a collective comparison of all of these R ⋯ R separations permits a hypothesis by which all results are consistent. That hypothesis indicates that where rare-earth phosphate glasses are near meta-phosphate, their minimum R ⋯ R distance lies at ∼4.0 Å whilst a second, much broader, nearest-neighbour R ⋯ R correlations is centered between 6.0–6.4 Å. However, glasses that contain rare-earth ions at least as heavy as holmium are likely to exhibit a very different structure, with a minimum R ⋯ R separation of 5.4–5.6 Å. Structures that lie intermediate between the ultra-phosphate and meta-phosphate composition may display mixed characteristics of these two extremes. If present in high levels, aluminium contamination arising from the synthetic process may also affect the R ⋯ R distribution significantly. Overall, there is excellent agreement between experiment and theory.     

Aqueous synthesis of single-crystalline ZnO prisms on graphite substrates

Morphological change from ZnO films to ZnO prisms is achieved by an electrochemical deposition method on a graphite substrate at the low temperature of 70 °C. The ZnO prisms, which are prism-shaped ZnO rods with a wide diameter, have hexagonal well-defined crystallographic facets. The ZnO prism is 1.4 μm in diameter and 1.3 μm in length. Transmission electron microscopy and electron diffraction patterns indicate that the ZnO prisms have a single-crystalline wurtzite structure with c-axis orientation. Additionally, cathodoluminescence shows that the annealed ZnO prisms in nitrogen gas emit a significant level of near-band-edge ultraviolet light.     

Positronium study of porous structure of sol–gel prepared SiO2: influence of pH

Positron annihilation lifetime and Doppler broadening of annihilation line techniques have been used to obtain information about the small-pore structure of SiO₂ prepared by the alkoxide method in different experimental conditions. Samples prepared in strong acidic environment (pH = 2) contain only small pores with mean radius R∼5 Å, while those prepared at pH = 6 and pH = 9 contain pores of two sizes, R∼5 and R∼17–26 Å. The influence of pH, water/alkoxide molar ratio and temperature of heat-treatment of the samples on their pore structure has been studied.     

Crystal growth of La2NaTaO6: A new monoclinically distorted double perovskite

Single crystals of La₂NaTaO₆ were grown out of a reactive high-temperature hydroxide melt. The structure was determined by single crystal X-ray diffraction. La₂NaTaO₆ adopts the monoclinically distorted double perovskite structure type with general formula A₂BB′O₆, where tantalum atoms are located on the B′ site. La₂NaTaO₆ crystallizes in the monoclinic space group P2₁/n with a=5.6904(2) Å, b=5.9824(2) Å, c=8.1423(2) Å and β=90.8650(10)°? An optical bandgap of 4.5 eV was estimated from the UV–vis diffuse reflectance spectrum.     

Raman spectroscopic study of some lead phosphate glasses with tungsten ions

The structure of xWO₃ · (100 − x)[2P₂O₅ · PbO] glass system with 0 ⩽ x ⩽ 50 mol% was investigated by Raman spectroscopy. The characteristic bands of these glasses due to the stretching and bending vibrations were identified and analyzed by the increasing of WO₃ content. This fact allowed us to identify the specific structural units which appear in these glasses and thus to point out the network modifier role of tungsten oxide for low concentrations and its former role at high concentrations.     

Network structure of multi-component sodium borosilicate glasses by neutron diffraction

Neutron diffraction structure study has been performed on multi-component sodium borosilicate based waste glasses with the composition of (65 − x)SiO_2. · xB₂O₃ · 25Na₂O · 5BaO · 5ZrO₂, x = 5–15 mol%. The maximum momentum transfer of the experimental structure factor was 30 Å⁻¹, which made available to determine the distribution function with high r-space resolution. Reverse Monte Carlo modelling was applied to calculate several partial atomic pair correlation functions, nearest neighbor distances and coordination numbers have been revealed. The characteristic features of Si–O and Si–Si distributions are similar for all glassy samples, suggesting that the Si–O network consisting of tetrahedral SiO₄ units is highly stable even in the multi-component glasses. The B–O correlations proved to be fairly complex, two distinct first neighbor distances are present at 1.40 Å and 1.60 Å, the latter equals the Si–O distance. Coordination number distribution analyzes has revealed 3 and four-coordinated boron atoms. The O–O distribution suggests a network configuration consisting of boron rich and silicon rich regions. Our findings are consistent with a structure model where the boron rich network contains mostly trigonal BO₃ units, and the silicon rich network is formed by a mixed continuous network of ^[4]Si–O–Si^[4] with several different ^[4]B–O–Si^[4] and ^[3]B–O–Si^[4] linkages.     

Novel monolithic mesoporous foamed carbons prepared using micro-colloidal particles as templates

Novel mesoporous foamed carbons were synthesized from carbonization of organic gels templated by polymer micro-colloidal particles. Resorcinol and formaldehyde were allowed to gel in dilute polymethylmethacrylate (PMMA) microemulsion latex, subsequently the water in the gel was solvent exchanged with methanol and the wet gel was dried under ambient pressure. Pyrolysis was carried out at 800 °C to afford carbon xerogels with porous structures similar to those of resorcinol–formaldehyde (RF) carbon aerogels, but of higher density (>1.2 g/cm³), which provide the carbon materials with relatively higher volumetric surface area (up to 918 m²/cm³). Brunauer–Emmett–Teller (BET) adsorption results indicate that PMMA micro-colloid particles with mean diameter 25 nm contributed to the formation of mesopores of mean diameter at 5 nm.     

In-situ crystallization of amorphous Fe73−xNbxAl4Si3B20 alloys through synchrotron radiation

In the present work Fe_73−xNb_xAl₄Si₃B₂₀ (x = 5, 10) alloys have been processed by melt-spinning with the aim of studying the crystallization sequence through annealing in suitable temperatures. Melt-spun ribbons were characterized by differential scanning calorimetry (DSC), X-ray diffractometry (XRD) through Cu-Kα (λ = 1.54 Å) and synchrotron radiation (λ = 1.77 Å) and transmission electron microscopy (TEM). Soft magnetic properties were measured through the hysteresis loop tracer. In-situ XRD through synchrotron radiation was very accurate in phase identification. Fe_73−xNb_xAl₄Si₃B₂₀ (x = 5, 10) alloys showed the possibility of forming ferromagnetic amorphous alloys composed of commercial Fe-based master alloys with fine nanocrystalline structure and good soft magnetic properties.     

Deposition of phosphorus doped a-Si:H and μc-Si:H using a novel linear RF source

A roll-to-roll PECVD system for thin film silicon solar cells on steel foil has been developed by ECN in collaboration with Roth and Rau AG. It combines MW–PECVD for fast deposition of intrinsic Si and novel linear RF sources, which apply very mild deposition conditions, for the growth of doped Si layers. The RF and MW sources can be easily scaled up to deposition widths of up to 150 cm. Here, we report on n-type doping, achieved by RF–PECVD from a H₂/SiH₄/PH₃ mixture in the reaction chamber. The best n-type a-Si:H layers showed E_act = 0.27 eV and σ_d = 2.7 × 10^?3 S/cm. Also thin layers down to 20 nm were of device quality and were deposited at a rate of 0.4 Å/s. Furthermore, n-type μc-Si:H layers with thicknesses of 150 nm, with E_act = 0.034 eV and σ_d = 2 S/cm were grown. Good quality n-type μc-Si:H layers can be made for layer thicknesses down to 50 nm at a rate of 0.15 Å/s. To conclude, the novel RF source is well-suited for the growth of n-doped a-Si:H and μc-Si:H layers for roll-to-roll solar cell production.     

Transparent SiO2 aerogels prepared by ambient pressure drying with ternary azeotropes as components of pore fluid

Transparent SiO₂ aerogels were prepared by two-step sol–gel processing followed by ambient pressure drying at temperatures from 70 to 250 °C. The wet gels were synthesized via acid–base catalysis using tetraethyl orthosilicate as a silica precursor and isopropanol as a solvent. Isopropanol was exchanged with n-butanol, and the gel surface was modified using a trimethylchlorosilane solution in n-butanol. Next, the solvent was exchanged in several steps with saturated hydrocarbon in order to obtain pore fluids containing azeotropic mixtures of water, n-butanol and a corresponding hydrocarbon (hexane, heptane, octane, nonane). Ambient pressure drying was performed in two steps, at the boiling points of the ternary azeotropes and hydrocarbons, respectively. In this way, transparent, crack-free aerogels of different shapes, with a specific surface area of 1000 m²/g, average pore diameter of ～40–55 Å and density in the range 0.4–0.57 g/cm³ were obtained.     

Coordination structure of Li+ in concentrated aqueous lithium alaninate solutions

Time-of-Flight (TOF) neutron diffraction measurements with the ⁶Li/⁷Li isotopic substitution technique were carried out for aqueous 18 mol% lithium alaninate solutions in D₂O in order to obtain structural information on the interaction between Li⁺ and the amino acid molecule in the concentrated aqueous solution. The first-order difference function, Δ_Li(Q), was obtained from the difference between scattering cross sections observed for solutions involving dl-CH₃CH(ND₂)COO⁶Li and dl-CH₃CH(ND₂)COO⁷Li. The distribution function around Li⁺, G_Li(r), exhibits well resolved first and second peaks that are tentatively attributable to the nearest neighbor Li⁺ ⋯ O and Li⁺ ⋯ D interactions. However, the coordination number, n_LiD, estimated from the area under the second peak is found to be much larger than the value, 2n_LiO, evaluated from the first peak of the present G_Li(r). This implies that the nearest neighbor Li⁺ ⋯ alaninate ion interaction may contribute to the second peak. Structural parameters concerning the first coordination shell of the Li⁺ has been determined through the least squares fitting analysis of the observed Δ_Li(Q). It has been revealed that the Li⁺ is surrounded by 2.4(1) D₂O molecules and 2.3(2) alaninate ions with interatomic distances of r(Li⁺ ⋯ O_D2O) = 1.97(1) Å, r(Li⁺ ⋯ D_D2O) = 2.62(1) Å and r(Li⁺ ⋯ O_alaninate) = 2.38(1) Å, respectively.     

Growth and characterization of the chalcopyrite LiGaTe2: A highly non-linear birefringent optical crystal for the mid-infrared

LiGaTe₂ crystals have been grown by the Bridgman–Stockbarger technique. The clear transparency range of LiGaTe₂ extends from 2.5 to 12 μm and its band-gap at room temperature is at 2.41 eV (515 nm). LiGaTe₂ is a positive uniaxial crystal which possesses sufficient birefringence for phase-matching. Its non-linear coefficient d₃₆ estimated by phase-matched second harmonic generation is 43 pm/V ± 10% at 4.5 μm. The properties of LiGaTe₂ are compared to those of other mid-IR chalcopyrite non-linear optical crystals with special emphasis on the frequency doubling potential for CO₂ lasers operating at 10.6 μm.     

Influence of europium ions on structure and crystallization properties of bismuth borate glasses and glass ceramics

Glasses of the xEu₂O₃ · (100?x)[2Bi₂O₃ · B₂O₃] system with 0 ? x ? 25 mol% have been characterized by X-ray diffraction and FTIR spectroscopy measurements. Melting at 1100 °C and the rapid cooling at room temperature permitted us to obtain glass samples. In order to improve the local order and to develop crystalline phases, the glass samples were kept at 625 °C for 24 h. After heat treatment two crystalline phases were put into evidence. One of the crystalline phases was observed for the host glass matrix, the x = 0 mol% sample, and belongs to the cubic system. The second one was observed for the x = 25 mol% sample and was find to be orthorhombic with two unit cell parameters very close to each other. For the samples with 0 < x < 25 mol% there is a mixture of the two mentioned phases. FTIR spectroscopy data suggest that both Bi₂O₃ and B₂O₃ play the glass network former role while the europium ions play the network modifier role in the studied glasses.     

An alumina mat with a nano microstructure prepared by centrifugal spinning method

Ceramic fiber products specially alumina mat because of low thermal conductivity and high melting point are used as high temperature insulating materials. Alumina has so high melting point (T_m > 2040 °C) that its mat can be produced through sol–gel method. In this research alumina mat has been manufactured by sol–gel spinning method using our laboratory-designed centrifugal spinneret. The desired viscosity of sol for spinning is 150 P. Phase transformation of the product begins at 600 °C and there is not any amorphous phase at 800 °C and theta alumina (θ-Al₂O₃) is the main phase. In this work, transformation of transitional phase to alpha alumina (α-Al₂O₃) takes place from 1000 °C to 1200 °C. The optimum percent of silica in alumina mat is 4 wt%. Fibers constitute network structure that their average diameter is about 10 μm and contains very fine grains (100 nm). The silica percent concerning the limits of this study (<10 wt%) does not effect on fiber diameter, but grain size decreases from about 200 nm to less than 100 nm while increasing silica percent.