Structure of potassium germanophosphate glasses by X-ray and neutron diffraction. Part 1: Short-range order

It has been reported that the addition of K₂O or P₂O₅ to binary germanate glasses increases the Ge−O coordination numbers (N_GeO). The present work describes X-ray and neutron diffraction studies aimed at clarifying the concomitant effects of both oxides on the structures of ternary K₂O-GeO₂-P₂O₅ glasses. The Ge−O coordination numbers obtained range from 4.2 to 5.1, less than what is predicted according to a model which assumes all oxygen atoms form network bridges similar to those found in the related crystal structures. This implies that the glass structures must include terminal oxygen sites, likely associated with the PO₄ tetrahedra, that are neutralized by coordinating K⁺ ions. The shapes of the high resolution first-neighbor diffraction peaks do not indicate distinctly different species of P−O and Ge−O bonds. The model for the increase of N_GeO which is based on an increase of the fraction of GeO₆ units, at the expense of GeO₄ units, is supported by the analysis of the two main components of the Ge−O peak used in the fits. However, the existence of a GeO₅ fraction cannot be excluded from the present data sets. A linear relation between the total Ge−O coordination numbers and mean Ge−O distances exists, assuming end members of units GeO₄ and GeO₆ with bond lengths of ∼0.175 and ∼0.190 nm, respectively.     

Structure of potassium germanophosphate glasses by X-ray and neutron diffraction: 3. Reverse Monte Carlo simulations

Reverse Monte Carlo (RMC) is used to investigate the origin of the first sharp diffraction peaks (FSDP) found for K₂O–GeO₂–P₂O₅ glasses at very small scattering vector Q = ～7.5 nm^?1. Structures of the ternary glass with the greatest intensity of FSDP (KGeP5 – 25/50/25 mol% K₂O/GeO₂/P₂O₅), of the binary combinations of the three oxides and of vitreous GeO₂ are modeled. Results are deduced from comparisons of the partial structure factors and inspections of model sections. The P sites are uniformly distributed in the structure of KGeP5. The K⁺ ions interact more with the PO₄ units (via O_T-corners) than with Ge-centered units. Main component of the FSDP comes from the S_GeGe(Q) factor. The FSDP is due to separations of ～1 nm between the longish Ge-rich clusters which are visible in the corresponding models. Different to our tentative structural models reported before, the PO₄ tetrahedra possess a broad distribution of numbers of O_T corners. The FSDP’s of the binary K₂O–GeO₂ and K₂O–P₂O₅ glasses (～10 nm^?1) are due to a chemical order between network former and network modifier regions. The MRO of a mixed GeO₂–P₂O₅ glass of small P₂O₅ content (FSDP at ～16 nm^?1) shows great similarity to the MRO of vitreous GeO₂.     

Tin valence and local environments in silicate glasses as determined from X-ray absorption spectroscopy

X-ray absorption spectroscopy (XAS) was used to characterize the tin (Sn) environments in four borosilicate glass nuclear waste formulations, two silicate float glasses, and three potassium aluminosilicate glasses. Sn K-edge XAS data of most glasses investigated indicate Sn⁴⁺O₆ units with average Sn-O distances near 2.03 Å. XAS data for a float glass fabricated under reducing conditions show a mixture of Sn⁴⁺O₆ and Sn²⁺O₄ sites. XAS data for three glasses indicate Sn-Sn distances ranging from 3.43 to 3.53 Å, that suggest Sn⁴⁺O₆ units linking with each other, while the 4.96 Å Sn-Sn distance for one waste glass suggests clustering of unlinked Sn⁴⁺O₆ units.     

The structure and optical properties of GeO2-GeS2 glasses

Oxy-chalcogenide glasses with compositions of xGeO₂-(100 − x)GeS₂, where 0 ? x ? 100 mol%, have been prepared and studied in terms of their structures and optical properties. X-ray fluorescence spectroscopy shows that Ge:S ratio can deviate from GeS₂ by ∼10 at.%, depending critically upon the preparation conditions. Raman scattering spectroscopy suggests that stoichiometric GeO₂-GeS₂ glasses have a heterogeneous structure in the scale of 1-100 nm. The optical gaps are nearly constant at 3.0-3.5 eV for glasses with 0 ? x ? 80 mol% and abruptly increase to ∼6 eV in GeO₂. This dependence suggests that the optical gap is governed by GeS₂ clusters, which are isolated and/or percolated. Composition-deviated glasses appear as orange and brown, and these glasses seem to have more inhomogeneous structures.     

Structure study of multi-component borosilicate glasses from high-Q neutron diffraction measurement and RMC modeling

A neutron diffraction structure study has been performed on multi-component borosilicate glasses with compositions (65 − x)SiO₂ · xB₂O₃ · 25Na₂O · 5BaO · 5ZrO₂, x = 5-15 mol%. The structure factor has been measured up to a rather high momentum transfer value of 30 Å⁻¹, which made high r-space resolution available for real space analyses. Reverse Monte Carlo simulation was applied to calculate the partial atomic pair correlation functions, nearest neighbor atomic distances and coordination number distributions. The Si-O network consists of tetrahedral SiO₄ units with characteristic first neighbor distances at r_Si-O = 1.60 Å and r_Si-Si = 3.0 Å. The boron environment contains two well-resolved B-O distances at 1.40 and 1.60 Å and both 3- and 4-fold coordinated B atoms are present. A chemically mixed network structure is proposed including ^[4]B-O-^[4]Si and ^[3]B-O-^[4]Si chain segments. The O-O and Na-O distributions suggest partial segregation of silicon and boron rich regions. The highly effective ability of Zr to stabilize glassy and hydrolytic properties of sodium-borosilicate materials is interpreted by the network-forming role of Zr ions.     

Structure of rare-earth phosphate glasses by X-ray and neutron diffraction

Previous diffraction studies of the structures of rare-earth phosphate glasses (R₂O₃)_x(P₂O₅)_1−x are extended to glasses with smaller R³⁺ ions with R = Sm, Gd, Dy, Er, Yb, Y for x = ∼0.25 and with R = Nd, Sm, Gd for x = ∼0.15. Parameters for the P–O, R–O and O–O first-neighbor peaks were obtained by Gaussian fitting. P–P and R–P distances were estimated from the positions of peak maxima. Effects of residual silica or alumina contents present as a result of glass processing were taken into account for selected samples. The P–O coordination number, N_PO, and the P–O, O–O, P–P distances are consistent with the presence of phosphate tetrahedra and are insensitive to the R species and the R₂O₃ content. Rare-earth coordination numbers, N_RO, decrease from ∼8 to ∼6.5 when x is increased from ∼0.15 to ∼0.25. N_OO and N_PP decrease with increasing R₂O₃ content indicating the network disintegration. The numbers N_RO of the metaphosphate glasses (x = ∼0.25) decreases from ∼7 to ∼6 when R is changed from La to Yb. This change is also indicated by the behavior of the R–O distances and by constant number densities of atoms. The decrease in N_RO with increasing R₂O₃ content is due to the reduction in the number of terminal O (O_T) available for coordination of the R³⁺ ions (six at metaphosphate composition). Especially for smaller R³⁺ ions sharing O_T between two R sites is not favored. The decrease by ∼0.04 nm of the prominent R–R first-neighbor distance with a change of R from La to Yb at the metaphosphate composition is indicated by a shift to higher magnitude of scattering vector of the shoulder occurring in front of the first main diffraction peak.     

Structure of titanophosphate glasses studied by X-ray and neutron diffraction

The structure of binary (TiO₂)_x(P₂O₅)_1−x glasses with x = 0.60, 0.65 and a ternary K₂O–TiO₂–P₂O₅ (KTP) glass were studied by X-ray and neutron diffraction. The experiments were performed at the high-energy beamline BW5 of the synchrotron DORIS (Hamburg/Germany) and at the GEM instrument of the neutron source ISIS (Chilton/UK). Gaussian fitting of well-resolved first-neighbor peaks in the correlation functions of the binary glasses with TiO₂ contents of 0.65 and 0.60 result in Ti–O coordination numbers of 5.65 ± 0.2 and 5.9 ± 0.2, respectively. Distorted TiO₆ octahedra and isolated PO₄ units form the glassy networks, with a small number of lower coordinated Ti sites for the 0.65 TiO₂ glass. For comparison, only TiO₆ octahedra are found for a ternary K₂O–TiO₂–P₂O₅ glass. The Ti–O coordination numbers are compared with a structural model where all oxygen atoms occupy sites in Ti–O–Ti, Ti–O–P or P–O–P bridges. The presence of three-coordinated oxygens must be assumed for the binary glasses, whereas a structure with nearly all oxygen atoms forming network bridges exists for the ternary KTP glass.     

Crystallization behavior of glasses in the system of Na2O-CaO-MgO-Fe2O3-Al2O3-SiO2 with high contents of nickel oxide

The structural behavior of nickel oxide in glassy and glass-ceramic materials, obtained in the system of Na₂O-CaO-MgO-Fe₂O₃-Al₂O₃-SiO₂, was investigated. The influence of the NiO content on the vitrification, crystallization, structure and exploitation properties of two model compositions, with different ratios [CaO]/[MgO] was analyzed. On the basis of DSC and XRD data, it is shown that NiO promoted the formation of bunsenite crystals, as nuclei for crystallization. On the other hand, NiO promoted formation of pyroxenes even for compositions with low MgO contents, which formed gehlenite without NiO admixtures. It is shown that in the composition with relatively high MgO contents, NiO could participate in the formation of two types of pyroxenes with the structure and chemical composition similar to (MgO_0.4NiO_0.6)(CaO_0.9NiO_0.1)Si₂O₆ and diopside-hedenbergite solid solutions. The optimal contents of NiO in both model compositions was about of 7 wt%, since higher contents reduced the exploitation properties. The glass-ceramics with optimal contents of NiO were also produced using Ni bearing galvanic slurry and coal ash; the resulting materials showed similar exploitation properties to those mentioned above.     

The effect of composition on the structure of sodium borophosphate glasses

Glasses in the system 40(P₂O₅)-x(B₂O₃)-(60 − x)(Na₂O) (10 ? x ? 30 mol%) have been prepared by the melt-quenching technique. Thermal properties were studied using differential thermal analysis and the relationship between composition and thermal stability was obtained. Structural characterization was achieved by a combination of experimental data (infrared and Raman spectroscopy, ¹¹B and ³¹P solid state NMR). In particular, variations in the phosphate network structure upon addition of B₂O₃ and Na₂O were investigated. Analysis of the data indicates that with increasing B₂O₃ content and decreasing Na₂O, the glass network shows increasing levels of cross-linking between phosphate and borate units. Evidence of direct B-O-P bonds was observed. In the compositional range investigated, borate groups contain boron almost exclusively in four-fold coordination.     

Towards the origin of the memory effect in oxide glasses

Glass samples with same composition and properties but different thermal histories can exhibit different behavior upon a subsequent heat-treatment, a phenomenon known as the memory effect. Generally, it is considered that the memory effect is due to nanoscale density fluctuation, which exists in all glasses and causes non-exponential relaxation with more than one relaxation time. Earlier, we studied the memory effect of various silica glasses and found that some pure silica glasses did not exhibit the memory effect while some silica glasses with higher impurity contents exhibited the memory effect. Based upon this finding, we suggested that the phenomenon originated from concentration fluctuation rather than density fluctuation. In this study, the memory effect in 6 mol% K₂O-94 mol% SiO₂ glass was investigated. The K₂O-SiO₂ glass system has a metastable immiscibility below the glass transition temperature and the chosen glass composition is the critical composition corresponding to the estimated critical temperature of the immiscibility boundary. Thus, it is expected that this glass composition would exhibit large super-critical concentration fluctuation, which increases with decreasing heat-treatment temperature. Density fluctuation, on the other hand, increases with increasing heat-treatment temperature. A much larger memory effect was observed at the lower heat-treatment temperature for the present glass. This result supports our earlier contention that the origin of the memory effect is composition fluctuation rather than density fluctuation.     

Electric conductivity of glasses in the system Na2O/CaO/SiO2/Fe2O3

The addition of polyvalent transition metal ions to the usually insulating traditional soda-lime-silica glasses can lead to semiconducting properties. We report on synthesis of glasses and glass-ceramics in a soda-lime-silicate based system containing Fe₂O₃ in the concentration range from 5 to 30 mol%. Two sub-systems were considered, in one of them the ratio [Na₂O]/[Fe₂O₃] was varied while in the other one, the ratio [SiO₂]/[Fe₂O₃] was changed. The phase composition of the synthesized products was characterized by X-ray diffraction and energy dispersive X-ray analysis, while the electrical properties were studied by impedance spectroscopy. Partially crystallized non-reduced samples are semiconducting even at room temperature while the glassy samples (both reduced and non-reduced) exhibit semiconducting properties at temperatures equal or larger than 100 °C. An attempt is done to predict the physical approximation explaining the conduction process in the glasses.     

Structures of lanthanum and yttrium aluminosilicate glasses determined by X-ray and neutron diffraction

We have measured the structures of lanthanum and yttrium aluminosilicate glasses by X-ray and neutron diffraction and determined the interatomic distances and nearest-neighbor coordination numbers. The results obtained with the two techniques are in good agreement with each other and with recent NMR studies. The Si-O and Al-O coordination numbers are found to be 4 and 4.5, respectively. All the glasses show pronounced intermediate-range order that exhibits a reduced length scale with increasing La or Y content.     

Structure of chalcogenide glasses by neutron diffraction

The purpose of this work is to study the change in the structure of the Ge–Se network upon doping with Ag. We report here a neutron diffraction study on two glasses of the system Ag_x(Ge_0.25Se_0.75)_100−x with different silver contents (x = 15 and 25 at.%) and for two different temperatures (10 and 300 K). The total structure factor S(Q) for the two samples has been measured by neutron diffraction using the two-axis diffractometer dedicated to structural studies of amorphous materials, D4, at the Institut Laue Langevin. We have derived the corresponding radial distribution functions for each sample and each temperature, which gives us an insight about the composition and temperature dependence of the correlation distances and coordination numbers in the short-range. Our results are compatible with the presence of both GeSe_4/2 tetrahedra and Se–Se bonds. The Ag atoms are linked to Se in a triangular environment. Numerical simulations allowing the identification of the main peaks in the total pair correlation functions have complemented the neutron diffraction measurements.     

1H-1,2,3-triazole,a promising precursor for chemical vapor deposition of hydrogenated carbon nitride

Well-crystallized hydrogenated carbon nitride thin films have been prepared by microwave plasma enhanced chemical vapor deposition (MWPECVD). 1H-1,2,3-triazole+N₂ and Si (1 0 0) were used as precursor and substrate, respectively. Substrate temperature during the deposition was recorded to be 850 °C. The synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photo-electron spectroscopy (XPS) analyses. The plasma compositions were checked by optical emission spectroscopy (OES). XRD observation strongly suggests that the films contain polycrystalline carbon nitride with graphitic structure of (1 0 0), (0 0 2), (2 0 0) and (0 0 4). XPS peak quantification reveals that the atomic ratio of the materials C:N:O:Si is 32:41:18:9. X-ray photo-electron peak deconvolution shows that the most dominant peak of C (1s) and N (1s) narrow scans correspond to sp² hybrid structure of C₃N₄. These observations indicate that 1H-1,2,3-triazole favors the formation of hydrogenated carbon nitride with graphitic phase by CVD method and thus is in good agreement with XRD results. SEM of surface and OES of plasma also support the formation of polycrystalline carbon nitride films from 1H-1,2,3-triazole+N₂ by CVD.     

Effect of microalloying of Nb on corrosion resistance and thermal stability of ZrCu-based bulk metallic glasses

Bulk metallic glasses (BMGs) of Zr_46−xNb_xCu_37.6Ag_8.4Al₈ with x = 0, 0.5, 1, 2 and 4 at.% were prepared by copper mould casting. The corrosion resistance of the ZrCu-based BMGs with different Nb contents was carefully examined by weight loss measurements and potentiodynamic polarization tests in 3 mass% NaCl, 1 N HCl and 1 N H₂SO₄ solutions, respectively. Nb addition improves the newly developed BMGs’ corrosion resistance in chloride-containing solutions and the alloys all exhibit excellent corrosion resistance in 1 N H₂SO₄. The corrosion behavior of the alloy containing 0 and 4 at.% Nb in phosphate-buffered solution was examined by electrochemical polarization tests. The influence of Nb addition on glass forming ability (GFA), thermal stability and mechanical property was investigated by X-ray diffraction, differential scanning calorimetry and compression tests, respectively. It is found that the addition of Nb can deteriorate the GFA and thermal stability of the base system, but little effect is observed on the mechanical properties, e.g., yielding strength and plasticity, of the ZrCu-based BMG alloys.     

Dense amorphous packing of binary hard sphere mixtures with chemical order: The stability of a solute ordered approximant

Recently, Miracle proposed that the intermediate structure in metallic glasses could be usefully characterized as an ordered face centered cubic packing of solute-centered coordination clusters. In this paper we examine the stability of such solute ordered arrangements in binary hard sphere mixtures subject to density maximization through local particle moves.     

Solubility of glasses in the system P2O5-CaO-MgO-Na2O-TiO2: Experimental and modeling using artificial neural networks

Phosphate glasses in the system P₂O₅-CaO-MgO-Na₂O-TiO₂ for use as degradable implant materials were produced. In order to classify their solubility behavior, dissolution experiments were performed in deionized water for 60 min at 98 °C. Resulting solutions were analyzed using ICP-OES. In addition, pH measurements were carried out in physiological NaCl solution. With increasing phosphorus oxide content, the glasses showed a higher solubility and gave lower pH values in aqueous solution. This was caused by changes in the glass structure, as long phosphate chains are more susceptible to hydration than smaller phosphate groups. These changes in glass structure were followed by ³¹P MAS-NMR experiments. Increasing sodium oxide concentrations in exchange for calcium or magnesium oxide also increased the glass solubility by disrupting ionic cross links between chains. By contrast, addition of titania made the glasses more stable towards dissolution by cross linking smaller phosphate groups. The aim of this study was to find a relationship between glass composition and solubility behavior. As classical linear methods of data analysis were unsuitable due to the complexity of the relationship, preliminary artificial neural networks analyses were performed and were found to be an interesting tool for modeling the solubility behavior of phosphate glasses.     

The structure of SiO2-GeO2 glasses: A spectroscopic study

Four glasses of the SiO₂-GeO₂ binary system have been synthesized via a sol-gel route followed by a heat treatment and a quench. Glass structure has been determined by Ge K-edge X-ray absorption spectroscopy (XAS) at low temperature and Raman spectroscopy. These mixed glasses present a continuous random network of interconnected GeO₄ and SiO₄ tetrahedra, with GeO₄ tetrahedra similar to the GeO₄ units in GeO₂ glass and continuous compositional variations from GeO₂-rich regions to SiO₂-rich regions. Such a random mixture is consistent with physical properties of these binary glasses as well as with the chemical dependence of their polyamorphism at high pressure. This EXAFS-derived mean Ge-O-Si angles are close to the Ge-O-Ge mean angle in GeO₂ glass, 134° and 130°, respectively. This misfit with the Si-O-Si angles might explain the ease of formation of isolated and pair defects centers, which are suspected to be at the origin of photo-induced modifications of optical properties in Ge-bearing SiO₂ glasses.     

Characterization of new sulfur and selenium-based glasses containing lead iodide

The aim of this work is to investigate and qualify vitreous regions in new chalcogenide systems containing highly polarizable elements like S, Se, As, Sb, Bi, Pb and I. The sulfur based system, As₂S₃-Sb₂S₃-Bi₂S₃-PbI₂, as well as the selenium containing glasses As₂Se₃-Sb₂Se₃-PbI₂ have been studied. Large vitreous regions have been defined in the both systems: sulfur and selenium. Indeed, several glass compositions can accept in the vitreous network a molar concentration near 50% of PbI₂. Physical properties such as glass transition temperature, crystallization temperature, optical transmission, band-gap wavelength have been measured versus glassy compositions.     

Effect of ZnO and Bi2O3 addition on linear and non-linear optical properties of tellurite glasses

Glasses in the system TeO₂-Bi₂O₃-ZnO were studied with respect to their linear refractive indices and optical absorption in the UV-vis range. The third order non-linear refractive indices were measured using degenerated four wave mixing (DFWM). The optical Kerr susceptibilities calculated hereof were in the range from 5.49 to 6.58 × 10⁻¹³ esu and hence 34-41 times larger than that of fused SiO₂. They are roughly proportional to values theoretically calculated by the theory of Lines.