Experimental photoluminescence and lifetimes at wavelengths including beyond 7 microns in Sm3+-doped selenide-chalcogenide glass fibers.

1000 ppmw Sm3+-doped Ge19.4Sb9.7Se67.9Ga3 atomic % chalcogenide bulk glass and unstructured fiber are prepared. Near- and mid-infrared absorption spectra of the bulk glass reveal Sm3+ electronic absorption bands, and extrinsic vibrational absorption bands, due to host impurities. Fiber photoluminescence, centred at 3.75 µm and 7.25 µm, is measured when pumping at either 1300 or 1470 nm. Pumping at 1470 nm enables the photoluminescent lifetime at 7.3 µm to be measured for the first time which was ∼100 µs. This is the longest to date, experimentally observed lifetime in the 6.5-9 µm wavelength-range of a lanthanide-doped chalcogenide glass fiber.

Neutron Diffraction and Raman Studies of the Incorporation of Sulfate in Silicate Glasses.

The oxidation state, coordination, and local environment of sulfur in alkali silicate (R2O-SiO2; R = Na, Li) and alkali/alkaline-earth silicate (Na2O-MO-SiO2; M = Ca, Ba) glasses have been investigated using neutron diffraction and Raman spectroscopy. With analyses of both the individual total neutron correlation functions and suitable doped-undoped differences, the S-O bonds and (O-O)S correlations were clearly isolated from the other overlapping correlations due to Si-O and (O-O)Si distances in the SiO4 tetrahedra and the modifier-oxygen (R-O and M-O) distances. Clear evidence was obtained that the sulfur is present as SO4 2- groups, confirmed by the observation in the Raman spectra of the symmetric S-O stretch mode of SO4 2- groups. The modifier-oxygen bond length distributions were deconvoluted from the neutron correlation functions by fitting. The Na-O and Li-O bond length distributions were clearly asymmetric, whereas no evidence was obtained for asymmetry of the Ca-O and Ba-O distributions. A consideration of the bonding shows that the oxygen atoms in the SO4 2- groups do not participate in the silicate network and as such constitute a third type of oxygen, "non-network oxygen", in addition to the bridging and non-bridging oxygens that are bonded to silicon atoms. Thus, each individual sulfate group is surrounded by a shell of modifier and is not connected directly to the silicate network. The addition of SO3 to the glass leads to a conversion of oxygen atoms within the silicate network from non-bridging to bridging so that there is repolymerization of the silicate network. There is evidence that SO3 doping leads to changes in the form of the distribution of Na-O bond lengths with a reduction in the fitted short-bond coordination number and an increase in the fitted long-bond coordination number, and this is consistent with repolymerization of the silicate network. In contrast, there is no evidence that SO3 doping leads to a change in the distribution of Li-O bond lengths with a total Li-O coordination number consistently in excess of 4.

In vitro cellular testing of strontium/calcium substituted phosphate glass discs and microspheres shows potential for bone regeneration.

Phosphate-based glasses (PBGs) are ideal materials for regenerative medicine strategies because their composition, degradation rates, and ion release profiles can easily be controlled. Strontium has previously been found to simultaneously affect bone resorption and deposition. Therefore, by combining the inherent properties of resorbable PBG and therapeutic activity of strontium, these glasses could be used as a delivery device of therapeutic factors for the treatment of orthopaedic diseases such as osteoporosis. This study shows the cytocompatibility and osteogenic potential of PBGs where CaO is gradually replaced by SrO in the near invert glass system 40P2 O5 ·(16-x)CaO·20Na2 O·24MgO·xSrO (x = 0, 4, 8, 12, and 16 mol%). Direct seeding of MG63 cells onto glass discs showed no significant difference in cell metabolic activity and DNA amount measurement across the different formulations studied. Cell attachment and spreading was confirmed via scanning electron microscopy (SEM) imaging at Days 3 and 14. Alkaline phosphatase (ALP) activity was similarly maintained across the glass compositions. Follow-on studies explored the effect of each glass composition in microsphere conformation (size: 63-125 µm) on human mesenchymal stem cells (hMSCs) in 3D cultures, and analysis of cell metabolic activity and ALP activity showed no significant differences at Day 14 over the compositional range investigated, in line with the observations from MG63 cell culture studies. Environmental SEM and live cell imaging at Day 14 of hMSCs seeded on the microspheres showed cell attachment and colonisation of the microsphere surfaces, confirming these formulations as promising candidates for regenerative medicine strategies addressing compromised musculoskeletal/orthopaedic diseases.

Multicomposition EPSR: Toward Transferable Potentials To Model Chalcogenide Glass Structures.

The structure of xAs40Se60-(1 - x)As40S60 glasses, where x = 1.000, 0.667, 0.500, 0.333, 0.250, and 0.000, is investigated using a combination of neutron and X-ray diffraction coupled with computational modeling using multicomposition empirical potential structure refinement (MC-EPSR). Traditional EPSR (T-EPSR) produces a set of empirical potentials that drive a structural model of a particular composition to agreement with diffraction experiments. The work presented here establishes the shortcomings in generating such a model for a ternary chalcogenide glass composition. In an enhancement to T-EPSR, MC-EPSR produces a set of pair potentials that generate robust structural models across a range of glass compositions. The structures obtained vary with composition in a much more systematic way than those taken from T-EPSR. For example, the average arsenic-sulfur bonding distances vary between 2.28 and 2.46 Å in T-EPSR but are 2.29 ± 0.02 Å in MC-EPSR. Similarly, the arsenic-selenium bond lengths from T-EPSR vary between 2.28 and 2.43 Å but are consistently 2.40 ± 0.02 Å in the MC-EPSR results. Analysis of these models suggests that the average separation of the chalcogen (S or Se) atoms is the structural origin of the changes in nonlinear refractive index with glass composition.

Correlating structure with non-linear optical properties in xAs40Se60·(1-x)As40S60 glasses.

A series of xAs40Se60·(100 - x)As40S60 glasses, where x = 0, 25, 33, 50, 67, 75 and 100 mol% As40Se60, has been studied using neutron and X-ray total scattering, Raman spectroscopy and (77)Se MAS-NMR. The results are presented with measurements of non-linear refractive indices, n2, and densities. There is no evidence for the formation of homopolar bonds in these glasses, but neutron correlation functions suggest that there is a non-random distribution of sulfur and selenium atoms in sulfur-rich glasses. The average number of sulfur atoms at a distance of 3-4 Å from a selenium atom, nSeS, deviates from a linear variation with x in glasses containing <50 mol% As40Se60; n2 for these glasses also varies non-linearly with x. Importantly, a direct comparison of n2 and nSeS gives a linear correlation, suggesting that n2 may be related to the distribution of chalcogen atoms in the glasses.

Characterisation of phosphate coacervates for potential biomedical applications.

In this study, amorphous (Na2O)x(CaO)0.50- x(P2O5)0.50·yH2O (where x = ~0.15 and y = ~3) samples were prepared by a coacervate method. Thermal analysis showed that two types of water molecules were present in the coacervate structures: one type loosely bound and the other part of the phosphate structure. Structural studies using Fourier transform infrared spectroscopy (FTIR) and X-ray total diffraction revealed the samples to have very similar structures to melt-quenched glasses of comparable composition. Furthermore, no significant structural differences were observed between samples prepared using calcium nitrate as the calcium source or those prepared from calcium chloride. A sample containing ~1 mol% Ag2O was prepared to test the hypothesis that calcium phosphate coacervate materials could be used as delivery agents for antibacterial ions. This sample exhibited significant antibacterial activity against the bacterium Psuedomonas aeruginosa. FTIR data revealed the silver-doped sample to be structurally akin to the analogous silver-free sample.

Local and average structure in zinc cyanide: toward an understanding of the atomistic origin of negative thermal expansion.

Neutron diffraction at 11.4 and 295 K and solid-state (67)Zn NMR are used to determine both the local and the average structures in the disordered, negative thermal expansion (NTE) material, Zn(CN)2. Solid-state NMR not only confirms that there is head-to-tail disorder of the C≡N groups present in the solid, but yields information about the relative abundances of the different Zn(CN)4­n(NC)n tetrahedral species, which do not follow a simple binomial distribution. The Zn(CN)4 and Zn(NC)4 species occur with much lower probabilities than are predicted by binomial theory, supporting the conclusion that they are of higher energy than the other local arrangements. The lowest energy arrangement is Zn(CN)2(NC)2. The use of total neutron diffraction at 11.4 K, with analysis of both the Bragg diffraction and the derived total correlation function, yields the first experimental determination of the individual Zn­N and Zn­C bond lengths as 1.969(2) and 2.030(2) Å, respectively. The very small difference in bond lengths, of ~0.06 Å, means that it is impossible to obtain these bond lengths using Bragg diffraction in isolation. Total neutron diffraction also provides information on both the average and the local atomic displacements responsible for NTE in Zn(CN)2. The principal motions giving rise to NTE are shown to be those in which the carbon and nitrogen atoms within individual Zn­C≡N­Zn linkages are displaced to the same side of the Zn···Zn axis. Displacements of the carbon and nitrogen atoms to opposite sides of the Zn···Zn axis, suggested previously in X-ray studies as being responsible for NTE behavior, in fact make negligible contributions at temperatures up to 295 K.

Structures of uncharacterised polymorphs of gallium oxide from total neutron diffraction.

A structural investigation is reported of polymorphs of Ga(2)O(3) that, despite much interest in their properties, have hitherto remained uncharacterised due to structural disorder. The most crystalline sample yet reported of γ-Ga(2)O(3) was prepared by solvothermal oxidation of gallium metal in ethanolamine. Structure refinement using the Rietveld method reveals γ-Ga(2)O(3) has a defect Fd3m spinel structure, while pair distribution function analysis shows that the short-range structure is better modelled with local F43m symmetry. In further solvothermal oxidation reactions a novel gallium oxyhydroxide, Ga(5)O(7)(OH), is formed, the thermal decomposition of which reveals a new, transient gallium oxide polymorph, κ-Ga(2)O(3), before transformation into ß-Ga(2)O(3). In contrast, the thermal decomposition of Ga(NO(3))(3)·9H(2)O first forms ε-Ga(2)O(3) and then ß-Ga(2)O(3). Examination of in situ thermodiffraction data shows that ε-Ga(2)O(3) is always contaminated with ß-Ga(2)O(3) and with this knowledge a model for its structure was deduced and refined--space group P6(3)mc with a ratio of tetrahedral/octahedral gallium of 2.2:1 in close-packed oxide layers. Importantly, thermodiffraction provides no evidence for the existence of the speculated bixbyite structured δ-Ga(2)O(3); at the early stages of thermal decomposition of Ga(NO(3))(3)·9H(2)O the first distinct phase formed is merely small particles of ε-Ga(2)O(3).

A structural investigation of the alkali metal site distribution within bioactive glass using neutron diffraction and multinuclear solid state NMR.

The atomic-scale structure of Bioglass and the effect of substituting lithium for sodium within these glasses have been investigated using neutron diffraction and solid state magic angle spinning (MAS) NMR. Applying an effective isomorphic substitution difference function to the neutron diffraction data has enabled the Na-O and Li-O nearest-neighbour correlations to be isolated from the overlapping Ca-O, O-(P)-O and O-(Si)-O correlations. These results reveal that Na and Li behave in a similar manner within the glassy matrix and do not disrupt the short range order of the network former. Residual differences are attributed solely to the variation in ionic radius between the two species. Successful simplification of the 2 < r (Å) < 3 region via the difference method has enabled all the nearest neighbour correlations to be deconvolved. The diffraction data provides the first direct experimental evidence of split Na-O nearest-neighbour correlations in these melt quench bioactive glasses, and an analogous splitting of the Li-O correlations. The observed correlations are attributed to the metal ions bonded either to bridging or to non-bridging oxygen atoms. (23)Na triple quantum MAS (3QMAS) NMR data corroborates the split Na-O correlations. The structural sites present will be intimately related to the release properties of the glass system in physiological fluids such as plasma and saliva, and hence to the bioactivity of the material. Detailed structural knowledge is therefore a prerequisite for optimizing material design.

Structure and properties of an amorphous metal-organic framework.

ZIF-4, a metal-organic framework (MOF) with a zeolitic structure, undergoes a crystal-amorphous transition on heating to 300 degrees C. The amorphous form, which we term a-ZIF, is recoverable to ambient conditions or may be converted to a dense crystalline phase of the same composition by heating to 400 degrees C. Neutron and x-ray total scattering data collected during the amorphization process are used as a basis for reverse Monte Carlo refinement of an atomistic model of the structure of a-ZIF. The structure is best understood in terms of a continuous random network analogous to that of a-SiO2. Optical microscopy, electron diffraction and nanoindentation measurements reveal a-ZIF to be an isotropic glasslike phase capable of plastic flow on its formation. Our results suggest an avenue for designing broad new families of amorphous and glasslike materials that exploit the chemical and structural diversity of MOFs.