Effects of rare-earth co-doping on the local structure of rare-earth phosphate glasses using high and low energy X-ray diffraction

Rare-earth co-doping in inorganic materials has a long-held tradition of facilitating highly desirable optoelectronic properties for their application to the laser industry. This study concentrates specifically on rare-earth phosphate glasses, (R2O3)x(R'2O3)y(P2O5)1-(x+y), where (R, R') denotes (Ce, Er) or (La, Nd) co-doping and the total rare-earth composition corresponds to a range between metaphosphate, RP3O9, and ultraphosphate, RP5O14. Thereupon, the effects of rare-earth co-doping on the local structure are assessed at the atomic level. Pair-distribution function analysis of high-energy X-ray diffraction data (Qmax = 28 Å-1) is employed to make this assessment. Results reveal a stark structural invariance to rare-earth co-doping which bears testament to the open-framework and rigid nature of these glasses. A range of desirable attributes of these glasses unfold from this finding; in particular, a structural simplicity that will enable facile molecular engineering of rare-earth phosphate glasses with 'dial-up' lasing properties. When considered together with other factors, this finding also demonstrates additional prospects for these co-doped rare-earth phosphate glasses in nuclear waste storage applications. This study also reveals, for the first time, the ability to distinguish between P-O and PO bonding in these rare-earth phosphate glasses from X-ray diffraction data in a fully quantitative manner. Complementary analysis of high-energy X-ray diffraction data on single rare-earth phosphate glasses of similar rare-earth composition to the co-doped materials is also presented in this context. In a technical sense, all high-energy X-ray diffraction data on these glasses are compared with analogous low-energy diffraction data; their salient differences reveal distinct advantages of high-energy X-ray diffraction data for the study of amorphous materials. © 2013 The Owner Societies.

The structure of the rare-earth phosphate glass(Sm2O3)0.205(P2O5)0.795 studied by anomalous dispersion neutron diffraction

The role of the Sm3+ ions in the structure of vitreous Sm2O3•4P2O5 has been investigated using the neutron diffraction anomalous dispersion technique, which employs the wavelength dependence of the real and imaginary parts of the neutron scattering length close to an absorption resonance. The data described here represent the first successful complete neutron anomalous dispersion study on an amorphous material. This experimental methodology permits one to determine exclusively the closest Sm• •• Sm separation. Knowledge of the R•••R (R = rare-earth) pairwise correlation is key to understanding the optical and magnetic properties of rare-earth phosphate glasses. The anomalous difference correlation function, ΔT''(r), shows a dominant feature pertaining to a Sm•••Sm separation, centred at 4.8 Å. The substantial width and marked asymmetry of this peak indicates that the minimum approach of Sm3+ ions could be as close as 4 Å. Information on other pairwise correlations is also revealed via analysis of T (r) and ΔT (r) correlation functions: Sm3+ ions display an average co-ordination number, n Sm(O), of 7, with a mean Sm–O bond length of 2.375(5) Å whilst the PO4 tetrahedra have a mean P–O bond length of 1.538(2) Å. Second- and third-neighbour correlations are also identified. These results corroborate previous findings. Such consistency lends support to the application of the anomalous dispersion technique to determine separations.

Direct observation of R...R distances in rare-earth (R) phosphate glasses by magnetic difference neutron diffraction

A magnetic difference neutron diffraction study of a rare-earth (Tb) phosphate glass has revealed exclusively the Tb...Tb distances. The difference between data taken with and without an applied magnetic field of 4 T shows Tb...Tb pairwise atomic correlations at 3.9 and 6.4 A, respectively, with relative coordination numbers of 1:14. The first distance arises when two Tb3+ ions share a common oxygen neighbor, and indicates a clustering of rare-earth ions. The second distance arises when two Tb3+ ions are coordinated to different oxygens in the same PO4 group, in a near-linear arrangement.

Structure of rare-earth phosphate glasses by neutron diffraction

Neutron diffraction was used to measure the structure of the phosphate glasses RAl0.30P3.05O9.62, where R denotes Dy or Ho, and RAl0.34P3.20O10.04, where R denotes La or Ce. For each glass, isomorphic structures were assumed and difference function methods were employed to separate, essentially, those correlations involving the rare-earth ion, R3+, from the remainder. The ratio of bridging oxygen, OB, to terminal oxygen, OT, atoms in the PO4 tetrahedra was quantified and in both materials R3+ and Al3+ are found to act as network modifying cations which bind to the OT. The R–OT coordination number is 6.7(1) and 7.5(2) for the Dy/Ho and La/Ce glasses respectively.

Identification of the relative distribution of rare-earth ions in phosphate glasses

The relative distribution of rare-earth ions R3+ (Dy3+ or Ho3+) in the phosphate glass RAl0.30P3.05O9.62 was measured by employing the method of isomorphic substitution in neutron diffraction. It is found that 7.9(7) R-R nearest neighbors reside at 5.62(6) Angstrom in a network made from interlinked PO4 tetrahedra. Provided that the role of Al is explicitly considered, a self-consistent account of the local matrix atom correlations can be developed in which there are 1.68(9) bridging and 2.32(9) terminal oxygen atoms per phosphorus.

(Table S1) Trace element and isotopic compositions of anhydrites sampled in the Manus Basin, Papua New Guinea

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REEN patterns measured in anhydrite from mid-ocean ridge deposits. The REEN patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. 87Sr/86Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate d34S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate d34S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO2 degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.

Table 1. Concentration of rare earth elements in ferromanganese nodule (crust), sediment and rock of the South China Sea

Based on the X-ray fluorescence spectrum analysis of 15 rare earth elements in 6 ferromanganese nodu1es and 5 ferro mangane se crusts from the South China Sea, their abundances, distribution patterns, sources and relationships with associated elements are discussed in detail in this paper. The results show that: 1) The average abundance of rare earth elements in ferromanganese nodu1es and crusts is 1. 625 g/kg and 2. 167 g/kg respectively, which is 1-2 tim es , 5-6 times and 15-20 times higher than that in the Pacific, in the sediments of the North Pacific and the South China Sea, respectively; 2) The distribution patterns of rare earth elements standardized by the globular aerolite in ferro mangane se nodules and crusts are basically similar, that is, Ce is positively abnormal and Eu is in deficit slightly; 3) The relationships between rare earth elements and associated elements, sediments and rocks show that the source of rare earth elements in ferromanganese nodules and crusts have mainly come from slow deposition caused by weathering and leaching of medium acidic rock of the South China Sea.