Spectroscopic and structural properties of YbF3-doped fluorophosphate glasses

Compositional influences on the spectroscopic properties of Yb3+ and the structural variations with the introduction of YbF3 were studied in fluorophosphate glasses. Emission cross-section (sigma(emi)) and gain coefficient (sigma(emi) x tau(f)) were calculated which exhibit maximum at RF2 = 33 mol%. YbF3 has an important effect on the glass forming ability of fluorophosphate glasses when RF2 is over 36 mol%. The study of Raman spectra showed big differences on the glass structure between non-Yb3+ and Yb3+ -doped glasses. The main building units in Yb3+-doped samples are metaphosphate groups, pyrophosphate groups (P-2(O,F)(7), PO3F), Al[F-6] +Al[O,F](6) and F3Al-O-AlF3 while those of the non-Yb3+-doped glasses are monophosphate group P(O,F)(4), little pyrophosphate group, Al[F-4] + Al[F-6] + Al[O,F](4) + Al[O,F](6) and F3Al-O-AlF3, which means Yb3+ ions contribute to a better glass polymerization and network uniformity. (C) 2004 Elsevier B.V. All rights reserved.

Special effects of YbF3 on the structural changes for fluorophosphate glass

From Raman and IR spectra, obvious differences of the glass structure were observed in non-Yb3+-doped and Yb3+ -doped fluorophosphate glasses. Results showed that Yb3+ ions can induce, in a better glass, polymerization and network uniformity. Compared with the monophosphate-mastered Yb3+-free glass, Yb3+-doped glass has a pyrophosphate environment. The main building blocks in Yb3+ -doped samples are metaphosphate groups, pyrophosphate groups (P-2(O,F)(7),PO3F), Al[F-6]+Al[O,F](6) and F3Al-O-AlF3 while those of the Yb3+ -free glasses are monophosphate groups P(O,F)(4), little pyrophosphate groups, Al[F-4]+Al[F-6]+Al[O,F](4)+Al[O,F](6) and F3Al-O-AlF3. The DSC analysis also showed a slight increase in crystallization stability. (c) 2005 Elsevier B.V. All rights reserved.

Structure and thermal stability of novel fluorophosphate glasses

A systematic investigation on glass formation in the PbF2-InF3-BaHPO4 ternary system has been carried out. These glasses have characterized by IR spectra, Raman spectra and differential thermal analysis. The results show that the structure of these glasses is mainly affected by BaHPO4 and InF3 contents. With decreasing BaHPO4 content, the glass structure gradually transforms from metaphosphate to polyphosphate. When InF3 content is low, it mainly acts as network modifier, when its content is high; it enters glass matrix and forms In(O,F)(6) groups connecting the polymerized phosphorus oxygen species. PbF2 mainly acts as network modifier in this system. Systematic variations of the glass transition temperature and the thermal stability index agree well with these results. The most stable glass with Delta T = 230 degrees C and S = 21.79 K is obtained. (c) 2004 Elsevier B.V. All rights reserved.

Phosphate treatment of frozen prawns. Pt. 1. Screening of various phosphates for prevention of drip loss

Various phosphates and their mixtures were screened for their efficiency of preventing drip loss in frozen prawns. The effectiveness of the phosphates decreased in the following order: Sodium tripolyphosphate — Sodium pyrophosphate — Sodium hexametaphosphate Sodium metaphosphate — Sodium dihydrogen phosphate; the last two being ineffective. Even though thaw drip loss was reduced by the above treatments the organoleptic quality of the thawed as well as cooked products was unsatisfactory, discoloration being the major defect. A solution of a mixture of 12% sodium tripolyphosphate and 8.6% sodium dihydrogen phosphate or 2% citric acid in water when used as dip prevented thaw drip loss, improved cooked yield and organoleptic quality without adversely affecting the biochemical characteristics. Commercial scale trials showed that the results are highly reproducible.

Comparison of effectiveness of different ashing auxiliaries for determination of phosphorus in natural waters, aquatic organisms and sediments by ignition method

An improved method for the determination of phosphorus in natural waters, aquatic organisms and sediments by ignition method is proposed. The recoveries of phosphorus (P) from selected inorganic and organic P-containing compound standards after ignition with different auxiliaries, such as MgSO4, Mg(NO3)(2), MgO2, Mg(Ac-2) and CaCl2, were compared. We found that the phosphorus from most compound standards could not be completely recovered when these compounds were ignited (450-500degreesC) with the MgSO4 as auxiliary and the baked residue was extracted with 0.2 mol l(-1) HCl for 30min at 80degreesC or at room temperature. P recoveries, for example, were poor, less than 85%, if pyrophosphate and metaphosphate were ignited with the addition Of MgSO4 prior to the extraction of the baked residue with 0.2 mol l(-1) HCl at 80degreesC for 30 min. In contrast, MgO2, Mg(Ac)(2) and CaCl2, as well as Mg(NO3)(2), could all yield complete P recoveries at routine ashing temperatures (450-500degreesC). The results demonstrate that MgC12 is a more effective auxiliary agent for the determination of phosphorus in natural waters, aquatic organisms and sediments by ignition method than MgSO4 which is commonly used. (C) 2003 Elsevier Science Ltd. All rights reserved.

Scandium fluorophosphate glasses: a structural approach

A systematic investigation on glass formation in the ternary system InF3-BaF2-[Sc(PO3)(3)](n) has been carried out. Scandium polyphosphate [Sc(PO3)(3)](n) has been used as a third component in order to investigate the possibilities of obtaining new stable glasses. The above long-chain polyphosphate has been prepared using a specially elaborated cryo-technique, which allowed the preparation of high-purity product. Stable ternary compositions have been obtained within the compositions range (in mol%): 5-75 InF3, 0-80% BaF2, 0-50% [Sc(PO3)(3)](n). Glasses were characterized by Differential Scanning Calorimetry, vibrational spectroscopy (Raman) and P-31 NMR. Structural features for the glass were put forward. Isolated P(O,F)4 groups or fluoroindated metaphosphate units could be identified depending on glass compositions. (C) 2002 Academie des sciences / Editions scientifiques et medicales Elsevier SAS.

Spectroscopic study and local coordination of polyphosphate colloidal systems

The interaction between metaphosphate chains and the metal ions Ca2+ and Eu3+ has been studied in water by Eu3+ luminescence, infrared absorption, and P-31 NMR spectroscopy. Two main families of sites could be identified for the metal ions in the aqueous polyphosphate colloidal systems: (1) cagelike sites provided by the polyphosphate chain and (2) a family which arises following saturation of cagelike sites. Occupation of this second family leads to supramolecular interactions between polyphosphate chains and the consequent destabilization of the colloidal system. In the polyphosphate-Ca2+ system, this destabilization appears as a coacervation process. Equilibrium existing between colloidal species as a function of the compositions could be reasoned based on the spectroscopic measurements. The determination of coordination numbers and the correlation of the results with the observation of coacervates show that Eu3+ luminescence properties can be used to probe in a unique way the coacervation process.

Enhanced Eu3+ Emission in Aqueous Phosphotungstate Colloidal Systems: Stabilization of Polyoxometalate Nanostructures

Luminescent Eu3+-containing polyphosphate tungstate aqueous colloidal systems were prgared and studied as a function of the relative polyphosphate tungstate content. In polyphosphate-rich solutions, Eu-H- ions occupy cagelike sites composed of phosphate groups from the metaphosphate chains. In these sites, an average number of 0.5 water molecule coordinates to an Eu3+ ion and the 500 emission quantum efficiency is 0.22. Tungstatc addition leads to important modifications in neighboring Eu3+ leading to coordination sites in the aqueous medium where metal ions are completely hidden from interactions with solvent molecules. Transmission electron microscopy results clearly show \V-rich nanoparticles with sizes between 5 and 10 nm for all tungstate relative concentrations. For high tungstatc relative contents (above 30 mol %), spectroscopic results suggest the presence of Eu34- in polyoxometalate (P0M)-like sites by comparison with the well-known decatungstoeuropate [EuW10O36](9-) structure. These new aqueous colloids display surprisingly high 5llo emission quantum efficiencies of ca 80% because of the strong ligand field provided by tungstate POM ligands and the complete absence of water molecules from the Eu3+ first coordination shell.

Er(3+) doped phosphoniobate glasses and planar waveguides: structural and optical properties

Phosphoniobate glasses with composition (mol%) (100-x) NaPO(3)-xNb(2)O(5) ( x varying from 11 to 33) were prepared and characterized by means of thermal analysis, Fourier transform infrared spectroscopy, Raman scattering and (31)P nuclear magnetic resonance. The addition of Nb(2)O(5) to the polyphosphate base glass leads to depolymerization of the metaphosphate structure. Different colors were observed and assigned as indicating the presence of Nb(4+) ions, as confirmed by electron paramagnetic resonance measurements. The color was observed to depend on the glass composition and melting temperature as well. Er(3+) containing samples were also prepared. Strong emission in the 1550 nm region was observed. The Er(3+4)I(15/2) emission quantum efficiency was observed to be 90% and the quenching concentration was observed to be 1.1 mol%( 1.45 x 10(20) ions cm(-3)). Planar waveguides were prepared by Na(+)-K(+)-Ag(+) ion exchange with Er(3+) containing samples. Optical parameters of the waveguides were measured at 632.8, 543.5 and 1550 nm by the prism coupling technique as a function of the ion exchange time and Ag(+) concentration. The optimized planar waveguides show a diffusion depth of 5.9 mu m and one propagating mode at 1550 nm.

Thermal and structural study of glasses in the binary system TeO2-Pb(PO3)(2)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Thermal and structural properties of tantalum alkali-phosphate glasses

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

More Than Charged Base Loss — Revisiting the Fragmentation of Highly Charged Oligonucleotides

Tandem mass spectrometry is a well-established analytical tool for rapid and reliable characterization of oligonucleotides (ONs) and their gas-phase dissociation channels. The fragmentation mechanisms of native and modified nucleic acids upon different mass spectrometric activation techniques have been studied extensively, resulting in a comprehensive catalogue of backbone fragments. In this study, the fragmentation behavior of highly charged oligodeoxynucleotides (ODNs) comprising up to 15 nucleobases was investigated. It was found that ODNs exhibiting a charge level (ratio of the actual to the total possible charge) of 100% follow significantly altered dissociation pathways compared with low or medium charge levels if a terminal pyrimidine base (3' or 5') is present. The corresponding product ion spectra gave evidence for the extensive loss of a cyanate anion (NCO–), which frequently coincided with the abstraction of water from the 3'- and 5'-end in the presence of a 3'- and 5'-terminal pyrimidine nucleobase, respectively. Subsequent fragmentation of the MNCO– ion by MS3 revealed a so far unreported consecutive excision of a metaphosphate (PO3–)-ion for the investigated sequences. Introduction of a phosphorothioate group allowed pinpointing of PO3– loss to the ultimate phosphate group. Several dissociation mechanisms for the release of NCO– and a metaphosphate ion were proposed and the validity of each mechanism was evaluated by the analysis of backbone- or sugar modified ONs.

The effect of zinc and titanium on the structure of calcium-sodium phosphate based glass

An array of different structural probes has been used to define the effect of adding Zn and Ti to a sodium-calcium phosphate glass. X-ray absorption spectroscopy at the Zn K-edge suggests that the Zn atoms occupy mixed (4- and 6-fold) sites within the glass matrix. X-ray diffraction reveals a feature at 2.03 angstrom that develops with the addition of Zn and Ti and is consistent with Zn-O and Ti-O near-neighbour distances. Neutron diffraction is used to resolve two distinct P-O distances and highlights the decrease in P center dot center dot center dot P coordination number from 2.0 to 1.7 as the Ti metal concentration rises, which is attributed to the O/P fraction moving away from the metaphosphate value of 3.0 to 3.1 with the addition of Ti. Other correlations, such as those associated with CaO(x) and NaO(x) polyhedra, remain largely unaffected. These results suggest that the network forming P center dot center dot center dot P correlation is most disrupted, with the disorder parameter rising from 0.07 to 0.10 angstrom with the additional modifiers. Zn appears to be introduced into the network as a direct replacement for Ca and causes no structural variation over the composition range studied.

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.