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At least 1,567 records · Page 87
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Three-dimensional microstructural characterization of bulk plutonium and uranium metals using focused ion beam technique

Nuclear forensics requires accurate quantification of discriminating microstructural characteristics of the bulk nuclear material to identify its process history and provenance. Conventional metallographic preparation techniques for bulk plutonium (Pu) and uranium (U) metals are limited to providing information in two-dimension (2D) and do not allow for obtaining depth profile of the material. In this contribution, use of dual-beam focused ion-beam/scanning electron microscopy (FIB-SEM) to investigate the internal microstructure of bulk Pu and U metals is demonstrated. Our results demonstrate that the dual-beam methodology optimally elucidate microstructural features without preparation artifacts, and the three-dimensional (3D) characterization of inner microstructures can reveal salient microstructural features that cannot be observed from conventional metallographic techniques. As a result, examples are shown to demonstrate the benefit of FIB-SEM in improving microstructural characterization of microscopic inclusions, particularly with respect to nuclear forensics.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Fabrication and thermophysical property characterization of UN/U 3 Si 2 composite fuel forms

High uranium density composite fuels composed of UN and U 3 Si 2 have been fabricated using a liquid phase sintering route at temperatures between 1873 K and 1973 K and spanning compositions of 10 vol% to 40 vol% U 3 Si 2 . Microstructural analysis and phase characterization revealed the formation of an U-Si-N phase of unknown structure. Microcracking was observed in the U-Si portion of the composite microstructure that likely originates from the mismatched coefficient of thermal expansion between the UN and U 3 Si 2 leading to stresses on heating and cooling of the composite. Thermal expansion coefficient, thermal diffusivity, and thermal conductivity were characterized for each of the compositions as a function of temperature to 1673 K. Hysteresis is observed in the thermal diffusivity for the 20 vol% through 40 vol% specimens between room temperature and 1273 K, which is attributed to the microcracking in the U-Si phase. Thermal conductivity of the composites was modeled using the MOOSE framework based on the collected microstructure data. In conclusion, the impact of irradiation on thermal conductivity was also simulated for this class of composite materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Characterization of mechanical properties and deformation behavior of highly irradiated 316L stainless steel from target modules at the Spallation Neutron Source using digital image correlation analysis

Tensile specimens with irradiation doses ranging from approximately 0.7 to 7.6 displacements per atom (dpa) were fabricated from 316L samples removed from Spallation Neutron Source (SNS) target vessels after service. Tensile tests were performed in conjunction with digital image correlation (DIC) characterization, which permitted detailed analysis of the strain distribution and deformation behavior of the specimen gauge sections during testing. The results show, while considerable hardening (500–700 MPa increase in yield strength) occurred in the 316L SNS target material with increasing dose, appreciable ductility (19–23% total elongation) remained in the material after irradiation to 7.6 dpa in the mixed neutron/proton environment of the SNS target region. The DIC data showed the strain distribution and deformation behavior of all irradiated specimens were nonuniform during testing. Strain localization in the form of deformation bands or “hotspots” was observed during testing, and in some specimens, the bands propagated as deformation waves along the gauge section. The “traveling wave” deformation behavior affected the amount of elongation each specimen achieved, and the scatter in the elongation data was attributed to the large variation in deformation behavior observed among different specimens. Bands of localized strain, or deformation bands, oriented at specific angles were observed in two-dimensional plots of the strain distribution in the gauge sections of some specimens. Overall, this paper describes the experimental procedures, results, and deformation behavior of tensile specimens from SNS targets after service and illustrates the value of DIC characterization during tensile testing of irradiated materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Characterization of zirconium carbide microspheres synthesized via internal gelation

Microspheres of zirconium carbide with grain size 40-320 nm were synthesized using internal gelation techniques and characterized by scanning electron microscopy, synchrotron X-ray diffraction, and neutron total scattering. Compared with a polycrystalline benchmark ZrC sample prepared by plasma vapor phase deposition, the microspheres display lower variance in grain size and considerably lower microstrain representative of a more homogenous internal microstructure. However, excess carbon was present in the microspheres, evident in both the X-ray and neutron diffraction data as well as a corresponding hypostoichiometric ZrC phase. Furthermore, the excess carbon phase is assumed to be pockets of carbon that remained unreacted through the combined internal gelation and subsequent carbothermic reduction synthesis process. Atomic-scale structural characterization with neutron PDF analysis confirmed the presence of localized nano-sized domains of graphite-like carbon material.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Postirradiation characterization of palladium as an additive for fuel cladding chemical interaction mitigation in metallic fuel

This work describes the microstructural and elemental characterization of irradiated metallic fuels containing palladium as an additive. The use of additives has been proposed to control Fuel-Cladding Chemical Interaction (FCCI) and thus to promote higher fuel utilization (i.e., higher burnup). In this work, Pd has been investigated as a potential additive to metallic fuel to bind lanthanides, impeding their migration and attack on the cladding. The influence of Pd on the microstructure, chemistry and performance of metallic fuel has been characterized via scanning electron microscopy for two metallic fuel designs—namely, annular and solid fuel. Pd was observed to play an important role in the chemistry of the fuel. Indeed, the addition of Pd leads to the formation of new phases. Pd was detected to combine not only with the lanthanides, as intended, but also with Zr, a main element of the fuel matrix. While Pd proved to be effective in preventing lanthanide migration and their attack on the cladding, the Pd-Zr compound may potentially lead to other unexpected fuel-performance issues, such as the formation of low-melting point phases and increased unalloyed U available for FCCI interaction with Fe in the cladding. Even the increase of Zr to 13wt%. did not completely mitigate this adverse phenomenon generated by the Pd-Zr interaction. Furthermore, the efficacy of using this additive needs further investigation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Characterization of modeling and experimental data inconsistencies from burst testing for high-burnup commercial fuel rod applications

Fuel fragmentation, relocation, and dispersal are some of the largest issues remaining in the nuclear industry before rod-average burnup can be increased beyond 62 GWd/tU. The issue is primarily related to the potential for fuel to be dispersed into the reactor primary system, which may increase public risk. One way to prevent dispersal is to avoid cladding burst. The objective of this work is to support the high burnup safety case by evaluating cladding burst under high-burnup, full-length fuel rods and to identify uncertainties that could improve model predictions. The results of this analysis will evaluate realistic, prototypic loss-of-coolant accident (LOCA) conditions; support future cladding burst test designs; and inform the development of mechanistic material models. Realistic high-burnup operating conditions were implemented in the BISON fuel performance code to simulate steady-state and LOCA transient fuel rod evolution to the point at which cladding burst occurred. Parametric studies are performed to assess code response to changes in rod internal pressures and heating rates. Results were compared with simulated LOCA experiments to identify inconsistencies between commercial fuel rod analysis and experimental validation. The representative full-length fuel rod LOCA simulation results did not agree with cladding burst tests. Cladding burst tests indicated burst occurring well below (100–150 °C) those calculated in the full-length fuel rod LOCA analysis. Further investigation indicated that the cladding burst tests do not appear to be representative for full-length fuel rods. The inconsistency investigated in this work showed that the differences between the BISON simulation and the experiment's cladding burst conditions arise from an incomplete characterization of the cladding surface temperature, detailed rodlet characterization, lack of cladding strain measurements, and uncertainty in the cladding creep and failure models.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Three-dimensional microstructural characterization of FBR MOX fuel and the contribution of microstructural features to the thermal conductivity of the fuel

Combination of microstructural characterization, property measurements, and phase field modeling is used to investigate fast breeder reactor (FBR) mixed oxide (MOX) fuel irradiated to burnup of 13.7% fissions per initial metal atom (FIMA). Here, the fuel was characterized at different radial locations, which revealed that grey phase can be present in the central region if it nucleates on five metal precipitates (FMPs). In addition, in the mid-radial region FMPs do not diffuse out of the region once formed and the size of Pd–Te precipitates is dictated by the porosity present in the region. Thermal conductivity measurements were conducted as a function of radial location and the microstructure of the fuel was correlated with the observed trend. Reconstructions of the 3D solid and gaseous fission product structures in different regions of the fuel were used to simulate the effective thermal conductivity (ETC) of the respective regions and determine which microstructural feature has the strongest impact on thermal conductivity. Based on conducted assessment, FMPs and Pd-Te precipitates improve local conductivity of central and mid-radial regions even in the presence of grey phase, but defects are primary contributor to the degradation of thermal conductivity on the periphery of the fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Characterization of the radial microstructural evolution in LWR UO 2 using electron backscatter diffraction

Studies on high burnup UO 2 subjected to loss-of-coolant accident conditions have shown that restructured regions of the fuel are susceptible to pulverization and eventual dispersal. Due to a lack of pre-test characterization, the distinct microstructural features rendering the fuel prone to fragmentation remain ambiguous. Four samples of commercially irradiated light-water reactor UO 2 have been characterized utilizing electron backscatter diffraction to assess the susceptible microstructure. The microscopy focused on determining the burnup and temperature conditions responsible for the formation of the different microstructural regions where the regions were denoted as the high-burnup structure (HBS), HBS transition, mid-radial, restructured central, and central region. Previous works have outlined the specific conditions required for the restructuring of the microstructure into the HBS, but the conditions responsible for the restructuring in the central region of the fuel are not well understood. The four analyzed samples confirm a burnup threshold of 61 GWd/tU, and an unknown temperature range is needed to facilitate the formation of the restructured central region. In conclusion, additional fuel performance evaluations are needed to quantify the temperature range promoting restructuring in the central region.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Formation and characterization of hydride rim structures in Zircaloy-4 nuclear fuel cladding tubes

Zirconium alloy tubes used as nuclear fuel cladding are subject to oxidation and subsequent hydrogen pickup during their long service in commercial light water reactors. The hydrogen picked up in the cladding can precipitate as a brittle hydride rim feature on the cladding outer surface. Here, to better understand the effect of hydride rims on the fracture behavior of stress-relieved zirconium alloy cladding tubes, a procedure to produce these rim-like structures has been developed and is described herein. Extensive characterization of the ‘as hydrided’ tubes is performed. The hydrogen charging apparatus consists of a tube furnace with a quartz chamber that is connected to a vacuum pump as well as a bottle of pure hydrogen gas. The charging station uses a static charge of hydrogen as opposed to a flowing gas. The chief advantage of this approach is the ability to monitor the pressure drop in the hydriding chamber and correlate this pressure drop to a known rate of hydrogen pickup in the cladding tube. It was found that the hydrogen partial pressure, metal temperature, and surface treatment all clearly played a role in whether a hydride rim was formed. Extensive characterization of the hydride rims shows they consist of needle like platelets of δ phase hydrides (ZrH1.66) oriented in the circumferential direction with a radial spacing of several microns in a sandwich-like structure.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2015

Characterizing the Li–Li 7 La 3 Zr 2 O 12 interface stability and kinetics as a function of temperature and current density

The stability and kinetics of the Li–Li 7 La 3 Zr 2 O 12 (LLZO) interface were characterized as a function of temperature and current density. Polycrystalline LLZO was densified using a rapid hot-pressing technique achieving 97 ± 1% relative density, and <10% grain boundary resistance; effectively consisting of an ensemble of single LLZO crystals. It was determined that by heating to 175 °C, the room temperature Li-LLZO interface resistance decreases dramatically from 5822 (as-assembled) to 514 Ω cm 2 ; a > 10-fold decrease. In characterizing the maximum sustainable current density (or critical current density – CCD) of the Li-LLZO interface, several signs of degradation were observed. In DC cycling tests, significant deviation from Ohmic behavior was observed. In post-cycling tests, regions of metallic Li were observed; propagating parallel to the ionic current. For the cells cycled at 30, 70, 100, 130 and 160 °C, the CCD was determined to be 50, 200, 800, 3500, and 20000 μA cm –2 , respectively. As a result, the relationships and phenomena observed in this work can be used to better understand the Li-LLZO interface stability, enabling the use of batteries employing Li metal anodes.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Hydraulic characterization of a fault zone from fracture distribution

A quantitative assessment of how faults control the migration of geofluids is critical in many areas of geosciences. Here we integrated geological fieldwork, quantitative analysis of the fractures distribution and numerical modeling to build a geometrical representation of a fault zone and to characterize its hydraulic properties. Our target is a fault located in the Majella Mountain (Italy). We collected 21 scan lines across the fault profile in order to characterize its architecture. The numerical modeling of the fracture network of the damage zones and their hydraulic parameters was performed using both commercial (Move ® ) and open source software (dfnWorks and PFLOTRAN). Move ® was used to build a representative model of the fault zone using fracture spacing as a proxy, and to model the hydraulic parameters of the different fault domains. dfnWorks and PFLOTRAN were employed to infer the hydraulic parameters of the damage zones of the fault and then upscale these properties to an equivalent continuum domain, suitable for fluid flow simulations through the whole fault zone. Our findings show how even in a relatively small area it is possible to describe changes in terms of hydraulic properties of a fault zone and to build models capable to represent these variations.

58 GEOSCIENCES↗
DOE OSTI2015

Synthesis and characterization of anionic/nonionic surfactant-interceded iron-doped TiO{sub 2} to enhance sorbent/photo-catalytic properties

We investigated the synthesis, characterization, and application of surfactant-interceded Fe nanoparticle-doped TiO{sub 2} (TiO{sub 2}/Fe-S1 and TiO{sub 2}/Fe-S2) that were used as adsorbents and photo-catalysts for the removal of As(V) ions from aqueous media. Two types of surfactant (anionic (sodium dodecyl sulfate), S1 and non-ionic (Triton X-100), S2) were used to obtain the separation and mono-dispersion of Fe(III) ions in the reaction solution. The nanocomposites were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), UV–vis, scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX) and elemental mapping analysis before and after As(V) removal. The Langmuir capacities (q{sub e}, mg/g) of the sodium dodecyl sulfate (SDS) and Triton X-100 interceded nanocomposites (TiO{sub 2}/Fe-S1 and TiO{sub 2}/Fe-S2, respectively) for arsenic removal were determined to be 65.79 and 50.76 mg/g, respectively, in aqueous media with As(V) concentration ranges of 0–10 mg/L at pH 6.5. - Highlights: • Fe(III) doped TiO{sub 2} nanocomposite was prepared with surfactant. • Anionic surfactant SDS enhanced the transfer of Fe(III) ions to TiO{sub 2}. • Surfactant-interceded nanocomposite enhanced As(V) removal. • Arsenic removal efficiency was as follows: dark phase>visible phase>UV region.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synthesis and characterization of La{sub 0.6}Sr{sub 0.4}Fe{sub 0.8}Cu{sub 0.2}O{sub 3−δ} oxide as cathode for Intermediate Temperature Solid Oxide Fuel Cells

Nanocrystalline La{sub 0.6}Sr{sub 0.4}Fe{sub 0.8}Cu{sub 0.2}O{sub 3−δ} (LSFCu) material was synthetized by combustion method using EDTA as fuel/chelating agent and NH{sub 4}NO{sub 3} as combustion promoter. Structural characterization using thermodiffraction data allowed to determine a reversible phase transition at 425 °C from a low temperature R-3c phase to a high temperature Pm-3m phase and to calculate the thermal expansion coefficient (TEC) of both phases. Important characteristics for cathode application as electronic conductivity and chemical compatibility with Ce{sub 0.9}Gd{sub 0.1}O{sub 2−δ} (CGO) electrolyte were evaluated. LSFCu presented a p-type conductor behavior with maximum conductivity of 135 S cm{sup −1} at 275 °C and showed a good stability with CGO electrolyte at high temperatures. This work confirmed that as prepared LSFCu has excellent microstructural characteristics and an electrical conductivity between 100 and 60 S cm{sup −1} in the 500–700 °C range which is sufficiently high to work as intermediate temperature Solid Oxide Fuel Cells (IT-SOFCs) cathode. However a change in the thermal expansion coefficient consistent with a small oxygen loss process may affect the electrode-electrolyte interface during fabrication and operation of a SOFC. - Graphical abstract: Nanocrystalline La{sub 0.6}Sr{sub 0.4}Fe{sub 0.8}Cu{sub 0.2}O{sub 3−δ} was prepared by gel combustion and characterized by X-ray thermodiffraction and its conductivity was determined. The phase shows a reversible rhombohedral to cubic structural phase transition at 425 °C and a semiconductor to metallic phase transition at 275 °C. - Highlights: • LSFCu was prepared by gel combustion route using EDTA and NH{sub 4}NO{sub 3}. • LSFCu shows a reversible phase transition at 425 °C from R-3c to Pm-3m phase. • The sample has a maximum conductivity value of 135 S cm{sup −1} at 275 °C. • LSFCu shows a good chemical compatibility with CGO at 900 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

High-temperature, high-pressure hydrothermal synthesis, characterization, and structural relationships of mixed-alkali metals uranyl silicates

Three mixed-alkali metals uranyl silicates, Na{sub 3}K{sub 3}[(UO{sub 2}){sub 3}(Si{sub 2}O{sub 7}){sub 2}]·2H{sub 2}O (1), Na{sub 3}Rb{sub 3}[(UO{sub 2}){sub 3}(Si{sub 2}O{sub 7}){sub 2}] (2), and Na{sub 6}Rb{sub 4}[(UO{sub 2}){sub 4}Si{sub 12}O{sub 33}] (3), have been synthesized by high-temperature, high-pressure hydrothermal reactions at 550 °C and 1440 bar, and characterized by single-crystal X-ray diffraction, photoluminescence, and thermogravimetric analysis. Compound 1 and 2 are isostructural and contain layers of uranyl disilicate. The smaller cation, Na{sup +}, is located in the intralayer channels, whereas the larger cations, K{sup +} and Rb{sup +}, and water molecule are located in the interlayer region. The absence of lattice water in 2 can be understood according to the valence-matching principle. The structure is related to that of a previously reported mixed-valence uranium(V,VI) silicate. Compound 3 adopts a 3D framework structure and contains a unique unbranched dreier fourfold silicate chain with the structural formula {uB,4"1_∞}[{sup 3}Si{sub 12}O{sub 33}] formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si. The connectivity of the Si atoms in the Si{sub 12}O{sub 33}{sup 18−} anion can be interpreted on the basis of Zintl–Klemm concept. Crystal data for compound 1: triclinic, P-1, a=5.7981(2) Å, b=7.5875(3) Å, c=12.8068(5) Å, α=103.593(2)°, β=102.879(2)°, γ=90.064(2)°, V=533.00(3) Å{sup 3}, Z=1, R1=0.0278; compound 2: triclinic, P-1, a=5.7993(3) Å, b=7.5745(3) Å, c=12.9369(6) Å, α=78.265(2)°, β=79.137(2)°, γ=89.936(2)°, V=546.02(4) Å{sup 3}, Z=1, R1=0.0287; compound 3: monoclinic, C2/m, a=23.748(1) Å, b=7.3301(3) Å, c=15.2556(7) Å, β=129.116(2)°, V=2060.4(2) Å{sup 3}, Z=2, R1=0.0304. - Graphical abstract: Three mixed-alkali metals uranyl silicates were synthesized under hydrothermal conditions at 550 °C and 1400 bar and structurally characterized by single-crystal X-ray diffraction. Two of them have a layer structure with the alkali metal cations within and between the layers. The third one adopts a 3D framework structure and contains a unique unbranched dreier fourfold silicate chain formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si. - Highlights: • Three new mixed-alkali metals uranyl silicates were synthesized by high-T, high-P hydrothermal method and structurally. • Two compounds adopt a layer structure and the third one has a 3D framework structure. • The 3D framework structure contains a unique unbranched dreier fourfold silicate chain formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Synthesis, structure, and characterization of two new bismuth(III) selenite/tellurite nitrates: [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) and [Bi(TeO{sub 3})](NO{sub 3})

Two new bismuth(III) selenite/tellurite nitrates, [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) and [Bi(TeO{sub 3})](NO{sub 3}), have been synthesized by conventional facile hydrothermal method at middle temperature 200 °C and characterized by single-crystal X-ray diffraction, powder diffraction, UV–vis–NIR optical absorption spectrum, infrared spectrum and thermal analylsis. Both [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) and [Bi(TeO3)](NO3) crystallize in the monoclinic centronsymmetric space group P2{sub 1}/c with a=9.9403(4) Å, b=9.6857(4) Å, c=10.6864(5) Å, β=93.1150(10)° for [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) and a=8.1489(3) Å, b=9.0663(4) Å, c=7.4729(3) Å, β=114.899(2)° for Bi(TeO3)(NO3), respectively. The two compounds, whose structures are composed of three different asymmetric building units, exhibit two different types of structures. The structure of [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) features a three-dimensional (3D) bismuth(III) selenite cationic tunnel structure [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}] {sup 3}{sub ∞} with NO{sub 3}{sup −} anion group filling in the 1D tunnel along b axis. The structure of [Bi(TeO{sub 3})](NO{sub 3}) features 2D bismuth(III) tellurite [Bi(TeO{sub 3}){sub 2}]{sup 2}{sub ∞} layers separated by NO{sub 3}{sup −} anion groups. The results of optical diffuse-reflectance spectrum measurements and electronic structure calculations based on density functional theory methods show that the two compounds are wide band-gap semiconductors. - Graphical abstract: Two novel bismuth{sup III} selenite/tellurite nitrates [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) with 3D tunnel structure and [Bi(TeO{sub 3})](NO{sub 3}) with 2D layer structure have been firstly synthesized and characterized. Display Omitted - Highlights: • Two novel bismuth{sup III} nitrates [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) and [Bi(TeO{sub 3})](NO{sub 3}) were firstly synthesized. • The two compounds were wide band-gap semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Phase equilibria in the NaF-CdO-NaPO{sub 3} system at 873 K and crystal structure and physico-chemical characterizations of the new Na{sub 2}CdPO{sub 4}F fluorophosphate

Isothermal sections of the diagram representing phase relationships in the NaF-CdO-NaPO{sub 3} system have been investigated by solid state reactions and powder X-ray diffraction. This phase diagram investigation confirms the polymorphism of the NaCdPO{sub 4} side component and the structure of the ß high temperature polymorph (orthorhombic, space group Pnma and unit cell parameters a=9.3118(2), b=7.0459(1), c=5.1849(1) Å has been refined. A new fluorophosphate, Na{sub 2}CdPO{sub 4}F, has been discovered and its crystal structure determined and refined from powder X-ray diffraction data. It exhibits a new 3D structure with orthorhombic symmetry, space group Pnma and unit cell parameters a=5.3731(1), b=6.8530(1), c=12.2691(2) Å. The structure is closely related to those of the high temperature polymorph of the nacaphite Na{sub 2}CaPO{sub 4}F and the fluorosilicate Ca{sub 2}NaSiO{sub 4}F but differs essentially in the cationic repartition since the structure is fully ordered with one Na site (8d) and one Cd site (4c). Relationships with other Na{sub 2}M{sup II}PO{sub 4}F (M{sup II}=Mg, Ca, Mn, Fe, Co, Ni) have been examined and the crystal-chemical and topographical analysis of these fluorophosphates is briefly reviewed. IR, Raman, optical and {sup 19}F, {sup 23}Na, {sup 31}P MAS NMR characterizations of Na{sub 2}CdPO{sub 4}F have been investigated. - Graphical abstract: The structure of the compound Na{sub 2}CdPO{sub 4}F, discovered during the study of the phase relationships in the NaF-CdO-NaPO{sub 3} system, has been determined and compared with other Na{sub 2}M{sup II}PO{sub 4}F fluorophosphates. - Highlights: • XRD analysis of the isothermal section of the NaF-CdO-NaPO{sub 3} system at 923 K. • Rietveld refinement of the high temperature polymorph β-NaCdPO{sub 4}. • Crystal structure of the new Na{sub 2}CdPO{sub 4}F fluorophosphate determined from powder XRD. • Crystal structure - composition relationships of Na{sub 2}M{sup II}PO{sub 4}F compounds are reviewed. • IR, Raman, optical and {sup 19}F, {sup 23}Na, {sup 31}P MAS NMR characterizations of Na{sub 2}CdPO{sub 4}F.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Solvothermal syntheses and characterization of three new silver(I)/copper(I)-thioarsenates based on As{sup 2+}/As{sup 3+} ions

Three new silver(I)/copper(I)-thioarsenates KAgAs{sup II}S{sub 2} (1), RbCu{sub 2}As{sup III}S{sub 3} (2) and RbCu{sub 4}As{sup III}S{sub 4} (3) have been solvothermally synthesized and structurally characterized. 1 exhibits a two-dimensional anionic network built up by As−As bond connecting the left- and right-handed helical [AgS{sub 2}]{sup 4−} chains, and represents the first examples of thioarsenates(II). The structure of 2 consists of two kinds of helical [Cu{sub 2}S{sub 3}]{sup 4–} chains linked by the arsenic atoms to form double layers with rubidium ions between the layers. Compound 3 is built up of infinite [Cu{sub 2}S{sub 2}]{sup 2–} chain and layered [Cu{sub 6}As{sub 2}S{sub 6}] linked to form a three-dimensional anionic framework, [Cu{sub 4}AsS{sub 4}]{sup –}, and containing channels in which the rubidium cations reside. The optical properties of 1–3 have been investigated by UV–vis spectroscopy. - Graphical abstract: Three new silver(I)/copper(I)-thioarsenates have been solvothermally synthesized and structurally characterized. 1 represents the first examples of thioarsenates(II) while compounds 2 and 3 possess noncondensed pyramidal AsS{sub 3}{sup 3–} unit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Electroless nickel – phosphorus coating on crab shell particles and its characterization

Being hydrophilic material, crab shell particles have only a limited number of applications. It is, therefore, necessary to modify the surface of the crab shell particles. To make them useful ever for the applications, the main theme we proposed in this article is to utilize crab shell particles (CSP) with the core coated with nickel phosphorus (NiP) as a shell using the electroless coating process. For dealing with serious environmental problems, utilization of waste bio-shells is always an important factor to be considered. Chelating ability of crab shell particles eliminates the surface activation in this work proceeding to the coating process. The functional group, phase structure, microstructure, chemical composition and thermal analysis of CSP and NiP/CSP were characterized using Fourier transform infra-red spectroscopy (FTIR), x-ray diffraction analyzer (XRD), scanning electron microscope (SEM), energy-dispersive x-ray spectroscopy (EDS), and thermogravimetric analysis (TGA). The combination of an amorphous and crystalline structure was exhibited by CSP and NiP/CSP. NiP/CSP has shown a better thermal stability when compared to uncoated CSP. Stability test, adsorption test, and conductivity test were conducted for the study of adsorption behavior and conductivity of the particles. CSP presented a hydrophilic property in contrast to hydrophobic NiP/CSP. NiP/CSP presented a conductivity of about 44% greater compared to the CSP without any fluctuations. - Highlights: • Utilization of crab shell waste is focused on. • NiP coating on crab shell particle is fabricated using electroless process. • Thermal analysis, stability test, adsorption test and conductivity test were done. • Organic matrix of crab shell particle favors the coating process. • Results demonstrate the characterization of CSP core – NiP shell structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗