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At least 1,657 records · Page 92

A Holographic Prism Based on Photo-Thermo-Refractive Glass: Requirements and Possibilities

A technology for multivalued holographic measurement of a plane angle—a holographic prism, which serves as the basis for a device for calibrating the testing tools for navigational equipment under rolling— has been developed. The holographic prism is a miniature sample of photosensitive material, which contains a system of superimposed holographic gratings, and a laser the radiation of which passes through gratings to form a fan of diffracted beams. The fan in a prism based on a calcium fluoride (fluorite) crystal with color centers contained six out-of-plane beams radiating from a region with a hard-to-localize center. This fact hindered calibration of the measure and its application in the testing device. The use of photothermo-refractive glass as a material for preparing a sample and recording a system of holograms in it makes it possible to eliminate the drawbacks of fluorite-based prism. The number of holograms rises up to 21, the fan becomes in-plane, and its center is localized in a small region, with a size of several tenths of the sample thickness (1–2 mm). The fan beams are energetically homogeneous, and each can be identified when using the fan in a testing device.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Do Minor Interactions Trigger Star Formation in Galaxy Pairs?

Abstract We analyze the galaxy pairs in a set of volume limited samples from the Sloan Digital Sky Survey to study the effects of minor interactions on the star formation rate (SFR) and color of galaxies. We carefully design control samples of isolated galaxies by matching the stellar mass and redshift of the minor pairs. The SFR distributions and color distributions in the minor pairs differ from their controls at >99% significance level. We also simultaneously match the control galaxies in stellar mass, redshift and local density to assess the role of the environment. The null hypothesis can be rejected at >99% confidence level even after matching the environment. Our analysis shows a quenching in the minor pairs where the degree of quenching decreases with the increasing pair separation and plateaus beyond 50 kpc. We also prepare a sample of minor pairs with H α line information. We calculate the SFR of these galaxies using the H α line and repeat our analysis. We observe a quenching in the H α sample too. We find that the majority of the minor pairs are quiescent systems that could be quenched due to minor interactions. Combining data from the Galaxy Zoo and Galaxy Zoo 2, we find that only ∼1% galaxies have a dominant bulge, 4%–7% galaxies host a bar and 5%–10% of galaxies show active galactic nucleus (AGN) activity in minor pairs. This indicates that the presence of bulge, bar or AGN activity plays an insignificant role in quenching the galaxies in minor pairs. The more massive companion satisfies the criteria for mass quenching in most of the minor pairs. We propose that the stripping and starvation likely caused the quenching in the less massive companion at a later stage of evolution.

Astronomy & Astrophysics↗

Synthesis and Characterization of Ni{sub 1−x}Cu{sub x}Bi{sub 3} Superconductor

In this paper, we characterized the microstructure and superconducting properties of Cu-doped NiBi{sub 3} samples. The polycrystalline Ni{sub 1−x}Cu{sub x}Bi{sub 3} (0 ≤ x ≤ 0.10) samples were prepared using a solid-state reaction method. The crystal structure and unit cell parameters were determined by Rietveld refinement of powder X-ray diffraction. The data showed that the main phase present corresponded to NiBi{sub 3} without dependence on the Cu concentration, but with small quantities of Ni and Bi. The SEM and AFM measurements revealed that the main phase was inhomogeneous at microscopic level, with Bi richer regions in comparison to other regions. However, Raman spectroscopy results did not show significant changes in the spectra with Cu doping and in different regions of the samples. Another finding was that regardless of Cu doping, the superconducting transition temperature was 4.05–4.06 K.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Data on Cu- and Ni-Si-Mn-rich solute clustering in a neutron irradiated austenitic stainless steel

The data presented in this article is supplementary to the research article “Phase instabilities in austenitic steels during particle bombardment at high and low dose rates” (Levine et al.). Needle-shaped samples were prepared with focused ion beam milling from a 304L stainless steel that was irradiated with fast neutrons (E 0.1 MeV) in the BOR-60 reactor at 318 °C to 47.5 dpa. Atom probe tomography (APT) experiments in voltage mode were then conducted on a Cameca LEAP 5000X HR. Atom position, range, and mass spectrum files after reconstruction with Cameca’s IVAS software are included. Cu- and Ni-Si-Mn-rich solute nanoclusters were identified and analyzed using the Open Source Characterization of APT Reconstructions (OSCAR) program. Python code for OSCAR, information on the program’s underlying algorithm, and sample output files are provided. A proximity histogram of a Ni-Si-Mn-rich cluster and a 1D density/solute concentration profile of a Cu-rich cluster are given to demonstrate OSCAR’s analytical functionalities. The provided APT dataset is valuable for benchmarking phase instabilities in neutron-irradiated austenitic stainless steels that occur at high doses. The OSCAR program can be reused to process other APT data sets where solute nanoclustering is of interest.

42 ENGINEERING↗

Systematic study on the influence of the morphology of α-MoO{sub 3} in the selective oxidation of propylene

A variety of morphologically different α-MoO{sub 3} samples were prepared by hydrothermal synthesis and applied in the selective oxidation of propylene. Their catalytic performance was compared to α-MoO{sub 3} prepared by flame spray pyrolysis (FSP) and a classical synthesis route. Hydrothermal synthesis from ammonium heptamolybdate (AHM) and nitric acid at pH 1–2 led to ammonium containing molybdenum oxide phases that were completely transformed into α-MoO{sub 3} after calcination at 550 °C. A one-step synthesis of α-MoO{sub 3} rods was possible starting from MoO{sub 3}·2H{sub 2}O with acetic acid or nitric acid and from AHM with nitric acid at 180 °C. Particularly, if nitric acid was used during synthesis, the rod-like morphology of the samples could be stabilized during calcination at 550 °C and the following catalytic activity tests, which was beneficial for the catalytic performance in propylene oxidation. Characterization studies using X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy showed that those samples, which retained their rod-like morphology during the activity tests, yielded the highest propylene conversion. - Graphical abstract: Hydrothermal synthesis from MoO{sub 3}·2H{sub 2}O in the presence of HNO{sub 3} led to rod-shaped particles which mainly expose (1 0 0) facets which are the most active surfaces. - Highlights: • Hydrothermal synthesis of MoO3 resulted in either rod or slab shaped particles depending on pH. • At pH<0 rods stable towards calcination and catalytic activity testing were formed. • Rod shaped particles had significantly higher activity than slab shaped ones. • The rod shaped particles mainly expose the (1 0 0) facets which are the most active surfaces. • Total surface area is not main determining factor for catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanical Behavior of UO 2 at Sub-grain Length Scales: Quantification of Elastic, Plastic and Creep Properties via Microscale Testing

Techniques were developed to measure properties at sub-grain scales using depleted Uranium Oxide (d-UO2) samples heat-treated to obtain different grain sizes and oxygen stoichiometries, through three main tasks: 1) sample processing and characterization, 2) microscale and conventional testing and 3) modeling. Grain size and crystallography were characterized using Scanning Electron Microscopy (SEM), in conjunction with Electron Backscattering Diffraction (EBSD) and Electron Channeling Contrast Imaging (ECCI). Grains were then carefully selected based on their crystallographic orientations to perform ex-situ micromechanical tests with samples machined via Focused Ion Beam (FIB), with emphasis on micro-cantilever bending. These experiments were performed under controlled atmospheres, to insure stoichiometry control, at temperatures up to 700 °C and allowed measurements involving elastic (effective Young’s modulus), plastic (critical resolved shear stresses) and creep (creep strain rates) behavior. Conventional compression experiments were performed simultaneously to compare with the ex-situ measurements and study potential size effects. Modeling was implemented using anisotropic elasticity and inelastic constitutive relations for plasticity and creep based on kinematics and kinetics of dislocation glide that account for the effects of crystal orientation, and stress. The models will be calibrated and validated using the experimental data. This project provided insight on correlations among stoichiometry, crystallography and mechanical behavior in advanced oxide fuels, provided valuable experimental data to validate and calibrate mesoscale fuel performance codes and also a framework to measure sub-grain scale mechanical properties that should be suitable for use with irradiated samples due to small volumes required. The goals and metrics of the ongoing study of thermo-mechanical behavior in depleted uranium dioxide (d-UO 2 ) outlined in this project have been concluded successfully, resulting in: 1) the successful fabrication, processing, and characterization of large-grained samples with various orientations (up to and including single crystals) having stoichiometric and hyper-stoichiometric O/U ratios; 2) formulation, calibration, and validation of a crystal plasticity constitutive model to describe the creep deformation of UO 2 at the sub-grain length scale (single crystal level) at intermediate temperatures; 3) the successful calibration of a crystal plasticity constitutive model to describe the elasto-plastic deformation of microcantilever beams, also at moderate temperatures. Samples were prepared from natural uranium oxide powder of production-quality provided by Areva. The powder was pressed in a die to a pressure of 100 MPa to produce green pellets with no sintering aids, lubricants, or any other additives. The green pellets were then heated up to 1700 °C under ultra-high purity argon atmosphere (~1 ppm O2). The atmosphere was then changed to 79% Argon, 21% O 2 and the temperature was held at 1700 °C for 2 hours to sinter the pellets under oxidative conditions [1] that are known to increase grain growth kinetics in UO 2 [2]. Samples were then cooled down under Ar-4%H2 atmosphere to reduce the samples back to stoichiometric UO 2 . For macro-scale procedures, testing of UO 2 samples with large grains was performed at 1200 °C using a modified load frame capable of applying dead-weight loads to ensure constant stress conditions, while displacement of the sample produced by the applied load was measured with high precision micrometers to obtain strains. Stress steps were used during testing and the strains were monitored to measured creep strain rates under steady state for each level of stress used, so that stress exponents could be obtained. The results of the mechanical testing, along with sample geometry and crystal orientation of the grains in the samples, as well as post-test sample characterization were used to formulate a viscoplastic model to account for steady state (stage II) creep behavior, along with basic assumptions from crystal plasticity and kinematic constraints due to testing fixtures. In the micro-scale, testing of microcantilever beams at temperatures ranging from 25 to 570 °C was performed in-situ with a scanning electron microscope with a special attachment to apply load and measure displacement while the samples were at temperature. The load-displacement curves obtained showed linear behavior before fracture for all temperatures attempted except 570 °C, where clear deviations from non-linearity were observed before fracture. These deviations were consistently observed for all samples tested for a given orientation. A viscoplastic model was used to account for the presence of inelastic strain, along with basic assumptions from crystal plasticity and beam theory. These models were kept as simple as possible, and results from tests performed in a set of samples with a given crystal orientation were used to calibrate the material constants for the model, while results from a different sample set were then used for validation, thus satisfying the conditions of all main tasks within the parameters of this project. Details of these efforts are outlined in this report.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Characterization of borate glasses doped with copper oxide for optical application

Borate glasses having the formula x CuO–(50 − x)B{sub 2}O{sub 3}–30Na{sub 2}O–20ZnO where x = 0, 0.2, 0.5, 1, 4 and 7 mol% were investigated. The samples were prepared using the conventional melt-quenching technique. Physical properties were studied such as; X-ray diffraction, FTIR spectra, and UV–visible transmission. The optical basicity, average electro negativity have been estimated. The estimated optical basicity, unlike electron negativity, exhibits an increase with increasing the CuO content. FTIR spectra show that BO{sub 4} ratio decreases with increasing CuO content leading to the formation of non-bridging oxygen’s. Some optical parameters such as the optical band gap, band tail width, crystal field strength and the UV and NIR cut off were determined. The transmission spectrum revealed that the glassy samples containing high content of copper oxide behave as bandpass filters at higher content. The characterized parameters of these filters were found to be highly affected by the addition of CuO. In these glasses the broad absorption band observed at the wavelength 550 nm is characterized by the existence of Cu{sup 2+} ions. The optical absorption and ESR studies suggest that, the Cu-ions exist in the Cu{sup 2+} state and act as modifiers by increasing the degree of disorder in the glass network. Hence, the present system behaves as a bandpass filter in the ultraviolet–visible region.

36 MATERIALS SCIENCE↗

Synthesis and characterization of magnetic ionic liquids containing multiple paramagnetic lanthanide and transition metal centers and functionalized diglycolamide ligands

Magnetic ionic liquids (MILs) containing paramagnetic centers have gained widespread recognition as sustainable solvents due to their ability to respond to an external magnetic field. The physico-chemical properties of MILs are dependent on the choice of anion/cation ligands and metal centers; the search for highly tunable ligands and precursors that can confer favorable characteristics, such as low viscosity, is ongoing. Diglycolamides employed as cationic ligands have been previously shown to form hydrophobic MILs that can simultaneously incorporate multiple lanthanide metal centers in both the anion/cation. Despite their enhanced magnetic susceptibility, the effect of diglycolamide chemical structure modifications on the physico-chemical properties of MILs has not been thoroughly studied. Additionally, the possibility of forming diglycolamide-based MILs with popularly employed transition metals has not been investigated and combinations that can simultaneously embed two different types of metal centers in both the anion/cation have not been explored. In this study, thirty (30) MILs comprised of lanthanide and transition metals were synthesized by examining their chelation to both straight-chained and branched diglycolamides. Here, transition metal-based MILs were found to possess high thermal stabilities up to 235 °C compared to 192 °C for those comprised of lanthanides. While MILs comprised of rare-earth metal centers exhibited the lowest viscosities, substituting lanthanides with transition metals in just the anion or cation resulted in enhanced thermal stability and reduced viscosity. The effective magnetic moment for these MILs varied between 4.71 and 21.08 µ B and was much higher compared to all previous classes of MILs prepared using the same metals. Results from this study explore all possible modifications that can be made to these MILs in an effort to demonstrate their structural tunability, which is often highly desirable in various applications, including organic synthesis and chemical separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magneto-optical studies of SrGa{sub 0.7} Co{sub 0.3} O{sub 3−δ} perovskite thin films with embedded cobalt nanoparticles

Sr(Ga{sub 0.7} Co{sub 0.3})O{sub 3−δ}/Co perovskite/metal thin films have been systematically studied by means of Faraday and Kerr magneto-optical spectroscopies. The samples were prepared by pulsed laser deposition on (001) (LaAlO{sub 3}) {sub 0.3}(Sr{sub 2}AlTaO{sub 6}) {sub 0.7} (LSAT) and Si substrates, and grew as a perovskite matrix containing approximately 6% by volume of embedded metallic Co nanoparticles with diameter less than 20 nm, which were distributed throughout the film and at the film-substrate interface. The film thickness ranged from 130 to 310 nm. The perovskite matrix was single crystal on LSAT and polycrystalline on Si. The magneto-optical spectroscopy was carried out in both Faraday and Kerr configurations in the photon energy range from 0.5 to 5 eV in magnetic fields sufficient for sample saturation, showing a strong thickness dependence of the magneto-optical effect. This dependence was attributed to the different metallic Co content, nanoparticle size, and accumulation at the film-substrate interface.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Application of Raman Spectroscopy to Determine Uranium Content in ADUN Solution

The work presented in this report is part of the ongoing efforts to address the nuclear material control and accounting needs for advanced reactor fuel fabrication facilities. This work was supported by the Materials Protection, Accounting, and Control Technologies (MPACT) program under the US Department of Energy Office of Nuclear Energy‘s Nuclear Fuel Cycle and Supply Chain program. The activities and engagements under the MPACT program are designed to support a robust US civilian nuclear energy enterprise. In the work described in this report, we supported MPACT objectives by developing measurement techniques that could be used for material accounting and process monitoring and by working with industry partners to identify existing gaps and areas for improvement. Oak Ridge National Laboratory has been working with commercial tristructural isotropic (TRISO) fuel fabricators such as Standard Nuclear to develop technology for rapid and cost-effective uranium content assessment. This work has focused on demonstrating advanced measurement techniques (e.g., Raman spectroscopy) that can be used for rapid, reliable, and cost-effective routine measurements of uranium content in feed solutions and liquid waste streams as well as for monitoring in-line process measurements and product streams. Specifically, this report explores techniques for accurately determining uranium content in acid-deficient uranyl nitrate (ADUN) solutions and detecting low uranium concentrations in ammonia solutions. Developing such measurement techniques will benefit TRISO fuel fabrication facilities, facilities involved in other parts of the fuel cycle that require online monitoring of aqueous solutions, and potentially molten salt fuel reactors. This work supports developing Raman spectroscopy procedures to determine uranium concentrations in ADUN solutions, which are used as feedstock in the sol–gel process for creating TRISO fuel. Some additional benefits of using Raman spectroscopy for uranium quantification in fabrication facilities include enabling online monitoring of the chemical process, which would provide near real-time feedback; eliminating the need for sample transfers, preparation, or dilution; providing nondestructive measurements; and user friendliness. In this fiscal year, FY25, we determined the identity of the unknown Raman band at approximately 853 cm−1 that was discovered in ADUN Raman spectra in FY24, created calibration curves and determined uranium concentrations of two ADUN solutions, and compared the Raman results to results obtained from inductively coupled plasma mass spectrometry and Davies–Gray titration. Furthermore, we have identified focus areas for experimentation in future fiscal years. A key result is that the accuracy of using Raman can provide accuracy comparable to destructive analysist techniques, With a well-developed calibration curve, using standards and a large number of samples (more than five samples), uncertainty on the order of 1%–3% is achievable. Given that the uncertainties achieved by Raman spectroscopy were on the order of the uncertainties achieved using ICP-MS, we conclude that with a well-developed procedure Raman spectroscopy can be used to determine uranium concentrations in ADUN solutions for NMC&A applications. The benefits of such an approach are that the time and effort will be less than that of comparable destructive analysis techniques, with approximately the same level of technical expertise. This will be attractive to operators of fuel fabrication facilities as it will lower costs and improve efficiencies.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The influence of silanized nano-SiO{sub 2} on the hydration of cement paste: NMR investigations

It is known that by adding a small amount of nanoparticles to the cement-based materials a strong influence on the workability, strength and durability is obtained. These characteristics of the material are fundamentally determined by the hydration process taking place after mixing the cement grains with water. In the present study the influence introduced by the addition of nano-silica with silanized surfaces on the hydration process was investigated using low-field nuclear magnetic resonance (NMR) relaxometry. The cement samples were prepared using gray cement at a water-to-cement ratio of 0.4 and a 5% addition of nanosilica. The surface of the nanoparticles was modified using a coating of Silane A174. The cement pastes were monitored during their standard curing time of 28 days. It was established that, by using unmodified nanosilica particles, an acceleration of the hydration process takes place as compared with the pure cement paste. On the other side, by adding silanized nanoparticles, the dormancy stage significantly extends and the hydration process is slower. This slowing down process could enhance the mechanical strength of cement based materials as a result of a better compaction of the hydrated samples.

36 MATERIALS SCIENCE↗

Crystal development during carbonation of lime-based mortars in different environmental conditions

Highlights: • High CO{sub 2} and DiloCarb® treatment favour advanced carbonation and self-healing. • In the lime mortar without ceramics, channel type pores occur in the aggregate border. • In the lime mortars with ceramics, vug type pores are produced in the binder during kneading. • The formation of tabular CaCO{sub 3} polymorphs caused an increase in stress leading to microshrinkage cracks. • The use of a ceramic provoked dissolution and then re-precipitation of more stable polymorphs. - Abstract: This study examines crystal development during the carbonation of lime mortars according to the additives used and curing conditions. Two types of samples were prepared, one with sand and the other one additionally including Roman ceramics. These mortars were cured: 1) by spraying with a carbonation accelerator product under laboratory conditions; 2) in a climate chamber under 20 °C, 60% relative humidity, and 1600 ppm CO{sub 2}; and 3) under laboratory conditions as controls. Polarized light microscopy, SEM-EDS and XRD were used at 28, 90, 120 and 180 days to monitor the carbonation process. Observations indicate the development of different CaCO{sub 3} polymorphs, which appeared as metastable phases. The early nucleation of a well-defined calcite phase as the most stable CaCO{sub 3} polymorph was only identified in the chamber-cured samples. Differences in the pore network were observed depending on the composition and morphology of the mortar components and the environmental curing conditions.

36 MATERIALS SCIENCE↗

Core-shell structured α-Fe2O3@CeO2 heterojunction for the enhanced visible-light photocatalytic activity

Highlights: • CeO{sub 2}–coated α-Fe{sub 2}O{sub 3} sample was prepared via a hydrothermal route. • α-Fe{sub 2}O{sub 3}@CeO{sub 2} presented the excellent photocatalytic activity and stability. • The heterojunction interface facilitated the separation of electron-hole pairs. • Ce{sup 4+}/Ce{sup 3+} redox couple promoted the efficient electron transfer. - Abstract: CeO{sub 2}-coated α-Fe{sub 2}O{sub 3} nanoparticles (α-Fe{sub 2}O{sub 3}@CeO{sub 2}) with the enhanced photocatalytic activity were synthesized by a hydrothermal route and performed for the visible light driven photo-degradation of methylene blue (MB). The photocatalytic activity of α-Fe{sub 2}O{sub 3}@CeO{sub 2} is greatly affected by the thickness of CeO{sub 2} shell under the same conditions. The core-shell structured α-Fe{sub 2}O{sub 3}@CeO{sub 2} sample exhibited a narrower band gap energy in comparison to the pure α-Fe{sub 2}O{sub 3} and CeO{sub 2} bulks, leading to the excellent photocatalytic activity and stability for the degradation of MB under visible light irradiation after five cycle times. The core-shell structured α-Fe{sub 2}O{sub 3}@CeO{sub 2} sample presented higher degradation activity than that of the supported 8-Fe/CeO{sub 2} bulks with optimized α-Fe{sub 2}O{sub 3} loading of 8%. It can be ascribed to the Ce{sup 4+}/Ce{sup 3+} redox couple and the heterojunction interfaces of core-shell structured α-Fe{sub 2}O{sub 3}@CeO{sub 2} sample, which can promote the electrons transfer and restrain the photoexcited electron-hole recombination, leading to the excellent degradation activity under visible light irradiation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Composite electrolytes ceramic Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}/glassy Li{sub 2}O-Y{sub 2}O{sub 3}-SiO{sub 2}

Highlights: • We synthesized Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}-x wt% 40.2Li{sub 2}O·5.7Y{sub 2}O{sub 3}·54.1SiO{sub 2} (x = 1–10) composites. • Density of the composite samples is higher than one of the sintered Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}. • The composition with x = 5 has high total conductivity, 2.5 × 10{sup −5} S cm{sup −1} at 25 °C. - Abstract: We have investigated the effect of lithium yttrium-silicate glass 40.2Li{sub 2}O·5.7Y{sub 2}O{sub 3}·54.1SiO{sub 2} on the density and total conductivity of tetragonal Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}. An optimal sintering temperature (1200 °C) was selected on the basis of a composite with 1 wt% of the glass having the highest density and total conductivity after annealing at this temperature. A series of composites Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}-x wt% 40.2Li{sub 2}O·5.7Y{sub 2}O{sub 3}·54.1SiO{sub 2} (x = 1–10) was prepared. The samples were characterized by X-ray diffraction, scanning electron microscopy and differential scanning calorimetry. The data revealed that the sintering additive interacted with Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}, causing the glass to crystallize during annealing. The conductivity of the composites was studied using complex impedance spectroscopy over a temperature range of 20–250 °C. The composite with x = 5 exhibited the highest total conductivity at room temperature: 2.5 × 10{sup −5} S cm{sup −1}.

36 MATERIALS SCIENCE↗

Mercury Speciation via Diffusive Gradients Thin-Films Technology

Objectives: Develop and test various diffusive gradient in thin films (DGT) samplers for mercury - SRNL is developing reactive DGTS (rDGTs). Test chemistry to differentiate methylmercury from total and/or inorganic mercury in environmental samples. Fabricate and test rDGT samplers for deployment. Deploy the rDGTs in variable settings. Mercury is a persistent-bioaccumulative-toxic environmental pollutant. Mercury exists in different species such as elemental, inorganic, and methyl. Mercury speciation determine mercury behavior and toxicity. For example, methylmercury strongly accumulates in biota such as fish resulting in potential human health impacts. DGTs are innovative samplers to measure water concentration by diffusion and capture. Types of Hg DGTs used: Total Hg, Inorganic Hg, and Methyl Hg. Deployment Sites: Upper Three Runs, Lower Three Runs, Steele Creek, East Fork Poplar Creek (SRNL Sites), Horizons Creek, NOA Creek, Bruners Creek (ORNL Sites). DGT concentration estimates closely matched alternative measurements for soluble mercury at each Oak Ridge site - DGTs did not respond to particulate mercury. DGTs provide a representative measure for biota uptake since they are left out longer which allows for an average exposure concentration. DMA-80 provided an efficient and quick analysis. Variability in site location made a difference in Hg species. DGT preparations and sampling wasn't as quick and simple as microcolumn technology. Copper reagent degraded agarose gel - more work and cleaner data are needed to assess speciation in rDGTs. Future Work: Use cross-linked polyacrylamide for the collection layer for a stronger plastic. Make a copper diffusion layer without agarose. Test copper separation in lab using realistic stream conditions such as high organic carbon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Temperature Dependent Raman Spectroscopic Study of the Fe Doped La{sub 0.67}Sr{sub 0.33}MnO{sub 3} Prepared Using Ball Milling Method

Polycrystalline samples of La{sub 0.67}Sr{sub 0.33}Mn{sub 0.65}Fe{sub 0.35}O{sub 3} (LSMFO) were synthesized using the standard ball mill method with different calcination temperatures ranging from 800 to 1100°C for 7 h. The phase purity of these samples was confirmed using X-ray diffraction (XRD) patterns. All samples were found to have rhombohedral crystal structure with R 3-bar c space group. The lattice parameters, cell volume, bond angle and bond length have been obtained using the Rietveld refinement by FullProf software. The average crystallite size calculated using the Debye-Scherrer formula was found between 27 and 60 nm. Surface morphology of the prepared samples has been examined using a scanning electron microscope (SEM). SEM images show the formation of well-arranged grain sizes distributed from 240 to 400 nm, much larger than one estimated using the Scherrer formula. All tiny particles are highly agglomerated with the increasing temperature and porosity decreases with increasing temperature. An analysis of the frequency and peak broadening of Raman modes as a function of temperature clearly shows the significant temperature effect on the A{sub 1g} and E{sub g} modes of LSMFO. The shifts and broadening of the A{sub 1g} and E{sub g} modes are discussed in light of the oxygen sublattice distortion. Our study shows the reduction in distortion with increasing calcination temperature, which suggests a decrease in the JT effect.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Corrosion resistance of ZrO{sub 2}–TiO{sub 2} nanocomposite multilayer thin films coated on carbon steel in hydrochloric acid solution

This work reports the achievement of preparing of x% zirconia (ZrO{sub 2})–titania (TiO{sub 2}) composite coatings with different ZrO{sub 2} percent on the carbon steel by dipping substrates in sol–gel solutions. The prepared coated samples were investigated by various surface techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDAX). Open-circuit potential (OCP), potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) methods were employed to investigate the corrosion resistance of the coated carbon steel substrates in 1.0 M HCl solution at 50 °C. The data showed that, the corrosion protection property is not always proportional to the percent of ZrO{sub 2}. It can be inferred that there is an optimum percent (10%ZrO{sub 2}) for beneficial effects of loading ZrO{sub 2} on the protection efficiency (98.70%), while higher loading percent of ZrO{sub 2} in the sol–gel coating leads to the formation of a fragile film with poor barrier properties. EDAX/SEM suggests that the metal surface was protected through coating with ZrO{sub 2}–TiO{sub 2} composite films. - Highlights: • Sol–gel TiO{sub 2} doped with ZrO{sub 2} films deposited on carbon steel substrate • XRD measurements of x wt.% ZrO{sub 2}–TiO{sub 2} showed the (101) peaks broader than that of TiO{sub 2}. • SEM results proved that, the cracking decreases with the number of layers. • The prepared films can improve the corrosion resistance of the carbon steel substrate. • 10%ZrO{sub 2} loading is the optimal percent for useful effects on the corrosion resistance.

36 MATERIALS SCIENCE↗