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Synthesis and Characterization of Er-Doped Nano ZnO Samples

Pure and erbium-doped ZnO nanoparticles (Zn{sub 1−x}Er{sub x}O), (0.00 ≤ x ≤ 0.10), were synthesized by wet chemical co-precipitation method. The structural, optical, and magnetic properties of the prepared samples were investigated using x-ray powder diffraction (XRD), transmission electron microscopy (TEM), ultraviolet-visible spectroscopy (UV), Fourier transform infrared spectroscopy (FTIR), M-H magnetic hysteresis, and electron paramagnetic resonance (EPR). XRD studies exhibit the presence of a single ZnO wurtzite hexagonal crystal structure for 0.00 ≤ x ≤ 0.06. A secondary phase of Er{sub 2}O{sub 3} appears for x > 0.06. This means that the solubility limit for doping Zn{sup 2+} ions by Er{sup 3+} ions is about x = 0.06 under our preparations condition. The lattice parameter a is not affected by the Erbium doping. On the other hand, the lattice parameter c and the unit cell volume V increase with the increase of x up to x = 0.06. This is attributed to the larger ionic size of Er{sup 3+} ions (0.88 Å) compared to Zn{sup 2+} ions (0.74 Å). Both c and V decrease for x > 0.06. TEM micrographs indicate that the shape and the size of the ZnO nanoparticles are modified by changing the doping level of Er. The UV measurements point out that band gap energy E{sub g} decreases with the increase of x up to x = 0.06. Then, it increases for both x = 0.08 and 0.10. FTIR spectra confirm the presence of O–H and Zn–O stretching modes at 3451.963 and 428.901 cm{sup − 1}, respectively, in pure and doped ZnO samples. The Zn–O stretching mode shifts toward a lower wavenumber for x = 0.06 and toward a higher wavenumber for x = 0.10. M-H hysteresis analysis, at room temperature, reveals that the pure ZnO has a ferromagnetic signal combined with diamagnetic and paramagnetic contributions. This ferromagnetism is reduced for the doped samples up to x = 0.02, and an antiferromagnetic alignment appears for 0.04 ≤ x ≤ 0.10. The saturation magnetization (M{sub s}), the coercivity (H{sub c}), the retentivity (M{sub r}), the anisotropy constant (K{sub a}), and the magnetic moment (μ{sub m}) were estimated and discussed in terms of erbium doping for the different samples. EPR spectra for Zn{sub 1−x}Er{sub x}O were measured at room temperature in order to study the effect of Er substitution on the g value, resonance field (H{sub r}), peak to peak line width (ΔH{sub pp}) and spin–spin relaxation time constant (T{sub 2}).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effect of Al Substitution in Structural and Magnetic Properties of MnCr{sub 2}O{sub 4}

Single-phase samples of Mn(Cr{sub 1−x}Al{sub x}){sub 2}O{sub 4} (x = 0 – 0.30) with cubic spinel structure were prepared and the lattice constant is found to decrease from a = 8.4396 Å for x = 0 to a = 8.3801 Å for x = 0.30. The substitution of Al at Cr site is confirmed from the blue shift of Raman modes. Magnetization measurements and analysis show all the prepared samples exhibit ferrimagnetic transition with transition temperature in the range of 46 K for x = 0 to 33 K for x = 0.30. The saturation magnetization (M{sub s}) and the estimated anisotropy constant (K) show an anomalous behavior up to x = 0.10 and beyond that they decrease monotonously. They are explained by considering different site preferences of Al {sup 3+} ions as the doping concentration is increased. The theoretical and experimental effective magnetic moment of the samples is found to be comparable and it decreases with increase in Al concentration.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Structural, optical, and electrical properties of SmNbO{sub 4}

Rare-earth orthoniobates constitute a class of materials that has been exploited due to their interesting physical properties depending on the lanthanide element. Besides paramagnetism, ferroelasticity, and negative compressibility, these materials are known by their interesting optical properties and mixed types of conduction processes (protonic, ionic, and electronic). In this work, two types of SmNbO{sub 4} samples were studied: polycrystalline samples, prepared by a sol-gel route using the Pechini method, and single crystalline fibres grown by the Laser Floating Zone technique. These samples were structurally characterized based on powder and single-crystal X-ray diffraction studies. A metastable tetragonal phase, stabilized by grain size, was identified in the synthesized powders. After a sintering process of such powders, a single monoclinic phase was obtained. Complementarily, scanning electron microscopy and Raman spectroscopy analyses were performed to these samples. Photoluminescence and photoluminescence excitation spectroscopic studies allowed identifying more than one optically active centre of the trivalent samarium ion in the analysed material. Impedance spectroscopy measurements have shown a large variation of the ac conductivity as a function of temperature, assigned to a protonic conduction and to native ionic conduction mechanisms.

36 MATERIALS SCIENCE↗

Temperature dependence anomalous dielectric relaxation in Co doped ZnO nanoparticles

Graphical abstract: Display Omitted Highlights: ► We prepared Co doped ZnO by facile gel-combustion method. ► Studied temperature dependent dielectric properties in detail. ► Relaxation time shifts toward the higher temperature as increase in Co content. ► SEM analysis shows formation and agglomeration of nanoparticles. ► Dielectric constants, loss and ac conductivity increases with rise in temperature. ► The dielectric constant, loss and ac conductivity decreases as Co ion increases. -- Abstract: We have reported temperature and frequency dependence of dielectric behavior of nanocrystalline Zn{sub 1−x}Co{sub x}O (x = 0.0, 0.01, 0.05 and 0.1) samples prepared by gel-combustion method. The synthesized samples were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM) and LCR-meter, respectively. The XRD analysis reveals that ZnO has a hexagonal (wurtzite) crystal structure. The morphology and size of the nanoparticles (∼10–25 nm) were observed by SEM for 5% Co doped ZnO sample. In dielectric properties, complex permittivity (ε{sup *} = ε′ − jε″), loss tangent (tan δ) and ac conductivity (σ{sub ac}) in the frequency range 75 kHz to 5 MHz were analyzed with temperature range 150–400 °C. The experimental results indicate that ε′, ε″, tan δ and σ{sub ac} decreases with increase in frequency and temperature. The transition temperature as obtained in dispersion curve of dielectric constant shifts toward higher temperature with increase Co content.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and activity of supported bimetallic NiPd nanoparticles: influence of preparation method on CO 2 reduction

Here, bimetallic Ni-Pd and monometallic reference catalysts were prepared by decomposing organometallic precursors, Ni(cod) 2 and Pd 2 (dba) 3 , leading to nanoparticles with sizes ranging from 3 to 6 nm. Two different synthesis procedures were followed: i) solution synthesis using capping ligand (hexadecylamine) followed by impregnation of pre-formed nanoparticles on SiO 2 , called Sol-immobilization (SI); and 2) direct precursor decomposition onto SiO 2 , without stabilizer, called Direct Decomposition (DD). Samples prepared by SI procedure are alloyed bimetallic nanoparticles, whereas samples obtained by DD one show phase segregation. Interestingly, DD samples show better activity for CO 2 hydrogenation into CO (reverse water-gas shift reaction - RWGS) than SI ones. The best compromise between activity for CO 2 activation (at lower temperature) and CO selectivity was achieved with Ni DD and NiPd DD catalysts. Moreover, the addition of palladium increased the concentration of surface undercoordinated sites, which chemisorb CO weakly, thus improving activity and selectivity, in opposition to other samples that chemisorb CO strongly, in multiband configuration. In the presence of Pd, different decomposition rates drive the formation of smaller and more active Ni clusters. The knowledge acquired here on the influence of synthesis conditions on the catalytic properties of Ni-Pd catalysts should guide us to better catalysts for CO 2 transformations into valuable products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced thermoelectric performance in spark plasma textured bulk n-type BiTe{sub 2.7}Se{sub 0.3} and p-type Bi{sub 0.5}Sb{sub 1.5}Te{sub 3}

Bulk p and n-type bismuth tellurides were prepared using spark plasma texturization method. The texture development along the uniaxial load in the 001 direction is confirmed from both x-ray diffraction analysis and electron backscattering diffraction measurements. Interestingly, those textured samples outperform the samples prepared by conventional spark plasma sintering (SPS) leading to a reduced thermal conductivity in the ab-plane. The textured samples of n-type BiTe{sub 2.7}Se{sub 0.3} and p-type Bi{sub 0.5}Sb{sub 1.5}Te{sub 3} showed a 42% and 33% enhancement in figure of merit at room temperature, respectively, as compared to their SPS counterparts, opening the route for applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Strength, Hardening, and Failure Observed by In Situ TEM Tensile Testing: Strength, Hardening, and Failure Observed by In Situ TEM Tensile Testing

We present in situ transmission electron microscope tensile tests on focused ion beam fabricated single and multiple slip oriented Cu tensile samples with thicknesses in the range of 100–200 nm. Both crystal orientations fail by localized shear. While failure occurs after a few percent plastic strain and limited hardening in the single slip case, the multiple slip samples exhibit extended homogenous deformation and necking due to the activation of multiple dislocation sources in conjunction with significant hardening. The hardening behavior at 1% plastic strain is even more pronounced compared to compression samples of the same orientation due to the absence of sample taper and the interface to the compression platen. Moreover, we show for the first time that the strain rate sensitivity of such FIB prepared samples is an order of magnitude higher than that of bulk Cu.

36 MATERIALS SCIENCE↗

Comparative study of NiFe{sub 2−x}Al{sub x}O{sub 4} ferrite nanoparticles synthesized by chemical co-precipitation and sol–gel combustion techniques

Graphical abstract: AFM images of NiFe{sub 2}O{sub 4} ferrite nanoparticles at room temperature synthesized by sol–gel technique. Highlights: ► Particle size reduces to less than 30 nm. ► DC electrical resistivity increases with substitution of Cr{sup 3+}. ► Dielectric constant decreases. -- Abstract: A series of aluminum substituted Ni-ferrite nanoparticles have been synthesized by chemical co-precipitation and sol–gel techniques. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscope (AFM), Fourier transform infrared spectroscopy (FTIR), DC electrical resistivity and dielectric properties. Analysis of the X-ray diffraction pattern of all the samples confirmed the formation of spinel structure. The crystallite sizes remain within the range 25–41 ± 3 nm. FTIR measurements show two fundamental absorption bands, assigned to the vibration of tetrahedral and octahedral sites. DC electrical resistivity increases from 6.60 × 10{sup 7} to 6.9 × 10{sup 10} Ω cm as the Al{sup 3+} concentration increases from 0.00 to 0.50. The dielectric constant and loss tangent decreases with increasing Al{sup 3+} concentration from 22 to 14, 0.354 to 0.27 respectively at 5 MHz for all the samples. Impedance measurements as a function of frequency (1 kHz–5 MHz) at room temperature further helped in analyzing the electrical properties of the prepared samples.

36 MATERIALS SCIENCE↗

Surface photoelectric and visible light driven photocatalytic properties of zinc antimonate-based photocatalysts

Highlights: ► N-doped and pristine ZnSb{sub 2}O{sub 6} photocatalysts were synthesized by a facile method. ► N-doped ZnSb{sub 2}O{sub 6} shows a significant enhanced visible light photocatalytic activity. ► The N-doped ZnSb{sub 2}O{sub 6} shows the reduced surface photovoltage signals. - Abstract: The N-doped and pristine ZnSb{sub 2}O{sub 6} photocatalysts were synthesized by a facile method. The samples were characterized by X-ray diffraction (XRD), UV–vis spectroscopy, surface photovoltage spectroscopy and scanning electron microscopy. The photocatalytic activities of the prepared samples were evaluated from the degradation of rhodamine B (RhB) under full arc and visible light irradiation of Xe lamp. The XRD and UV–vis results indicated that the N-doping did not change the crystal structure, but decrease the band gap in comparison with the pristine one. The N-doped ZnSb{sub 2}O{sub 6} shows the reduced surface photovoltage signals and the significantly enhanced photocatalytic activity under two irradiation conditions.

36 MATERIALS SCIENCE↗

Tailored Fano resonance and localized electromagnetic field enhancement in Ag gratings

Metallic gratings can support Fano resonances when illuminated with EM radiation, and their characteristic reflectivity versus incident angle lineshape can be greatly affected by the surrounding dielectric environment and the grating geometry. By using conformal oblique incidence thin film deposition onto an optical grating substrate, it is possible to increase the grating amplitude due to shadowing effects, thereby enabling tailoring of the damping processes and electromagnetic field couplings of the Fano resonances, hence optimizing the associated localized electric field intensity. To investigate these effects we compare the optical reflectivity under resonance excitation in samples prepared by oblique angle deposition (OAD) and under normal deposition (ND) onto the same patterned surfaces. We observe that by applying OAD method, the sample exhibits a deeper and narrower reflectivity dip at resonance than that obtained under ND. This can be explained in terms of a lower damping of Fano resonance on obliquely deposited sample and leads to a stronger localized electric field. This approach opens a fabrication path for applications where tailoring the electromagnetic field induced by Fano resonance can improve the figure of merit of specific device characteristics, e.g. quantum efficiency (QE) in grating-based metallic photocathodes.

36 MATERIALS SCIENCE↗

Simulation of Space Experiments for Nuclear Planetology: Measurement of Relative Intensities of Lines of Gamma Ray Emitted upon Thermal-Neutron Capture by Nuclei

The results obtained by experimentally studying gamma rays emitted by samples prepared as analogs of planetary matter and irradiated with thermal neutrons are presented. The intensities of spectral lines of gamma rays emitted by such samples differing in chemical composition are compared. These results will be used in processing data on gamma-ray spectra of the Moon and Mercury from measurements performed onboard spacecrafts with the aim of studying the composition of the surface of these celestial bodies.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

FY23 Post-LOCA Characterization of Irradiated Fuel (NSUF Award 17-12985)

This report summarizes the sample preparation and data collection on fuel pins following integral LOCA testing in the Severe Accident Test Station at Oak Ridge National Laboratory. The test sample cross-sections show post-transient fragmentation behavior of UO 2 commercially irradiated above 67 MWd/kgU. Ring compression testing and hydrogen measurements were collected on the cladding segments.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Thermoelectric refrigeration for temperatures below 100 K: A study of titanium sesquioxide

Previous measurements of the specific heat of V-doped Ti2O3 at low temperatures were explained by a model which also suggested the material would have a high thermoelectric figure-of-merit. The sample preparation, experimental apparatus, and the results of measurements on the thermal conductivity, thermoelectric power, and electrical resistivity of a single crystal Ti2O3 - 4% V sample are described. The results are used to derive the thermoelectric figure-of-merit between 5 and 300 K. The figure-of-merit is much smaller than expected and of little practical value because of the very high phonon thermal conductivity.

Redebaugh, R.↗

STARDUST and Interplanetary Dust Particles - Big Science from Small Samples

Comets are primitive bodies that are widely believed to be a reservoir of preserved interstellar and circumstellar grains, and molecular cloud materials (organics). Direct samples of cometary dust along with interstellar grains will be returned by the STARDUST Mission in 2006. Analyses of interplanetary dust particles (IDPs) and analogue materials in the laboratory provide constraints and serve as "ground truth" for evaluating various hypotheses on the nature of comets and interstellar grains. Anhydrous IDPs are the most primitive remnants of the primordial Solar System, and are our only known samples of comets. These cometary lDPs are rich in preserved interstellar organic compounds II]. In addition, abundant interstellar silicates have recently been discovered in cluster lDPs [2]. In some of these IDPs, the presolar silicate abundance reaches 1 wt %, exceeding the total presolar grain abundance in meteorites by three orders of magnitude, where presolar silicates are still notably absent. The results to date support the idea that comets are rich in presolar materials, but are at odds with the common perception that they are 'pristine aggregates of interstellar grains'. These results underscore the scientific importance of sample return missions to comets. The technology for the analysis of micrometer-sized samples is well advanced. The newest generation of ion probe instruments allow for isotopic analyses at the submicrometer level. The nature of the organic matter is analyzed using Infrared and soft X-ray spectroscopy techniques on synchrotron-based instruments, also at the micrometer-scale and smaller. Electron microscopy and spectroscopy provide details on the mineralogy and chemistry of constituent grains in !DPs at nearly the atomic scale. Novel sample preparation techniques have been developed such that all of these measurements can now be made on the same 10 micrometer diameter particle. Returned comet samples captured in aerogel will pose new challenges in sample analysis, but should provide a major leap in our understanding of the fundamental building blocks of our Solar System.

Keller, L. P.↗

Morphologies and magnetism of AxB1-xFe2O4 self-assembled nanospheres

Highlights: • A modified solvothermal method are successfully applied to prepare bimetallic ferrite microspheres. • The replaced ions coexist in same spinel lattice and cause its distortion. • The morphologies and magnetic properties are affected by type and content of ions. • As-prepared samples belong to paramagnetic materials with low coercivity. - Abstract: A series of A{sub x}B{sub 1-x}Fe{sub 2}O{sub 4} (x = 0.05–0.50) (A, B as Zn{sup 2+}, Ni{sup 2+}, Co{sup 2+}) micro-nanospheres were prepared using a facile one-pot solvothermal method. All products are spinel structures with grain sizes of around 11–15 nm as characterised by using XRD. SEM and TEM images show that Ni{sub x}Zn{sub 1-x}Fe{sub 2}O{sub 4} (x = 0.05–0.50) are microspheres self-assembled by nanoparticles with an average diameter of 200–300 nm, but the sizes of Ni{sub x}Co{sub 1-x}FeO{sub 4} (x = 0.10–0.50) and Zn{sub x}Co{sub 1-x}Fe{sub 2}O{sub 4} (x = 0.10–0.50) micro-nanospheres increase from 20 nm to 200 nm with increasing amounts of Ni{sup 2+} and Zn{sup 2+}. As-prepared A{sub x}B{sub 1-x}Fe{sub 2}O{sub 4} samples are paramagnetic materials with coercivities of no more than 177.5 Oe. The morphologies and magnetism of A{sub x}B{sub 1-x}Fe{sub 2}O{sub 4} could be adjusted by changing the amount of A{sup 2+} and B{sup 2+}.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Direct Observation of Wet Biological Samples by Graphene Liquid Cell Transmission Electron Microscopy

Recent development of liquid phase transmission electron microscopy (TEM) enables the study of specimens in wet ambient conditions within a liquid cell; however, direct structural observation of biological samples in their native solution using TEM is challenging since low-mass biomaterials embedded in a thick liquid layer of the host cell demonstrate low contrast. Furthermore, the integrity of delicate wet samples is easily compromised during typical sample preparation and TEM imaging. To overcome these limitations, we introduce a graphene liquid cell (GLC) using multilayer graphene sheets to reliably encapsulate and preserve biological samples in a liquid for TEM observation. We achieve nanometer scale spatial resolution with high contrast using low-dose TEM at room temperature, and we use the GLC to directly observe the structure of influenza viruses in their native buffer solution at room temperature. The GLC is further extended to investigate whole cells in wet conditions using TEM. We also demonstrate the potential of the GLC for correlative studies by TEM and fluorescence light microscopy imaging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

TRISO PARTICLE FUEL POLISHING PROCESS COMPARISON

The investigation of the TRISO coated particles is important in terms of verification the quality of the nuclear fuel samples before placing them in the reactor core. To determine the degree of damage to the coated particles, the samples must be properly polished in order to uncover the inner layers. The poster presents a comparison of two polishing methods. Mechanical polishing method, which is used frequently for sample preparations generates additional mechanical damages in the studied fuel particle, thus directly affecting the experimental results. Due to that, a novel way to polish the samples is presented - an ionic polishing method. Based on the obtained results, it was concluded that the ion polishing method is better because the level of interference with the structures of the individual layers of the tested samples is much lower than with the mechanical method.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗