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At least 991 records · Page 55

XRD, Electron Microscopy and Vibrational Spectroscopy Characterization of Simulated High-Fe/Al HLW Glasses - 15666

Sample glasses have been made using SB6 high level waste (HLW) simulant (high in both Al and Fe) with 12 different frit compositions at a constant waste loading of 36 wt.%. As follows from X-ray diffraction (XRD) and optical and scanning electron microscopy (SEM) data, all the samples are composed of primarily glass and minor concentration of spinel phases which form both isometric grains and fine cubic (∼1 μm) crystals. Infrared (IR) spectra of all the glasses within the range of 400-1600 cm-1 consist of the bands due to stretching and bending modes in silicon-oxygen, boron-oxygen, aluminum-oxygen and iron-oxygen structural groups. Raman spectra showed that for the spectra of all the glasses within the range of 850-1200 cm{sup -1} the best fit is achieved by suggestion of overlapping of three major components with maxima at 911-936 cm{sup -1}, 988-996 cm{sup -1} and 1020-1045 cm{sup -1}. The structural network is primarily composed of metasilicate chains and possibly rings with embedded AlO{sub 4} and FeO{sub 4} tetrahedra. Major BO{sub 4} tetrahedra and BO{sub 3} triangles form complex borate units and are present as separate constituents. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Tribological Behavior of a Cr{sub 2}O{sub 3} Ceramic Coating/Steel Couple Under Dry Sliding and Heavy Loading Conditions

This work evaluates the effects of heavy loadings on a Cr{sub 2}O{sub 3} ceramic coating/steel couple under dry sliding and in conditions similar to those occurring in heavy-duty diesel engines. Two types of wear tests were performed by a standard pin-on-disc tribometer under high constant and variable loads. Before wear tests, microstructure and mechanical properties of coating and steel were determined by optical emission spectrometry, optical microscopy, roughness, microhardness and x-ray diffractometry (XRD). The friction coefficient was directly calculated by the tribometer. The wear rate of Cr{sub 2}O{sub 3} ceramic coating was evaluated by the wear volume and that of pins by weighing them before and after tests. The wear tracks on pins and coating surfaces were analyzed by XRD and by scanning electron microscopy with energy-dispersive spectroscopy. For all loads except the lowest constant one, the results indicated high friction and wear involving material removal from the coating surface, through a severe-oxidational wear associated with extensive cracking of the surface of the coating, softening of the carburizing steel and removal of the carburized layer of pins. The wear mechanism was mild-oxidational under the lowest constant load, which was therefore suggested as the limit for acceptable performance of the sliding couple under study.

36 MATERIALS SCIENCE↗

Contact-free reversible switching of improper ferroelectric domains by electron and ion irradiation

Focused ion beam (FIB) and scanning electron microscopy (SEM) are used to reversibly switch improper ferroelectric domains in the hexagonal manganite ErMnO 3 . Surface charging is achieved by local ion (positive charging) and electron (positive and negative charging) irradiation, which allows controlled polarization switching without the need for electrical contacts. Polarization cycling reveals that the domain walls tend to return to the equilibrium configuration obtained in the as-grown state. The response of sub-surface domains is studied by FIB cross-sectioning, enabling imaging in the direction perpendicular to the applied electric field. The results clarify how the polarization reversal in hexagonal manganites progresses at the level of domains, resolving both domain wall movements and the nucleation and growth of new domains. Our FIB-SEM based switching approach is applicable to all ferroelectrics where a sufficiently large electric field can be built up via surface charging, facilitating contact-free high-resolution studies of the domain and domain wall response to electric fields in 3D.

36 MATERIALS SCIENCE↗

Advanced Characterization of Irradiated Fuels and Materials at INL

Advanced characterization of the irradiated fuels and materials is crucial to help understanding the material and fuel property changes under irradiation. Microstructural defect evolution down to nanometer scale could strongly affect the material and fuel performance on macroscale. Radiation-induced material degradation include dimensional instability, hardening and embrittlement, intergranular cracking, radiation-enhanced chemical interaction at the interfaces and breakaway swelling. To mitigate the radiation damage, advanced characterization on irradiated microstructure, microchemistry, micromechanical property and local thermal property is necessary to identify the controlling mechanisms that are responsible to the degradations. This presentation provides a summary of the advanced characterization capabilities at the Irradiation Materials Characterization Laboratory (IMCL), Materials and Fuels Complex (MFC), Idaho National Laboratory (INL). It highlights the recently established capabilities including shield sample preparation area (SSPA), shield confinement cells for two focused ion beam (FIB) systems, a shielded electron probe microanalysis (EPMA), the thermal property microscopy (TPM) along with non-shielded instruments like scanning electron microscopy (SEM), X-ray diffractometer, and transmission electron microscopy (TEM). Some examples on advanced characterizations on irradiated structural materials and fuels will be presented. It demonstrates the power of combining sample preparation of highly radioactive materials with the advanced characterization down to atomic resolutions within one facility.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Photoresponse properties of large-area MoS{sub 2} atomic layer synthesized by vapor phase deposition

Photoresponse properties of a large area MoS{sub 2} atomic layer synthesized by vapor phase deposition method without any catalyst are studied. Scanning electron microscopy, atomic force microscopy, Raman spectrum, and photoluminescence spectrum characterizations confirm that the two-dimensional microstructures of MoS{sub 2} atomic layer are of high quality. Photoelectrical results indicate that the as-prepared MoS{sub 2} devices have an excellent sensitivity and a good reproducibility as a photodetector, which is proposed to be ascribed to the potential-assisted charge separation mechanism.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Synthesis of coaxial CoFe{sub 2}O{sub 4} - K{sub 0.5}Na{sub 0.5}NbO{sub 3} nanotubes by sol-gel technique using inexpensive templates

A modified sol-gel method was introduced by employing a cost effective novel template to synthesize coaxial one dimensional (1-D) composite nanostructures based on CoFe{sub 2}O{sub 4} (CFO) - K{sub 0.5}Na{sub 0.5}NbO{sub 3} (KNN) and magnetic nanostructures based on CoFe{sub 2}O{sub 4} (CFO). The studies with scanning electron microscopy (SEM) and atomic force microscopy (AFM) revealed that the composite material is characterized by the 1-D tubular structure. The absorption edge is blue shifted for both KNN and CFO nanotubes due to the lattice strain effect.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Cation-Driven Assembly of Bilayered Vanadium Oxide and Graphene Oxide Nanoflakes to Form Two-Dimensional Heterostructure Electrodes for Li-Ion Batteries

Lithium preintercalated bilayered vanadium oxide (LVO or δ-Li x V 2 O 5 ·nH 2 O) and graphene oxide (GO) nanoflakes were assembled using a concentrated lithium chloride solution and annealed under vacuum at 200 °C to form two-dimensional (2D) δ-Li x V 2 O 5 ·nH 2 O and reduced GO (rGO) heterostructures. Here we found that the Li + ions from LiCl enhanced the oxide/carbon heterointerface formation and served as stabilizing ions to improve structural and electrochemical stability. The graphitic content of the heterostructure could be easily controlled by changing the initial GO concentration prior to assembly. We found that increasing the GO content in our heterostructure composition helped inhibit the electrochemical degradation of LVO during cycling and improved the rate capability of the heterostructure. A combination of scanning electron microscopy and X-ray diffraction was used to help confirm that a 2D heterointerface formed between LVO and GO, and the final phase composition was determined using energy-dispersive X-ray spectroscopy and thermogravimetric analysis. Scanning transmission electron microscopy and electron energy-loss spectroscopy were additionally used to examine the heterostructures at high resolution, mapping the orientations of rGO and LVO layers and locally imaging their interlayer spacings. Further, electrochemical cycling of the cation-assembled LVO/rGO heterostructures in Li-ion cells with a non-aqueous electrolyte revealed that increasing the rGO content led to improved cycling stability and rate performance, despite slightly decreased charge storage capacity. The heterostructures with 0, 10, 20, and 35 wt % rGO exhibited capacities of 237, 216, 174, and 150 mAh g –1 , respectively. Moreover, the LVO/rGO-35 wt % and LVO/rGO-20 wt % heterostructures retained 75% (110 mAh g–1) and 67% (120 mAh g –1 ) of their initial capacities after increasing the specific current from 20 to 200 mA g –1 , while the LVO/rGO-10 wt % sample retained only 48% (107 mAh g –1 ) of its initial capacity under the same cycling conditions. In addition, the cation-assembled LVO/rGO electrodes exhibited enhanced electrochemical stability compared to electrodes prepared through physical mixing of LVO and GO nanoflakes in the same ratios as the heterostructure electrodes, further revealing the stabilizing effect of a 2D heterointerface. The cation-driven assembly approach, explored in this work using Li + cations, was found to induce and stabilize the formation of stacked 2D layers of rGO and exfoliated LVO. The reported assembly methodology can be applied for a variety of systems utilizing 2D materials with complementary properties for applications as electrodes in energy storage devices.

25 ENERGY STORAGE↗

Hanford Tank Waste Particle Atlas

Several methods have been utilized to perform solid phase characterization. Polarized light microscopy (PLM) is used to identify individual particles based on size, shape, color, and optical properties (e.g., refractive index1, birefringence, extinction positions, and interference figures). Scanning electron microscopy with energy-dispersive spectroscopy (SEM/EDS) is used to detect which elements are present in individual particles and to infer chemical phase identification based on the metals present in combination with the size and shape of the particles. Powder X-ray diffraction (XRD) is used to identify crystalline phases present in bulk samples by matching the X-ray patterns with a library of known patterns for pure phases. Transmission electron microscopy (TEM) is used to identify individual particles by their X-ray diffraction patterns. RAMAN analysis is used to identify bulk sample compositions by matching RAMAN spectra with a library of known patterns. Other specialized techniques have not been employed routinely for Hanford tank waste samples.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Analysis of InGaN nanodots grown by droplet heteroepitaxy using grazing incidence small-angle X-ray scattering and electron microscopy

We present a detailed structural investigation of self-assembled indium gallium nitride nanodots grown on c-plane aluminum nitride templates by the droplet heteroepitaxy technique in a plasma-assisted molecular beam epitaxy reactor. Various growth parameters, including the total coverage of the metal species, relative and total metal effusion fluxes, and nitridation temperature were investigated. Analyses of in situ reflection high-energy electron diffraction patterns and comparison with simulations showed that the resulting crystal structure was a mixture of wurtzite and twinned zinc blende phases, with the zinc blende phase increasingly dominant for lower metal coverages and lower nitridation temperatures, and the wurtzite phase increasingly dominant for higher nitridation temperature. Studies by field emission scanning electron microscopy and atomic force microscopy revealed that the nanodots exhibit trimodal size distributions, with the dot morphologies of the intermediate size mode often resembling aggregations of distinct clusters. Nanodots grown at higher nitridation temperatures had larger inter-dot spacings, with hexagonal in-plane ordering observable at a sufficiently high temperature. Using grazing incidence small angle X-ray scattering, we determined the nanodots to be approximately truncated cone shaped, and extracted the mean radius, height, and inter-dot distance for each distribution. Microstructural investigations of the nanodots by cross-sectional transmission electron microscopy indicated that the majority of the dots were formed in dislocation-free regions, and confirmed that the intermediate size dots were approximately truncated cone shaped and consisted of both zinc blende and wurtzite regions. Mapping of the elemental distributions by energy dispersive X-ray spectroscopy in scanning transmission electron microscopy mode indicated highly nonuniform indium distributions within both small and intermediate size dots which are potentially indicative of indium clustering and kinetically controlled nanoscale phase separation rather than the spinodal decomposition associated with bulk diffusion. In conclusion, the observed enrichment in indium concentration towards the tops of the nanodot layers could be ascribed to the compositional pulling effect.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Latent Mechanisms of Polarization Switching from In Situ Electron Microscopy Observations

In situ scanning transmission electron microscopy enables observation of the domain dynamics in ferroelectric materials as a function of externally applied bias and temperature. The resultant data sets contain a wealth of information on polarization switching and phase transition mechanisms. However, identification of these mechanisms from observational data sets has remained a problem due to a large variety of possible configurations, many of which are degenerate. Here, an approach based on a combination of deep learning-based semantic segmentation, rotationally invariant variational autoencoder (VAE), and non-negative matrix factorization to enable learning of a latent space representation of the data with multiple real-space rotationally equivalent variants mapped to the same latent space descriptors is introduced. By varying the size of training sub-images in the VAE, the degree of complexity in the structural descriptors is tuned from simple domain wall detection to the identification of switching pathways. Importantly, this yields a powerful tool for the exploration of the dynamic data in mesoscopic electron, scanning probe, optical, and chemical imaging. Moreover, this work adds to the growing body of knowledge of incorporating physical constraints into the machine and deep-learning methods to improve learned descriptors of physical phenomena.

36 MATERIALS SCIENCE↗

Diminution in the Optical Band Gap and Near Band Edge Emission of Nickel-Doped Zinc Oxide Thin Films Deposited by Sol-Gel Method

Thin films of nickel-doped zinc oxide (Zn1−{sub x}Ni{sub x}O) show redshift in the optical band gap and in the near band edge (NBE) emission of the photoluminescence spectra. The Zn1−{sub x}Ni{sub x}O thin films obtained by sol-gel spin coating method show narrowing of the band gap from 3.23 to 3.00 eV as the concentration of nickel is increased from x = 0.00 to x = 0.06. All the Zn1−{sub x}Ni{sub x}O thin films have hexagonal wurtzite structure and show a decrease of 119 meV in the NBE emission as the dopant concentration is increased. X-ray diffraction (XRD) spectroscopy confirms the formation of ZnO in the films; Fourier transform infrared (FTIR) spectroscopy reaffirms this. Energy dispersive analysis (EDX) also ascertains the presence of Ni in the films and calculates the amount of dopant present in the films. Scanning electron microscopy (SEM) shows that all the Ni-doped ZnO thin films possess granular surface morphology.

36 MATERIALS SCIENCE↗

Nanostructuring on zinc phthalocyanine thin films for single-junction organic solar cells

Vertically aligned and random oriented crystalline molecular nanorods of organic semiconducting Zinc Phthalocyanine (ZnPc) have been grown on ITO coated glass substrate using solvent volatilization method. Interesting changes in surface morphology were observed under different solvent treatment. Vertically aligned nanorods of ZnPc thin film were observed in the films treated with acetone, where as the random oriented nanorods were observed in the films treated with chloroform. The X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) have been used for characterization of nanostructures. The optical properties of the nanorods have been investigated by UV-Vis. absorption spectroscopy.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Morphology, UV–visible and ellipsometric studies of sodium lithium orthovanadate

Sodium lithium orthovanadates were prepared by the classic ceramic method technique. Structure, phase purity, composition, and morphology were characterized by X-ray powder diffraction, infrared spectroscopy, energy dispersive spectroscopy, scanning-electron microscopy and atomic force microscopy. The optical properties of Na{sub x}Li{sub 1−x}CdVO{sub 4} (x = 0.5, 1) compounds prepared were recorded at room temperature using ultra-visible and ellipsometric spectroscopies in the spectral range (200–800) nm. The average reflectance of the pellets showed high reflectivity (over 80%) in the visible spectrum. The UV–Vis absorption bands are assigned to the charge transfer from the oxygen ligands to the central vanadium atom inside the [VO{sub 4}]{sup 3−} groups in the orthovanadate compounds. The optical band gaps E{sub g} of both samples are evaluated using Kubelka–Munk function. The analysis of the data revealed the existence of optical allowed direct transition for Na{sub x}Li{sub 1−x}CdVO{sub 4} (x = 0.5, 1). Spectroscopic ellipsometry measurements have been performed on Na{sub x}Li{sub 1−x}CdVO{sub 4} (x = 0.5, 1) specimens and their optical properties were analyzed using the Cauchy model.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Transmission Kikuchi diffraction and transmission electron forescatter imaging of electropolished and FIB manufactured TEM specimens

We present a study of the efficiency of the utility of scanning electron microscope (SEM)-based transmission methods for characterizing grain structure in thinned bulk metals. Foils of type 316 stainless steel were prepared by two methods commonly used for transmission electron microscopy — double-jet electropolishing and focused ion beam milling. A customized holder allowed positioning of the foils in a configuration appropriate for both transmission electron forward scatter diffraction, and for transmission imaging by the use of a forescatter detector with two diodes. We found that both crystallographic orientation maps and dark-field transmitted images could be obtained for specimens prepared by either method. However, for both methods, preparation-induced artifacts may affect the quality or accuracy of transmission SEM data, especially those acquired by the use of transmission Kikuchi diffraction. Generally, the quality of orientation data was better for specimens prepared by electropolishing, due to the absence of ion-induced damage. - Highlights: • The transmission imaging and diffraction techniques are emerging in scanning electron microscopy (SEM) as promising new field of materials characterization. • The manuscript titled: “Transmission Kikuchi Diffraction and Transmission Electron Forescatter Imaging of Electropolished and FIB Manufactured TEM Specimens” documents how different specimen thinning procedures can effect efficiency of transmission Kikuchi diffraction and transmission electron forescatter imaging. • The abilities to make precision crystallographic orientation maps and dark-field images in transmission was studied on electropolished versus focus ion beam manufactured TEM specimens. • Depending on the need, electropolished and focused ion beam technique may produce suitable specimens for transmission imaging and diffraction in SEM.

36 MATERIALS SCIENCE↗

Growth of boron doped hydrogenated nanocrystalline cubic silicon carbide (3C-SiC) films by Hot Wire-CVD

Highlights: • Boron doped nc-3C-SiC films prepared by HW-CVD using SiH{sub 4}/CH{sub 4}/B{sub 2}H{sub 6}. • 3C-Si-C films have preferred orientation in (1 1 1) direction. • Introduction of boron into SiC matrix retard the crystallanity in the film structure. • Film large number of SiC nanocrystallites embedded in the a-Si matrix. • Band gap values, E{sub Tauc} and E{sub 04} (E{sub 04} > E{sub Tauc}) decreases with increase in B{sub 2}H{sub 6} flow rate. - Abstract: Boron doped nanocrystalline cubic silicon carbide (3C-SiC) films have been prepared by HW-CVD using silane (SiH{sub 4})/methane (CH{sub 4})/diborane (B{sub 2}H{sub 6}) gas mixture. The influence of boron doping on structural, optical, morphological and electrical properties have been investigated. The formation of 3C-SiC films have been confirmed by low angle XRD, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier transform infra-red (FTIR) spectroscopy and high resolution-transmission electron microscopy (HR-TEM) analysis whereas effective boron doping in nc-3C-SiC have been confirmed by conductivity, charge carrier activation energy, and Hall measurements. Raman spectroscopy and HR-TEM analysis revealed that introduction of boron into the SiC matrix retards the crystallanity in the film structure. The field emission scanning electron microscopy (FE-SEM) and non contact atomic force microscopy (NC-AFM) results signify that 3C-SiC film contain well resolved, large number of silicon carbide (SiC) nanocrystallites embedded in the a-Si matrix having rms surface roughness ∼1.64 nm. Hydrogen content in doped films are found smaller than that of un-doped films. Optical band gap values, E{sub Tauc} and E{sub 04} decreases with increase in B{sub 2}H{sub 6} flow rate.

36 MATERIALS SCIENCE↗

Non-toxic novel route synthesis and characterization of nanocrystalline ZnS{sub x}Se{sub 1−x} thin films with tunable band gap characteristics

Highlights: • A simple, inexpensive, and non-toxic CBD route is used to deposit ZnS thin films. • The ZnS{sub x}Se{sub 1−x} thin films formation takes place via annealing of ZnS thin films in Se atmosphere. • S/(S + Se) ratio found to be temperature dependent and easy tuning of band gap has been done by Se atom deposition. - Abstract: An environmentally benign chemical bath deposition (CBD) route was employed to deposit zinc sulfide (ZnS) thin films. The CBD-ZnS thin films were further selenized in a furnace at various temperatures viz. 200, 300, 400, and 500 °C and the S/(S + Se) ratio was found to be dependent on the annealing temperature. The effects of S/(S + Se) ratio on the structural, compositional and optical properties of the ZnS{sub x}Se{sub 1−x} (ZnSSe) thin films were investigated. EDS analysis showed that the S/(S + Se) ratio decreased from 0.8 to 0.6 when the film annealing temperature increased from 200 to 500 °C. The field emission scanning electron microscopy and atomic force microscopy studies showed that all the films were uniform, pin hole free, smooth, and adhered well to the glass substrate. The X-ray diffraction study on the ZnSSe thin films showed the formation of the cubic phase, except for the unannealed ZnSSe thin film, which showed an amorphous phase. The X-ray photoelectron spectroscopy revealed Zn-S, Zn-Se, and insignificant Zn-OH bonds formation from the Zn 2p{sub 3/2}, S 2p, Se 3d{sub 5/2}, and O 1s atomic states, respectively. The ultraviolet–visible spectroscopy study showed ∼80% transmittance in the visible region for all the ZnSSe thin films having various absorption edges. The tuning of the band gap energy of the ZnSSe thin films was carried out by selenizing CBD-ZnS thin films, and as the S/(S + Se) ratio decreased from 0.8 to 0.6, the band gap energy decreased from 3.20 to 3.12 eV.

36 MATERIALS SCIENCE↗

Synthesis, characterization and hydrophilic properties of ZnFe{sub 2}O{sub 4}–TiO{sub 2} composite film

Highlights: • ZnFe{sub 2}O{sub 4}–TiO{sub 2} composite films have been successfully prepared via a sol–gel method. • It was deposited on glass slides through dip coating process. • 7% ZnFe{sub 2}O{sub 4}–TiO{sub 2} film exhibits a superhydrophilic property with a contact angle 0°. • The self-cleaning glasses also display antifogging property. - Abstract: ZnFe{sub 2}O{sub 4}–TiO{sub 2} composite films have been successfully prepared via a sol–gel method and deposited on glass slides through dip coating process. The hydrophilicity of ZnFe{sub 2}O{sub 4}–TiO{sub 2} composite films was investigated by the contact angles measurements under different conditions, including heat treatment temperature, molar ratios of ZnFe{sub 2}O{sub 4} to TiO{sub 2} and coating layers. The results revealed that the 7 mol% ZnFe{sub 2}O{sub 4}-TiO{sub 2} composite film exhibits an excellent superhydrophilic performance with a contact angle 0°. Compared with normal glass, the self-cleaning glasses also display antifogging property. The transmittance of ZnFe{sub 2}O{sub 4}–TiO{sub 2} composite films was characterized by UV–vis spectra in details. Coating layers and different molar percents of ZnFe{sub 2}O{sub 4} all have impact on the light transmittance. Moreover, the structure and morphology of the ZnFe{sub 2}O{sub 4}–TiO{sub 2} sample were investigated by means of X-ray diffraction (XRD), energy dispersive X-ray spectrometry (EDS) and scanning electron microscopy (SEM)

36 MATERIALS SCIENCE↗

Nano-textured high sensitivity ion sensitive field effect transistors

Nano-textured gate engineered ion sensitive field effect transistors (ISFETs), suitable for high sensitivity pH sensors, have been realized. Utilizing a mask-less deep reactive ion etching results in ultra-fine poly-Si features on the gate of ISFET devices where spacing of the order of 10 nm and less is achieved. Incorporation of these nano-sized features on the gate is responsible for high sensitivities up to 400 mV/pH in contrast to conventional planar structures. The fabrication process for this transistor is inexpensive, and it is fully compatible with standard complementary metal oxide semiconductor fabrication procedure. A theoretical modeling has also been presented to predict the extension of the diffuse layer into the electrolyte solution for highly featured structures and to correlate this extension with the high sensitivity of the device. The observed ultra-fine features by means of scanning electron microscopy and transmission electron microscopy tools corroborate the theoretical prediction.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗