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Axisymmetric and Focusing Analyzers to Enable Efficient Powder and Residual Stress Neutron Diffractometers

Project Summary: Company: Adelphi Technology, Inc., Redwood City, CA 94063-4121 DOE Phase 1 STTR PI: Dr. Jay Theodore Cremer, Jr. Chief Scientist at Adelphi Technology, Inc. DOE Phase 1 STTR with: Dr. Boris Khaykovich of Massachusetts Institute of Technology (MIT) MIT Nuclear Reactor Laboratory DOE Phase 1 STTR Title: Axisymmetric and Focusing Analyzers to Enable Efficient Powder and Residual Stress Neutron Diffractometers Statement of the problem or situation that is being addressed: Although thermal and cold neutron scattering is widely used, and is critical for success in many areas of materials science and engineering, relatively low neutron fluxes severely limit applications of not only laboratory neutrons generators, but also large national neutron facilities. State-of-the-art thermal and cold neutron sources are large expensive national facilities, which serve diverse community of scientific and industrial users. The constant need to improve the instruments performance, stems from the fact that neutron methods are gaining in popularity, and becoming more and more powerful, while new neutron sources are not being constructed, so as to keep pace with the developments and needs of the scientific community. Small research reactors at universities and National Labs, and laboratory-based neutron generators, are necessary not only for education and training, but also when samples cannot be transported to other facilities. However, the standard neutron techniques, which were developed for high-flux facilities, require much higher efficiencies to be used effectively with the low fluxes of small sources. Thus, the efficient use of neutron sources, such as with our proposed analyzer, is important for the progress and broader use of these neutron techniques. General statement of how this problem is being addressed: We strive to achieve the goal of efficient use of available thermal and cold neutrons, by introducing here, novel analyzers for powder diffraction and stress-strain measurements. These analyzers will enable polychromatic cold and thermal neutron diffractometers, which will have much higher throughput than existing instruments. At large national facilities, such as at Oak Ridge National Laboratory, these analyzers would enable very fast instruments for screening of multiple samples, for measuring kinetic processes, or for measuring residual stress tensors. Commercial Applications and Other Benefits: By combining the novel analyzers with the Adelphi thermal neutron generator, we will open a new market, which includes the testing of samples that cannot be transported, such as nuclear fuels, or the testing of parts during production. Given the reasonable cost and size of our proposed analyzer systems, along with the continuing development of more powerful thermal neutron generators, the proposed analyzers will be suitable for weak neutrons sources, which are installed at small to large university, industrial, and government laboratories. Key Words: Neutron powder diffraction, residual stress measurements, thermal neutron generators, TRIGA reactors, low flux thermal and cold neutron sources, neutron diffraction. Summary for Members of Congress: Thermal and cold neutron beams are a powerful materials science probe, which provide unique information about the structure of matter. The proposed innovations expand the reach of neutron-based investigations to new materials and industries by enabling new instrumentation capabilities, thereby greatly enhancing and expanding the role of small, laboratory-based neutron instrumentation, and improving education and training of neutron users.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Neutron diffraction studies for realtime leaching of catalytic Ni

The leaching of Al from intermetallic samples of Nickel Aluminium alloys to form Raney-type nickel catalysts is widely used in the hydrogenation industry, however, little is known of the leaching process itself. In this study, the leaching of Al was measured in realtime, in situ, using the high-flux powder neutron diffractometer, D20, at the Institut Laue-Langevin. Despite the liberation of hydrogen and effervescent nature of the reaction the transformation of the dry powder phases into Raney-type Ni was determined. Samples produced by gas-atomisation were found to leach faster than those produced using the cast and crushed technique. Regardless of processing route of the precursor powder, the formation of spongy-Ni occurs almost immediately, while Ni{sub 2}Al{sub 3} and NiAl{sub 3} continue to transform over longer periods of time. Small-angle scattering and broadening of the diffraction peaks is an evidence for the formation of the smaller Ni particles. Understanding the kinetics of the leaching process will allow industry to refine production of catalysts for optimum manufacturing time while knowledge of leaching dynamics of powders produced by different manufacturing techniques will allow further tailoring of catalytic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

VERDI: VERsatile DIffractometer with wide-angle polarization analysis for magnetic structure studies in powders and single crystals

The VERsatile DIffractometer will set a new standard for a world-class magnetic diffractometer with versatility for both powder and single crystal samples and capability for wide-angle polarization analysis. The instrument will utilize a large single-frame bandwidth and will offer high-resolution at low momentum transfers and excellent signal-to-noise ratio. A horizontal elliptical mirror concept with interchangeable guide pieces will provide high flexibility in beam divergence to allow for a high-resolution powder mode, a high-intensity single crystal mode, and a polarized beam option. A major science focus will be quantum materials that exhibit emergent properties arising from collective effects in condensed matter. The unique use of polarized neutrons to isolate the magnetic signature will provide optimal experimental input to state-of-the-art modeling approaches to access detailed insight into local magnetic ordering.

36 MATERIALS SCIENCE↗

Evidence of Room Temperature Ferromagnetism in Zn{sub 1−x}Sn{sub x}S Thin Films

Tin (Sn)-doped zinc sulfide (Zn{sub 1−x}Sn{sub x}S) thin films at different tin (Sn) concentrations (= 0.00, 0.02, 0.05, and 0.08) were coated onto Corning 7059 glass substrates using the electron beam evaporation technique. The films were subjected to different characterization techniques to study the physical properties of the thin films. The structural properties of the films were studied using a powder X-ray diffractometer (XRD), and it was found that the films were cubic in structure without any impurity phases. The crystallite size increased with an increase of Sn concentration, and the mean crystallite size was 21 nm. The chemical composition and surface morphology of the films were studied using scanning electron microscopy (FE-SEM) with energy-dispersive analysis of X-rays (EDAX). Optical properties such as transmittance and absorbance were recorded using a diffuse reflectance spectroscope (UV–vis–NIR). All the films exhibited high optical transmittance of 85% in the visible region of the solar spectrum. The band gap of the films was calculated using Tauc’s relation, and it was found that it increased from 3.53 to 3.57 eV with an increase in the Sn doping concentration from x = 0.02 to x = 0.08. The room temperature photoluminescence studies of the films were recorded using a fluorescence spectrophotometer, and it was found that the films exhibited a prominent emission peak at 420 nm. The magnetic properties of the films and glass substrates at room temperature were studied using a vibrating sample magnetometer. From this, it was found that the films were weakly ferromagnetic at room temperature and the strength of magnetization increased with an increase of doping concentration from x = 0.02 to x = 0.05 and decreased at higher doping concentrations (x = 0.08). The films showed high magnetization at x = 0.05. The films at x = 0.05 exhibited the magnetization (M{sub s}), retentivity (M{sub r}), and coercive fields (H{sub c}) 18 × 10{sup − 6} emu/cm{sup 3}, 1.6 × 10{sup − 6} emu/cm{sup 3}, and 91.80 Oe, respectively.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Simple polyol route to synthesize heptanoic acid coated magnetite (Fe{sub 3}O{sub 4}) nanoparticles

Highlights: ► Heptanoic acid@Fe{sub 3}O{sub 4} nanocomposite has been prepared via simple polyol. ► Heptanoic acid used as both surfactant and solvents. ► Magneto polymer composite with adjustable Ea has a potential usage as functional composites. - Abstract: Magnetite (Fe{sub 3}O{sub 4}) nanoparticles were prepared via polyol method by using FeCl{sub 2} as only source of iron. As-prepared samples were characterized by powder X-ray diffractometer (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analyzer (TGA) and vibrating sample magnetometer (VSM). Crystalline phase was identified as Fe{sub 3}O{sub 4} and the crystallite sizes were calculated as 19.1 ± 1.1 and 22 ± 1.3 nm for uncalcinated and calcinated products from X-ray line profile fitting. The capping of heptanoic acid around Fe{sub 3}O{sub 4} nanoparticles was confirmed by FT-IR spectroscopy, the interaction being via bridging oxygen's of the carboxylate and the nanoparticle surface and also by TG analysis. VSM measurements showed that both samples exhibited typical superparamagnetic behavior at room temperature with different Ms values. The ε′ decreases with increasing frequency for both composites and permeability has almost same values for all temperatures at higher frequencies. As synthesized and calcinated samples conductivity increase linearly with the temperature.

36 MATERIALS SCIENCE↗

Machine Learning Based System for Automated Estimation of Crystal Unit Cell Parameters from X-ray Diffraction Powder Patterns (MLCell) v0.1

This software uses machine learning models to perform inference on X-ray diffraction powder patterns, output from a diffractometer, to estimate all 6 unit cell parameters of crystalline lattices. Novel aspects of this software originated from the incorporation of concepts from crystallography to an ML-based approach; The resulting method achieves new performance capabilities without significant loss of accuracy and with less computationally intensive models.

Oklejas, Vanessa↗

One-step synthesis of homogeneous BaFe{sub 12}O{sub 19}/Y{sub 3}Fe{sub 5}O{sub 12} composite powders

Highlights: • A simple one-step sol–gel method was used to synthesize composite magnets. • The composite powders show good homogeneity and exchange coupling. • The M{sub r}/M{sub s} value increases with the BaM concentration. - Abstract: BaFe{sub 12}O{sub 19}/Y{sub 3}Fe{sub 5}O{sub 12} (BaM/YIG) composite powders were synthesized via a simple one-step sol–gel method. The phase composition and morphology of the as-synthesized composite powders were characterized using an X-ray diffractometer and a scanning electron microscopy equipped with energy dispersive X-ray spectroscopy. The magnetic properties of the composite powders were investigated by a vibrating sample magnetometer. Compared with the composite powders prepared by the conventional physical mixing method, the BaM/YIG composite powders show better homogeneity and exchange coupling.

36 MATERIALS SCIENCE↗

Effect of hydrothermal condition on the formation of multi-component oxides of Ni-based metallic glass under high temperature water near the critical point

The specific feature of multi-component oxides synthesized by hydrothermal process under high temperature (633 K) and highly pressurized water (18.9 MPa) near critical point. Effects of hydrothermal processing duration times 24 hours and 72 hours, respectively, on the oxide formation of the Ni{sub 59}Zr{sub 20}Ti{sub 16}Si{sub 2}Sn{sub 3} metallic glass synthesized by powder metallurgy process were characterized by X-ray diffractometer, differential scanning calorimeter along with the particle size, morphology and crystalline phase of the oxides. The crystallization of the needle-shape NiTiO{sub 3}, ZrTiO{sub 4} and ZrSnO{sub 4} ternary oxide phases observed on the surface of metallic glass at below glass transition temperature and the morphology of oxide phases changed to plate-shape around 2 μm in diameter by the increase processing time. This hydrothermal processing in subcritical water provides accelerated dense metal oxide crystals due to the reaction medium being at higher pressure than conventional oxidation processing.

36 MATERIALS SCIENCE↗

Dielectrical properties of PANI/TiO{sub 2} nanocomposites

Conducting polyaniline/titanium dioxide (PANI/TiO{sub 2}) composites have been succesfully synthesized by insitu polymerization technique. The PANI/TiO{sub 2} nanocomposites of different compositions were prepared by varying weight percentage of TiO{sub 2} nanoparticles such as 10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt% into the fixed amount of the aniline monomer. The prepared powder samples were characterized by X-ray diffractometer (XRD) and Scanning electron microscope (SEM). The intensity of diffraction peaks for PANI/TiO{sub 2} composites is lower than that for TiO{sub 2}. SEM pictures show that the nanocomposite were prepared in the form of long PANi chains decorated with TiO{sub 2} nanoparticles. The dielectric properties and AC conductivity were studied in the frequency range1K Hz–10M Hz. At higher frequencies, the composites exhibit almost zero dielectric loss and maximum value of σ{sub ac} is found for a concentration of 20 wt% TiO{sub 2} in polyaniline. The interface between polyaniline and TiO{sub 2} plays an important role in yielding a large dielectric constant in nanocomposites.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Influence of compositional variation on electrical properties of PANI/SnO{sub 2} nanocomposites

Conducting polyaniline/tin oxide (PANI/SnO{sub 2}) nanocomposites have been successfully synthesized by in-situ polymerization technique. The PANI/SnO{sub 2} nanocomposites of different compositions were prepared by varying weight percentage of SnO{sub 2} nanoparticles such as 10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt% into the fixed amount of the aniline monomer. The prepared powder samples were characterized by X-ray diffractometer (XRD), Fourier Transform Infrared spectroscopy (FT-IR) and Scanning electron microscope (SEM). The intensity of diffraction peaks for PANI/SnO{sub 2} composites is increases with increasing SnO{sub 2} wt%. SEM observation showed that the prepared SnO{sub 2} nanoparticles were uniformly dispersed and highly stabilized throughout the macromolecular chain that formed a uniform metal-polymer nanocomposite material. AC electrical conductivity and dielectric properties were studied in the frequency range of 1 KHz -1 MHz. At higher frequencies, the composites exhibit almost zero dielectric loss and maximum value of AC electrical conductivity (σ{sub ac}) of 0.21 S/m is found for a concentration of 30 wt% of SnO{sub 2} in polyaniline.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

What Is the Limit of Quantification for the Minor Phase in Time-of-Flight Neutron Diffraction? A Case Study on Fe and Ni Powder Mixtures at VULCAN

A phase present in small quantities within materials may not simply serve as a secondary component; it can play a crucial role in determining the integrity, properties, and performance of the material. These minor but important phases usually draw attention in material design and processing for fundamental understanding as well as material quality control. Accurately quantifying a minor phase amid a majority phase, especially at extremely low fractions, remains a challenging task. Time-of-flight neutron diffraction, coupled with advanced pattern analysis techniques like Rietveld refinement, is a powerful tool for crystal structure identification and phase quantification. The deep penetrating capability of neutrons enables the detection and quantification of trace phases within materials. In this study, the quantification limits of time-of-flight neutron diffraction were explored using the VULCAN diffractometer at the Spallation Neutron Source, using Fe–Ni powder mixtures as a sample system. By comparing the refinement results to the known weighed values, it was determined that the reliable quantification of a minor Ni phase is achievable down to about 0.1 wt% while a Ni fraction as low as 0.02 wt% is difficult to trace. Effective control of the refinement parameters, especially the profile function parameters, are found to significantly influence the convergence of fittings and the accuracy of phase quantification.

Rietveld refinement↗

Mössbauer Studies and the Microwave Properties of Al{sup 3+}- and In{sup 3+}-Substituted Barium Hexaferrites

The correlation of the chemical composition, the structure, and the microwave characteristic of solid solutions of the BaFe{sub 12–x}D{sub x}O{sub 19} (0.1 ≤ x ≤ 1.2) barium hexaferrite substituted with diamagnetic Al{sup 3+} and In{sup 3+} ions has been studied. The precise data on the crystal structure have been obtained by powder neutron diffraction using a high-resolution Fourier diffractometer (Dubna, JINR). The data on the distribution of the diamagnetic substituting ions in the hexaferrite structure have been obtained by Mössbauer spectroscopy. The microwave properties (the transmittance and the reflectance) have been studied in the frequency range 20–65 GHz and in external magnetic fields to 8 kOe. It is found that the transmission spectra are characterized by a peak that corresponds to the resonant frequency of the electromagnetic energy absorption, which is due to the ferromagnetic resonance phenomenon. The correlation of the chemical composition, the features of the ion distribution in the structure, and the electromagnetic properties has been revealed. It is shown that external magnetic fields shift the absorption peak of electromagnetic radiation to higher frequencies due to an increase in the magnetocrystal anisotropy. The results enable the conclusion that the features of the intrasublattice interactions and the electromagnetic properties should be explained using the phenomenological Goodenough–Kanamori model.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Position-Dependent Neutron Time-of-Flight Deviation at VULCAN Diffractometer

In neutron diffraction, it is critical to precisely measure the lattice spacing, as it is an indicator of a material’s physical characteristics, such as lattice strain, thermal expansion, and phase structures. In time-of-flight (TOF) measurements, the lattice spacing is determined by the recorded TOF from a well-calibrated instrument. However, changes in neutron time-of-flight are sensitive to many factors, such as the alignment of instrument optics, temperature, sample positions, sample dimensions, internal strains, and chemical or physical heterogeneities at the grain level. At VULCAN (SNS, ORNL), which is a high-flux engineering neutron diffractometer, we used a 1-mm-diameter diamond powder sample to scan for changes in TOF by measuring d-spacing values at different sample positions under several configurations. The 2D map of the TOF deviation or d-spacing deviation, in terms of lattice shift/lattice strain, is reported. The change in TOF is dependent on the scanned location in the beam as well as on detector locations. The results are informative for experimental planning, data interpretation, and future instrument design.

36 MATERIALS SCIENCE↗

High-resolution neutron diffraction study of microstructural changes in nanocrystalline ball-milled niobium carbide NbC{sub 0.93}

High resolution neutron diffraction was applied for elucidating of the microstructural evolution of nanocrystalline niobium carbide NbC{sub 0.93} powders subjected to high-energy ball milling. The diffraction patterns were collected with the high resolution Fourier diffractometer HRFD by using the reverse time-of-flight (RTOF) mode of data acquisition. The traditional single diffraction line analysis, the Rietveld method and more advanced Whole Powder Pattern Modeling technique were applied for the data analysis. The comparison of these techniques was performed. It is established that short-time milling produces a non-uniform powder, in which two distinct fractions with differing microstructure can be identified. Part of the material is in fact milled efficiently, with a reduction in grain size, an increase in the quantity of defects, and a corresponding tendency to decarburize reaching a composition NbC{sub 0.80} after 15 h of milling. The rest of the powder is less efficiently processed and preserves its composition and lower defect content. Larger milling times should have homogenized the system by increasing the efficiently milled fraction, but the material is unable to reach a uniform and homogeneous state. It is definitely shown that RTOF neutron diffraction patterns can provide the very accurate data for microstructure analysis of nanocrystalline powders. - Highlights: • The NbC{sub 0.93} powder was processed by high-energy ball milling. • The microstrain and dislocation density increase with milling time increase. • The corresponding decrease in crystallite size with milling time was observed. • The material exhibits the presence of two fractions after ball milling. • The RTOF neutron diffraction data are suitable for accurate microstructure analysis.

36 MATERIALS SCIENCE↗

Temperature dependent DC electrical conductivity studies of ZnO nanoparticle thick films prepared by simple solution combustion method

ZnO nanoparticles of different size were prepared by varying the molar ratio of glycine and zinc nitrate hexahydrate as fuel and oxidizer (F/O = 0.8, 1.11, 1.7) by simple solution combustion method. Powder samples were characterized by UV-Visible spectrophotometer, X-ray diffractometer, Scanning electron microscope (SEM). DC electrical conductivity measurements at room temperature and in the temperature range of 313-673K were carried out for the prepared thick films and it was found to increase with increase of temperature which confirms the semiconducting nature of the samples. Activation energies were calculated and it was found that, F/O molar ratio 1.7 has low E{sub AL} (Low temperature activation energy) and high E{sub AH} (High temperature activation energy) compared to other samples.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Effect of Sc{sup 3+} on structural and magnetic properties of Mn-Zn nano ferrites

In the present investigation, for the first time, we report on the effect of Sc{sup 3+} on the structural and magnetic properties of Mn{sub 0.5}Zn{sub 0.5}Sc{sub y}Fe{sub 2-y}O{sub 4} (y = 0.01, 0.03 and 0.05) nanoferrites synthesized by solution combustion method using the mixture of fuels. As synthesized powders were characterized for the detailed structural analysis by X-ray diffractometer (XRD), Fourier transmission infrared spectroscopy (FTIR) and room temperature magnetic properties by using vibrating sample magnetometer (VSM). The results of XRD and FTIR confirm that the formation of nano crystalline, single-phased Mn-Zn ferrite with cubic spinel structure belongs to Fd-3m space group. The room temperature magnetic studies shows that, the saturation magnetization (M{sub S}), remanence magnetization (M{sub R}) and magnetic moment (η{sub B}), magnetic particle size (D{sub m}) have found to increase with Sc{sup 3+} ion concentration up to x = 0.3 and then decrease. The values of αY-K and the magnetic particle size (D{sub m}) are found to be in the range of 68-75° and 10-19 nm respectively, with Sc{sup 3+} concentration.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

The First Neptunium Dioxide Neutron Diffraction Experiment at HFIR

Here we present the first neutron diffraction experiment of a 50 mg sample of neptunium(IV) dioxide (NpO 2 ) powder at the High Flux Isotope Reactor (HFIR) using the wide-angle neutron diffractometer (WAND 2 ) HB-2C. We also provide a brief literature survey to pinpoint gaps in the crystal, electronic, and magnetic structure of NpO 2 to determine the optimum experiment to be pursued in the next HFIR user proposal cycle. Characterizing actinide materials with neutron diffraction, inelastic scattering, neutron imaging, polarized neutron studies, and small-angle neutron scattering techniques will increase our understanding of 5f electron behavior and elucidate atomic and magnetic structural properties. This strategy will help fill gaps in the literature and provide theoretical physicists with the data needed to build physical and chemical models to guide and validate computational methods. These methods may be used for predicting structural and chemical features of actinide-based materials. This proof-of-principle effort begins to uncover how to advance actinide science and technology at Oak Ridge National Laboratory (ORNL) using neutron capabilities. This effort has already sparked collaborative discussions between researchers outside the Radioisotope Science and Technology Division, including theoretical physicists from the Nuclear Nonproliferation Division and beamline scientists in the Neutron Scattering Division. We intend to continue pursuing neutron experiments and develop a scientific strategy focused on studying transuranium elements (e.g., Np, Pu, Am, and Cm) using the advanced neutron capabilities at ORNL.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗