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At least 883 records · Page 49

Ultrasonic Application of Nanostructured Coatings on Metals

A method is developed for applying metallic, intermetallic, or ceramic coatings to a metal surface by means of ultrasound (high-frequency acoustic vibrations). The method may also be used to reinforce metallic surfaces by means of particles of another metal or ceramic. Under the action of ultrasound, chemical reactions and solid-phase diffusion are accelerated. That is accompanied by strong adhesion of the metal matrix to the particles; solid-phase transformations; and the formation of intermetallides, oxides, carbides, nitrides, and other compounds, depending on the surrounding gas and the powder composition. As a result, a composite coating or layer with nanostructure or microstructure is formed on the surface.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Inhibit the strain accumulation for 5V spinel cathode by mitigating the phase separation during high voltage stage

LiNi 0.5 Mn 1.5 O 4 (LNMO) spinel cathode is a potential cathode material for high-power, low-cost lithium-ion batteries (LIBs) due to its low raw material cost, high operating voltage and efficient lithium-ion transport channel. However, LNMO suffers from structural stability due to the two-phase-transformation during charge/discharge process, leading to poor cycling performance. Here, to address the issues, we have constructed a homogeneous aggregated LNMO cathode with a multifaceted primary particle, namely the LNMO with single-crystal secondary particles (SSP LNMO). Ex situ and in situ characterizations including the synchrotron X-ray diffraction, the neutron diffraction and full pouch cell validated that the SSP LNMO exhibit a single solid-solution reactions with a restrained lattice evolution during the delithiation/lithiation process. This is in contrast to the normal LNMO cathode, which demonstrates a significant two-phase transition from spinel Li 1-x Ni 0.5 Mn 1.5 O 4 to rock-salt MnO 2 at high voltage. Therefore, the SSP LNMO has greatly improved cycle life compared to the normal LNMO cathode. Overall, this study demonstrates the possibility of constructing LNMO based on primary-grain morphology modulation to improve the intrinsic stability of LIBs.

25 ENERGY STORAGE↗

Microstructure and Tensile Properties of the Fe-32%Ni-4%Co Alloy During Cryorolling and Subsequent Annealing

The Fe-32%Ni-4%Co alloy was cryorolled to produce thickness reductions of 10, 40, 60 and 90%; then, the strips with a final thickness of 0.52 mm were annealed at 893, 923 and 943 K for different soaking times. The x-ray diffraction measurements indicated that both thermally induced α′-martensite (α′-M) and deformation-induced α′-M were present in the tested alloy. The thermally induced α′-M was mainly lath-shaped, while the morphology of the deformation-induced α′-M gradually changed from lath-shaped to irregular-shaped according to transmission electron microscopy observations. After the 90% reduction due to cryorolling, the total volume fraction of α′-M reached 75.6%, and the average ultimate tensile strength (UTS{sub av.}) was significantly improved from 430.3 to 1306.8 MPa. Upon subsequent annealing at 923 K for 5 min, the tested alloy mainly consisted of a large number of fine grains and a few coarse grains (CGs). In addition, several deformed structures were also observed. As the annealing time increased to 10 and 30 min, the fraction of CGs increased, and a bimodal grain size distribution was obtained, while the deformed structures were still present. The temperature of the reverse phase transformation of α′-M → γ was lower than the recrystallization temperature, which may be the main reason for the bimodal grain distribution. With this bimodal grain structure, the alloy exhibited a combination tensile strength of 543.3 MPa and an average elongation of 34.1%.

36 MATERIALS SCIENCE↗

Post weld heat treatment and operating temperature effect on tribological behavior of laser cladded stellite 21 coating

This study intends to investigate the feasibility of using laser cladding as a potential process to repair hot working tools by a hardfacing process. A Stellite 21 alloy coating was printed on a 350 maraging steel via laser cladding and the coating microstructure and tribological performance were characterized in as printed conditions and after heat treatment. Such a laser-processed coating showed a high integrity with little porosity and good bonding with the substrate. The Stellite coating produced substantially lower friction and a smoother contact area but had inferior wear resistance compared with the maraging steel substrate. Post process heat treatment at 650 °C for 20 h led to significant amount of strain-induced FCC to HCP phase transformation but had little improvement in wear resistance. Detailed materials characterization using X-ray diffraction and electron microscopy provided fundamental insights to the underlying mechanisms. This study opens the door for future R&D for tool surface repair by laser cladding.

36 MATERIALS SCIENCE↗

Mechanism of Influence of Nanocrystal Sizes on the Parameters of the Curves of the Pseudoelastic and Thermoelastic Deformations of Alloys with the Shape Memory Effect

The data available in the literature on the influence of the nanocrystal sizes of alloys with the shape memory effect on the parameters of the curves of their pseudoelastic and thermoelastic deformation are analyzed in the framework of the theory of diffuse martensitic transitions (DMT). The peculiarity of the DMT theory is that it is based on both thermodynamic and kinetic relationships that make it sensitive to the alloy structure on the mesoscopic scale. This enables one to state the functional dependence of the parameter of the martensitic deformation of the nanocrystals on the size of their cross section D. As a result of the analysis, it is found that the coefficient of the strain (martensitic) hardening and the hysteresis of the pseudoelastic strain curves of submicrocrystals of the Ni{sub 54}Fe{sub 19}Ga{sub 27} are changed with D by law 1/D{sup 2}. The temperature range (M{sub s} – M{sub f}) of the martensitic transition in TiNi alloy nanocrystals is changed by analogy law. These dependences are results of the constrained displacement of dislocations of the phase transformation by transverse sizes of the crystal. A kinetic mechanism of the appearance of the critical nanocrystal size D{sub k} is established; the transition of austenite to martensite does not occur at transverse crystal sizes smaller than the critical size.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Investigation of nanostructured Al-10 wt.% Zr material prepared by ball milling for high temperature applications

Ground chips of as-cast Al-10 wt.% Zr alloy were subjected to mechanical alloying (MA) with 5 vol.% of nanodiamond addition in a high energy planetary ball-mill. The aim of this work was to investigate the microstructure, phase transformation and mechanical properties of the material both after MA and after subsequent annealing. Optical and transmission electron microscopes were used for morphological and microstructural analysis. The effect of milling time on powder microhardness, Al lattice parameter, lattice microstrain and crystallite size was determined. It was shown that mechanical alloying of as-cast Al-10wt.%Zr alloy during 20 h leads to a complete dissolution of the primary tetragonal Al{sub 3}Zr crystals in aluminum. At the same time, the powder microhardness increases to 370 HV. Metastable cubic Al{sub 3}Zr phase nanoparticles precipitate from the Al solution due to its decomposition after annealing, however, the Al solid solution remains supersaturated and nanocrystalline. Compression tests at room temperature and at 300 °C showed that the strength values of the hot-pressed samples reach 822 MPa and 344 MPa, respectively. - Highlights: •As-cast Al-10 wt.% Zr alloy was mechanically alloyed with 5 vol.% nanodiamond. •The primary tetragonal Al{sub 3}Zr crystals were completely dissolved in Al after 20 h. •Cubic Al{sub 3}Zr phase nanoparticles precipitated from Al solution after aging. •The aged bulk material showed a high strength at room and elevated temperatures.

36 MATERIALS SCIENCE↗

Crystallographic texture and microstructural changes in fusion welds of recrystallized Zry-4 rolled plates

This study presents a detailed characterization of the microstructural and crystallographic texture changes observed in the transition region in a weld between two Zircaloy-4 cold rolled and recrystallized plates. The microstructural study was performed by optical microscopy under polarized light and scanning electron microscopy (SEM). Texture changes were characterized at different lengthscales: in the micrometric size, orientation imaging maps (OIM) were constructed by electron backscatter diffraction (EBSD), in the millimetre scale, high energy XRD experiments were done at the Advanced Photon Source (USA) and compared to neutron diffraction texture determinations performed in the HIPPO instrument at Los Alamos National Laboratory. In the heat affected zone (HAZ) we observed the development of Widmanstätten microstructures, typical of the α( hcp ) to β( bcc ) phase transformation. Associated with these changes a rotation of the c-poles is found in the HAZ and fusion zone. While the base material shows the typical texture of a cold rolled plate, with their c-poles pointing 35° apart from the normal direction of the plate in the normal-transversal line, in the HAZ, c-poles align along the transversal direction of the plate and then re-orient along different directions, all of these changes occurring within a lengthscale in the order of mm. The evolution of texture in this narrow region was captured by both OIM and XRD, and is consistent with previous measurements done by Neutron Diffraction in the HIPPO diffractometer at Los Alamos National Laboratory, USA. The microstructural and texture changes along the HAZ were interpreted as arising due to the effect of differences in the cooling rate and β grain size on the progress of the different α variants during transformation. Fast cooling rates and large β grains are associated to weak variant selection during the β–>α transformation, while slow cooling rates and fine β grains result in strong variant selection.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Synchrotron x-Ray Study of Heterostructured Materials: A Review

Heterostructured materials (HSMs) have shown great potential for breaking the strength-ductility tradeoff. HSMs consist of heterogeneous zones that may have different sizes, shapes, compositions, structures, etc. Interactions and competitions among them often lead to unprecedented properties. However, due to the complex structures in a broad range of length scales, it is challenging to unravel deformation physics and strengthening mechanisms underlying extraordinary mechanical properties. Synchrotron x-rays provide powerful techniques and indispensable tools for investigating HSMs at various length scales. Here, we will present in situ high-energy x-ray diffraction and Laue x-ray microdiffraction techniques and their application in studying the HSMs. In this study, the principles of these techniques will be briefly introduced. We will focus on their application in studying stress partitioning and plastic accommodation during tensile deformation, thermo-driven and/or stress-driven phase transformations and various deformation microstructures like geometrically necessary dislocations and local stress/strain distributions, etc., in HSMs. Some important findings will be summarized. Challenging issues remain in studying HSMs and will be discussed.

36 MATERIALS SCIENCE↗

An investigation of the reduction of TiO 2 by Mg in H 2 atmosphere

Hydrogen assisted magnesiothermic reduction (HAMR) of TiO 2 is a promising new process developed recently to produce Ti metal with low cost and less energy consumption. Here this work focuses on the understanding and optimization of the reduction process to control the quality of the reduced product. TiO 2 precursor particles with different relative densities were prepared, and the effects of the relative densities on reduction by Mg in H 2 were studied. The changes of oxygen contents vs. reduction time at various temperatures were investigated. The phase transformations during the reduction were analyzed both theoretically and experimentally. The relationship between the morphology of the reduced products and the relative densities of the TiO 2 precursors was analyzed by SEM characterization and the likely reason for the morphology evolution was discussed.

42 ENGINEERING↗

Synthesis, Structural Characterization, and Growth Mechanism of Li 1+ x V 3 O 8 Submicron Fibers for Lithium-Ion Batteries

Here, we report on the synthesis of submicron Li 1+x V 3 O 8 fibers through a facile mixed ethanol/water solution-mediated solvothermal route in the absence of surfactants. All the raw materials used are commercially available, relatively inexpensive, and low-toxic, and these can be handled in an ambient atmosphere, rendering this synthetic route as reasonably facile and efficient. To ensure a desirable and acceptable sample crystallinity and purity, we introduced a postannealing treatment at 500°C. The monoclinic phase formation of the fiber sample was probed in detail using a series of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, infrared spectroscopy, X-ray photoelectron spectroscopy, high resolution transmission electron microscopy, and selected area electron diffraction measurements. Both morphology and chemical composition could be carefully and systematically tuned in terms of generating a class of novel, pure, and well-defined motifs of Li 1+x V 3 O 8 . A plausible mechanism for the formation of submicron-diameter fibers has been discussed in addition to the expected phase transformation within our Li-V-O materials. Our comprehensive study should provide for needed fundamental insights into putting forth a viable synthesis strategy for the generation of well-defined morphological variants of layered oxide materials for battery applications.

25 ENERGY STORAGE↗

Synthesis method comparison of compositionally complex rare earth-based Ruddlesden–Popper n = 1 T'-type cuprates

The multicomponent approach has been successfully expanded to the Ruddlesden–Popper structure with the synthesis of two different high-entropy cuprate compositions: (La 0.2 Nd 0.2 Gd 0.2 Tb 0.2 Dy 0.2 ) 2 CuO 4 and (La 0.2 Pr 0.2 Nd 0.2 Sm 0.2 Eu 0.2 ) 2 CuO 4 . Additionally, the effect of synthesis method is explored using both solid-state reaction and polymeric steric entrapment (PSE) methods. It is found that PSE leads to more randomly distributed cation species, providing an advantageous method of synthesis for the growing field of high entropy oxides. In situ high-temperature x-ray diffraction tracks the amorphous to crystalline phase transformation in (La 0.2 Nd 0.2 Gd 0.2 Tb 0.2 Dy 0.2 ) 2 CuO 4 powder, synthesized using the PSE method. Using the High-Temperature XRD data, a method for gaining information on the kinetic behavior is also applied. Magnetometry of both compositions indicates ferrimagnetic behavior at low temperatures.

36 MATERIALS SCIENCE↗

Unusual Temperature Dependence of Water Sorption in Semicrystalline Hydrogels

Abstract Water vapor sorption is a ubiquitous phenomenon in nature and plays an important role in various applications, including humidity regulation, energy storage, thermal management, and water harvesting. In particular, capturing moisture at elevated temperatures is highly desirable to prevent dehydration and to enlarge the tunability of water uptake. However, owing to the thermodynamic limit of conventional materials, sorbents inevitably tend to capture less water vapor at higher temperatures, impeding their broad applications. Here, an inverse temperature dependence of water sorption in poly(ethylene glycol) (PEG) hydrogels, where their water uptake can be doubled with increasing temperature from 25 to 50 °C, is reported. With mechanistic modeling of water–polymer interactions, this unusual water sorption is attributed to the first‐order phase transformation of PEG structures, and the key parameters for a more generalized strategy in materials development are identified. This work elucidates a new regime of water sorption with an unusual temperature dependence, enabling a promising engineering space for harnessing moisture and heat.

36 MATERIALS SCIENCE↗

On Possible States of the Crystal Structure Preceding to a Phase Transition in Zn{sub 1 –} {sub x}V{sub x}Se (0.01 ≤ x ≤ 0.10) Crystals

The systematic new formations observed in the reciprocal lattice of the cubic structural modification of a II–VI compound are characterized using a detailed neutron diffraction study of bulk semiconducting ZnSe crystals with an increased vanadium content. Direct evidence that the additional sites k = (1/3 1/3 1/3) 2π/a (k is the wave vector and a is cubic unit cell parameter) observed by neutron scattering in the crystals, in the case when they belong to mutually penetrated rotated sublattices, contain a superstructure contribution formed by short-wave deformation, is obtained for the first time. This structure state is determined as a pretransition to the concentration fcc–hcp phase transformation, and the basis functions that allow one to analyze atomic displacements, the correlation between which create distortion-type superstructures, are indicated for the transition through one-arm channel, considering the transitions by the star of wave vector k{sub 5} of the fcc lattice.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High-Temperature Heat Capacity and Thermal Extension of FeTa{sub 2}O{sub 6}

The heat capacity of synthesized iron tantalate FeTa{sub 2}O{sub 6} was measured in the temperature range of 323–1103 K by the ratio method using a thermal analyzer combining thermogravimetry and scanning calorimetry. The temperatures of phase transformations were determined. Structural changes and thermal expansion of oxide were studied in the range of 300–1173 K by high-temperature X-ray diffraction. The temperature dependences of the unit cell parameters were approximated by third order polynomials. The values of thermal expansion coefficients and anisotropy factors were calculated based on the obtained data.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Shock-Driven Hydrodynamic Instability Growth Near Phase Boundaries and Material Property Transitions: Final Report

Activities for this grant included: 1) Development of dynamic impact experiments to probe strength and phase transition influence on dynamic deformation, 2) development of modern strength and phase aware simulation capabilities, 3) and post-processing of experimental data with simulation and closed form analytical techniques. Two different dynamic experiments were developed to probe material strengths in solid metals (largely copper and iron in this effort). In the first experiment a flyer plate impacts a flat target with an opposite rippled surface that is partially supported by a weaker window material. Post mortem analysis of the target sample showed a strong and repeatable residual plastic deformation dependence on grain orientation. Yield strengths for strain rates near 10 5 s -1 and plastic strains near ~50% were estimated to be around 180 to 240 MPa, varying in this range with grain orientation. Unfortunately dynamic real-time measurements were difficult with this setup due to diagnostic laser scattering; hence, an additional experimental setup was developed to complement these results. In the second set of experiments a rippled surface was ablated by a controlled laser pulsed, which launched a rippled shock front to an opposite initially flat diagnostic surface that was monitored in real-time with spatially resolved velocimetry techniques, e.g., line VISAR in addition to Transient Imaging Displacement Interferometry (TIDI) displacement measurements. This setup limited the displacements at the diagnostic surface to a reasonable level for TIDI measurements (~ less than one micrometer). These experiments coupled with analytical and numerical solutions provided evidence that viscous and elastic deviatoric strength affect shock front perturbation evolution in clearly different ways. Particularly, normalized shock front perturbation amplitudes evolve with viscosity (η) and perturbation wavelength (λ) as η/λ, such that increasing viscosity (or decreasing the initial wavelength) delays the perturbation decay. Conversely our experimental data, analysis and simulations show that for materials with elastic yield strength Y the normalized shock perturbation amplitude evolves with Yλ/A 0 , which shows wavelength increases have the opposite effect as in viscous materials and perturbation decay is also dependent on initial amplitude A 0 (viscous materials are independent of this parameter). Materials where strength had clear strain rate dependence, e.g., such as a PTW material law, behaved similarly to materials with only an effective yield stress (elastic-perfectly plastic) in the shock front perturbation studies obeying a Y eff λA 0 relationship where Y eff was a constant (near ~400 MPa for Cu for strain rates around 10 6 s -1 ). Magnitude changes in strain rate would increase Y eff as would be expected from the PTW behavior, but small perturbations (typical of regions behind the shock front) near a mean had little effect. Additional work based on simulations showed that phase transformation kinetics can affect the behavior of the perturbed shock front as well as the evolution of the RM-like instability that develops due to the imprint of the perturbed shock front on the initially flat surface as the shock breaks out.

36 MATERIALS SCIENCE↗

Luminescence switching in Ce{sup 3+} ion sensitized YPO{sub 4}:Tb{sup 3+} through Redox reaction

Highlights: • Simple polyol method for preparation of Ce{sup 3+} sensitized Tb{sup 3+} ion doped YPO{sub 4} nanophosphor. • Enhanced green color emission with incorporation of Ce{sup 3+} ion into the matrix of YPO{sub 4}:Tb{sup 3+} nanophosphor. • Highly crystalline tetragonal YPO{sub 4}:Tb{sup 3+} without any impurity phase. • Use of alternate oxidising and reducing agent for luminescence switching (ON and OFF). - Abstract: Ce{sup 3+} sensitized Tb{sup 3+} ion doped YPO{sub 4} nanophosphor is synthesized by simple polyol method using ethylene glycol as capping agent as well as reaction medium. Green emission from Tb{sup 3+} ion doped YPO{sub 4} nanophosphor has been enhanced with incorporation of Ce{sup 3+} ion into the matrix of YPO{sub 4}:Tb{sup 3+}. XRD of YPO{sub 4}:Tb{sup 3+} annealed at 900 °C reveals crystalline tetragonal structure without any impurity phase. Morphology of YPO{sub 4}:Tb{sup 3+} nanophosphor was also studied. Homogenous incorporation of rare earth, RE (RE = Tb{sup 3+}, Ce{sup 3+}) ion into the host matrix were given in EDAX spectra. TGA/DTA analysis shows phase transformation of the as-prepared sample. Also, it is found that the as-prepared sample were readily re-dispersible in water due to presence of −OH group. By using an alternate oxidising and reducing agent, behaviour of luminescence switching (ON and OFF) can be examined. Lifetime decay of Tb{sup 3+} ion doped YPO{sub 4} nanophosphor was also studied.

36 MATERIALS SCIENCE↗

Modeling of melting and erosion in high velocity microparticle impacts

High velocity collisions can cause melting, a situation involving elasticity, plasticity, and phase transformations in tandem, which is very challenging for mechanical modeling. Here, this paper advances the use of smoothed particle hydrodynamics (SPH) simulations for this complex situation, investigating stainless steel microspheres impacting a tin substrate. After extensive validation against a range of mechanical and geometrical measurements of experimental impacts, the model provides a detailed, quantitative view of melt volume production over a broad range of impact velocities. It also enables direct decomposition of the impact energy partitioning, including analysis of the energy absorbed by plasticity in the impactor, the system kinetic energy, and the adiabatic heating of the substrate in addition to the melting itself. Since these quantities are not available experimentally, SPH modeling substantially enhances the quantitative understanding of such impacts. Finally, the model speaks to the phase characteristics of the ejecta formed during impact, confirming the experimental inference that the ejected material likely contains a significant fraction of solid material.

Constitutive modeling↗

Manipulate the Electronic and Magnetic States in NiCo 2 O 4 Films through Electric-Field-Induced Protonation at Elevated Temperature

Ionic-liquid-gating- (ILG-) induced proton evolution has emerged as a novel strategy to realize electron doping and manipulate the electronic and magnetic ground states in complex oxides. While the study of a wide range of systems (e.g., SrCoO 2.5 , VO 2 , WO 3 , etc.) has demonstrated important opportunities to incorporate protons through ILG, protonation remains a big challenge for many others. Furthermore, the mechanism of proton intercalation from the ionic liquid/solid interface to whole film has not yet been revealed. Here, with a model system of inverse spinel NiCo 2 O 4 , an increase in system temperature during ILG forms a single but effective method to efficiently achieve protonation. Moreover, the ILG induces a novel phase transformation in NiCo 2 O 4 from ferrimagnetic metallic into antiferromagnetic insulating with protonation at elevated temperatures. Finally, this study shows that environmental temperature is an efficient tuning knob to manipulate ILG-induced ionic evolution.

36 MATERIALS SCIENCE↗