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At least 271 records · Page 15

Experimental Procedure and Results for Contact Thermal Conductance Measurements performed during FY 2021

Weapons Test Engineering groups at LANL are responsible for testing and simulating weapon assemblies and subassemblies in support of qualification and certification of nuclear weapon systems. The complex nature of the assemblies themselves coupled with the loading environments, gives rise to low confidence and high uncertainties in the interpretation of both experimental and simulated results. In an effort to reduce these uncertainties, a project was started at LANL to perform focused and systematic experiments combined with simulations to increase confidence in both arenas. A key goal of the work performed under the Delivery Environments (DE) Testbeds to Reduce Uncertainties in Simulations and Tests TRUST program, focuses on identifying and minimizing sources of uncertainty associated with experimental and computational techniques. Specifically, with the above as motivation, a measurement procedure was developed by MST-8 to perform thermal conductivity measurements on cylinders of both similar and dissimilar metallic systems as a function of loading conditions and varying material interface morphologies between these components.

36 MATERIALS SCIENCE↗

Grain growth kinetics in liquid-phase-sintered zinc oxide-barium oxide ceramics

Grain growth of ZnO in the presence of a liquid phase of the ZnO-BaO system has been studied for temperatures from 1300 to 1400 C. The specimens were treated in boiling water and the grains were separated by dissolving the matrix phase in an ultrasonic bath. As a consequence 3D grain size measurements were possible. Microstructural examination shows some grain coalescence with a wide range of neck size ratios and corresponding dihedral angles, however, most grains are isolated. Lognormal grain size distributions show similar shapes, indicating that the growth mechanism is invariant over this time and temperature. All regressions between G exp n and time for n = 2 and 3 proved statistically significant. The rate constants calculated with the growth exponent set to n = 3 are on the same order of magnitude as in metallic systems. The apparent activation energy for growth is estimated between 355 and 458 kJ/mol.

Yang, Sung-Chul↗

Conceptual design of HFIR irradiation experiment for material compatibility study on liquid Sn divertor

Liquid Sn is one of the promising coolants for liquid surface divertor concept of fusion reactors. However, the compatibility between liquid Sn and structural materials is an important issue that has to be addressed, because liquid Sn is extremely corrosive to steels at high temperatures. The corrosion may be mitigated when a protective Al2O 3 layer is formed on the surface of alumina forming steels. However, the effect of neutron irradiation on the integrity of protective layer is not made clear so far. Japan and US joint research project “FRONTIER” started in 2019 to investigate the material compatibility under neutron irradiation. The purpose of the present study is to develop the conceptual design of the irradiation test capsule which enables material compatibility tests for the alumina forming steels - liquid metal systems under neutron irradiation in the High Flux Isotope Reactor at Oak Ridge National Laboratory, TN, USA. The three dimensional drawing of capsule structure was then developed. The validity of the material selections for the capsule design was investigated by means of corrosion tests of SiC, Si3N4, Ti, and Mo in liquid Sn at 773 K for 262 hr.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Group Conductivity and Nonadiabatic Born Effective Charges of Disordered Metals, Warm Dense Matter, and Hot Dense Plasma

The average ionization state is a critical parameter in plasma models for charged particle transport, equations of state, and optical response. The dynamical or nonadiabatic Born effective charge (NBEC), calculated via first principles time-dependent density-functional theory, provides exact ionic partitioning of bulk electron response for both metallic and insulating materials. The NBEC can be transformed into a “group conductivity,” i.e., the electron conductivity ascribed to a subset of ions. We show that for disordered metallic systems, such as warm dense matter (WDM) and hot dense plasma, the static limit of the NBEC is different from the average ionization states, but that the ionization state can be extracted from the group conductivity even in mixed systems. Here we demonstrate this approach using a set of archetypical examples, including cold and warm aluminium, low- and high-density WDM carbon, and a WDM carbon-beryllium-hydrogen mixture.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Large-scale metal strip for power storage and energy conversion applications by machining-based deformation processing

Machining-based deformation processing is used to produce metal foil and flat wire (strip) with suitable properties and quality for electrical power and renewable energy applications. In contrast to conventional multistage rolling, the strip is produced in a single-step and with much less process energy. Examples are presented from metal systems of varied workability, and strip product scale in terms of size and production rate. By utilizing the large-strain deformation intrinsic to cutting, bulk strip with ultrafine-grained microstructure, and crystallographic shear-texture favourable for formability, are achieved. In conclusion, implications for production of commercial strip for electric motor applications and battery electrodes are discussed.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Atomic ionization: sd energy imbalance and Perdew–Zunger self-interaction correction energy penalty in 3d atoms

To accurately describe the energetics of transition metal systems, density functional approximations (DFAs) must provide a balanced description of s- and d- electrons. One measure of this is the sd transfer error, which has previously been defined as E ( 3 d n − 1 4 s 1 ) − E ( 3 d n − 2 4 s 2 ) . Theoretical concerns have been raised about this definition due to its evaluation of excited-state energies using ground-state DFAs. A more serious concern appears to be strong correlation in the 4s 2 configuration. Here, we define a ground-state measure of the sd energy imbalance, based on the errors of s- and d-electron second ionization energies of the 3d atoms, that effectively circumvents the aforementioned problems. We find an improved performance as we move from the local spin density approximation (LSDA) to the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA) to the regularized and restored Strongly Constrained and Appropriately Normed (r 2 SCAN) meta-GGA for first-row transition metal atoms. However, we find large (∼2 eV) ground-state sd energy imbalances when applying a Perdew–Zunger 1981 self-interaction correction. This is attributed to an “energy penalty” associated with the noded 3d orbitals. A local scaling of the self-interaction correction to LSDA results in a balance of s- and d-errors.

Science & Technology - Other Topics↗

A shear sensitive monomer-polymer liquid crystal system for wind tunnel applications

Characteristics of a liquid crystal system, comprised of a shear-sensitive cholesteric-monomer liquid crystal thin-film coated on a liquid-crystal polymer substrate, are described. The system provides stable Grandjean texture, a desirable feature for shear-stress measurements using selective reflection from the monomer liquid-crystal helix structure. Impingement of gas or air flow on the monomer liquid-crystal free surface changes the wavelength of the selective reflection for an incident white light from red toward blue with increase in the rate of gas flow. The contrast of the selectively reflected light improves considerably by providing a thin black coating of about 5 microns at the monomer-polymer interface. The coating thickness is such that the steric interactions are still sufficiently strong to maintain Grandjean texture. For a small angle of incidence of a monochromatic light, the measurement of the reflected light intensity normal to the monomer-polymer liquid-crystal interface enables the determination of the wavelength for selective reflection as a function of the gas-flow differential pressure applied in the plane of the interface. The variation of the wavelength with the pressure is linear with a slope of about 2 nm/mmHg. Furthermore, the shear-stress effects are reversible unlike for monomer liquid crystal-metal systems used for flow visualization on wind-tunnel model surfaces. The present system offers a suitable method for direct on-line measurement of shear stress field from measurements of the wavelength for selective reflection for an incident white light.

Parmar, D. S.↗

Directional Solidification of Monotectic and Hypermonotectic Aluminum-indium Alloys Under Micron-g

The objective of this program is to analyze the mechanisms involved in the composite solid structure formation obtained from a miscibility gap alloy under microgravity. The metallic system aluminum-indium was chosen for its low critical temperature, broad miscibility gap, and rather well-known thermodynamic properties. The experiment was performed aboard the Salyut-7 spacecraft. The theories of capture of particulates by an advancing front were not able to explain the observations made on SPAR and Salyut-7 experiments. A new model was developed based on the filtration theory considering the globules population: the solid/liquid interface is like a filter of negligible thickness for the globules and its efficiency is limited by a pressure barrier measured for Al-In alloys by ground based experiments. The Materials Experiment Assembly (MEA)-3 experiment was consequently adjusted to take into account the new model. The behavior of the globules in an interacting population on the solid front is, of course, an essential factor in the theory. The theory is at present being completed by results obtained by the Laboratoire d'Aerothermique of Meudon. The hydrodynamic and thermal interactions between pairs of globules placed in a temperature gradient have been calculated showing a large reduction of the Marangoni effect compared to the isolated globule. Physico-chemical properties of metallic liquid interface are currently being investigated.

Potard, C.↗

High-temperature mass spectrometry - Vaporization of group 4-B metal carbides

The high temperature vaporization of the metal-carbon systems TiC, ZrC, HfC, and ThC was studied by the Knudsen effusion - mass spectrometric method. For each system the metal dicarbide and tetracarbide molecular species were identified in the gas phase. Relative ion currents of the carbides and metals were measured as a function of temperature. Second- and third-law methods were used to determine enthalpies. Maximum values were established for the dissociation energies of the metal monocarbide molecules TiC, ZrC, HfC, and ThC. Thermodynamic functions used in the calculations are discussed in terms of assumed molecular structures and electronic contributions to the partition functions. The trends shown by the dissociation energies of the carbides of Group 4B are compared with those of neighboring groups and discussed in relation to the corresponding oxides and chemical bonding. The high temperature molecular beam inlet system and double focusing mass spectrometer are described.

Stearns, C. A.↗

Solid Phase Gradient Alloying Method via ShAPE

Alloying has been used to confer desirable properties to various metallic systems since the bronze age. For example, Ni, Mn, and Cr are alloyed into an Fe matrix to make steel, which has improved strength and corrosion resistance (as displayed in Fig. 1). In addition to the type of alloying elements, the amount of alloying elements added into a matrix is also very critical for a material’s mechanical property, physical property, machinability, and cost. Conventionally, new alloys are discovered by combining alloy precursors and elemental constituents into a mixture and melting them together. The solidified product or ingot represents a usually non-homogeneous combination of the chemistry with a microstructure dictated by the physics of solidification. It is time and energy intensive to optimize the alloying amounts via the casting process and hence, economically not conducive to rapid alloy discovery. In addition, the cast microstructure seen in the as-cast ingot is often not the ideal, nor even desired structure for optimized performance. Cast materials often need further processing such as homogenization, annealing, and deformation work put in through rolling, forging, extruding, etc. to have favorable microstructures and properties. A faster method to discover new alloy combinations and evaluate them in their worked or processed form is needed. Recently, Laser Engineered Net Shaping was applied to fabricate gradient compositional material for alloy designing. However, the mechanical properties of this gradient alloy were poor due to the existence of impurities, oxidation and cracks that are inherent in the melt-solidification process. Because of these limitations, we propose to use a solid-phase process (ShAPE) to create bulk materials (extrudates) that vary in composition from one end of the extruded solid to the other. Various manufacturing methods for alloy design including conventional casting method, laser based combinatorial method and current solid phase gradient alloying method are displayed and compared in Fig. 2. ShAPE machine and a schematic of ShAPE process are displayed in Fig. 3. Starting material is processed by a rotating and plunging die to form an extrudate. We are proposing through this methodology to invent a new, bulk-scale combinatorial technique. With this novel technique, alloying element can be dissolved into the matrix with a continued gradient without bulk melting. Formation of inter-metallics and defects originating from melt processing can be avoided. In addition, the ShAPE process creates the mixed alloy chemistry, and meanwhile subjects the material to severe plastic strain, which induces the favorable “worked” microstructure. Products from the ShAPE process can be tested in hardness directly providing a path to rapid evaluation of mechanical properties. The ability to create graded structures using friction stir processing (FSP) has been demonstrated, however using the ShAPE process we believe will lead to much faster and higher fidelity results. When combined with high throughput screening methods of physical, mechanical and microstructural property characterization, efficiency and accuracy of alloy design can be significantly improved.

36 MATERIALS SCIENCE↗

Controlling Exsolution Dynamics in High‐Entropy Oxides for Highly Active and Selective Acetylene Semi‐Hydrogenation

Exsolution-derived catalysts feature robust metal–support interactions that enhance catalytic performance; yet achieving precise control over exsolution dynamics in multicomponent oxides remains challenging. In this study, we demonstrate that exsolution behavior in high-entropy oxides (HEOs) can be rationally tuned through coupled lattice- and valence-engineering to create a highly active and selective catalyst for acetylene semi-hydrogenation. Incorporation of Li + into a rock salt-structured HEO (LiNiMgCuZnCoO x and LiHEO) induces local lattice distortion, generates oxygen vacancies, and partially oxidizes Co sites from Co 2+ to Co 3+ , collectively modulating local charge redistribution. This strategy enables facilitated Cu nanoparticle exsolution and alters the exsolution sequence from Cu 0 > Ni 0 > Co 0 in pristine HEO to Cu 0 > Co 0 > Ni 0 in the LiHEO. The resulting catalyst via controlled exsolution exhibits superior activity and ethylene selectivity, outperforming state-of-the-art transition metal systems. This work establishes entropy-enabled lattice and valence engineering as a facile route to programmable exsolution for enhanced catalysis.

36 MATERIALS SCIENCE↗

Radiative metallic thermal protection systems - A status report

During the early stages of the space shuttle program there were a number of technological uncertainties concerning the applicability of metallic thermal protection systems (TPS) to the multimission environment of the shuttle. To resolve the uncertainties and to advance the state-of-the-art, the NASA-Langley Research Center initiated a broad-based technology program to develop metallic TPS over the temperature range from 810 K to 1590 K. Wind tunnel tests conducted to assess the influence of surface/stream interaction of wavy surfaces on the design of metallic TPS indicate small increases in heat flux and surface drag for flow angles less than 20 deg. Analytical and experimental investigations, recently completed, have significantly improved prediction methods for cyclic creep behavior of TPS components repeatedly exposed to complex mission cycles. Thermal/structural concept optimization studies to minimize mass while maintaining structural integrity have led to advanced designs with unit masses which are competitive with those for shuttle RSI. In addition, the durability and reusability of metallic TPS have been repeatedly demonstrated in tests of full-scale systems. The current state-of-the-art strongly suggests that radiative metallic TPS have come of age.

Bohon, H. L.↗

High‐Efficiency Magnon‐Mediated Magnetization Switching in All‐Oxide Heterostructures with Perpendicular Magnetic Anisotropy

Abstract The search for efficient approaches to realize local switching of magnetic moments in spintronic devices has attracted extensive attention. One of the most promising approaches is the electrical manipulation of magnetization through electron‐mediated spin torque. However, the Joule heat generated via electron motion unavoidably causes substantial energy dissipation and potential damage to spintronic devices. Here, all‐oxide heterostructures of SrRuO 3 /NiO/SrIrO 3 are epitaxially grown on SrTiO 3 single‐crystal substrates following the order of the ferromagnetic transition metal oxide SrRuO 3 with perpendicular magnetic anisotropy, insulating and antiferromagnetic NiO, and metallic transition metal oxide SrIrO 3 with strong spin–orbit coupling. It is demonstrated that instead of the electron spin torques, the magnon torques present in the antiferromagnetic NiO layer can directly manipulate the perpendicular magnetization of the ferromagnetic layer. This magnon mechanism may significantly reduce the electron motion‐related energy dissipation from electron‐mediated spin currents. Interestingly, the threshold current density to generate a sufficient magnon current to manipulate the magnetization is one order of magnitude smaller than that in conventional metallic systems. These findings suggest a route for developing highly efficient all‐oxide spintronic devices operated by magnon current.

Zheng, Dongxing↗

Additive-Free Formic Acid Dehydrogenation Using a Pincer- Supported Iron Catalyst

The iron complex ( iPr PN Me P)Fe(H) 2 (CO) ( iPr PN Me P = CH 3 N(CH 2 CH 2 P i Pr 2 ) 2 ), which features a pincer ligand with a tertiary amine, can give up to 100,000 turnovers for additive-free formic acid dehydrogenation (FADH). This is two orders of magnitude higher than any previously reported base metal system. Furthermore, mechanistic studies reveal the catalytic reaction pathway and provide guidance for the development of improved catalytic systems for additive-free FADH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An additively manufactured near-eutectic Al-Ce-Ni-Mn-Zr alloy with high creep resistance

A new additively manufactured (AM) Al-7.5Ce-4.5Ni-0.4Mn-0.7Zr (wt.%) near-eutectic alloy is reported, which shows unprecedented creep resistance up to 400 °C (a homologous temperature of 0.72). The eutectic solidification microstructure comprises ~ 27 vol% of coarsening-resistant second phase network with an ultrafine (<100 nm) inter-phase spacing. Both Mn and Zr contribute to creep resistance of the alloy. Small amount of Mn addition promotes selection of coarsening resistant phases without compromising the alloy processability. Zr not only improves hot-tearing resistance, but further enhances the second phase coarsening resistance resulting in improved creep resistance. Neutron diffraction performed during creep deformation reveals that the underlying mechanism for creep resistance in this alloy is impedance to dislocation motion stemming from the ultrafine eutectic solidification microstructure, whereas load transfer strengthening becomes less effective as the creep temperature increases. The second phase forms a continuous network in the as-fabricated condition, which is maintained during long-term creep at 300 °C. However, this network is fragmented into fine dispersoids at higher temperatures. It is proposed that the rate-limiting deformation mechanism at 300–400 °C is (i) dislocation climb for the alloy with fragmented second phase dispersoids and (ii) Orowan looping for the alloy with a continuous second phase network. In conclusion, the present design of an AM-processable multicomponent eutectic alloy with high creep resistance can be applied to other metallic systems exhibiting eutectic reactions, with expected extreme creep resistance.

36 MATERIALS SCIENCE↗

Operando synchrotron X-ray analysis of melt pool dynamics in an Al-Sn immiscible alloy

The melt flow in an Al-50vol.% Sn immiscible alloy, produced by single-track laser melting of Al and Sn elemental powders, was studied in real time. High-speed synchrotron X-ray imaging was used to track Al and Sn liquids’ movements, and also to examine elemental distributions in the laser tracks, complimented by electron microscopy after solidification. Key aspects, including melt pool geometry, keyhole instability, and flow dynamics (flow pattern and velocity), were examined using digital image analysis. Relatively deeper melt pools formed at 400 W and 300 mm/s exhibited greater stability, with smooth surfaces, consistent outward flow, and minor vortices near the keyhole. In contrast, shallower pools produced at higher scanning speeds (>500 mm/s) demonstrated greater instability with increased surface waviness, and stronger velocity fluctuations, leading to numerous micro-vortices and increased Al-Sn heterogeneity. Velocity scale estimations, supported by experimental observations, examined the roles of vapour pressure, Marangoni effect, buoyancy, inertial, and surface tension forces in the flow. The results revealed that vapour pressure and mechanical waves dominated at high scanning speeds (shallow pools), while Marangoni forces were equally significant in deep pools at lower speeds (300 mm/s). Buoyancy was found to have minimal impact in both cases. Furthermore, the interaction between inertial and surface tension forces played a critical role in determining the degree of waviness of the pools’ surfaces. These findings offer valuable insights into melt pool dynamics during laser processing of immiscible alloys and other metallic systems using elemental powders, and provide guidance for developing high-fidelity computational fluid dynamics models.

immiscible alloys↗

From electricity to fuels: Descriptors for C 1 selectivity in electrochemical CO 2 reduction

Electrochemical reduction of carbon dioxide (CO 2 RR) over transition metals follows a complex reaction network. Here, we combine observations from experimental literature with a theoretical analysis of energetics to rationalize that not all intermediates in the reduction of CO 2 are formed through direct protonation steps. We derive a selectivity map for two-electron products (carbon monoxide (CO) and formate) on pure metal surfaces using only the CO and OH binding energies as descriptors. For the pure metals that are selective towards CO formation, the variation of the CO binding energy is sufficient to further subdivide the map into domains that predominantly form H 2 , CO, and more reduced products. Our analysis rationalizes experimentally observed product distributions in CO 2 RR across pure metal systems. Overall, we highlight the need for additional material screening descriptors for CO 2 R and the importance of considering competition from the elementary steps of the hydrogen evolution reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pd and octahedra do not get along: Square planar [PdS 4 ] units in non-centrosymmetric La 6 PdSi 2 S 14

Non-linear optical (NLO) materials require a balance of high second-harmonic generation (SHG) signal and laser damage threshold (LDT), as well as phase matchable behavior. Herein, we report a new member of the (RE) 6 (TM) x (Tt) 2 Q 14 family of compounds, La 6 PdSi 2 S 14 , which, unlike all other reported TM analogues crystallizing in hexagonal P6 3 space group, crystallizes in the non-centrosymmetric monoclinic P2 1 space group. The crystal structure contains chains of edge-sharing distorted square planar [PdS 4 ] units. The square-planar coordination of Pd in La 6 PdSi 2 S 14 exhibits remarkable NLO properties with high SHG (3.7 × AgGaS 2 ) and LDT (3 × AgGaS 2 ) values as well as phase matchability. This shows the promise of novel materials with distorted structural motifs for enhanced NLO properties. Further, upon formation of bimetallic chiral sulfides containing both Cu and Pd, Cu occupies the opposite faces of the octahedra forming [CuS 3 ] units while Pd can be stabilized in the center of PdS 6 octahedra in the hexagonal P6 3 crystal structure of La 6 Pd 0.5 CuSi 2 S 14 . This suggests that it is possible to form mixed metal systems which could further enhance NLO properties by incorporation of additional structural distortions.

36 MATERIALS SCIENCE↗