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DOE OSTI2021

Kinetics of solid–liquid interface motion in molecular dynamics and phase-field models: crystallization of chromium and silicon

The results of molecular dynamics (MD) simulations of the crystallization process in one-component materials and solid solution alloys reveal a complex temperature dependence of the velocity of the crystal–liquid interface featuring an increase up to a maximum at 10–30% undercooling below the equilibrium melting temperature followed by a gradual decrease of the velocity at deeper levels of undercooling. At the qualitative level, such non-monotonous behaviour of the crystallization front velocity is consistent with the diffusion-controlled crystallization process described by the Wilson–Frenkel model, where the almost linear increase of the interface velocity in the vicinity of melting temperature is defined by the growth of the thermodynamic driving force for the phase transformation, while the decrease in atomic mobility with further increase of the undercooling drives the velocity through the maximum and into a gradual decrease at lower temperatures. At the quantitative level, however, the diffusional model fails to describe the results of MD simulations in the whole range of temperatures with a single set of parameters for some of the model materials. The limited ability of the existing theoretical models to adequately describe the MD results is illustrated in the present work for two materials, chromium and silicon. It is also demonstrated that the MD results can be well described by the solution following from the hodograph equation, previously found from the kinetic phase-field model (kinetic PFM) in the sharp interface limit. The ability of the hodograph equation to describe the predictions of MD simulation in the whole range of temperatures is related to the introduction of slow (phase field) and fast (gradient flow) variables into the original kinetic PFM from which the hodograph equation is obtained. The slow phase-field variable is responsible for the description of data at small undercoolings and the fast gradient flow variable accounts for local non-equilibrium effects at high undercoolings. The introduction of these two types of variables makes the solution of the hodograph equation sufficiently flexible for a reliable description of all nonlinearities of the kinetic curves predicted in MD simulations of Cr and Si. This article is part of the theme issue ‘Transport phenomena in complex systems (part 1)’.

Science & Technology - Other Topics↗

NASA NTRS2007

Analytical Approach for Estimating Preliminary Mass of ARES I Crew Launch Vehicle Upper Stage Structural Components

In January 2004, President Bush gave the National Aeronautics and Space Administration (NASA) a vision for Space Exploration by setting our sight on a bold new path to go back to the Moon, then to Mars and beyond. In response to this vision, NASA started the Constellation Program, which is a new exploration launch vehicle program. The primary mission for the Constellation Program is to carry out a series of human expeditions ranging from Low Earth Orbit to the surface of Mars and beyond for the purposes of conducting human exploration of space, as specified by the Vision for Space Exploration (VSE). The intent is that the information and technology developed by this program will provide the foundation for broader exploration activities as our operational experience grows. The ARES I Crew Launch Vehicle (CLV) has been designated as the launch vehicle that will be developed as a "first step" to facilitate the aforementioned human expeditions. The CLV Project is broken into four major elements: First Stage, Upper Stage Engine, Upper Stage (US), and the Crew Exploration Vehicle (CEV). NASA's Marshall Space Flight Center (MSFC) is responsible for the design of the CLV and has the prime responsibility to design the upper stage of the vehicle. The US is the second propulsive stage of the CLV and provides CEV insertion into low Earth orbit (LEO) after separation from the First Stage of the Crew Launch Vehicle. The fully integrated Upper Stage is a mix of modified existing heritage hardware (J-2X Engine) and new development (primary structure, subsystems, and avionics). The Upper Stage assembly is a structurally stabilized cylindrical structure, which is powered by a single J-2X engine which is developed as a separate Element of the CLV. The primary structure includes the load bearing liquid hydrogen (LH2) and liquid oxygen (LOX) propellant tanks, a Forward Skirt, the Intertank structure, the Aft Skirt and the Thrust Structure. A Systems Tunnel, which carries fluid and electrical power functions to other Elements of the CLV, is included as secondary structure. The MSFC has an overall responsibility for the integrated US element as well as structural design an thermal control of the fuel tanks, intertank, interstage, avionics, main propulsion system, Reaction Control System (RCS) for both the Upper Stage and the First Stage. MSFC's Spacecraft and Vehicle Department, Structural and Analysis Design Division is developing a set of predicted mass of these elements. This paper details the methodology, criterion and tools used for the preliminary mass predictions of the upper stage structural assembly components. In general, weight of the cylindrical barrel sections are estimated using the commercial code Hypersizer, whereas, weight of the domes are developed using classical solutions. HyperSizer is software that performs automated structural analysis and sizing optimization based on aerospace methods for strength, stability, and stiffness. Analysis methods range from closed form, traditional hand calculations repeated every day in industry to more advanced panel buckling algorithms. Margin-of-safety reporting for every potential failure provides the engineer with a powerful insight into the structural problem. Optimization capabilities include finding minimum weight panel or beam concepts, material selections, cross sectional dimensions, thicknesses, and lay-ups from a library of 40 different stiffened and sandwich designs and a database of composite, metallic, honeycomb, and foam materials. Multiple different concepts (orthogrid, isogrid, and skin stiffener) were run for multiple loading combinations of ascent design load with and with out tank pressure as well as proof pressure condition. Subsequently, selected optimized concept obtained from Hypersizer runs was translated into a computer aid design (CAD) model to account for the wall thickness tolerance, weld land etc for developing the most probable weight of the components. The flow diram summarizes the analysis steps used in developing these predicted mass.

Aggarwal, Pravin↗

DOE OSTI2020

Charge Transport in Zirconium-Based Metal–Organic Frameworks

Metal–organic frameworks (MOFs) are a class of crystalline porous materials characterized by inorganic nodes and multitopic organic linkers. Because of their molecular-scale porosity and periodic intraframework chemical functionality, MOFs are attractive scaffolds for supporting and/or organizing catalysts, photocatalysts, chemical-sensing elements, small enzymes, and numerous other functional-property-imparting, nanometer-scale objects. Notably, these objects can be installed after the synthesis of the MOF, eliminating the need for chemical and thermal compatibility of the objects with the synthesis milieu. Thus, postsynthetically functionalized MOFs can present three-dimensional arrays of high-density, yet well-separated, active sites. Depending on the application and corresponding morphological requirements, MOF materials can be prepared in thin-film form, pelletized form, isolated single-crystal form, polycrystalline powder form, mixed-matrix membrane form, or other forms. For certain applications, most obviously catalytic hydrolysis and electro- or photocatalytic water splitting, but also many others, an additional requirement is water stability. MOFs featuring hexa-zirconium(IV)-oxy nodes satisfy this requirement. For applications involving electrocatalysis, charge storage, photoelectrochemical energy conversion, and chemiresistive sensing, a further requirement is electrical conductivity, as embodied in electron or hole transport. As most MOFs, under most conditions, are electrically insulating, imparting controllable charge-transport behavior is both a chemically intriguing and chemically compelling challenge. Herein, we describe three strategies to render zirconium-based metal–organic frameworks (MOFs) tunably electrically conductive and, therefore, capable of transporting charge on the few nanometers (i.e., several molecular units) to few micrometers (i.e., typical dimensions for MOF microcrystallites) scale. The first strategy centers on redox-hopping between periodically arranged, chemically equivalent sites, essentially repetitive electron (or hole) self-exchange. Zirconium nodes are electrically insulating, but they can function as grafting sites for (a) redox-active inorganic clusters or (b) molecular redox couples. Alternatively, charge hopping based on linker redox properties can be exploited. Marcus’s theory of electron transfer has proven useful for understanding/predicting trends in redox-hopping based conductivity, most notably, in accounting for variations as great as 3000-fold depending on the direction of charge propagation through structurally anisotropic MOFs. In MOF environments, propagation of electronic charge via redox hopping is necessarily accompanied by movement of charge-compensating ions. Consequently, rates of redox hopping can depend on both the identity and concentration of ions permeating the MOF. In the context of electrocatalysis, an important goal is to transport electronic charge fast enough to match or exceed the inherent activity of MOF-based or MOF-immobilized catalysts. Bandlike electronic conductivity is the focus of an alternative strategy: one based on the introduction of molecular guests capable of forming donor–acceptor charge transfer complexes with the host framework. Theory again can be applied predictively to alter conductivity. A third strategy similarly emphasizes electronic conductivity, but it makes use of added bridges in the form of molecular oligomers or inorganic clusters that can then be linked to span the length of a MOF crystallite. For all strategies, retention of molecular-scale porosity is emphasized, as this property is key to many applications. Lastly, while our focus is on Zr-MOFs, the described approaches clearly are extendable to other MOF compositions, as has already been demonstrated, in part, in studies by others.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Non-nuclear Component Signatures for Warhead Dismantlement Confirmation

The verification of warhead dismantlement is expected to be an important component in future arms reduction treaties. Historic approaches developed with future arms control treaty verification in mind often involve intrusive measurements, process monitoring, and/or inspector presence to provide confidence that an authentic warhead has been dismantled. This work explores the possibility of reducing the negative impacts of these invasive approaches while also delivering a method that is more likely to provide non-sensitive data that can be shared with not only other nuclear weapons states but also non-nuclear weapons states partners. This work explores a novel approach for verifying dispositioned non-nuclear weapon components, providing confidence post-dismantlement that a treaty accountable item that was dismantled was in fact a treaty-relevant nuclear weapon system as declared. This method provides an alternative to intrusive inspection processes in nuclear weapons production environments, which would require significant changes to the host’s operational behaviors. It achieves this by identifying intrinsic neutron-induced signatures of non-nuclear components to determine their authenticity and estimate the duration they were exposed within a nuclear weapons system using technologies that are already in use for other national security applications. Intrinsic radiation effects studies are already a part of the stockpile aging and surveillance evaluations. However, none of these technologies and approaches have been previously considered for verification applications of non-nuclear component disposition. In this report, we introduce modeling studies that have been used to identify the most promising candidate parts and materials with signatures that are measurable and actionable. These models have been validated with laboratory measurements of signatures induced by the exposure of candidate materials to neutrons over a range of times. Predictive modeling then demonstrates the methodology for estimating exposure times and/or limits. Laboratory measurements of authentic non-nuclear parts from a dismantled warhead demonstrate the feasibility of employing these signature measurements. And finally, a concept of operations (CONOPS) for the potential use of this methodology is presented.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

NASA NTRS2013

Detection and Quantification of Nitrogen Compounds in Martian Solid Samples by the Sample Analysis at Mars (SAM) Instrument Suite

The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity Rover detected both reduced and oxidized nitrogen-bearing compounds during the pyrolysis of surface materials from three sites at Gale Crater. Preliminary detections of nitrogen species include NO, HCN, ClCN, CH3CN, and TFMA (trifluoro-Nmethyl-acetamide). On Earth, nitrogen is a crucial bio-element, and nitrogen availability controls productivity in many environments. Nitrogen has also recently been detected in the form of CN in inclusions in the Martian meteorite Tissint, and isotopically heavy nitrogen (delta N-15 approx +100per mille) has been measured during stepped combustion experiments in several SNC meteorites. The detection of nitrogen-bearing compounds in Martian regolith would have important implications for the habitability of ancient Mars. However, confirmation of indigenous Martian nitrogen bearing compounds will require ruling out their formation from the terrestrial derivatization reagents (e.g. N-methyl-N-tert-butyldimethylsilyl-trifluoroacetamide, MTBSTFA and dimethylformamide, DMF) carried for SAM's wet chemistry experiment that contribute to the SAM background. The nitrogen species we detect in the SAM solid sample analyses can also be produced during laboratory pyrolysis experiments where these reagents are heated in the presence of perchlorate, a compound that has also been identified by SAM in Mars solid samples. However, this does not preclude a Martian origin for some of these compounds, which are present in nanomolar concentrations in SAM evolved gas analyses. Analysis of SAM data and laboratory breadboard tests are underway to determine whether nitrogen species are present at higher concentrations than can be accounted for by maximum estimates of nitrogen contribution from MTBSTFA and DMF. In addition, methods are currently being developed to use GC Column 6, (functionally similar to a commercial Q-Bond column), to separate and identify unretained compounds such as NO, N2O, and NO2, which are difficult to detect by EGA-MS due to mass interferences at 30, 44 and 46, respectively. Here we present evolved gas analysis-mass spectrometry (EGA-MS) and gas chromatography mass spectrometry (GC-MS) data on the identification and quantification of these nitrogen-bearing compounds, and suggestions for their origins

Stern, Jennifer C.↗

DOE OSTI2022

The stability of expanding reactive shocks in a van der Waals fluid

Despite the extensive literature accumulated since the pioneering works of D'yakov and Kontorovich in the 1950s, the stability of steady shocks is still an open question when realistic boundary conditions are accounted. The consideration of a supporting mechanism, which is indeed a necessary condition for shock steadiness, modifies the perturbation shock dynamics in the unstable range. The Noh problem is a suitable example to form steady expanding shocks. This configuration is of great interest to the high-energy-density-physics community because of its direct application to inertial confinement fusion and astrophysics, for which the stagnation of a supersonically converging material via an accretion shock front is ubiquitous. Here in this work, we extend the generalized Noh problem, both base-flow solution and linear stability analysis, to conditions where endothermic or exothermic transformations undergo across the shock. Within the spontaneous acoustic emission conditions found for a van der Waals gas, we find that cylindrical and spherical expanding shocks become literally unstable for sufficiently high mode numbers. Counterintuitively, the effect of exothermicity or endothermicity across the shock is found to be stabilizing or destabilizing, respectively.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2025

Visible-light H 2 evolution using dye-sensitized TiO 2 : effects of physicochemical properties of TiO 2 on excited carrier dynamics and activity

Dye-sensitized photocatalysts have emerged as promising materials for solar-driven water splitting due to their ability to utilize visible light, in contrast to conventional wide-band-gap semiconductors. However, the relationship between semiconductor properties and charge carrier dynamics remains insufficiently understood. In this study, we investigated Pt/TiO 2 systems sensitized with a visible-light-absorbing Ru(II) polypyridyl complex (RuP), focusing on how the crystal phase and specific surface area of TiO 2 influence excited carrier dynamics and H 2 evolution activity. To isolate the effects of TiO 2 properties, Pt and RuP loadings were standardized across samples. Emission lifetime analysis showed similarly efficient electron injection from RuP to TiO 2 in all cases, suggesting that injection efficiency does not account for observed differences in activity. Transient absorption measurements revealed that back electron transfer (BET) rates depended strongly on the TiO 2 phase, with anatase and P25 exhibiting slower BET and higher activity for H 2 evolution than rutile. The highest apparent quantum yield for H 2 evolution was 12.0% at 450 nm. Among anatase samples, larger surface areas correlated with higher activity, while smaller-area samples exhibited slower BET rates but still low H 2 evolution activity, implying a role for RuP dye–dye interactions in performance loss. This was further supported by improvements in H 2 evolution activity by lowering RuP loading or adding co-adsorbents. Overall, these results demonstrate that both BET suppression and control over RuP dye aggregation are essential for designing efficient dye-sensitized photocatalytic systems.

Harada, Kakeru [Institute of Science Tokyo (Japan)↗

DOE OSTI2020

A phase-field model for non-isothermal phase transformation and plasticity in polycrystalline yttria-stabilized tetragonal zirconia

Here we propose an elastoplastic phase-field (PF) model to investigate the mechanics of tetragonal-to-monoclinic phase transformation (TMPT) and elastoplastic deformation of polycrystalline yttria-stabilized tetragonal zirconia (YSTZ). A Landau polynomial with non-vanishing chemical energy at the equilibrium temperature is introduced to account for the actual formation energies of the phases. The effects of different grain orientations, latent heat, and temperature on TMPT and deformation mechanisms are considered. The suppressive transformation effects of the grain boundaries (GBs) is modeled using an inhomogeneous kinetic coefficient in the bulk and GBs. The simulation results for single crystals demonstrate the capability of the model to reproduce the orientation-dependent compressive deformation of YSTZ similar to atomistic simulations and micropillar experiments. The single crystal with [100] crystallographic orientation along the loading direction (SC[100]) displays both TMPT and plasticity, SC[101] experiences only phase transformation, while SC[001] undergoes only plastic yielding. The TMPT induced by compressive loading exhibits shape memory effect (SME) below the equilibrium transformation temperature and pseudoelasticity above it, while the critical transformation stress increases with increasing loading temperature. The irrecoverable plastic strain is found to trap a part of the monoclinic phase, which prevents a complete reverse transformation. The polycrystalline cases also display SME and PE at low and high temperatures, respectively. Due to the orientation differences between grains and the stress concentrations at geometric nonlinearities, plastic deformation occurs in polycrystalline YSTZ for an applied load less than the yield stress. The results suggest a possible limitation of plasticity and an improvement of the shape recovery of YSTZ if one can control the orientation of the grains and/or increase the density of stacking faults at the GBs during material processing.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Photothermal alternative to device fabrication using atomic precision advanced manufacturing techniques

The attachment of dopant precursor molecules to depassivated areas of hydrogen-terminated silicon templated with a scanning tunneling microscope (STM) has been used to create electronic devices with subnanometer precision, typically for quantum physics experiments. This process, which we call atomic precision advanced manufacturing (APAM), dopes silicon beyond the solid-solubility limit and produces electrical and optical characteristics that may also be useful for microelectronic and plasmonic applications. However, scanned probe lithography lacks the throughput required to develop more sophisticated applications. In this work, we demonstrate and characterize an APAM device workflow where scanned probe lithography of the atomic layer resist has been replaced by photolithography. An ultraviolet laser is shown to locally and controllably heat silicon above the temperature required for hydrogen depassivation on a nanosecond timescale, a process resistant to under- and overexposure. STM images indicate a narrow range of energy density where the surface is both depassivated and undamaged. Modeling that accounts for photothermal heating and the subsequent hydrogen desorption kinetics suggests that the silicon surface temperatures reached in our patterning process exceed those required for hydrogen removal in temperature-programmed desorption experiments. A phosphorus-doped van der Pauw structure made by sequentially photodepassivating a predefined area and then exposing it to phosphine is found to have a similar mobility and higher carrier density compared with devices patterned by STM. Lastly, it is also demonstrated that photodepassivation and precursor exposure steps may be performed concomitantly, a potential route to enabling APAM outside of ultrahigh vacuum.

nanoscale devices↗

NASA NTRS1960

Thermal-Fatigue Crack-Growth Characteristics and Mechanical Strain Cycling Behavior of A-286 Discaloy, and 16-25-6 Austenitic Steels

Thermal-fatigue crack-growth characteristics of notched- and unnotched-disk specimens of A-286, Discaloy, hot-cold worked 16-25-6, and overaged 16-25-6 were experimentally studied. Separately controlled variables were total strain range (0.0043 to 0.0079 in./in.), maximum cycle temperature (1300 and 1100 F), and hold time at maximum temperature (O and 5 min). A limited number of mechanical, push-pull, constant-strain cycle tests at room temperature were made using notched and un-notched bars of the same materials. In these tests the number of cycles to failure as well as the variation of load change with accumulated cycles was measured, and the effects of mean stress were observed. Constant-strain-range mechanical-fatigue tests at room temperature revealed notched-bar fatigue life to be strongly influenced by mean stress. For a specific strain range, the longest fatigue life was always found to be associated with the least-tensile (or most compressive) mean stress. By defining thermal-fatigue life as the number of cycles required to produce a crack area of 6000 square mils, the relative thermal-fatigue resistances of the test materials were established. Notched-disk specimens of A-286 and Discaloy steels exhibited longer fatigue lives than either hot-cold worked or overaged 16-25-6. On the other hand, unnotched-disk specimens of Discaloy and hot-cold worked 16-25-6 had longer lives than A-286 and overaged 16-25-6. Separation of the crack-growth data into microstage and macrostage periods revealed that the macrostage period accounted for the greatest part of the difference among materials when tested in the notched configuration, while the microstage was largely responsible for the differences encountered in unnotched disks.

Smith, Robert W.↗

DOE OSTI2020

Tunable chemical complexity to control atomic diffusion in alloys

Abstract In this paper we report a new fundamental understanding of chemically-biased diffusion in Ni–Fe random alloys that is tuned/controlled by the intrinsic quantifiable chemical complexity. Development of radiation-tolerant alloys has been a long-standing challenge. Here we show how intrinsic chemical complexity can be utilized to guide the atomic diffusion and suppress radiation damage. The influence of chemical complexity is shown by the example of interstitial atom (IA) diffusion that is the most important defect in radiation effects. We use μs-scale molecular dynamics to reveal sluggish diffusion and percolation of IAs in concentrated Ni–Fe alloys. We develop a mean field diffusion model to take into account the effect of migrating defect energy properties on diffusion percolation, which is verified by a new kinetic Monte Carlo approach addressing detailed processes. We demonstrate that the local variations in the ground state energy of IA configurations in alloys, reflecting the chemical difference between alloying components, drives the percolation effects for atomic diffusion. Percolation, chemically-biased and sluggish diffusion are phenomena that are directly related to the chemical complexity intrinsically to multicomponent alloys.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Electrochemical Switching of a Fluorescent Molecular Rotor Embedded within a Bistable Rotaxane

We report how the nanoconfined environment, introduced by the mechanical bonds within an electrochemically switchable bistable [2]rotaxane, controls the rotation of a fluorescent molecular rotor, namely, an 8-phenyl-substituted boron dipyrromethene (BODIPY). The electrochemical switching of the bistable [2]rotaxane induces changes in the ground-state coconformation and in the corresponding excited-state properties of the BODIPY rotor. In the starting redox state, when no external potential is applied, the cyclobis(paraquat-p-phenylene) (CBPQT4+) ring component encircles the tetrathiafulvalene (TTF) unit on the dumbbell component, leaving the BODIPY rotor unhindered and exhibiting low fluorescence. Upon oxidation of the TTF unit to a TTF2+ dication, the CBPQT4+ ring is forced toward the molecular rotor, leading to an increased energy barrier for the excited state to rotate the rotor into the state with a high nonradiative rate constant, resulting in an overall 3.4-fold fluorescence enhancement. On the other hand, when the solvent polarity is high enough to stabilize the excited charge-transfer state between the BODIPY rotor and the CBPQT4+ ring, movement of the ring toward the BODIPY rotor produces an unexpectedly strong fluorescence signal decrease as the result of photoinduced electron transfer from the BODIPY rotor to the CBPQT4+ ring. The nanoconfinement effect introduced by mechanical bonding can effectively lead to modulation of the physicochemical properties as observed in this bistable [2]rotaxane. On account of the straightforward synthetic strategy and the facile modulation of switchable electrochromic behavior, our approach could pave the way for the development of new stimuli-responsive materials based on mechanically interlocked molecules for future electro-optical applications, such as sensors, molecular memories, and molecular logic gates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1999

Dynamical and Chemical Behavior of the Lower Stratosphere and Interactions with the Troposphere

Equivalent-barotropic calculations, in tandem with Lagrangian analyses, reveal how changes of total ozone follow from vertical and horizontal transport by planetary waves. Those calculations also throw light on how diabatic motions comprising the Brewer-Dobson circulation develop from quasi-horizontal advection by planetary waves. Potential temperature along a material surface indicates organized subsidence inside the polar-night vortex, resembling tracer observations from UARS. Lagrangian histories illustrate that this sinking motion follows in large part from parcels being driven out of thermodynamic equilibrium by planetary waves, especially at high latitudes. Irreversible heat transfer then produces a net drift of air across isentropic surfaces as parcels orbit about the displaced vortex. By driving mean-meridional overturning in the stratosphere, this downward drift is ultimately responsible for transferring ozone from the tropics to the extratropical lower stratosphere. It also introduces horizontal structure into the distribution of total ozone, which surfaces clearly in ozone trends. High-resolution global cloud imagery constructed from 6 satellites simultaneously observing the Earth was used to investigate the spectrum of equatorial waves generated by tropical convection and propagating vertically into the stratosphere. The results indicate that temperature variability is dominated by planetary-scale equatorial waves like the Kelvin mode, which agrees with satellite observations of the tropical stratosphere. However, the Kelvin mode accounts for only about 30 - 50% of the eastward momentum flux radiating into the stratosphere, the remainder coming from gravity waves. An algorithm was developed to determine 3-dimensional atmospheric motion from satellite tracer measurements. Based on Lagrangian constraints, the algorithm circumvents limitations of the traditional scheme for inferring motion from temperature measurements and determines the circulation in the tropics as reliably as elsewhere. A study of deep convection revealed that the highest towers (those penetrating into stratospheric air and controlling tropopause height and composition through convective mixing) occur in close association with the diurnal cycle of convection. Clouds colder than 220 K develop almost entirely in association with the diurnal cycle of convection over tropical landmasses and substantially in association with it even over maritime regions.

Salby, Murry L.↗

DOE OSTI2021

Design Principles for Efficient and Stable Water Splitting Photoelectrocatalysts

Photoelectrochemical water splitting is a promising avenue for sustainable production of hydrogen used in the chemical industry and hydrogen fuel cells. The basic components of most photoelectrochemical water splitting systems are semiconductor light absorbers coupled to electrocatalysts, which perform the desired chemical reactions. A critical challenge for the design of these systems is the lack of stability for the majority of desired semiconductors under operating water splitting conditions. One strategy to address this issue is to protect the semiconductor by covering it with a stabilizing insulator layer, creating a metal–insulator–semiconductor (MIS) architecture, which has demonstrated improved stability. In addition to enhanced stability, the insulator layer may significantly affect the electron and hole transfer, which governs the recombination rates. Furthermore, the insertion of an insulator layer leads to the introduction of additional insulator/electrocatalyst and insulator/semiconductor interfaces. These interfaces can impact the system’s performance significantly, and they need to be carefully engineered to optimize the efficiencies of MIS systems. In this Account, we describe our recent progress in shedding light on the critical role of the insulator and the interfaces on the performance of MIS systems. We discuss our findings by focusing on the concrete example of planar n-type Si protected by a HfO 2 insulator layer and coupled to a Ni or Ir electrocatalyst that performs the oxygen evolution reaction, one of the water splitting half-reactions. To improve our fundamental understanding of the insulator layer, we precisely control the HfO 2 insulator thickness using atomic layer deposition (ALD), and we perform a series of rigorous electrochemical experiments coupled with theory and modeling. We demonstrate that by tuning the insulator thickness, we can control the flux and recombination of photogenerated electrons and holes to optimize the generated photovoltage. Despite optimizing the thickness, we find that the maximum generated photovoltage in MIS systems is often significantly lower than the upper performance limit, i.e., there are additional losses in the system that could not be addressed by optimizing the insulator thickness. We identify the sources of these losses and describe strategies to minimize them by a combination of improving the semiconductor light absorption, removing nonidealities associated with interfacial defects, and finding alternative insulators with improved charge carrier selectivity. Finally, we quantify the improvements that can be obtained by implementing these specific strategies. Our collective work outlines strategies to analyze MIS systems, identify the sources of efficiency losses, and optimize the design to approach the fundamental performance limits. Furthermore, these general approaches are broadly applicable to photoelectrochemical materials that utilize sunlight to produce value-added chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Characterizing Absolute Orientations in DNA Self-Assembly of Single Molecules

DNA self-assembly of single molecules (i.e., dyes) with deterministic orientations is a powerful approach for engineering mo-lecular excitons. However, current determination methods of the dye orientation relative to DNA do not account for the orien-tation of the dye plane, which is a missing degree of freedom needed to define absolute three-dimensional orientations. In this work, we combine fluorescence-detected linear dichroism, defocused dipole imaging, and DNA points accumulation for imaging in nanoscale topography (DNA-PAINT) super-resolution microscopy to determine the absolute three-dimensional orientations of single Cy5 dyes relative to host DNA duplexes which includes the dye plane orientation. The data revealed that the absorption and emission dipoles are perpendicular to the DNA duplex, and the mean dye plane is parallel to the DNA bases, which supports the notion that Cy5 dyes intercalate between DNA base pairs. The presented methodology will inspire the investigation of the dye plane orientation for controlling dye arrangement configurations beyond spontaneous π-stacking between dyes as well as achieving novel dye-DNA arrangements.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Role of element-specific damping in ultrafast, helicity-independent, all-optical switching dynamics in amorphous (Gd,Tb)Co thin films

Ultrafast control of the magnetization in ps timescales by fs laser pulses offers an attractive avenue for applications such as fast magnetic devices for logic and memory. However, ultrafast helicity-independent all-optical switching (HI-AOS) of the magnetization has thus far only been observed in Gd-based, ferrimagnetic amorphous (a-) rare earth-transition metal (a-RE-TM) systems, and a comprehensive understanding of the reversal mechanism remains elusive. Here, we report HI-AOS in ferrimagnetic a-Gd 22-x Tb x Co 78 thin films, from x=0 to 18, and elucidate the role of Gd in HI-AOS in a-RE-TM alloys and multilayers. Increasing Tb content results in increasing perpendicular magnetic anisotropy and coercivity, without modifying magnetization density, and slower remagnetization rates and higher critical fluences for switching but still shows picosecond HI-AOS. Simulations of the atomistic spin dynamics based on the two-temperature model reproduce these results qualitatively and predict that the lower damping on the RE sublattice arising from the small spin-orbit coupling of Gd (with L=0) is instrumental for the faster dynamics and lower critical fluences of the Gd-rich alloys. Annealing a-Gd 10 Tb 12 Co 78 leads to slower dynamics which we argue is due to an increase in damping. These simulations strongly indicate that accounting for element-specific damping is crucial in understanding HI-AOS phenomena. The results suggest that engineering the element-specific damping of materials can open up new classes of materials that exhibit low-energy, ultrafast HI-AOS.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2021

Numerical study to predict the effect of surface roughness on the thermal and hydraulic performance of additively manufactured heat exchangers

Heat exchangers are used in many industries to transfer thermal energy between two or more objects with an associated thermal and hydraulic performance indicated by thermal effectiveness and pressure drop respectively. Many investigations have aimed to enhance the thermal effectiveness of heat exchangers by introducing turbulent flow inducers that increase the heat transfer rate at the expense of increasing pressure drop. Flow inducers like surface roughness can be controlled with advanced manufacturing methods like additive manufacturing for heat exchanger production. Selecting and manufacturing an optimal surface roughness for heat exchangers requires a more comprehensive approach that accounts for the surface roughness effect on the thermal and hydraulic performance of a sample. Since fabricating samples with additive manufacturing to a desired surface roughness can be an extensive experimental process, this study will fundamentally investigate the effect of surface roughness on the thermal and velocity boundary layers for various surface roughness profiles with physics-based computational modeling. To accurately model the surface roughness effect on thermohydraulic performance, correlations like roughness ratio, friction factor, and Nusselt number are investigated. This study expects to indicate correlations for different flow regimes which can successfully predict the effect of surface roughness on thermohydraulic performance. Results generated from modeling surface roughness effect with unique correlations are then compared to experimental data obtained from literature for validation. The results of this study will provide insight to understand the thermal fluid physics associated with surface roughness and design guidelines for heat exchangers produced with additive manufacturing.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Evaluation of BISON's Transient Fission Gas Release Model on High-Burnup UO 2 MiniFuel

BISON's fission gas release (FGR) model has been evaluated and tested over several hypothetical thermal transient cases at high burnup and validated against FGR experimental data from an annealing test at high burnup. Diffusion-controlled FGR is accounted for in the model by including several physical mechanisms such as the diffusion of fission gas to grain faces, grain boundary sweeping, grain growth, and intergranular bubble growth. Under temperature variations, FGR is increased due to the development of micro-cracks at grain faces. This existing transient capability, however, was developed based on transient fuel behavior during power ramps and the associated micro-cracking process. Nevertheless, a fraction of the FGR during temperature transients such as LOCA can ensue from different mechanisms (in particular, fuel fragmentation) and present an important dependency on local burnup and high burnup structure formation. It follows that the performance and necessary developments of the existing BISON fission gas model for the analysis of LOCA-type transients need to be investigated through a systematic assessment study. Such a study is performed in this work. The model shows an overall good qualitative agreement with experimental observations on FGR during annealing tests with different temperature conditions. It also accounts well for microstructural effects on FGR. When quantitatively compared to FGR data from previously irradiated 103 MWd/kgU UO 2 discs under thermal annealing, the model shows a less satisfactory agreement with the experimental data.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗