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DOE OSTI2024

Chaotic LLM billiards

Abstract We study null geodesics of the ten-dimensional LLM geometries. In particular, we show that there are a subset of these null geodesics that are confined to the LLM plane. The effective dynamics of these in-plane geodesics is that of a Hamiltonian system with two degrees of freedom (a phase space of dimension 4). We show that these are chaotic. In the two-coloring of the LLM plane, if they start in the empty region, they cannot penetrate the filled region and viceversa. The dynamical problem is therefore very similar to that of a billiards problem with fixed obstacles. We study to what extent LLM geometries with many droplets may be treated as an incipient black hole and draw analogies with the fuzzball proposal. We argue that for in-plane null geodesics deep in the interior of a region with a lot of droplets, in order to exit towards theAdSboundary they will need to undergo a process that resembles diffusion. This mechanism can account for signals getting lost in the putative black hole for a very long time.

Physics↗

DOE OSTI2017

Experimental and Modeling Studies for the Removal of Crystal Violet Dye from Aqueous Solutions using Eco-friendly Gracilaria corticata Seaweed Activated Carbon/Zn/Alginate Polymeric Composite Beads

This research article describes, an eco-friendly activated carbon prepared from the Gracilaria corticata seaweeds which was employed for the preparation of biodegradable polymeric beads for the efficient removal of crystal violet dye in an aqueous solution. The presence of chemical functional groups in the adsorbent material was detected using FTIR spectroscopy. The morphology and physical phases of the adsorbent materials were analyzed using SEM and XRD studies respectively. Batch mode dye adsorption behavior of the activated carbon/Zn/alginate polymeric beads was investigated as a function of dosage, solution pH, contact time, initial dye concentration and temperature. Maximum dye removal was observed at a pH of 5.0, 1 g of adsorbent dosage with 60 mg/L dye concentration, 50 min of contact time and at 30 °C. The equilibrium modeling studies were analyzed with Freundlich and Langmuir adsorption isotherms and the adsorption dynamics was predicted with Lagergren’s pseudo-first order, pseudo-second order equations and intra particle diffusion models. The process of dye removal followed a pseudo second-order kinetics rather than pseudo first order. The thermodynamic parameters like standard Gibbs free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) were determined and the results imply that the adsorption process was spontaneous, endothermic and increases the randomness between the adsorbent and adsorbate. The results from the experimental and correlation data reveal that the Gracilaria corticata activated carbon/Zn/alginate polymeric beads have proved to be an excellent adsorbent material for the removal of CV dye.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Effect of Specimen Thickness on Microstructural Changes During Oxidation of the NiCrW Alloy 230 at 950–1050°C

An accurate procedure for predicting oxidation-induced damage and lifetime limits is crucial for the reliable operation of high-temperature metallic components in practical applications. In order to develop a predictive oxidation lifetime model for Ni–Cr alloys, specimens of wrought NiCrW alloy 230 with different thicknesses were cyclically oxidized in air at 950–1050°C for up to 3000 h. After prolonged exposure, two types of carbides as well as a Cr-rich nitride (π-phase) precipitated in the γ-Ni matrix. In the case of oxidation-induced loss of Cr from the alloy resulted in the formation of subscale zones, which were free of the Cr-rich carbide and nitride but also of the Ni-W rich M 6 C. The width of the M 6 C-free zone was smaller than that free of the Cr-rich precipitates. Thermodynamic and diffusion calculations of the observed time- and temperature-dependent Cr depletion processes identified that back diffusion of C occurred which resulted in an increased volume fraction of M 23 C 6 in the specimen core. Moreover, with increasing time and temperature, the amount of π-phase in the specimen core increased. The subscale depletion of the initially present Cr-nitrides and the formation of Cr-nitrides in the specimen center is believed to be related to a mechanism which is qualitatively similar to that described for the Cr carbide enrichment. However, with increasing time and decreasing specimen thickness, N uptake from the atmosphere becomes apparent. As a result, the precipitates present in the specimen center eventually consisted almost exclusively of nitrides.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Phase Field Modeling of Pressure Induced Densification in Solid Electrolytes

Adoption of dense and homogeneous solid electrolytes can possibly mitigate the propagation of lithium dendrites and enable lithium metal anodes. Application of external pressure helps to minimize the sintering temperature in oxide ceramics and can potentially densify softer sulfide electrolytes even under room temperature conditions. Here, a previously developed phase field-based computational scheme for predicting the high-temperature sintering-induced densification of oxide ceramic solid electrolytes is extended in the present context to capture the influence of external pressure for densifying solid electrolytes. Two different bulk deformation mechanisms, namely, "reorganization" and "creep deformation," are dominant under external pressure, which is different from the surface and grain-boundary diffusion-induced densification of solid electrolytes that occurs during high temperature sintering. External pressure also increases the points of contact between the particles, which further enhances the propensity of diffusion-induced sintering process. Results obtained from simulations indicate that densification under external pressure is independent of the solid electrolyte particle morphology. Finally, a phase map is generated between applied pressure and temperature for achieving complete densification of oxide ceramics, which can possibly guide the synthesis of thin and dense solid electrolyte separators.

25 ENERGY STORAGE↗

DOE OSTI2022

Effect of pinholes in Nb 4 C 3 MXene sheets on its electrochemical behavior in aqueous electrolytes

Two-dimensional (2D) niobium carbide, Nb 4 C 3 T x (T x : O, OH, and F), a representative member of the 43 MXene structural motif, has shown promising electrochemical performance in acidic electrolytes. The capacitive performance of Nb 4 C 3 T x in neutral aqueous electrolytes has been reported as moderate, but little effort has been made to improve it. In this paper, we report a method to introduce nanopores (pinholes) in Nb 4 C 3 T x MXene flakes by adjusting the etching time. The pinholes generated during the etching process improve ion diffusion pathways, which are otherwise hindered by the restacking of the 2D flakes. The “holey Nb 4 C 3 T x ” shows a 50 % improved rate capability at charge/discharge time scales of 1–2 s in 1 M Li 2 SO 4 , Na 2 SO 4 , and (NH 4 ) 2 SO 4 electrolytes. Our strategy of controlling the permeability of Nb 4 C 3 T x sheets can potentially be applied to other MXenes, providing guidance for improving the capacitance and rate capability of 2D materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Kinetic and equilibrium reactions on natural and laboratory generation of thermogenic gases from Type II marine shale

The phenomenon that laboratory pyrolysis experiments produce much wetter gases than those in natural reservoirs is a long-recognized and debated problem in the investigation of natural gases in sedimentary basins. In this study, we explore the discrepancy by pyrolyzing a type II kerogen from the Woodford Shale in Oklahoma, compared with the previous results on the produced natural gases from the Arkoma Basin generated from the same source rock (Liu et al., 2019) with the discussion of gas and isotopic compositions at bulk and position-specific (PS) levels. An improved GC-pyrolysis-GC IRMS method is applied for the determination of PS δ 13 C of propane produced in the pyrolysis of the Woodford Shale at Easy %R o from 0.76 to 3.27. Kinetic and thermodynamic considerations of the chemical and isotopic compositions of the natural and laboratory pyrolysis gases suggest that the generation of light hydrocarbons involves uni-directional cracking reactions, exchange reactions with water, and likely reversible reactions among light hydrocarbons and other H-containing volatiles. After the gas generation in the unconventional Woodford Shale reservoirs, the C 1 -C 4 gases might have approached close to chemical equilibrium of C 1 -C 3 and isotope equilibrium of C 2 -C 1 and C 3 -C 1 pairs at their peak temperatures. The capping H for the generation of C 1 -C 4 in the Woodford Shale gases appears to have experienced at least partial exchange with the water, while that in the pyrolysis gases is only originated from organic-bound compounds with large kinetic isotope effects (KIE). Our findings indicate that elevated compound-specific and PS δ 13 C values of propane in the wet-gas cracking stage are significantly influenced by the breakdown of the thermally stable compounds (e.g., remaining kerogen, residues). A first synthesis of PS δ 13 C and δ 2 H isotopic compositions of propane from this study and the literature data suggests relatively similar isotopic structures of propane precursors in kerogens. Finally, this study demonstrates that PS isotope analysis of propane can contribute to identifying various geological (e.g., maturation, wet-gas cracking, H exchange, diffusion) and biodegradation processes.

58 GEOSCIENCES↗

DOE OSTI2015

Oxidation behaviors of porous Haynes 214 alloy at high temperatures

The oxidation behaviors of porous Haynes 214 alloy at temperatures from 850 to 1000 °C were investigated. The porous alloys before and after the oxidation were examined by optical microscopy, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) analyses, and X-ray photoelectron spectroscopy (XPS). The oxidation kinetics of the porous alloy approximately follows a parabolic rate law and exhibits two stages controlled by different oxidation courses. Complex oxide scales composed of Cr{sub 2}O{sub 3}, NiCr{sub 2}O{sub 4} and Al{sub 2}O{sub 3} are formed on the oxidized porous alloys, and the formation of Cr{sub 2}O{sub 3} on its outer layer is promoted with the oxidation proceeding. The rough surface as well as the micropores in the microstructures of the porous alloy caused by the manufacturing process provides fast diffusion paths for oxygen so as to affect the formation of the oxide layers. Both the maximum pore size and the permeability of the porous alloys decrease with the increase of oxidation temperature and exposure time, which may limit its applications. - Highlights: • Two-stage oxidation kinetics controlled by different oxidation courses is showed. • Oxide scale mainly consists of Cr{sub 2}O{sub 3}, NiCr{sub 2}O{sub 4} and Al{sub 2}O{sub 3}. • Rough surface and micropores lead to the formation of uneven oxide structure. • Content of Cr{sub 2}O{sub 3} in the outer layer of the scale increases with time at 1000 °C. • Maximum pore size and permeability decrease with increasing temperature and time.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Investigation of carbon segregation during low temperature tempering in a medium carbon steel

Low temperature tempering is important in improving the mechanical properties of steels. In this study, the thermoelectric power method was employed to investigate carbon segregation during low temperature tempering ranging from 110 °C to 170 °C of a medium carbon alloyed steel, combined with micro-hardness, transmission electron microscopy and atom probe tomography. Evolution of carbon dissolution from martensite and segregation to grain boundaries/interfaces and dislocations were investigated for different tempering conditions. Carbon concentration variation was quantified from 0.33 wt.% in quenching sample to 0.15 wt.% after long time tempering. The kinetic of carbon diffusion during tempering process was discussed through Johnson-Mehl-Avrami equation. - Highlights: • The thermoelectric power (TEP) was employed to investigate the low temperature tempering of a medium carbon alloyed steel. • Evolution of carbon dissolution was investigated for different tempering conditions. • Carbon concentration variation was quantified from 0.33 wt.% in quenching sample to 0.15 wt.% after long time tempering.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Influence of sintering conditions on the microstructure and optical properties of Eu: CaF{sub 2} transparent ceramic

Highlights: • Eu: CaF2 ceramics sintering at different conditions were fabricated by HP method. • The results show that the temperatures have great effect on the microstructure. • The ceramic sintered at 600 °C/30 MPa has high transmittance and pore-free structure. • The diffusion and densification process mainly occurs between 350 °C and 500 °C. • The optical losses in ceramic were caused by structure defects and polishing damage. - Abstract: Nanopowders of the 5 at.% Eu doped CaF{sub 2} have been synthesized by co-precipitated method. X-ray diffraction (XRD) indicated that the samples corresponds to the cubic CaF{sub 2} phase and scanning electron microscopy (SEM) showed that the morphology of nanopowders were approximately spherical. The Eu: CaF{sub 2} transparent ceramics were fabricated by hot-pressing (HP) method at different P-T conditions in a vacuum environment. The fracture surface, the relative density, average grain size and shrinkage displacements were also studied to analysis the influence of sintering conditions on Eu: CaF{sub 2} ceramic. In comparison with other samples, the proper sintering temperature and pressure was 600 °C/30 MPa. The transmittance of ceramic was up to 79.7% and 88.85% at the wavelength of 760 nm and 2400 nm. Furthermore, the emission spectra of Eu: CaF{sub 2} transparent ceramics under 393.5 nm excitation was also discussed.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Electron-Stimulated Formation and Release of Molecular Hydrogen and Oxygen from Boehmite Nanoplatelet Films

Here, the production and release of H 2 and O 2 during and after electron (100–1000 eV) irradiation of boehmite nanoplatelet films was studied. H 2 and O 2 produced during irradiation likely correspond to electron-induced dissociation of the hydroxyls primarily in the terminal surface layers of the boehmite followed by the H· + H· → H 2 (g) and O + O → O 2 (g) combinative desorption reactions as well as the abstraction reactions H· + >OH – → H 2 (g) + >O·̅. Postirradiation temperature-programmed desorption shows a temperature-dependent release of H 2 but no additional release of O 2 . This process likely involves diffusion and recombination of H· atoms initially trapped between the γ-AlOOH planes followed by recombination at edge and surface sites. H 2 production upon thermal-annealing-irradiated material shows no dependence on incident electron flux, suggesting the precursor species (H·) trapped within the bulk are long-lived.

Jones, Brant M.↗

DOE OSTI2018

Manipulating Triplet Yield through Control of Symmetry-Breaking Charge Transfer

The efficiency of an organic solar cell depends on the efficacy of exciton diffusion and dissociation processes, and this can be enhanced by reducing the exciton binding energy and increasing the exciton lifetime. Zinc chlorodipyrrin (ZCl) complexes exhibit reduced exciton binding energy due to ultrafast generation of intramolecular charge transfer (ICT) states via symmetry breaking charge transfer in polar media. This paper explores the fate of the ICT states using nanosecond transient absorption. In cyclohexane, ZCl undergoes intersystem-crossing to produce triplets with ~8 ns time constant (~30% yield) and no ICT states are generated. However, in more polar solvents, triplets are generated within 1 ns via ICT state recombination with ~3 times higher yield than produced via ISC. Furthermore, this high triplet yield in toluene (89%) and acetonitrile (76%) via ICT state recombination is a beneficial pathway to spin-protect the excited state decay for additional charge generation from triplet excited states.

14 SOLAR ENERGY↗

DOE OSTI2021

Titanium Carbide MXene Shows an Electrochemical Anomaly in Water-in-Salt Electrolytes

Identifying and understanding charge storage mechanisms is important for advancing energy storage. Well-separated peaks in cyclic voltammograms (CVs) are considered key indicators of diffusion-controlled electrochemical processes with distinct Faradaic charge transfer. Herein, we report on an electrochemical system with separated CV peaks, accompanied by surface-controlled partial charge transfer, in 2D Ti 3 C 2 T x MXene in water-in-salt electrolytes. The process involves the insertion/desertion of desolvation-free cations, leading to an abrupt change of the interlayer spacing between MXene sheets. This unusual behavior increases charge storage at positive potentials, thereby increasing the amount of energy stored. This also demonstrates opportunities for the development of high-rate aqueous energy storage devices and electrochemical actuators using safe and inexpensive aqueous electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Inner Belt Electron Decay Timescales: A Comparison of Van Allen Probes and DREAM3D Losses Following the June 2015 Storm

Abstract NASA's Van Allen Probes observed significant, long‐lived fluxes of inner belt electrons up to ∼1 MeV after geomagnetic storms in March and June 2015. Reanalysis of Magnetic Electron Ion Spectrometer (MagEIS) data with improved background correction showed a clearer picture of the relativistic electron population that persisted through 2016 and into 2017 above the Fennell et al. (2015, https://doi.org/10.1002/2014gl062874 ) limit. The intensity and duration of these enhancements allow estimation of decay timescales for comparison with simulated decay rates and theoretical lifetimes. We compare decay timescales from these data and DREAM3D simulations based on them using geomagnetic activity‐dependent pitch angle diffusion coefficients derived from plasmapause‐indexed wave data (Malaspina et al., 2016, https://doi.org/10.1002/2016gl069982 , 2018, https://doi.org/10.1029/2018gl078564 ) and phase space densities derived from MagEIS observations. Simulated decay rates match observed decay rates more closely than the theoretical lifetime due to significantly nonequilibrium pitch angle distributions in simulation and data. We conclude that nonequilibrium effects, rather than a missing diffusion or loss process, account for observed short decay rates.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2017

Construction of hierarchically porous metal–organic frameworks through linker labilization

One major goal of metal–organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. W present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragments by acid treatment. We also demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Phase-field model of pitting corrosion kinetics in metallic materials

This study presents a thermodynamically consistent phase field model for the quantitative prediction of the pitting corrosion kinetics in metallic materials. An order parameter is introduced to represent the metal’s physical state at each point in the entire domain. The free energy of the metal-electrolyte system is defined in terms of its metal ion concentration and the order parameter. The mass transport in the electrolyte and the electrochemical reactions in the electrolyte/metal interface are taken into consideration in the model to simulate metal corrosion in a corrosive environment. The governing equations for mass transport and the order parameter are solved in such a manner that the system’s free energy is reduced as a result of diffusion and migration processes, and the distribution of electrostatic potential is governed by Poisson’s equation. A calibration study is performed to couple the kinetic interface parameter with the corrosion current density, which results in a direct relationship between overpotential and the kinetic interface parameter. A comparative study is performed to validate the phase field model against the experimental results. Several case studies are also examined to understand the corrosion behavior of closely located pits, stressed material, ceramic particles-reinforced steel, and crystallographic orientation dependence.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Role of filler and its heterostructure on moisture sorption mechanisms in polyimide films

Moisture sorption and diffusion exacerbate hygrothermal aging and can significantly alter the chemical and mechanical properties of polymeric-based components over time. In this study, we employ a multipronged multi-scale approach to model and understand moisture diffusion and sorption processes in polyimide polymers. A reactive transport model with triple-mode sorption (i.e., Henry’s, Langmuir, and pooling), experiments, and first principles atomistic computations were combined to synergistically explore representative systems of Kapton H and Kapton HN polymers. We find that the CaHPO 4 processing aid used in Kapton HN increases the total moisture uptake (~0.5 wt%) relative to Kapton H. Henry’s mode is found to play a major role in moisture uptake for both materials, accounting for >90% contribution to total uptake.However, the pooling mode uptake in Kapton HN was ~5 times higher than in Kapton H. First principles thermodynamics calculations based on density functional theory predict that water molecules chemisorb (with binding energy ~17–25 kcal/mol) on CaHPO 4 crystal surfaces. We identify significant anisotropy in surface binding affinity, suggesting a possible route to tune and mitigate moisture uptake in Kapton-based systems through controlled crystal growth favoring exposure of CaHPO 4 (101) surfaces during manufacturing.

36 MATERIALS SCIENCE↗

DOE OSTI2020

The role of geography in the complex diffusion of innovations

The urban–rural divide is increasing in modern societies calling for geographical extensions of social influence modelling. Improved understanding of innovation diffusion across locations and through social connections can provide us with new insights into the spread of information, technological progress and economic development. In this work, we analyze the spatial adoption dynamics of iWiW, an Online Social Network (OSN) in Hungary and uncover empirical features about the spatial adoption in social networks. During its entire life cycle from 2002 to 2012, iWiW reached up to 300 million friendship ties of 3 million users. We find that the number of adopters as a function of town population follows a scaling law that reveals a strongly concentrated early adoption in large towns and a less concentrated late adoption. We also discover a strengthening distance decay of spread over the life-cycle indicating high fraction of distant diffusion in early stages but the dominance of local diffusion in late stages. The spreading process is modelled within the Bass diffusion framework that enables us to compare the differential equation version with an agent-based version of the model run on the empirical network. Although both model versions can capture the macro trend of adoption, they have limited capacity to describe the observed trends of urban scaling and distance decay. We find, however that incorporating adoption thresholds, defined by the fraction of social connections that adopt a technology before the individual adopts, improves the network model fit to the urban scaling of early adopters. Controlling for the threshold distribution enables us to eliminate the bias induced by local network structure on predicting local adoption peaks. Finally, we show that geographical features such as distance from the innovation origin and town size influence prediction of adoption peak at local scales in all model specifications.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2014

A sliding cell technique for diffusion measurements in liquid metals

The long capillary and shear cell techniques are the usual methods for diffusion measurements in liquid metals. Here we present a new “sliding cell technique” to measure interdiffusion in liquid alloys, which combines the merits of these two methods. Instead of a number of shear cells, as used in the shear cell method, only one sliding cell is designed to separate and join the liquid diffusion samples. Using the sliding cell technique, the influence of the heating process (which affects liquid diffusion measurements in the conventional long capillary method) can be eliminated. Time-dependent diffusion measurements at the same isothermal temperature were carried out in Al-Cu liquids. Compared with the previous results measured by in-situ X-ray radiography, the obtained liquid diffusion coefficient in this work is believed to be influenced by convective flow. The present work further supports the idea that to obtain accurate diffusion constants in liquid metals, the measurement conditions must be well controlled, and there should be no temperature gradients or other disturbances.

36 MATERIALS SCIENCE↗