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At least 649 records · Page 36

Irreversible reactions and diffusive escape: Stationary properties

We study three basic diffusion-controlled reaction processes—annihilation, coalescence, and aggregation. We examine the evolution starting with the most natural inhomogeneous initial configuration where a half-line is uniformly filled by particles, while the complementary half-line is empty. We show that the total number of particles that infiltrate the initially empty half-line is finite and has a stationary distribution. We determine the evolution of the average density from which we derive the average total number N of particles in the initially empty half-line; e.g. for annihilation $\langle N\rangle = \frac{3}{16}+\frac{1}{4\π}$ . For the coalescence process, we devise a procedure that in principle allows one to compute P(N), the probability to find exactly N particles in the initially empty half-line; we complete the calculations in the first non-trivial case (N = 1). As a by-product we derive the distance distribution between the two leading particles.

97 MATHEMATICS AND COMPUTING↗

Collective Summary of sCO2 Materials Development Part II: High-Temperature Alloy Corrosion Behavior within Compact Heat Exchangers.

Materials compatibility is a major concern for the design and operation of supercritical carbon dioxide (sCO2) power cycles. Two areas were recently identified for which very little prior knowledge was available. These were the behavior of polymer materials in low-temperature sCO2 environments as well as the high-temperature corrosion behavior for alloys that have been fabricated into compact heat exchangers. A critical need exists to increase understanding in both areas. As such, the Sandia sCO2 Materials Development program initiated a series of experiments for both areas in FY19. The progress that has been made in understanding the behavior of polymers in sCO2 was summarized in the Part I report, while this Part II report describes progress in the area of compact heat exchanger corrosion. For the compact heat exchangers being developed for use in supercritical CO2 power cycles, alloy corrosion is important to understand as it may lead to reduced flow path area, reduced heat transfer, and blocked flow channels. The fabrication of these heat exchangers involve thermal processes such as brazing or diffusion bonding, where the influence of these processes on the corrosion behavior of the alloys is unknown. Candidate alloys for these heat exchangers are typically evaluated for corrosion behavior as witness coupons, without being subjected to these thermal processes. To close this gap in understanding, a series of experiments were completed that utilized small heat exchanger samples subjected to flowing CO2 for 500 hours at 750°C. Small sections of the heat exchanger samples were characterized before and after the 500 hour exposure in order to characterize the oxide growth in the channels as well as the hardness of the alloys. Results are compared to witness coupons of the same alloys.

36 MATERIALS SCIENCE↗

Reaction-diffusive dynamics of number-conserving dissipative quantum state preparation

The use of dissipation for the controlled creation of nontrivial quantum many-body correlated states is of much fundamental and practical interest. What is the result of imposing number conservation, which, in closed system, gives rise to diffusive spreading? For this work, we investigate this question for a paradigmatic model of a two-band system, with dissipative dynamics aiming to empty one band and to populate the other, which had been introduced before for the dissipative stabilization of topological states. Going beyond the mean-field treatment of the dissipative dynamics, we demonstrate the emergence of a diffusive regime for the particle and hole density modes at intermediate length- and timescales, which, interestingly, can only be excited in nonlinear response to external fields. We also identify processes that limit the diffusive behavior of this mode at the longest length- and timescales. Strikingly, we find that these processes lead to a reaction-diffusion dynamics governed by the Fisher-Kolmogorov-Petrovsky-Piskunov equation, making the designed dark state unstable towards a state with a finite particle and hole density.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Explosive nucleation and growth of Pb islands on Ge(111) below room temperature via collective diffusion

Nucleation is a fundamental process in nature controlling phase transitions and pattern formation. Classical nucleation is based on the gradual aggregation of diffusing atoms after a critical cluster size is reached. Contrary to these expectations, we have observed in real time the formation of perfect Pb(111) islands with more than 10 5 atoms emerging out of the compressed wetting layer within a few seconds during growth of Pb on Ge(111) below room temperature. Pb deposited on Ge(111) in a temperature range between −30 °C and 10 °C exhibited explosive nucleation of height-selected islands upon reaching a critical coverage of 1.33 ± 0.07 ML with respect to Ge(111). Island nucleation was fueled by the 2% compression of the Pb wetting layer at the critical coverage. The island areas grew linearly with time, exhibiting collective diffusion, where thousands of atoms follow correlated, non-random walk diffusion. The total growth rate was higher with increasing temperature. Density functional theory simulations of the chemical potential and binding sites of the Pb/Ge(111) system give insight into the role of the compression of the wetting layer and the strain within the growing Pb layers, which explain this nonclassical behavior of the system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Morphogenic Growth 3D Printing

Inspired by nature's morphogenesis, a new 3D printing process –growth printing (GP)– takes advantage of a self‐propagating curing front to produce 3D polymeric parts following a growth‐like development plan. The propagation of the curing front is driven by the exothermic polymerization of dicyclopentadiene (DCPD), which transforms the liquid resin into a stiff polymer as it propagates at 1 mm s −1 . GP is triggered when a heated initiator contacts the uncured liquid resin in an open container. The initiator nucleates the frontal polymerization reaction and the isotropic radial propagation of the growth front. Simultaneously, the initiator is moved up across the free surface of the resin, pulling the cured object out of the uncured resin. The motion trajectory of the initiator with respect to the free resin surface controls the growth morphology of the 3D part. An inverse design algorithm is developed to produce 3D parts by modeling the reaction‐diffusion‐driven solidification process. This process has substantial energy savings and high printing speeds.

3D printing↗

Tunable Growth of Layered Double Hydroxide Nanosheets through Hydrothermal Conversion of Atomic Layer Deposition Seed Layers

To enable the design and manufacturing of hierarchical nanomaterial architectures, there is a need for synthesis and processing methods that can enable tunable geometric control at the nanoscale while maintaining conformality on complex 3-D templates. Here, in this study, we explore the programmable control of vertically oriented Zn-Al layered double hydroxide (LDH) nanosheet arrays using atomic layer deposition (ALD) to deposit a seed layer of Al 2 O 3 , which is subsequently consumed and converted into the LDH phase under hydrothermal growth conditions. We demonstrate tunable control over the spacing and length of the nanosheets by varying the thickness of the initial ALD seed layer with subnanometer precision. This can be viewed as a nanoscale titration reaction, where Al acts as the limiting reagent during the hydrothermal synthesis of the nanosheets. Elemental mapping demonstrates the dynamic evolution of the resulting morphology, which is driven by surface diffusion and nucleation processes. The conformal nature of ALD allows for hierarchical growth of nanosheets on the surface of a variety of nonplanar substrate geometries, including microposts, paper fibers, and porous ceramic supports. This illustrates the power of ALD to enable bottom-up growth of 3-D nanoarchitectures with tunable geometries by controlling nucleation and growth in subsequent solution reactions.

36 MATERIALS SCIENCE↗

Sensing of molecules using quantum dynamics

Significance We explore the viability of using intrinsically quantum phenomena for molecular sensing. We formulate a theory for coherent sensing by combining the full analytical description of electronic relaxation processes with mass diffusion and charge transport models. This theory produces molecular-scale design criteria for sensors with responses rooted in quantum mechanical coherence phenomena. For example, the sensitivity of the detector can increase with decreased coupling between the molecular binding sites and the sensor substrate. Exploiting quantum properties of the analyte and the sensing element (e.g., electronic affinity, polarizability, etc.) enables enhanced discrimination among multiple analytes.

74 ATOMIC AND MOLECULAR PHYSICS↗

Three-dimensional reconstruction and morphologic characteristics of porous metal fiber sintered sheet

This paper presents an approach to achieve morphological characterizing for complex porous materials based on micro X-ray tomography images, with an example of a novel porous metal fiber sheet produced through solid-state sintering method. The geometrical reconstruction was performed after selection of volume of interest and image processing of anisotropic diffusion smooth. The reconstructed gray level images were then transferred into binary images by adjusting binarization threshold according to the actual porosity. Taking into account the tubular structural feature of the fibers, skeleton extraction algorithm based on the distance transform function was applied and further improved by the scale axis transform method. The skeleton was later pruned and segmented according to the contact points to perform morphological characterizing. Compared with actual manufacturing parameters, the style, length, radius, orientation and tortuosity of fiber segments were discussed. The results show that our proposed method can well describe the actual geometrical and morphological characteristics, which will provide a promising method for the structural description of fibrous networks. - Highlights: • Micro-CT technology was used to achieve the 3D geometrical reconstruction. • Skeleton extraction algorithm was modified to get the medial skeleton. • Skeleton filter operation was adopted to deal with the segmented skeleton. • Useful morphological statistics was obtained through skeleton segments. • Relationship between structure and manufacturing processes was discussed.

36 MATERIALS SCIENCE↗

Chemical explosive mode analysis of lean blowout in a gas turbine combustor

In this study, stabilization and lean blowout (LBO) mechanisms in a gas turbine combustor are numerically studied based on large eddy simulation (LES) data and the chemical explosive mode analysis (CEMA). Three CEMA-based local combustion modes, that is, auto-ignition, diffusion-assisted ignition, and extinction, are employed to quantify interactions between local diffusion and chemical processes in complex turbulent fields. The capability of CEMA-based local modes in extinction detection is first demonstrated in a one-dimensional non-premixed flamelet undergoing transient extinction. Flame structure and dynamics in the gas turbine combustor are then examined in detail using CEMA and the local combustion modes for both the stably burning and lean blowout conditions. Local structure comprised of all the three modes are identified, and each mode is found to play an important role in determining the overall burning rate. The heat release rate attributed to each local mode remains nearly constant at the stably burning condition. In contrast, the flame during LBO shows a two-stage extinction behavior: at the initial stage, the extinction mode is largely enhanced and becomes dominant over the assisted-ignition model; at the second stage, all three modes are suppressed, signifying global extinction. It is therefore suggested that the excessive local extinction mode, due to an increased amount of heat and radical losses through diffusion, finally leads to lean flame blowout.

chemical explosive mode↗

Growth and nucleation regimes in boron doped silicon by dynamical x-ray diffraction

The oxygen precipitation of highly (17.5 mΩ cm) and moderately (4.5 Ω cm) boron (B) doped silicon (Si) crystals at 780 °C is investigated by following in-situ the evolution of diffraction Pendellösung oscillations. All samples show an initial diffusion-driven growth process which may change over into Ostwald ripening. For the highly doped sample and involving a nucleation step at 450 °C for 30 h, the precipitate density ρ is enhanced by a factor of 8 as compared to the moderately doped sample. The influence of a high B concentration on ρ is dramatically higher for the samples directly heated to 780 °C, where an enhancement factor of 80 is found. Considering Ostwald ripening as a second growth regime reveals consistent ripening rates and surface energies σ with those found at 900 °C in a previous publication.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

CaloScore v2: single-shot calorimeter shower simulation with diffusion models

Diffusion generative models are promising alternatives for fast surrogate models, producing high-fidelity physics simulations. However, the generation time often requires an expensive denoising process with hundreds of function evaluations, restricting the current applicability of these models in a realistic setting. In this work, we report updates on the CaloScorearchitecture, detailing the changes in the diffusion process, which produces higher quality samples, and the use of progressive distillation, resulting in a diffusion model capable of generating new samples with a single function evaluation. Here we demonstrate these improvements using the Calorimeter Simulation Challenge 2022 dataset.

47 OTHER INSTRUMENTATION↗

Effect of lithium diffusion into Ga 2 O 3 thin films

The integration of lithium based compounds (e.g., Li:NiO/Ga 2 O 3 , LiGa 5 O 8 /Ga 2 O 3 ) in Ga 2 O 3 based pn-heterojunctions raises concerns about interface stability, i.e., Li diffusion effects on Ga 2 O 3 properties. In this work the ex-situ diffusion of Li is investigated in three different Ga 2 O 3 epilayers systems [(001) κ-Ga 2 O 3 and (−201) β-Ga2O3 heteroepitaxy on (001) α-Al 2 O 3 , and (010) β-Ga 2 O 3 homoepitaxy] at relevant temperatures for the synthesis / processing of Li-based epilayers. It is here experimentally demonstrated and quantified the Li diffusion in all the investigated Ga 2 O 3 epilayers systems and Li bulk (D Li,bulk ) and 2D defects (D Li,2D ) diffusion coefficients are provided. In the case of the (010) β-Ga 2 O 3 homoepitaxial layer (nominally free of structural defects), hybrid functional theory calculations foresee a diffusion mechanism mediated by Ga vacancies (VGa). Moreover, in the (010) β-Ga 2 O 3 homo-layer a significant effect on its functional properties (e.g., additional Raman vibrational modes, induced conductivity in an otherwise insulating sample) upon the Li-diffusion process is experimentally highlighted and tentatively related to the passivation of acceptor defects (i.e., formation of V Ga -nLi complexes).

Defects↗

Advanced analysis of laser-driven pulsed magnetic diffusion based on quantum molecular dynamics simulation

Magnetic diffusion plays an important role in inertial confinement fusion with strong magnetic fields. In this paper, we improve a previous analysis of the generation and diffusion of the magnetic field [Morita et al., Phys. Plasmas 25, 094505 (2018)]. For the generation process, we calculate the temporal evolution of the coil current using a self-consistent circuit model. The results show that the peak of the calculated magnetic field is delayed by 1.2 ns compared with that of the incident laser pulse. For the diffusion process, we evaluate the electrical conductivity of warm dense gold over a wide temperature range (300 K–100 eV) by combining the Kubo–Greenwood formula based on a quantum molecular dynamics simulation with the modified Spitzer model. Our simulation shows that the maximum magnetic field (530 T) that penetrates the cone is delayed by 2.5 ns compared with the laser peak. This result is consistent with experiments [Sakata et al., Nat. Commun. 9, 3937 (2018)] that showed that applying a strong magnetic field improved the heating efficiency of fusion fuel.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Source and seed populations for relativistic electrons: Their roles in radiation belt changes

Strong enhancements of outer Van Allen belt electrons have been shown to have a clear dependence on solar wind speed and on the duration of southward interplanetary magnetic field. However, individual case study analyses also have demonstrated that many geomagnetic storms produce little in the way of outer belt enhancements and, in fact, may produce substantial losses of relativistic electrons. In this study, focused upon a key period in August–September 2014, we use GOES geostationary orbit electron flux data and Van Allen Probes particle and fields data to study the process of radiation belt electron acceleration. One particular interval, 13–22 September, initiated by a short-lived geomagnetic storm and characterized by a long period of primarily northward interplanetary magnetic field (IMF), showed strong depletion of relativistic electrons (including an unprecedented observation of long-lasting depletion at geostationary orbit) while an immediately preceding, and another immediately subsequent, storm showed strong radiation belt enhancement. We demonstrate with these data that two distinct electron populations resulting from magnetospheric substorm activity are crucial elements in the ultimate acceleration of highly relativistic electrons in the outer belt: the source population (tens of keV) that give rise to VLF wave growth and the seed population (hundreds of keV) that are, in turn, accelerated through VLF wave interactions to much higher energies. ULF waves may also play a role by either inhibiting or enhancing this process through radial diffusion effects. Furthermore, if any components of the inner magnetospheric accelerator happen to be absent, the relativistic radiation belt enhancement fails to materialize.

58 GEOSCIENCES↗

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↗

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↗

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↗

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↗