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At least 199 records · Page 11

In Situ Observation of Growth Dynamics in DECLIC Directional Solidification Insert Onboard ISS: DSI-R Flight Campaign

The study of solidification microstructure formation is of utmost importance for materials design and processing, as solid-liquid interface patterns largely govern mechanical and physical properties. Pattern selection occurs under dynamic conditions of growth in which the initial morphological instability evolves nonlinearly and undergoes a reorganization process. The dynamic and nonlinear nature of this instability renders in situ observation of the interface an invaluable tool to gain knowledge on the time-evolution of the interface pattern. Transparent organic analogs, which solidify like metallic alloys, allow direct visualization of interface dynamics. Extensive ground-based studies of both metallic and organic bulk samples have established the presence of significant convection during solidification processes that alters the formation of interfacial microstructures. A reduced-gravity environment is therefore mandatory for fluid flow elimination in bulk samples. In the framework of the CNES project MISOL3D (MIcrostrutures de SOLidification 3D) and the NASA projects DSIP (Dynamical Selection of 3D Interface Patterns), SPADES (SPAtiotemporal Evolution of three-dimensional DEndritic array Structures) and CAMUS (ComputAtional Studies of MicrostrUcture Formation During Alloy Solidification in Microgravity), we participated in the development of the Directional Solidification Insert (DSI) of the DEvice for the study of Critical Liquids and Crystallization (DECLIC). The DECLIC-DSI is dedicated to in situ and real-time characterization of solid-liquid interface patterns during directional solidification of transparent alloys in diffusive transport regime. Between April 2010 and March 2011, the first ISS campaign (DSI) explored the entire range of microstructures resulting in unprecedented observations. A second campaign (DSI-R), performed between October 2017 and December 2018, in which the insert contained an alloy of higher solute concentration, allowed to complete the benchmark database. The increase of solute concentration resulted in well-developed dendritic patterns at lower velocities (lower interface curvature and larger tip radius). The microstructure resulting from dendritic growth is dominant in metallurgy so that it is fundamental to understand the mechanisms of its formation. The main aims of this experimental campaign are to understand: the mechanisms of the cell to dendrite transition, the fundamental mechanisms of sidebranching formation, the dependence of dendrite tip shapes on growth conditions, the interaction of primary array and secondary sidebranches, and the influence of subgrain boundaries on the spatiotemporal organization of the array structure. Preparation, analysis and interpretation of the experiments performed onboard ISS are considerably enhanced by experiments performed on ground using thin-samples (Pr. Trivedi’s group) and phase-field simulations of microstructure formation in a diffuse growth regime (Pr. Karma’s group). In this summary, we will present an initial assessment of the results obtained during the DSI-R campaign. Nomenclature Vp: pulling velocity G: thermal gradient L: solidified length rtip: tip curvature radius Acronyms/Abbreviations CADMOS: Centre d'Aide au Développement des activités en Micro-pesanteur et des Opérations Spatiales CNES: Centre National d’Études Spatiales DECLIC: Device for the study of Critical LIquids and Crystallization DSI: Directional Solidification Insert DSI-R: Directional Solidification Insert - Refurbish ISS: International Space Station NASA: National Aeronautics and Space Administration PF: phase-field SCN: Succinonitrile 3D: three-dimensional

Mota, F.L.↗

Some fundamental aspects of solidification in a supercooled melt

A model of dendritic growth in both supercooled pure and alloy melts is presented. In a pure melt, dendrite morphology is determined by the value of the dimensionless parameter sigma = 2 alpha (L)d(o)/sq Rr(t) whereas, in an alloy melt it is determined by the parameter sigma = 2 lambda (c)D(L)/sq Rr(t). The application of the above analysis to cylindrical and spherical growth morphologies obtained in highly supercooled melts has been discussed. An upper and lower bound for the particle or tip radius in this case has been obtained in terms of the growth rate and the initial bath supercooling.

Laxmanan, V.↗

The Role of Convection and Growth Competition in Phase Selection in Microgravity: Controlled Convection in the Containerless Processing of Steel Alloys

Containerless processing using electromagnetic levitation (EML) is a powerful technique in the investigation of reactive molten metal systems. On ground, the power required to overcome the weight of the sample is sufficient to cause significant heating and induce substantial melt convection. In microgravity, the heating and positioning fields may be decoupled and the field strength may be varied to achieve the desired level of convection within the limits set by the geometry of the levitation coil and the sample size. From high-speed digital images of the double recalescence behavior of Fe-Cr-Ni alloys in ground-based testing and in reduced-gravity aboard the NASA KC-135 parabolic aircraft, we have shown that phase selection can be predicted based on a growth competition model. An important parameter in this model is the delay time between primary nucleation and subsequent nucleation of the stable solid within the liquid/metastable solid array. This delay time is a strong function of composition and a weak function of the undercooling of the melt below the metastable liquidus. From the results obtained during the first Microgravity Sciences Laboratory (MSL-1) mission, we also know that convection may significantly influence the delay time, especially at low undercoolings. Currently, it is unclear what mechanism controls the formation of a heterogeneous site that allows nucleation of the austenitic phase on the pre-existing ferrite skeleton. By examining the behavior of the delay time under different convective conditions, we hypothesize that we can differentiate between several of these mechanisms to gain an understanding of how to control microstructural. evolution. We will anchor these predictions by examining samples quenched at different times following primary recalescence in microgravity. A second important parameter in the growth competition model is the identification of the growth rate of the stable phase into the semi-solid array that formed during primary recalescence. Current dendritic growth theory is inadequate in predicting solidification behavior under these conditions as metallographic analyses show that stable phase growth proceeds along the interface between the metastable solid and residual liquid. Since growth velocity is independent of the initial undercooling relative to the metastable liquidus, we hypothesize that purely thermal effects can be separated from other important growth model parameters by careful selection of the liquid composition in a ternary system.

Matson, D. M.↗

Microstructure and Macrosegregation Study of Directionally Solidified Al-7Si Samples Processed Terrestrially and Aboard the International Space Station

This talk reports research that has been carried out under the aegis of NASA as part of a collaboration between ESA and NASA for solidification experiments on the International Space Station (ISS). The focus has been on the effect of convection on the microstructural evolution and macrosegregation in hypoeutectic Al‐Si alloys during directional solidification (DS). The DS‐experiments have been carried out under 1‐g at Cleveland State University (CSU) and under low‐g on the International Space Station (ISS). The thermal processing‐history of the experiments is well defined for both the terrestrially‐processed samples and the ISS‐processed samples. We have observed that the primary dendrite arm spacings of two samples grown in the low‐g environment of the ISS show good agreement with a dendrite‐growth model based on diffusion controlled growth. The gravity‐driven convection (i.e., thermosolutal convection) in terrestrially grown samples has the effect of decreasing the primary dendrite arm spacings and causes macrosgregation. In order to process DS‐samples aboard the ISS, dendritic‐seed crystals have to partially remelted in a stationary thermal gradient before the DS is carried out. Microstructural changes and macrosegregation effects during this period are described.

Angart, Samuel↗

Zinc dendrite removal in a nickel-zinc battery with flow-through electrodes

The development and deployment of inexpensive energy storage technologies is critical to realizing a clean energy grid. Batteries are being used in this role, but there remains a need for research on systems that are designed specifically for stationary energy storage, with a focus on lowering the overall cost rather than prioritizing the system energy density, specific energy, and power output. Here, we report the development of ultra-thick (1 cm thick) electrodes with engineered flow channels and explore the variables determining how thick these electrodes can feasibly be. Our proof of concept cell, utilizing the alkaline Ni-Zn chemistry, shows stable cycling over the initial 60 cycles but still suffers from the common Zn dendrite growth at the anode. To extend the life of these systems we report our novel methodology to completely remove Zn dendrites by exploiting the flow-through nature of our electrode architecture.

Collins-Wildman, Daniel L↗

Polyvinyl alcohol coating induced preferred crystallographic orientation in aqueous zinc battery anodes

The development of rechargeable aqueous zinc batteries is mainly hindered by the Zn anode, which suffers from dendrite growth, corrosion, hydrogen evolution, and surface passivation. Herein, a thin polyvinyl alcohol (PVA) coating layer on Zn anode has enabled dendrite-free, long-life aqueous Zn batteries by effectively regulating the interfacial ion diffusion and inducing the homogeneous Zn nucleation and deposition of stacked plates with preferentially crystallographic orientation along (002) Zn planes. The PVA@Zn anode achieved an ultralong cycle lifespan of thousands of hours at 0.25 and 1 mA cm -2 . Outstanding durability under a deep cycling capacity (5 mA h cm -2 ), high current density (10 mA cm -2 ), and long duration conditions were achieved. The superior cyclability of PVA@Zn anode was also demonstrated in PVA@Zn//V 2 O 5 full cells. In conclusion, the insights of PVA induced Zn deposition with preferred crystal orientation and interfacial regulation shed light on the future development of stable Zn anodes.

Crystallographic orientation↗

In Situ Neutron Reflectometry Reveals the Interfacial Microenvironment Driving Electrochemical Ammonia Synthesis

Electrified interfaces are critical to the performance of energy systems and often demonstrate substantial complexity under operating conditions. A nanoscale understanding of the interfacial microenvironment, i.e., the solid-electrolyte interphase (SEI), in lithium-mediated nitrogen reduction (Li–N 2 R) is key for realizing efficient ammonia (NH 3 ) production. Herein, we used time-resolved neutron reflectometry (NR) to observe SEI formation under Li–N 2 R conditions. We found that the LiBF 4 -based electrolyte provided a substantially more well-defined SEI layer than previous SEI NR interrogations that used LiClO 4 , highlighting the underlying chemistry that dictates electrolyte design and enabling new NR-based studies. Using in situ NR, we found that the LiBF 4 -derived SEI under Li–N 2 R conditions comprises a thick, diffuse outer layer and a thin, compact inner layer at low current cycling (<2 mA/cm 2 ), revealing a structure which ex situ studies have not been able to probe. Increased current cycling and sustained current cycling led to the merging of the layers into a single-layer SEI. Here, we used isotope contrast methods with d 6 -EtOH and d 8 -THF to drive time-resolved tracking of SEI growth at low current cycling, revealing that the proton donor modifies the inner layer, and the solvent modifies the outer layer. Li dendritic growth was observed in the absence of a proton donor. Neutron absorption also indicated the presence of boron in the SEI, underscoring the value of neutron-based interrogation. Our results inform Li-based systems and reaction microenvironments, and these methods can be applied broadly to interfacial energy technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microsegregation in directionally solidified Pb-8.4 at. pct Au alloy

The dependence of microsegregation behavior on growth rate and thermal gradient has been examined in a Pb-8.4 at. pct Au alloy material partially directionally solidified and quenched. The composition of the quenched 'liquid' at the dendrite tip (Ct), that of the eutectic-like solid phase freezing from the interdendritic liquid at the base of dendrite (Cse), the volume fraction of this eutectic-like region (fe), and solute profiles in the interdendritic quenched liquid and ahead of the dendrite have been measured. Two dendritic growth models for solidification of a binary alloy melt in a positive thermal gradient at the liquid-solid interface, one for dendrites with 'minimum undercooled dendrite tip' and the other for an Ivantsov type of dendrite with 'marginally stable tip', have been examined for a quantitative comparison with measured values of Ct, Cse, and fe. Convection in the melt, possibly due to horizontal density gradients, is found to be a serious limitation for theoretical understanding of the observed experimental behavior and meaningful comparison of theories.

Tewari, S. N.↗

Rapid solidification of levitation melted Ni-Sn alloy droplets with high undercooling

Experimental results obtained by high-speed optical temperature sensing for the rapid solidification of highly undercooled, levitation-melted Ni-Sn alloy droplets are presented. These data suggest a solidification model proceeding according to overlapping steps: (1) dendritic growth within the bulk undercooled melt, (2) continued recalescence as supersaturation of the interdendritic liquid dissipates, (3) fine-scale remelting within the dendrites, (4) ripening of the fine structure, and (5) solidification of remaining liquid at the end of recalescence.

Shiohara, Yuh↗

Shape Parameter for a Non-Axisymmetric Isothermal Dendrite

In previous work, we found approximate solutions for paraboloids having perturbations with four-fold axial symmetry in order to model dendritic growth in cubic materials. These solutions provide self-consistent corrections through second order in a shape parameter e to the Peclet number-supercooling relation of the Ivantsov solution. The parameter e is proportional to the amplitude of the four-fold correction to the dendrite shape, as measured from the Ivantsov paraboloid of revolution. We calculate e by comparing the dendrite tip shape to the portion of the equilibrium shape near the growth direction, (001), for anisotropic surface free energy, where the ni are components of the unit normal of the crystal surface. This comparison results in epsilon = -2(epsilon 4), independent of the Peclet number. From the experimental value of epsilon 4, we find epsilon approximately 0.011, in good agreement with the measured value epsilon approximately 0.008 of LaCombe et al.

McFadden, G. B.↗

Stabilization of garnet/Li interphase by diluting the electronic conductor

The high interfacial resistance and lithium (Li) dendrite growth are two major challenges for solid-state Li batteries (SSLBs). The lack of understanding on the correlations between electronic conductivity and Li dendrite formation limits the success of SSLBs. Here, by diluting the electronic conductor from the interphase to bulk Li during annealing of the aluminium nitride (AlN) interlayer, we changed the interphase from mixed ionic/electronic conductive to solely ionic conductive, and from lithiophilic to lithiophobic to fundamentally understand the correlation among electronic conductivity, Li dendrite, and interfacial resistance. During the conversion-alloy reaction between AlN and Li, the lithiophilic and electronic conductive Li x Al diffused into Li, forming a compact lithiophobic and ionic conductive Li 3 N, which achieved an ultrahigh critical current density of 2.6/14.0 mA/cm 2 in the time/capacity-constant mode, respectively. The fundamental understanding on the effect of interphase nature on interfacial resistance and Li dendrite suppression will provide guidelines for designing high-performance SSLBs.

25 ENERGY STORAGE↗

Progress toward goals in silicon sheet development

One of the goals of the national photovoltaic program in the U.S. is the establishment of an industry producing photovoltaic material which can be sold at a price not exceeding $0.70/W by 1986. A key element concerning the achievement of this goal is the development and utilization of improved methods for producing silicon sheet. Specific technologies being investigated in this connection can be divided into two categories. Methods of one category are based on a utilization of sheet growth techniques including film-fed growth, dendritic web, and silicon-on-ceramic processes. The approaches used by methods of the second category involve ingot and wafering processes, including Czochralski growth, the heat exchanger method, multiblade procedures, and the use of a fixed abrasive multiwire. It is found that using $84/kg silicon, most sheet technologies would yield module prices in the $2.00/Wp to $3.00/Wp range.

Koliwad, K. M.↗

Reaction Current Heterogeneity at the Interface between a Lithium Electrode and Polymer/Ceramic Composite Electrolytes

Although lithium metal anodes are expected to increase the energy density of next-generation batteries, dendrite growth during charge remains a major bottleneck preventing widespread implementation. Composite solid electrolytes with ceramic particles embedded in a polymer matrix have the potential to prevent dendrites owing to the higher mechanical stiffness while also possessing the flexibility to maintain contact with the electrode. However, microscopically, the different mechanical and electrochemical properties of the polymer and ceramic domains can cause inhomogeneous charge transfer at the Li/electrolyte interface, which can lead to nonuniform Li deposition and propagation of dendrites. Here, we computationally examine the coupled electrochemical, transport, and mechanical processes at the interface to determine the propensity for dendrite formation and possible approaches to mitigate this issue. Predictions of two possible microstructures at the interface, namely, (i) where both the polymer and ceramic come in contact with Li metal and (ii) when only the polymer comes in contact with Li metal, suggest that the former has a greater tendency for nonuniform plating. In addition, predictions suggest that minimizing the interfacial resistance between polymers and ceramics and incorporating interlayers between the electrode and electrolyte help mitigate current heterogeneity. In conclusion, these predictions provide guidance for experimental approaches to prevent dendrites in composite electrolytes.

25 ENERGY STORAGE↗

Suppressing electrolyte-lithium metal reactivity via Li + -desolvation in uniform nano-porous separator

Lithium reactivity with electrolytes leads to their continuous consumption and dendrite growth, which constitute major obstacles to harnessing the tremendous energy of lithium-metal anode in a reversible manner. Considerable attention has been focused on inhibiting dendrite via interface and electrolyte engineering, while admitting electrolyte-lithium metal reactivity as a thermodynamic inevitability. Here, we report the effective suppression of such reactivity through a nano-porous separator. Calculation assisted by diversified characterizations reveals that the separator partially desolvates Li + in confinement created by its uniform nanopores, and deactivates solvents for electrochemical reduction before Li 0 -deposition occurs. The consequence of such deactivation is realizing dendrite-free lithium-metal electrode, which even retaining its metallic lustre after long-term cycling in both Li-symmetric cell and high-voltage Li-metal battery with LiNi 0.6 Mn 0.2 Co 0.2 O 2 as cathode. The discovery that a nano-structured separator alters both bulk and interfacial behaviors of electrolytes points us toward a new direction to harness lithium-metal as the most promising anode.

25 ENERGY STORAGE↗

Evaluation of Physical Microphysical Property Retrieval Algorithms During the 2020 IMPACTS Field Campaign

The NASA Investigation of Microphysics and Precipitation for Atlantic Coast Threatening Snowstorms (IMPACTS) field campaign provides high-quality, high-altitude aircraft lidar (532 nm), radar (W-band) and in-cloud microphysical aircraft data taken during wintertime storm events impacting the United States. This study evaluates two mass-dimensional relationships (Brown and Francis (1995, BF95); Heymsfield (2014, H14) and two lidar-radar microphysical retrieval algorithms (Cloudsat and CALIPSO Ice Cloud Property Product (2C-ICE); VarPy (a variational method derived from the satellite lidar-radar data community)) to estimate aircraft-retrieved volume extinction coefficient (σ), ice water content (IWC), and effective radius (r e ) during the 2020 IMPACTS deployment. BF95 and H14 have a close 1:1 correlation (R 2 = 0.98) with in-situ observations of σ. However, only BF95 displays a linear, consistent, and almost temperature-independent low bias for IWC and r e , which likely arises from the environmental conditions used to determine each. Unlike the field-campaign-derived BF95 and H14 relationships, VarPy and 2C-ICE directly ingest the aircraft-based lidar and radar data to simulate σ, IWC, and r e . For all three microphysical parameters, VarPy and 2C-ICE retrieval errors became notably more pronounced around the dendritic growth zone (-15°C to -10°C) and near freezing (≥-5°C), which suggests that both algorithms experience difficulty addressing riming and aggregation processes and with larger particles (dendrites and plates) due in part to their simplified ice particle assumptions. However, the mean-melt diameter ice-particle assumption did yield more accurate IWC estimates, which led to slightly better overall results for VarPy.

54 ENVIRONMENTAL SCIENCES↗

Oscillating-Crucible Technique for Silicon Growth

Technique yields better mixing of impurities and superior qualiity crystals. Accellerated motion stirs melt which reduces temperature gradients and decreases boundary layer for diffusion of impurities near growing surface. Results better mixing of impurities into melt, decrease in tendency for dendritic growth or cellular growth and crystals with low dislocation density. Applied with success to solution growth and Czochralski growth, resulting in large crystals of superior quality.

Daud, T.↗

Exascale-capable cellular automaton for nucleation and grain growth

This model is a cellular automata-based algorithm used to predict grain-scale microstructure development. Nucleation and growth of existing grains are considered in an initially liquid domain, where the temperature field evolution is either driven through heat transport simulation data or a frozen temperature approximation (i.e., a constant cooling rate and a fixed thermal gradient). The growth of grains is based on the decentered octahedron algorithm published by Gandin and Rappaz (https://doi.org/10.1016/S1359-6454(96)00303-5), where the grain envelopes are tracked as approximations of the evolving dendritic growth front. The input heat transport data, which can come from simulation of an arbitrary processing technique, consists of coordinates and times at which said coordinates fall below the liquidus and solidus temperatures for the final time. As a result, only the final solidification of a given region is modeled (no remelting). The code is designed to be compatible with pre-Exascale architectures, and uses MPI and the Kokkos library to decompose the computational domain and offload solidification calculations to GPUs.

Rolchigo, MatthewR.↗