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At least 127 records · Page 7

Effects of SRPPF ARS Effluent Variations on Magnesium Oxysulfate Solidification

A magnesium oxysulfate (MOS) grout formulation has been identified to solidify the liquid effluent from the Savannah River Plutonium Processing Facility (SRPPF) Aqueous Recovery System (ARS). The formulation uses reactive, light burnt MgO (28 wt%), anhydrous MgSO 4 (10 wt%), and dead burnt MgO (62 wt%), resulting in a grout with good mixability, acceptable density, acceptable setting times, and a leachate pH around 9.4, within the assumed Waste Isolation Pilot Plant (WIPP) brine pH range. A series of tests were then designed to observe how this formula reacted to variations in the liquid effluent. Liquid effluent temperature, the caustic pH level, concentration of NaNO 3 , and the presence of neutralization products, trace metals, and/or sodium sulfate (all potential residuals found in the effluent from upstream processing), were evaluated to see how each impacts the grout mixing time, peak temperature, setting time, presence of bleed water, leachate pH, and density. The standard mix has an average mixing time of 18 minutes, peak temperature of 100.5 °C, and set time of 60 minutes. Increasing the temperature of the liquid effluent increased the reaction rate of the mix and reduced mixing and setting times. Between 30 and 40°C the change was relatively small, raising no more than 6 °C compared to the standard mix maximum temperature. Increasing the pH of the liquid effluent had no significant impact on the mix. The addition of neutralization products and trace metals had an overall impact of decreasing the reactivity of the mix. The addition of more ions in the liquid effluent, such as an increase in the concentration of NaNO 3 and the addition of Na 2 SO 4 , generally decreased the reactivity of the mix. None of the variations to the liquid effluent hindered solidification as indicated by the lack of bleed water found on all the samples. The leachate pH values for all mixes tested did not significantly vary from the expected pH of 9.4 and none of the density values fell below 1.8 g/cm 3 . Overall, changes to the liquid effluent were found to have a minimal impact on the formulation suggesting the grout's ability to properly form despite increased temperatures and the presence of residuals typically found in the liquid effluent from the ARS.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Electrolyte Design and Optimization for Alkali Metal‐Sulfur Batteries

Alkali metal-sulfur batteries, including lithium-sulfur (Li-S), sodium-sulfur (Na-S), and potassium-sulfur (K-S) systems, have garnered significant attention as promising electrochemical energy storage (EES) technologies. Among them, Li-S batteries stand out as strong contenders for next-generation energy storage, owing to their high energy density and the cost-effectiveness of sulfur-based cathodes. However, with the rapid technological advances and the escalating energy demand, lithium resources are becoming increasingly scarce, making it imperative to explore alternative metal anodes to replace lithium. Therefore, Na-S and K-S batteries, serving as counterparts to Li-S systems, are emerging as formidable contenders for next-generation energy storage technologies due to the abundant and cost-effective nature of sodium and potassium. Although Na-S and K-S batteries possess considerable potential in the energy sector, their development is still in its infancy, with performance constrained by the nascent state of electrolyte design and optimization. This review article provides a comprehensive overview of recent advancements and developments in liquid electrolytes for alkali metal-sulfur batteries. Additionally, it identifies key challenges and proposes future research directions aimed at enhancing electrolyte stability, optimizing interfacial compatibility, and improving the overall performance of alkali metal-sulfur batteries.

25 ENERGY STORAGE↗

Computational Analysis of Different Sparging Systems and their Influence in the Fluid-Dynamic Behavior of Bubble Column Reactors

Bubble column bioreactors are being actively considered for gas fermentation applications, specifically for CO2 utilization, and sugars to fuels conversion. Their main advantages include good mass transfer without any moving parts and low-cost of operation and maintenance. However, the design and scale-up of such reactors is challenging specifically for carbon capture applications where a mixture of gases (e.g. CO2/CO/H2) with variable solubilities is used. The overall performance of scaled-up bioreactors (e.g., mass transfer rate) is largely affected by gas holdup, bubble size distribution (BSD), and multiphase hydrodynamics. We investigate the effect of gas sparger designs on the performance of these large-scale bioreactors using computational fluid dynamics simulations in this work, so as to improve CO2 conversion at scale. The gas distribution systems in bubble column reactors not only determines operational regime, but also affects the evolution of the BSD, which in turn influences interfacial mass transfer and ultimately the efficiency of the gas-liquid exchange process. In addition to the BSD, uniformity in gas sparging affects gas holdup and bubble residence time which constitute important metrics of performance in gas-liquid systems. In this work, we use computational models to simulate high fidelity representations of different sparger designs and their effect on the operation of a bubble column reactor. Four different types of spargers have been selected for the computational study (Fig. 1): ladder, multi-ring, single-ring and toroidal. Their effect on superficial velocity, gas holdup mixing efficiency, and BSD will be evaluated in this work. The model uses a multiphase Eulerian framework similar to [1] and include a composition of mixtures of H2/CO/CO2 gases, common in fermentation applications.

BIOMASS FUELS,MATHEMATICS AND COMPUTING↗

Elucidating the Role of Hydroxide Electrolyte on Anion-Exchange-Membrane Water Electrolyzer Performance

Many solid-state devices, especially those requiring anion conduction, often add a supporting electrolyte to enable efficient operation. The prototypical case is that of anion-exchange-membrane water electrolyzers (AEMWEs), where addition of an alkali metal solution improves performance. However, the specific mechanism of this performance improvement is currently unknown. This work investigates the functionality of the alkali metal solution in AEMWEs using experiments and mathematical models. The results show that additional hydroxide plays a key role not only in ohmic resistance of the membrane and catalyst layer but also in the reaction kinetics. The modeling suggests that the added liquid electrolyte creates an additional electrochemical interface with the electrocatalyst that provides ion-transport pathways and distributes product gas bubbles; the total effective electrochemical active surface area in the cell with 1 M KOH is 5 times higher than that of the cell with DI water. In the cell with 1 M KOH, more than 80% of the reaction current is associate with the liquid electrolyte. These results indicate the importance of high pH of electrolyte and catalyst/electrolyte interface in AEMWEs. The understanding of the functionality of the alkali metal solution presented in this study should help guide the design and optimization of AEMWEs.

25 ENERGY STORAGE↗

Declining carbohydrate solubilization with increasing solids loading during fermentation of cellulosic feedstocks by Clostridium thermocellum: documentation and diagnostic tests

Abstract Background For economically viable 2nd generation biofuels, processing of high solid lignocellulosic substrate concentrations is a necessity. The cellulolytic thermophilic anaerobe Clostridium thermocellum is one of the most effective biocatalysts for solubilization of carbohydrate harbored in lignocellulose. This study aims to document the solubilization performance of Clostridium thermocellum at increasing solids concentrations for two lignocellulosic feedstocks, corn stover and switchgrass, and explore potential effectors of solubilization performance. Results Monocultures of Clostridium thermocellum demonstrated high levels of carbohydrate solubilization for both unpretreated corn stover and switchgrass. However, fractional carbohydrate solubilization decreases with increasing solid loadings. Fermentation of model insoluble substrate (cellulose) in the presence of high solids lignocellulosic spent broth is temporarily affected but not model soluble substrate (cellobiose) fermentations. Mid-fermentation addition of cells ( C. thermocellum ) or model substrates did not significantly enhance overall corn stover solubilization loaded at 80 g/L, however cultures utilized the model substrates in the presence of high concentrations of corn stover. An increase in corn stover solubilization was observed when water was added, effectively diluting the solids concentration mid-fermentation. Introduction of a hemicellulose-utilizing coculture partner, Thermoanaerobacterium thermosaccharolyticum, increased the fractional carbohydrate solubilization at both high and low solid loadings. Residual solubilized carbohydrates diminished significantly in the presence of T. thermosaccharolyticum compared to monocultures of C. thermocellum, yet a small fraction of solubilized oligosaccharides of both C 5 and C 6 sugars remained unutilized. Conclusion Diminishing fractional carbohydrate solubilization with increasing substrate loading was observed for C. thermocellum -mediated solubilization and fermentation of unpretreated lignocellulose feedstocks. Results of experiments involving spent broth addition do not support a major role for inhibitors present in the liquid phase. Mid-fermentation addition experiments confirm that C. thermocellum and its enzymes remain capable of converting model substrates during the middle of high solids lignocellulose fermentation. An increase in fractional carbohydrate solubilization was made possible by (1) mid-fermentation solid loading dilutions and (2) coculturing C. thermocellum with T. thermosaccharolyticum , which ferments solubilized hemicellulose. Incomplete utilization of solubilized carbohydrates suggests that a small fraction of the carbohydrates is unaffected by the extracellular carbohydrate-active enzymes present in the culture.

09 BIOMASS FUELS↗

ShupeTurner cloud microphysics

This product is the ShupeTurner cloud microphysics product derived for the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition in the central Arctic. The product includes time-height derivations of the cloud type (phase type) and the condensed water content and characteristic effective particle size for liquid and ice hydrometeor populations. Additionally, it includes the vertical integral of the condensed water content for liquid and ice, i.e., the liquid water path and ice water path. These are derived using a combination of sensors, including: cloud radar, depolarization lidar, microwave radiometer, ceilometer, and radiosondes. During MOSAiC, these sensors were installed and operated onboard the Polarstern icebreaker while within the Arctic sea ice. Most data were obtained while Polarstern was moored to the MOSAiC sea ice floe, passively drifting through the Arctic. However, the data from 16 May 2020 - 17 June 2020 and 31 July 2020 - 21 August 2020 were obtained while Polarstern was underway transiting through the sea ice during relocations of the expedition. General details of the retrieval algorithm, its application, and uncertainties are provided in Shupe et al. (2015), with the cloud classification being described in more detail in Shupe (2007). General details about the MOSAiC expedition including instruments, locations, and meteorological context is provided in Shupe et al. (2022).

54 ENVIRONMENTAL SCIENCES↗

Are Contact Angle Measurements Useful for Oxide-Coated Liquid Metals?

This work establishes that static contact angles for gallium-based liquid metals have no utility despite the continued and common use of such angles in the literature. In the presence of oxygen, these metals rapidly form a thin (~1–3 nm) surface oxide “skin” that adheres to many surfaces and mechanically impedes its flow. This property is problematic for contact angle measurements, which presume the ability of liquids to flow freely to adopt shapes that minimize the interfacial energy. We show here that advancing angles for a metal are always high (>140°)—even on substrates to which it adheres—because the solid native oxide must rupture in tension to advance the contact line. The advancing angle for the metal depends subtly on the substrate surface chemistry but does not vary strongly with hydrophobicity of the substrate. During receding measurements, the metal droplet initially sags as the liquid withdraws from the “sac” formed by the skin and thus the contact area with the substrate initially increases despite its volumetric recession. Furthermore, the oxide pins at the perimeter of the deflated “sac” on all the surfaces are tested, except for certain rough surfaces. With additional withdrawal of the liquid metal, the pinned angle gets smaller until eventually the oxide “sac” collapses. Thus, static contact angles can be manipulated mechanically from 0° to >140° due to hysteresis and are therefore uninformative. We also provide recommendations and best practices for wetting experiments, which may find use in applications that use these alloys such as soft electronics, composites, and microfluidics.

36 MATERIALS SCIENCE↗

Virtual prototyping of liquid metal blanket performance in fusion pilot plant

Liquid metal blanket is a dominant design option for the next step fusion devices responsible for harvesting energy from fusion reaction, and simultaneously producing fuel for the same reaction through tritium breeding. Liquid metal blankets introduce additional complexity to the design due to fluid motion, fluid structure interaction, and magnetohydrodynamic (MHD) effects arising from the motion of the conducting fluid through the magnetic field. They are also directly affected by the plasma heat flux and neutronic fluence. PPPL is currently developing a virtual prototyping system for numerical analysis of the liquid metal blankets for future fusion devices. The system has a customized 3D computational fluid dynamics (CFD) code in its core, allowing MHD flow and conjugate heat transfer analysis in blankets fluids and solids. The code was successfully used before for dual coolant blanket analysis [A. Khodak et al., Fusion Eng. and Des. 137 (2018)]. Recently the same code was modified to allow verified simulation of MHD flows at high Hartmann numbers of several thousand typical for blanket applications. CFD code receives volumetric heat source distribution from the neutronic analysis based on MCNP code. In addition, direct tritium breeding simulation will be performed allowing optimization of the blanket performance. 2D axisymmetric version of neutronics code will be used for rapid optimization, with 3D version employed for detailed analysis. The surface heat distribution on the plasma facing wall will be defined by the software HEAT allowing 3D modeling of the heat flux based on the magnetic field distribution including gyro-orbit effects. Results of thermal analysis are imported into structural analysis code also included in the system. Finally, direct import of CAD geometry will be used for analyzing all components and as a result design option can be efficiently optimized.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Parametric optimization of the liquid sampling-atmospheric pressure glow discharge ionization source coupled to an Orbitrap mass spectrometer for neodymium isotope ratio determinations

Isotope ratio determinations are a valuable tool in several application areas. In nuclear forensics, the isotope ratios of uranium and plutonium are commonly used as a signature for the nuclear material's provenance and processing history. However, signatures from other coexisting elements, such as neodymium and samarium, can offer additional insights. Here, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) ionization source coupled to an Orbitrap mass spectrometer (MS) has demonstrated its utility for actinide measurements. This instrumental platform can leverage the high resolution offered by the Orbitrap MS to overcome potential isobaric interferences, such as 144 Nd- 144 Sm, 148 Nd- 148 Sm, and 150 Nd- 150 Sm pairs. The work presented herein demonstrates the rapid, accurate, and precise determination of the isotope ratios for neodymium using the LS-APGD/Orbitrap MS. Both the LS-APGD and Orbitrap MS parameters were optimized systematically, with NdO + found to be the most abundant, most reduced species after applying the optimal collision-induced dissociation modalities. A limit of detection of 3 pg of 142 Nd was achieved when data was acquired and processed using the FTMS Booster, an external data acquisition and processing system offered by Spectroswiss. Excellent accuracy of better than 99 % and precision of <1 % RSD were achieved when a solution of the well-characterized neodymium standard (JNdi-1 standard) was analyzed under the optimized condition, indicating the LS-APGD/Orbitrap's great potential for isotope ratio analysis of Nd and other REEs for diverse applications.

47 OTHER INSTRUMENTATION↗

Synchrotron radiography of Richtmyer–Meshkov instability driven by exploding wire arrays

We present a new technique for the investigation of shock-driven hydrodynamic phenomena in gases, liquids, and solids in arbitrary geometries. The technique consists of a pulsed power-driven resistive wire array explosion in combination with multi-MHz synchrotron radiography. Compared to commonly used techniques, it offers multiple advantages: (1) the shockwave geometry can be shaped to the requirements of the experiment, (2) the pressure (P > 300 MPa) generated by the exploding wires enables the use of liquid and solid hydrodynamic targets with well-characterized initial conditions (ICs), (3) the multi-MHz radiography enables data acquisition to occur within a single experiment, eliminating uncertainties regarding repeatability of the ICs and subsequent dynamics, and (4) the radiographic measurements enable estimation of compression ratios from the x-ray attenuation. In addition, the use of a synchrotron x-ray source allows the hydrodynamic samples to be volumetrically characterized at a high spatial resolution with synchrotron-based microtomography. This experimental technique is demonstrated by performing a planar Richtmyer–Meshkov instability (RMI) experiment on an aerogel–water interface characterized by Atwood number A0∼−0.8 and Mach number M∼1.5. The qualitative and quantitative features of the experiment are discussed, including the energy deposition into the exploding wires, shockwave generation, compression of the interface, startup phase of the instability, and asymptotic growth consistent with Richtmyer's impulsive theory. Additional effects unique to liquids and solids—such as cavitation bubbles caused by rarefaction flows or initial jetting due to small perturbations—are observed. It is also demonstrated that the technique is not shape dependent by driving a cylindrically convergent RMI experiment.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

2D IR Microscopy—Technology for Visualizing Chemical Dynamics in Heterogeneous Environments (Final Technical Report)

The primary focus of this project was the design, prototype, and demonstration of a 2D IR microscope. The start date of this project was July 15, 2016 and the project end date was July 14, 2022. In the early years of this project our team designed, prototyped, and completely integrated a homebuilt microscope head with our high-repetition rate 2D IR spectrometer. Once in place our research team focused on characterizing the 2D IR microscope and using it to investigate model systems relevant to energy technologies. As part of this process, we identified two initial chemical systems to use to further develop 2D IR imaging modalities. The first chemical system developed was a room temperature ionic liquid (RTIL) electrolyte system and the second chemical system was a mixture of carbonates and salts developed as a battery electrolyte system. The completion of this project resulted in the full characterization of chemical dynamics in a bulk RTIL system and the demonstration of 2D IR imaging across the RTIL cast as a microdroplet in silicon oil. In addition, we explored the liquid structures and dynamics of organic carbonate mixtures from the vantage point of the vibrational probe, methyl thiocyanate. By the end of the project, we had moved toward in-depth studies of the organic carbonate mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Role of surface wetting on tribological behavior for laser nanotextured steel using ionic liquid lubricants

Here, this research evaluates the effect of surface wettability on the tribological performance through ball-on-flat tribology testing. The substrate material, M2 tool steel, is laser processed and then functionalized with fluorocarbon and nitrile chemistry to achieve distinct oleophobicity and oleophilicity, respectively, but with a similar nanoscale surface texture. The baseline lubricant is poly-alpha-olefin (PAO) oil, and ionic liquids (ILs) are used as additives for this study. The interaction between the nanoscale textured steel surface and ionic liquid-based oils is investigated. A set of reciprocating wear tests are performed to investigate the tribological behavior of the tribo-system consisting of the surface-engineered, flat M2 tool steel specimen and a standard, surface-polished steel ball. Results show that the oleophobic flat surface results in a lower friction, while the oleophilic surface modification leads to a better wear protection to the flat surface. Ammonium-based IL provides the highest friction reduction, while the phosphonium-based ILs provide an improved wear protection.

36 MATERIALS SCIENCE↗

Atmospheric temperature, water vapour and liquid water path from two microwave radiometers during MOSAiC

The microwave radiometers HATPRO (Humidity and Temperature Profiler) and MiRAC-P (Microwave Radiometer for Arctic Clouds - Passive) continuously measured radiation emitted from the atmosphere throughout the Multidisciplinary drifting Observatory for the Study of the Arctic Climate (MOSAiC) expedition on board the research vessel Polarstern. From the measured brightness temperatures, we have retrieved atmospheric variables using statistical methods in a temporal resolution of 1 s covering October 2019 to October 2020. The integrated water vapour (IWV) is derived individually from both radiometers. In addition, we present the liquid water path (LWP), temperature and absolute humidity profiles from HATPRO. To prove the quality and to estimate uncertainty, the data sets are compared to radiosonde measurements from Polarstern. The comparison shows an extremely good agreement for IWV, with standard deviations of 0.08–0.19 kg m -2 (0.39–1.47 kg m -2 ) in dry (moist) situations. The derived profiles of temperature and humidity denote uncertainties of 0.7–1.8 K and 0.6–0.45 gm -3 in 0–2 km altitude.

54 ENVIRONMENTAL SCIENCES↗

Phosphorus replenishment to improve the contact resistivity of light-induced Al contacts on Si solar cells

A method to repair laser-induced phosphorus loss from the n-type emitter of Si solar cells during light-induced Al plating is demonstrated. The ability to add a water-reactive phosphorus compound, PCl 5 , into the Al plating bath gives a unique advantage to Al over Cu for front contacts on Si solar cells. The contact resistivity between light-induced Al and Si emitter is reduced to as low as 0.1 mΩ-cm 2 . Cyclic voltammetry performed on a plating bath composed of 81 wt% 1-ethyl-3-methylimidazolium tetrachloroaluminate, 19 wt% AlCl 3 , and 0.2 wt% PCl 5 reveals multiple reduction reactions of PCl 5 , although incomplete decomposition of PCl 5 is possible. A decrease in nucleation loop size during cyclic voltammetry is also observed suggesting that PCl 5 , while being consumed, modifies the growth mechanism during Al plating. Structural analysis confirms that the addition of PCl 5 produces an Al film which is levelized and compact. Here, a pulsed voltage profile coupled with chemical analysis verifies that phosphorus incorporation is electrolytically activated and is likely the cause for the low contact resistivity.

14 SOLAR ENERGY↗

Alignment switching in 3D-printed smectic liquid crystal elastomers

Extrusion-based additive manufacturing has emerged as a powerful platform for designing shape-morphing materials through controlled orientation. However, existing approaches primarily rely on a single mode of flow-induced alignment, limiting orientation programmability. Herein, we present a direct-ink-writing approach for smectic liquid crystal elastics that exploits two distinct alignment modes within a single ink. The smectic ink exhibits shear- and temperature-dependent orientation switching, enabling molecular alignment either perpendicular or parallel to the print direction. Combined rheological, X-ray, and molecular dynamics analyses reveal that this alignment inversion arises from the preservation or collapse of smectic layers under flow. This reversible switching encodes both contractile and elongational actuation within individual filaments, greatly expanding the design freedom of printed liquid crystal elastomers. We demonstrate 2D and 3D structures with diverse programmed shape transformations, highlighting the potential of this platform for adaptive soft actuators and architected functional materials.

Lee, Jin Hyeong [Pusan National University, Busan,↗

Solidification of SRPPF Aqueous Recovery Liquid: Process Disruptions

Savannah River National Laboratory has identified a magnesium oxysulfate grout formulation to solidify the liquid effluent from the Savannah River Plutonium Processing Facility (SRPPF) Aqueous Recovery System (ARS). The formulation uses reactive, light burnt MgO, anhydrous MgSO 4 , and dead burnt MgO and provides good mixability, similar density to the original Portland Cement-based mix, and a leachate pH of 9.39, within the assumed Waste Isolation Pilot Plant (WIPP) brine pH range. The formulation will solidify the effluent using a solid first, lost paddle design, within a 55-gallon drum. A series of seven different process disruptions, or irregular processing during the expected ARS liquid effluent solidification process, were completed to assess the severity of the impact of the process disruption and how the formulation behaves under these conditions. Seven process disruptions were investigated including: No Mixing, Partial Mixing, Compacted/Stratified, Sealed, Overfilled, Underfilled, and Undermixed. The impact on solidification, leachate pH, Er (a Pu/Am surrogate) distribution, and density of the resulting grout were established. Overall, four of the process disruptions, No Mixing, Partial Mixing, Compacted/Stratified, and Overfilled, resulted in basic, unabsorbed liquid that would require additional solidification to be acceptable for WIPP. Most solids generated in this testing met the expected WIPP leachate pH requirements. Solids from the Compacted/Stratified process disruption test, however, produced a leachate pH slightly above the assumed range in the WIPP performance assessment. The distribution of Er for most of the tests was relatively consistent. The No Mixing process disruption test, however, resulted in non-homogeneous Er distribution, indicating that radioactive material would not be evenly distributed throughout this solid’s matrix. The Overfilled test is the only mix with a density slightly below the acceptable value. The Sealed and Overmixed tests produced a solid closest to the standard mix with no unabsorbed liquid, expected leachate pH levels, consistent Er concentrations, and expected density, indicating these process disruptions do not have a negative impact on the final grout form. Based on the other process disruptions, it is critical to have premixed dry materials and a well-defined mixing process to produce a solid, homogeneous magnesium oxysulfate cement, with no unabsorbed liquid. These process disruption tests show that the lack of adequate mixing is fundamental to creating an improperly solidified material that may require remediation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Evaluation of Hanford Supernatant Waste Evaporation

• Hanford site in Washington has 27 underground “double-shell” storage tanks containing radioactive waste. Storage space is utilized to max capacity. • Construction of new tanks is undesirable, but volume reduction is still possible by vacuum evaporation of liquid waste. • Excess evaporation may create additional problems in solids precipitation, waste density and corrosivity. • Evaporation of liquid waste was simulated to determine possible outcomes.

Barkai, Benjamin [Savannah River National Laborato↗

Nucleation and Growth of PbBrF Crystals at the Liquid Mercury–Electrolyte Interface Studied by Operando X-ray Scattering

In this work, detailed in operando studies of electrochemically induced PbBrF deposition at the liquid mercury/liquid electrolyte interface are presented. The nucleation and growth were monitored using time-resolved X-ray diffraction and reflectivity combined with electrochemical measurements, revealing a complex potential-dependent behavior. PbBrF deposition commences at potentials above –0.7 V with the rapid formation of an ultrathin adlayer of one unit cell thickness, on top of which (001)-oriented three-dimensional crystallites are formed. Two potential regimes are identified. At low overpotentials, slow growth of a low surface density film of large crystals is observed. At high overpotentials, crossover to a potential-independent morphology occurs, consisting of a compact PbBrF deposit with a saturation thickness of 25 nm, which forms within a few minutes. This potential behavior can be rationalized by the increasing supersaturation near the interface, caused by the potential-dependent Pb2+ deamalgamation, which changes from a slow reaction-controlled process to a fast transport-controlled process in this range of overpotentials. In addition, growth on the liquid substrate is found to involve complex micromechanical effects, such as crystal reorientation and film breakup during dissolution.

36 MATERIALS SCIENCE↗