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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Simulating Southern Ocean Aerosol and Ice Nucleating Particles in the Community Earth System Model Version 2

Southern Ocean (SO) low-level mixed phase clouds have been a long-standing challenge for Earth system models to accurately represent. While improvements to the Community Earth System Model version 2 (CESM2) resulted in increased supercooled liquid in SO clouds and improved model radiative biases, simulated SO clouds in CESM2 now contain too little ice. Previous observational studies have indicated that marine particles are major contributor to SO low-level cloud heterogeneous ice nucleation, a process that initiates a number of cloud processes that govern cloud radiative properties. In this study, we utilize detailed aerosol and ice nucleating particle (INP) measurements from two recent measurement campaigns to assess simulated aerosol abundance, number size distributions, and composition and INP parameterizations for use in CESM2. Our results indicate that CESM2 has a positive bias in simulated surface-level total aerosol surface area at latitudes north of 58°S. Measured INP populations were dominated by marine INPs and we present evidence of refractory INPs present over the SO assumed here to be mineral dust INPs. Results highlight a critical need to assess simulated mineral dust number and size distributions in CESM2 in order to adequately represent SO INP populations and their response to long-term changes in atmospheric transport patterns and land use change. Furthermore, we also discuss important cautions and limitations in applying a commonly used mineral dust INP parameterization to remote regions like the pristine SO.

58 GEOSCIENCES↗
DOE OSTI2025

Immersion Freezing in Particle-Based Aerosol-Cloud Microphysics: A Probabilistic Perspective on Singular and Time-Dependent Models

Cloud droplets containing immersed ice-nucleating particles (INPs) may freeze at temperatures above the homogeneous freezing threshold temperature in a process referred to as immersion freezing. In modeling studies, immersion freezing is often described using either so-called “singular” or “time-dependent” parameterizations. Here, we compare both approaches and discuss them in the context of probabilistic particle-based (super-droplet) cloud microphysics modeling. First, using a box model, we contrast how both parameterizations respond to idealized ambient cooling rate profiles and quantify the impact of the polydispersity of the immersed surface spectrum on the frozen fraction evolution. Presented simulations highlight that the singular approach, constituting a time-integrated form of a more general time-dependent approach, is only accurate under a limited range of ambient cooling rates. The time-dependent approach is free from this limitation. Second, using a prescribed-flow two-dimensional cloud model, we illustrate the macroscopic differences in the evolution in time of ice particle concentrations in simulations with flow regimes relevant to ambient cloud conditions. The flow-coupled aerosol-budget-resolving simulations highlight the benefits and challenges of modeling cloud condensation nuclei activation and immersion freezing on insoluble ice nuclei with super-particle methods. The challenges stem, on the one hand, from heterogeneous ice nucleation being contingent on the presence of relatively sparse immersed INPs, and on the other hand, from the need to represent a vast population of particles with relatively few so-called super particles (each representing a multiplicity of real particles). We discuss the critical role of the sampling strategy for particle attributes, including the INP size, the freezing temperature (for singular scheme) and the multiplicity.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Multiple Charge Density Waves and Superconductivity Nucleation at Antiphase Domain Walls in the Nematic Pnictide Ba 1– x Sr x Ni 2 As 2

How superconductivity interacts with charge or nematic order is one of the great unresolved issues at the center of research in quantum materials. Ba 1– x Sr x Ni 2 As 2 (BSNA) is a charge ordered pnictide superconductor recently shown to exhibit a sixfold enhancement of superconductivity due to nematic fluctuations near a quantum phase transition (at $x_c$ = 0.7). The superconductivity is, however, anomalous, with the resistive transition for $0.4 < x < x_c$ occurring at a higher temperature than the specific heat anomaly. Here, using x-ray scattering, we discovered a new charge density wave (CDW) in BSNA in this composition range. The CDWis commensurate with a period of two lattice parameters, and is distinct from the two CDWs previously reported in this material. We argue that the anomalous transport behavior arises from heterogeneous superconductivity nucleating at antiphase domain walls in this CDW. We also present new data on the incommensurate CDW, previously identified as being unidirectional, showing that it is a rotationally symmetric “4$\textit{Q}$” state with $C_4$ symmetry. Our study establishes BSNA as a rare material containing three distinct CDWs, and an exciting test bed for studying coupling between CDW, nematic, and SC orders.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

The impact of aerosol mixing state on immersion freezing: insights from classical nucleation theory and particle-resolved simulations

Immersion freezing, initiated by ice-nucleating particles (INPs) in supercooled aqueous droplets, plays an important role in the formation of ice crystals within clouds. The efficiency of immersion freezing depends strongly on INP composition and, crucially, on the mixing state – how chemical species are distributed across the particle population. Here, we quantify the impact of aerosol mixing state on immersion freezing using a combined theoretical and particle-resolved modeling approach. We derive analytical expressions for the frozen fraction of internally and externally mixed INP populations based on classical nucleation theory, showing that the frozen fraction is sensitive to whether ice-active species are present in all particles or only in a subset of the population. We introduce a multi-species immersion freezing scheme into the particle-resolved model PartMC, using the water activity-based immersion freezing model (ABIFM) to compute freezing probabilities for mixed-composition particles. To improve computational efficiency, we implement a Binned Tau-Leaping algorithm and demonstrate an order-of-magnitude speedup with minimal accuracy loss. Simulations reproduce the analytical trends in limiting cases and extend the analysis to more general aerosol populations, where mixing state continues to exert a substantial control on frozen fraction. Sensitivity analyses across particle size, species type, and cooling condition reveal that the mixing state effect is most pronounced when small amounts of highly efficient INPs are mixed with less efficient materials. These findings underscore the need to represent aerosol mixing state explicitly in models of heterogeneous ice nucleation to reduce uncertainty in cloud-phase partitioning.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Generalized Synthesis of Highly-Dispersed, Ultrafine Transition Metal Nanoparticles on Silica Spheres for Enhanced Optical Absorption

Robust synthesis of ultrafine metal nanoparticles (ufMNPs) below 5 nm with clean surfaces and strong optical absorption in the visible spectral range is challenging due to their instability originating from large surface-to-volume ratios. Here, this work reports a general strategy involving two sequential steps: i) loading metal precursor ions onto the surface of silica nanospheres (SiO x NSs) by forming a uniform coating of metal oxyhydroxide [MO y (OH) z ] through preferred surface acid–base reactions and ii) thermally reducing MO y (OH) z in forming gas at elevated temperatures to form ufMNPs evenly dispersed on the surface of SiO x NSs. The capability of this synthesis strategy is verified by loading ufMNPs of various transition metals and bimetallic combinations onto the SiO x NSs. The ufMNPs exhibit strong optical absorption enhanced by the optical scattering resonances in the SiO x NSs, which generate intense electric fields near the surface of the SiO x NSs. The SiO x NSs also support stabilizing the ufMNPs, which do not need additional organic capping reagents. The successful synthesis of SiO x -NS-supported ufMNPs with clean surfaces and enhanced optical absorption is promising for exploring the photocatalytic properties of ufMNPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The microstructure of a selective laser melting (SLM)-fabricated NiTi shape memory alloy with superior tensile property and shape memory recoverability

A selective laser melting (SLM)-fabricated NiTi with superior tensile property and shape memory recoverability was obtained by using a unique stripe rotation scanning strategy. Here, the alloy characteristics, formation mechanisms and evolution in terms of twins, dislocations and precipitations of the alloy were systematically studied. Compared to the conventional smelting-followed-by-machining, the SLM fabrication process involves rapid solidification and repeated heating, which confer distinctive characteristics to the microstructures of SLM-fabricated NiTi alloys. Rapid solidification promotes the formation of a supersaturation solid solution matrix containing a high concentration vacancies, which in turn aggregate to generate a high density of dislocations. During subsequent repeated heating stages, these dislocations occur thermal motion along three directions of <001 > , <111> and <110 >, leading to the formation of thermal kinks, helical dislocations and wave morphology. Simultaneously, precipitated particles Ti 3 Ni 4 repeatedly nucleate and heterogeneous grow with the movement of dislocation. Such precipitation behavior, termed repeated precipitation, has not been previously reported in the conventional NiTi alloys, suggesting that it could be a unique characteristic of such alloy. After martensitic transformation, only two twins, {1 1¯ 1} type I twin and compound twin, are detected. The twinning lamellae of these two twins, where precipitation and dislocation pile-ups exist, often have uneven thickness and chaotic arrangement. Besides, the unique self-accommodated microstructures, such as secondary {1 1¯ 1} type I twin and compound twin with “herring-bone’’ lamellae, which often appear in the deformed or nanocrystalline NiTi, can also be observed. These unique microstructures may confer the distinctive properties to the SLM-fabricated NiTi.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Flow boiling transient critical heat flux tests with stainless steel and FeCrAl: Transient correlation implementation, model calibration, and sensitivity analysis

In this study, steady-state and transient internal-flow critical heat flux (CHF) experiments were carried out under two flow conditions, at atmospheric pressure, on 316 stainless steel (316-SS) and iron-chromium-aluminum (FeCrAl) tubes. Slow power transients at a low mass flow (300 kg/m 2 - s) with very low subcooling (X e =-0.0054) generated premature CHFs, which were prevented by faster power transients and high mass flow (1000 kg/m 2 - s). The measured transient CHFs increased linearly with increasing power transients, compared with the steady-state CHF. Yet, the wall superheat at the CHFs decreased with faster power transients. Transient CHF correlations highlighting heterogeneous spontaneous nucleation were calibrated to the measured CHFs and compared with other existing correlations. Transient CHF multipliers were acquired from pool and flow boiling empirical CHF correlations that were generated. The multipliers were applied to the RELAP5-3D nuclear system code to analyze the discrepancies between the measured data and the predicted CHF and post-CHF behavior, which improved peak cladding temperature predictions by 24.6%. A variance-based global sensitivity study perturbing the experimental uncertainties and cladding material thermal properties showed the diminishing influence of flow boiling heat transfer with increasing power transients, highlighting the significance of the volumetric heat capacity for the cladding integrity during transients. Transient CHF correlations were applied to the most limiting design basis accident: a hot-zero-power reactivity-initiated accident on a generic pressurized water reactor RELAP5-3D model.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Ice nucleation by volcanic ash greatly alters cirrus cloud properties

The formation of ice crystals in the atmosphere strongly affects cloud properties and climate. While volcanic ash (VA) has been shown to nucleate ice crystals efficiently in laboratory settings, its importance for ice formation in the atmosphere remains elusive. Here, we show evidence of cirrus modification by volcanic eruptions through ice nucleation on VA, revealed by abrupt changes in cirrus properties following volcanic eruptions based on satellite measurements. The distinct changes captured are a phenomenal decrease in number, an increase in size of ice crystals in cirrus clouds, and an increase in cirrus occurrences after ash-rich volcanic eruptions. Conversely, no such changes were detected following the ash-poor eruption. We propose a cirrus formation mechanism where VA nucleates ice heterogeneously, suppressing homogeneous freezing and resulting in fewer but larger ice crystals. This suppression of homogeneous freezing by VA is supported by process-level cloud microphysical simulations. Our findings advance the understanding of aerosol–ice cloud interactions and illuminate cirrus geoengineering.

Lin, Lin [Texas A & M Univ., College Station, TX (↗
DOE OSTI2020

Modelling mixed-phase clouds with the large-eddy model UCLALES–SALSA

The large-eddy model UCLALES–SALSA, with an exceptionally detailed aerosol description for both aerosol number and chemical composition, has been extended for ice and mixed-phase clouds. Comparison to a previous mixed-phase cloud model intercomparison study confirmed the accuracy of newly implemented ice microphysics. A further simulation with a heterogeneous ice nucleation scheme, in which ice-nucleating particles (INPs) are also a prognostic variable, captured the typical layered structure of Arctic mid-altitude mixed-phase cloud: a liquid layer near cloud top and ice within and below the liquid layer. In addition, the simulation showed a realistic freezing rate of droplets within the vertical cloud structure. The represented detailed sectional ice microphysics with prognostic aerosols is crucially important in reproducing mixed-phase clouds.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Automatic Time Step Control to Resolve Hydromechanically Driven Fault Reactivation, Spontaneous Nucleation, and Seismic Arrest

Abstract A physical understanding of the progression from flow‐driven (quasi‐static) poromechanical deformation to dynamic fault rupture is critical to the resilient operations of several engineering systems. These processes are bridged by a progression from fault reactivation to the spontaneous nucleation of unstable sliding. Toward addressing this challenge, novel automatic time step size control methods are developed to enable accurate and efficient simulation of these dynamics and transitions from the first principles. The controllers combine local models for discretization error and Coulomb failure conditions to automatically adjust the time step size across several orders of magnitude. The methods do not require additional empirical or theoretical input and can resolve the pre‐rupture, interseismic, and seismic periods to the allowed accuracy. The computational results reveal that the proposed methods automatically capture the onset of reactivation and nucleation for homogeneous and heterogeneous fields. Hydrodynamic and structural heterogeneity lead to disparate critical nucleation sizes compared to those predicted by theory. The results highlight its potential in predicting induced seismicity in realistic subsurface engineering systems and at practical scales.

Environmental Sciences & Ecology↗
DOE OSTI2025

Model form and sensitivity analysis of CALPHAD-based nucleation models in b-stabilized Ti alloys

Accurate prediction of α-phase nucleation and growth in β-stabilized titanium alloys is crucial for designing heat treatments to optimize mechanical properties in additively manufactured lightweight components. Ideally, predictions of nucleation and growth would incorporate both top-down observations of past experimental heat treatments and bottom-up modeling of phase transformations; however, the appropriate method of combining these information sources is not self-evident. Combining top-down and bottom-up information requires a unified form of model that can connect between spatiotemporal scales, as well as sets of fitting parameters that can be identified by each data source. The selection of which parameters to fit to which data source can be made based on expert opinion, or by performing a sensitivity analysis. In solid-solid nucleation, direct observation of the nucleation and growth process is challenging. Most data on the heat treatment-controlled phase transformations are not in-situ. To predict the process and outcome of the nucleation, growth and coarsening of precipitates, theoretical models of the nucleation pathway are used to bridge the gap. Many sources of uncertainty affect the modeling of this nucleation process. It can be influenced by small variations in the thermomechanical processing history, chemical composition, and initial microstructure. If molecular dynamics (MD) simulations are used to determine thermodynamic quantities and inform CALPHAD modeling, additional uncertainty can be introduced and accounted for using Bayesian methods. Top-down uncertainties require additional steps to quantify. The influence of nucleation model form on the sensitivity of predictions to input parameters and physical conditions is the focus of this study. Classical nucleation theory (CNT) allows modeling to formulate the nucleation as homogeneous or, more commonly, heterogeneous. Non-classical nucleation models are also increasingly explored as a means of reconciling top-down and bottom-up data. In this study, the sensitivity of the intragranular nucleation of α in a β-annealed, slow-cooled aging (BASCA) heat treatment of β-stabilized Ti5553 alloy is explored using CNT and both heterogeneous and homogeneous assumptions. The Kampmann-Wagner Numerical model of precipitate nucleation and growth is employed. Using open-source tools (pyCalphad and thermodynamic modeling of TiMo as a surrogate system, a sensitivity analysis is performed to measure variations in key parameters, including chemical driving force, interfacial energy, and diffusivity, as they relate to predictions of precipitate number density. The inclusion of top-down and bottom-up data in selection of nucleation model form is discussed.

Rodriguez Negron, A. M.↗
DOE OSTI2023

Re-evaluating cloud chamber constraints on depositional ice growth in cirrus clouds – Part 1: Model description and sensitivity tests

Abstract. Ice growth from vapor deposition is an important process for the evolution of cirrus clouds, but the physics of depositional ice growth at the low temperatures (<235 K) characteristic of the upper troposphere and lower stratosphere is not well understood. Surface attachment kinetics, generally parameterized as a deposition coefficient αD, control ice crystal habit and also may limit growth rates in certain cases, but significant discrepancies between experimental measurements have not been satisfactorily explained. Experiments on single ice crystals have previously indicated the deposition coefficient is a function of temperature and supersaturation, consistent with growth mechanisms controlled by the crystal's surface characteristics. Here we use observations from cloud chamber experiments in the Aerosol Interactions and Dynamics in the Atmosphere (AIDA) aerosol and cloud chamber to evaluate surface kinetic models in realistic cirrus conditions. These experiments have rapidly changing temperature, pressure, and ice supersaturation such that depositional ice growth may evolve from diffusion limited to surface kinetics limited over the course of a single experiment. In Part 1, we describe the adaptation of a Lagrangian parcel model with the Diffusion Surface Kinetics Ice Crystal Evolution (DiSKICE) model (Zhang and Harrington, 2014) to the AIDA chamber experiments. We compare the observed ice water content and saturation ratios to that derived under varying assumptions for ice surface growth mechanisms for experiments simulating ice clouds between 180 and 235 K and pressures between 150 and 300 hPa. We found that both heterogeneous and homogeneous nucleation experiments at higher temperatures (>205 K) could generally be modeled consistently with either a constant deposition coefficient or the DiSKICE model assuming growth on isometric crystals via abundant surface dislocations. Lower-temperature experiments showed more significant deviations from any depositional growth model, with different ice growth rates for heterogeneous and homogeneous nucleation experiments.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Molecular Insights into Novel Struvite–Hydrogel Composites for Simultaneous Ammonia and Phosphate Removal

Struvite (NH 4 MgPO 4 ·6H 2 O) mineralization is an effective technique for removing ammonium and phosphate species from wastewater. However, its wider use faces obstacles because of the copresence of various pollutants in wastewater and the additional requirement for magnesium to achieve proper supersaturation conditions. To address these challenges, this study developed novel mineral–hydrogel composites that can remove ammonium and phosphate simultaneously via heterogeneous struvite and calcium phosphate (CaP) mineralization in hydrogel matrices. The composites include in situ formed struvite and CaP mineral seeds, decreasing the nucleation energy barrier of struvite and CaP formation and promoting their heterogeneous nucleation kinetics even under undersaturation conditions in bulk solution. The dual struvite and CaP seeded composites can simultaneously reduce the ammonium and total phosphate concentrations up to 60% (26.3 mg of N/g) and 91% (9.54 mg of P/g), respectively. Furthermore, the average particle sizes in composites were increased from 6.12 to 14.8 nm after wastewater treatment. Moreover, various ions commonly existing in wastewater did not significantly interfere with the removal of ammonium and phosphate. Thus, these new mineral–hydrogel composites can provide an innovative way to lower nutrient levels before discharge to streams. Moreover, encapsulating ammonium and phosphate in mineral-hydrogel composites enables their upcycling in agricultural or biorefinery applications.

Cations↗
DOE OSTI2022

Crystallization kinetics and nanoparticle ordering in semicrystalline polymer nanocomposites

There has been considerable interest in the nucleation and crystallization of polymers in the presence of nanoparticles (NPs, or nanofillers in general, NFs). Most of the extensive work in this area has focused on anisotropic, non-Brownian NFs (e.g., clay sheets, carbon nanotubes) whose spatial dispersion state in these nanocomposites is controlled by the process by which they are formed. Hence, NF spatial dispersion is generally limited and often remains poorly characterized. Thermodynamic handles that can be used to control NF dispersion state in the polymer melt include (a) favorable interactions between the polymer chains and the bare NP surfaces, or (b) the density and length of the chains, with the same chemistry as the matrix, grafted to the NP surface. These relatively large NFs merely act as stationary objects that affect the kinetics of nucleation by providing heterogeneous sites, and the crystallization rate by confining the polymer in the melt state. The dispersion state of the NFs can dramatically affect the nucleation and crystallization of the matrix, but in most cases reported, the NFs increase nucleation efficiency relative to the neat polymer. At higher NF loadings, the effect of polymer confinement by the NFs dominates, leading to a decrease in crystal growth rates. This review describes the most important lessons learned from these commonly studied systems and then extends to polymer composite systems containing small, mobile spherical NPs (typically smaller than 100 nm in size). The role of NP mobility, which provides for dynamic confinement of the polymer melt, on the kinetics of polymer crystallization (nucleation, growth, and overall crystallization) and how this behavior is mostly consistent with the case of immobile NF is a second important focus of this review. In addition to the role of NFs on crystallization kinetics, recently reported nanoparticle ordering phenomena such as the effect of matrix crystallization on the organization of small spherical NPs within the amorphous regions of the semicrystalline morphology are discussed. In conclusion, such phenomena are clearly not observed for large NFs and hence provide a point of departure from past works in this area.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Multimodal Analysis of Spatially Heterogeneous Microstructural Refinement and Softening Mechanisms in Three-Pass Friction Stir Processed Al4Si Alloy

Multiple thermally and thermomechanically induced microstructural refinement mechanisms can be activated in metallic alloys when subjected to solid phase processing methods such as friction stir processing (FSP). In this work, we provide detailed descriptions of the relationship between region-specific microstructural refinement mechanisms and the variation in microhardness, through a systematic and multimodal microstructural characterization of an FSP-processed 75% cold-rolled Al-4 at.% Si model binary alloy. Spatially resolved high-energy synchrotron X-ray diffraction, electron backscattered diffraction, and scanning transmission electron microscopy were used to understand the spatially heterogeneous microstructural evolution due to FSP. Results provide insights into how mechanisms such as static recovery, static recrystallization, dynamic recovery and recrystallization, geometric and continuous dynamic recrystallization, and particle-stimulated static or dynamic grain nucleation may occur heterogeneously in the microstructure as a function of the distance from the stir zone in processed alloys, directly influencing the degree of softening. The systematic analysis of microstructures and hardness in the FSP-processed model binary alloy given in this work highlights the rich microstructural domains that can be uniquely harnessed through solid phase processing of metallic alloys.

Al4Si, Friction Stir Processing, Geometric Dynamic↗
DOE OSTI2025

Mitigating CaCO 3 crystal nucleation and growth through continuous ion displacement via alternating electric fields

Mineral crystal formation poses a challenge on surfaces (e.g., heat exchangers, pipes, membranes, etc.) in contact with super-saturated fluids. Applying alternating currents (AC) to such surfaces can prevent surface crystallization under certain conditions. Here, we demonstrate that ion displacement induced by periodic charging and discharging of the electrical double layer (EDL) inhibits both heterogeneous and homogeneous nucleation (and crystal growth) of CaCO 3 . Titanium sheets (meant to simulate metallic heat exchanger surfaces) are immersed in super-saturated CaCO 3 solutions with a saturation index >11. We show that at relatively high AC frequencies, incomplete EDL formation leads to an alternating electric field that propagates far into the bulk solution, inducing rapid ion migration that overwhelms the Brownian motion of ions. Electrochemical characterization reveals EDL charging/discharging under AC conditions that greatly inhibits precipitation. Operating at 4 V pp , 0.1–10 Hz reduces turbidity by over 96% and reduces CaCO 3 coverage on the metal plates by over 92%. Based on electrokinetic and crystallization models, the ion displacement velocity (exceeding the mean Brownian velocity) and displacement length disrupts ion collision and crystal nucleation. Overall, the technique has potential for preventing mineral crystal formation in heat exchangers and many other industrially relevant systems.

42 ENGINEERING↗
DOE OSTI2021

Labile Fe(III) supersaturation controls nucleation and properties of product phases from Fe(II)-catalyzed ferrihydrite transformation

We report Fe(II)-catalyzed ferrihydrite (Fh) transformation to more crystalline iron (oxyhydr)oxide phases is a widely occurring geochemical process which has been extensively studied as a function of Fe(II)/Fh ratios at fixed Fh loadings. However, recent isolation of an intermediate Fe(III) species resulting from Fe(II)-Fh contact that facilitates transformation by dissolution/reprecipitation suggests that the kinetics and properties of product phases will instead depend mostly on its rate of accumulation to a critical concentration, consistent with principles in the classical nucleation theory (CNT). This suggests a dependence both on the loading of Fe(II) on the surface, which controls the rate of labile Fe(III) formation, as well as the available volume of solution, which also impacts how fast it can achieve its critical concentration to nucleate product phases. To specifically examine the latter effect, here we studied transformation of 15 mg Fh in 1 mM FeSO 4 solutions at pH 7.2 in batch suspensions of 30 mL, 150 mL, and 450 mL volumes. Time-dependent concentrations of aqueous Fe(II), surface-associated Fe(II), and resulting labile Fe(III) were monitored along with bulk solids characterization as a function of time. Transmission electron microscopy (TEM) was used to visualize the evolution of phases at identical locations on TEM grids. The collective results show that the rates of Fh loss and emergence of product lepidocrocite (Lp) and goethite (Gt) as well as their phase proportions, nucleation mode and morphological properties depend directly on the rate of accumulation of the labile Fe(III) precursor to its critical concentration, which in our experiments was controlled simply by varying the available volume of solution into which it enters. Statistical analyses of TEM image data suggest that while both heterogeneous and homogeneous nucleation occurred in all experiments, the former was increasingly favored at lower Fh/solution ratio due to its lower nucleation barrier being more favorable at attendant lower supersaturations of Fe(III).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Influence of zwitterionic amphiphilic copolymers on heterogeneous gypsum formation: A promising approach for scaling resistance

Here, this study aims to investigate the influence of zwitterionic amphiphilic copolymers (ZACs) in the nucleation and growth of heterogeneous CaSO4 at the zwitterion-water interface, which is crucial for the prevention of mineral scaling and consequent downtime or suboptimal performance in industries like membrane desalination, heat exchangers, and pipeline transportation. In situ grazing incidence small angle X-ray Scattering (GISAXS), and quartz crystal microbalance with dissipation (QCM-D) techniques were used to analyze the evolution of CaSO 4 particles on two new ZAC coatings: poly-(trifluoroethyl methacrylate-random-sulfobetaine methacrylate) (PTFEMA-r-SBMA, or PT:SBMA) and poly(trifluoroethyl methacrylate-random-2-methacryloyloxyethyl phosphorylcholine) (PTFEMA-r-MPC, or PT:MPC). The results showed that PT:MPC coatings promoted nucleation but inhibited crystal growth, resulting in slower overall reaction kinetics on PT:MPC coatings compared to PT:SBMA coatings. Interfacial interactions involving the substrates, sulfate minerals, and ions were examined, revealing that calcium ion adsorption, primarily governed by electrostatic attraction, played a crucial role in the nucleation and growth processes on both ZAC coatings. The crystal characterization revealed a phase transition from bassanite to gypsum on both ZAC coatings, suggesting that these zwitterionic materials can influence the mineral phase of heterogeneously formed CaSO 4 crystals. These findings enhance our understanding of the fundamental mechanisms underlying heterogeneous CaSO 4 scaling in the presence of zwitterionic materials.

42 ENGINEERING↗