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At least 955 records · Page 53

Protein crystal nucleation kinetics using relative light-scattering techniques: Center director's discretionary fund

Light-scattering intensity measurements are a sensitive method for following changes in the hydrodynamic radius of particles in solution. The approach used in this report utilizes the light-scattering intensity ratios of a polydisperse to a monodisperse system. By numerically modeling the process, and fitting the model curves to the data, estimates have been obtained for the dimerization equilibrium constant, the dimer + dimer yields tetramer equilibrium constant, and the association rate constant for the dimerization process.

Pusey, Marc Lee↗

Sub-micrometer random-pyramid texturing of silicon solar wafers with excellent surface passivation and low reflectance

Select emerging solar cell technologies, ranging from very narrow screen-printed fingers to perovskite/silicon tandems, would benefit from a reduction of the height of the standard pyramidal texture of monocrystalline silicon wafers to below 1 μm. However, fabricating such small surface features usually compromises the requisite low reflectance and high passivation quality. Through systematic design of experiments, we demonstrate that conventional alkaline-based wet-chemical etching processes can be tuned to produce dense, spatially homogeneous, and uniformly sized sub-micrometer pyramids. Precise texture size can be further controlled by adding potassium silicate to the texturing solution to effectively slow the pyramid growth rate and promote nucleation. With pyramid size distribution data—extracted from multiple atomic force microscopy images across each wafer—we demonstrate 16 nanotextures with average pyramid sizes ranging from 62 to 512 nm, with the largest having only 0.3% of its pyramids taller than 1 μm. Six of the nanotextures exhibit light trapping and surface defect densities comparable to state-of-the-art microtextured wafers. In conclusion, the best nanotexture achieved an AM1.5G-weighted reflectance of 11.8% and a minority-carrier lifetime of 3.4 ms after passivation with amorphous silicon, demonstrating that smaller textures need not deteriorate solar cell performance.

14 SOLAR ENERGY↗

Effect of the Precursor Chemistry on the Crystallization of Triple Cation Mixed Halide Perovskites

Triple cation, mixed halide perovskite compositions have been reported to be more thermally stable, exhibit fewer phase impurities, and show higher power conversion efficiency and better reproducibility than single cation perovskites. In this work, we explain the formation of Cs0.05FA0.81MA0.14Pb(I0.85Br0.15)3 via a multimodal in situ study combining structural information from synchrotron grazing-incidence wide-angle X-ray scattering (GIWAXS) and optical properties from photoluminescence (PL) spectroscopy with density functional theory calculations (DFT). The focus here is on the effects of the solvent and antisolvent during crystallization. The predominantly used solvents N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and the antisolvent chlorobenzene (CB) as well as the solvent-antisolvent-precursor interactions are investigated. Given the high elemental complexity and mutual interdependencies between solvent, antisolvent, and perovskite precursors, we found significant differences in the crystallization pathways. DMF-pure precursors show the formation of the DMF-containing intermediate phase and the nucleation of compositionally distinct perovskite phases, while when DMSO is added, only crystalline α- and δ-phases were found. In addition, the presence of DMSO helps the formation of α-perovskite. Coordination energy and bond order (BO) calculations support our experimental findings. Dripping of CB induces nucleation at room temperature, slows the α-phase formation rate, and appears to reduce the nucleation radius. These findings provide novel insights into solvent, antisolvent, and perovskite precursor interactions and their formation pathways. The complexity of interactions between solvents and reagents highlights the importance of understanding these effects to further improve the reproducibility and optimize processing conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic electron tomography in three and four dimensions

Atomic electron tomography (AET) has become a powerful tool for atomic-scale structural characterization in three and four dimensions. It provides the ability to correlate structures and properties of materials at the single-atom level. With recent advances in data acquisition methods, iterative three-dimensional (3D) reconstruction algorithms, and post-processing methods, AET can now determine 3D atomic coordinates and chemical species with sub-Angstrom precision, and reveal their atomic-scale time evolution during dynamical processes. In this work, we review the recent experimental and algorithmic developments of AET and highlight several groundbreaking experiments, which include pinpointing the 3D atom positions and chemical order/disorder in technologically relevant materials and capturing how atoms rearrange during early nucleation at four-dimensional atomic resolution.

30 DIRECT ENERGY CONVERSION↗

Upgrading Metallurgical-Grade Silicon

Closed-loop process produces semiconductor-grade silicon. Metallurgical-grade silicon converted to ultrapure silicon by reacting with hydrogen and silicon tetrahalide to form trihalosilane, purifying this intermediate and again decomposing to high purity silicon in third stage. Heterogeneously and homogeneously nucleated polycrystalline silicon used in semiconductor device applications and in silicon photovoltaic solar cell fabrication.

Woerner, L. M.↗

Fluoride glass: Crystallization, surface tension

Fluoride glass was levitated acoustically in the ACES apparatus on STS-11, and the recovered sample had a different microstructure from samples cooled in a container. Further experiments on levitated samples of fluoride glass are proposed. These include nucleation, crystallization, melting observations, measurement of surface tension of molten glass, and observation of bubbles in the glass. Ground experiments are required on sample preparation, outgassing, and surface reactions. The results should help in the development and evaluation of containerless processing, especially of glass, in the development of a contaminent-free method of measuring surface tensions of melts, in extending knowledge of gas and bubble behavior in fluoride glasses, and in increasing insight into the processing and properties of fluoride glasses.

Doremus, R. H.↗

Pool boiling on metal-foam enhanced tube bundle: heat transfer characteristics and flow visualization

A flooded evaporator configuration is common in large central air conditioning or process cooling systems. It is basically a shell and tube heat exchanger, in which a secondary fluid (brine or water) circulates inside the tube bundle and is cooled by the vaporization of the refrigerant on the outside surface of the tubes. The enhanced pool boiling process enables the compact design of flooded evaporators, which substantially reduces the refrigerant charge. High-porosity metal foam, with a large surface-area-to-volume ratio, could provide an extended heat transfer area and a high-density of nucleation sites. This study experimentally investigated the pool boiling heat transfer and flow characteristics on metal-foam enhanced tube bundles. The enhanced bundle consists of four aluminum tubes with aluminum foam brazed around the outer surface, which are horizontally mounted in a staggered arrangement. The results showed that the metal-foam enhanced tube bundles improved the heat transfer coefficient by 100-160% with a lower wall temperature difference of 1-10°C, compared to the baseline. In addition, the tube pitch played a significant role in determining the pool boiling behavior of the tube bundles.

Yang, Cheng-Min↗

Understanding solidification of near eutectic alloy using Cellular Automata (CA)

The solidification microstructure of an alloy strongly influences the mechanical properties. Dendritic and eutectic solidification are two important pathways of alloy solidification. The formation of phases, and their size and distribution depend on which pathway to take. In contrast to the Scheil model that has been widely used in describing the solidification pathways of alloys manufactured from conventional casting approach, more sophisticated solidification models are required to describe the state-of-the art manufacturing processes, such as additive manufacturing where distinctly different phase morphology, size and distribution than conventional casting can form, due to the vast difference in cooling conditions. Therefore, this work is to develop a computational Cellular Automata framework which includes the modeling of nucleation and growth of dendritic and eutectic solidification, as well as their competition as a function of alloy composition, undercooling and cooling rate. Further, after individual solidification models were validated against analytical solutions, the models were then combined to predict the competition between dendritic and eutectic solidification in alloys with off-eutectic compositions. This work predicts increased cooling rates suppress the dendritic solidification and promote eutectic solidification. Although quantitative validation is needed, this finding is consistent with qualitative observation in literature.

36 MATERIALS SCIENCE↗

Crystallographic Mapping and Tuning of Water Adsorption in Metal–Organic Frameworks Featuring Distinct Open Metal Sites

Crucial steps toward designing water sorption materials and fine-tuning their properties for specific applications include precise identification of adsorption sites and establishment of rigorous molecular-level insight into the water adsorption process. We report stepwise crystallographic mapping and DFT computations of adsorbed water molecules in ALP-MOF-1, a metal-organic framework decorated with distinct open metal sites and carbonyl functional groups that serve as water anchoring sites for seeding the nucleation of a complex water network. Identification of an unusual water adsorption step in ALP-MOF-1 motivated the tuning of metal ion composition to carefully adjust water uptake. These studies provide direct evidence that the identity of the open metal sites in MOFs can dramatically affect water adsorption behavior between 0 and ~20% RH and that multiple proximal water anchoring sites along the MOF skeleton facilitate water uptake steps which could be potentially useful for applications requiring rapid and energetically facile water sorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In situ electron microscopy: atomic-scale dynamics of metal oxidation and corrosion

Corrosion degrades metals through complex microscopic processes that traditional methods often fail to capture. In-situ transmission electron microscopy (TEM) bridges this gap by providing real-time atomic-scale imaging of oxidation and corrosion dynamics. Gas-phase TEM uncovers critical oxidation mechanisms like oxide nucleation and alloying effects, while liquid-phase TEM tracks corrosion initiation. Coupled with emerging techniques like ultrafast direct electron detection cameras, these advancements promise unprecedented resolution in understanding material degradation.

36 MATERIALS SCIENCE↗

Silicon production in a fluidized bed reactor

Part of the development effort of the JPL in-house technology involved in the Flat-Plate Solar Array (FSA) Project was the investigation of a low-cost process to produce semiconductor-grade silicon for terrestrial photovoltaic cell applications. The process selected was based on pyrolysis of silane in a fluidized-bed reactor (FBR). Following initial investigations involving 1- and 2-in. diameter reactors, a 6-in. diameter, engineering-scale FBR was constructed to establish reactor performance, mechanism of silicon deposition, product morphology, and product purity. The overall mass balance for all experiments indicates that more than 90% of the total silicon fed into the reactor is deposited on silicon seed particles and the remaining 10% becomes elutriated fines. Silicon production rates were demonstrated of 1.5 kg/h at 30% silane concentration and 3.5 kg/h at 80% silane concentration. The mechanism of silicon deposition is described by a six-path process: heterogeneous deposition, homogeneous decomposition, coalescence, coagulation, scavenging, and heterogeneous growth on fines. The bulk of the growth silicon layer appears to be made up of small diameter particles. This product morphology lends support to the concept of the scavenging of homogeneously nucleated silicon.

Rohatgi, N. K.↗

Gravitational Effects on the Morphology and Kinetics of Photodeposition of Polydiacetylene Thin Films From Monomer Solutions

The goal of this proposed work is to study gravitational effects on the photodeposition of polydiacetylene thin films from monomer solutions onto transparent substrates. Polydiacetylenes have been an extensively studied class of organic polymers because they exhibit many unusual and interesting properties, including electrical conductivity and optical nonlinearity. Their long polymeric chains render polydiacetylenes readily conducive to thin film formation, which is necessary for many applications. These applications require thin polydiacetylene films possessing uniform thicknesses, high purity, minimal inhomogeneities and defects (such as scattering centers), etc. Also, understanding and controlling the microstructure and morphology of the films is important for optimizing their electronic and optical properties. The lack of techniques for processing polydiacetylenes into such films has been the primary limitation to their commercial use. We have recently discovered a novel method for the formation of polydiacetylene thin films using photo-deposition from monomer solutions onto transparent substrates with UV light. This technique is very simple to carry out, and can yield films with superior quality to those produced by conventional methods. Furthermore, these films exhibit good third-order properties and are capable of waveguiding. We have been actively studying the chemistry of diacetylene polymerization in solution and the photo-deposition of polydiacetylene thin films from solution. It is well-known that gravitational factors such as buoyancy-driven convection and sedimentation can affect chemical and mass transport processes in solution. One important aspect of polydiacetylene thin film photodeposition in solution, relevant to microgravity science, is that heat generated by absorption of UV radiation induces thermal density gradients that under the influence of gravity, can cause fluid flows (buoyancy-driven convection). Additionally, changes in the chemical composition of the solution during polymerization may cause solutal convection. These fluid flows affect transport of material to and from the film surface and thereby affect the kinetics of the growth process. This manifests itself in the morphology of the resulting films; films grown under the influence of convection tend to have less uniform thicknesses, and can possess greater inhomogeneities and defects. Specifically, polydiacetylene films photodeposited from solution, when viewed under a microscope, exhibit very small particles of solid polymer which get transported by convection from the bulk solution to the surface of the growing film and become embedded. Even when carried out under conditions designed to minimize unstable density gradients (i.e., irradiating the solution from the top), some fluid flow still takes place (particles remain present in the films). It is also possible that defect nucleation may be occurring within the films or on the surface of the substrate; this, too, can be affected by convection (as is the case with crystal growth). Hence films grown in 1-g will, at best, still possess some defects. The objective of this proposal is to investigate, both in 1-g and in low-g, the effects of gravitational factors (primarily convection) on the dynamics of these processes, and on the quality, morphology, and properties of the films obtained.

Paley, Mark S.↗

Statistical evaluation of microscale stress conditions leading to void nucleation in the weak shock regime

Here, we investigate the heterogeneity of the stress state driven by anisotropic deformation response at the single crystal level through five statistical volume element (SVE) calculations of polycrystalline BCC tantalum. This work focuses on grain boundaries as a prominent material defect type prone to void nucleation based upon experimental observations of predominantly intergranular void nucleation in this material. The SVEs are constructed to be statistically representative of larger volumes of material and are meshed such that mean and standard deviation of grain size and orientation information is reconstructed. The computational meshes feature hexahedral (brick) elements and smooth conformal grain boundaries where significant stress concentration is known to occur, a tail effect of interest in the extreme events process of dynamic ductile damage. An existing micromechanical crystallographic plasticity model shown to capture the single crystal behavior of BCC tantalum well is used to perform the polycrystal calculations. The model includes representation of the non-Schmid effect of non-planar screw dislocation kinetics in tantalum. A three-dimensional stress state time profile predicted by damage modeling of a flyer plate impact experiment is applied as boundary conditions to each SVE. Resulting grain boundary stress state statistics are strongly non-Gaussian. Significant structural evolution is observed within the compressive hold before unloading into tension in the stress profile. Strong angular dependence of grain boundary traction magnitude with shock direction is observed. Non-Schmid effects continue to suggest their influence on propensity of microstructural defect types to nucleate voids. A general void nucleation criterion is proposed using probability theory. The general framework is specified to polycrystalline BCC tantalum in the weak shock regime to include the SVE calculations and literature molecular dynamics calculations of grain boundary void nucleation strength. Probability density functions (PDFs) are used to describe the interaction between the local stress state heterogeneity and the distributed grain boundary void nucleation strength state. A causation entropy maximization procedure removes the requirement for ad hoc selection of a PDF functional form and provides a rigorous procedure for data-based PDF determination. The resulting physically informed PDF describes the spatial appearance frequency of nucleated voids as a function of applied macroscale pressure. Lower length scale physics are thus packaged in a precise and computationally efficient way to provide computational plasticity insight to macroscale dynamic ductile damage models.

36 MATERIALS SCIENCE↗

Stress-Induced Structural Transformations in Au Nanocrystals

Nanocrystals can exist in multiply twinned structures like icosahedron or single crystalline structures like cuboctahedron. Transformations between these structures can proceed through diffusion or displacive motion. Experimental studies on nanocrystal structural transformations have focused on high-temperature diffusion-mediated processes. Limited experimental evidence of displacive motion exists. We report structural transformation of 6 nm Au nanocrystals under nonhydrostatic pressure of 7.7 GPa in a diamond anvil cell that is driven by displacive motion. X-ray diffraction and transmission electron microscopy were used to detect the structural transformation from multiply twinned to single crystalline. Single crystalline nanocrystals were recovered after unloading, then quickly reverted to the multiply twinned state after dispersion in toluene. Furthermore, the dynamics of recovery was captured using TEM which showed surface recrystallization and rapid twin boundary motion. Molecular dynamics simulations showed that twin boundaries are unstable due to defects nucleated from the interior of the nanocrystal.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Nanoscale observations of Fe(ii)-induced ferrihydrite transformation

Because of its sorption properties, transformation of the nanomineral ferrihydrite (Fh) into more stable lepidocrocite (Lp) or goethite (Gt) has important impacts on the fate of metals, nutrients, and contaminants in soils/sediments. Although it is well known that the transformation rate is greatly accelerated under suboxic conditions by aqueous Fe(II), the enabling mass transfer process remains an ongoing debate among various mechanisms including dissolution/reprecipitation, solid-state recrystallization, and particle-mediated growth. In this paper, using electron microscopy, we examine the mineralogical evolution of 2-line Fh to Lp/Gt catalyzed by Fe(II) under strict anoxic conditions, including evaluation of Cl–SO 4 –HCO 3 anion effects. Emergence of Lp/Gt crystallites at the nanoscale was observed at ~20 min of reaction, earlier than previously reported. Lp is the first phase to nucleate in Cl-rich solutions without HCO 3 – ; whereas Lp and Gt concomitantly nucleate in SO 4 2– -rich solutions, and also when co-solute HCO 3 – is added. Lp crystallites nucleate as quasi-2D nanosheets one-unit-cell thick that contour the Fh surface; in contrast, rod-shaped (in Cl/SO 4 ) or acicular needle-shaped (in HCO 3 ) Gt crystals nucleate and grow radially outward from the Fh aggregates. Stages of transformation monitored by in situ μ-XRD coupled with aqueous Fe(II) uptake/release measurements are correlated with a short initial sorption stage followed by the onset of Lp/Gt growth that then progresses to Lp loss in favor of Gt. Microscopy data overwhelmingly support dissolution/reprecipitation as the underlying mechanism, including direct evidence for classical ion-by-ion Lp/Gt growth and Lp dissolution. The collective findings imply that the iron mass transfer through solution to distal Lp/Gt growth fronts is a critical enabling process facilitating rapid transformation.

54 ENVIRONMENTAL SCIENCES↗

Effects of Cooling Rates on Self-Reinforced Polyethylene Composites via Multiscale Experimental Characterizations

This study investigates cooling rate effects on self-reinforced polyethylene composites (PE-SRCs), focusing on macroscopic thermal and mechanical properties, and micro- to sub-micron morphologies. Unlike conventional fiber-reinforced composites (e.g., carbon and glass fiber based), cooling rate effects on SRCs remain less studied. PE-SRCs were fabricated from ultrahigh molecular weight polyethylene (UHMWPE) fabric and high-density polyethylene (HDPE) matrix with cooling rates from 0.76°C/min to 425°C/min. Tensile properties, including modulus (~9.5 GPa), strength (~360 MPa), and ultimate elongation (~6%), showed no significant cooling rate dependence. However, thermal analysis revealed melting temperature of HDPE matrix decreased from ~130°C to ~126.5°C with total crystallinity reducing from 84% to 75%. Wide-angle X-ray scattering confirmed decreasing crystallinity but at lower values (67%–59%), as thermal analysis might overestimate crystallinity. Small-angle X-ray scattering showed long period decreased from 24.3 to 17.4 nm, attributed to thinner lamellae and closer packing, suggesting limited crystal growth and faster nucleation. While cooling rates alter melting point and crystalline structures of HDPE matrix, these changes do not translate to substantial impact on macroscale mechanical properties of PE-SRCs. This insensitivity might be related to low interfacial shear strength at PE/PE interfaces, enabling process optimization while maintaining mechanical performance.

Cooling rate↗

Autonomous Synthesis of Metastable Materials Using a Modular Mixed-Flow Reactor

Understanding and controlling atomic-level processes at solid-liquid interfaces is key to advancing technologies in energy storage, carbon capture, critical element recovery, and materials synthesis. Many of these processes are dominated by the formation of short-lived intermediate precipitates that determine the final properties of synthesized materials. However, studying these intermediates is challenging due to their sensitivity and the reliance on trial-and-error methods. To address this, we developed an automated variable-volume mixed-flow reactor (MFR) to optimize metastable material synthesis and investigate rapid kinetic processes. This state-of-the-art MFR system, paired with an automated modeling framework, enables efficient synthesis and real-time analysis of transient phases. Benchmarking with advanced capabilities, such as wide-/small-angle X-ray scattering, allows us to resolve fast nucleation and growth dynamics that were previously inaccessible. By combining automation, ML-guided optimization, and tailored kinetic modeling, this approach provides a robust platform for improving material design and achieving precise control over solid-liquid reactions.

36 MATERIALS SCIENCE↗

Microgravity nucleation and particle coagulation experiments support

A preliminary model for diffusion between concentric hemispheres was adapted to the cylindrical geometry of a microgravity nucleation apparatus, and extended to include the effects of radiation and conduction through the containment walls. Computer programs were developed to calculate first the temperature distribution and then the evolving concentration field using a finite difference formulation of the transient diffusion and radiation processes. The following estimations are made: (1) it takes approximately 35 minutes to establish a steady temperature field; (2) magnesium vapors released into the argon environment at the steady temperature distribution will reach a maximum supersaturation ratio of approximately 10,000 in the 20-second period at a distance of 15 cm from the source of vapors; and (3) approximately 750W electrical power will be required to maintain steady operating temperatures within the chamber.

Lilleleht, L. U.↗