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At least 1,729 records · Page 96

Improving nanoparticle superlattice stability with deformable polymer gels

The self-assembly of colloidal nanoparticles into ordered superlattices typically uses dynamic interactions to govern particle crystallization, as these non-permanent bonds prevent the formation of kinetically trapped, disordered aggregates. However, while the use of reversible bonding is critical in the formation of highly ordered particle arrangements, dynamic interactions also inherently make the structures more prone to disassembly or disruption when subjected to different environmental stimuli. Thus, there is typically a trade-off between the ability to initially form an ordered colloidal material and the ability of that material to retain its order under different conditions. Here, we present a method for embedding colloidal nanoparticle superlattices into a polymer gel matrix. This encapsulation strategy physically prevents the nanoparticles from dissociating upon heating, drying, or the introduction of chemicals that would normally disrupt the lattice. However, the use of a gel as the embedding medium still permits further modification of the colloidal nanoparticle lattice by introducing stimuli that deform the gel network (as this deformation in turn alters the nanoparticle lattice structure in a predictable manner). Moreover, encapsulation of the lattice within a gel permits further stabilization into fully solid materials by removing the solvent from the gel or by replacing the solvent with a liquid monomer that can be photopolymerized. This embedding method therefore makes it possible to incorporate ordered colloidal arrays into a polymer matrix as either dynamic or static structures, expanding their potential for use in responsive materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A study on computational fluid dynamics modeling of a refrigerated container for COVID-19 vaccine distribution with experimental validation

A key issue with the distribution of vaccines to prevent COVID-19 is the temperature level required during transport, storage, and distribution. Typical refrigerated transport containers can provide a temperature-controlled environment down to -30 °C. However, the Pfizer vaccine must be carefully transported and stored under a lower temperature between -80 °C and -60 °C. One way to provide the required temperature is to pack the vaccine vials into small packages containing dry ice. Dry ice sublimates from a solid to a gas, which limits the allowable transport duration. This can be mitigated by transporting in a -30 °C refrigerated container. Moreover, because the dry ice will sublimate and thereby release CO 2 gas into the transport container, monitoring the CO 2 concentration within the refrigerated container is also essential. In the present work, a 3D computational fluid dynamics model was developed based on a commercially available refrigerated container and validated with experimental data. The airflow, temperature distribution, and CO 2 concentration within the container were obtained from the simulations. The modeling results can provide guidance on preparing experimental setups, thus saving time and lowering cost, and also provide insight into safety precautions needed to avoid hazardous conditions associated with the release of CO 2 during vaccine distribution.

59 BASIC BIOLOGICAL SCIENCES↗

DETAIL Component Scaling and Methodology Comparison

The purpose of this study was to develop a process to convert input signals from one facility into another by reflecting geometric and environmental settings. The Dynamic Energy Transport and Integration Laboratory (DETAIL) is a research facility in development. Its aim is to emulate the daily interactions among power production industry systems and receive real-time data from those systems as inputs. To convert signals and ensure that the temporal sequences and magnitudes reflect laboratory settings, the ability to scale and project data is essential. To demonstrate this ability, Dynamical System Scaling (DSS) and Hierarchical Two-Tiered Scaling (H2TS) (methodologies that enable systems to scale and project or extrapolate data sets to desired environments while conserving the observed behavior based on first principles) were applied to DETAIL’s thermocline thermal storage system in the Thermal Energy Distribution System (TEDS) facility and solid-oxide electrolysis cell in the High Temperature Hydrogen Electrolysis (HTHE) facility. Both thermocline and electrolysis cell systems were successfully scaled, and test cases were conducted to generate a doubly accelerated energy charge and discharge in reference to past experimental data from the facilities. The research results represented a case for the thermocline system that required signals to be accelerated without altering the stored energy. To enhance the quality of the accelerated data, error propagation analyses were conducted on DSS post-processing terms to determine the consequences of raw-data-associated errors.

08 HYDROGEN↗

Vibrational Dynamics and Phase Transitions of Hydrazine to 50 GPa

The high pressure behavior of hydrazine, N 2 H 4 , has been investigated to 50 GPa at room temperature using infrared and Raman spectroscopy to explore pressure induced phase transitions and changes in hydrogen bonding. Three solid–solid phase transitions were detected at 11, 21, and 32 GPa on room temperature compression through dramatic changes in the lattice vibration and N–H stretching regions with increasing pressure in both measurement techniques. The transition to phase IV, which appears at 32 GPa, exhibits increased hydrogen bonding with significant hysteresis, persisting to 9 GPa on decompression. This work presents a detailed analysis of the pressure dependence of mode shifts and calculations of mode Grüneisen parameters as well as a determination of an approximate thermodynamic Grüneisen parameter. We compare these results to the behavior of other small molecular materials such as ammonia and water and explore the evolution of hydrogen bonding in hydrazine toward the symmetrically hydrogen bonded state, which has previously been suggested by theoretical computations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observing the Surface Termination of LaScO 3 Perovskite Using Solid-State Nuclear Magnetic Resonance

Materials with well-defined surfaces are drawing increased attention for the design of bespoke catalysts and nanomaterials. Gaining a detailed understanding of the surfaces of these materials is an important challenge, which is often complicated by surface polymorphism and dynamic restructuring. We introduce the use of surface-enhanced NMR spectroscopy for the observation of such surfaces, focusing on LaScO 3 as an example. Here, we show that double-resonance NMR experiments correlating surface oxygen and probe molecules to the 139 La and 45 Sc nuclei at the surface reveal the material to be terminated by a ScO x monolayer. Surface-selective 17 O and 45 Sc NMR experiments further showed the material to be hydroxyl terminated and that the surface may be prone to dynamic restructuring as a result of moisture exposure. Perhaps most interestingly, surface-selective 139 La NMR experiments revealed the existence of previously undetected surface lanthanum defects, suggesting that surface-enhanced NMR may be useful as a guide in the synthesis of defect-free surfaces in the design of various nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Planet Formation by Gas-assisted Accretion of Small Solids

We compute the accretion efficiency of small solids, with radii 1 cm ≤ R s ≤ 10 m, on planets embedded in gaseous disks. Planets have masses 3 ≤ M p ≤ 20 Earth masses (M ⊕ ) and orbit within 10 au of a solar mass star. Disk thermodynamics is modeled via 3D radiation-hydrodynamics calculations that typically resolve the planetary envelopes. Both icy and rocky solids are considered, explicitly modeling their thermodynamic evolution. The maximum efficiencies of 1 ≤ R s ≤ 100 cm particles are generally ≲10%, whereas 10 m solids tend to accrete efficiently or be segregated beyond the planet’s orbit. A simplified approach is applied to compute the accretion efficiency of small cores, with masses M p ≤ 1 M ⊕ and without envelopes, for which efficiencies are approximately proportional to $M^{2/3}_{p}$. The mass flux of solids, estimated from unperturbed drag-induced drift velocities, provides typical accretion rates dM p /dt ≲ 10 -5 M ⊕ yr -1 . In representative disk models with an initial gas-to-dust mass ratio of 70–100 and total mass of 0.05–0.06 M ⊙ , the solids’ accretion falls below 10 -6 M ⊕ yr -1 after 1–1.5 Myr. The derived accretion rates, as functions of time and planet mass, are applied to formation calculations that compute dust opacity self-consistently with the delivery of solids to the envelope. Assuming dust-to-solid coagulation times of ≈0.3 Myr and disk lifetimes of ≈3.5 Myr, heavy-element inventories in the range 3–7 M ⊕ require that ≈90–150 M ⊕ of solids cross the planet’s orbit. The formation calculations encompass a variety of outcomes, from planets a few times M ⊕ , predominantly composed of heavy elements, to giant planets. The peak luminosities during the epoch of the solids’ accretion range from ≈10 -7 to ≈10 -6 L ⊙ .

79 ASTRONOMY AND ASTROPHYSICS↗

Liquefaction dynamics of n-octadecane in cylindrical coordinates

The study presents one method of mathematically modeling the effects of gravity-induced free convection upon the melting phenomena of a finite paraffin slab. The theoretical model is based on the numerical computer solution of the solid phase and liquid phase energy equations, coupled with an imposed ideal-viscous flow approximation. An implicit alternating-direction technique is used as the finite-difference approximation for the basic energy equations in the numerical solution. The theoretical predictions are compared to experimental data from an annular test cell, in which n-octadecane, C18H38, was used as the test material. The results show that the model is a good first approximation to the solution of solid-liquid phase change involving gravity-induced free convection.

Bain, R. L.↗

Molecular-level architecture of Chlamydomonas reinhardtii’s glycoprotein-rich cell wall

Abstract Microalgae are a renewable and promising biomass for large-scale biofuel, food and nutrient production. However, their efficient exploitation depends on our knowledge of the cell wall composition and organization as it can limit access to high-value molecules. Here we provide an atomic-level model of the non-crystalline and water-insoluble glycoprotein-rich cell wall of Chlamydomonas reinhardtii . Using in situ solid-state and sensitivity-enhanced nuclear magnetic resonance, we reveal unprecedented details on the protein and carbohydrate composition and their nanoscale heterogeneity, as well as the presence of spatially segregated protein- and glycan-rich regions with different dynamics and hydration levels. We show that mannose-rich lower-molecular-weight proteins likely contribute to the cell wall cohesion by binding to high-molecular weight protein components, and that water provides plasticity to the cell-wall architecture. The structural insight exemplifies strategies used by nature to form cell walls devoid of cellulose or other glycan polymers.

09 BIOMASS FUELS↗

Unseeded, spontaneous nucleation of spherulitic magnesium calcite

Most of the sedimentary carbonates deposited in the marine environments are composed of calcium carbonate minerals with varying amounts of incorporated Mg 2+ . However, understanding how interactions of impurities with carbonate and their incorporation affect sediments behavior remains a challenge. Here, a new insight is obtained by monitoring solution composition, morphology, and electrokinetic potential of carbonate particles formed in a spontaneous unseeded batch precipitation experiment using electrochemical and scanning electron microscopy methods. The solid composition and growth rate are extracted from changes in the bulk composition and fitted to chemical affinity rate law, revealing that the precipitation pathway consists of second-order dissolution and first-order precipitation. The molecular dynamics simulations show that the lattice strain induced by randomly substituting Ca 2+ by Mg 2+ stabilizes spherical nanoparticles and reduces their surface area and volume. Combining kinetics and thermodynamics insight, we conclude that variation in the carbonate bulk and interfacial energies, along with the solution supersaturation, lead to the dissolution-precipitation transformation pathway from Mg-rich to Mg-poor carbonate phase that preserves spherulitic morphology. Furthermore, our findings are relevant for long-standing questions of how impurities influence diagenesis of carbonate sediments and spherulitic carbonate particles' origin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamics and growth rate implications of ribosomes and mRNAs interaction in E. coli

Understanding how cells grow and adapt under various nutrient conditions is pivotal in the study of biological stoichiometry. Recent studies provide empirical evidence that cells use multiple strategies to maintain an optimal protein production rate under different nutrient conditions. Mathematical models can provide a solid theoretical foundation that can explain experimental observations and generate testable hypotheses to further our understanding of the growth process. In this study, we generalize a modeling framework that centers on the translation process and study its asymptotic behaviors to validate algebraic manipulations involving the steady states. Using experimental results on the growth of E. coli under C-, N-, and P-limited environments, we simulate the expected quantitative measurements to show the feasibility of using the model to explain empirical evidence. Our results support the findings that cells employ multiple strategies to maintain a similar protein production rate across different nutrient limitations. Moreover, we find that the previous study underestimates the significance of certain biological rates, such as the binding rate of ribosomes to mRNA and the transition rate between different ribosomal stages. Furthermore, our simulation shows that the strategies used by cells under C- and P-limitations result in a faster overall growth dynamics than under N-limitation. In conclusion, the general modeling framework provides a valuable platform to study cell growth under different nutrient supply conditions, which also allows straightforward extensions to the coupling of transcription, translation, and energetics to deepen our understanding of the growth process.

59 BASIC BIOLOGICAL SCIENCES↗

Analysis of AC-DC Converters for Grid-tied High Temperature Steam Electrolysis Systems

Grid-tied HTSE systems have the prospects to produce clean hydrogen enabling power and broad energy systems decarbonization. Most commercially available power electronic converter systems (PECS) are designed for batteries, solar PVs, wind, and other well-established renewable energy resources. Standards (such as IEEE 1547, UL 1741, CA Rule-21, HI Rule-14) exist for PECS used for renewable energy systems such as battery storage and solar PVs. However, those that consider the dynamic behavior of HTSEs and that can be used for large-scale H2 systems are yet to be developed. This paper investigates the performance of these PECS for the HTSE application that are set up at the Idaho National Laboratory for hydrogen production testing, research and development. In particular, the performance analysis of two grid-tied PECS (A and B) is conducted for a 100 kW solid oxide HTSE system. System A consists of 6 units of 30kW MOSFET-switched bidirectional AC-DC rectifier while system B has a single unit of 150kW thyristor-switched ACDC rectifier. Both systems are connected to the HTSE stacks via a DC-DC converter. Different operational conditions of the HTSE system are tested to analyze the dynamic response of the HTSE’s PECS. The experimental results show the need to develop advanced control strategies for PECS that incorporates the dynamics of HTSE systems for improved performance.

08 - HYDROGEN↗

Revealing multiscale competing processes in the solid-state synthesis of single-crystalline layered oxide positive electrodes

Solid-state synthesis involves a web of coupled chemical reactions and physical changes that unfold across multiple scales. Efforts to fine-tune its parameters have historically followed heuristic, trial-driven workflows that demand significant time and resources. In this study, we aimed to open this black box by employing multiscale in situ synchrotron imaging and diffraction. Using LiNi 0.5 Mn 0.3 Co 0.2 O 2 battery positive electrode material as a model system and Ba-based sintering aids, we reveal dopant segregation, intergranular mass transport, and porosity evolution as key drivers of single-crystalline particle formation. Notably, we uncovered a dynamic competition between particle-level grain coalescence and atomic-scale cation disordering, both of which are thermally activated yet have opposing impacts on battery performance. These findings highlight the coupled, multiscale nature of structure development and offer a mechanistic basis for optimizing the solid-state synthesis process. This framework provides a path toward more controlled, efficient, and scalable production of high-performance battery positive electrode materials.

36 MATERIALS SCIENCE↗

Emergence of complex-regular eutectic patterns in Al–Ge: Observations from correlative nano-imaging

Eutectic solidification exemplifies nonequilibrium pattern formation, making it a well-studied moving boundary problem. Yet the mechanisms behind the formation of complex-regular microstructures – particularly in highly anisotropic systems with a significant volume fraction of a faceted phase – remain poorly understood. Our understanding of such systems is made complicated by the nonlinear interface kinetics and unique growth dynamics characteristic of faceted phases. To address these challenges, we investigate a model Al–Ge eutectic system, where the faceted Ge phase constitutes a substantial volume fraction (~0.35) and where the two solid phases arrange into so-called “fishbone” or “feather” complex-regular patterns. Using synchrotron-based x-ray nano-imaging and nanotomography with high spatial resolution (22 nm per pixel), we capture in real-time the evolution of the solid–liquid interfaces and the resulting three-dimensional microstructures in this faceted/non-faceted eutectic system. By integrating these observations with electron backscattered diffraction, we elucidate the crystallographic biases on the solidification process and the mechanisms driving the formation of such complex-regular microstructures. These findings inform a new growth model for irregular eutectics in (near-)symmetrical phase diagrams, offering insight on advanced microstructural design and processing strategies. More broadly, we demonstrate how interfacial curvature is generated in irregular eutectic alloys and how it depends on the volume fraction of the faceted phase.

36 MATERIALS SCIENCE↗

Dual-function lignin monomers enable high-performance graphene electrodes via interface confinement and proton transfer enhancement

Graphene oxide (GO)-based energy storage faces dual bottlenecks: unsustainable reduction methods and sluggish proton transfer kinetics. Here, we introduce a groundbreaking green strategy using lignin-derived vanillyl alcohol (VA) as a dual-function monomer to simultaneously address these challenges. By thermally annealing GO/VA films at mild temperatures (<100 °C), VA triggers an interface-confined reduction of GO while self-polymerizing into redox-active oligomers (P-VA) that intercalate between graphene layers. This dual role-reducing agent and proton highway enables a 3D conductive network with minimized graphene restacking, abundant redox sites, and rapid H + transport pathways. Density Functional Theory (DFT) reveals how P-VA optimizes proton dynamics, while the resulting rGO-P-VA4-T90 electrode achieves a record volumetric capacitance of 311.1F/cm 3 (777.8F/cm 2 ) and retains 87.8 % capacity after 10,000 cycles. Flexible solid-state supercapacitors deliver 94.2 μWh/cm 2 energy density at 63.8 μW/cm 2 , rivaling state-of-the-art devices. Furthermore, this work redefines sustainable graphene engineering, merging biomass valorization with high-performance energy storage in a scalable, eco-friendly paradigm.

Graphene oxide reduction↗

Versatile system for ion energy measurements generated by pulsed laser ionization: Insights into electron-ion dynamics

Ion energy distributions generated by pulsed laser interactions with materials are essential for applications ranging from materials science to oncology. Ion energy characterization is particularly important for an emerging mass spectrometry technique called virtual-slit cycloidal mass spectrometry (VS-CMS). The ion energy distribution influences the design and performance of VS-CMS instruments, as well as the efficacy of laser-driven ionization methods in various fields. Several established techniques, including the retarding potential method, time-of-flight (TOF) analysis, and electrostatic energy analyzers, have been employed to measure ion energy distributions. The wide range of ion energies reported highlights the strong dependence of ion energy on laser parameters, target materials, and experimental conditions, as well as the necessity of making independent measurements of the ion energy distribution for specific laser systems and materials. This paper presents the design and characterization of a simple TOF-based apparatus for measuring ion energy distributions from pulsed laser ionization without external fields. This approach minimizes perturbation of electron-ion dynamics and enables simultaneous energy measurements at multiple spatial positions. Here, the apparatus was tested using a nanosecond pulsed Nd:YAG laser operating at 1064 nm, 532 nm, and 266 nm on solid copper sheets at various laser fluences. Simultaneous measurements at different distances provide new insights into ion-electron interactions post-ionization and demonstrate the influence of laser wavelength and fluence on ion energy distributions.

Ion energy↗

First-Principles Grand-Canonical Simulations of Water Adsorption in Proton-Exchanged Zeolites

Water appears by design or as impurities in many important reactive systems. For those catalyzed by porous solid acids, such as widely used zeolites, experimentally quantifying the amount or elucidating the structure of adsorbed water clusters at reaction conditions is challenging, while computational studies (e.g., first-principles molecular dynamics simulations) often need to assume the loading to examine solvation effects. Furthermore, we perform first-principles grand-canonical simulations to predict water adsorption to H-ZSM-5 zeolites under specified experimental conditions. Presampling with inexpensive force fields and a pool-based parallelization algorithm are used to improve simulation efficiency, while molecular dynamics is used to sample configurations involving hydronium species. We observe that H + exchange dramatically increases the hydrophilicity of zeolite MFI and an appreciable amount of water is present at very low relative humidities. At all conditions examined, the zeolitic protons are found to dissociate readily from the surface basic sites and become mobile by participating in the hydrogen-bonded chains of adsorbed water molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A mechanistic study of the dopant-induced breakdown in halide perovskites using solid state energy storage devices

Doping halide perovskites (HPs) with extrinsic species, such as alkali metal ions, plays a critical, albeit often elusive role in optimising optoelectronic devices. Here, we use solid state lithium ion battery inspired devices with a polyethylene oxide-based polymer electrolyte to dope HPs controllably with lithium ions. We perform a suite of operando material analysis techniques while dynamically varying Li doping concentrations. We determine and quantify three doping regimes; a safe regime, with doping concentrations of <10 20 cm –3 (2% Li : Pb mol%) in which the HP may be modified without detrimental effect to its structure; a minor decomposition regime, in which the HP is partially transformed but remains the dominant species; and a major decomposition regime in which the perovskite is superseded by new phases. We provide a mechanistic description of the processes mediating between each stage and find evidence for metallic Pb (0) , LiBr and LiPbBr 2 as final decomposition products. Combining results from synchrotron X-ray diffraction measurements with in situ photoluminescence and optical reflection microscopy studies, we distinguish the influences of free charge carriers and intercalated lithium independently. We find that the charge density is equally as important as the geometric considerations of the dopant species and thereby provide a quantitative framework upon which the future design of doped-perovskite energy devices should be based.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗