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At least 739 records · Page 41

In Situ Ultra-Small- and Small-Angle X-ray Scattering Study of ZnO Nanoparticle Formation and Growth through Chemical Bath Deposition in the Presence of Polyvinylpyrrolidone

ZnO inverse opals combine the outstanding properties of the semiconductor ZnO with the high surface area of the open-porous framework, making them valuable photonic and catalysis support materials. One route to produce inverse opals is to mineralize the voids of close-packed polymer nanoparticle templates by chemical bath deposition (CBD) using a ZnO precursor solution, followed by template removal. To ensure synthesis control, the formation and growth of ZnO nanoparticles in a precursor solution containing the organic additive polyvinylpyrrolidone (PVP) was investigated by in situ ultra-small- and small-angle X-ray scattering (USAXS/SAXS). Before that, we studied the precursor solution by in-house SAXS at T = 25 °C, revealing the presence of a PVP network with semiflexible chain behavior. Heating the precursor solution to 58 °C or 63 °C initiates the formation of small ZnO nanoparticles that cluster together, as shown by complementary transmission electron microscopy images (TEM) taken after synthesis. The underlying kinetics of this process could be deciphered by quantitatively analyzing the USAXS/SAXS data considering the scattering contributions of particles, clusters, and the PVP network. A nearly quantitative description of both the nucleation and growth period could be achieved using the two-step Finke–Watzky model with slow, continuous nucleation followed by autocatalytic growth.

36 MATERIALS SCIENCE↗

Evaluation of Nuclear Spent Fuel Disposal in Clay-Bearing Rock - Process Model Development and Experimental Studies

This report represents the milestone deliverable M2SF-23SN010301072 “Evaluation of Nuclear Spent Fuel Disposal in Clay-Bearing Rock - Process Model Development and Experimental Studies” The report provides a status update of FY23 activities for the work package Argillite Disposal work packages for the DOE-NE Spent Fuel Waste Form Science and Technology (SFWST) Program. Clay-rich geological media (often referred as shale or argillite) are among the most abundant type of sedimentary rock near the Earth’s surface. Argillaceous rock formations have the following advantageous attributes for deep geological nuclear waste disposal: widespread geologic occurrence, found in stable geologic settings, low permeability, self-sealing properties, low effective diffusion coefficient, high sorption capacity, and have the appropriate depth and thickness to host nuclear waste repository concepts. The DOE R&D program under the Spent Fuel Waste Science Technology (SFWST) campaign has made key progress (through experiment, modeling, and testing) in the study of chemical and physical phenomena that could impact the long-term safety assessment of heat-generating nuclear waste disposition in clay/shale/argillaceous rock. International collaboration activities comprising field-scale heater tests, field data monitoring, and laboratory-scale experiments provide key information on changes to the engineered barrier system (EBS) material exposed high thermal loads. Moreover, consideration of direct disposal of large capacity dual-purpose canisters (DPCs) as part of the back-end SNF waste disposition strategy has generated interest in improving our understanding of the effects of elevated temperatures on the engineered barrier system (EBS) design concepts. Chemical and structural analyses of sampled bentonite material from laboratory tests at elevated temperatures are key to the characterization of thermal effects affecting bentonite clay barrier performance. The knowledge provided by these experiments is crucial to constrain the extent of sacrificial zones in the EBS design during the thermal period. Thermal, hydrologic, mechanical, and chemical (THMC) data collected from heater tests and laboratory experiments have been used in the development, validation, and calibration of THMC simulators to model near-field coupled processes. This information leads to the development of simulation approaches to assess issues on coupled processes involving porous media flow, transport, geomechanical phenomena, chemical interactions with barrier/geologic materials, and the development of EBS concepts. These lines of knowledge are central to the design of deep geological backfilled repository concepts where temperature plays a key role in the EBS behavior, potential interactions with host rock, and long-term performance in the safety assessment.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Electrochromic Properties of Perovskite NdNiO 3 Thin Films for Smart Windows

Semiconductors with electrically tunable band gaps are of great interest in controlling transparency to electromagnetic radiation. Thin films of perovskite nickelate NdNiO 3 (NNO), a class of correlated oxides, were deposited on single-crystal (LaAlO 3 (LAO)) and polycrystalline (fluorine-doped tin oxide-coated glass (FTO)) substrates by magnetron sputtering, chemical solution deposition (CSD), and atomic layer deposition (ALD). Their electrochromic behaviors were investigated using a three-electrode setup in basic (KOH solution, pH = 12) electrolyte. During bleaching/coloration process, the proton intercalation/deintercalation and simultaneous electron compensation in the NNO lattice under electrical bias led to crossover of the material between the pristine-conducting phase (Ni 3+ ) and the strongly correlated insulating phase (Ni 2+ ), which serves as the working principle for electrochromic (tunable opacity in the visible range) behavior. Cyclic voltammetry (CV) scans demonstrate that NNO films are electrochemically stable in basic solutions for all three film deposition methods explored here. CV scans at varying rates enabled the extraction of diffusion coefficient of protons in thin film NNO, which is similar to 10 –7 cm 2 s –1 among all films studied. Large light transmittance modulation by bleaching and coloration was observed on films grown on both LAO and FTO substrates, suggesting its potential as an electrochromic material candidate for smart windows and optical shutter applications. Here, porous NNO films obtained by chemical solution deposition tend to demonstrate stronger electrochromic activity than dense films grown by sputtering or ALD.

36 MATERIALS SCIENCE↗

Probing the Morphology and Mobility of Amines in Porous Silica CO 2 Sorbents by 1 H T 1 – T 2 Relaxation Correlation NMR

Molecular and oligomeric amines supported in porous oxide supports are a promising class of CO 2 sorbent materials studied for CO 2 removal from diverse streams such as flue gas and ambient air. Among the various amines investigated, low molecular weight, hyperbranched poly(ethyleneimine) (PEI), and tetraethylenepentamine (TEPA) are among the most extensively studied. While macroscopic structure–performance relationships relating the support structure, amine loading, and other factors affecting CO 2 sorption capacities and kinetics have been developed, structural and dynamic information about the organic amine phase in the porous support is less plentiful. The structure and mobility of amines impregnated in the pores of porous supports directly impact gas sorption, as the accessibility of amine sites in the pores directly relates to amine distribution in the pores and overall pore filling as well as the dynamics of the amine chains. Here, we prepare a family of mesoporous silica SBA-15 materials containing varying loadings of oligomeric (PEI) and molecular (TEPA) amines. 1 H T 1 –T 2 relaxation correlation solid-state NMR experiments are used to characterize the structural and dynamic properties of the confined amines. Both TEPA and PEI are shown to form multiple different domains in the pores, each with distinguishable dynamic properties. TEPA and PEI form more rigid layers around the silica support walls at lower organic loading fractions, characterized by lower mobilities, followed by the formation of more mobile domains less engaged in pore wall interactions at higher loadings. TEPA shows faster mobilities than PEI because of its lower molecular weight. TEPA also appears to more easily transfer between domains within the pores, leading to generally faster CO 2 uptake rates with higher sorption capacities, while PEI located closer to the pore walls remained much less mobile and is thus less engaged in CO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Generalized thermo-mechanical framework for heterogeneous materials through asymptotic homogenization

Abstract A fundamental understanding of the interaction between microstructure and underlying physical mechanisms is essential, especially for developing more accurate multi-physics models for heterogeneous materials. Effects of microstructure on the material response at the macroscale are modeled by using the generalized thermomechanics. In this study, strain gradient theory is employed as a higher-order theory on the macroscale with thermodynamics modeled as a first-order theory on the microscale. Hence, energy depends only on the temperature such that we circumvent an extension of Fourier’s law and analyze the “simplest” thermo-mechanical model in strain gradient elasticity. Developing multiphysics models for heterogeneous materials is indeed a challenge and even this “simplest” model in generalized thermomechanics creates dozens of parameters to be determined. We develop a thermo-mechanical framework, in which microstructure is modeled as a periodic structure and through asymptotic homogenization approach, higher-order parameters at macroscopic scale are calculated. To illustrate the importance of higher-order parameters in overall thermo-mechanical response of a heterogeneous materials, finite element method (FEM) is employed with the aid of open-source codes (FEniCS). Verification example of a bulk system and several case studies of porous structures demonstrate how such numerical framework can be beneficial in the design of materials with tailored microstructures.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Local measurement of bulk thermal diffusivity using photothermal radiometry

Here, an experimental methodology using photothermal radiometry is developed for the accurate measurement of bulk thermal diffusivity of nuclear fuels and materials irradiated to high doses. Under these conditions, nuclear fuels, such as uranium oxide, and moderator materials, such as graphite, become friable, which requires characterization techniques that can accommodate irregularly shaped fragments. Photothermal radiometry, a good candidate for this application, involves locally heating a sample by using a laser and measuring the temperature field by monitoring blackbody radiation. The interaction volume for this study, less than a millimeter, is carefully chosen to sample a statistically significant number of large-scale structural features, such as pores and gas filled bubbles, and is small enough that the sample fragments can be treated as a thermal half-space. The thermal diffusivity standards considered in this study cover a range of thermal diffusivities representative of both fresh and spent nuclear fuels. We also consider a sample having a porous microstructure representative of large-scale structures found in materials irradiated to high doses. Our measurement methodology circumvents complex thermal wave models that address optical diffraction, nonlinear transfer function associated with blackbody radiation, and finite sample size effects. Consequently, the large measurement uncertainty associated with modeling these effects can be avoided. While the emphasis here is on nuclear fuels and materials, this measurement approach is well suited to measure thermal transport in a variety of technologically important materials associated with advanced synthesis techniques. Examples range from small, exotic single crystals grown using hydrothermal growth techniques to additively manufactured components having complex geometries.

36 MATERIALS SCIENCE↗

Effect of Silica and Mixing Time on Microstructures of Porous Polymer Composite by Emulsion Templating

Porous polymer composite with tailored porosity is applied in the myriads of areas such as energy storage, oil/water absorption, bioengineering, and advanced areas of material science. The emulsion templating technology is one of the most popular methods for synthesizing porous polymer composite. It involves solidifying a two-phase mixture of porogen and polymer, then removing porogen to create pores within the continuous emulsion phase by polymerization or curing. The surfactant plays a pivotal role in accomplishing a stable emulsion, a key factor in designing the internal porous structure. This study highlights the effect of silica filler and mixing time on pore morphology, i.e., shape, size, and distribution. on polydimethylsiloxane (PDMS) porous structure utilizing the water-in-oil emulsion templating method. Span® 80 is used as a surfactant to reduce the surface tension between water, silica, and PDMS and simultaneously create a strong foaming effect. Different weight concentrations of silica (1-10 wt%) were chosen while keeping the internal phase, i.e., water (50 wt%) constant. The designed porous structures were further characterized through scanning electron microscopy (SEM). Porous composite specimens fabricated with higher silica content and mixing time consistently exhibit smaller pore sizes than specimens fabricated with lower mixing time and silica content. A breakthrough of pore morphology is seen at silica content higher than 5wt% at 1 min mixing, however, pore morphology drastically changes when mixing time increases from 1 min to 6 min. Variation of finer mixing time beyond 1 min shows stepwise changes in pore morphology from a large single-phase porous structure to a bi-modal porous structure which eventually become a smaller single-mode porous structure. Thus, the emulsion templating technique, in combination with different filler content and mixing time, will effectively aid in designing engineered porous polymer composite with varying stiffness and pore morphology.

Porous polymer, Emulsion templating, Surfactant, P↗

In-situ localized growth of porous metal oxide films on microheater platform for low temperature gas detection

A solid-state, low power microheater sensor platform that is configurable with selected metal oxide films for particular gas sensing applications is described. The sensor platform is configured by selecting a chemiresistive or catalytic material that is suitable for detecting a desired gas and then forming a porous nanostructured film on the designated surfaces of the microheater platform. Also described are methods for creating a highly porous, nanostructured metal oxide film in a controlled location from a liquid precursor using a localized heat source. By fast annealing deposited liquid precursors with the microheater, a highly porous, nanocrystalline metal oxide film can be generated in-situ and locally on the sensor platform.

Maboudian, Roya↗

Prediction of local concentration fields in porous media with chemical reaction using a multi scale convolutional neural network

The study of solute transport in porous media is of interest in many chemical engineering systems. Some example applications include packed bed catalytic reactors, filtration devices, and batteries. The pore scale modeling of these systems is time consuming and may require large computing resources, for this reason computational fluid dynamics (CFD) simulations are not practical if a large number of simulations is required, like in multiscale modeling, where a model at a large scale calls for pore scale simulations. It has been shown that neural networks can be trained with a dataset of flow simulations and then predict fields orders of magnitude faster, and with less computational resources, in new domains. However, it is crucial to provide the neural network with an effective description of the domain and the undergoing operating conditions to be able to train models that generalize accurately in unseen samples. Therefore, research is needed to employ neural networks in new complex systems. The appropriate training of a network for predicting coupled flow and solute transport processes is an outstanding problem due to the complex interplay between geometry and operating conditions. In this work, we train a multi scale convolutional neural network (MSNet) with a diverse dataset of simulations of transport and chemical reaction in porous media to predict the local concentration fields in images of porous media. Our dataset contains a wide diversity of sphere pack arrangements under different operating conditions (Péclet and Reynolds numbers). Further, we train a robust model by employing different input descriptors that represent the medium and the different operating conditions of each system. Our trained model is able to provide nearly instantaneous predictions, compared to around twenty hours of the CFD workflow, with less than 3.5% error on new geometries and transport conditions. Thus the model could be easily integrated in a multiscale workflow where fast response is needed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Porous FeCo Glassy Alloy as Bifunctional Support for High-Performance Zn-Air Battery

Zn-air battery (ZAB) is attracting increasing attention due to its high safety and performance. However, the practical application of ZAB relies heavily on developing durable support materials to replace conventional carbon supports which have unrecoverable corrosion issues, severely jeopardizing ZAB performance. Herein, a novel porous FeCo glassy alloy was developed as bifunctional catalytic support for ZAB. Specifically, the conducting skeleton of the porous glassy alloy was used to stabilize oxygen reduction cocatalysts, and more importantly, the FeCo served as the primary phase for oxygen evolution. To prove the concept of catalytic glassy alloy support, ultra-small Pd nanoparticles were anchored, as oxygen reduction active sites, on the porous FeCo (noted as Pd/FeCo) for ZAB. The Pd/FeCo exhibited a significantly improved electrocatalytic activity for oxygen reduction (a half-wave potential of 0.85 V) and oxygen evolution (a potential of 1.55 V to reach 10 mA cm –2 ) in the alkaline media. When used in the ZAB, the Pd/FeCo delivered an output power density of 117 mW cm –2 and outstanding cycling stability for over 200 h (400 cycles), surpassing the conventional carbon-supported Pt/C+IrO 2 catalysts. Such an integrated design of combining highly active components with porous architecture provides a new strategy to develop novel nanostructured electrocatalysts.

36 MATERIALS SCIENCE↗

Methane Adsorption on Heteroatom-Modified Maquettes of Porous Carbon Surfaces

Experimental and theoretical studies disagree on the energetics of methane adsorption on carbon materials. However, this information is critical for the rational design and optimization of the structure and composition of adsorbents for natural gas storage. The delicate nature of dispersion interactions, polarization of both the adsorbent and the adsorbate, interplay between H-bonding and tetrel bonding, and induced dipole/Coulomb interactions inherent to methane physisorption require computational treatment at the highest possible level of theory. In this study, we employed the smallest reasonable computational model, a maquette of porous carbon surfaces with a central site for substitution and methane binding. The most accurate predictions of methane adsorption energetics were achieved by electron-correlated molecular orbital theory CCSD(T) and hybrid density functional theory MN15 calculations employing a saturated, all-electron basis set. Here, the characteristic geometry of methane adsorption on a carbon surface (“lander approach”) arises due to bonding interactions of the adsorbent π-system with the proximal H–C bonds of methane, in addition to tetrel bonding between the antibonding orbital of the distal C–H bond and the central atom of the maquette (C, B, or N). The polarization of the electron density, structural deformations, and the comprehensive energetic analysis clearly indicate a ∼3 kJ mol –1 preference for methane binding on the N-substituted maquette. The B-substituted maquette showed a comparable or lower binding energy than the unsubstituted, pure C model, depending on the level of theory employed. The calculated thermodynamic results indicate a strategy for incorporating electron-enriched substitutions (e.g., N) into carbon materials as a way to increase methane storage capacity over electron-deficient (e.g., B) modifications. The thermochemical analysis was revised for establishing a conceptual agreement between the experimental isosteric heat of adsorption and the binding enthalpies from statistical thermodynamics principles.

03 NATURAL GAS↗

Cooperative Research and Development Agreement between National Energy Technology Laboratory and Electric Power Research Institute (EPRI) [Abstract]

Carbon dioxide (CO 2 ) capture from flue gas generated by fossil fuel-fired power plants has been proposed as an efficient approach to limit CO 2 emissions to the atmosphere. Due to the high cyclic CO 2 sorption capacity, well-tuned adsorption chemistry and non-volatility, solid sorbents are widely studied for CO 2 capture processes such as pressure swing adsorption (PSA) and temperature swing adsorption (TSA). Realistic applications of traditional solid sorbent systems face many challenges since moisture and heat management are problematic and solid-solid heat exchange is inefficient. Recently, a novel solid sorbent system, the sorbent polymer composite (SPC), has been developed to overcome those challenges in an energy-saving CO 2 capture process using TSA membrane contactors. A SPC material is comprised of a powdered solid sorbent embedded into a hydrophobic and porous polymer matrix. It allows gases to permeate through and achieve full contact with the sorbents while rejecting water moisture in the CO 2 capture process. In this collaborative research, NETL will conduct performance testing of a novel SPC material and EPRI will conduct a cost analysis based on that performance data.

20 FOSSIL-FUELED POWER PLANTS↗

Effect of strain rate on the deformation of hollow CoS nanoboxes and doubly porous self-assembled films

Nanomaterials with multiscale porosity are attractive as lightweight structural materials because unique deformation mechanisms can be programmed at different length scales. Here, we explore this concept by investigating the mechanics of hollow nanoboxes, as well as films self-assembled from nanoboxes. Hollow CoS nanoboxes with lengths of 900 nm and <30 nm wall thickness are synthesized using colloidal methods. Individual nanoboxes are compressed inside a scanning electron microscope at strain rates of 0.001 s –1 , 0.01 s –1 , and 0.1 s –1 . Nanoboxes are found to have a first peak stress of 15 MPa and loading modulus of ~240 MPa regardless of strain rate. The nanoboxes deform through ductile, plastic bending of side walls at 0.001 s –1 strain rate, while brittle fracture occurs at the higher strain rates. Self-assembly of these nanoboxes results in films with relative density of <0.1. Nanoindentation shows strain rate independent behavior with average modulus and hardness of ~15 MPa and ~230 kPa, respectively. Furthermore, the mechanical behavior of the film is compared to that of the nanobox building blocks, cellular foams and granular materials.

36 MATERIALS SCIENCE↗

Unveiling 3D Morphology of Multiscale Micro-Nanosilver Sintering for Advanced Electronics Manufacturing by Ptychographic X-ray Nanotomography

The sintering processing–structure–property relationship of a multiscale silver materials is investigated: microparticles with nanofeatures, particularly on their three-dimensional (3D) morphology. The target application is to replace conventional lead-based solders in advanced electronic manufacturing. Unlike lead-based solders, silver powders are suited to satisfy increasingly demanding mechanical, electrical, and thermal requirements, meanwhile being free of health effect. Sintering the material at a low temperature and without applied pressure are desirable conditions, which results in a preferred use of silver nanoparticles, as nanofeatures have higher driving force to sinter with the decrease in particle size. However, nanosized powders present potential health/environmental effects. To address the trade-off between the benefits and shortcomings of nano-versus microparticles, this work studies a novel multiscale silver paste, namely micron-sized powders with nanosized features. To get quantitative 3D visualization of micro- and nanoscale features, ptychographic X-ray computed nanotomography is applied. The correlations between conditions (thermal aging, pressure, and substrate metallization), mechanical properties, and morphological parameters are established. Finally, using novel 3D X-ray nanoimaging technique, it is demonstrated that one can design multiscale materials while balancing complex demands required in advanced electronics manufacturing and research directions in materials design and characterization.

36 MATERIALS SCIENCE↗

Leveraging Exchange Kinetics for the Synthesis of Atomically Precise Porous Catalysts

Metal-organic frameworks (MOFs) have attracted significant attention as porous catalyst platforms due to the synthetic modularity of these materials and the diversity of lattice-confined catalytic active sites that are readily embedded within periodic crystalline frameworks. MOFs offer platforms to heterogenize molecular catalysts, stabilize novel coordination motifs, and leverage confinement effects in catalysis. Crystallinity allows diffraction-based methods to be employed in the characterization of these catalysts. Access to crystalline MOFs typically requires reversible construction of the metal-ligand (M-L) bonds that connect the SBUs, which provides a mechanism to anneal defects during crystallization. While the required M-L bond reversibility is often promoted by synthesis at elevated temperature, access to crystalline materials based on either transition metals with characteristic slow exchange kinetics or highly basic donor ligands remains a synthetic challenge. Here in this paper, we highlight synthetic strategies that leverage M-L exchange kinetics to access MOFs based on kinetically inert ions and extensions of these strategies to the assembly of atomically precise multimetallic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Boosting High-Rate Zinc-Storage Performance by the Rational Design of Mn 2 O 3 Nanoporous Architecture Cathode

Manganese oxides are regarded as one of the most promising cathode materials in rechargeable aqueous Zn-ion batteries (ZIBs) because of the low price and high security. However, the practical application of Mn 2 O 3 in ZIBs is still plagued by the low specific capacity and poor rate capability. Herein, highly crystalline Mn 2 O 3 materials with interconnected mesostructures and controllable pore sizes are obtained via a ligand-assisted self-assembly process and used as high-performance electrode materials for reversible aqueous ZIBs. The coordination degree between Mn 2+ and citric acid ligand plays a crucial role in the formation of the mesostructure, and the pore sizes can be easily tuned from 3.2 to 7.3 nm. Ascribed to the unique feature of nanoporous architectures, excellent zinc-storage performance can be achieved in ZIBs during charge/discharge processes. The Mn 2 O 3 electrode exhibits high reversible capacity (233 mAh g -1 at 0.3 A g -1 ), superior rate capability (162 mAh g -1 retains at 3.08 A g -1 ) and remarkable cycling durability over 3000 cycles at a high current rate of 3.08 A g -1 . Moreover, the corresponding electrode reaction mechanism is studied in depth according to a series of analytical methods. These results suggest that rational design of the nanoporous architecture for electrode materials can effectively improve the battery performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbon aerogels with integrated engineered macroporous architectures for improved mass transport

Carbon aerogels (CAs) combine unique properties including ultra-high surface area, high electrical conductivity, corrosion resistance, and robust mechanical properties making them ideal materials for electrochemical applications. Traditional CA synthesis results in isotropic, random nanoporous networks that work well for applications relying on diffusional mass transport. However, many applications would benefit from integration of engineered macroporous network structures that enable directed pressure-gradient-driven mass transport. In this study, we report on using 3D-printed sacrificial polymeric templates to generate templated CAs (t-CAs) with integrated engineered nonrandom macroporous network structures. Specifically, we used projection micro-stereo-lithography (PμSL) and two-photon polymerization direct laser writing (2PP-DLW) to fabricate millimeter-to-centimeter-sized 3D sacrificial polymeric templates with features ranging from tens of microns (PμSL) to 100s of nanometers (2PP-DLW). T-CAs were fabricated by infiltrating the templates with resorcinol-formaldehyde (RF) precursor solution, followed by carbonization at 1050 °C to simultaneously convert the RF gel to a CA and decompose the 3D-printed template, leaving an embedded templated macroporous network structure behind. X-ray computer tomography confirms integration of the macroporous architecture defined by the template. The templated macroporous architecture improves mass transport in t-CAs compared to traditional bulk CA as demonstrated by more uniform activation and their response in electrochemical cyclic voltammetry and galvanostatic charge-discharge tests.

36 MATERIALS SCIENCE↗