Quantitative structure-property relationship (QSPR) analysis of calcium aluminosilicate glasses based on molecular dynamics simulations
Not provided.
nuclear, defects, corrosion↗
SEARCH · Search NASA
Results for “Composite design”
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Phase Stability and Electrochemical Performance of La-Site-Doped Li6La3Zr0.5Nb0.5Ta0.5Hf0.5O12 High-Entropy Garnets
We investigate La-site substitution in the high-entropy garnet Li6La3Zr0.5Nb0.5Ta0.5Hf0.5O12 (LLZNTH) using Ba2+, Sr2+, and Sm3+ to elucidate how dopant governs phase stability, Li-site distribution, and electrochemical behavior. X-ray diffraction shows that Sr2+ is incorporated homogeneously into the garnet lattice, whereas the larger Ba2+ and smaller Sm3+ ions partially exceed the structural tolerance, generating secondary phases. Nevertheless, the Sm-doped composition (x = 0.05) exhibits the highest room-temperature ionic conductivity (2.7 × 10–4 S cm–1). Neutron powder diffraction reveals that Sm substitution drives a redistribution of Li+ from the tetrahedral 24 d sites into the higher-mobility 96 h positions, enhancing the connectivity of the three-dimensional Li-ion migration network. A Sm-doping series (x = 0.01–0.05) further shows that only sufficiently high Sm levels induce this redistribution, whereas lower concentrations retain Li arrangements similar to the undoped garnet. Critical current density measurements demonstrate that La-site dopants also influence interfacial stability against Li metal, underscoring a trade-off between bulk transport enhancement and mechanical robustness. Collectively, these findings reveal that in high-entropy garnets improved ionic conductivity can originate not only from phase-pure structures but also from targeted modification of the Li sublattice, even when accompanied by secondary phases, offering a compositional design principle for garnet electrolytes.
Li, Chang [Mechanical Engineering, School of Scien↗
The Relationship between Ionic Conductivity and Solvation Structures of Localized High-Concentration Fluorinated Electrolytes for Lithium-Ion Batteries
Localized high concentration electrolyte (LHCE) combines a diluent with high concentration electrolyte (HCE), offering promising properties. The ions, solvent, and diluent interact to form a complex heterogenous liquid structure, where high salt concentration clusters are embedded in diluent. Optimizing LHCE for desired electrolyte properties like high ionic conductivity, low viscosity, effective solid electrolyte interphase (SEI) formability, within the vast chemical and compositional design space requires deeper understanding and theoretical guidance. For this work, we investigated the structures and conductivity of LHCEs based on a fluorinated solvent with two different diluents at varying concentrations. The 2,2,3,3-tetrafluoropropyl trifluoroacetate (TFPTFA) enters the solvation cluster due to its stronger Li-ion interactions, whereas 1,1,2,2-tetrafuoroethyl 2,2,2-trifuoroethyl ether (TFETFE) enters only at extremely high diluent concentrations. The ionic conductivity increases with decreasing diluent concentrations, with a slope change during cluster percolation. Overall, TFETFE demonstrates higher effectiveness than TFPTFA, forming higher local salt concentration clusters, and resulting in higher ionic conductivity.
cluster chemistry↗
Impact of Controlled Storage Conditions on the Hydrolysis and Surface Morphology of Amorphous-UO 3
The hydration and morphological effects of amorphous (A)-UO 3 following storage under varying temperature and relative humidity have been investigated. This study provides valuable insight into U-oxide speciation following aging, the U-oxide quantitative morphological data set, and, overall, the characterization of nuclear material provenance. A-UO 3 was synthesized via the washed uranyl peroxide synthetic route and aged based on a 3-factor circumscribed central composite design of experiment. Target aging times include 2.57, 7.00, 14.0, 21.0, and 25.4 days, temperatures of 5.51, 15.0, 30.0, 45.0, and 54.5 °C, and relative humidities of 14.2, 30.0, 55.0, 80.0, and 95.8% were examined. Following aging, crystallographic changes were quantified via powder X-ray diffraction and an internal standard Rietveld refinement method was used to confirm the hydration of A-UO 3 to crystalline schoepite phases. The particle morphology from scanning electron microscopy images was quantified using both the Morphological Analysis of MAterials software and machine learning. Results from the machine learning were processed via agglomerative hierarchical clustering analysis to distinguish trends in morphological attributes from the aging study. Significantly hydrated samples were found to have a much larger, plate-like morphology in comparison to the unaged controls. Predictive modeling via a response surface methodology determined that while aging time, temperature, and relative humidity all have a quantifiable effect on A-UO 3 crystallographic and morphological changes, relative humidity has the most significant impact.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Bioconversion of Agave Bagasse Lignin to Medium-Chain-Length Polyhydroxyalkanoates by Pseudomonas putida
Inadequate disposal of Agave tequilana bagasse (ATB) brings environmental and economic issues to tequila producing regions. Recent works have proposed technologies for valorization of the polysaccharide’s fractions of ATB. However, lignin bioconversion has not been investigated due to its recalcitrant nature. In this work, a systematic pretreatment is proposed to release the lignocellulosic fractions and produce medium-chain-length polyhydroxyalkanoates (PHA) from the lignin fraction of ATB. Nuclear magnetic resonance (NMR) analyses revealed that ATB lignin contained 63% of β-O-4 interunit linkages, making this lignin more suitable for pretreatment and biodegradation compared to other lignins. Exploratory experiments revealed that two-stage fermentation is suitable for PHA production from ATB lignin using wild type and engineered Pseudomonas putida strains. PHA increased from 0.09 to 0.39 g/L compared to single batch fermentation. Further improvement to 0.76 g/L was possible by using a central composite design to optimize the inoculum, substrate, and nitrogen concentrations. Finally, PHA depolymerase gene phaZ was knocked out from P. putida and tested at optimal conditions, enabling a PHA titer of 0.97 g/L. Analyses by NMR and GC-MS confirmed lignin derivatives consumption and decrease of β-O-4 linkages. This study lays the foundations to enable agave lignin bioprocessing and opens new avenues for ATB biorefineries.
PHA↗
Symmetry Breaking Induced by Chiral Phosphonic Acids in a 2D Tin-Halide Perovskite
The ability to induce and modulate chirality in metal halide perovskite semiconductors (MHPs) using chiral additives expands the compositional design space and offers a means of tuning chiroptical properties. Motivated by the ability of phosphonic acids to interact with metal ions, we designed three chiral phosphonic acids (CPAs) to impose chirality in otherwise achiral 2D MHP, phenylammonium tin iodide (PA 2 SnI 4 ). We found that both the position of the phosphonic acid relative to the bond between the two naphthalene rings (i.e., the chiral axis) and the distance between the phosphonic acid and the binaphthyl chiral units significantly impact the transfer of structural chirality into the MHP lattice. The compound with a phosphonic acid directly bound to one of the naphthalene rings at the carbon adjacent to the chiral axis resulted in the largest circular dichroism dissymmetry factor of the three phosphonic acids. Furthermore, optical pump-terahertz probe measurements reveal an increase in the charge carrier mobility in the MHPs following the addition of CPAs. This dual functionality of CPAs in inducing chirality and improving charge transport properties in MHPs is promising for chiral-optoelectronic applications.
14 SOLAR ENERGY↗
Dynamic Atomistic Polar Structure Underpins Ultrahigh Linear Electro-Optic Coefficient in Transparent Ferroelectric Ceramics
Transparent ferroelectrics with high linear electro-optic (EO) coefficients are critical for advanced electro-optical devices. However, achieving optical transparency in ferroelectric ceramics remains challenging due to visible light scattering caused by defects such as domain walls, grain boundaries, and pores. Here, we report the successful fabrication of transparent ferroelectric ceramics through innovative chemical composition design and an advanced two-step sintering process in the La-doped Pb(Mg 1/3 Nb 2/3 )O 3 –PbTiO 3 system. The optical transparency, which is near the theoretical upper limit, can be attributed to the wide band gap and the minimization of light scattering of defects. By minimizing porosity and engineering grain/domain sizes to differ significantly from the wavelengths of visible light, we suppress scattering, achieving optical transparency near the theoretical upper limit. Strikingly, these ceramics exhibit an ultrahigh linear EO coefficient of ∼1417 pm/V, over 65 times greater than that of LiNbO 3 single crystals, the current industry standard. We attribute this exceptional performance to dynamic atomistic polar structures within switchable, thermally stable domains, which enhance electronic polarization sensitivity. This mechanism is corroborated by dielectric spectroscopy, high-resolution transmission electron microscopy and simulation. Our findings offer insights into the design of cost-effective transparent materials with exceptional EO properties, paving the way for next-generation electro-optical devices.
36 MATERIALS SCIENCE↗
An electrochemically stable homogeneous glassy electrolyte formed at room temperature for all-solid-state sodium batteries
All-solid-state sodium batteries (ASSSBs) are promising candidates for grid-scale energy storage. However, there are no commercialized ASSSBs yet, in part due to the lack of a low-cost, simple-to-fabricate solid electrolyte (SE) with electrochemical stability towards Na metal. In this work, we report a family of oxysulfide glass SEs (Na 3 PS 4-x O x , where 0 < x ≤ 60) that not only exhibit the highest critical current density among all Na-ion conducting sulfide-based SEs, but also enable high-performance ambient-temperature sodium-sulfur batteries. By forming bridging oxygen units, the Na 3 PS 4-x Ox SEs undergo pressure-induced sintering at room temperature, resulting in a fully homogeneous glass structure with robust mechanical properties. Furthermore, the self-passivating solid electrolyte interphase at the Na|SE interface is critical for interface stabilization and reversible Na plating and stripping. The new structural and compositional design strategies presented here provide a new paradigm in the development of safe, low-cost, energy-dense, and long-lifetime ASSSBs.
25 ENERGY STORAGE↗
Tensile deformation behavior of twist grain boundaries in CoCrFeMnNi high entropy alloy bicrystals
High entropy alloys (HEA) are a class of materials that consist of multiple elemental species in similar concentrations. The use of elements in far from dilute concentrations introduces a multi-dimensional composition design space by which the properties of metallic systems can be tailored. While the mechanical behavior of HEAs has been the subject of active research recently, the role of grain boundaries (GBs) in their deformation behavior remains poorly understood. Motivated by recent experiments on HEAs demonstrating that GBs act as nucleation sites for deformation twins, herein, we leverage atomistic simulations to construct a series of equiatomic CoCrFeMnNi HEA bicrystals with $\langle 110 \rangle$ and $\langle 111 \rangle$ symmetric twist GBs and examine their tensile behavior and underlying deformation mechanisms at 77 K. Simulation results reveal that plastic deformation proceeds by the nucleation of partial dislocations from GBs, which then grow with further loading by bowing into the bulk crystals leaving behind stacking faults. Variations in the nucleation stress exist as function of GB character, defined in this work by the twist angle. Our results provide future avenues to explore GBs as a microstructure design tool to develop HEAs with tailored properties.
36 MATERIALS SCIENCE↗
Enhanced medium chain length-polyhydroxyalkanoate production by co-fermentation of lignin and holocellulose hydrolysates
Biological lignin conversion to medium chain length-polyhydroxyalkanoates (mcl-PHA) has recently emerged as an attractive alternative to petroleum-based plastics due to the renewable nature of lignin and the value-added applications of mcl-PHA. Previous reports suggested that addition of limited glucose can improve mcl-PHA accumulation in Pseudomonas putida KT2440 grown in lignin substrates. Herein, we propose a biorefinery process to systematically release lignin and sugars from lignocellulosic biomass and evaluate the potential of co-utilization of all biomass components for conversion to mcl-PHA. Our results indicate that a sequential treatment composed of acid pretreatment, enzymatic hydrolysis and alkaline treatment produces a suitable lignin stream for mcl-PHA production in engineered P. putida. In addition, the PHA titer could be increased by 71% when the lignin stream (AH) was combined with the enzymatic hydrolysate (EH) at a ratio of 75 : 25. Higher ratios of EH : AH negatively affect mcl-PHA accumulation as well as mixtures with sugars from the acid hydrolysate. The optimization of the fermentation conditions, including the inoculum (OD 600 ) and substrate (soluble solid content (SSC)), was carried out by a central composite design. The optimal conditions were achieved at OD 600 = 2.17 and SSC = 68.28 g L –1 . Under these conditions, the titer increased 4.3 fold, achieving a mcl-PHA production of 1.38 g L –1 . Lignin characterization before and after fermentation by nuclear magnetic resonance and gas chromatography showed that p-coumarates were mainly consumed during the fermentation for mcl-PHA production. Overall, this biorefinery strategy allowed us to increase mcl-PHA production by utilizing the different lignocellulosic fractions. Unlike previous studies, no model substrates were utilized at any stage of the fermentation process, representing a step forward towards process feasibility.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
One-pot ethanol production under optimized pretreatment conditions using agave bagasse at high solids loading with low-cost biocompatible protic ionic liquid
Agave bagasse (AG) is a potential bioenergy feedstock due to its high biomass productivity, even in semiarid lands. In particular, ionic liquid (IL) pretreatment using aprotic ILs (AILs) has greatly reduced AG recalcitrance towards downstream processing by lowering lignin content and achieving high sugar yields. However, AIL's low biocompatibility towards enzymes and bacteria combined with the high initial cost has limited further development of this technology. In a wash-free one-pot (OP) ethanol conversion process, the evaluation of AG pretreatment with a biocompatible low-cost protic IL (PIL), 2-hydroxyethylammonium acetate ([2-HEA][OAc]) was achieved, where PIL pretreatment was followed by enzymatic saccharification, then ethanol fermentation in a single vessel. The pretreatment conditions were optimized using a central composite design to enable high sugar conversion at low PIL content. Under optimized pretreatment conditions (160 °C, 60% IL loading and 1.5 h), a yield of 132 kg of ethanol per Ton of untreated biomass was estimated using high solids loading (30% solids loading) under a PIL-OP scheme. High lignin removal (>50%), a decreased cellulose crystallinity, and high glucan conversion (>85%) were achieved with PIL-pretreated AG comparable to yields obtained in an AIL-AG pretreated sample using 1-ethyl-3-methyl-imidazolium acetate ([C 2 C 1 Im][OAc]). Here, these results using [2-HEA][OAc] demonstrate the potential of AG in an OP scheme with improved total ethanol yields paving the way towards a more feasible IL-based biorefinery.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Scalable mechanochemical synthesis of high-quality Prussian blue analogues for high-energy and durable potassium-ion batteries
Prussian blue analogues (PBAs) are recognized as promising cathode materials for potassium-ion batteries (PIBs), particularly the low-cost and high-energy K 2 Mn[Fe(CN) 6 ](KMnF). However, conventional solution-based synthesis inevitably introduces [Fe(CN) 6 ] 4− defects and lattice water while suffering low synthesis efficiency, unfavorable to the improvement of electrochemical performance and scalability. Here, in this work, we report a simple solvent-free mechanochemical strategy for the synthesis of a wide variety of K 2 M[Fe(CN) 6 ] (M = Mn, Mg, Ca, etc.) with negligible defects and water, and it is unprecedented to achieve kilogram-level products of high-quality KMnF within just 10 minutes. The as-prepared KMnF delivers a high energy density of 590 Wh kg −1 at 0.2 C and exhibits an astonishing stability over 10 000 cycles and rate ability up to 50 C in a potassium metal half-cell. Encouragingly, a high-areal-capacity pouch cell with 2.2 mAh cm −2 (16.5 mg cm −2 ) exhibits a capacity retention of 80.7% after 500 cycles. Furthermore, systematic in situ characterization reveals underlying mechanism insights into structure–performance relationships. Specifically, the fully coordinated Mn–N 6 octahedral configuration effectively suppresses Mn 3+ Jahn–Teller distortion, enabling reversible phase transitions under both high-voltage and long-term cycling conditions. In addition, minimal defects provide sufficient redox centers, while the continuous three-dimensional framework facilitates rapid K + diffusion kinetics. This work provides a new opportunity for the ultrafast, universal and scalable synthesis of high-quality PBAs, facilitating the practical application of PIBs while enabling precise structural and compositional design of novel PBAs.
Mechanochemical method↗
Thermodynamic modeling of the Ti-Nb-Sn system and its preliminary applications in aging precipitation and solidification simulations
Abstract Gasping the thermodynamic and phase diagram of the materials being studied is essential for further guiding the development process, like composition design, heat treatment optimization and so on. Nb and Sn are common alloying elements in Ti-based biomedical alloys. In this work, the Ti-Nb-Sn system has been thermodynamically assessed based on experimental phase equilibria. A self-consistent thermodynamic description for the Ti-Nb-Sn system including two ternary compounds Ti 3 Nb 3 Sn 2 and Ti 3 NbSn has been obtained. Based on the comparison between the calculated and experimental phase equilibria, the reliability of the presently obtained thermodynamic description has been verified. The influence of Nb and Sn contents on the precipitation temperature and amount of hcp α -Ti phase in bcc β -(Ti, Nb) has been investigated based on thermodynamic calculations. Results show that the increase of Nb or Sn content in Ti-based alloys would significantly reduce the precipitation amount and transformation temperature of hcp α -Ti phase in bcc β -(Ti, Nb) and the influence of Nb content is more effective than that of Sn. The solidified phases in several as-cast alloys have been thermodynamically predicted based on Scheil solidification simulations. The presently developed thermodynamic description of the Ti-Nb-Sn system can serve as a sub-ternary one in the thermodynamic database for multicomponent Ti-based biomedical alloys.
Peng, Yingbiao↗
Impact of non‐framework cation mixing on the structure and crystallization behavior of model high‐level waste glasses
Abstract Spinel crystallization is known to be detrimental to the operation of Joule heated ceramic melters during the vitrification of iron‐rich high‐level nuclear wastes (HLW) into borosilicate glasses. The literature on this subject focuses on tackling the problem by developing empirical constraints to design compositions, which limit the fraction of spinels formed in the melter or by developing empirical models to predict the settling behavior of spinels in the melter as a function of the glass composition. While these empirical models can predict the behavior of most of the compositions, they are not failsafe as there are always some compositions, whose behavior is beyond the predictive ability of these models. This can lead to undesirable situations during the vitrification of the nuclear waste, and therefore an in‐depth investigation of the chemo‐structural descriptors controlling the crystallization behavior in these glasses is warranted. Accordingly, the present study aims to understand the impact of non‐framework cation mixing (i.e., Li + /Na + and Ca 2+ /Na + ) on the structure (through Raman spectroscopy and Mössbauer spectroscopy) and crystallization behavior (through XRD, SEM‐EDS, and vibrating sample magnetometry) of iron‐rich model HLW glasses in the system: (mol.%) x M y O–(25− x ) Na 2 O–9.12 B 2 O 3 –6.4 Al 2 O 3 –51.25 SiO 2 –7.22 Fe 2 O 3 –0.38 MnO–0.08 Cr 2 O 3 –0.55NiO (M y O = Li 2 O or CaO).
Balasubramanya, Nikhila↗
Design Trade-Offs in Composite Fuel Cell Membranes: Effects of Reinforcement and Chemical Additives
Perfluorosulfonic acid (PFSA) membranes are critical components in proton exchange membrane fuel cells, where performance depends on balancing ionic conductivity, mechanical durability, and chemical stability. This study characterizes a composite membrane (NC700) featuring PFSA-impregnated expanded polytetrafluoroethylene (ePTFE) reinforcement and cerium-based radical scavengers, benchmarked against unreinforced NR211. Complementary techniques, including electron microscopy, X-ray scattering, infrared spectroscopy, thermogravimetric analysis, and dynamic mechanical analysis, identify the structural and compositional strategies employed in NC700. Water sorption isotherms reveal lower water uptake for NC700 across all conditions, attributed to reinforcement and cerium incorporation. Reinforcement reduces in-plane swelling from 11% to 2.1% at 90% RH, confirming strong swelling anisotropy, while maintaining mechanical properties at elevated temperatures. While the ionic conductivity of NC700 is approximately 10% lower than that of NR211, the reduced thickness yields a 40% decrease in calculated area-specific resistance, suggesting the composite architecture can favorably shift the conductivity-stability trade-off. The composite structure also reduces gas permeability, indicating potential for improved separator function alongside favorable transport properties. Systematic deconvolution of reinforcement and additive contributions shows that conductivity losses from cerium incorporation are largely offset by gains from the lower equivalent-weight polymer, providing quantitative relationships that may guide composite membrane design for fuel cells and other electrochemical applications.
25 ENERGY STORAGE↗
Progress and outlook of Sn–Pb mixed perovskite solar cells
Abstract Organic–inorganic hybrid perovskites have revolutionized solar cell research owing to their excellent material properties. Most previous research has been done on Pb-based perovskites. Recently, efforts to discover a Pb-free or Pb-less perovskite material with an ideal bandgap ranging 1.1–1.3 eV have led researchers to investigate Sn–Pb mixed perovskites. Sn–Pb mixed perovskites have a bandgap of ~ 1.25 eV, which is suitable for high-efficiency single-junction and perovskite/perovskite tandem solar cells. Moreover, the Pb content of Sn–Pb mixed perovskites is 50–60% lower than that of Pb-based perovskites, partially mitigating the Pb toxicity issue. However, incorporating Sn 2+ into the crystal structure also causes various drawbacks, such as inhomogeneous thin film morphologies, easy oxidation of Sn 2+ , and more vulnerable surface properties. Researchers have made substantial progress in addressing these challenges through improvements in compositional design, structural optimization, precursor design, and surface treatments. In this review, we provide a comprehensive overview of the progress in Sn–Pb mixed perovskite solar cells. Furthermore, we analyze the key variables and trends as well as provide an outlook for future directions in the research on Sn–Pb mixed perovskites. Graphical Abstract
14 SOLAR ENERGY↗
Alginate–Amorphous Calcium Carbonate Hydrogels for Controlled Therapeutic Release
Alginate hydrogels are widely explored as biocompatible matrices for transdermal delivery of therapeutic compounds but burst release and mechanical stability remain persistent challenges in drug delivery systems. This experimental study investigated alginate–amorphous calcium carbonate (ACC) hydrogel composites designed to regulate release of model anti-inflammatory compound, ibuprofen. Hydrogels containing 1.6–2.0 wt% sodium alginate were crosslinked with CaCl₂ and combined with ACC through two incorporation pathways: (i) separate addition of ACC and ibuprofen or (ii) co-precipitation of ACC onto ibuprofen prior to hydrogel incorporation. Hydrogels without ACC served as Control. Biocomposite structure and properties were characterized and release profiles quantified using Korsmeyer–Peppas (KP) model.Burst release was curbed as crosslinking time increased, highlighting importance of network density in diffusion control. Co-precipitating ACC with ibuprofen prior to incorporating into the hydrogel suppressed burst release and sustained release for > ~72 h. Rheological measurements indicate ACC reinforces hydrogel network, increasing storage modulus while maintaining hydration and flexibility. KP model indicates release is diffusion-controlled, with deviations reflecting contributions from diffusion barriers and morphologic/structural changes near the ACC coated ibuprofen. ACC within alginate hydrogels provides a strategy for tuning drug release while preserving mechanical properties relevant to transdermal applications.
36 MATERIALS SCIENCE↗
Cold Sintered Ceramics and Cements for Part Encapsulation
In this project, ceramic encapsulation materials were studied for high temperature (>~°500 C) applications where typical polymer encapsulants are unstable. A new low temperature (<~°200 C) method of processing ceramics, the cold sintering process was examined. Additionally, commercially available high temperature ceramic cements were investigated. In both cases, the mechanical strengths of available materials are less than desired (i.e., desired strengths similar to Si 3 N 4 ), limiting applicability. Composite designs to increase mechanical strength are suggested. Additionally, non-uniformities in stresses and densification while embedding alumina sheets in encapsulants via cold sintering using uni-axial pressing led to fracture of sheets, and an alternative iso-static based approach is recommended for future studies.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗