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At least 199 records · Page 11

Self‐Assembled Metal–Dielectric Hybrid Metamaterials in Vertically Aligned Nanocomposite Form with Tailorable Optical Properties and Coupled Multifunctionalities

Metal–dielectric hybrid metamaterials have attracted increasing research interest in recent years because of their novel optical properties and promising applications in the fields of electronic and photonic devices. Dielectric permittivity is a key parameter that strongly influences the optical properties of materials. By self‐assembling the metallic and dielectric components in a pillar‐in‐matrix structure, a strong anisotropic structure forms and results in opposite signs of permittivity components (i.e., ε || > 0 and ε ⊥ < 0, or vice versa) and exotic optical responses including hyperbolic dispersion in the visible to near‐infrared region. Herein, the main approaches of tuning the permittivity in self‐assembled metal–dielectric vertically aligned nanocomposite (VAN) thin films are reviewed, including tuning the metal pillar density and geometry, film strain state and background pressure during growth, and seeking other metal‐free and complex structure designs. Future research directions are also proposed, including unique approaches to improve their thermal stability, integrate on flexible substrates toward wearable device fabrication, and explore real‐time tunable metamaterials.

Zhang, Di↗

Flux Synthesis of A-site Disordered Perovskite La 0.5 M 0.5 TiO 3 (M$=$Li, Na, K) Nanorods Tailored for Solid Composite Electrolytes

Inorganic fillers play an important role in improving the ionic conductivity of solid composite electrolytes (SCEs) for Li-ion batteries. Among inorganic fillers, perovskite-type lithium lanthanum titanate (LLTO) stands out for its high bulk Li + conductivity on the order of 10 -3 S cm -1 at room temperature. According to a literature survey, the optimal LLTO filler should possess the following characteristics: i) a single-crystal structure to minimize grain boundaries; ii) a small particle size to increase the filler/polymer interface area; iii) a 1D morphology for efficient interface channels; and iv) cubic symmetry to facilitate rapid bulk Li + diffusion within the filler. However, the synthesis of single crystal, 1D LLTO nanomaterials with cubic symmetry is challenging. Herein, a flux strategy is developed to synthesize La 0.5 M 0.5 TiO 3 (LMTO, M$=$Li, Na, and K) single-crystal nanorods with an A-site-disordered, cubic perovskite phase. The flux media promotes the oriented growth of nanorods, prevents nanorods from sintering, and provides multiple alkali metal ion doping at M sites to stabilize the cubic phase. SCEs compositing the Li + -conducting LMTO nanorods as fillers and poly[vinylene carbonate- co -lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate] matrix exhibit more than twice the conductivity of the neat polymer electrolyte (30.6 vs 14.0 µS cm -1 at 303 K).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring Ion Transport in Li 3‐3y Ho 1+y Cl 6‐x Br x via Transition‐Metal Free Structural Planes and Charge Carrier Distribution

Abstract Localized atomistic disorder in halide‐based solid electrolytes (SEs) can be leveraged to boost Li + mobility. In this study, Li + transport in structurally modified Li 3 HoCl 6 , via Br − introduction and Li + deficiency, is explored. The optimized Li 3‐3 y Ho 1+ y Cl 6‐ x Br x achieves an ionic conductivity of 3.8 mS cm −1 at 25 °C, the highest reported for holmium halide materials. 6,7 Li nuclear magnetic resonance and relaxometry investigations unveil enhanced ion dynamics with bromination, attaining a Li + motional rate neighboring 116 MHz. X‐ray diffraction analyses reveal mixed‐anion‐induced phase transitions with disproportionate octahedral expansions and distortions, creating Ho‐free planes with favorable energetics for Li + migration. Bond valence site energy analysis highlights preferred Li + transport pathways, particularly in structural planes devoid of Ho 3+ blocking effects. Molecular dynamics simulations corroborate enhanced Li + diffusion with Br − introduction into Li 3 HoCl 6 . Li‐Ho electrostatic repulsions in the (001) plane presumably drive Li + diffusion into the Ho‐free (002) layer, enabling rapid intraplanar Li + motion and exchange between the 2d and 4h sites. Li 3‐3 y Ho 1+ y Cl 6‐ x Br x also demonstrates good battery cycling stability. These findings offer valuable insights into the intricate correlations between structure and ion transport and will help guide the design of high‐performance fast ion conductors for all‐solid‐state batteries.

Chemistry↗

Engineering of Grain Boundaries in CeO 2 Enabling Tailorable Resistive Switching Properties

Abstract Defect engineering in valence change memories aimed at tuning the concentration and transport of oxygen vacancies are studied extensively, however mostly focusing on contribution from individual extended defects such as single dislocations and grain boundaries. In this work, the impact of engineering large numbers of grain boundaries on resistive switching mechanisms and performances is investigated. Three different grain morphologies, that is, “random network,” “columnar scaffold,” and “island‐like,” are realized in CeO 2 thin films. The devices with the three grain morphologies demonstrate vastly different resistive switching behaviors. The best overall resistive switching performance is shown in the devices with “columnar scaffold” morphology, where the vertical grain boundaries extending through the film facilitate the generation of oxygen vacancies as well as their migration under external bias. The observation of both interfacial and filamentary switching modes only in the devices with a “columnar scaffold” morphology further confirms the contribution from grain boundaries. In contrast, the “random network” or “island‐like” structures result in excessive or insufficient oxygen vacancy concentration migration paths. The research provides design guidelines for grain boundary engineering of oxide‐based resistive switching materials to tune the resistive switching performances for memory and neuromorphic computing applications.

36 MATERIALS SCIENCE↗

Mechanistic Elucidation of Electronically Conductive PEDOT:PSS Tailored Binder for a Potassium‐Ion Battery Graphite Anode: Electrochemical, Mechanical, and Thermal Safety Aspects

Potassium-ion batteries (KIBs) are considered more appropriate for grid-scale storage than lithium-ion batteries (LIBs) due to similar operating chemistry, abundant precursors, and compatibility with low-cost graphite anodes. However, a larger ion reduces rate capabilities and exacerbates capacity fading from volumetric expansion. In this report, conductive polymer, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), is substituted for standard insulating polyvinylidene fluoride (PVDF). Half-cells using carbon black (CB) in continuously conductive PEDOT:PSS/CB binder outperforms PVDF/CB by mitigating electrically isolated “dead” graphite, improving 100 cycle capacity retention at C/10 from 63 to 80%. Enhanced electrical contact with PEDOT:PSS/CB also reduces ion impedance and improves rate capabilities. Without CB however, PEDOT:PSS binder performs poorly in electrochemical studies despite promising ex situ electronic conductivity. This discrepancy is mechanistically elucidated through identification of redox activity between PEDOT:PSS and K + which results in high impedances in the anode operating voltage window. Additionally, the impact of conducting binder on mechanical properties and thermal safety of the anode is investigated. Brittleness and poor wettability of PEDOT:PSS are identified as issues, but greater stability against reactive KC 8 reduces overall heat generation. Binder substitution offers a promising means of mitigating issues with current KIB anodes regardless of active material, and the work herein addresses issues towards further improvement.

electrochemical impedance spectroscopy↗

Bulk Oxygen Stabilization via Electrode–Electrolyte Interphase Tailored Surface Activities of Li–Rich Cathodes

The O3-type Li-rich layered oxides (LLOs) are approaching industrial applications as high-energy cathode materials for Li-ion batteries (LIBs), however, they suffer from rapid performance decay associated with oxygen activities. The interplay between surface and bulk transformations in LLOs, especially the electrochemical behaviors of oxygen anions, remains elusive. Here, by regulating the surface of an O3-type LLO (Li 1.13 Mn 0.517 Ni 0.256 Co 0.097 O 2 ) using an all-fluorinated electrolyte, an enhanced capacity retention from 57.4% to 85.3% and a suppressed voltage decay from 1.34 mV cycle –1 to 0.58 mV cycle –1 within 300 cycles are realized. The performance enhancement is attributed to the thin, uniform, robust, and compact F-rich cathode-electrolyte interphase (CEI), which suppresses various types of oxygen-related surface degradation and, more importantly, stabilizes the bulk oxygen reactions. Finally, through the combined experimental and theoretical studies, this work directly reveals the intriguing association between the surface and bulk oxygen activities and demonstrates that optimizing the interphase is an effective approach for improving the stability of high-energy battery cathodes involving oxygen redox reactions.

25 ENERGY STORAGE↗

Selective Electrochemical Reduction of CO 2 to Metal Oxalates in Nonaqueous Solutions Using Trace Metal Pb on Carbon Supports Enhanced by a Tailored Microenvironment

In this work, the electroreduction of carbon dioxide (CO 2 ) to oxalate is enabled by incorporating trace metallic lead (Pb) on carbon‐based supports (CBS) with polymer overlayers. These composite materials serve as an efficient electrocatalytic system for the facile conversion and storage of CO 2 , a pernicious atmospheric pollutant. Results from controlled potential electrolysis experiments indicate that 1) trace metallic Pb on the ppb scale is active toward the reductive coupling of CO 2 to oxalate at comparable Faradaic efficiencies to bulk metallic Pb and 2) polymer encapsulation of this trace metallic Pb leads to promotion of CO 2 reduction (CO 2 R) selectively to metal oxalates over other products such as CO. Importantly, metal oxalates are important alternative cementitious materials and precursors for other materials’ synthesis applications. The solid products undergo rigorous spectroscopic characterization, including 13 CO 2 labeling experiments, to ensure the metal oxalates are in fact produced from CO 2 R. These findings serve as a model for leveraging microenvironment effects to enhance activity and selectivity for CO 2 R using trace‐metal catalysts for carbon utilization and storage technologies.

alternative cementitious materials↗

Thermal Unequilibrium of PdSn Intermetallic Nanocatalysts: From In Situ Tailored Synthesis to Unexpected Hydrogenation Selectivity

Abstract Effective control on chemoselectivity in the catalytic hydrogenation of C=O over C=C bonds is uncommon with Pd‐based catalysts because of the favored adsorption of C=C bonds on Pd surface. Here we report a unique orthorhombic PdSn intermetallic phase with unprecedented chemoselectivity toward C=O hydrogenation. We observed the formation and metastability of this PdSn phase in situ. During a natural cooling process, the PdSn nanoparticles readily revert to the favored Pd 3 Sn 2 phase. Instead, using a thermal quenching method, we prepared a pure‐phase PdSn nanocatalyst. PdSn shows an >96 % selectivity toward hydrogenating C=O bonds of various α,β‐unsaturated aldehydes, highest in reported Pd‐based catalysts. Further study suggests that efficient quenching prevents the reversion from PdSn‐ to Pd 3 Sn 2 ‐structured surface, the key to the desired catalytic performance. Density functional theory calculations and analysis of reaction kinetics provide an explanation for the observed high selectivity.

Chen, Minda↗

Tailoring Electrochemical CO 2 Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors

Abstract Electrochemical CO 2 reduction (CO 2 RR) on copper (Cu) shows promise for higher‐value products beyond CO. However, challenges such as the limited CO 2 solubility, high overpotentials, and the competing hydrogen evolution reaction (HER) in aqueous electrolytes hinder the practical realization. We propose a functionalized ionic liquid (IL) which generates ion‐CO 2 adducts and a hydrogen bond donor (HBD) upon CO 2 absorption to modulate CO 2 RR on Cu in a non‐aqueous electrolyte. As revealed by transient voltammetry, electrochemical impedance spectroscopy (EIS), and in situ surface‐enhanced Raman spectroscopy (SERS) complemented with image charge augmented quantum‐mechanical/molecular mechanics (IC‐QM/MM) computations, a unique microenvironment is constructed. In this microenvironment, the catalytic activity is primarily governed by the IL and HBD concentrations; former controlling the double layer thickness and the latter modulating the local proton availability. This translates to ample CO 2 availability, reduced overpotential, and suppressed HER where C 4 products are obtained. This study deepens the understanding of electrolyte effects in CO 2 RR and the role of IL ions towards electrocatalytic microenvironment design.

Coskun, Oguz Kagan↗

Ion‐Specific Interactions Engender Dynamic and Tailorable Properties in Biomimetic Cationic Polyelectrolytes

Abstract Biomaterials such as spider silk and mussel byssi are fabricated by the dynamic manipulation of intra‐ and intermolecular biopolymer interactions. Organisms modulate solution parameters, such as pH and ion co‐solute concentration, to effect these processes. These biofabrication schemes provide a conceptual framework to develop new dynamic and responsive abiotic soft material systems. Towards these ends, the chemical diversity of readily available ionic compounds offers a broad palette to manipulate the physicochemical properties of polyelectrolytes via ion‐specific interactions. In this study, we show for the first time that the ion‐specific interactions of biomimetic polyelectrolytes engenders a variety of phase separation behaviors, creating dynamic thermal‐ and ion‐responsive soft matter that exhibits a spectrum of physical properties, spanning viscous fluids to viscoelastic and viscoplastic solids. These ion‐dependent characteristics are further rendered general by the merger of lysine and phenylalanine into a single, amphiphilic vinyl monomer. The unprecedented breadth, precision, and dynamicity in the reported ion‐dependent phase behaviors thus introduce a broad array of opportunities for the future development of responsive soft matter; properties that are poised to drive developments in critical areas such as chemical sensing, soft robotics, and additive manufacturing.

Aubrecht, Filip J.↗

Tailoring Electrochemical CO 2 Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors

Electrochemical CO 2 reduction (CO 2 RR) on copper (Cu) shows promise for higher-value products beyond CO. However, challenges such as the limited CO 2 solubility, high overpotentials, and the competing hydrogen evolution reaction (HER) in aqueous electrolytes hinder the practical realization. We propose a functionalized ionic liquid (IL) which generates ion-CO 2 adducts and a hydrogen bond donor (HBD) upon CO 2 absorption to modulate CO 2 RR on Cu in a non-aqueous electrolyte. As revealed by transient voltammetry, electrochemical impedance spectroscopy (EIS), and in situ surface-enhanced Raman spectroscopy (SERS) complemented with image charge augmented quantum-mechanical/molecular mechanics (IC-QM/MM) computations, a unique microenvironment is constructed. In this microenvironment, the catalytic activity is primarily governed by the IL and HBD concentrations; former controlling the double layer thickness and the latter modulating the local proton availability. This translates to ample CO 2 availability, reduced overpotential, and suppressed HER where C 4 products are obtained. This study deepens the understanding of electrolyte effects in CO 2 RR and the role of IL ions towards electrocatalytic microenvironment design.

25 ENERGY STORAGE↗

Tailoring P2/P3‐Intergrowth in Manganese‐Based Layered Transition Metal Oxide Positive Electrodes via Sodium Content for Na‐Ion Batteries

High-manganese content sodium-ion positive electrodes have received heightened interest as an alternative to contemporary Li-ion chemistries due to their high abundance, low toxicity, and even geographical distribution. However, these materials typically suffer from poor capacity, unstable cycling performance, and sluggish Na + kinetics. Herein, we explore a manganese-based layered transition metal oxide (Na x N 0.25 Mn 0.75 O 2 ) and show by X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) that careful variation of the sodium content can instigate the formation of a biphasic intergrowth. This intergrown P2/P3 material offered a higher capacity than its monophasic P2 counterpart due to the P3 structure having greater low-voltage Mn 3+/4+ redox. Further, the intergrowth material offers greatly enhanced kinetics and cycling stability when compared to single-phase P3 material, due to the stabilizing nature of the P2 structure, elucidated by galvanostatic intermittent titration technique (GITT) and operando synchrotron X-ray diffraction. These results highlight the beneficial effect that the intergrowth structure has on the electrochemical performance of high-manganese content positive electrode for future sodium-ion batteries.

25 ENERGY STORAGE↗

Differentiating Ligand Tailoring and Cation Incorporation as Strategies for Tuning Heterobimetallic Cerium Complexes

Tuning of redox-active complexes featuring metals with high coordination numbers by incorporation of secondary redox-inactive cations has received far less attention than it deserves. Here, appending moderate steric bulk to a tripodal ligand framework has been tested for its influence on secondary-cation-driven structural and electrochemical tuning of cerium, a lanthanide that tends to adopt high coordination numbers. A quasi -C 3 -symmetric cerium(III) complex denoted [Ce] has been prepared that features pendant benzyloxy groups, and this work demonstrates that this species offers a site capable of binding single Na + or Ca 2+ ions. Electrochemical and UV-visible spectroscopic studies reveal equilibrium binding affinity of [Ce] for Na + in acetonitrile solvent, contrasting with tight binding of all cations in all other previously studied systems of this type. The modulated cation binding can be attributed to the bulky benzyloxy groups, which impact the thermodynamics of cation binding but do not impede the formation of cerium centers with coordination number 8 upon binding of either Na + or Ca2 + . Finally, the Ce(IV/III) reduction potential was found to be tunable under the equilibrium binding conditions, highlighting the potentially significant role that controlled structural changes can play in modulating the solution properties of heterobimetallic complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring Chemical Absorption-Precipitation to Lower the Regeneration Energy of a CO 2 Capture Solvent

Solvent-based CO 2 capture consumes significant amounts of energy for solvent regeneration. To improve energy efficiency, this study investigates CO 2 fixation in a solid form through solvation, followed by ionic self-assembly-aided precipitation. Based on the hypothesis that CO 3 2- ions may bind with monovalent metal ions, we introduced Na + into an aqueous hexane-1,6-diamine solution where CO 2 forms carbamate and bicarbonate. Then, Na + ions in the solvent act as a seed for ionic self-assembly with diamine carbamate to form an intermediate ionic complex. The recurring chemical reactions lead to the formation of an ionic solid from a mixture of organic carbamate/carbonate and inorganic sodium bicarbonate (NaHCO 3 ), which can be easily removed from the aqueous solvent through sedimentation or centrifugation and heated to release the captured CO 2 . Mild-temperature heating of the solids at 80–150 °C causes decomposition of the solid CO 2 -diamine-Na molecular aggregates and discharge of CO 2 . This sorbent regeneration process requires 6.5–8.6 GJ/t CO 2 . It was also found that the organic carbamate/carbonate solid, without NaHCO 3 , contains a significant amount of CO 2 , up to 6.2 mmol CO 2 /g-sorbent, requiring as low as 2.9–5.8 GJ/t CO 2 . In conclusion, molecular dynamic simulations support the hypothesis of using Na + to form relatively less stable, yet sufficiently solid, complexes for the least energy-intensive recovery of diamine solvents compared to bivalent carbonate–forming ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring Binder Molecular Weight to Enhance Slurry-Cast NMC Cathodes for Sulfide Solid-State Batteries

We demonstrate for the first time the critical influence of binder molecular weight on the performance of slurry-cast lithium nickel manganese cobalt oxide (NMC) cathodes in sulfide-based all-solid-state batteries (SSBs). SSBs are increasingly recognized as a safer and potentially more efficient alternative to traditional Li-ion batteries, owing to the superior ionic conductivities and inherent safety features of sulfide solid electrolytes. However, the integration of high-voltage NMC cathodes with sheet-type sulfide solid electrolytes presents significant fabrication challenges. Our findings reveal that higher molecular weight binders not only enhance the discharge capacity and cycle life of these cathodes but also ensure robust adhesion and structural integrity. By optimizing binder molecular weights, we effectively shield the active materials from degradation and mechanical stress, significantly boosting the functionality and longevity of SSBs. These results underscore the paramount importance of binder properties in advancing the practical application of high-performance all-solid-state batteries.

25 ENERGY STORAGE↗

Fabrication and characterization of dextran/zein hybrid electrospun fibers with tailored properties for controlled release of curcumin

Abstract BACKGROUND In recent years, there has been considerable interest in the use of biopolymer electrospun nanofibers for various food applications due to the biocompatibility, biodegradability, and high loading capacity. Herein, we fabricated and characterized novel hybrid electrospun fibers from dextran (50%, w/v ) and zein (0–30%, w/v ) solutions, and the effects of various zein concentrations on the properties of the hybrid electrospun fibers were investigated. RESULTS When zein was added at low concentrations (5% and 10%), dextran and zein showed poor miscibility, as reflected by significantly decreased viscosity of the solutions, and the poor mechanical properties of the derived fiber membranes. When zein was added at medium concentrations (15–25%), hydrogen bonds were formed between dextran and zein molecules, as indicated by the red shift of Fourier‐transform infrared bands and β‐sheet to α‐helix structural transformations. The fiber membranes electrospun from a solution with 25% zein showed the most hydrophobic surface, with a water contact angle of 116.9°. The homogenous dispersion of dextran and zein resulted in improved mechanical properties for fibers electrospun from a solution with 30% zein. Curcumin encapsulating dextran/zein electrospun fibers exhibited effective radical scavenging activity and ferric reducing power, along with the desired controlled release behavior for curcumin delivery. CONCLUSION Food grade dextran/zein hybrid electrospun fibers demonstrated tunable properties, and appear to be promising as delivery systems for bioactive and edible antimicrobial food packaging. © 2021 Society of Chemical Industry.

Luo, Shiyuan↗

Tailoring compatibilization potential of maleic anhydride–grafted polypropylene by sequential rheochemical processing of polypropylene and polyamide 66 blends

Reactive compatibilization of immiscible polymer blends using a preferred compatibilizer leaves the following question: How much loading of a compatibilizer is good enough and what maximum properties can be achieved? A good understanding of the process can help solve the reutilization of mixed waste plastics. Here, the reactive compatibilization of polypropylene-graft-maleic anhydride (PP-g-MAH) on polypropylene/polyamide 66 (PP/PA66) blends is quantitatively assessed using thermorheological, microoptical, spectroscopic, and x-ray scattering-based characterization tools. The overall compositions of all PP(60%)/PA66(30%)/PP-g-MAH(10%) blends are kept constant while systematically controlling the degree of the chemical reaction by varying the sequential addition of PP-g-MAH to the melt mixture. The first feeding of PP-g-MAH (x%, 0 ≤ x ≤ 10) is conducted at 280°C and the second feeding of (10–x)% is at 200°C. During the first step, a larger amount of chemical activity is observed up to 4%–6% addition of PP-g-MAH. Furthermore, the constant chemical composition allows a systematic comparison of the compatibilizer-dependent thermal, rheological, morphological, and mechanical properties. With an increased degree of interfacial reaction, the size of dispersed PA66 domains decreases to register improved interfacial adhesion with the PP matrix, yielding enhanced Young's modulus and absolute failure strength of the isotropic matrix.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solution‐Like Water Transport Across Molecular to Macroscopic Length Scales in Crosslinked Poly(Ethylene Glycol Diacrylate) Networks With Tailored Sidechains

Poly(ethylene glycol) (PEG)‐based materials, like PEG‐diacrylate (PEGDA), are prized for their hydrophilic, inert properties, and leveraged in hydrogels and as membrane mimics. While network chemistry is often tuned for selective transport and antifouling, fundamental understanding of water dynamics at the network surface and the impact on bulk transport is limited. We utilize Overhauser dynamic nuclear polarization (ODNP) to measure nanoscale water diffusivity near a tethered spin label at the water‐polymer surface and compare it to bulk water diffusivity from pulsed field gradient (PFG) NMR. Via active ester chemistry, spin labels and varied sidechain chemistries are introduced, modulating network hydrophilicity. Tuning network hydration through crosslinker content and functional groups further impacts water diffusivity. Results show rapid nanoscale water transport at the polymer surface, reflecting network volumetric water content, with further modulation by sidechain functionality. These findings demonstrate PEGDA's utility as a membrane mimic and the critical impact of network chemistry on water transport.

hydrogels↗