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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.

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At least 307 records · Page 17

Tailoring solid-electrolyte interphase and solvation structure for subzero temperature, fast-charging, and long-cycle-life sodium-ion batteries

The sluggish Na + reaction kinetics with carbon materials limits the fast-charging capability, Coulombic efficiency, and cycle life of sodium-ion batteries, especially at low temperatures. Herein, free-standing carbon nanofiber films, with controllable crystallinity and surface chemistry, are used as a platform to investigate the correlation between Na + reaction kinetics, storage mechanism, and electrolyte environment. The ion solvation effect and solid-electrolyte interphase (SEI) properties determine the kinetics and storage mechanism. A strong Na + -solvent interaction, such as Na + -diglyme, tends to form a "pseudo-SEI" layer dominated by anion decomposition, enabling fast Na + -solvent co-intercalation kinetics. Tuning the SEI chemistries by pre-cycling in the weakly solvated electrolyte (e.g., ester electrolyte), the intercalation capacity rapidly disappears due to the high energy barrier for Na + transport. Finally, such mechanistic insights allow us to develop the optimal combination of electrode materials and electrolyte chemistry to achieve high initial Coulombic efficiency, ultra-long cycle life under fast charging, and excellent low-temperature performance.

25 ENERGY STORAGE↗

Ultralow platinum loading for redox-flow battery by electrospinning the electrocatalyst and the ionomer in core-shell fibers

Hydrogen Bromine Redox Flow Batteries (HBRFB) are promising candidates for large scale energy storage, having an excellent balance of system, inexpensive and abundant electrolytes, high power density and near zero kinetic limitations. However, they suffer from corrosion of the hydrogen electrode due to bromine species crossover, which requires a high loading of precious group metal (PGM) electrocatalyst. Herein, a standard catalyst has been used in an electrospun (ES) fiber mat electrode, allowing for a significant (six-fold) reduction in platinum loading from 0.3 mg Pt /cm 2 down to 0.05 mg Pt /cm 2 . At this very low loading, the electrospun electrode attained an impressive specific power of 11.5W/mg Pt , and exhibited excellent durability, with constant power output for 140 charge/discharge cycles. Further, the excellent performance of the electrospun hydrogen electrode is attribute to its unique core-shell nanofiber structure, which improves the stability of the catalyst by preventing bromide species from reaching the catalyst surface.

25 ENERGY STORAGE↗

Designing sequence-defined peptoids for fibrillar self-assembly and silicification

In the biological environment, mineral crystals exquisitely controlled by biomacromolecules often show intricate hierarchical structures and superior mechanical properties. Among these biominerals, spicules, hybrid silica/protein superstructures serving as skeletal elements in demosponges, represent an excellent example for motivating the synthesis of silica materials. Herein, by designing sequence-defined peptoids containing side chains with a strong binding to silica, we demonstrated that self-assembly of these peptoids into fiber structures enables the mimicking of both biocatalytic and templating functions of silicatein filaments for the formation of silica fibers at near-neutral pH and ambient temperature. We further showed that the presence of amino groups is significant for the nucleation of silica on self-assembled peptoid nanofibers. Molecular dynamics simulation further confirmed that having silica-binding of amino side chains is critical for self-assembled peptoid fibers in triggering silica formation. Here, we demonstrated that tuning inter-peptoid interactions by varying carboxyl and amino side chains significantly influences the assembly kinetics and final morphologies of peptoid assemblies as scaffolds for directing silica mineralization to form silica spheres, fibers, and sheets. The formation of silica shell on peptoid fibers increased the mechanical property of peptoid hydrogel materials by nearly 1000-fold, highlighting the great potential of using silicification to enhance the mechanical property of hydrogel materials for applications including tissue engineering. Since peptoids are highly robust and programmable, we expect that self-assembly of peptoids containing solid-binding side chains into hierarchical materials opens new opportunities in the design and synthesis of highly tunable scaffolds that direct the formation of composite nanomaterials.

59 BASIC BIOLOGICAL SCIENCES↗

Nanostructured ligament and fiber Al–doped Li 7 La 3 Zr 2 O 12 scaffolds to mediate cathode-electrolyte interface chemistry

In this study, scaffold structures of electrospun aluminum–substituted lithium lanthanum zirconate Li 7 La 3 Zr 2 O 12 (Al-LLZO) were synthesized and used as an additive in a LiNi 0.6 Mn 0.2 Co 0.2 O 2 composite cathode. The scaffolds were crystalized in the cubic phase after calcination at 700 °C. The Al-LLZO scaffold morphology was dependent on the precursor formulation (aqueous and dimethylformamide. The aqueous precursors resulted in scaffolds of densely coalesced ligaments, whereas the dimethylformamide precursors resulted in high–aspect ratio nanofiber scaffolds. The long-term cycling stability and rate performance of the cells were found to depend on the Al-LLZO scaffold morphology. The uniformly dispersed Al-LLZO fibers resulted in a more stable cathode electrolyte interface formation through the reduced decomposition of the LiPF 6 salt during cycling, resulting in a better high-rate and long-term cycling performance.

25 ENERGY STORAGE↗

Protection against Chemical Warfare Agents and Biological Threats Using Metal–Organic Frameworks as Active Layers

The SARS-CoV-2 pandemic outbreak and the unfortunate misuse of toxic chemical warfare agents (CWAs) highlight the importance of developing functional materials to protect against these chemical and pathogen threats. Metal–organic frameworks (MOFs), which comprise a tunable class of crystalline porous materials built from inorganic nodes and organic linkers, have emerged as a class of heterogeneous catalysts capable of rapid detoxification of multiple classes of these harmful chemical or biological hazards. In particular, zirconium-based MOFs (Zr-MOFs) feature Lewis acidic nodes that serve as active sites for a wide range of catalytic reactions, including the hydrolysis of organophosphorus nerve agents within seconds in basic aqueous solutions. In addition, postsynthetic modification of Zr-MOFs enables the release of active species capable of reacting with and deactivating harmful pathogens. Despite this impressive performance, utilizing Zr- MOFs in powder form is not practical for application in masks or protective uniforms. To address this challenge, our team sought to develop MOF/fiber composite systems that could be adapted for use under realistic operating conditions to protect civilians, military personnel, and first responders from harmful pathogens and chemical warfare agents. Over the last several years, our group has designed and fabricated reactive and biocidal MOF/fiber composites that effectively capture and deactivate these toxic species. In this Account, we describe the evolution of these porous and reactive MOF/fiber composites and focus on key design challenges and considerations. First, we devised a scalable method for the integration of Zr-MOFs onto textile substrates using aqueous precursor solutions and without using pretreated textiles, highlighting the potential scalability of this method. Moving beyond standard textiles, we also developed a microbial synthesis strategy to prepare hierarchically porous MOF/bacterial cellulose nanofiber composite sponges that can both capture and detoxify nerve agents when exposed to contaminated gas flows. The mass loading of the MOF in the nanofibrous composite sponge is up to 90%, affording higher work capacities compared to those of textile-fiber-based composites with relatively lower MOF loadings. Next, we demonstrated that heterogeneous polymeric bases are suitable replacements for volatile liquid bases typically used in solution-phase reactions, and we showed that these composite systems are capable of effectively hydrolyzing nerve agents in the solid state by using only water that is present as humidity. Moreover, incorporating a reactive dye precursor into the composite affords a dual function sensing and detoxifying material that changes color from white to orange upon reaction with the byproduct following nerve agent hydrolysis, demonstrating the versatility of this platform for use in decontamination applications. We then created chlorine-loaded MOF/fiber composites that act as biocidal and reactive textiles that are capable of not only detoxifying sulfur-mustard-based chemical warfare agents and simulants but also deactivating both bacteria and the SARS-CoV-2 virus within minutes of exposure. Lastly, we synthesized a mixed-metal Ti/Zr-MOF coating on cotton fibers to afford a photoactive biocidal cloth that shows fast and broad-spectrum biocidal performance against viruses and Gram-positive and Gram-negative bacteria under visible light irradiation. Given the tunable, multifunctional nature of these MOF/fiber composites, we believe that this Account will offer new insights for the rational design and preparation of functional MOF/fiber composites and pave the way toward the development of next-generation reactive and protective textiles.

36 MATERIALS SCIENCE↗

Computational Prediction of Coiled–Coil Protein Gelation Dynamics and Structure

Protein hydrogels represent an important and growing biomaterial for a multitude of applications, including diagnostics and drug delivery. We have previously explored the ability to engineer the thermoresponsive supramolecular assembly of coiled–coil proteins into hydrogels with varying gelation properties, where we have defined important parameters in the coiled–coil hydrogel design. Using Rosetta energy scores and Poisson–Boltzmann electrostatic energies, we iterate a computational design strategy to predict the gelation of coiled–coil proteins while simultaneously exploring five new coiled–coil protein hydrogel sequences. Provided this library, we explore the impact of in silico energies on structure and gelation kinetics, where we also reveal a range of blue autofluorescence that enables hydrogel disassembly and recovery. As a result of this library, we identify the new coiled–coil hydrogel sequence, Q5, capable of gelation within 24 h at 4 °C, a more than 2-fold increase over that of our previous iteration Q2. The fast gelation time of Q5 enables the assessment of structural transition in real time using small-angle X-ray scattering (SAXS) that is correlated to coarse-grained and atomistic molecular dynamics simulations revealing the supramolecular assembling behavior of coiled–coils toward nanofiber assembly and gelation. This work represents the first system of hydrogels with predictable self-assembly, autofluorescent capability, and a molecular model of coiled–coil fiber formation.

36 MATERIALS SCIENCE↗

Electron Spin Polarization and Rectification Driven by Chiral Perylene Diimide-Based Nanodonuts

The chirality-induced spin selectivity (CISS) effect allows thin-film layers of chiral conjugated molecules to function as spin filters at ambient temperature. Through solvent-modulated dropcasting of chiral l- and d-perylene diimide (PDI) monomeric building blocks, two types of aggregate morphologies, nanofibers and nanodonuts, may be realized. Spin-diode behavior is evidenced in the nanodonut structures. Stacked PDI units, which form the conjugated core of these nanostructures, dominate the nanodonut–Au electrode contact; in contrast, the AFM tip contacts largely the high-resistance solubilizing alkyl chains of the chiral monomers that form these nanodonuts. Current–voltage responses of the nanodonuts, measured by magnetic conductive AFM (mC-AFM), demonstrate substantial spin polarizations as well as spin current rectification ratios (>10) that exceed the magnitudes of those determined to date for other chiral nanoscale systems. Furthermore, these results underscore the potential for chiral nanostructures, featuring asymmetric molecular junctions, to enable CISS-based nanoscale spin current rectifiers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic-Scale Imaging of Condensed Counterions

Here, the functioning of a wide variety of charged macromolecules, from DNA to fuel cell membranes, is dependent on how the counterions surrounding them are arranged. In order to decrease Coulombic repulsion, some of the fixed charges on these molecules are neutralized by a fraction of the counterions-this phenomenon is called counterion condensation. The nature of counterion condensation can be only be inferred indirectly from traditional experiments such as X-ray scattering and modern experiments such as single molecule electrometry. The prevalent conclusion in the literature, based on both theory and experiment, is that the distribution of counterions is peaked right next to the macromolecule, i.e., condensation results in the formation of contact ion pairs. In this study, cryogenic electron microscopy (cryo-EM) was used to study the arrangement of condensed halide counterions near a positively charged polypeptoid nanofiber. The locations of both condensed and fixed charges were determined directly from atomic-scale images. Our experimentally determined counterion distributions were peaked at distances of about 5 Å away from the fixed positive charge, indicating the presence of a layer of water molecules between condensed ion pairs. We posit that this distribution is driven by the entropy of the condensed ions.

36 MATERIALS SCIENCE↗

Key Intermediate Nanostructures in the Self-Assembly of Amphiphilic Polypeptoids Revealed by Cryo-TEM

Amphiphilic copolypeptoids are known to form a variety of nanostructures (fibers, tubes, sheets, etc.), but the assembly mechanisms and key intermediates remain underexplored. This study investigates the intermediate structures formed during the early stages of self-assembly in diblock copolypeptoids using cryo-transmission electron microscopy (cryo-TEM). Here we focused on two diblock copolypeptoids, one with a free N-terminus and the other with a capped N-terminus, which ultimately form less-ordered nanofibers and well-ordered nanosheets, respectively. Through cryo-TEM imaging of vitrified solutions at various time points during the self-assembly process, the study identified micelles and vesicles as key intermediate structures. Notably, the formation of vesicles as intermediates is unusual in crystallization-driven self-assembly and suggests a unique pathway in polypeptoid self-assembly. The study provides direct imaging evidence of key intermediates in polypeptoid self-assembly, advancing the understanding of their self-assembly mechanisms.

59 BASIC BIOLOGICAL SCIENCES↗

Statistical Analysis of Intertube Tunneling Contacts in the Macroscopic Electrical Conductivity of Carbon Nanotube Fibers

Here, this study investigates the influence of tunneling contact resistances between carbon nanotubes (CNTs) on electron transport and electrical conductivity of macroscopic carbon nanofibers (CNFs), which profoundly impacts the performance of CNT thin film electronics, CNF electron emitters and cathodes, and energy conversion and storage devices. Utilizing a self-consistent electrical contact model coupling a transmission line model with tunneling current, we calculate the contact resistances of a plethora of CNT-CNT contacts within a CNF fiber, which consists of aligned, densely packed CNTs. A statistical analysis is conducted, using Gaussian distributions to account for variations in contact lengths, tunneling gap distances, and single CNT aspect ratios, to calculate the CNT-CNT contact resistance and the overall resistance of CNT fiber. By scaling our model to a macroscopic level, our results are in good agreement with experimental measurements. Our calculation suggests that while increasing the contact overlap length diminishes individual CNT-CNT contact resistance, it could paradoxically increase macroscopic CNT fiber resistance for a given constant CNF mass density, which is due to that fact that a larger overlap length allows more CNTs to pack along an electrical conduction path per unit length, leading to more tunneling contact junctions connected in series and thus less number of parallel conduction paths within the fiber cross section. Increasing tunneling gap distance increases both individual contact and overall fiber resistance. This research provides a simple design tool for tailoring CNT fiber electrical properties to promote real-world applications using CNTs or similar low-dimensional materials.

36 MATERIALS SCIENCE↗

In Situ Synthesis of Phosphate-Based CelloMOF as a Promising Separator for Li–Ion Batteries

Nowadays, battery separators play a critical role in determining the sustainability, electrochemical efficiency, and safety of lithium-ion batteries (LIBs). In this contribution, we developed fire-resistant composite membranes called CelloMOF by in situ grafting of metal-organic framework, ZIF-67, onto phosphorylated cellulose nanofibers (P-CNFs) followed by a vacuum filtration process akin to papermaking. The hybrid ZIF-67@P-CNF membrane exhibits superior properties than a polyolefin-based commercial separator (CS) in terms of enhanced thermal and dimensional stability, flame-retardant properties, better surface wettability, and improved electrolyte uptake. Thermal dimensional stability tests revealed that the ZIF-67@P-CNF separator maintained its structure even at 200 °C, whereas CS suffered severe shrinkage, potentially leading to internal short circuits. Combustion tests showed a peak heat release rate (PHRR) of 34.5 W/g and a total heat release (THR) of 1.61 kJ/g for ZIF-67@P-CNF, significantly lower than the PHRR (1111.82 W/g) and THR (40.89 kJ/g) of CS. The composite separator also demonstrated significantly improved wettability, with a contact angle of 32 ± 1.04°, compared to 92 ± 1.07° for CS, highlighting its hydrophilic nature. Electrochemical evaluations in LiFePO 4 /Li half-cells indicated a higher discharge capacity of 149 mA h g -1 at 0.2 C and superior capacity retention of 86% after 50 cycles, outperforming CS (145 mA h g -1 and 84%, respectively). In conclusion, these results underscore the potential of the ZIF-67@P-CNF membrane to advance safe, high-performance LIBs by addressing critical challenges in thermal stability, flame retardancy, and electrolyte compatibility.

ZIF-67↗

Photostability of Ambient-Processed, Conjugated Polymer Electrochromic Devices Encapsulated by Bioderived Barrier Films

Polymer-based electrochromic devices (ECDs) are a promising technology for enabling low-voltage, disposable displays, yet are currently limited by photo-oxidative bleaching of the active materials. Here, renewable barrier films composed of cellulose and chitin are presented as an alternative to poly(ethylene terephthalate) (PET) for encapsulating ECDs. To assess barrier film effectiveness, lateral ECDs composed of poly(3,4-propylenedioxythiophene-(CH 2 OEtHx) 2 ) (P(ProDOT)) active layers were constructed and encapsulated with a multilayer barrier consisting of chitin nanofibers and cellulose nanocrystals spray cast onto a cellulose acetate substrate (oxygen transmission rate (OTR) = 29 cm 3 m –2 day –1 ), a commercially available PET film (OTR = 8.5 cm 3 m –2 day –1 ), and a high-performance PET-Al 2 O 3 multilayer barrier film (OTR < 1 cm 3 m –2 day –1 ). The photodegradation of the P(ProDOT) active layer was determined by measuring the evolution of the colorimetric contrast (ΔE*) and switching speeds as a function of light exposure (100 mW cm –2 , AM 1.5 G light). Photodegradation was found to proceed at a similar rate for all encapsulated devices (roughly 10 times more slowly than unencapsulated devices), highlighting the opportunity for replacing petroleum packaging with bioderived barrier films. Analysis of the switching kinetics, the shifts in optical absorbance, and evidence of chemical degradation indicate that both photochemical breakdown of the electrolyte and cross-linking of the P(ProDOT) active material are key drivers for loss of device performance when oxygen flux to the active material is limited. Furthermore, pathways toward better understanding photodegradation are then proposed with sustainability in mind for future ECD design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deep Eutectic Solvents for Efficient Fractionation of Lignocellulose to Produce Uncondensed Lignin and High-Quality Cellulose

Simultaneously inhibiting lignin condensation and cellulose degradation remains a major challenge for achieving holistic valorization of lignocellulose. Here, we developed a deep eutectic solvent (DES), composed of l-cysteine (Cys) and lactic acid (LA), to fractionate both uncondensed lignin and high-quality cellulose from eucalyptus wood by leveraging the unique properties of Cys, i.e., highly nucleophilic groups (–SH) and hydrogen bond acceptor/donor groups (–NH 2 and –COOH). The nucleophilic –SH in Cys effectively quenches the benzylic carbocations (C α + ions, formed at the benzylic sites of lignin) that lead to lignin condensation. This enables the high yield of uncondensed lignin (81%) with high retention of β–O–4 bonds (up to 90%). The separated uncondensed lignin is further depolymerized to prepare monophenols in a satisfactory 43% yield, equivalent to 73% of the theoretical yield. Moreover, the –NH 2 and –COOH groups in Cys form extensive hydrogen bonds with the hydroxyl groups in cellulose, thus decreasing the interaction energy of DES on cellulose. As a result, the cellulose achieves an astonishing 99% retention and maintains a high degree of polymerization of 1160. The obtained high-quality cellulose is further conversed into cellulose nanofibers for strong and transparent films. Furthermore, this study provides new insights into the efficient separation of uncondensed lignin and high-quality cellulose from lignocellulose by a novel DES system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymorphism in Self-Assembly of Short Peptoid Sequences

Due to various applications enabled by diverse morphologies of self-assembled sequence-defined polymers, controlling the self-assembly of synthetic peptidomimetics into designed morphologies has emerged as a promising route for the development of bioinspired functional materials. Herein, we report morphological control over the assembly of a series of short peptoids, or poly-N-substituted glycines, that contain asymmetric hydrophobic domains. We demonstrate that the inherent flexibility of amphiphilic peptoid bilayers drives assembly polymorphism, resulting in the coexistence of nanosheets, twisted ribbons, and nanofibers three distinct morphologies. By tuning peptoid molecular interactions through variations in sequence design, solution pH, and temperature, we demonstrate precise control over the twisting and folding of peptoid bilayers, enabling the formation of well-defined nanosheets and nanohelices. Molecular dynamics simulations further unravel how the introduction of asymmetric hydrophobic domains enables the flexibility of peptoid bilayers and results in peptoid assembly polymorphism. By tuning peptoid molecular interactions through heating, we further demonstrate the transformation of nanosheets into nanohelices. We envision that our mechanistic investigation of peptoid assembly polymorphism provides a strong foundation for leveraging peptoid sequences and chemistries to achieve controlled molecular interactions, driving the creation of biomimetic materials with tailored morphologies and functionalities.

assembly polymorphism↗

High-fidelity topochemical polymerization in single crystals, polycrystals, and solution aggregates

Topochemical polymerization (TCP) emerges as a leading approach for synthesizing single crystalline polymers, but is traditionally restricted to transformations in solid-medium. The complexity in achieving single-crystal-to-single-crystal (SCSC) transformations due to lattice disparities and the untapped potential of performing TCP in a liquid medium with solid-state structural fidelity present unsolved challenges. Herein, by using X-rays as the primary means to overcome crystal disintegration, we reveal the details of SCSC transformation during the TCP of chiral azaquinodimethane (AQM) monomers through in situ crystallographic analysis while spotlighting a rare metastable crystalline phase. Complementary in situ investigations of powders and thin films provide critical insights into the side-chain dependent polymerization kinetics of solid-state reactions. Furthermore, we enable TCP of AQM monomers in a liquid medium via an antisolvent-reinforced aggregated state, yielding polymer nanofibers with high crystallinity akin to that of solid-state. This study testifies high structural precision of TCP performed in different states and media, offering critical insights into the synthesis of processable nanostructured polymers with desired structural integrity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mapping in situ the assembly and dynamics in aqueous supramolecular polymers

Supramolecular polymers, bonded through directional non-covalent interactions, closely mimic dynamic behaviors of biological nanofibers. However, the complexity of assembly pathways makes it highly challenging to unravel the nature of supramolecular dynamics in aqueous environments. Here we introduce a precise combinatorial titration methodology to probe in situ the assembly of peptide amphiphiles (PAs). This approach reveals a binary assembly mechanism governed by equilibrium between spheroidal micelles and β-sheet polymers. Weakening hydrogen bonding shifts the equilibrium towards micelles and decreases the internal structural order of filamentous polymers, promoting supramolecular dynamics. Extending this methodology to two-component copolymerization systems, we find a surprising tendency to form blocky nanostructures with reduced internal phase separation as the mismatch in peptide sequence decreases. Interestingly, while well-mixed copolymers acquire different dynamics, mismatched ones retain the characteristic supramolecular motion of their homopolymer counterparts. These critical insights into supramolecular dynamics offer strategies to tailor the dynamic functions of supramolecular nanomaterials.

Molecular self-assembly↗

Natural nanoparticle complexes at water-water interfaces

Aqueous two-phase systems (ATPSs) with multifunctional attributes have significant promise as biomimetic materials, but current approaches do not harness their full potential. Here, we show that ATPSs can be stabilized to form microcapsules by the interfacial assembly of chitin nanofibers (ChNF) and rod-like cellulose nanocrystals (CNC). The high structural stability of the ChNF/CNC complexes integrates permeability and transport across the membrane at the liquid/liquid interface. Driven by density and osmotic stress gradients, the microcapsules show switchable motility, including cyclic meniscus-climbing and subsurface transport. These observations demonstrate a self-regulating system with potential for cargo transfer, cell biomimicry, as well as ATPSs-based microreactors and microrobots.

Bioinspired materials↗

Nano-layer deposition of metal oxides via a condensed water film

Abstract Nanocoatings on solids can be achieved by various processes, including sol-gel and atomic layer deposition. However, challenges remain for achieving uniform nanocoatings on nanoscale substrates at a large scale. Here, we report a versatile and fundamentally different technique, termed condensed layer deposition, for depositing conformal metal oxide nanocoatings on nanoparticles and nanofibers. This approach involves water in liquid hydrocarbons condensing as a nanoscale water film on the substrate surface, enabled by interfacial tension between polar water and nonpolar liquid hydrocarbons. Chemical precursors are then added, which react with the condensed water film to form a metal oxide nanocoating. We demonstrate this for titania, alumina, and niobia on substrates including carbon nanotubes, iron oxide particles and carbon black. Condensed layer deposition can achieve oxide nanocoatings on a variety of substrates with tunable thickness, in one pass, at room temperature.

36 MATERIALS SCIENCE↗