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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 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

O · , H · , and · OH radical etching probability of polystyrene obtained for a radio frequency driven atmospheric pressure plasma jet

Atmospheric pressure plasma jets have great potential for the surface modification of polymers. In this work, the authors report on polystyrene etching by a radio frequency driven atmospheric pressure plasma jet with a focus on the role of H · , O · , and · OH radicals in this process. The absolute flux of H · , O · , and · OH radicals reaching the surface of the polymer was determined by a COMSOL MULTIPHYSICS reacting fluid dynamics model incorporating detailed transport phenomena in the boundary layer near the substrate. The simulated results of H · and · OH densities in the jet effluent were experimentally verified by two-photon absorption laser induced fluorescence and laser induced fluorescence, respectively. The carbon atom removal flux from the polystyrene surface was taken from previously reported measurements using the same plasma source. The authors show that the boundary layer effects in the interfacial region above the substrate can have a significant impact on the calculated etching probabilities. The reaction probability (β) has a significant uncertainty although a variation of 2 orders of magnitude in β leads to uncertainties of approximately 1 order of magnitude variation in the determined etching probability. The etching probability of polystyrene by · OH radicals was confirmed to be at least an order of magnitude larger than the polystyrene etching probability by O · radicals. The authors also confirmed the weak polystyrene etching probability by H · radicals. The model suggests that the presence of a 30 ppm O 2 impurity can lead to the production of · OH radicals in the far effluent of the Ar + 1% H 2 plasma jet close to the substrate at sufficient densities to enable effective etching.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Controlling Amphiphilic Polymer Folding beyond the Primary Structure with Protein-Mimetic Di(Phenylalanine)

While methods for polymer synthesis have proliferated, their functionality pales in comparison to natural biopolymers–strategies are limited for building the intricate network of noncovalent interactions necessary to elicit complex, protein-like functions. Using a bioinspired di(phenylalanine) acrylamide (FF) monomer, we explored the impact of various noncovalent interactions in generating ordered assembled structures. Amphiphilic copolymers were synthesized that exhibit β-sheet-like local structure upon collapsing into single-chain assemblies in aqueous environments. Here, the systematic analysis of a series of amphiphilic copolymers illustrated that the global collapse is primarily driven by hydrophobic forces. Hydrogen-bonding and aromatic interactions stabilize local structure, as β-sheet-like interactions were identified via circular dichroism and thioflavin T fluorescence. Similar analysis of phenylalanine (F) and alanine-phenylalanine acrylamide (AF) copolymers found that distancing the aromatic residue from the polymer backbone is sufficient to induce β-sheet-like local structure akin to the FF copolymers; however, the interactions between AF subunits are less stable than those formed by FF. Further, hydrogen-bond donating hydrophilic monomers disrupt internal structure formed by FF within collapsed assemblies. Collectively, these results illuminate design principles for the facile incorporation of multiple facets of protein-mimetic, higher-order structure within folded synthetic polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Direct laser writing of volumetric gradient index lenses and waveguides

Abstract Direct laser writing (DLW) has been shown to render 3D polymeric optical components, including lenses, beam expanders, and mirrors, with submicrometer precision. However, these printed structures are limited to the refractive index and dispersive properties of the photopolymer. Here, we present the subsurface controllable refractive index via beam exposure (SCRIBE) method, a lithographic approach that enables the tuning of the refractive index over a range of greater than 0.3 by performing DLW inside photoresist-filled nanoporous silicon and silica scaffolds. Adjusting the laser exposure during printing enables 3D submicron control of the polymer infilling and thus the refractive index and chromatic dispersion. Combining SCRIBE’s unprecedented index range and 3D writing accuracy has realized the world’s smallest (15 µm diameter) spherical Luneburg lens operating at visible wavelengths. SCRIBE’s ability to tune the chromatic dispersion alongside the refractive index was leveraged to render achromatic doublets in a single printing step, eliminating the need for multiple photoresins and writing sequences. SCRIBE also has the potential to form multicomponent optics by cascading optical elements within a scaffold. As a demonstration, stacked focusing structures that generate photonic nanojets were fabricated inside porous silicon. Finally, an all-pass ring resonator was coupled to a subsurface 3D waveguide. The measured quality factor of 4600 at 1550 nm suggests the possibility of compact photonic systems with optical interconnects that traverse multiple planes. SCRIBE is uniquely suited for constructing such photonic integrated circuits due to its ability to integrate multiple optical components, including lenses and waveguides, without additional printed supports.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Morphology and Transport of Multivalent Cation-Exchanged Ionomer Membranes Using Perfluorosulfonic Acid–Ce Z+ as a Model System

Perfluorosulfonic acids (PFSAs) are commonly used as solid polymer electrolyte membranes (PEMs) in electrochemical energy devices, where they are vulnerable to attack by radical species during operation. A popular strategy to combat this problem is to introduce radical scavengers like cerium (Ce) ions that neutralize these species before they attack the PFSA. Such cation doping creates a multi-ion system, in which understanding the mechanisms of cation solvation and transport becomes important for the effective design and utilization of PFSA–cation systems. Ce ions also provide a representative model system for multication-exchanged ionomers in electrochemical systems. In this study, hydration and conductivity measurements, along with X-ray fluorescence and scattering, are employed to elucidate how Ce ion exchange alters PFSA’s ionic solvation, as well as nano- and mesoscale morphologies, which ultimately control its ion transport properties. A molecular transport model is used to deconvolute the impact of Ce ions on the local solvation structure of water in the membrane from mesoscale changes of the transport pathways. The combined experimental and theoretical analysis reveals a nonlinear decrease in conductivity driven by cation solvation at the molecular level and morphological changes at longer length scales. Migration–diffusion coupling, its nonlinear dependence on ion exchange and hydration, and its overall implications for ionomer performance are also discussed. Finally, these findings have the potential to be translated into other mixed cation–ionomer systems for a wide range of energy and environmental devices.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Comparing the Effects of Side Chain Dipole–Dipole Interactions and Hydrogen Bonding on the Mechanical and Electrical Properties of Poly(3-hexylthiophene)

Poly(3-alkylthiophenes) are simple conjugated polymers with good electrical properties, but tend to be brittle, limiting their application. Here, we investigate how side chain modifications can improve their toughness without compromising their charge transport. Specifically, we compare a weak dipole–dipole interaction of ester groups with a stronger hydrogen-bonding interaction of the hydroxyl groups. Two copolymers with targeted 5 and 10 mol % ester-functionalized side chains were synthesized and hydrolyzed in the solid state to introduce hydroxyl groups. Both hydrolyzed polymers became insoluble in most organic solvents, providing a path to layer-by-layer solution processing. All polymers’ optical, thermal, structural, electrical, and mechanical properties were investigated. Optical spectroscopy revealed that functionalization at these low levels did not significantly affect aggregation or π–π stacking. Differential scanning calorimetry indicated reduced crystallinity in the functionalized copolymers compared to that of P3HT. Grazing-incidence wide-angle X-ray diffraction data showed that functionalization led to an increase in lamellar spacing without altering molecular orientation or π–π stacking. Mechanical testing highlighted that at the lower functionalization level, both ester and hydroxyl groups similarly enhanced toughness, suggesting that disorder, rather than the specific nature of the functional group, was responsible for these improvements. At the higher functionalization level, hydroxyl groups significantly increased the elastic modulus while also negatively impacting charge carrier mobility. This study suggests that with stronger hydrogen-bonding groups, only very small amounts can improve P3HT’s toughness. For a wider tunable range, it may be a better strategy to use weak interactions such as dipole–dipole interactions of ester groups.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Ionic-content-driven restructuring of spirobisindane ionene networks: implications for mechanics, self-healing, and gas transport

Polymers of intrinsic microporosity (PIMs) offer exceptional gas permeability but remain brittle and susceptible to physical aging, limiting their durability in separation applications. Here, we introduce a reconfigurable microporous polymer network that uniquely integrates permanent PIM microporosity with autonomous, intrinsic self-healing driven by imidazolium-based ionic motifs. Spirobisindane units generate the intrinsic free-volume architecture, while an imidazolium-containing polyamide ionene supplies dynamic ionic and hydrogen-bonding interactions that reorganize under mild activation. Incorporation of imidazolium-based ionic liquids further tunes cohesion, mobility, and densification, enabling the network to relax, re-associate, and retain microporosity without structural collapse. Through a comprehensive multiscale approach combining spectroscopy, scattering, thermal and mechanical characterization with all-atom molecular dynamics and density functional theory calculations, we elucidate how ionic content, as a single control parameter that reshapes free-volume distributions, modulates local coordination environments, and governs relaxation and healing kinetics. At intermediate ionic loadings, the networks achieve rapid, repeatable self-healing while maintaining CO$_2$ selectivity, demonstrating an optimal balance between segmental mobility and structural integrity. By establishing how hierarchical ionic interactions couple structure, dynamics, and transport in microporous ionene networks, this work provides generalizable design rules for adaptive soft-matter systems that require simultaneous mechanical resilience, reconfigurability, and selective gas transport.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Uniqueness of relaxation times determined by dielectric spectroscopy

Dielectric spectroscopy is extremely powerful to study molecular dynamics, because of the very broad frequency range. Often multiple processes superimpose resulting in spectra that expand over several orders of magnitude, with some of the contributions partially hidden. For illustration, we selected two examples, (i) normal mode of high molar mass polymers partially hidden by conductivity and polarization and (ii) contour length fluctuations partially hidden by reptation using the well-studied polyisoprene melts as example. The intuitive approach to describe experimental spectra and to extract relaxation times is the addition of two or more model functions. Here, we use the empirical Havriliak-Negami function to illustrate the ambiguity of the extracted relaxation time, despite an excellent agreement of the fit with experimental data. We show that there are an infinite number of solutions for which a perfect description of experimental data can be achieved. However, a simple mathematical relationship indicates uniqueness of the pairs of the relaxation strength and relaxation time. Sacrificing the absolute value of the relaxation time enables to find the temperature dependence of the parameters with a high accuracy. For the specific cases studied here, the time temperature superposition (TTS) is very useful to confirm the principle. However, the derivation is not based on a specific temperature dependence, hence, independent from the TTS. We compare new and traditional approaches and find the same trend for the temperature dependence. The important advantage of the new technology is the knowledge of the accuracy of the relaxation times. Relaxation times determined from data for which the peak is clearly visible are the same within the experimental accuracy for traditional and new technology. However, for data where a dominant process hides the peak, substantial deviations can be observed. Finally, we conclude that the new approach is particularly helpful for cases in which relaxation times need to be determined without having access to the associated peak position.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Fundamentals of Scalable Nanoparticle Assembly in Engineering Polymres

Systematically improving the properties of polymer nanocomposites is contingent on effectively controlling nanoparticle (NP) dispersion; further, it is necessary to attain this at scale if these methods are to impact practical applications. While most past work has focused on amorphous polymers, ≈ 70% of all polymers sold annually are semicrystalline. Inspired by this apparent disconnect, our work in the current DOE funded grant and this renewal proposal employs a novel handle, polymer crystallization, to organize NPs into the various amorphous zones of the lamellar semicrystalline morphology (interlamellar, interfibrillar and interspherulitic domains) of stereoregular polymers. We hypothesize that the isothermal crystallization rate of a polymer host, G, and NP diffusivity, are the two relevant control parameters in this context. In the case where the NPs are miscible in the melt, they remain spatially well-dispersed when the polymer is crystallized at a rate that is fast relative to NP diffusion. In contrast, monolayer-thick NP sheets with intersheet spacing of ~10-100nm form in slowly crystallized samples. This sheet stacking is remarkably similar to that seen in natural materials, e.g., Nacre. There is also ordering of the NPs at the larger interfibrillar scale. Importantly, the relative fraction of engulfed, interlamellar and interfibrillar NPs is determined by G. Further, the modulus of these materials can increase by a factor of 2-3 due to the organization state of the NPs, while leaving fracture toughness unaffected. We have established the broad applicability of this approach in two polymers, polyethylene (PE) and polyethyleneoxide (PEO). To achieve this goal we developed a method for grafting long PE chains from NPs with controlled graft density and molecular weight, giving us the ability to tailor their dispersion in the PE melt prior to crystallization. In this renewal proposal, we will develop the fundamental, quantitative understanding that will allow us to independently tailor polymer crystallization rate, NP diffusivity and NP agglomeration state in semicrystalline polymers so as to facilely control NP ordering and hence properties. A program that tightly integrates experiment and theory is proposed, and a key outcome of this research will be a three-dimensional design map for different regimes of NP organization (and hence properties) that can be achieved by polymer crystallization. A second independent outcome is the role of directional solidification and how it competes with the rates of polymer crystallization and NP mobility to affect the organization of the NP.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A combined experimental and computational analysis of failure mechanisms in open-hole cross-ply laminates under flexural loading

In this work, integrated experimental tests and computational modeling are proposed to investigate the failure mechanisms of open-hole cross-ply carbon fiber reinforced polymer (CFRP) laminated composites. In particular, we propose two effective methods, which include width-tapered double cantilever beam (WTDCB) and fixed-ratio mixed-mode end load split (FRMMELS) tests, to obtain the experimental data more reliably. We then calibrate the traction-separation laws of cohesive zone model (CZM) used among laminas of the composites by leveraging these two methods. The experimental results of fracture energy, i.e. G Ic and G Tc , obtained from WTDCB and FRMMELS tests are generally insensitive to the crack length thus requiring no effort to accurately measure the crack tip. Moreover, FRMMELS sample contains a fixed mixed-mode ratio of G IIc /G Tc depending on the width taper ratio. Examining comparisons between experimental results of FRMMELS tests and failure surface of B–K failure criterion predicted from a curve fitting, good agreement between the predictions and experimental data has been found, indicating that FRMMELS tests are an effective method to determine mixed-mode fracture criterion. In addition, a coupled experimental-computational modeling of WTDCB, edge notched flexure, and FRMMELS tests are adopted to calibrate and validate the interfacial strengths. Finally, failure mechanisms of open-hole cross-ply CFRP laminates under flexural loading have been studied systematically using experimental and multi-scale computational analyses based on the developed CZM model. The initiation and propagation of delamination, the failure of laminated layers as well as load-displacement curves predicted from computational analyses are in good agreement with what we have observed experimentally.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Unraveling the mysteries of the thin film composite reverse osmosis membrane

A recent article in Science by Culp, Kumar, Gomez, and colleagues introduces a new approach to characterizing reverse osmosis thin film composite membranes to provide critical insights into understanding how polymer membrane microstructure affects water permeability. Such approaches offer a degree of microstructure characterization that has up until now been unavailable to the membrane science community. Here, combined with modeling of water diffusion coefficient in the polymer membrane itself, this effort has begun to answer decades-old questions about how polyamide reverse osmosis membranes function.

McCutcheon, Jeffrey R.↗
DOE OSTI2024

Unraveling the Molecular Origin of Prey-Wrapping Spider Silk's Unique Mechanical Properties and Assembly Process Using NMR

Prey wrapping spider silk's unique mechanical properties are investigated confirming the silk's high degree of extensibility and superior toughness compared to other types of spider silk. For the first time, the pre-spinning dope phase is studied in isotope-enriched intact aciniform (AC) silk glands using solution NMR that reveals a combination of α-helical domains linked by disordered random coil chains consistent with previously proposed “beads-on-a-string” models. The model is further refined through the AlphaFold2 protein structure prediction tool. Finally, extensive magic angle spinning (MAS) solid-state (SS) NMR data for isotopically-enriched fibers is used to refine the structural model for AC silk from two species, A. aurantia and A. argentata. The SSNMR data shows that the AC silk fibers are highly α-helical, coiled-coil in structure but, also exhibit significant β-sheet components that can be traced back to the Gly-rich disordered linker regions in the pre-spinning dope phase that are converted to β-sheet structures during fiber formation. This combination of mechanical and structural characterization enhances the understanding of AC silk's liquid-to-solid transition and structure-mechanics relationship. In conclusion, these prey wrap silk results and models will provide the basis for the design of biomimetic materials inspired by the AC spider silk system.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Bioinspired design toward nanocellulose-based materials

Nature provides lots of inspiration for material and structural design for various applications. Deriving design principles from the investigation of nature can provide a rich source of inspiration for the development of multifunctional materials. The bioinspired design templates mainly include mussels, nacre, and various plant species. As a sustainable and renewable feedstock, nanocellulose can be used to fabricate advanced materials with multifunctional properties through bioinspired designs. However, challenges and opportunities remain for realizing the full potential in the design of novel materials. Here, this article reviewed recent development in the bioinspired nanocellulose based materials and their application. This article summarizes the functions (e.g., surface wetting) and applications (e.g., composite) of bioinspired nanocellulose-based materials. The bioinspired design templates are discussed along with strategies, advantages, and challenges to the development of synthetic mimics. Additionally, mechanisms and processes (e.g., chemical modification, self-assembly) leading to biomimetic design are discussed. Finally, future research directions and opportunities of bioinspired nanocellulose-based materials are highlighted.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Family of Robust and Strongly Luminescent CuI-Based Hybrid Networks Made of Ionic and Dative Bonds

The CuI-derived inorganic–organic hybrid compounds are considered as promising phosphors for the lighting industry. Herein, exploiting N-monoalkylated hexaminium salts, [R-HMTA]X (R = Me, Et, Pr, and propargyl; X = Cl and I), as multibridging ligands, we have designed and synthesized a unique class of one-dimensional and two-dimensional hybrid CuI-materials. The reactions of these salts with CuI give rise to All-in-One (AIO) type compounds combining ionic and dative bonds between inorganic and organic components. The latter is formed by structurally unique inorganic [Cu x I y ] (y–x)– clusters, chains, or sheets interconnected through [R-HMTA] + cations via multiple Cu–N bonds. The so-designed compounds at ambient temperature exhibit tunable luminescence spanning from deep blue to red color (λ em = 430–625 nm) with microsecond lifetimes and the quantum efficiency of up to 78%. Remarkably, the AIO materials feature nontrivial excitation- (ED) and temperature-dependent (TD) luminescence, allowing their emission color to be finely adjusted from deep blue to red through changing the excitation wavelength and/or temperature. Based on the TD emission spectroscopy and theoretical calculations, a possible mechanism of the luminescence has been proposed. In conclusion, the very interesting luminescence characteristics coupled with good thermal and photostability render these AIO hybrid materials possible candidates for applications in energy-efficient lighting devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Pretreatment of Biomass by Selected Type-III Deep Eutectic Solvents and Evaluation of the Pretreatment Effects on Hydrothermal Carbonization

Hydrothermal carbonization (HTC) is a novel thermochemical conversion that converts wet biomass into energy dense solid fuel. Residual moisture under subcritical conditions reacts with a lignin-cellulose-hemicellulose matrix with the major reactions being identified as dehydration and decarboxylation. Among other reaction parameters (e.g., temperature, time, pressure), biomass morphology often plays a key role in HTC. The hypothesis of this study was enhancing the porous structure of biomass without significantly affecting biopolymer composition would augment hydrothermal carbonization (HTC). To prove the hypothesis, two type-III deep eutectic solvents (DESs), namely choline chloride:urea (ChCl:Urea, 1:2 mol/mol) and methyltriphenylphosphonium bromide:ethylene glycol (MTPB:EG, 1:4 mol/mol), were studied to pretreat loblolly pine at room temperature and ambient pressure for 1 h. DES pretreatment shows swelling of the biomass, increasing the surface fiber-to-fiber gap length by 52% and 185% for ChCl:Urea and MPTB:EG pretreatments, respectively. The total pore volume remained intact (2.6 × 10 –3 cm 3 /g), although new small pores evolved, and existing pores were abated with DES pretreatment. Hydrochars prepared from DES pretreated loblolly pine showed a high O/C and H/C ratio resulting in a significant increase of energy content (up to 42%) and a decrease of mass yield (up to 50 wt %), indicating an enhancement of HTC severity due to the alteration of surface morphology by DES. Finally, a preliminary process economics revealed that integrated DES pretreatment-HTC would increase fixed capital investment but decrease the cost of operation and manufacturing than the standalone HTC process.

09 BIOMASS FUELS↗
DOE OSTI2020

Plasmon Energy Transfer in Hybrid Nanoantennas

Plasmonic metal nanoparticles exhibit large dipole moments upon photoexcitation and have the potential to induce electronic transitions in nearby materials, but fast internal relaxation has to date limited the spatial range and efficiency of plasmonic mediated processes. In this work, we use photo-electrochemistry to synthesize hybrid nanoantennas comprised of plasmonic nanoparticles with photoconductive polymer coatings. Here, we demonstrate that the formation of the conductive polymer is selective to the nanoparticles and that polymerization is enhanced by photoexcitation. In situ spectroscopy and simulations support a mechanism in which up to 50% efficiency of nonradiative energy transfer is achieved. These hybrid nanoantennas combine the unmatched light-harvesting properties of a plasmonic antenna with the similarly unmatched device processability of a polymer shell.

36 MATERIALS SCIENCE↗