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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 487 records · Page 27

Surface acoustic wave oxygen sensor

A surface acoustic wave (SAW) device that responds to oxygen pressure was developed by coating a 158 MHz quartz surface acoustic wave (SAW) device with an oxygen binding agent. Two types of coatings were used. One type was prepared by dissolving an oxygen binding agent in a toluene solution of a copolymer containing the axial ligand. A second type was prepared with an oxygen binding porphyrin solution containing excess axial ligand without a polymer matrix. In the polymer based coatings, the copolymer served to provide the axial ligand to the oxygen binding agent and as a coating matrix on the surface of the SAW device. The oxygen sensing SAW device has been shown to bind oxygen following a Langmuir isotherm and may be used to measure the equilibrium constant of the oxygen binding compound in the coating matrix.

Collman, James P.↗

Synthesis of long Prebiotic Oligomers on Mineral Surfaces

Most theories of the origin of biological organization assume that polymers with lengths in the range of 30-60 monomers are needed to make a genetic system viable. But it has not proved possible to synthesize plausibly prebiotic polymers this long by condensation in aqueous solution, because hydrolysis competes with polymerization. The potential of mineral surfaces to facilitate prebiotic polymerization was pointed out long ago. Here we describe a system that models prebiotic polymerization by the oligomerization of activated monomers -both nucleotides and amino acids. We find that whereas the reactions in solution produce only short oligomers (the longest typically being a 10-mer), the presence of mineral surfaces (montmorillonite for nucleotides, illite and hydroxylapatite for amino adds) induces the formation of oligomers up to 55 monomers long. These are formed by successive "feedings" with the monomers; polymerization takes place on the mineral surfaces in a manner akin to solid-phase synthesis of biopolymers.

Ferris, James P.↗

Reflective Silvered Polyimide Films Via In Situ Thermal Reduction Silver (I) Complexes

Self-metallizing. flexible polyimide films with highly reflective surfaces are prepared by an in situ self-metallization procedure involving thermally initiated reduction of polymer-soluble silver(I) complexes. Polyamic acid solutions are doped with silver(I) acetate and solubilizing agents. Thermally curing the silver(I) doped resins leads to flexible. metallized films which have reflectivities as high as 100%. abrasion-resistant surfaces. thermal stability and, in some cases, electrical conductivity, rendering them useful for space applications.

Southward, Robin E.↗

Adhesive Properties of Cured Phenylethynyl Containing Imides

Considerable attention has been directed towards acetylene terminated oligomers over the last 20 years' and recent work has focused on phenylethynyl terminated imide (PETI) oligomers. These reactive oligomers possess several features which make them attractive candidates for use as composite matrices and adhesives. The phenylethynyl group can be readily incorporated into many different functionalized oligomers. The reactive oligomers possess relatively low melt viscosities and thermally cure without the evolution of volatile by-products. Once cured, they typically display high glass transition temperatures (Tgs), excellent solvent resistance and high mechanical properties. new modified phenylethynyl-terminated imide (LaRC MPEI) oligomers were synthesized at various molecular weights utilizing a small amount of trifunctional amine. As long as the amount of triamine is relatively small, this approach produces a mixture of linear, star-shaped and branched polymer chains that has lower melt and solution viscosity than an equivalent molecular weight linear phenylethynyl terminated imide oligomers. The work reported herein involves the synthesis and characterization of a copolymer using this approach and the preparation of blends utilizing a phenylethynyl containing reactive plasticizer of lower molecular weight called LaRC LV-121. The chemistry and properties of this new MPEI as well as some blends of MPEI with LV-121, are presented and compared to the linear version, LARC-PETI-5.

Jensen, Brian J.↗

Multiscale modeling of solute diffusion in triblock copolymer membranes

We develop a multiscale simulation model for diffusion of solutes through porous triblock copolymer membranes. The approach combines two techniques: self-consistent field theory (SCFT) to predict the structure of the self-assembled, solvated membrane and on-lattice kinetic Monte Carlo (kMC) simulations to model diffusion of solutes. Solvation is simulated in SCFT by constraining the glassy membrane matrix while relaxing the brush-like membrane pore coating against the solvent. The kMC simulations capture the resulting solute spatial distribution and concentration-dependent local diffusivity in the polymer-coated pores; we parameterize the latter using particle-based simulations. We apply our approach to simulate solute diffusion through nonequilibrium morphologies of a model triblock copolymer, and we correlate diffusivity with structural descriptors of the morphologies. We also compare the model’s predictions to alternative approaches based on simple lattice random walks and find our multiscale model to be more robust and systematic to parameterize. Furthermore, our multiscale modeling approach is general and can be readily extended in the future to other chemistries, morphologies, and models for the local solute diffusivity and interactions with the membrane.

36 MATERIALS SCIENCE↗

Mechanisms of Metal Additive-Induced Ordering During SNIPS Membrane Formation

Isoporous membranes can be fabricated by combining self-assembly with nonsolvent induced phase separation (SNIPS) using an amphiphilic block copolymer like polystyrene-b-poly(4-vinylpyridine) (SV). Poly(4-vinylpyridine) (V) is known to complex with metal salts, which are hypothesized to stabilize solution ordering and preserve structure during casting. We explored how the molar ratio of metal additive to the poly(4-vinylpyridine) block affected the final membrane morphology via scanning electron microscopy (SEM). Dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and in situ grazing-incidence SAXS were used to track changes in solution ordering and chain conformation as a function of the molar ratio of the additive to the V block. Additives induced aggregation, promoted the formation of more compact conformations in solution, and facilitated micelle ordering onto lattices at optimal ratios. Furthermore, these experimental results were supported by random phase approximation calculations, which helped explain how the thermodynamic order–disorder transition shifts with additive binding strength. Stronger additive–polymer interactions reduced the block copolymer volume fraction required for ordering in solution, allowing ordered domains to form at lower polymer concentrations.

Additives↗

Conductive Organometallic Polymers from Soluble Superatom Ions

Superatomic crystals comprising ligand-capped, metal chalcogenide clusters and fullerenes are modular materials that exhibit enhanced electronic, magnetic, and thermal conductivity properties. We find that neutral, M 4 S 4 (M = Fe, Co) clusters stabilized with N -heterocyclic carbenes (NHCs) can transfer charge to C 60 fullerene to form binary superatomic crystals. Notably, these compounds are soluble in various organic solvents, allowing their properties to be investigated in solution, unlike traditional fullerene-based superatomic crystals. The ion pairs can be further assembled into organometallic polymers using Janus-bis(NHCs) to cross-link the oxidized M 4 S 4 units. We show that the superatomic polymers are more conductive than both the precursor superatomic crystals and the polymers containing only neutral M 4 S 4 clusters. Similar conductivity values can be obtained when neutral M 4 S 4 –NHC polymers are doped with solutions of C 60 fullerene. These findings demonstrate that next generation superatomic materials can be prepared via the combination of charge transfer and polymerization with appropriate cross-linking agents.

carbon nanomaterials↗

Surface-Initiated Atom Transfer Radical Polymerization Using Hydrogel Reactors

Atom transfer radical polymerization (ATRP) is a controlled radical polymerization method that enables the synthesis of tailored polymeric materials with low dispersity, highlighting its immense potential for green fabrication of advanced materials. However, its broader implementation is limited by challenges in product isolation, maintaining catalyst activity, and mitigating atmospheric sensitivity arising from oxygen-sensitive metal catalysts. Here, gelatin hydrogels (GHs) are introduced as a soft “reactor” matrix for interfacial ATRP, operating with minimal metal-catalyst loading while exhibiting possibly an organoreductive behavior. This strategy leverages activator regeneration via electron transfer through a ligand–metal charge-transfer (LMCT) mechanism to reduce oxidized metal catalysts within the GH network. Polymerization is evaluated by growing polymer brushes at an active interface formed between GHs swollen in monomer solution and an initiating surface, and sequential growth experiments confirmed that GH-mediated ATRP preserves living character. Under UV illumination, LMCT is activated, producing polymers both at the desired interface and within the GH bulk. UV–Vis spectroscopy revealed active reduction of Cu(II) to Cu(I) along with concentration-dependent complex formation, indicating dynamic coordination chemistry within the hydrogel. The redox-active arginine- and glutamic acid-rich gelatin backbone coordinates and reduces the metal center, enabling ATRP at ppm-level catalyst concentrations. While polymerization proceeds in GH-Cu(II) reactors, adding external mobile ligands to the GH results in longer polymer brushes. Here, the results reported here are exploratory. More experiments are needed to characterize polymer brush growth in GHs and compare it to conventional surface-initiated polymerization in solution.

Absorption↗

Use of a Multiple Hydride Donor To Achieve an n-Doped Polymer with High Solvent Resistance

We report the ability to insolubilize doped semiconducting polymer layers can help enable the fabrication of efficient multilayer solution-processed electronic and optoelectronic devices. Here, we present a promising approach to simultaneously n-dope and largely insolubilize conjugated polymer films using tetrakis[{4-(1,3-dimethyl-2,3-dihydro-1H-benzo[d]imidazol-2-yl)phenoxy}methyl]methane (tetrakis-O-DMBI-H), which consists of four 2,3-dihydro-1H-benzoimidazole (DMBI-H) n-dopant moieties covalently linked to one another. Doping a thiophene-fused benzodifurandione-based oligo(p-phenylenevinylene)-co-thiophene polymer (TBDOPV-T) with tetrakis-O-DMBI-H results in a highly n-doped film with bulk conductivity of 15 S cm –1 . Optical absorption spectra provide evidence for film retention of ~93% after immersion in o-dichlorobenzene for 5 min. The optical absorption signature of the charge carriers in the n-doped polymer decreases only slightly more than that of the neutral polymer under these conditions, indicating that the exposure to solvent also results in negligible dedoping of the film. Moreover, thermal treatment studies on a tetrakis-O-DMBI-H-doped TBDOPV-T film in contact with another undoped polymer film indicate immobilization of the molecular dopant in TBDOPV-T. This is attributed to the multiple electrostatic interactions between each dopant tetracation and up to four nearby anionic doped polymer segments.

36 MATERIALS SCIENCE↗

Solid‐Adsorbed Polymer‐Electrolyte Interphases for Stabilizing Metal Anodes in Aqueous Zn and Non‐Aqueous Li Batteries

Abstract Polymers are known to adsorb spontaneously from liquid solutions in contact with high‐energy substrates to form configurationally complex, but robust phases that often exhibit higher durability than might be expected from the individual physical bonds formed with the substrate. Rational control of the physical, chemical, and transport properties of such interphases has emerged as a fundamental opportunity for scientific and technological advances in energy storage technology but requires in‐depth understanding of the conformation states and electrochemical effect of the adsorbed polymers. Here, we analyze the interfacial adsorption of oligomeric polyethylene glycol (PEG) chains of moderate sizes dissolved in protic and aprotic liquid electrolytes and find that there is an optimum polymer molecular weight of approximately 400 Da at which the highest columbic efficiency is achieved for both Zn and Li deposition. These findings point to a simple, versatile approach for extending the lifetime of batteries.

Jin, Shuo↗

Solid–Adsorbed Polymer–Electrolyte Interphases for Stabilizing Metal Anodes in Aqueous Zn and Non–Aqueous Li Batteries

Polymers are known to adsorb spontaneously from liquid solutions in contact with high-energy substrates to form configurationally complex, but robust phases that often exhibit higher durability than might be expected from the individual physical bonds formed with the substrate. Rational control of the physical, chemical, and transport properties of such interphases has emerged as a fundamental opportunity for scientific and technological advances in energy storage technology but requires in-depth understanding of the conformation states and electrochemical effect of the adsorbed polymers. Here, we analyze the interfacial adsorption of oligomeric polyethylene glycol (PEG) chains of moderate sizes dissolved in protic and aprotic liquid electrolytes and find that there is an optimum polymer molecular weight of approximately 400 Da at which the highest columbic efficiency is achieved for both Zn and Li deposition. Furthermore, these findings point to a simple, versatile approach for extending the lifetime of batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lyotropic Liquid Crystal Mediated Assembly of Donor Polymers Enhances Efficiency and Stability of Blade-Coated Organic Solar Cells

Conjugated polymers can undergo complex, concentration-dependent self-assembly during solution processing, yet little is known about its impact on film morphology and device performance of organic solar cells. Herein, lyotropic liquid crystal (LLC) mediated assembly across multiple conjugated polymers is reported, which generally gives rise to improved device performance of blade-coated non-fullerene bulk heterojunction solar cells. Using D18 as a model system, the formation mechanism of LLC is unveiled employing solution X-ray scattering and microscopic imaging tools: D18 first aggregates into semicrystalline nanofibers, then assemble into achiral nematic LLC which goes through symmetry breaking to yield a chiral twist-bent LLC. The assembly pathway is driven by increasing solution concentration – a common driving force during evaporative assembly relevant to scalable manufacturing. This assembly pathway can be largely modulated by coating regimes to give 1) lyotropic liquid crystalline assembly in the evaporation regime and 2) random fiber aggregation pathway in the Landau–Levich regime. The chiral liquid crystalline assembly pathway resulted in films with crystallinity 2.63 times that of films from the random fiber aggregation pathway, significantly enhancing the T80 lifetime by 50-fold. The generality of LLC-mediated assembly and enhanced device performance is further validated using polythiophene and quinoxaline-based donor polymers.

14 SOLAR ENERGY↗

Boundary layer description of directional polymer crystallisation

Nearly fifty years ago Lovinger and Gryte suggested that the directional crystallization of a polymer was analogous to the quiescent isothermal crystallization experiment but at a supercooling where the crystal growth velocity was equal to the velocity of the moving front. Our experiments showed that this equivalence holds in a detailed manner at low directional velocities. To understand the underlying physics of these situations, we modeled the motion of a crystallization front in a liquid where the left side boundary is suddenly lowered below the melting point (Stefan's problem) but with the modification that the crystallization kinetics follow a version of the Avrami model. Our numerical results surprisingly showed that the results of the polymer analog track with the Stefan results which were derived for a simple liquid that crystallizes completely at its melting point; in particular, the position of the crystal growth-front evolved with time exactly as in the Stefan problem. The numerical solution also showed that the temperature in the immediate vicinity of the growth-front decreased with increasing front velocity, which is in line with Lovinger and Gryte's ansatz. To provide a clear theoretical understanding of these numerical results we derive a boundary layer solution to the governing coupled differential equations of the polymer problem. The analytical results are in agreement with our observations from experiments and numerical computations but show that this equivalence between the small molecule and polymer analog only holds in the limit where the crystallization enthalpy is much larger than the rate at which heat is conducted away in the polymer. In particular, in the context of the temperature profile, the enthalpy generated by the crystallisation process which is spread out over a narrow spatial region can be approximated as a point source whose location and temperature correspond to the Lovinger–Gryte ansatz.

36 MATERIALS SCIENCE↗

Gravitational Effects on the Morphology and Kinetics of Photodeposition of Polydiacetylene Thin Films From Monomer Solutions

The goal of this proposed work is to study gravitational effects on the photodeposition of polydiacetylene thin films from monomer solutions onto transparent substrates. Polydiacetylenes have been an extensively studied class of organic polymers because they exhibit many unusual and interesting properties, including electrical conductivity and optical nonlinearity. Their long polymeric chains render polydiacetylenes readily conducive to thin film formation, which is necessary for many applications. These applications require thin polydiacetylene films possessing uniform thicknesses, high purity, minimal inhomogeneities and defects (such as scattering centers), etc. Also, understanding and controlling the microstructure and morphology of the films is important for optimizing their electronic and optical properties. The lack of techniques for processing polydiacetylenes into such films has been the primary limitation to their commercial use. We have recently discovered a novel method for the formation of polydiacetylene thin films using photo-deposition from monomer solutions onto transparent substrates with UV light. This technique is very simple to carry out, and can yield films with superior quality to those produced by conventional methods. Furthermore, these films exhibit good third-order properties and are capable of waveguiding. We have been actively studying the chemistry of diacetylene polymerization in solution and the photo-deposition of polydiacetylene thin films from solution. It is well-known that gravitational factors such as buoyancy-driven convection and sedimentation can affect chemical and mass transport processes in solution. One important aspect of polydiacetylene thin film photodeposition in solution, relevant to microgravity science, is that heat generated by absorption of UV radiation induces thermal density gradients that under the influence of gravity, can cause fluid flows (buoyancy-driven convection). Additionally, changes in the chemical composition of the solution during polymerization may cause solutal convection. These fluid flows affect transport of material to and from the film surface and thereby affect the kinetics of the growth process. This manifests itself in the morphology of the resulting films; films grown under the influence of convection tend to have less uniform thicknesses, and can possess greater inhomogeneities and defects. Specifically, polydiacetylene films photodeposited from solution, when viewed under a microscope, exhibit very small particles of solid polymer which get transported by convection from the bulk solution to the surface of the growing film and become embedded. Even when carried out under conditions designed to minimize unstable density gradients (i.e., irradiating the solution from the top), some fluid flow still takes place (particles remain present in the films). It is also possible that defect nucleation may be occurring within the films or on the surface of the substrate; this, too, can be affected by convection (as is the case with crystal growth). Hence films grown in 1-g will, at best, still possess some defects. The objective of this proposal is to investigate, both in 1-g and in low-g, the effects of gravitational factors (primarily convection) on the dynamics of these processes, and on the quality, morphology, and properties of the films obtained.

Paley, Mark S.↗

Elucidating the assembly of Nanoparticle Organic Hybrid Materials (NOHMs) near an electrode interface with varying potential using Neutron Reflectivity

A critical concern regarding electrolyte formulation in an electrochemical environment is the impact of the interaction of the multiple components (i.e., supporting electrolyte or additive) with the electrode surface. Recently, liquid-like neat Nanoparticle Organic Hybrid Materials (NOHMs) have been considered as an electrolyte component to improve the transport of redox-active species to the electrode surface. However, the structure and assembly of the NOHMs near the electrode surface is unknown and could significantly impact the electrode-electrolyte interface. Hence, we have investigated the depth profile of polyetheramine (HPE) polymer and NOHM-I-HPE (nanoparticles with ionically bonded HPE polymer) in deuterated water (D2O) in the presence of two different salts (KHCO3 and ZnCl2) near two different electrode surfaces using neutron reflectometry. Moreover, the depth profile of the NOHM-I-HPE near the electrode surface in a potential has also been studied with in-situ reflectivity experiments. Our results indicate that a change in the chemical structure/hydrophilicity of the electrode surface does not significantly impact the ordering of HPE polymer or NOHM-I-HPE near the surface. Here, this study also indicates that the NOHM-I-HPE particles form a clear layer near the electrode surface immediately above an adsorbed layer of free polymer on the electrode surface. The addition of salt does not impact the layering of NOHM-I-HPE, though it does alter the conformation of the polymer grafted to the nanoparticle surface and free polymer sequestered near the surface. Finally, the application of negative potential results in an increased amount of free polymer near the electrode surface. Correlating the depth profile of free polymer and NOHM-I-HPE particles with the electrochemical performance indicates that this assembly of free polymer near the electrode surface in NOHM-I-HPE solutions contributes to the higher current density of the system. Therefore, this holistic study offers insight into the importance of the assembly of NOHM-I-HPE electrolyte and free polymer near the electrode surface in an electrochemical milieu on its performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetic particles

Magnetic polymer particles are formed by swelling porous, polymer particles and impregnating the particles with an aqueous solution of precursor magnetic metal salt such as an equimolar mixture of ferrous chloride and ferric chloride. On addition of a basic reagent such as dilute sodium hydroxide, the metal salts are converted to crystals of magnetite which are uniformly contained througout the pores of the polymer particle. The magnetite content can be increased and neutral buoyancy achieved by repetition of the impregnaton and neutralization steps to adjust the magnetite content to a desired level.

Chang, Manchium↗

Ion-Conducting Thermoresponsive Films Based on Polymer-Grafted Cellulose Nanocrystals

Mechanically robust, thermo-responsive, ion-conducting nanocomposite films are prepared from poly(2-phenylethyl methacrylate) grafted cellulose nanocrystals (MxG-CNC-g-PPMA). One-component nanocomposite films of the polymer grafted nanoparticle (PGN) MxG-CNC-g-PPMA are imbibed with 30 wt% imidazolium-based ionic liquid, to produce flexible ion-conducting films. These films with 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (MxG-CNC-g-PPMA/[H]) not only displays remarkable improvements in toughness (>25 times) and tensile strength (>70 times) relative to the corresponding nanocomposites consisting of the ionic liquid imbibed in the two component CNC/PPMA nanocomposite, but also shows higher ionic conductivity than the corresponding neat PPMA with the same wt.% of ionic liquid. Notably, the one-component film containing 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (MxG-CNC-g-PPMA/[E]) exhibits temperature responsive ionic conduction. The ionic conductivity decreases at around 60°C as a consequence of the lower critical solution temperature (LCST) phase transition of the grafted polymer in the ionic liquid, which leads to phase separation. Moreover, holding the MxG-CNC-g-PPMA/[E] film at room temperature for 24 hours returns the film to its original homogenous state. These materials exhibit properties relevant to thermal cutoff safety devices (e.g., thermal fuse) where a reduction in conductivity above a critical temperature is needed.

36 MATERIALS SCIENCE↗

Rigid-Rod Sulfonated Polyamide as an Aqueous-Processable Binder for Li-Ion Battery Electrodes

Polymer binders are important components of most battery electrodes, ensuring high performance and long-term durability. Increasing demand for lithium-ion batteries in the automotive, stationary power, and portable electronics industries calls for a greener binder to replace poly(vinylidene difluoride) (PVDF). We evaluate the performance of aqueous solution-processed electrodes prepared with a rigid-rod polymer binder, poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) (PBDT). The polyamide backbone and double-helical configuration of PBDT give rise to its mechanical strength and rigidity, and its functional nature (H-bonding amides and sulfonates) can provide specific binding with electrode particles. LiFePO 4 electrodes prepared with 3 wt% PBDT show mechanical integrity and cycling stability, achieving over 1000 cycles at 4C rate with negligible capacity decay. These electrodes demonstrate comparable rate performance with their PVDF counterparts while eliminating fluorine from the electrode as well as the organic solvents needed for processing. Furthermore, this study reveals that PBDT holds great potential as a binder for advanced sustainable batteries.

25 ENERGY STORAGE↗