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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 235 records · Page 13

Surface Functionalization of Carbon Black for PEM Fuel Cell Electrodes

Abstract Carbon‐based materials are extensively used in fuel cell applications due to their crucial role in maintaining high performance. Particularly, carbon black (CB) stands out as a preferred electrode material for fuel cells, owing to its high electrical conductivity and large surface area. This review focuses on the functionalization of CB and its use as a support for Pt‐based catalysts in proton exchange membrane fuel cells. Functionalization strategies include oxidation, covalent functionalization, as well as polymer grafting or impregnation. Various approaches to functionalize the CB surface are discussed that effectively tailor the surface properties of electrodes, leading to improved fuel cell performance. The improvements are seen in enhanced dispersibility of catalyst particles, better ionomer distribution, increased catalyst stability, and reduced carbon corrosion. This review provides an overview of various modifications applied to CB to enhance their structural and electrochemical properties, thereby boosting fuel cell performance.

74 ATOMIC AND MOLECULAR PHYSICS↗

Autonomous alignment and healing in multilayer soft electronics using immiscible dynamic polymers

Self-healing soft electronic and robotic devices can, like human skin, recover autonomously from damage. While current devices use a single type of dynamic polymer for all functional layers to ensure strong interlayer adhesion, this approach requires manual layer alignment. In this study, we used two dynamic polymers, which have immiscible backbones but identical dynamic bonds, to maintain interlayer adhesion while enabling autonomous realignment during healing. These dynamic polymers exhibit a weakly interpenetrating and adhesive interface, whose width is tunable. When multilayered polymer films are misaligned after damage, these structures autonomously realign during healing to minimize interfacial free energy. Finally, we fabricated devices with conductive, dielectric, and magnetic particles that functionally heal after damage, enabling thin-film pressure sensors, magnetically assembled soft robots, and underwater circuit assembly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer-carbon black composite sensors in an electronic nose for air-quality monitoring

An electronic nose that uses an array of 32 polymer-carbon black composite sensors has been developed, trained, and tested. By selecting a variety of chemical functionalities in the polymers used to make sensors, it is possible to construct an array capable of identifying and quantifying a broad range of target compounds, such as alcohols and aromatics, and distinguishing isomers and enantiomers (mirror-image isomers). A model of the interaction between target molecules and the polymer-carbon black composite sensors is under development to aid in selecting the array members and to enable identification of compounds with responses not stored in the analysis library.

NASA Discipline Life Sciences Technologies↗

Scattering evidence of positional charge correlations in polyelectrolyte complexes

Polyelectrolyte complexation plays an important role in materials science and biology. The internal structure of the resultant polyelectrolyte complex (PEC) phase dictates properties such as physical state, response to external stimuli, and dynamics. Small-angle scattering experiments with X-rays and neutrons have revealed structural similarities between PECs and semidilute solutions of neutral polymers, where the total scattering function exhibits an Ornstein–Zernike form. In spite of consensus among different theoretical predictions, the existence of positional correlations between polyanion and polycation charges has not been confirmed experimentally. Here, we present small-angle neutron scattering profiles where the polycation scattering length density is matched to that of the solvent to extract positional correlations among anionic monomers. The polyanion scattering functions exhibit a peak at the inverse polymer screening radius of Coulomb interactions, q* ≈ 0.2 Å –1 . This peak, attributed to Coulomb repulsions between the fragments of polyanions and their attractions to polycations, is even more pronounced in the calculated charge scattering function that quantifies positional correlations of all polymer charges within the PEC. Screening of electrostatic interactions by adding salt leads to the gradual disappearance of this correlation peak, and the scattering functions regain an Ornstein–Zernike form. Experimental scattering results are consistent with those calculated from the random phase approximation, a scaling analysis, and molecular simulations.

74 ATOMIC AND MOLECULAR PHYSICS↗

CO 2 Capture with Capsules of Ionic Liquid/Amines

Carbon capture remains an urgent issue that has gained a great deal of attention over the past few decades. Aqueous amines have excellent selectivity, but present corrosion and volatility issues, whereas ionic liquids (ILs) have negligible volatility and tunable physical properties, but high viscosities. One approach to improve the practical performance of these liquids is encapsulating them in a CO 2 permeable polymer shell to enhance the accessibility of the liquid and the CO 2 absorption rate. In this work, we report the encapsulation of a mixture of amine and IL (i.e., monoethanolamine (MEA) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF 4 ])) and demonstrate enhanced carbon capture performance. A soft-template approach and interfacial polymerization are used to give capsules with liquid core (64 wt %) and polyurea shell. Compared to the bulk liquid, the encapsulated liquid shows improved thermal stability over cycles of absorption at 25 °C, and desorption at 75 °C. The capsules with core of [BMIM][BF 4 ]-MEA show 0.2 mol CO 2 /kg of capsules at 1 bar CO 2 , compared to the bulk liquid, which has 0.05 mol CO 2 /kg of sorbent. This is attributed to the limited evaporation of the amines. Alternatively, the same capsules but with 5 wt % of piperazine (Pz) in the core have doubled gravimetric CO 2 capacity of the capsules (0.4 mol CO 2 /kg of capsules); performance is evaluated over 10 capture–release cycles showing minimal mass loss. Characterization of the CO 2 uptake of the polymer shell itself reveals that the shell contributes only ~10% of the observed capacity, likely attributed to amine functionalities of the polymer. Here, this facile approach to encapsulating such “active” liquids can be applied to other CO 2 selective solvents that are volatile, viscous, and corrosive.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer-gas reactions (air pollutants: NO2 and SO2) as function of pressure, UV light, temperature, and morphology: A survey

Reactions of various polymers, such as polystyrene and its stereo-specific isomers, butylrubber, nylon, etc., with nitrogen dioxide and sulfur-dioxide were studied over the past few years. More recently, work has been initiated on the influence of polymer morphology on degradation of polymers in presence of these gases, near UV radiation and oxygen. Unexpected effects have been observed during chain scission near room temperature. Thus, for instance, isotactic polystyrene of various crystallinities, as far as extent and type are concerned, show marked differences in their degradation characteristics. Thus, for instance, crystalline polymers show faster degradation than amorphous ones, which seems to be contrary to expectations. However, this phenomenon can be explained in quite a consistent manner. The importance of all these reactions in connection with air pollution is briefly discussed.

Jellinek, H. H. G.↗

Biomimetic/Optical Sensors for Detecting Bacterial Species

Biomimetic/optical sensors have been proposed as means of real-time detection of bacteria in liquid samples through real-time detection of compounds secreted by the bacteria. Bacterial species of interest would be identified through detection of signaling compounds unique to those species. The best-characterized examples of quorum-signaling compounds are acyl-homoserine lactones and peptides. Each compound, secreted by each bacterium of an affected species, serves as a signal to other bacteria of the same species to engage in a collective behavior when the population density of that species reaches a threshold level analogous to a quorum. A sensor according to the proposal would include a specially formulated biomimetic film, made of a molecularly imprinted polymer (MIP), that would respond optically to the signaling compound of interest. The MIP film would be integrated directly onto an opticalwaveguide- based ring resonator for optical readout. Optically, the sensor would resemble the one described in Chemical Sensors Based on Optical Ring Resonators (NPO-40601), NASA Tech Briefs, Vol. 29, No. 10 (October 2005), page 32. MIPs have been used before as molecular- recognition compounds, though not in the manner of the present proposal. Molecular imprinting is an approach to making molecularly selective cavities in a polymer matrix. These cavities function much as enzyme receptor sites: the chemical functionality and shape of a cavity in the polymer matrix cause the cavity to bind to specific molecules. An MIP matrix is made by polymerizing monomers in the presence of the compound of interest (template molecule). The polymer forms around the template. After the polymer solidifies, the template molecules are removed from the polymer matrix by decomplexing them from their binding sites and then dissolving them, leaving cavities that are matched to the template molecules in size, shape, and chemical functionality. The cavities thus become molecular-recognition sites that bind only to molecules matched to the sites; other molecules are excluded. In a sensor according to the proposal, the MIP would feature molecular recognition sites that would bind the specific signaling molecules selectively according to their size, shape, and chemical functionality (see figure). As the film took up the signaling molecules in the molecular recognition sites, the index of refraction and thickness of the film would change, causing a wavelength shift of the peak of the resonance spectrum. It has been estimated that by measuring this wavelength shift, it should be possible to detect as little as 10 picomoles of a peptide signaling compound.

Homer, Margie↗

Designing Imidazolium Poly(amide-amide) and Poly(amide-imide) Ionenes and Their Interactions with Mono- and Tris(imidazolium) Ionic Liquids

Here we introduce the synthesis and thermal properties of a series of sophisticated imidazolium ionenes with alternating amide-amide or amide-imide backbone functionality, and investigate the structural effects of mono(imidazolium) and unprecedented tris(imidazolium) ionic liquids (ILs) in these ionenes. The new set of poly(amide-amide) (PAA) and poly(amide-imide) (PAI) ionenes represent the intersection of conventional high-performance polymers with the ionene archetype–presenting polymers with alternating functional and ionic elements precisely sequenced along the backbone. The effects of polymer composition on the thermal properties and morphology were analyzed. Five distinct polymer backbones were synthesized and combined with a stoichiometric equivalent of the IL 1-benzyl-3-methylimidazolium bistriflimide ([Bnmim][Tf 2 N]), which were studied to probe the self-assembly, structuring, and contributions of intermolecular forces when IL is added. Furthermore, three polyamide (PA) or polyimide (PI) ionenes with simpler xylyl linkages were interfaced with [Bnmim][Tf 2 N] as well as a novel amide-linked tris(imidazolium) IL, to demonstrate the structural changes imparted by the inclusion of functional, ionic additives dispersed within the ionene matrix. This work highlights the possibilities for utilizing concepts from small molecules which exhibit supramolecular self-assembly to guide creative design and manipulate the structuring of ionenes.

36 MATERIALS SCIENCE↗

Thermally-rearranged polymer blends for gas separation membranes

Polymer blends comprising an ortho-functionalized polyimide homo or copolymer and a polybenzimidazole homo or copolymer, wherein the ortho-functionalized polyimide thermally rearranges to a polymer comprising a phenylene heterocyclic group, such as, polybenzoxazole, polybenzothiazole, polybenzimidazole and/or other heterocyclic structure upon heating. Also disclosed are method of forming a polymer blend comprising dissolving an ortho-functionalized polyimide homo or copolymer and a polybenzimidazole homo or copolymer in a solvent, and optional compatibilizer, to form a polymer solution; contacting a support with the polymer solution; and evaporating the solvent to provide a thin layer comprising the polymer blend on the support. Further, methods of heat treating these polymer blends to thermally rearrange the disclosed polyimides are disclosed, as are the polymer blends prepared thereby. Methods of using these polymer blends to separate gases are also disclosed.

Freeman, Benny D.↗

Green Electrode Processing Enabled by Fluoro-Free Multifunctional Binders for Lithium-Ion Batteries

The eco-friendly processing of conjugated polymer binder for lithium-ion batteries demands improved polymer solubility by introducing functional moieties, while this strategy will concurrently sacrifice polymer conductivity. Employing the polyfluorene-based binder poly(2,7-9,9 (di(oxy-2,5,8-trioxadecane))fluorene) (PFO), soluble in water-ethanol mixtures, a novel approach is presented to solve this trade-off, which features integration of aqueous solution processing with subsequent controlled thermal-induced cleavage of solubilizing side chains, to produce hierarchically ordered structures (HOS). The thermal processing can enhance the intermolecular π–π stacking of polyfluorene backbone for better electrochemical performance. Notably, HOS-PFO demonstrated a substantial 6–7 orders of magnitude enhancement in electronic conductivity, showcasing its potential as a functional binder for lithium-ion batteries. As an illustration, HOS-PFO protected SiOx anodes, utilizing in situ side chain decomposition of PFO surrounding SiOx particles after aqueous processing are fabricated. HOS-PFO contributed to the stable cycling and high-capacity retention of practical SiOx anodes (3.0 mAh cm -2 ), without the use of any conducting carbon additives or fluorinated electrolyte additives. It is proposed that this technique represents a universal approach for fabricating electrodes with conjugated polymer binders from aqueous solutions without compromising conductivity.

25 ENERGY STORAGE↗

Understanding Depolymerization and Repolymerization Toward Repurposing Polymer Waste Into Valuable Chemicals & Materials

The versatility of synthetic polymers has led to their continual and escalating production that has accompanied mismanagement at their end-of-life. Exploring and understanding complementary avenues to repurpose plastic waste beyond traditional mechanical recycling can unlock new opportunities in providing feedstock flexibility, securing supply chains, recovering valuable materials, and enabling new valorization paths. Chemical recycling allows for the return to monomers, tailored oligomers, and polymers, even from mixed states of post-consumer waste plastics. This review article summarizes our research team's efforts on elucidating key insights surrounding plastic depolymerization and repolymerization into valorized products. We revealed organocatalyst design rules lead to highly effective and selective deconstruction of condensation polymers. The intricacies of tailoring the reaction environment to produce products of specific lengths and desired functionalities transform low-value waste feedstocks into high-performance materials with embedded circularity. Other types of polymers, including polyolefins and polyakenamers, have also been designed and converted into valuable products. There remain opportunities for further developments such as low-energy and precision depolymerization, adoption of cutting-edge small molecule transformation to access functionalized polymer scaffolds typically inaccessible otherwise, as well as precision design and understanding through the aid of advanced tools.

Galan, Nick [ORNL]↗

Electrical Transfer Function and Poling Mechanisms for Nonlinear Optical Polymer Modulators

Electro-Optic Polymers hold great promise in increased electro-optic coefficients as compared to their inorganic corollaries. Many researchers have focused on quantum chemistry to describe how the dipoles respond to temperature and electric fields. Much work has also been done for single layer films to confirm these results. For optical applications, waveguide structures are utilized to guide the optical waves in 3 layer stacks. Electrode poling is the only practical poling method for these structures. This research takes an electrical engineering approach to develop poling models and electrical and optical transfer functions of the waveguide structure. The key aspect of the poling model is the large boundary charge density deposited during the poling process. The boundary charge density also has a large effect on the electrical transfer function which is used to explain the transient response of the system. These models are experimentally verified. Exploratory experiment design is used to study poling parameters including time, temperature, and voltage. These studies verify the poling conditions for CLDX/APC and CLDZ/APEC guest host electro optic polymer films in waveguide stacks predicted by the theoretical developments.

Watson, Michael Dale↗

Fused filament fabrication of novel phase-change material functional composites

Additively manufactured polymer heat exchangers are of recent interest in the thermal sciences due to their lightweight and intricate heat-transfer-enhancing geometrical features. The goal of the present research is to directly encapsulate phase-change material (PCM) into polymer filament for the purpose of 3D printing polymer heat exchangers capable of latent heat thermal energy storage and management. PCMs have the ability to absorb large amounts of latent heat while undergoing a solid-to-liquid phase change at a nearly constant temperature. Encapsulation or containment of PCMs is necessary to prevent leaking since the material continuously cycles between a liquid and a solid state. An organic-based PCM and high-density polyethylene (HDPE) were combined and extruded into a functional composite filament. For the first time, with the aid of a heated enclosure and HDPE build plates, it was demonstrated that these functional composite materials can be printed using fused filament fabrication (FFF). Printing HDPE is known to be difficult; however, based on what was observed in the current study, the PCM and HDPE composite was easier to print than pure HDPE. Thermal properties, such as latent heat of fusion, phase-change temperature, and thermal conductivity, of the composite filament and 3D printed samples were investigated and compared with compression-molded bulk material. Finally, the microstructures of the composite filament and 3D printed samples were visualized, and the basic structures of the HDPE and PCM within both the filament and 3D printed parts were clearly delineated.

36 MATERIALS SCIENCE↗

Shear rheological characterization of motor oils

Measurements of high pressure viscosity, traction coefficient, and EHD film thickness were performed on twelve commercial automotive engine oils, a reference oil, two unformulated base oils and two unformated base oil and polymer blends. An effective high shear rate inlet viscosity was calculated from film thickness and pressure viscosity coefficient. The difference between measured and effective viscosity is a function of the polymer type and concentration. Traction measurements did not discriminate mileage formulated oils from those not so designated.

Bair, Scott↗

Tailored Mesoporous Microspheres by Polymerization-Induced Microphase Separation in Suspension

We describe the preparation of block polymer beads by aqueous suspension polymerization to create poly(caprolactone) (PCL)-block-poly(styrene-co-divinylbenzene) beads that can be selectively etched under basic conditions to yield mesoporous polymer microspheres with uniform pore size. Polyvinylalcohol was used to stabilize the suspension polymerization in which styrene and divinylbenzene monomers were polymerized from a PCL macrochain transfer agent (macroCTA). The resulting polymerization-induced microphase separation process led to a nanostructured bicontinuous morphology. The particle size and pore size were independently tunable: the particle size was controlled by the stir rate of the suspension polymerization-yielding average diameters ranging from 60 to 300 μm-while the pore size was determined by the molar mass of the PCL block, with the mode pore diameters being 6 nm and 11 nm after etching beads made using 13 and 45 kg/mol PCL blocks, respectively. Based on nitrogen sorption measurements, the surface areas of the beads were ~300 m 2 /g when using a PCL macroCTA of 13 kg/mol. The beads were homogenous throughout on the micron length scale as determined by confocal Raman microscopy and lacked an impermeable skin layer as confirmed by scanning electron microscopy. Furthermore, the scalability of suspension polymerization allows for the simple synthesis of large quantities of thermoset microspheres with uniform pore size. We also demonstrate the ability to incorporate functional pore walls into the beads using multiblock precursor polymers. These functionalized mesoporous polymer beads show high affinity for ionic dyes in aqueous solutions (as a proof of principle) and remove dye from the solution at rates exceeding those of commercial ion-exchange resins. The developed procedure could be used to generate other functional surface chemistries with important applications in heterogeneous catalysis, chromatography, and water remediation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gold‐Catalyzed C−H Functionalization Polycondensation for the Synthesis of Aromatic Polymers

Abstract Homogeneous gold (Au) complexes have demonstrated tremendous utility in modern organic chemistry; however, their application for the synthesis of polymers remains rare. Herein, we demonstrate the first catalytic application of Au complexes toward the polycondensation of alkyne‐containing comonomers and heteroarene nucleophiles. Polymerization occurs through successive intermolecular hydroarylation reactions to produce high molecular weight aromatic copolymers with 1,1‐disubstituted alkene backbone linkages. Clear correlations between the rate and degree of polymerization (DP) were established based on catalyst structure and counterion pairing, thus enabling polymerization reactions that proceeded with remarkable efficiency, high reactivity, and exceptional DPs. The reactivity is broad in scope, enabling the copolymerization of highly functionalized aromatic and aliphatic monomers. These results highlight the untapped utility of Au catalysis in providing access to new macromolecular constructs.

King, Eric R.↗

Gold–Catalyzed C–H Functionalization Polycondensation for the Synthesis of Aromatic Polymers

Homogeneous gold (Au) complexes have demonstrated tremendous utility in modern organic chemistry; however, their application for the synthesis of polymers remains rare. Herein, we demonstrate the first catalytic application of Au complexes toward the polycondensation of alkyne-containing comonomers and heteroarene nucleophiles. Polymerization occurs through successive intermolecular hydroarylation reactions to produce high molecular weight aromatic copolymers with 1,1-disubstituted alkene backbone linkages. Clear correlations between the rate and degree of polymerization (DP) were established based on catalyst structure and counterion pairing, thus enabling polymerization reactions that proceeded with remarkable efficiency, high reactivity, and exceptional DPs. The reactivity is broad in scope, enabling the copolymerization of highly functionalized aromatic and aliphatic monomers. Furthermore, these results highlight the untapped utility of Au catalysis in providing access to new macromolecular constructs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗