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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 1,099 records · Page 61

The impact of radical loading and oxidation on the conformation of organic radical polymers by small angle neutron scattering

Electrodes comprised of organic polymeric materials containing stable radicals have become attractive for incorporation into organic radical batteries. Specifically, the radical polymer poly(2,2,6,6-tetramethylpeperidinyloxy-4-yl methacrylate) (PTMA) exhibits extremely rapid electron charge transport rates, comparable to traditional transition metal ions. However, the structural reorganization that the polymer undergoes during charging is not well understood. Using small angle neutron scattering, we have investigated the structural changes the PTMA polymer exhibits with variation of radical concentration or oxidation. The results indicate that as the radical concentration is increased, the polymer becomes more inflexible and begins to aggregate with neighboring polymer chains as the radicals on the polymer align with neighboring solvated chains. Additional studies monitor the conformational changes of the PTMA copolymers with oxidation to mimic the structural changes that the polymer undergoes during charging. These results show that polymers with low radical densities are more susceptible to reorientation with charging than a polymer that is fully saturated with radical moieties. This study therefore provides seminal fundamental information that identifies the relationship between radical density and molecular structure providing crucial insight that is needed to improve the performance of organic radical batteries.

36 MATERIALS SCIENCE↗

Functional Biomimetic Polymers with Antimicrobial Activity

At PNNL, we have developed a completely new class of synthetic biomimetic sequence-defined polymers based on triazine chemistry, which we call TZPs. PNNL's new polymers offer the opportunity to achieve similar functions to natural macromolecules; specifically we designed and synthesized a diversity of test molecules for antimicrobial activity. Antimicrobial activity against a variety of wild type and drug resistant pathogens was found.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improving Thermal Stability of Perovskite Solar Cells by Suppressing Ion Migration Using Copolymer Grain Encapsulation

Thermal stability of organic–inorganic hybrid perovskites (OIHPs) remains as one of the critical challenges against the stable operation of perovskite solar cells (PSCs) in direct sunlight with elevated temperatures. Here, we show that the addition of a polystyrene-co-polyacrylonitrile (SAN) copolymer can significantly enhance thermal stability of OIHPs and improve the stability of the corresponding PSCs by suppressing the migration of organic cations in OHIP. The methylammonium lead iodide (MAPI) with SAN incorporated within the perovskite layer featured a superior thermal stability compared to pure MAPI without SAN, only displaying an average of 5–15% decrease in PCE even after continuous thermal aging for 24 h at 100 °C. The secondary ion mass spectrometry revealed that the thermal degradation of the pure MAPI was largely associated with MA+ out-migration. Conducting atomic force microscopy analysis further indicated that the incorporated SAN led to a suppression of ionic currents present at the grain boundaries of the perovskite film, which was understood by high immiscibility between SAN and MA+ components as confirmed by the experimentally estimated Flory–Huggins parameter between them. This study newly identifies a potential of using polymer grain encapsulation for enhancing thermal stability of OIHPs and their solar cell performance by suppressing the out-diffusion of cationic organic components.

36 MATERIALS SCIENCE↗

On the progress of 3D-printed hydrogels for tissue engineering

Additive manufacturing or more commonly known as 3D printing, is currently driving innovations and applications in diverse fields such as prototyping, manufacturing, aerospace, education, and medicine. Recent technological and materials research breakthroughs have enabled 3D bioprinting, where biomaterials and cells are used to create scaffolds and functional living tissues (e.g. skin, cartilage, etc.). This prospective focuses on the classification and applications of hydrogels, and design considerations in their production (i.e. physical and biological parameters). Herein, the materials for 3D printing of hydrogels, such as biopolymers, synthetic polymers, and nanocomposites, are mainly discussed. More importantly, future perspectives on 3D printing hydrogels including new materials, 4D printing, emerging printing technologies, etc. and their importance in biomedical and bioengineering applications are discussed.

36 MATERIALS SCIENCE↗

Single-Crystal Polycationic Polymers Obtained by Single-Crystal-to-Single-Crystal Photopolymerization

The efficient preparation of single-crystalline ionic polymers and fundamental understanding of their structure–property relationships at the molecular level remains a challenge in chemistry and materials science. Herein, we observe the single-crystal structure of a highly ordered polycationic polymer (polyelectrolyte) and its proton conductivity. The polyelectrolyte single crystals can be prepared on a gram-scale in quantitative yield, by taking advantage of an ultraviolet/sunlight-induced topochemical polymerization, from a tricationic monomer—a self-complementary building block possessing a preorganized conformation. A single-crystal-to-single-crystal photopolymerization was revealed unambiguously by in situ single-crystal X-ray diffraction analysis, which was also employed to follow the progression of molecular structure from the monomer, to a partially polymerized intermediate, and, finally, to the polymer itself. Collinear polymer chains are held together tightly by multiple Coulombic interactions involving counterions to form two-dimensional lamellar sheets (1 nm in height) with sub-nanometer pores (5 Å). The polymer is extremely stable under 254 nm light irradiation and high temperature (above 500 K). The extraordinary mechanical strength and environmental stability—in combination with its impressive proton conductivity (~3 × 10 –4 S cm –1 )—endow the polymer with potential applications as a robust proton-conducting material. By marrying supramolecular chemistry with macromolecular science, the outcome represents a major step toward the controlled synthesis of single-crystalline polyelectrolyte materials with perfect tacticity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and properties of polymerized ionic liquids

Polymerization of ionic liquids results in the formation of ionic polymers, which are called poly (ionic liquid)s or polymerized ionic liquids (PIL). This is a brand new form of ionicity in polymer chains with a broad range of applications, though ionic polymers have a long history with the sub-families of polyelectrolytes and ionomers. Although mobility of ions in ionic liquids has named them as the promising candidates for various applications, their applicability is limited in many practical systems because of not having the advantages of neither liquids nor solids, suffering from both leakage issue and high viscosity. PILs perfectly fit with the practical requirements while having almost all features of ionic liquids. This review summarizes some potential applications of PILs. The architecture of PILs can be easily re-designed by both the polymer backbone and outer ion. Not only by post-polymerization but also by in situ ion exchange, the chemical and mechanical properties of PILs can be tuned. Lastly, owing to the high chemical activity and flexible architecture, PILs are the promising candidates for sensors and actuators, electroactive binders, solid and gel electrolytes, non-blocking matrix of nanocomposites, etc.

36 MATERIALS SCIENCE↗

Transparent Conductive Adhesives for Tandem Solar Cells

Methods of making silicon based tandem cells include wafer bonding, depositing absorber layers on the surface, and mechanical stacking. Of these, mechanically stacking after growth retains the individual cell quality during production, but typically requires a four-terminal device. We present a transparent conductive adhesive (TCA) interlayer, designed for transparency in wavelengths that Si absorbs, conductivity for out-of-plane conductivity between cells, and adhesive strength, enabling two-terminal stacked tandems. The developed TCA material is a polymer-particle blend of common transparent adhesives and metal-coated flexible microspheres, capable of bridging micro-scale gaps between uneven/textured surfaces. At 10% microsphere coverage, experimental and theoretical series resistance is compatible with high-efficiency tandem cells on silicon.

14 SOLAR ENERGY↗

Manufacturing Energy Intensity and Opportunity Analysis for Fiber-Reinforced Polymer Composites and Other Lightweight Materials

With their high strength-to-weight ratios, fiber-reinforced polymer (FRP) composites are important materials for lightweighting in structural applications; however, manufacturing challenges such as low process throughput and poor quality control can lead to high costs and variable performance, limiting their use in commercial applications. One of the most significant challenges for advanced composite materials is their high manufacturing energy intensity. This study explored the energy intensities of two lightweight FRP composite materials (glass- and carbon-fiber-reinforced polymers), with three lightweight metals (aluminum, magnesium, and titanium) and structural steel (as a reference material) included for comparison. Energy consumption for current typical and state-of-the-art manufacturing processes were estimated for each material, deconstructing manufacturing process energy use by sub-process and manufacturing pathway in order to better understand the most energy intensive steps. Energy saving opportunities were identified and quantified for each production step based on a review of applied R&D technologies currently under development in order to estimate the practical minimum energy intensity. Results demonstrate that while carbon fiber reinforced polymer (CFRP) composites have the highest current manufacturing energy intensity of all materials considered, the large differences between current typical and state-of-the-art energy intensity levels (the 'current opportunity') and between state-of-the-art and practical minimum energy intensity levels (the 'R&D opportunity') suggest that large-scale energy savings are within reach.

36 MATERIALS SCIENCE↗

High-Resolution Imaging of Unstained Polymer Materials

Electron microscopy has played an important role in polymer characterization. Traditionally, electron diffraction is used to study crystalline polymers while transmission electron microscopy is used to study microphase separation in stained block copolymers and other multiphase systems. We describe developments that eliminate the barrier between these two approaches - it is now possible to image polymer crystals with atomic resolution. The focus of this Review is on high-resolution imaging (30 Å and smaller) of unstained polymers. Recent advances in hardware allow for capturing numerous (as many as 105) low-dose images from an unperturbed specimen; beam damage is a significant barrier to high-resolution electron microscopy of polymers. Machine-learning-based software is then used to sort and average the images to retrieve pristine structural information from a collection of noisy images. Acknowledging the heterogeneity in polymer samples prior to averaging is essential. Molecular conformations in a wide range of amphiphilic block copolymers, polymerized ionic liquids, and conjugated polymers can be gleaned from two-dimensional projections (2D), three-dimensional (3D) tomograms, and four-dimensional (4D) scanning transmission electron microscopy (STEM) data sets where 2D diffraction patterns are taken as a function of position. Some methods such as phase contrast STEM have been used to image closely related materials such as metal-organic frameworks but not polymers. With improvements in hardware and software, such methods may soon be applied to polymers. Our goal is to provide a comprehensive understanding of the strategies toward the high-resolution imaging of radiation sensitive polymer materials at different length scales.

36 MATERIALS SCIENCE↗

An Integrated Theoretical and Experimental Approach to Achieve Highly Polarizable Relaxor Ferroelectric Liquid Crystalline Polymers

In this project, we have designed and synthesized a series of aliphatic sulfonlyated chiral and achiral polyether. The major objective is to achieve ferroelectric liquid crystalline polymers with a high spontaneous polarization (0.04-0.08 C/m2). Due to the strong dipole-dipole interaction among the sulfonyl side groups, which resembles that among water molecules, these polyethers can exhibit various liquid crystalline self-assemblies without any rigid mesogens. By tuning the position of the sulfonyl groups, single versus double sulfonyl groups, and spacer/tail length and methyl branches, the liquid crystalline phases include smectic A, smectic C, and hexagonal columnar phases. When the single sulfonyl group is next to the main chain or disulfonyl groups are separated by a short C3 spacer, the dipolar interaction is too strong to allow any dipole switching. As a result, the linear dielectric behavior is observed with a low dielectric constant of 5-7. When the single sulfonyl groups are away from the main chain, the paraelectric behavior is obtained with a high dielectric constant around 20. From this study, we predict that by further tailoring the intermolecular interactions among the disulfonyl side groups, it is possible to achieve ferroelectric property for these liquid crystalline polymers. If successful, these ferroelectric liquid crystalline polymers can be used for efficient electrocaloric cooling applications.

36 MATERIALS SCIENCE↗

Enhanced thermal conductance of polymer composites through embedding aligned carbon nanofibers

The focus of this work is to find a more efficient method of enhancing the thermal conductance of polymer thin films. This work compares polymer thin films embedded with randomly oriented carbon nanotubes to those with vertically aligned carbon nanofibers. Thin films embedded with carbon nanofibers demonstrated a similar thermal conductance between 40–60 μm and a higher thermal conductance between 25–40 μm than films embedded with carbon nanotubes with similar volume fractions even though carbon nanotubes have a higher thermal conductivity than carbon nanofibers

36 MATERIALS SCIENCE↗

Sequential Doping of Ladder-Type Conjugated Polymers for Thermally Stable n-Type Organic Conductors

Doping of organic semiconductors is a powerful tool to optimize the performance of various organic (opto)electronic and bioelectronic devices. Despite recent advances, the low thermal stability of the electronic properties of doped polymers still represents a significant obstacle to implementing these materials into practical applications. Hence, the development of conducting doped polymers with excellent long-term stability at elevated temperatures is highly desirable. Here, we report on the sequential doping of the ladder-type polymer poly(benzimidazobenzophenanthroline) (BBL) with a benzimidazole-based dopant (i.e., N-DMBI). By combining electrical, UV–vis/infrared, X-ray diffraction, and electron paramagnetic resonance measurements, we quantitatively characterized the conductivity, Seebeck coefficient, spin density, and microstructure of the sequentially doped polymer films as a function of the thermal annealing temperature. Importantly, we observed that the electrical conductivity of N-DMBI-doped BBL remains unchanged even after 20 h of heating at 190 °C. This finding is remarkable and of particular interest for organic thermoelectrics.

36 MATERIALS SCIENCE↗

B‐Staging and Crosslinking of Polycarbosilane at Room Temperature: Cure Mechanism and Properties

The viscosity of polycarbosilane (PCS) polymers is not advantageous for free forming. Various fillers and heat are used to obtain a formable paste. Due to the low yield stress, structures and preforms tend to slump or resin will flow out, especially during the curing of the polymer. B-staging of PCS allows for a more stable structure from room temperature until the full cure of the allyl groups occurs with heat. Additionally, hydrosilation is an effective means of crosslinking at room temperature and controlling viscosity. A network structure was formed in SMP-10 using silane and a vinyl-based crosslinker to bridge each polymer chain. Pt addition catalysts were added to enhance the increase in viscosity to make a lightly crosslinked gel to aid in thickening and forming and to improve the ceramic yield at 1000°C. In conclusion, this enables several options for controlling rheology and improving the properties of preceramic polymers to avoid slumping during curing.

inorganic polymers↗

Conductive polymer and Si nanoparticles composite secondary particles and structured current collectors for high loading lithium ion negative electrode application

Embodiments of the present invention disclose a composition of matter comprising a silicon (Si) nanoparticle coated with a conductive polymer. Another embodiment discloses a method for preparing a composition of matter comprising a plurality of silicon (Si) nanoparticles coated with a conductive polymer comprising providing Si nanoparticles, providing a conductive polymer, preparing a Si nanoparticle, conductive polymer, and solvent slurry, spraying the slurry into a liquid medium that is a non-solvent of the conductive polymer, and precipitating the silicon (Si) nanoparticles coated with the conductive polymer. Another embodiment discloses an anode comprising a current collector, and a composition of matter comprising a silicon (Si) nanoparticle coated with a conductive polymer.

36 MATERIALS SCIENCE↗

Dual-Responsive Reversible Plasmonic Behavior of Core–Shell Nanostructures with pH-Sensitive and Electroactive Polymer Shells

In this paper, we report novel dual-responsive plasmonic core–shell anisotropic nanostructures composed of gold nanorod (AuNR) and responsive polyaniline (PANI) shells with plasmonic mode appearance reversibly modulated through orthogonal stimuli (i.e., electrical potential and pH change). In this system, the PANI shells provide AuNR cores with three different refractive index environments depending on stimuli (pH and electrical potential). Therefore, no additional secondary responsive component is necessary to induce the dual-responsive properties of AuNR cores. Furthermore, in this study, dual-responsive properties can be realized for nanostructures fixed on substrates, whereas previously reported dual-responsive plasmonic systems can only be controlled in solution. Here, the highest localized surface plasmonic resonance (LSPR) shift of the AuNR cores can be induced by changing both local pH and applying electric potential. Notably, a significant plasmon band shift by 107 nm is realized with only 8 nm thick PANI shell due to the large refractive index change at the gold–polymer interface. A maximum shift of the longitudinal plasmon mode of 149 nm is obtained by applying a modest electrical potential (below ±1 V), a large shift rarely reported in the literature for metal nanostructures. Moreover, our anisotropic core/shell nanostructures exhibit stable and reversible dual-responsive LSPR behavior over 100 cycles without degradation.

36 MATERIALS SCIENCE↗