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At least 613 records · Page 34

Improved Single-Ion Conductivity of Polymer Electrolyte via Accelerated Segmental Dynamics

Single-ion conducting polymer electrolytes (SICPEs) have many advantages for solid-state battery applications, while low conductivities remain the bottleneck for their practical applications. In this paper, a strategy that can significantly improve the ionic conductivity of SICPEs based on the concept of accelerated segmental dynamics was demonstrated by the evaluation of the thermal property, rheological behavior, morphology analysis, molecular dynamics simulation, and conductivity performance. With both “soft” poly(dimethylsiloxane) (PDMS) backbone and poly(ethylene glycol) (PEG) side chains, the obtained SICPE possesses faster segmental relaxation and higher lithium-ion conductivity. With lithium “transference” number close to unity, the obtained SICPE also shows excellent electrochemical stability against lithium metal electrodes. The clear relationship established between the segmental dynamics of polymer electrolyte and its ionic conductivity should contribute to achieve a solid electrolyte with improved ionic conductivity toward the next-generation solid-state battery.

Segmental Dynamics↗

Dual-Ion Intercalation and High Volumetric Capacitance in a Two-Dimensional Non-Porous Coordination Polymer

Intercalation is a promising ion-sorption mechanism for enhancing the energy density of electrochemical capacitors (ECs) because it offers enhanced access to the electrochemical surface area. It requires a rapid transport of ions in and out of a host material, and it must occur without phase transformations. Materials that fulfil these requirements are rare; those that do intercalate almost exclusively cations. Herein, we show that Ni3(benzenehexathiol) (Ni 3 BHT), a non-porous two-dimensional (2D) layered coordination polymer (CP), intercalates both cations and anions with a variety of charges. Whereas cation intercalation is pseudocapacitive, anions intercalate in a purely capacitive fashion. The excellent EC performance of Ni3BHT provides a general basis for investigating similar dual-ion intercalation mechanisms in the large family of non-porous 2D CPs.

36 MATERIALS SCIENCE↗

Predictive coarse-grained (CG) modeling of morphologies in polymer nanocomposites with specific and directional intermolecular interactions (Final Report)

The overarching goal of the proposed work was to develop predictive models for investigating structure and dynamics in soft materials with chemistries that have specific and directional molecular interactions. The motivation behind studying materials with specific and directional interactions lies in the many desirable features these interactions provide when designing novel soft materials. Soft materials with specific and direction interactions (such as hydrogen bonds or H-bonds) can have a) thermally reversible phase behavior with different functions with varying temperature, b) precisely tuned nanostructure with desirable geometries that afford unique physical properties (e.g., color response, mechanical properties) and c) well-mixed/blended morphologies that are useful for variety of applications in energy field (e.g., materials for batteries require use of blended polymers where one domain gives superior mechanical properties and one domain promotes electrical conduction). Notably, biology makes extensive use of specific and directional interactions, in many cases based on H-bonds, to construct materials with precisely defined architectures and properties. Engineered soft materials with precisely tuned nanostructures and improved processiblity through thermoresponsive phase behavior are useful in numerous applications that are relevant to the Department of Energy (DOE) including high efficiency electronic devices, light-weight high-strength composite materials for batteries and fuel cells, and polymer membranes for separations, etc. While past computational studies have been tremendously useful in understanding molecular phenomena and guiding synthesis of new macromolecular soft materials for a wide variety of applications, the inability to capture small scale specific and directional interactions alongside macromolecular length and time scales represented a key limitation of most studies to date. Our work in this project addressed this grand challenge in computational materials chemistry, i.e., ability to model the anisotropic, directional, and specific interactions that govern the behavior of many macromolecular soft matter systems of interest, thus, has greatly expanded the predictive potential of simulations. Specifically the key outcomes were: successful development of new coarse-grained (CG) polymer models to study generic and specific polymer chemistries in which hydrogen-bonding interactions are dominant. These CG models were then used in molecular simulations to study structure and thermodynamics in polymer nanocomposites and blends; some studies were conducted in collaboration with experimentalists. We also published a perspective and a viewpoint which included some of the work we completed in this DOE project; we believe these perspective and viewpoint articles guide other researchers in the soft materials community on how to extend the computational approaches and models we have developed for the purposes of their studies.

36 MATERIALS SCIENCE↗

Water stable molecular n-doping produces organic electrochemical transistors with high transconductance and record stability

From established to emergent technologies, doping plays a crucial role in all semiconducting devices. Doping could, theoretically, be an excellent technique for improving repressively low transconductances in n-type organic electrochemical transistors – critical for advancing logic circuits for bioelectronic and neuromorphic technologies. However, the technical challenge is extreme: n-doped polymers are unstable in electrochemical transistor operating environments, air and water (electrolyte). Here, the first demonstration of doping in electron transporting organic electrochemical transistors is reported. The ammonium salt tetra-n-butylammonium fluoride is simply admixed with the conjugated polymer poly(N,N’-bis(7-glycol)-naphthalene-1,4,5,8-bis(dicarboximide)-co-2,2’-bithiophene-co-N,N’-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide), and found to act as a simultaneous molecular dopant and morphology-additive. The combined effects enhance the n-type transconductance with improved channel capacitance and mobility. Furthermore, operational and shelf-life stability measurements showcase the first example of water-stable n-doping in a polymer. Overall, the results set a precedent for doping/additives to impact organic electrochemical transistors as powerfully as they have in other semiconducting devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tacky Elastomers to Enable Tear-Resistant and Autonomous Self-Healing Semiconductor Composites

Mechanical failure of π-conjugated polymer thin films is unavoidable under cyclic loading conditions, due to intrinsic defects and poor resistance to crack propagation. Here, the first tear-resistant and room-temperature self-healable semiconducting composite is presented, consisting of conjugated polymers and butyl rubber elastomers. This new composite displays both a record-low elastic modulus (<1 MPa) and ultrahigh deformability with fracture strain above 800%. More importantly, failure behavior is not sensitive to precut notches under deformation. Autonomous self-healing at room temperature, both mechanical and electronic, is demonstrated through the physical contact of two separate films. The composite film also shows device stability in the ambient environment over 5 months due to much-improved barrier property to both oxygen and water. Butyl rubber is broadly applicable to various p-type and n-type semiconducting polymers for fabricating self-healable electronics to provide new resilient electronics that mimic the tear resistance and healable property of human skin.

36 MATERIALS SCIENCE↗

Direct Observation of Two-Step, Stratified Crystallization and Morphology in Conjugated Polymer Thin Films

A two-step stratified crystallization process has been directly observed during cooling of poly(3-hexylthiophene) (P3HT) thin films of thickness h = 20-250 nm: a thin (<20 nm) layer at the free surface crystallizes ~25 °C higher than the bulk crystallization temperature (T C,bulk ), whereas the rest of the film (i.e. the underlayer) crystallizes near T C,bulk . In-situ measurements of films with and without a free surface unequivocally ascribe the high-temperature crystallization to a surface-induced process, which correlates with the formation of large birefringent structures and highly oriented edge-on crystallites at the air–polymer interface. In contrast, crystallization of the bulk-like underlayer leads to mostly edge-on-oriented crystallites in thinner films and becomes increasingly isotropic in thicker films. For h < 20 nm, free-surface effects dominate and only high-temperature crystallization is observed. These results highlight the potential of melt crystallization to tailor morphology and orientation across thin film thickness for specific electronic applications.

36 MATERIALS SCIENCE↗

Blending Compostable Plastics for Packaging Applications

Non-sustainable packaging materials (polymers) are a large portion of the increasing amount of plastic waste that become environmental pollutants. While many biodegradable or compostable polymers have been developed in recent years, most fail to compete with the non-sustainable polymers dominating the market, due to lack of certain desired properties, such as thermal (high melt temperature) and mechanical (high ductility) performance. For example, the popular compostable polymer polylactic acid (PLLA) has a high melt temperature but is very brittle. Another polymer, poly(d-valerolactone) (PVL) demonstrates great ductility but has a very low melt temperature. By blending PLLA and PVL, there is an opportunity to create a new biodegradable material with synergistic desired properties for packaging applications. In this study, we produce several (9) physical blends of PVL and PLLA with varying compositions of the two polymers while applying three different materials to make them more compatible (compatibilizers). We test the success of compatibilization by scanning electron microscopy (SEM), mechanic testing (strain at break) and differential scanning calorimetry (melting temperature). Overall, we highlight several promising materials with high compatibility and desired thermomechanical properties for sustainable packaging. Ideally, these materials could help mitigate future plastic pollution in Colorado and beyond.

blending↗

Side Chain Dynamics of Poly(norbornene)- g -Poly(propylene oxide) Bottlebrush Polymers

The segmental dynamics of the side chains of poly(norbornene)- g -poly(propylene oxide) (PNB- g -PPO) bottlebrush polymer in comparison to PPO is studied by quasi-elastic neutron scattering. Having experimental time and length scale information simultaneously allows to extract spatial information in addition to relaxation time. Tethering one end of the PPO side chain onto a stiff PNB backbone slows down the segmental relaxation, over the length and time scales investigated. The power law dependence of the relaxation time on the momentum transfer, Q , indicates a more heterogeneous relaxation pattern for the bottlebrush polymer, whereas the linear PPO has less deviations from a homogenous relaxation. Similar conclusions can be drawn from the time dependent mean square displacement, $\langle$ r 2 ( t )$\rangle$, and the non-Gaussian parameter, α 2 ( t ). Herein, the bottlebrush polymer shows a more restricted dynamics, whereas the linear PPO reaches $\langle$ r 2 ( t )$\rangle$∝ t 0.5 at the highest temperature. The deviations from Gaussian behavior are evident at the α 2 ( t ). Both samples show a decaying α 2 ( t ). Finally, the non-Gaussian parameter supports the results from the power law dependence of the relaxation times, with lower α 2 ( t ) values for PPO compared to those for PNB-g-PPO, pointing to less deviations from Gaussian behavior.

36 MATERIALS SCIENCE↗

Introducing Low-Cost Pyrazine Unit into Terpolymer Enables High-Performance Polymer Solar Cells with Efficiency of 18.23%

Recently, a random ternary copolymerization strategy has become a promising and efficient approach to develop high-performance polymer donors for polymer solar cells (PSCs). Here, in this study, a low-cost electron-withdrawing unit, 2,5-bis(4-(2-ethylhexyl)thiophen-2-yl)pyrazine (PZ-T), is incorporated into the polymer backbone of PM6 as the third component, and three D-A 1 -D-A 2 type terpolymers PMZ-10, PMZ-20, and PMZ-30 are synthesized by the random copolymerization strategy, with the PZ-T proportion of 10%, 20%, and 30%, respectively. The terpolymers exhibit downshifted highest occupied molecular orbital energy levels than PM6, which is beneficial for obtaining higher open-circuit voltage (V oc ) of the PSCs with the polymer as a donor. Importantly, the PSCs based on PMZ-10:Y6 demonstrate efficient exciton dissociation, higher and balanced electron/hole mobilities, desirable aggregation, and high power conversion efficiency of 18.23%, which is the highest efficiency among the terpolymer-based PSCs so far. The results indicate that the ternary copolymerization strategy with PZ-T as the second A-unit is an efficient approach to further improve the photovoltaic performance and reduce the synthetic cost of the D-A copolymer donors.

36 MATERIALS SCIENCE↗

Inline Rolling Shear Alignment: Deposition and Long-Range Order of Block Polymer Templates in a Fast, Single-Step Process

We report the first demonstration of a rapid, single-step technique to align block polymer, thin-film nanostructures that is amenable to continuous speeds ≥10 mm/s. This method, termed Inline Rolling Shear Alignment (IRSA), uses an elastomeric roller coupled with an electric hysteresis brake to shear films before the casting solvent fully evaporates, and it can enable high throughput, large-area manufacturing of patterns such as nanowire templates. IRSA is adaptable to various polymer systems including diblock and triblock polymers, and a post-shear annealing step can yield high-quality nanostructures with orientation parameters >0.99 and defect densities as low as 5 defect-pairs/μm 2 . To demonstrate the effectiveness of IRSA, platinum nanowires were produced from this rapid deposition and alignment approach using poly(styrene-b-2-vinylpyridine), followed by open-air, atmospheric-pressure plasma etching. Furthermore, this integrated concept, with 50x faster operation than existing processes, could be leveraged for cost-effective manufacturing of macroscopically aligned nanostructures in roll-to-roll systems.

36 MATERIALS SCIENCE↗

Carbohydrate-Containing Conjugated Polymers: Solvent-Resistant Materials for Greener Organic Electronics

Organic semiconducting polymers are exciting materials for electronic applications because of their good mechanical and optoelectronic properties. A major advantage of organic semiconductors is their solution processability. This allows access to a variety of simple and cost-effective device fabrication methods compared to the expensive, high-temperature processing methods required for silicon-based electronics. However, these materials often have low solubility, which limits their processing to toxic halogenated solvents. Also, their limited solubility often leads to interfacial mixing during device fabrication. Herein, this work explores the incorporation of environmentally friendly carbohydrate side chains in conjugated polymers to enhance processability in eco-friendly solvents. Moreover, a mild postprocessing treatment was designed to enable solvent resistance. Isoindigo-based polymers with varied ratios of acetyl-protected galactose side chains were synthesized to improve solubility in o-anisole in the protected state, while inducing solvent resistance through intramolecular hydrogen bonding in the deprotected state. Solvent resistance was confirmed both visually upon submersion in various solvents and using UV–visible spectroscopy. Importantly, the mild basic treatment to achieve solvent resistance has no negative impact on the electronic performance of these materials in organic field-effect transistors, even after subsequent submersion in various solvents, making them a valuable platform for the production of green processable multilayer electronics.

36 MATERIALS SCIENCE↗

Highly stretchable polymer semiconductor thin films with multi-modal energy dissipation and high relative stretchability

Abstract Stretchable polymer semiconductors (PSCs) have seen great advancements alongside the development of soft electronics. But it remains a challenge to simultaneously achieve high charge carrier mobility and stretchability. Herein, we report the finding that stretchable PSC thin films (<100-nm-thick) with high stretchability tend to exhibit multi-modal energy dissipation mechanisms and have a large relative stretchability ( rS ) defined by the ratio of the entropic energy dissipation to the enthalpic energy dissipation under strain. They effectively recovered the original molecular ordering, as well as electrical performance, after strain was released. The highest rS value with a model polymer (P4) exhibited an average charge carrier mobility of 0.2 cm 2 V −1 s −1 under 100% biaxial strain, while PSCs with low rS values showed irreversible morphology changes and rapid degradation of electrical performance under strain. These results suggest rS can be used as a parameter to compare the reliability and reversibility of stretchable PSC thin films.

36 MATERIALS SCIENCE↗

Role of Bottlebrush Additives on the Structure of Block Copolymers in the Bulk and Thin Films

Blending block copolymers (BCP) with additives is a useful approach for controlling BCP morphology and properties. In athermal systems, blends of BCPs with polymer additives having very high molecular (M n ) mass generally result in macrophase separation. Bottlebrush polymers, which consist of a linear backbone and grafted side chains, present an interesting alternative where the overall M n of the system can be very large but the low M n side chains may drive miscibility with the BCP. Here, in this study, a bottlebrush with a polynorbornene backbone and polystyrene (PS) side chains is blended with PS-b-poly(methyl methacrylate) (PS-b-PMMA) of varying M n , and the resulting morphologies are examined in both the bulk and thin films. Two different M n of PS-b-PMMA were used in the bulk study, and the analysis of small-angle X-ray scattering data shows that the blends were miscible and lamellar at all concentrations. This deviates from reference series of both low and high M n linear polymer additives, which either showed morphological transitions from lamellae to cylinders (low M n ) or were immiscible at all mass fractions studied (high M n ). The relative molecular mass of the side chain (N SC ) and the corresponding component in the BCP (N A ) dictate the distribution of the bottlebrush throughout the BCP, analogous to BCP/linear blends or grafted nanoparticles in a homopolymer matrix. The studies on thin films show a thickness dependence for bottlebrush mass fractions at or above 0.17, a behavior which may be driven by conformational changes of the bottlebrush upon confinement.

36 MATERIALS SCIENCE↗

Role of aggregates and microstructure of mixed-ionic–electronic-conductors on charge transport in electrochemical transistors

Synthetic efforts have delivered a library of organic mixed ionic–electronic conductors (OMIECs) with high performance in electrochemical transistors. The most promising materials are redox-active conjugated polymers with hydrophilic side chains that reach high transconductances in aqueous electrolytes due to volumetric electrochemical charging. Current approaches to improve transconductance and device stability focus mostly on materials chemistry including backbone and side chain design. However, other parameters such as the initial microstructure and microstructural rearrangements during electrochemical charging are equally important and are influenced by backbone and side chain chemistry. In this study, we employ a polymer system to investigate the fundamental electrochemical charging mechanisms of OMIECs. We couple in situ electronic charge transport measurements and spectroelectrochemistry with ex situ X-ray scattering electrochemical charging experiments and find that polymer chains planarize during electrochemical charging. Our work shows that the most effective conductivity modulation is related to electrochemical accessibility of well-ordered, interconnected aggregates that host high mobility electronic charge carriers. Electrochemical stress cycling induces microstructural changes, but we find that these aggregates can largely maintain order, providing insights on the structural stability and reversibility of electrochemical charging in these systems. Finally, this work shows the importance of material design for creating OMIECs that undergo structural rearrangements to accommodate ions and electronic charge carriers during which percolating networks are formed for efficient electronic charge transport.

36 MATERIALS SCIENCE↗

Real-time cure monitoring of fiber-reinforced polymer composites using infrared thermography and recursive Bayesian filtering

Despite the desirable characteristics of fiber-reinforced polymer (FRP) composites, their utilization in high volume production industries is limited by a lack of efficient manufacturing techniques. Monitoring the curing process of these composites can help with improving the quality and efficiency of the manufacturing process. This article discusses a method that uses Kalman-filter-based fusion of the information obtained from infrared thermography (surface temperature measurements) and a heat conduction model to estimate degrees of cure and internal temperatures of curing FRP composite parts in real time. The effectiveness of the methodology is demonstrated by successfully monitoring the curing of an FRP composite part in a laboratory experiment. Finally, the proposed methodology is a crucial step towards identifying anomalies in the curing process that negatively impact the quality of FRP composite parts.

36 MATERIALS SCIENCE↗

Untangling the threads of cellulose mercerization

Naturally occurring plant cellulose, our most abundant renewable resource, consists of fibers of long polymer chains that are tightly packed in parallel arrays in either of two crystal phases collectively referred to as cellulose I. During mercerization, a process that involves treatment with sodium hydroxide, cellulose goes through a conversion to another crystal form called cellulose II, within which every other chain has remarkably changed direction. We designed a neutron diffraction experiment with deuterium labelling in order to understand how this change of cellulose chain direction is possible. Here we show that during mercerization of bacterial cellulose, chains fold back on themselves in a zigzag pattern to form crystalline anti-parallel domains. This result provides a molecular level understanding of one of the most widely used industrial processes for improving cellulosic materials.

59 BASIC BIOLOGICAL SCIENCES↗

Effect of Co 2 N impurity on the superconducting properties of δ-MoN thin films grown by polymer assisted deposition

We report the effect of Co 2 N impurity on the superconducting properties of δ-MoN thin films grown by polymer-assisted deposition on c-cut sapphire (Al 2 O 3 ). The films show a superconducting transition temperature of 10.4 K and an upper critical field H c2 (0) perpendicular to the film surface around 3 T. The latter corresponds to a relatively large coherence length ξ, which enhances the two-dimensional limit when the magnetic field is applied parallel to the film surface. In comparison with pure δ-MoN films, the inclusion of Co 2 N impurity in the δ-MoN films could significantly modify the critical current density at the vortex-free state. In conclusion, the ability to tune the superconducting properties of metal-nitride superconductors by introducing chemically and structurally compatible impurity may find potential applications for superconducting single-photon detectors.

36 MATERIALS SCIENCE↗

Robust fluorescent calcium coordination polymers as Cu 2+ sensors with high sensitivity and fast response

A three-dimensional (3D) and highly fluorescent calcium-based coordination polymer (Ca-CP) has been synthesized and structurally characterized. Furthermore, built on a strongly fluorescent (FL) chromophore ligand, [Ca(H 2 tcbpe)(H 2 O) 2 ] (1) (H 4 tcbpe = 4',4''',4''''',4'''''''-(ethene-1,1,2,2-tetrayl)tetrakis(([1,1'-biphenyl]-4-carboxylic acid))) is highly luminescent. Photoluminescence (PL) studies indicate that 1 undergoes a bathochromic shift in emission energy from blue to green color upon outgassing or under mechanic force. Notably, 1 exhibits selective FL sensing for Cu 2+ ions with a detection limit (LOD) of 0.064 ppm, far below the U.S. WHO and EPA standard for drinking water. Detailed investigation of the sensing mechanism reveals that uncoordinated COO– groups in 1 play a major role in recognizing Cu 2+ ions.

36 MATERIALS SCIENCE↗