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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Tailoring Polymer Colloids Derived Porous Carbon Spheres Based on Specific Chemical Reactions

Porous carbon spheres derived from polymer colloids with regular geometry, monodispersed morphology, well-controlled contents and structures play important roles in many areas of application, such as energy storage/conversion, gas adsorption/separation, catalysis, and chemo-photothermal therapy. Suitable polymerization reaction and synthetic strategy are both critical for the obtainment of stable polymer colloids as carbon precursors. Basic polymerization reactions are the cornerstones of synthetic strategies, which directly provides the direct molecular-based design of functionalized polymer/ carbon spheres. Thus, this progress report mainly focuses on the summary of suitable polymerization reactions for colloidal polymer derived porous carbon spheres. Recent advances in the synthetic strategies and applications are also discussed, including their corresponding polymerization reactions. Finally, the perspectives for the development of polymer derived porous carbon spheres are provided based on the controlled synthesis of polymer colloids and optimization over the carbonization process to achieve highly functionalized carbon spheres for practical applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-Coupling

Thin films of poly(arylene ethynylene)-conjugated polymers, including low-energy-gap donor–acceptor polymers, can be prepared via stepwise polymerization utilizing surface-confined Sonogashira cross-coupling. This robust and efficient polymerization protocol yields conjugated polymers with a precise molecular structure and with nanometer-level control of the organization and the uniform alignment of the macromolecular chains in the densely packed film. In addition to high stability and predictable and well-defined molecular organization and morphology, the surface-confined conjugated polymer chains experience significant interchain electronic interactions, resulting in dominating intermolecular π-electron delocalization which is primarily responsible for the electronic and spectroscopic properties of polymer films. The fluorescent films demonstrate remarkable performance in chemosensing applications, showing a turn-off fluorescent response on the sub-ppt (part per trillion) level of nitroaromatic explosives in water. This unique sensitivity is likely related to the enhanced exciton mobility in the uniformly aligned and structurally monodisperse polymer films.

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

Bimolecular crystal instability and morphology of bulk heterojunction blends in organic and perovskite solar cells

The performance of polymer:fullerene bulk heterojunction (BHJ) solar cells is significantly influenced by the morphology of electron donor and acceptor blends under the premise that electronic structure is complimentary regarding donor and acceptor materials. There are many cases where intimate mixing of donor and acceptor perturbs the electronic structure, which fundamentally changes the transport and photovoltaic characteristics. In this work, we present the bimolecular crystal packing of polymers and fullerenes, and investigate the correlation between device performance and structural details. We find that bimolecular crystallization can reorganize polymer chain packing, leading to poor electron transport and device performance. The size compatibility and the passivation of entropy penalty led to cocrystallization instability, which was clearly seen by in situ GIWAXS data. PC 61 BM is found to intercalate into side chains of PQT by reorganizing both PQT and PC 61 BM, forming stable, highly ordered bimolecular crystals. The poor electron transport in bimolecular crystal domain could account for the poor device performance in both perovskite and organic solar cells. Bis-PC 61 BM, on the other hand, only forms loosely packed aggregates in solution, and then rapidly phase separated into large domains with an edge-on interfacial orientation and performed poorly in solar cells.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Efficient, Thermally Stable, and Mechanically Robust All-Polymer Solar Cells Consisting of the Same Benzodithiophene Unit-Based Polymer Acceptor and Donor with High Molecular Compatibility

All-polymer solar cells (all-PSCs) are a highly attractive class of photovoltaics for wearable and portable electronics due to their excellent morphological and mechanical stabilities. Recently, new types of polymer acceptors (P A s) consisting of non-fullerene small molecule acceptors (NFSMAs) with strong light absorption have been proposed to enhance the power conversion efficiency (PCE) of all-PSCs. However, polymerization of NFSMAs often reduces entropy of mixing in PSC blends and prevents the formation of intermixed blend domains required for efficient charge generation and morphological stability. One approach to increase compatibility in these systems is to design P A s that contain the same building blocks as their polymer donor (P D ) counterparts. Here, a series of NFSMA-based P A s [P(BDT2BOY5-X), (X = H, F, Cl)] are reported, by copolymerizing NFSMA (Y5-2BO) with benzodithiophene (BDT), a common donating unit in high-performance P D s such as PBDB-T. All-PSC blends composed of PBDB-T PD and P(BDT2BOY5-X) P A show enhanced molecular compatibility, resulting in excellent morphological and electronic properties. Specifically, PBDB-T:P(BDT2BOY5-Cl) all-PSC has a PCE of 11.12%, which is significantly higher than previous PBDB-T:Y5-2BO (7.02%) and PBDB-T:P(NDI2OD-T2) (6.00%) PSCs. Additionally, the increased compatibility of these all-PSCs greatly improves their thermal stability and mechanical robustness. For example, the crack onset strain (COS) and toughness of the PBDB-T:P(BDT2BOY5-Cl) blend are 15.9% and 3.24 MJ m -3 , respectively, in comparison to the PBDB-T:Y5-2BO blends at 2.21% and 0.32 MJ m -3 .

14 SOLAR ENERGY↗
NASA NTRS1997

Process for controlling morphology and improving thermal-mechanical performance of high performance interpenetrating and semi-interpenetrating polymer networks

In the process of the present invention, a non-polar, aprotic solvent is removed from an oligomer/polymer solution by freeze-drying in order to produce IPNs and semi-IPNs. By thermally quenching the solution to a solid in a short length of time, the size of the minor constituent-rich regions is greatly reduced as they are excluded along with the major constituent from the regions of crystallizing solvent. The use of this process sequence of controlling phase morphology provides IPNs and semi-IPNs with improved fracture toughness, microcracking resistance, and other physical-mechanical properties as compared to IPNs and semi-IPNs formed when the solvent is evaporated rather than sublimed.

Pater, Ruth H.↗
NASA NTRS1966

Morphology of PET, part II

Morphology of polyethylene terephthalate studied, emphasizing morphology of glass and effect of strain induced crystallization of polymer

POLYETHYLENE TEREPHTHALATE↗
DOE OSTI2021

Influence of side-chain isomerization on the isothermal crystallization kinetics of poly(3-alkylthiophenes)

Flexible alkyl side chain in conjugate polymers (CPs) improves the solubility and promotes solution processability, in addition, it affects interchain packing and charge mobilities. Despite the well-known charge mobility and morphology correlation for these semi-crystalline polymers, there is a lack of fundamental understanding of the impact of side chain on their crystallization kinetics. In the present work, isothermal crystallization of five poly(3-alkylthiophene-2,5-diyl) (P3ATs) with different side-chain structures were systematically investigated. To suppress the extremely fast crystallization and trap the sample into amorphous glass, an advanced fast scanning chip calorimetry technique, which is able to quench the sample with few to tens thousands of K/s, was applied. Results show that the crystallization of P3ATs was greatly inhibited after incorporation of branched side chains, as indicated by a dramatic up to six orders of magnitude decrease in the crystallization rate. The suppressed crystallization of P3ATs were correlated with an increased π–π stacking distance due to unfavorable side-chain steric interaction. This research provides a pathway to use side-chain engineering to control the crystallization behavior for CPs, thus to control device performance.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Tunable structure and reinforcement of polyvinyl alcohol (PVA) hydrogels using fungal chitin particles

Polysaccharides, including chitin, are one of the most abundant biopolymers in nature and are increasingly recognized as a sustainable alternative to petroleum-derived plastics and synthetic fillers in polymer composites. Traditionally sourced from crustacean shells, chitin offers mechanical strength and biocompatibility with limitations also in processability and functionality. Fungal-derived chitin material represents a promising alternative, with advantages including scalable fermentation on low-cost substrates, absence of shellfish allergens, and tunable molecular architectures that vary by species, developmental stage, and growth environment. Here, in this study, we systematically examined chitinous materials obtained from taxonomically and functionally distinct fungi, Laccaria bicolor, Trichoderma reesei and Rhizopus oryzae, to assess their structural, chemical, and morphological properties as reinforcement agents in polymer composites. Mild alkaline pretreatment was employed to obtain mycelium chitin particles, thereby improving accessibility to chitin and co-occurring β-D-glucans while maintaining microparticle integrity. Comprehensive FTIR and solid-state NMR analyses revealed species-specific differences in chemical composition and microstructure, with R. oryzae exhibiting a unique spectral signature. These fungal-derived chitin were then incorporated into poly(vinyl alcohol) (PVA) hydrogels, where they acted as reinforcing fillers without the need for additional chemical crosslinkers. Comparative evaluation of hydrogel properties demonstrated that fungal chitin significantly enhanced mechanical performance, with all mycelium fillers mitigating the water weakening in PVA hydrogels. R. oryzae-derived composites tripled the hydrogel tensile strength while the submicron fibrous morphology in L. bicolor contributes to over 45 % tensile improvement in dry PVA composites. Our findings highlight the potential of fungal biomass as a tunable, sustainable platform for producing chitin-based reinforcing agents.

Chitin↗
DOE OSTI2024

The Impact of Lithium Anode Interface on Capacity Fade in Polymer Electrolyte-Based Solid-State Batteries

This study investigates the Li stripping-plating morphology and failure mechanisms in full cells consisting of a solid polymer electrolyte (SPE) with two commercial Li anodes: Li chip and Li foil. The primary identified failure mechanism of the SPE cell is capacity fade, regardless of the Li manufacturer. While the cathode’s role in capacity fade is evident, the Li anode significantly influences cycling performance, with Li foil cells cycling 50% longer than Li chip cells, a statistical difference. Further, post-mortem scanning electron microscopy and X-ray photoelectron spectroscopy results attribute the Li chip’s faster capacity fade to a loss of contact and continuous growth of the solid electrolyte interphase (SEI). Conversely, Li foil maintains consistent contact with the solid polymer, displaying a thin and stable SEI. Additionally, failure mechanisms between a gel electrolyte in previous work and the dry SPE are compared.

25 ENERGY STORAGE↗
NASA NTRS2002

Morphologies, Processing and Properties of Ceramic Foams from Pre-Ceramic Foams from Pre-Ceramic Polymer Routes

The current research is focused on processing ceramic foams that have potential as a thermal protection material. Ceramic foams with different architectures were formed from the pyrolysis of pre-ceramic polymers at 1200 C in different atmospheres. In some systems a sacrificial polyurethane was used as the blowing agent. We have also processed foams using sacrificial fillers to introduce controlled cell sizes. Each sacrificial filler or blowing agent leads to a unique morphology. The effect of different fillers on foam morphologies will be presented. The presentation will also focus on characterization of these foams in terms of mechanical and thermal properties. Foams processed using these approaches having bulk densities ranging from 0.15 to 0.9 g per cubic centimeter and a cell sizes from 5 to 500 micrometers. Compression strengths ranged from 2 to 7 MPa for these materials.

Stackpoole, Mairead↗
DOE OSTI2021

Polymer intercalation synthesis of glycoboehmite nanosheets

In this work, novel materials based on the aluminum oxyhydroxide boehmite phase were prepared using a glycothermal reaction in 1,4-butanediol. Under the synthesis conditions, the atomic structure of the boehmite phase is altered by the glycol solvent in place of the interlayer hydroxyl groups, creating glycoboehmite. The structure of glycoboehmite was examined in detail to determine that glycol molecules are intercalated in a bilayer structure, which would suggest that there is twice the expansion identified previously in the literature. This precursor phase enables synthesis of two new phases that incorporate either polyvinylpyrrolidone or hydroxylpropyl cellulose nonionic polymers. These new materials exhibit changes in morphology, thermal properties, and surface chemistry. All the intercalated phases were investigated using PXRD, HRSTEM, SEM, FT-IR, TGA/DSC, zeta potential titrations, and specific surface area measurement. These intercalation polymers are non-ionic and interact through wetting interactions and hydrogen bonding, rather than by chemisorption or chelation with the aluminum ions in the structure.

36 MATERIALS SCIENCE↗
DOE OSTI2023

New Chemical Dopant and Counterion Mechanism for Organic Electrochemical Transistors and Organic Mixed Ionic–Electronic Conductors

Abstract Organic mixed ionic–electronic conductors (OMIECs) have varied performance requirements across a diverse application space. Chemically doping the OMIEC can be a simple, low‐cost approach for adapting performance metrics. However, complex challenges, such as identifying new dopant materials and elucidating design rules, inhibit its realization. Here, these challenges are approached by introducing a new n‐dopant, tetrabutylammonium hydroxide (TBA‐OH), and identifying a new design consideration underpinning its success. TBA‐OH behaves as both a chemical n‐dopant and morphology additive in donor acceptor co‐polymer naphthodithiophene diimide‐based polymer, which serves as an electron transporting material in organic electrochemical transistors (OECTs). The combined effects enhance OECT transconductance, charge carrier mobility, and volumetric capacitance, representative of the key metrics underpinning all OMIEC applications. Additionally, when the TBA + counterion adopts an “edge‐on” location relative to the polymer backbone, Coulombic interaction between the counterion and polaron is reduced, and polaron delocalization increases. This is the first time such mechanisms are identified in doped‐OECTs and doped‐OMIECs. The work herein therefore takes the first steps toward developing the design guidelines needed to realize chemical doping as a generic strategy for tailoring performance metrics in OECTs and OMIECs.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Stretchable Photodiodes with Polymer-Engineered Semiconductor Nanowires for Wearable Photoplethysmography

Healthcare systems worldwide have been stressed to provide sufficient resources to serve the increasing and aging population in our society. The situation became more challenging at the time of pandemic. Technology advancement, especially the adoption of wearable health monitoring devices, has provided an important supplement to current clinical equipment. Most health monitoring devices are rigid, however, human tissues are soft. Such a difference has prohibited intimate contact between the two and jeopardized wearing comfortableness, which hurdles measurement accuracy especially during longtime usage. Here, in this work, we report a soft and stretchable photodiode that can conformally adhere onto the human body without any pressure and measure cardiovascular variables for an extended period with higher reliability than commercial devices. The photodiode used a composite light absorber consisting of an organic bulk heterojunction embedded into an elastic polymer matrix. It is discovered that the elastic polymer matrix not only improves the morphology of the bulk heterojunction for obtaining the desired mechanical properties but also alters its electronic band structure and improves the electrical properties that lead to a reduced dark current and enhanced photovoltage in the stretchable photodiode. The work has demonstrated high fidelity measurements and longtime monitoring of heat rate variability and oxygen saturation, potentially enabling next-generation wearable photoplethysmography devices for point-of-care diagnosis of cardiovascular diseases in a more accessible and affordable way.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Aqueous Polymer Modification of Cellulose Nanofibrils by Grafting‐Through a Reactive Methacrylate Group

Abstract Modifying the surface of cellulose nanofibrils (CNFs) produced by mechanical refinement with a variety of polymer functional groups in an entirely water‐based system is challenging because only surface hydroxyl groups are accessible. To address this limitation, an entirely water‐based, polymer modification scheme is developed. CNFs are functionalized with a reactive methacrylate functional group followed by subsequent grafting‐through polymerization. This modification worked with a variety of water‐soluble and water‐insoluble (meth)acrylates and (meth)acrylamides, grafting up to 45 wt% polymer on to the CNFs. The reaction conditions introducing the methacrylate functional group are adjusted to vary the degree of functionality. Soxhlet extraction of modified samples demonstrates that the reactive methacrylate group is necessary to facilitate polymer grafting. The degree of functionalization of the polymers is studied via quantitative transmission IR spectroscopy and the morphology of the resulting cellulose nanofibrils is studied via a combination of optical, scanning electron, and atomic force microscopy. High levels of polymer modification do not significantly affect the micrometer‐scale fibril morphology.

Kelly, Peter V.↗
DOE OSTI2024

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↗
DOE OSTI2020

Uncovering the Relationship between Diameter and Height of Electrodeposited Lithium Protrusions in a Rigid Electrolyte

A promising approach for enabling rechargeable batteries with significantly higher energy densities than current lithium-ion batteries is by deploying lithium-metal anodes. However, the growth of lithium protrusions during charging presents significant challenges. Since these protrusions are often branched and filamentous in conventional liquid electrolytes, this problem is referred to in the literature as the “dendrite problem”. While solid electrolytes have the potential to solve this problem, protrusions grow in all electrolytes when the current density exceeds a critical value. Fundamentally understanding the formation is necessary to develop a rational approach for increasing the critical current density, but it is challenging due to the complex interplay between electrochemical and material properties. The diameters and heights of protrusions on lithium-metal anodes stabilized by a rigid block copolymer electrolyte were measured in situ by synchrotron hard X-ray microtomography. The diameter of the shorting protrusions increased linearly with increasing electrolyte thickness. Further, a universal linear relationship between protrusion height and diameter of both shorting and non-shorting protrusions was observed. A model based on the concentrated solution theory was used to establish the electrochemical and mechanical sources for our observations. Here, the computational analysis indicates that elastic and plastic deformation of both the lithium metal and the polymer are important to describe protrusion growth. Both stress-induced current density effects due to the deformation of the electrolyte near the protrusion and plastic deformation of lithium metal combine to give the counterintuitive result: the fastest-growing protrusions have the largest diameter.

25 ENERGY STORAGE↗
NASA NTRS2003

Ceramic Spheres From Cation Exchange Beads

Porous ZrO2 and hollow TiO2 spheres were synthesized from a strong acid cation exchange resin. Spherical cation exchange beads, polystyrene based polymer, were used as a morphological-directing template. Aqueous ion exchange reaction was used to chemically bind (ZrO)(2+) ions to the polystyrene structure. The pyrolysis of the polystyrene at 600 C produces porous ZrO2 spheres with a surface area of 24 sq m/g with a mean sphere size of 42 microns. Hollow TiO2 spheres were synthesized by using the beads as a micro-reactor. A direct surface reaction - between titanium isopropoxide and the resin beads forms a hydrous TiO2 shell around the polystyrene core. The pyrolysis of the polystyrene core at 600 C produces hollow anatase spheres with a surface area of 42 sq m/g with a mean sphere size of 38 microns. The formation of ceramic spheres was studied by XRD, SEM and B.E.T. nitrogen adsorption measurements.

Dynys, F. W.↗