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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 1,387 records · Page 77
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Mixed interlayers at the interface between PEDOT:PSS and conjugated polymers provide charge transport control

Poly(3,4-ethylenedioxythiophene)-poly(styrenesulphonate) (PEDOT:PSS) is the most used organic hole injecting or hole transporting material. The hole carrying matrix PEDOT is highly doped by the acidic dopant PSS. When coated onto a substrate, PEDOT:PSS makes a highly uniform conductive layer and a thin (<5 nm) overlayer of PSS covers the air interface. Semiconducting polymer layers for organic photovoltaics or light emitting diodes are coated on top. In this article, we demonstrate that the PSS layer will mix with almost all conjugated polymers upon thermal annealing. Depending on the Fermi energy of the polymer an electrochemical reaction can take place, p-type doping the polymer at the interface between the PEDOT:PSS and the semiconducting polymer. We use chemical and spectroscopic analysis to characterize the polymer/PSS interlayer. We show that the stable and insoluble interlayer has a great effect on the charge injection and extraction from the interface. Lastly we demonstrate and electronically model organic photovoltaic devices that are fabricated using these mixed interlayers.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Naphthodipyrrolidone (NDP) based conjugated polymers with high electron mobility and ambipolar transport properties

Two novel donor–acceptor π-conjugated polymers based on naphthodipyrrolidone (NDP) were synthesized and characterized. The polymers possess low band gaps and suitable molecular orbital levels as ambipolar semiconductors. The thin film organic field effect transistor of NDP polymers exhibited ambipolar transport properties with a high electron mobility up to 0.67 cm 2 V –1 s –1 . The grazing-incidence wide-angle X-ray scattering (GIWAXS) studies demonstrated that the polymer molecules pack into a long-range-ordered lamellar structure with isotropically oriented crystalline domains. Thermal annealing promoted edge-on lamellar stacking as evidenced by the increased diffraction intensity along the out-of-plane direction. In conclusion, the polymer with NDP and bithiophene units achieved the best edge-on lamellar stacking after thermal annealing, which yielded the best electron transport performance in this work.

36 MATERIALS SCIENCE↗
DOE OSTI2018

A vinyl flanked difluorobenzothiadiazole–dithiophene conjugated polymer for high performance organic field-effect transistors

Fluorine containing conjugated polymers have been widely applied in high performance organic solar cells, but their use in field-effect transistors is still quite limited. In this work, a conjugated polymer PTFBTV based on difluorobenzothiadiazole (DFBT) and dithiophene was synthesized, utilizing multiple vinylene as linkers. The polymer exhibits a relatively high hole mobility up to 2.0 cm 2 V -1 s -1 compared with the reported DFBT–oligothiophene based polymers, yet its structural complexity is much simpler. The polymer thin film exhibits a typical ‘face on’ molecular orientation. A single crystal of its monomer revealed a non-covalent intramolecular contact between fluorine and the neighbouring proton, which strengthens the backbone co-planarity. Meanwhile an intermolecular F∙∙∙F contact was also observed, which might cause rather scattered lamellar crystallinity for PTFBTV in the solid state.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Study of segmental dynamics and ion transport in polymer–ceramic composite electrolytes by quasi-elastic neutron scattering

Composite electrolytes composed of a polymer electrolyte and an ion-conducting ceramic electrolyte are promising in fulfilling the requirements for a stable lithium metal anode. In this work, we identify the effects of the surface of a lithium-ion-conducting ceramic, the Ohara LICGC™ ceramic, on the segmental dynamics and ionic conductivity of polymer electrolyte consisting of poly(ethylene oxide) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Using quasi-elastic neutron scattering, we study the segmental motion of PEO chains under the confinement of LiTFSI salt and Ohara ceramic, in their melt state (363 K). We compare the relaxation time, τ, and the monomeric friction coefficient, ζ, of four samples: neat PEO, PEO + Ohara ceramic, PEO + LiTFSI and PEO + LiTFSI + Ohara ceramic. In the absence of LiTFSI, Ohara ceramic posed negligible change in the segmental dynamics of PEO. In contrast, with the presence of LiTFSI, Ohara ceramic slowed down the segmental motion of PEO chains by ~60% compared to neat PEO + LiTFSI. The intrinsic ionic conductivity of the polymer phase in the composite decreased by ~30% compared to the neat polymer electrolyte. The underpinnings of these results may be that polymer chains in the vicinity of the ceramic surface are less mobile due to coordination with surface bound lithium ions.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Tunable thermal conductivity of π-conjugated two-dimensional polymers

Two-dimensional (2D) polymers are organic analogues of graphene. Compared to graphene, 2D polymers offer a higher degree of tunability in regards to structure, topology, and physical properties. The thermal transport properties of 2D polymers play a crucial role in their applications, yet remain largely unexplored. Using the equilibrium molecular dynamics method, we study the in-plane thermal conductivity of dubbed porous graphene that is comprised of π-conjugated phenyl rings. In contrast to the conventional notion that π-conjugation leads to high thermal conductivity, we demonstrate, for the first time, that π-conjugated 2D polymers can have either high or low thermal conductivity depending on their porosity and structural orientation. The underlying mechanisms that govern thermal conductivity were illustrated through phonon dispersion. The ability to achieve two orders of magnitude variance in thermal conductivity by altering porosity opens up exciting opportunities to tune the thermal transport properties of 2D polymers for a diverse array of applications.

Chemistry↗
DOE OSTI2018

Engineering the anchoring behavior of nematic liquid crystals on a solid surface by varying the density of liquid crystalline polymer brushes

Controlling the orientation of liquid crystal (LC) molecules towards contacting surfaces is a crucial requirement for the development of LC displays and passive electro-optical devices. Up to now, research has been focused on photo-responses of a LC azobenzene polymer system to obtain either planar or homeotropic orientation of LCs. It remains a challenge, however, to tune the polar angle of LC molecules on the solid surface and gain more insights about the polymer chain conformation extending in LC medium. Here, we deposit a liquid crystalline side chain polymer brush, poly(6-(4-methoxy-azobenzene-4'-oxy)hexyl methacrylate) (PMMAZO), onto the solid surface with film thickness varying between ~3 nm and 13 nm; therefore, the grafting density of the brush layer ranges from 0.0219 to 0.0924 chains per nm 2 . When LCs are confined in hybrid cells with a top surface eliciting uniform homeotropic anchoring and a bottom surface covered by the PMMAZO brush, the out-of-plane polar angle of 4-pentyl-4'-cyanobiphenyl (5CB) on the brush layer gradually changes from ~0° to ~62° by simply increasing the grafting brush density. The surface forces apparatus (SFA) measurement is used to determine 5CB as a good solvent for the PMMAZO brush and understand the relationship between the chain conformation in 5CB and the anchoring behavior of LC molecules on the polymer brush layer. Here, for high grafting density, the polymer chain in 5CB extends significantly away from the substrate, making the side chain mesogens on average almost parallel to the substrate; for the low-density case, the main chain extends in the narrow region around the surface for aligning the mesogens perpendicular to the substrate.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Influence of dopant size and electron affinity on the electrical conductivity and thermoelectric properties of a series of conjugated polymers

Here, chemical doping is widely used to manipulate the electrical and thermoelectric properties of organic semiconductors, yet intelligent design of polymer–dopant systems remains elusive. It is challenging to predict the electrical and thermoelectric properties of doped organic semiconductors due to the large number of variables impacting these properties, including film morphology, dopant and polymer energetics, dopant size, and degree of polaron delocalization. Herein, a series of dopants with varying sizes and electron affinities (EAs) are combined with polymers of differing ionization energies (IEs) to investigate how the difference between polymer IE and dopant EA influences the doping efficiency and electrical conductivity, and how the dopant size influences the thermoelectric properties. Our experiments demonstrate that at low doping levels the doping efficiency strongly depends on the difference between the polymer IE and dopant EA; the effectiveness of doping on increasing electrical conductivity drastically decreases at high loadings for the molybdenum dithiolene complexes, while FeCl 3 remains effective at high loadings; and the large molybdenum complexes lead to more delocalized polarons as compared to FeCl 3 . To take advantage of the complementary doping characteristics of the molybdenum complexes and FeCl 3 , both dopants are employed simultaneously to reach high power factors at relatively low dopant concentrations.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Polar polymer–solvent interaction derived favorable interphase for stable lithium metal batteries

Lithium metal has long been regarded as one of the most promising anode materials for future rechargeable batteries. However, the severe reaction of Li with carbonate electrolytes and the rapid growth of Li-dendrites at high current densities hinder its practical application in Li-metal batteries. In this work, we report a polar polymer protective layer to suppress highly corrosive cyclic carbonates by tuning polymer–solvent interactions. The C≡N groups of polyacrylonitrile (PAN) polymer chains in the polar polymer network can effectively reduce high reactivity of the C=O groups of carbonate solvents leading to a stable solid electrolyte interphase (SEI) layer with higher inorganic components. In situ optical and electron microscopes demonstrate that the polar polymer network effectively restrained the formation and growth of Li-dendrites, which helps to stabilize the plating/stripping behavior of Li in a symmetric Li|Li cell and a Li|LiNi 1/3 Co 1/3 Mn 1/3 O 2 cell. This study provides a useful perspective of controlling electrolyte coordination to form a stable SEI layer in carbonate electrolytes for Li-metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2019

Structure-performance correlations of cross-linked boronic acid polymers as adsorbents for recovery of fructose from glucose–fructose mixtures

Recovery of bio-oxygenates from reaction mixtures is one of the major challenges for future bio-refineries. Isolation of fructose produced by isomerization of glucose presents a typical example at a very early stage of the value chain. Here, we propose to recover fructose from a solution containing a mixture of glucose and fructose by adsorption on polymers bearing phenylboronate moieties. p-Vinylphenylboronic acid was polymerized with various cross-linkers, namely polar aliphatic, low-polarity aliphatic, and aromatic. The cross-linker content was in the range 5–40 mol%. The polymers exhibit high capacities for fructose, with a maximum loading of up to 1 mol Fru mol B -1 . Fructose loading depends significantly on the length and content of cross-linker, as well as pre-treatment of the polymer. In general, the maximum fructose capacity correlates with the swelling ability of the polymers, since phenylboronate moieties become available for adsorption upon swelling. In contrast, maximum glucose loadings are much lower, in the range 0.1–0.3 mol Glu mol B -1 , and depend only slightly on the type of cross-linker. The structures of the glucose and fructose complexes and the kinetics of their uptake were studied by in situ MAS NMR. Efficient desorption of fructose was observed in acidic medium, and more importantly, using CO 2 . The structures of the polymers after repeated adsorption and desorption remain unchanged, as confirmed by solid-state NMR. Adsorption-assisted isomerization of glucose catalyzed by soluble carbonates was also studied. A 56% yield of fructose was achieved after 8 successive cycles of reaction and adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Long-term chemothermal stability of delithiated NCA in polymer solid-state batteries

Here, the long-term chemothermal stability of chemically delithiated Li 0.3 Ni 0.8 Co 0.15 Al 0.05 O 2 (Li 0.3 NCA) was systematically investigated at relevant operating temperatures of polymer solid-state batteries using ex situ synchrotron-based hard and soft X-ray absorption spectroscopy. The reduction of nickel on the surface, subsurface, and in the bulk of secondary NCA particles was studied and directly related to aging time, temperature, the presence of polymeric electrolyte (poly(ethylene oxide) or polycaprolactone), and lithium salt (lithium tetrafluoroborate or lithium bis(trifluoromethanesulfonyl)imide). Depending on the polymer and/or lithium salt accompanying the delithiated Li 0.3 NCA, reduction of nickel at the surface, subsurface, and bulk occurs to varying extents, starting at the surface and propagating into the bulk material. Our findings predict how degradation (reduction of nickel) is strongly correlated to temperature, time, and the presence of blended polymer and/or lithium salt in the cathode. The relative stability of the NCA material in cathodes having different polymer and lithium salt combinations identified in the ex situ spectroscopy study is directly demonstrated in solid-state polymer batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Dielectric polymers for high-temperature capacitive energy storage

Polymers are the preferred materials for dielectrics in high-energy-density capacitors. The electrification of transport and growing demand for advanced electronics require polymer dielectrics capable of operating efficiently at high temperatures. In this review, we critically analyze the most recent development in the dielectric polymers for high-temperature capacitive energy storage applications. While general design considerations are discussed, emphasis is placed on the elucidation of the structural dependence of the high-field dielectric and electrical properties and the capacitive performance, including discharged energy density, charge–discharge efficiency and cyclability, of dielectric polymers at high temperatures. Here, advantages and limitations of current approaches to high-temperature dielectric polymers are summarized. Challenges along with future research opportunities are highlighted at the end of this article.

25 ENERGY STORAGE↗
DOE OSTI2022

Templated synthesis enhances the cobalt adsorption capacity of a porous organic polymer

Divalent transition metals such as Co(II) are important targets for removal from water sources, due to their potential toxicity as well as their high value. In this study, we found that a series of porous organic polymers based on amide-linked tetraphenylmethane units are effective Co(II) ion adsorbents in aqueous solution. To increase the density of Co(II) binding sites, we then developed a templated synthesis in which the branched, rigid monomers are pre-assembled around Co(II) ions prior to polymerization. Furthermore, after polymer formation, the Co(II) template ions are removed to yield a material rich in Co(II) binding sites. Ion adsorption isotherms show that the Co(II)-templated material has an ion adsorption capacity significantly greater than those of the non-templated materials, highlighting the utility of a templated synthetic route. SEM and TEM images show the morphology of the templated polymer to be dramatically different from the non-templated polymers and to be similar in size and shape to the Co(II)–monomer precursors, emphasizing the role of the template ions in directing the formation of the resulting polymer. This guest-templated approach requires no functionalization of the generic monomer and represents a promising synthetic route to high-capacity ion adsorbents for water purification and aqueous separations.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Boundary layer description of directional polymer crystallisation

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

36 MATERIALS SCIENCE↗
DOE OSTI2021

Performance and durability of anion exchange membrane water electrolyzers using down-selected polymer electrolytes

Over the last decade, several stable anion exchange polymer electrolytes have been developed for electrochemical devices. Herein, we investigate how chemical structure and physical properties of polymer electrolytes affect performance and durability of anion exchange membrane water electrolyzers (AEMWEs). We select polymer electrolytes with high alkaline stability and consider their polymer properties including conductivity, mechanical/chemical stability, and material interactions to interpret the performance and durability of AEMWEs. Here, the AEMWE with a poly(phenylene) membrane and a poly(fluorene) ionomeric binder exhibited the best performance among those tested in this study; the AEMWE showed ~1 A cm –2 at 2 V under 1 wt% K 2 CO 3 -fed conditions. The voltage degradation rate was 270–550 μV h –1 for several hundred operating hours at a constant current density of 750 mA cm –2 and a differential pressure of 100 pounds per square inch gauge. Based on these results, we discuss research needs of polymer electrolytes for practical AEMWEs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

The association of structural chirality and liquid crystal anchoring in polymer stabilized cholesteric liquid crystals

Polymer stabilized cholesteric liquid crystals (PSCLCs) are electrically reconfigurable reflective elements. Prior studies have hypothesized and indirectly confirmed that the electro-optic response of these composites is associated with the electrically mediated distortion of the stabilizing polymer network. The proposed mechanism is based on the retention of structural chirality in the polymer stabilizing network, which upon deformation is spatially distorted, which accordingly affects the pitch of the surrounding low molar-mass liquid crystal host. Here, we utilize fluorescent confocal polarized microscopy to directly assess the electro-optic response of PSCLCs. By utilizing dual fluorescent probes, sequential imaging experiments confirm that the periodicity of the polymer stabilizing network matches that of the low molar-mass liquid crystal host. Further, we isolate distinct ion-polymer interactions that manifest in certain photopolymerization conditions.

Radka, Brian P.↗
DOE OSTI2026

Investigating PVC polymer–plasticizer interactions with atomistic MD simulations and potential of mean force calculations

For this work, atomistic molecular dynamics (MD) simulations coupled with potential of mean force (PMF) calculations were employed to investigate the interactions between PVC polymer chains containing 6–20 repeating units and various plasticizers, with the goal of identifying potential replacements for the toxic plasticizer di(2-ethylhexyl)phthalate (DEHP) used in blood bags. The selected plasticizers belong to various chemical families, such as orthophthalates, citrates, adipates, and the terephthalate DEHT. Both the polymer and the plasticizers lack ionizable groups, and their interactions are primarily governed by van der Waals and electrostatic forces. A model correlating PMF profiles with interaction forces was developed and validated across polyvinyl chloride (PVC) polymers of different lengths and all investigated plasticizers. This model provides insight into how structural variations in plasticizers influence their respective PMF values. The study ranks the investigated plasticizers based on binding affinity, identifying TOTM (tris(2-ethylhexyl) trimellitate, TEHTM), BTHC (butyryl trihexyl citrate, Citroflex B-6), ATHC (acetyl trihexyl citrate, Citroflex A-6, CA-6), and DEHT (bis(2-ethylhexyl)terephthalate, DOTP/DEHTP) as promising alternatives for further investigation. This comprehensive study encompasses PVC polymers of four different lengths and 14 plasticizers, with all data averaged over 30 independent simulations. The approach provides a deeper understanding of molecular interactions, enabling the tailoring of polymer–plasticizer systems for diverse applications, including extractables and leachables, with relevance spanning materials science to biomedical engineering, and also serves as a basis for developing coarse-grained simulation protocols. Overall, this study provides valuable insights for designing safer and more efficient plasticizer substitutes and is well supported by other studies.

Shet, Sai Athmeeya G. [Sri Sathya Sai Institute of↗
DOE OSTI2026

A divergent synthetic route to functional copolymer libraries via modular polymers

High-throughput polymer synthesis enables rapid exploration of chemical space but remains limited by batch-to-batch inconsistencies that can obscure structure–property relationship trends. To address this challenge, we developed a synthetic approach to produce multifunctional copolymers using post-polymerization modification of activated ester modular polymers with commercially available amines. Easily derivitized parent polymers—poly(tetrafluorophenyl acrylate) and poly(tetrafluorophenyl styrene sulfonate)—were synthesized by RAFT polymerization to yield single polymer batches containing highly reactive tetrafluorophenyl esters or sulfonate esters on each repeat unit. Tuning post-polymerization modification reaction conditions enabled the addition of sub-stoichiometric amounts of amines (relative to the repeat unit) to yield partially functionalized intermediates that could then be further derivatized. Reaction monitoring by 19 F NMR spectroscopy confirmed good control over these sequential post-polymerization modifications. This synthetic route produced a variety of copolymers with defined comonomer ratios while preserving the underlying polymer structure (degree of polymerization, dispersity, tacticity) for both the acrylate and styrene sulfonate backbones. We further applied this approach in a divergent manner to create a small library of structurally distinct copolymers from a single parent batch in three synthetic steps. This modular, divergent synthesis demonstrates a general route to structurally consistent copolymer libraries that enable systematic studies of structure–property relationships and can accelerate functional materials discovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Electrospinning of ultra-high molecular weight polymers into aligned nanofibers and their application in chemical separations

Ultra-high molecular weight (UHMW, >10 6 g mol −1 ) vinyl polymers are increasingly accessible through photoiniferter polymerization, yet their behavior in electrospinning has received comparatively little attention. Here, we explore the electrospinning of UHMW poly(methyl acrylate), poly(methyl methacrylate), poly(N,N-dimethylacrylamide), and poly(styrene-co-pentafluorostyrene) synthesized by photoiniferter polymerization, with number-average molecular weights (M n ) greater than 1000 kDa and dispersities below 1.4. UHMW polymers form stable Taylor cones and discrete fibers at solution concentrations as low as 0.5 wt% due to their large number of entanglements, a threshold unachievable with low molecular weight (M n = 20–54 kDa) polymers of the same chemistry. Using poly(methyl methacrylate) and poly(styrene-co-pentafluorostyrene) as model systems, we demonstrate that fiber diameter can be tuned from 350 nm to 20 μm through systematic variation of polymer concentration (0.01 to 4 wt%) and flow rate (0.5 to 10 mL h −1 ). Additionally, we find that collector rotation rate governs fiber alignment, with highly aligned mats obtained with drum rotation speeds of 1000 RPM. Reversing the polarity of the electric field during electrospinning reorients the surface chemistry of these fiber mats without altering their microscale morphology, shifting the water contact angle by 7° (89° to 96°) and providing a two-fold binding capacity enhancement in cationic dye uptake. These results show that the high entanglement densities of UHMW vinyl polymers shift the accessible electrospinning window to dilute solutions and that electric-field polarity is a useful lever to control the surface chemistry in the resulting fibers.

Marquez, Joshua D. [University of Florida, Gainesv↗