Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Polymer”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,261 records · Page 70
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Tailoring Hierarchical Structure and Rare Earth Affinity of Compositionally Identical Polymers via Sequence Control

Macromolecule sequence, structure, and function are inherently intertwined. While well-established relationships exist in proteins, they are more challenging to define for synthetic polymer nanoparticles due to their molecular weight, sequence, and conformational dispersities. Furthermore, to explore the impact of sequence on nanoparticle structure, we synthesized a set of 16 compositionally identical, sequence-controlled polymers with distinct monomer patterning of dimethyl acrylamide and a bioinspired, structure-driving di(phenylalanine) acrylamide (FF). Sequence control was achieved through multiblock polymerizations, yielding unique ensembles of polymer sequences which were simulated by kinetic Monte Carlo simulations. Systematic analysis of the global (tertiary- and quaternary-like) structure in this amphiphilic copolymer series revealed the effect of multiple sequence descriptors: the number of domains, the hydropathy of terminal domains, and the patchiness (density) of FF within a domain, each of which impacted both chain collapse and the distribution of single- and multichain assemblies. Furthermore, both the conformational freedom of chain segments and local-scale, β-sheet-like interactions were sensitive to the patchiness of FF. To connect sequence, structure, and target function, we evaluated an additional series of nine sequence-controlled copolymers as sequestrants for rare earth elements (REEs) by incorporating a functional acrylic acid monomer into select polymer scaffolds. We identified key sequence variables that influence the binding affinity, capacity, and selectivity of the polymers for REEs. Collectively, these results highlight the potential of and boundaries of sequence control via multiblock polymerizations to drive primary sequence ensembles hierarchical structures, and ultimately the functionality of compositionally identical polymeric materials.

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

Low-Temperature Pyrolysis of Aliphatic Polymers Using a Fluorinated Amorphous Silica–Alumina: Cooperative Reactivity between a Redox-Active Radical and an Aluminum Lewis Site

Fluorinated amorphous silica–alumina (F-ASA) prepared by the thermolysis of Krossing’s Al(OC(CF 3 ) 3 ) 3 (PhF) Lewis superacid supported on silica is a very reactive catalyst that promotes the pyrolysis (cracking) of aliphatic polymer melts to produce low molecular weight hyperbranched oils. Initial spectroscopic studies reported previously (Gao, J.; Perras, F. A.; Conley, M. P. J. Am. Chem. Soc . 2025 , 147, 18145–18154) showed that this material contains a distribution of four-, five-, and six-coordinate aluminum sites and a small amount of Brønsted acid sites, similar to typical amorphous silica–alumina materials that are far less reactive in the pyrolysis of aliphatic polymer melts. The objective of this study was to determine whether other active sites present in F-ASA could facilitate pyrolysis reactions. This study provides evidence for the presence of a redox-active silicon oxycarbide persistent radical ((≡Si) 3 C•) in F-ASA. Mims ENDOR EPR experiments show that (≡Si) 3 C• is located close to aluminum. Contacting F-ASA with thianthrene (Th) results in oxidation to form the [Th •+ ][F–ASA] ion-pair, while reactions with 1-hydroxy-2,2,6,6-tetramethylpiperidine (TEMPOH) result in H atom transfer to form TEMPO radical and F-ASA-H containing a mildly acidic (≡Si) 3 C–H. Poisoning studies show that both Lewis acidity and (≡Si) 3 C• are required for polymer pyrolysis reactivity. Finally, we propose that F-ASA promotes the formation of alkyl radicals in polymer melts, which are key intermediates in the thermal pyrolysis reactions of aliphatic polymers, involving the cooperative reactivity of both the Lewis acid and (≡Si) 3 C•.

aluminum↗
DOE OSTI2016

Intrinsically stretchable and healable semiconducting polymer for organic transistors

Developing a molecular design paradigm for conjugated polymers applicable to intrinsically stretchable semiconductors is crucial toward the next generation of wearable electronics. Current molecular design rules for high charge carrier mobility semiconducting polymers are unable to render the fabricated devices simultaneously stretchable and mechanically robust. Here in this paper, we present a new design concept to address the above challenge, while maintaining excellent electronic performance. This concept involves introducing chemical moieties to promote dynamic non-covalent crosslinking of the conjugated polymers. These non-covalent covalent crosslinking moieties are able to undergo an energy dissipation mechanism through breakage of bonds when strain is applied, while retaining its high charge transport ability. As a result, our polymer is able to recover its high mobility performance (>1 cm 2 /Vs) even after 100 cycles at 100% applied strain. Furthermore, we observed that the polymer can be efficiently repaired and/or healed with a simple heat and solvent treatment. These improved mechanical properties of our fabricated stretchable semiconductor enabled us to fabricate highly stretchable and high performance wearable organic transistors. This material design concept should illuminate and advance the pathways for future development of fully stretchable and healable skin-inspired wearable electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2023

High-efficiency stretchable light-emitting polymers from thermally activated delayed fluorescence

Stretchable light-emitting materials are the key components for realizing skin-like displays and optical biostimulation. All the stretchable emitters reported to date, to the best of our knowledge, have been based on electroluminescent polymers that only harness singlet excitons, limiting their theoretical quantum yield to 25%. Here we present a design concept for imparting stretchability onto electroluminescent polymers that can harness all the excitons through thermally activated delayed fluorescence, thereby reaching a near-unity theoretical quantum yield. We show that our design strategy of inserting flexible, linear units into a polymer backbone can substantially increase the mechanical stretchability without affecting the underlying electroluminescent processes. As a result, our synthesized polymer achieves a stretchability of 125%, with an external quantum efficiency of 10%. Additionally, we demonstrate a fully stretchable organic light-emitting diode, confirming that the proposed stretchable thermally activated delayed fluorescence polymers provide a path towards simultaneously achieving desirable electroluminescent and mechanical characteristics, including high efficiency, brightness, switching speed and stretchability as well as low driving voltage.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Diversity-oriented synthesis of polymer membranes with ion solvation cages

Microporous polymers feature shape-persistent free volume elements (FVEs), which are permeated by small molecules and ions when used as membranes for chemical separations, water purification, fuel cells, and batteries. It remains a significant challenge to identify FVEs with analyte specificity, due to difficulties in generating microporous polymer libraries with sufficient diversity for screening their properties. Here, we describe a diversity-oriented synthetic (DOS) strategy for microporous polymer membranes from which we identified those whose FVEs serve as solid solvation cages for lithium ions (Li + ). Furthermore, key elements of our strategy included diversification of bis(catechol)-type monomers via multi-component Mannich reactions to introduce Li+-coordinating functionality within individual FVEs, topology-enforcing polymerizations for generating macromolecular skeletal diversity for networking FVEs into different pore architectures, and several classes of on-polymer reactions for diversifying pore geometries and dielectric properties. Lead candidate polymer membranes featuring explicit ion solvation cages exhibited both higher ionic conductivity and higher cation transference number than control membranes where FVEs were aspecific, which indicates conventional bounds for membrane permeability and selectivity for ion transport can be overcome.4 These advantages are tied to enhanced Li + partitioning from the electrolyte when the cages are present, higher diffusion barriers for anions within the pores, and network-enforced restrictions on the number of solvent molecules bound to Li+ by comparison to the bulk electrolyte, which reduces the effective mass of the working ion. Such membranes show promise as anode-stabilizing interlayers in high-voltage lithium-metal batteries for electric mobility.

42 ENGINEERING↗
DOE OSTI2013

Nanophotonic Filters and Integrated Networks in Flexible 2D Polymer Photonic Crystals

Polymers have appealing optical, biochemical, and mechanical qualities, including broadband transparency, ease of functionalization, and biocompatibility. However, their low refractive indices have precluded wavelength-scale optical confinement and nanophotonic applications in polymers. Here, we introduce a suspended polymer photonic crystal (SPPC) architecture that enables the implementation of nanophotonic structures typically limited to high-index materials. Using the SPPC platform, we demonstrate nanophotonic band-edge filters, waveguides, and nanocavities featuring quality (Q) factors exceeding 2, 300 and mode volumes (V-mode) below 1.7(l/n) 3 . The unprecedentedly high Q/V-mode ratio results in a spectrally selective enhancement of radiative transitions of embedded emitters via the cavity Purcell effect with an enhancement factor exceeding 100. Moreover, the SPPC architecture allows straightforward integration of nanophotonic networks, shown here by a waveguide-coupled cavity drop filter with sub-nanometer spectral resolution. The nanoscale optical confinement in polymer promises new applications ranging from optical communications to organic opto-electronics, and nanophotonic polymer sensors.

PHOTONIC CRYSTALS↗
DOE OSTI2020

Quinonoid vs. aromatic structures of heteroconjugated polymers from oligomer calculations

Conjugated polymers with quinonoid ground states can display low optical band gaps. The design of novel conjugated polymers with quinonoid ground states offers insights into the relative stabilities of aromatic vs. quinonoid structures. In this work, we present parameters such as the quinonoid (Q)/aromatic (A) energy difference, the band gap, and the C–C distances between the repeat units. This study reveals eight new polymers which exist in quinonoid ground state among twenty-nine polymers of varying structural composition that were subject to analysis. We expect that copolymerizing such quinonoid ground state monomers with aromatic ground state monomers will modulate the bandgap of the resulting polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Porous bipolar polymers as organic cathodes for sustainable sodium/potassium-ion batteries

Redox-active porous polymers are becoming promising organic electrode materials for alkali-ion batteries because of their tunable pore size, flexible chemical structure, and high thermal stability. This work presents various porous bipolar polymers as cathodes in Na-ion batteries (NIBs) and K-ion batteries (KIBs). Two structural units containing carbonyl and amine active centers, respectively, were introduced into the repeating units of the polymers by the polycondensation of N,N,N',N'-tetrakis(4-aminophenyl)-1,4-phenylenediamine (TAP) and various dianhydrides. Here, the resulting bipolar polymers undergo multi-electron redox reactions involving both cations and anions during battery charge and discharge. The impacts of extended conjugation structures and porosity on the electrochemical performances were investigated by tuning the conjugation structures in the dianhydride monomers. The bipolar polymers with extended conjugation structures and small pore size exhibit superior electrochemical performance in NIBs and KIBs in terms of high redox potentials, long cycle life, and fast-charging capability, demonstrating great promise as organic cathode materials for alkali-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Dynamics of bottlebrush polymers

Bottlebrushes are an interesting class of polymers which shows intriguing material properties often associated with dynamics. While dynamical phenomena in linear polymers are well understood and existing theories can describe them in a good way, bottlebrush dynamics have only rarely been investigated. Therefore, we performed dielectric spectroscopy and quasi-elastic neutron scattering to study the dynamics of polydimethylsiloxane-based bottlebrush polymers, PDMS-g-PDMS focusing mostly on the segmental dynamics of the side chains. Comparing the relaxation times of the α – relaxation, tracked with dielectric spectroscopy, of bottlebrush polymers with those of their respective linear side chains show a slowing down once the side chains are attached to the backbone. This effect diminishes and finally vanishes with increasing side chain length. The time and length scale, offered by quasi-elastic neutron scattering, fits for the segmental dynamics together with faster processes. The Q -dependence of the segmental relaxation times allows to classify bottlebrush polymers as heterogenous including a non-Gaussian character. For such a dynamical system, the mean square displacement needs to be separated into single processes before an overall mean square displacement can be generated by applying the time temperature superposition principle.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Theory of polymer-dispersed cholesteric liquid crystals

A mean field theory is presented to describe cholesteric phases in mixtures of a polymer and a cholesteric liquid crystal. Taking into account an anisotropic coupling between a polymer and a liquid crystal, we examine the helical pitch, twist elastic constant, and phase separations. Analytical expressions of the helical pitch of a cholesteric phase and the twist elastic constant are derived as a function of the orientational order parameters of a polymer and a liquid crystal and two intermolecular interaction parameters. We also find isotropic-cholesteric, cholesteric-cholesteric phase separations, and polymer-induced cholesteric phase on the temperature-concentration plane. We demonstrate that an anisotropic coupling between a polymer and a liquid crystal can stabilize a cholesteric phase in the mixtures. Our theory can also apply to mixtures of a nematic liquid crystal and a chiral dopant. We discuss the helical twisting power, which depends on temperature, concentration, and orientational order parameters. It is shown that our theory can qualitatively explain experimental observations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Conductivity behavior of very thin gold films ruptured by mass transport in photosensitive polymer film

We report on conductivity behavior of very thin gold layer deposited on a photosensitive polymer film. Under irradiation with light interference pattern, the azobenzene containing photosensitive polymer film undergoes deformation at which topography follows a distribution of intensity, resulting in the formation of a surface relief grating. This process is accompanied by a change in the shape of the polymer surface from flat to sinusoidal together with a corresponding increase in surface area. The gold layer placed above deforms along with the polymer and ruptures at a strain of 4%. The rupturing is spatially well defined, occurring at the topographic maxima and minima resulting in periodic cracks across the whole irradiated area. We have shown that this periodic micro-rupturing of a thin metal film has no significant impact on the electrical conductivity of the films. We suggest a model to explain this phenomenon and support this by additional experiments where the conductivity is measured in a process when a single nanoscopic scratch is formed with an AFM tip. Our results indicate that in flexible electronic materials consisting of a polymer support and an integrated metal circuit, nano- and micro cracks do not alter significantly the behavior of the conductivity unless the metal is disrupted completely.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Real-time x-ray scattering study of the initial growth of organic crystals on polymer brushes

We studied the early-stage growth structures of pentacene organic crystals grown on polymer brushes using real-time x-ray scattering techniques. In situ x-ray reflectivity and atomic force microscopy analyses revealed that at temperatures close to the glass transition temperature of polymer brush, the pentacene overlayer on a polymer brush film showed incomplete condensation and 3D island structures from the first monolayer. A growth model based on these observations was used to quantitatively analyze the real-time anti-Bragg x-ray scattering intensities measured during pentacene growth to obtain the time-dependent layer coverage of the individual pentacene monolayers. The extracted total coverage confirmed significant desorption and incomplete condensation in the pentacene films deposited on the polymer brushes. These effects are ascribed to the change in the surface viscoelasticity of the polymer brushes around the glass transition temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

New insights on the nature of two-dimensional polarons in semiconducting polymers: Infrared absorption in poly(3-hexylthiophene)

Infrared absorption of positively charged polarons in conjugated polymer chains and π-stacked aggregates is investigated theoretically, employing a Holstein-based Hamiltonian which treats electronic coupling, electron-vibrational coupling, and disorder on equal footing. The spectra evaluated from the Hamiltonian expressed in a one- and two-particle basis set are essentially exact, insofar as the main, aromatic-quinoidal vibrational mode is treated fully nonadiabatically. Diagonal and off-diagonal (“paracrystalline”) disorder are resolved along the polymer axis (x) and the aggregate stacking axis (y). Disorder along the polymer axis selectively attenuates the x-polarized spectrum, which is dominated by the polaron peak P{sub 1}. Disorder along the stacking axis selectively attenuates the y-polarized spectrum, which is dominated by the lower-energy charge-transfer peak, DP{sub 1}. Calculated spectra are in excellent agreement with the measured induced-absorption and charge-modulation spectra, reproducing the peak positions and relative peak intensities within a line shape rich in vibronic structure. Our nonadiabatic approach predicts the existence of a weak, x-polarized peak P{sub 0}, slightly blueshifted from DP{sub 1}. The peak is intrinsic to single polymer chains and appears in a region of the spectrum where narrow infrared active vibrational modes have been observed in nonaggregated conjugated polymers. The polaron responsible for P{sub 0} is composed mainly of two-particle wave functions and cannot be accounted for in the more conventional adiabatic treatments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

The role of spin exchange in charge transfer in low-bandgap polymer: Fullerene bulk heterojunctions

Formation, relaxation and dynamics of polarons and methanofullerene anion radicals photoinitiated in poly[N-9″-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′, 3′-benzothiadiazole)]:-[6,6]-phenyl-C{sub 61}-butyric acid methyl ester (PCDTBT:PC{sub 61}BM) bulk heterojunctions were studied mainly by light-induced EPR (LEPR) spectroscopy in wide photon energy and temperature ranges. Some polarons are pinned by spin traps whose number and depth are governed by the composite morphology and photon energy. The proximity of the photon energy and the polymer bandgap reduces the number of such traps, inhibits recombination of mobile charge carriers, and facilitates their mobility in polymer network. Spin relaxation and charge carrier dynamics were studied by the steady-state saturation method at wide range of temperature and photon energy. These processes were shown to be governed by spin exchange as well as by the photon energy. Charge transfer in the composite is governed by the polaron scattering on the lattice phonons of crystalline domains embedded into amorphous polymer matrix and its activation hopping between polymer layers. The energy barrier required for polaron interchain hopping exceeds that of its intrachain diffusion. Anisotropy of polaron dynamics in the PCDTBT:PC61BM composite is less than that of poly(3-alkylthiophenes)-based systems that evidences for better ordering of the former. Lorentzian shape of LEPR lines of both charge carriers, lower concentration of spin traps as well as behaviours of the main magnetic resonance parameters were explained by layer ordered morphology of polymer matrix.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Identification and design of novel polymer-based mechanical transducers: A nano-structural model for thin film indentation

Mechanical characterization is important for understanding small-scale systems and developing devices, particularly at the interface of biology, medicine, and nanotechnology. Yet, monitoring sub-surface forces is challenging with current technologies like atomic force microscopes (AFMs) or optical tweezers due to their probe sizes and sophisticated feedback mechanisms. An alternative transducer design relying on the indentation mechanics of a compressible thin polymer would be an ideal system for more compact and versatile probes, facilitating measurements in situ or in vivo. However, application-specific tuning of a polymer's mechanical properties can be burdensome via experimental optimization. Therefore, efficient transducer design requires a fundamental understanding of how synthetic parameters such as the molecular weight and grafting density influence the bulk material properties that determine the force response. In this work, we apply molecular-level polymer scaling laws to a first order elastic foundation model, relating the conformational state of individual polymer chains to the macroscopic compression of thin film systems. A parameter sweep analysis was conducted to observe predicted model trends under various system conditions and to understand how nano-structural elements influence the material stiffness. We validate the model by comparing predicted force profiles to experimental AFM curves for a real polymer system and show that it has reasonable predictive power for initial estimates of the force response, displaying excellent agreement with experimental force curves. We also present an analysis of the force sensitivity of an example transducer system to demonstrate identification of synthetic protocols based on desired mechanical properties. These results highlight the usefulness of this simple model as an aid for the design of a new class of compact and tunable nanomechanical force transducers.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

Nonequilibrium thermodynamics of dilute polymer solutions in flow

Modern materials processing applications and technologies often occur far from equilibrium. To this end, the processing of complex materials such as polymer melts and nanocomposites generally occurs under strong deformations and flows, conditions under which equilibrium thermodynamics does not apply. As a result, the ability to determine the nonequilibrium thermodynamic properties of polymeric materials from measurable quantities such as heat and work is a major challenge in the field. Here, we use work relations to show that nonequilibrium thermodynamic quantities such as free energy and entropy can be determined for dilute polymer solutions in flow. In this way, we determine the thermodynamic properties of DNA molecules in strong flows using a combination of simulations, kinetic theory, and single molecule experiments. We show that it is possible to calculate polymer relaxation timescales purely from polymer stretching dynamics in flow. We further observe a thermodynamic equivalence between nonequilibrium and equilibrium steady-states for polymeric systems. In this way, our results provide an improved understanding of the energetics of flowing polymer solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Lattice cluster theory for dense, thin polymer films

While the application of the lattice cluster theory (LCT) to study the miscibility of polymer blends has greatly expanded our understanding of the monomer scale molecular details influencing miscibility, the corresponding theory for inhomogeneous systems has not yet emerged because of considerable technical difficulties and much greater complexity. Here, we present a general formulation enabling the extension of the LCT to describe the thermodynamic properties of dense, thin polymer films using a high dimension, high temperature expansion. Whereas the leading order of the LCT for bulk polymer systems is essentially simple Flory-Huggins theory, the highly non-trivial leading order inhomogeneous LCT (ILCT) for a film with L layers already involves the numerical solution of 3(L − 1) coupled, highly nonlinear equations for the various density profiles in the film. The new theory incorporates the essential “transport” constraints of Helfand and focuses on the strict imposition of excluded volume constraints, appropriate to dense polymer systems, rather than the maintenance of chain connectivity as appropriate for lower densities and as implemented in self-consistent theories of polymer adsorption at interfaces. The ILCT is illustrated by presenting examples of the computed profiles of the density, the parallel and perpendicular bonds, and the chain ends for free standing and supported films as a function of average film density, chain length, temperature, interaction with support, and chain stiffness. The results generally agree with expected general trends.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Lattice model of linear telechelic polymer melts. I. Inclusion of chain semiflexibility in the lattice cluster theory

The lattice cluster theory (LCT) for the thermodynamics of polymer systems has recently been reformulated to treat strongly interacting self-assembling polymers composed of fully flexible linear telechelic chains [J. Dudowicz and K. F. Freed, J. Chem. Phys. 136, 064902 (2012)]. Here, we further extend the LCT for linear telechelic polymer melts to include a description of chain semiflexibility, which is treated by introducing a bending energy penalty whenever a pair of consecutive bonds from a single chain lies along orthogonal directions. An analytical expression for the Helmholtz free energy is derived for the model of semiflexible linear telechelic polymer melts. The extension provides a theoretical tool for investigating the influence of chain stiffness on the thermodynamics of self-assembling telechelic polymers, and for further exploring the influence of self-assembly on glass formation in such systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗