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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 145 records · Page 8

Degradation of ESR in Polymer Tantalum Capacitors During High Temperature Storage

Replacement of MnO2 cathodes with conductive polymers in chip tantalum capacitors allows for a substantial reduction of the equivalent series resistance (ESR), improvement of frequency characteristics, and elimination of the possibility of ignition during failures. One of the drawbacks of chip polymer tantalum capacitors (CPTCs) is a relatively poor long-term stability at high temperatures. Due to degradation processes in conductive polymer materials, the existing quality assurance testing that has been developed for MnO2 capacitors is not sufficient to guarantee long-term stability of CPTCs. Insertion of CPTCs in hi-rel systems requires development of models that can predict degradation of the parts at operating conditions. In this work, variations of AC characteristics (capacitance, DF and ESR) in different types of capacitors from three manufacturers have been monitored during storage at temperatures from 100ºC to 175ºC for periods of up to 15,000 hours. Results show that the most sensitive to degradation parameter is ESR. Distributions of times to parametric failure during storage have been simulated using a Weibull-Arrhenius model that allowed for assessments of activation energies of degradation and prediction of times to failure at use temperatures. Mechanisms of degradation and the effect of packaging are discussed.

equivalent series resistance (ESR)↗

Electrical conduction in polymer dielectrics

The use of polymer dielectrics with moderate resistivities could reduce or eliminate problems associated with spacecraft charging. The processes responsible for conduction and the properties of electroactive polymers are reviewed, and correlations drawn between molecular structure and electrical conductivity. These structure-property relationships led to the development of several new electroactive polymer compositions and the identification of several systems that have the requisite thermal, mechanical, environmental and electrical properties for use in spacecraft.

Cotts, D. B.↗

A Review on Application of Poly(3,4-ethylenedioxythiophene) (PEDOT) in Rechargeable Batteries

Since the very first patent on poly(3,4-ethylenedioxythiophene) (PEDOT) that was filed in 1988, this polymer has been widely utilized and has achieved great success owing to its high electrical conductivity and excellent stability. The application of the conducting polymer, PEDOT, in renewable energy devices, especially rechargeable batteries, is attracting increasing attention due to its potential to solve the energy and climate crisis. In this review, we summarize the research over the past few decades directed toward the application of PEDOT in rechargeable batteries aimed at improving their electrochemical performance. We focus on PEDOT synthesized via oxidative chemical vapor deposition (oCVD), a relatively new process known for its ability to grow conducting polymer thin films with uniform, pinhole-free properties, and controllable thickness and conformality. For a comparison purpose, PEDOT synthesized via solution-based methods is also briefly summarized. Finally, future research directions for applying oCVD PEDOT in rechargeable batteries are discussed. Introduction PEDOT Synthesis Methods Application of oCVD PEDOT in Rechargeable Batteries Applications of Solution-Based PEDOT in Rechargeable Batteries Conclusions and Outlook

25 ENERGY STORAGE↗

Electric-Field-Driven Localization of Molecular Nanowires in Wafer-Scale Nanogap Electrodes

As integrated circuits continue to scale toward the atomic limit, bottom-up processes, such as epitaxial growth, have come to feature prominently in their fabrication. At the same time, chemistry has developed highly tunable molecular semiconductors that can perform the functions of ultimately scaled circuit components. Hybrid techniques that integrate programmable structures comprising molecular components into devices however are sorely lacking. Here we demonstrate a wafer-scale process that directs the localization of a conductive polymer, M w = 20 kg mol –1 polyaniline, from dilute solutions into 50 nm vertical nanogap device architectures using electric-field-driven self-assembly. The resulting metal–polymer–metal junctions were characterized by electron microscopy, Raman spectroscopy and transport measurements demonstrating that our technique is highly selective, assembling conductive polymers only in electrically activated nanogaps. Our results represent a step toward scalable hybrid nanoelectronics that seamlessly integrate established lithographic top-down fabrication with bottom-up synthesized molecular functional circuit components.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Thermal Conductivity of Polymer Copoly(Ethylene Vinyl Acetate)/Nano-Filler Blends

The development of flexible, thermally conductive fabrics and plastic tubes for the Liquid Cooling and Ventilation Garment (LCVG) are needed to reduce weight and improve the mobility, comfort, and performance of future spacesuits. Such improvements would allow astronauts to operate more efficiently and safely for extended extravehicular activities. As a continuation of our work on the improvement of thermal conductivity (TC) of polymeric materials, nanocomposites were prepared from copoly(ethylene vinyl acetate), trade name Elvax 260 , metallized carbon nanofibers (CNFs), nickel (Ni) nanostrands, boron nitride both alone and as mixtures with aluminum powder. The nanocomposites were prepared by melt mixing at various loading levels and subsequently fabricated into several material forms (i.e., ribbons, tubes, and compression molded plaques) for analysis. Ribbons and tubes were extruded to form samples in which the nanoparticles were aligned in the direction of flow. The degree of dispersion and alignment of the nanoparticles were investigated using high-resolution scanning electron microscopy. Tensile properties of the aligned samples were determined at room temperature. TC measurements were performed using a laser flash (Nanoflash ) technique. The TC of the samples was measured in both the direction of alignment as well as transverse. Tubing of comparable dimensions to that used in the LCVG was extruded from select compositions and the thermal conductivities of the tubes measured.

Ghose, S.↗

Polymeric Coatings for Electrodynamic Tethers

Two polymeric coatings have been developed for the Propulsive Small Expendable Deployer System (ProSEDS) mission. ProSEDS is designed to provide an on-orbit demonstration of the electrodynamic propulsion capabilities of tethers in space. The ProSEDS experiment will be a secondary payload on a Delta II unmanned expendable booster scheduled for launch in August 2000. A 5-km conductive tether is attached to the Delta 11 second stage and collects current from the low Earth orbit (LEO) plasma to facilitate de-orbit of the spent stage. The conductive tether is attached to a 10-km non-conductive tether, the other end of which is attached to an endmass containing several scientific instruments. A bare metal tether would have the best conductivity but thermal concerns preclude this design. A conductive polymer developed by Triton Systems has been optimized for conductivity and thermo-optical properties. The current design for the ProSEDS conductive tether is seven strands of 28 AWG aluminum wire individually coated with 8.7 micrometers (0.35 mil) of an atomic oxygen-resistant conductive polymer composed of a mixture of 87% Clear Oxygen-Resistant polymer (COR) and 13% polyanaline (PANi), wrapped around a braided Kevlar (TM) 49 core. Extensive testing has been performed at the Marshall Space Flight Center (MSFC) to qualify this material for flight on ProSEDS. Atomic oxygen exposure was performed, with solar absorptance and infrared emittance measured before and after exposure. Conductivity was measured before and after atomic oxygen exposure. High voltage tests, up to 1500 V, of the current collecting ability of the COR/PANi have been completed. Approximately 160 meters of the conductive tether closest to the Delta 11 second stage is insulated to prevent any electron reconnection to the tether from the plasma contactor. The insulation is composed of polyimide overcoated with TOR-BP, another polymeric coating developed by Triton for this mission. TOR-BP acts as both insulator and a protective coating against atomic oxygen erosion. The insulation has been tested to withstand 5000 V.

Vaughn, Jason A.↗

Ion diffusion coefficients in poly(3-alkylthiophenes) for energy conversion and biosensing: role of side-chain length and microstructure

Conductive polymers are promising materials as active elements for energy storage and conversion devices due to mixed ion–electron conduction. The ion diffusion coefficient is a relative measure of the efficacy of ion transport, allowing for comparison between materials and electrochemical conditions. In this work, diffusion coefficients of hexafluorophosphate (PF6–) counterions in poly(3-alkylthiophene) (P3AT) materials are measured as a function of both side-chain length and microstructure using electrochemical impedance spectroscopy (EIS). For semi-crystalline films, the diffusion coefficient is found to be anomalous and nearly independent of applied electrochemical potential. Here, the anomalous behavior of diffusion indicates that spin casting yields compact films with an enthalpic barrier to ion transport, attributed to ionic trapping. Diffusion coefficient values ~10 –11 cm 2 s –1 were measured for all films, indicating interchain spacing, in the absence of strong intermolecular interactions with the electrolyte, is not a viable design strategy to control ion transport. For the prototypical system of poly(3-hexylthiophene), we observe almost no potential dependence in ion transport for regioregular and regiorandom films of comparable molecular weight, with both exhibiting anomalous diffusion. Alternatively, changing the microstructure of poly(3-hexylthiophene) to a mostly amorphous, ion-imprinted structure yields ~500× increase in the diffusion coefficient to ~2 × 10 –8 cm 2 s –1 at 0.8 V vs. Ag/Ag + with behavior closer to ordinary diffusion. Collectively, these results indicate new insight into ion transport in conductive polymers, where ionic trapping effects can be mitigated through electrodeposition protocols over post-synthesis processing (i.e. spin coating).

14 SOLAR ENERGY↗

Conductive Tether Coating for Electrodynamic Tethers

The Propulsive Small Expendable Deployer System (ProSEDS), which is an on-orbit demonstration of the propulsion capabilities of electrodynamic tethers in space, is a secondary payload on a Delta 11 unmanned expendable booster. The ProSEDS tether consists of a 5 km bare electrodynamic tether and a 1 0-km non-conductive leader tether. Near the Delta 11, 160 m of the conductive tether is insulated to prevent plasma electron collection from the plasma contactor and for other science requirements. The remainder of the 5-km conductive tether is coated with a new conductive coating to collect plasma electrons. A bare metal tether easily collects electrons from the plasma, but thermal concerns preclude this design. A highly emissive conductive polymer developed by Triton Systems, Inc. has been optimized for both conductivity and thermo-optical properties. The current design for the ProSEDS conductive tether is seven individually coated strands of 28 AWG aluminum wire, coated with an atomic oxygen-resistant conductive polymer composed of a mixture of COR (Colorless Oxygen Resistant) and polyanaline (PANI) known as C-COR (Conductive-Colorless Oxygen Resistant). The conductive-coated wire strands are cold-welded to individually coated strands of the insulated tether. The insulated tether is coated with 1 mil of polyimide and an atomic oxygen resistant polymer TOR-BP. The insulated tether must stand off the entire voltage of the tether (1 200 V) at various times during the mission. All seven wires are twisted around a Kevlar-29 core using the Hi-wire design. Extensive testing has been performed at the Marshall Space Flight Center to qualify both the conductive coating and insulating coating for use on the ProSEDS tether. The conductive coating has been exposed to a plasma to verify the coatings ability to collect electrons from the space plasma from 0 to 1500 V, and to verify the coatings ability to collect electrons after atomic oxygen exposure. The insulated coating has been tested to verify its dielectric strength both in a vacuum and air. Thermal optical properties on both coatings have been measured before and after atomic oxygen testing. The results of these tests will be presented.

Jason A Vaughn↗

What is the Role of Relative Humidity on Conductivity in Polymer Electrolytes?

Ion transport properties in polymer electrolytes have been widely studied under rigorously dry and highly water-swollen conditions. However, the transition between these extremes, i.e., the low hydration regime, is still poorly understood at the molecular level and relevant to applications ranging from battery electrolytes to electrophoretic separations. Here, in this study, we apply atomistic molecular dynamics simulations to probe the role of hydration on ion mobilities and conductivities in LiTFSI-doped polyethers at low water content (less than 10% water by volume), which corresponds to 0−80% relative humidity conditions. With increasing water content, Li + ions exhibit two distinct regimes in their mobilities. At low water content, the majority of the Li + ions are weakly hydrated (two or fewer water molecules per Li + ion), maintaining strong interactions with their polymer solvation cage, and therefore exhibit only a weak increase in mobility relative to dry conditions. As water content increases, Li + ions form complete hydration shells, residing within water-rich domains that promote faster mobilities. Further, Li + mobilities increase more significantly in polymer electrolytes composed of more hydrophilic polymers and higher salt concentrations due to the formation of larger water-rich domains. In contrast, TFSI − has comparatively weak interactions with both the polymer and water, exhibiting a monotonic increase in mobility as a function of water content. Overall, these results help clarify the molecular mechanisms underlying ionic mobilities and conductivities in polymer electrolytes at low water content.

36 MATERIALS SCIENCE↗

Broadband THz Modulation via Solid–State Organic Electrochemical Devices

The sub-Terahertz and Terahertz bands play a critical role in next-generation wireless communication and sensing technologies, thanks to the large amount of available bandwidth in this spectral regime. While long-wavelength (microwave to mm-Wave) and short-wavelength (near-infrared to ultraviolet) devices are well-established and studied, the sub-THz to THz regime remains relatively underexplored and underutilized. Traditional approaches used in the aforementioned spectral regions are more difficult to replicate in the THz band, leading to the need for the development of novel devices and structures that can manipulate THz radiation effectively. Herein a novel organic, solid-state electrochemical device is presented, capable of achieving modulation depths of over 90% from ≈500 nm of a conducting polymer that switches conductivity over a large dynamic range upon application of an electronically controllable external bias. The stability of such devices under long-term, repeated voltage switching, as well as continuous biasing at a single voltage, is also explored. Switching stabilities and long-term bias stabilities are achieved over two days for both use cases. Additionally, both depletion mode (always “ON”) and accumulation mode (always “OFF”) operation are demonstrated. These results suggest applications of organic electrochemical THz modulators in large area and flexible implementations.

36 MATERIALS SCIENCE↗

Development of Polymer Coatings for the ProSEDS Tether

The ProSEDS mission is designed to provide an on-orbit demonstration of the electrodynamic propulsion capabilities of tethers in space. The ProSEDS experiment will be a secondary payload on a Delta 11 unmanned, expendable booster. A 5 km conductive tether is attached to the deployer baseplate on the Delta 11 second stage and collects current from the low Earth orbit (LEO) plasma to facilitate de-orbit of the Delta II second stage. The conductive tether is attached to a 10-15 km non-conductive tether, which in turn is attached to an endmass. A bare metal tether would have the best conductivity but thermal concerns preclude this design. A conductive polymer developed by Triton Systems has been optimized for optimum conductivity and thermo-optical properties. The current design for the ProSEDS conductive tether is seven individually coated strands of 28 AWG aluminum wire, coated with 12.7 micrometers (0.5 mil) atomic oxygen-resistant conductive polymer composed of a mixture of COR and PANi, wrapped around a braided Kevlar 29 core. Extensive testing has been performed at the Marshall Space Flight Center to qualify this material for flight on ProSEDS. Atomic oxygen exposure has been performed, with solar absorptance and infrared emittance measured before and after exposure. Plasma chamber tests have been completed, as well as tether deployment tests. Also developed for the ProSEDS mission was the insulating polymer TOR-BP. Approximately 200 meters of the conductive tether closest to the Delta II second stage is insulated to prevent any electron reconnection to the tether from the plasma contactor. The insulating material is TOR-BP with a dielectric strength of TBD.

Vaughn, Jason A.↗

Potential for exciton condensation in a highly conductive amorphous polymer

An outstanding challenge in synthesis and theory is to develop molecular materials at ambient conditions that exhibit highly efficient energy transfer. Here, in this study, we demonstrate the potential of a recently synthesized, highly conductive amorphous material—a nickel tetrathiafulvalene-tetrathiolate (NiTTFtt) polymer—to become an exciton condensate—a Bose-Einstein condensate of particle-hole pairs, known as excitons, that supports dissipationless flow of excitation energy. While exciton condensates have recently been realized in ordered materials, we show by advanced electronic structure calculations that this highly correlated phenomenon can potentially be realized in molecularly tailored, amorphous materials. In contrast to the Bechgaard salts that support superconductivity at compressed geometries requiring high pressures, we show that the recently synthesized, amorphous NiTTFtt polymer exhibits the computational signature of exciton condensation at experimentally realizable geometries, occurring at ambient pressures. Results suggest that superfluidity in this system and related systems—including van der Waals structures, molecular metals with extended-TTF dithiolate ligands, and Bechgaard salts—may occur via a nontraditional excitonic mechanism tuneable according to system composition, geometry, size, and charge. This study prompts further experimental investigation of the rational design of molecularly scaled exciton condensates with potential applications to efficient transport in technologically relevant materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Interpreting Ionic Conductivity for Polymer Electrolyte Fuel Cell Catalyst Layers with Electrochemical Impedance Spectroscopy and Transmission Line Modeling

A cathode catalyst layer containing optimally distributed ionomer is critical to reduce the platinum loading and increase its utilization in polymer electrolyte fuel cells. Here, electrochemical impedance spectroscopy (EIS) was used to measure effective ionic conductivity of pseudo catalyst layers (PCLs) at a relative humidity (RH) range of 50%-120%. These results are compared to previous work using the hydrogen pump (HP) method. EIS effective ionic conductivity results reported here are higher than those from the HP because in the HP set-up ionic pathways must be effectively connected through the PCL to be counted, whereas in the EIS measurement, ionomer segments that are in contact with the membrane but are not effectively connected all the way through the PCL can be detected. Double layer capacitances and effective ionic conductivities of Pt/C catalyst layers with various supports and ionomer to carbon (I/C) ratios were studied. High surface area carbon support resulted in a lower effective ionic conductivity compared to the graphitized carbon support due to worse ionomer dispersion. Effective ionic conductivities of Pt/C layers were compared to that of PCLs. On average, effective ionic conductivities of Pt/C layers were higher than PCLs because of possible carbon agglomeratio n within the PCLs.

25 ENERGY STORAGE↗

Computer Simulation of Spatial Arrangement and Connectivity of Particles in Three-Dimensional Microstructure: Application to Model Electrical Conductivity of Polymer Matrix Composite

Computer simulation is a powerful tool for analyzing the geometry of three-dimensional microstructure. A computer simulation model is developed to represent the three-dimensional microstructure of a two-phase particulate composite where particles may be in contact with one another but do not overlap significantly. The model is used to quantify the "connectedness" of the particulate phase of a polymer matrix composite containing hollow carbon particles in a dielectric polymer resin matrix. The simulations are utilized to estimate the morphological percolation volume fraction for electrical conduction, and the effective volume fraction of the particles that actually take part in the electrical conduction. The calculated values of the effective volume fraction are used as an input for a self-consistent physical model for electrical conductivity. The predicted values of electrical conductivity are in very good agreement with the corresponding experimental data on a series of specimens having different particulate volume fraction.

Louis, P.↗

Selective ion transport through hydrated micropores in polymer membranes

Abstract Ion-conducting polymer membranes are essential in many separation processes and electrochemical devices, including electrodialysis 1 , redox flow batteries 2 , fuel cells 3 and electrolysers 4,5 . Controlling ion transport and selectivity in these membranes largely hinges on the manipulation of pore size. Although membrane pore structures can be designed in the dry state 6 , they are redefined upon hydration owing to swelling in electrolyte solutions. Strategies to control pore hydration and a deeper understanding of pore structure evolution are vital for accurate pore size tuning. Here we report polymer membranes containing pendant groups of varying hydrophobicity, strategically positioned near charged groups to regulate their hydration capacity and pore swelling. Modulation of the hydrated micropore size (less than two nanometres) enables direct control over water and ion transport across broad length scales, as quantified by spectroscopic and computational methods. Ion selectivity improves in hydration-restrained pores created by more hydrophobic pendant groups. These highly interconnected ion transport channels, with tuned pore gate sizes, show higher ionic conductivity and orders-of-magnitude lower permeation rates of redox-active species compared with conventional membranes, enabling stable cycling of energy-dense aqueous organic redox flow batteries. This pore size tailoring approach provides a promising avenue to membranes with precisely controlled ionic and molecular transport functions.

Science & Technology - Other Topics↗

Electrically Conducting Polymer-Copper Sulphide Composite Films, Preparation by Treatment of Polymer-Copper (2) Acetate Composites with Hydrogen Sulfide

Polymer copper sulfide composite films were prepared by treatment of polymer poly(vinyl chloride), poly(acrylonitrile), copolymer of vinyl chloride and vinyl acetate (90:10), and ABS resin copper (2) acetate composites with hydrogen sulfide. The films showed electrical conductivity higher than 0.015 S/cm when they contained more than 20 wt percent of copper sulfide. A poly(acrylonitrile)-copper sulfide composite film containing 40 to 50 wt percent of copper sulfide showed electrical conductivity of 10 to 150.0 S/cm and had relatively high mechanical strength to be used in practical purposes.

Yamamoto, Takakazu↗

A quantum theoretical study of polyimides

One of the most important contributions of theoretical chemistry is the correct prediction of properties of materials before any costly experimental work begins. This is especially true in the field of electrically conducting polymers. Development of the Valence Effective Hamiltonian (VEH) technique for the calculation of the band structure of polymers was initiated. The necessary VEH potentials were developed for the sulfur and oxygen atoms within the particular molecular environments and the explanation explored for the success of this approximate method in predicting the optical properties of conducting polymers.

Burke, Luke A.↗