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At least 1,441 records · Page 80

Extinction of the Stagnation Point Diffusion Flame: Effect of Conductive Heat Loss into Solid Interior

The flammability boundary of a solid is U-shaped with the ordinate as ambient oxygen percentage (or total pressure) and the abscissa represents flow velocity, gravity level, stretch rate, etc. The left side of the flammability boundary is the quenching branch, and the right side is the blow-off branch. Quenching is due to a weak flame whose heat release from combustion cannot overcome the excessive heat losses from, for example, radiation. Blow-off is due to a short gas residence time that is smaller than the chemical reaction time (traditionally referred to as the small Damköhler number effect). For thick solids, the heat conduction into the solid interior has a long transient after ignition before the solid temperature reaches the steady state. During this slow transient, there is excessive (i.e. more than that at the steady state) gas phase heat conduction into the solid interior. From the viewpoint of the quasi-static gaseous flame, this is an additional heat loss that will affect the gas flame's flammability. In this work, a previously developed one-dimensional axisymmetric stagnation-point diffusion flame model is extended to account for the excessive heat loss into the solid beyond the steady burning state. A non-dimensional excessive conductive heat loss parameter Ψ is defined in the paper to account for the transient solid effect. For each Ψ, the gas phase is considered reaching a quasi-steady state. Extensive numerical computations have been performed to determine the extinction boundary and the characteristics of near-limit flames. The U-shaped flammability boundary is now a series of boundaries with Ψ as a parameter. Flame structures under the same environment condition but with different Ψ are compared. For a given oxygen ambient, the extinction boundary Ψ vs stretch rate is an inverted U-shape. The boundary consists of a blowoff branch and a radiative quenching branch. Extensive computed data including flame and pyrolysis temperatures, burning rate, flame standoff distance, species concentration, and reaction rate are presented along the extinction boundaries. Heat balance analysis is performed for both the gas phase and the gas-solid interface. Along the extinction boundary, the relative importance of conduction, convection, radiation, and chemical reaction are analyzed in detail.

Stagnation point diffusion flame↗

Highly Thermally Conductive Hybrid Carbon Fiber Polymer Composite for Radiator Application

Carbon fiber (CF) reinforced polymer composites have been used for aerospace structures because they have low mass, high specific strength, high specific stiffness, and low life-cycle maintenance compared to aluminum alloys. However, due to their relatively low thermal conductivity, pristine CF polymer composites fail to provide effective heat flow for certain applications such as heat exchange systems and radiators. The technology described in this paper provides novel CF polymer composites that possess high thermal conductivity by incorporating pyrolytic graphite sheets (PGS). The thermal conductivities of novel hybrid PGS/CF polymer composites were measured to be about 10 to 30 times higher than that of pristine CF polymer composite, and about two times higher than that of aluminum alloy 6061. This new material with sufficient thermal conductivity is applicable to composite radiators of heat exchange systems.

Thermal Conductivity↗

A Study of Space Environment Effect on Highly Thermally Conductive Hybrid Carbon Fiber Polymer Composites

A set of novel highly thermally conductive hybrid carbon fiber (CF) polymer composites has been developed for lightweight thermal radiator applications in space missions. This study investigates the effects of the space environment on these materials following exposure in low-Earth orbit (LEO) during the Materials International Space Station Experiment (MISSE)-17 flight mission, where samples experienced 159 days of combined atomic oxygen (AO), ultraviolet (UV) radiation, high vacuum, space radiation and thermal cycling. Post-flight characterization included weight loss, surface morphology, thermo-optical properties, molecular structures, glass transition temperature, thermal degradation and thermal conductivity analyses. The pyrolytic graphite sheet (PGS) samples exhibited negligible weight loss, stable thermo-optical property, and only minor oxidation signature on the exposed surface. Although AO erosion of the epoxy polymer matrix was evident, carbon nanotube (CNT)-infused PGS/CF epoxy composites retained high thermal emissivity and preserved their high thermal conductivities. These results demonstrate that the novel highly thermally conductive hybrid CF composites possess strong environmental resilience and are promising candidates for lightweight thermal radiators and thermal management components in future space exploration missions.

Space Environment↗

Printed Conductive Transparent Films for the Fabrication of Sensors by Aerosol Inkjet Systems

Fabrication of sensors using additive manufacturing printers holds the promise for low-cost sensors for continuous and real time monitoring of physical and chemical parameters in industrial settings. Aerosol inkjet systems have demonstrated the capability to print small feature sizes with high precision using a variety of materials. Here, advances in nanomaterials suitable for use by such printers raises the possibility of having transparent, conductive films and sensors. Typically, transparent conductive films are fabricated using metallic oxides and complicated procedures on rigid substrates. In this paper, we present the results of the combination of silver nanowires formulations and aerosol inkjet systems for the fabrication of transparent conductive films by printing and its characterization. Implications for utilization of conductive, transparent sensors in manufacturing and industrial processes settings are discussed.

42 ENGINEERING↗

Printed Conductive Transparent Films for the Fabrication of Sensors by Aerosol Inkjet Systems

Fabrication of sensors using additive manufacturing printers holds the promise for low-cost sensors for continuous and real time monitoring of physical and chemical parameters in industrial settings. Aerosol inkjet systems have demonstrated the capability to print small feature sizes with high precision using a variety of materials. Advances in nanomaterials suitable for use by such printers raises the possibility of having transparent, conductive films and sensors. Typically, transparent conductive films are fabricated using metallic oxides and complicated procedures on rigid substrates. In this paper, we present the results of the combination of silver nanowires formulations and aerosol inkjet systems for the fabrication of transparent conductive films by printing and its characterization. Further, implications for utilization of conductive, transparent sensors in manufacturing and industrial processes settings are discussed.

42 ENGINEERING↗

Characterization of unsaturated hydraulic conductivity in fractured media using the multistep outflow method - 15461

The multistep outflow method is routinely used to characterize the unsaturated hydraulic conductivity of soils. The technique involves placing a soil sample in a pressure plate apparatus, subjecting the sample to multiple gas pressures in discrete steps through time, and measuring the transient volume of pore fluid extracted. Unsaturated hydraulic property values are estimated through inverse modeling of the experimental conditions. In this study the multistep outflow concept was applied to micro-cracked cementitious materials to assess the efficacy of the technique for these materials. The cementitious materials tested were salt-waste simulant grout samples artificially damaged through oven-drying. Compared to typical soils, fractured media exhibit higher saturated conductivity and lower air-entry pressure, and the volume of fluid extractable from fractures is much lower than soil porosity. To accommodate these material differences the standard test apparatus was modified to incorporate a higher conductivity ceramic pressure plate, a high-precision digital balance for logging outflow mass, a low volume (diameter) effluent line, multiple in-line high-precision gas regulators, and a high-precision low-range pressure gauge. Testing to date indicates that the modified apparatus can provide a viable means to measure the unsaturated hydraulic properties of micro-fractured cementitious materials. However the accuracy/uniqueness of inverse modeling is limited by the inherent characteristics of fractured media: high saturated conductivity, low air-entry pressure, and strong non-linearities. Hydraulic property results in the form of van Genuchten / Mualem curves are presented for three fractured grout specimens. DOE Performance Assessments often involve cementitious barriers and/or waste forms that are predicted or assumed to degrade over time due to various mechanisms such as carbonation-influenced reinforcing steel corrosion, external sulfate attack, differential settlement, and seismic activity. Physical degradation typically takes the form of small-scale cracking / fracturing, and the affected materials reside in unsaturated hydrogeologic zones. In these cases, unsaturated hydraulic properties are needed for fractured cementitious materials to simulate moisture movement and contaminant transport within and around the facility. The outflow extraction method, as implemented in the present study, provides a suitable method for estimating these material properties. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Comparisons of Peak Cladding Temperature and Effective Thermal Conductivity: CFD Simulation on PWR Spent Fuel Assemblies - 16278

When spent fuel assemblies from the reactor of nuclear power plants (NPPs) are transported or stored, the assemblies are exposed to a variety of environments that can affect the peak cladding temperature of spent fuel assemblies. There are four methods to calculate the peak cladding temperature of spent fuel assemblies in a cask: Manteufel and Todreas's two-region model, Bahney Lotz's effective thermal conductivity model, Wooton-Epstein correlation, and computational fluid dynamics (CFD) simulation. The CFD simulation based on the FLUENT code is used to calculate the peak cladding temperature and effective thermal conductivity of a spent fuel assemblies used in Republic of Korea NPPs: 14x14, 16x16 ACE7, 16x16 PLUS7 and 17x17 PWR spent fuel assemblies. The CFD simulation results show that the effective thermal conductivity of the 16x16 ACE7 was more conservative than those for the other assemblies. Therefore the effective thermal conductivity using 16x16 ACE7 is used for thermal evaluation of the KORAD's developing cask which can load 14x14, 16x16 ACE7, 16x16 PLUS7 and 17x17 spent fuel assembly. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effect of Reactor Radiation on the Thermal Conductivity of Graphite-based Dispersion Fuel

The Fukushima Daiichi nuclear accident in 2011 stimulated materials development efforts to improve the current fuel design for Light Water Reactors (LWRs). From fuel element to fuel cladding, new concepts in advanced nuclear fuel development have been proposed, studied, and tested. The new fuel systems are expected to have better resistance to damage, melting, and chemical reaction during accident scenarios. To test the performance and accident tolerance of the advanced fuel, it is highly preferable to simulate off-normal transients in addition to standard in-core fuel performance tests (available at High Flux Isotope Reactor at Oak Ridge National Laboratory and Advanced Test Reactor at Idaho National Laboratory). The Transient Reactor Test Facility (TREAT) is now being prepared to restart its operation, performing transient testing to assist advanced fuel development. TREAT was operated from 1959 to 1994, and was extensively used to generate thousands of reactor transients for different programs. The reactor has not operated since 1994. The original fuel used at TREAT was graphite-based dispersion fuel with highly-enriched uranium (HEU, 93.1% enriched uranium). For nonproliferation purposes, a fuel conversion program, supported by U.S. Department of Energy, National Nuclear Safety Administration (NNSA), Office of Material Management and Minimization (NA-23) Reactor Conversion Program, is underway to develop a replacement core in which the UO{sub 2} contains only low-enriched uranium (LEU). The preliminary LEU core design has shown a much lower carbon/uranium atomic ratio and enrichment than in the HEU core design. To achieve performance similar to the HEU core, the prospective LEU core will contain a much higher density of UO{sub 2} particles. As a result, a higher level of radiation damage, particularly from fission fragments emerging from the UO{sub 2} particles, can be expected dependent on the UO{sub 2} particle size within the fuel. To support LEU fuel design, the present study investigates the effect of reactor radiations on the thermal conductivity of graphite-based dispersion fuel. Both neutron- and fission-radiation induced degradations of the fuel are modeled, and validated based on the available experimental data. In this study, the reactor-radiation induced thermal conductivity degradation of graphite-based dispersion fuel was analyzed. A semi-empirical method to model the relative thermal conductivity with reactor radiations was proposed and validated. The proposed method can be further applied to predict the changes in the thermal conductivity of the prospective LEU TREAT fuel during long-term operation. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A Radial Heat Flow Apparatus for Thermal Conductivity Characterisation of Cylindrical Samples

During the last two decades, silicon carbide based ceramic composites (SiC/SiC) have become a candidate material for nuclear fuel cladding, first for advanced nuclear systems, such as the GFR, and recently also as potential replacement material for nuclear fuel cladding in light water reactors. This work is contributing to the General Atomics/Westinghouse led CARAT project. In this frame, the thermal conductivity (TC) of cladding prototype sections are measured both before and after neutron irradiation with the purpose of better understanding the effects of neutron irradiation on the pyrolytic carbon interphase linking the SiC fibres to the SiC matrix. To this end, an apparatus has been designed and built to measure the TC of short cylindrical samples, whose lengths range from 5 to 20 cm, by the radial heat flow method. To avoid oxidation issues, the experiments are carried out in vacuum. Today the most common measurement method used to characterise the TC of materials is the so-called laser-flash technique, whereby a short high intensity laser pulse is shot on one surface of a thin flat sample and the energy transfer through the sample is analysed on the other side. Though much faster and easier to implement than the apparatus presented in this work, laser-flash equipment does have issues when dealing with highly anisotropic materials or capturing shape effects such as those present in large aspect ratio samples such as cladding tube sections. The two aforementioned effects are exactly what the developed equipment has been built to capture. The radial heat flow method is based on the principle of measuring the temperature difference building up through a piece of material as this material acts as a thermal resistance against a known heat flow crossing it. This paper presents a new implementation of one of the classical thermal conductivity measurement techniques. Since the development of the laser-flash method in the sixties, steady-state measurements such as the radial heat flow have fallen in disuse. In this discussion, it is shown that a direct measurement method can be used and even be preferable in the case of highly anisotropic materials such as SiC/SiC composites. The advantage of this experimental setup is that the actual transverse conductivity is obtained, whereas laser-flash measurements yield a response in which both the transverse and axial conductivities are mixed. Further steps of this study will include the measurements of samples irradiated with neutrons in the MITR test-reactor. The aim will be to evidence the role played by the pyrolytic carbon interphase by linking the TC measurements with energy filtered electron microscopy. We would like to acknowledge General Atomics and Westinghouse for their support in the frame of the CARAT research program. Providing us with actual prototype clad sections is a unique opportunity. Furthermore the Swiss CCEM.ch project MeAWaT is acknowledged for partially financing the development of the measurement device. (authors)

36 MATERIALS SCIENCE↗

Local Measurement in Annular Flows Using a Two-Sensor Droplet-Capable Conductivity Probe

Two-sensor electrical conductivity probes have been widely used for detailed local measurement in two-phase flow systems. However application of conductivity probes in liquid-dispersed flows has been limited. In the churn-turbulent to annular transition and annular flow regimes, the liquid phase exists as a continuous phase in the film and ligaments, and as a dispersed phase in the droplets. The conventional design of a conductivity probe is not valid because it cannot distinguish the dispersed liquid phase from the gas phase. In this paper, the Two-Sensor Droplet-Capable Conductivity Probe (DCCP-2) is designed in order to extend measurement capability to liquid-dispersed flows. The liquid phase is classified into droplets and ligaments. The interface velocity, volume fraction, interfacial area concentration, as well as the chord length of liquid droplets and ligaments, can be calculated from the raw signal. The radial distribution of these parameters and the probability distribution of chord length and velocity are obtained for downwards flow in a vertical pipe. The results show that although the average volume fraction of droplets is only on the order of 1%, droplets contribute to around 20%-30% to the entrained liquid phase in the gas core, the remainder as ligaments. The interfacial area concentration from droplets and ligaments are in the order of 300 m{sup -1}. (authors)

42 ENGINEERING↗

Predicting mesoscale spectral thermal conductivity using advanced deterministic phonon transport techniques

We present a review, demonstration and simulation of phonon transport for the purposes of predicting materials performance at the mesoscale. We focus primarily on the development and implementation of a unified methodology to enable predictive heat transport. We report on the current state of the art as it pertains to deterministic phonon transport methodologies, discussing various topics concerning phonons. In application, we focus on the Self-Adjoint Angular Flux (SAAF) formulation of the Boltzmann transport equation for phonons, and develop the spatial, angular, and material property discretization required to accurately simulate the predictive physics of heat transport in dielectrics. We discuss thermal interfacial resistance and present our formulation of the diffuse mismatch model for simulating phonon interactions at internal boundaries. We have recently developed a deterministic, spectral phonon transport method for predicting effective thermal conductivity ($\kappa_{\textrm{eff}}$), using Bose-Einstein source terms coupled through an average material temperature. In this method, we introduce a closure term to the phonon transport system which acts as a redistribution function for the total energy of the system, and serves as a guide for the amount of non-equilibrium behavior occurring in the system. This method predicts thermal conductivity and equilibrium temperature distributions in homogeneous and heterogeneous materials using data generated by ab initio density functional theory methods. We employ polarization, density of states and full dispersion spectra to resolve thermal conductivity with numerous angular and spatial discretizations. Our implementation utilizes a Richardson iteration on a modified version of the phonon scattering source. The equations associated with this method are solved via a modification of traditional source iteration. We compare the performance of source iteration applied to an existing uncoupled, traditional SAAF method to our new method and comment on the iterative performance of each. We observe ballistic and diffusive phonon scattering as acoustic thickness of the domain changes, and are able to make comparisons between the accuracy and efficiency of both methods.

36 MATERIALS SCIENCE↗

Toward a new parameterization of hydraulic conductivity in climate models: Simulation of rapid groundwater fluctuations in N orthern C alifornia

Abstract Preferential flow through weathered bedrock leads to rapid rise of the water table after the first rainstorms and significant water storage (also known as “rock moisture”) in the fractures. We present a new parameterization of hydraulic conductivity that captures the preferential flow and is easy to implement in global climate models. To mimic the naturally varying heterogeneity with depth in the subsurface, the model represents the hydraulic conductivity as a product of the effective saturation and a background hydraulic conductivity K bkg , drawn from a lognormal distribution. The mean of the background K bkg decreases monotonically with depth, while its variance reduces with the effective saturation. Model parameters are derived by assimilating into Richards’ equation 6 years of 30 min observations of precipitation (mm) and water table depths (m), from seven wells along a steep hillslope in the Eel River watershed in Northern California. The results show that the observed rapid penetration of precipitation and the fast rise of the water table from the well locations, after the first winter rains, are well captured with the new stochastic approach in contrast to the standard van Genuchten model of hydraulic conductivity, which requires significantly higher levels of saturated soils to produce the same results. “Rock moisture,” the moisture between the soil mantle and the water table, comprises 30% of the moisture because of the great depth of the weathered bedrock layer and could be a potential source of moisture to sustain trees through extended dry periods. Furthermore, storage of moisture in the soil mantle is smaller, implying less surface runoff and less evaporation, with the proposed new model.

58 GEOSCIENCES↗

A Reactive Inkjet Printing Process for Fabricating Biodegradable Conductive Zinc Structures

A novel reactive inkjet printing (RIJ) process for fabricating environmentally benign, conductive zinc structures on biodegradable substrates is reported. A precursor consisting of oxidized zinc microparticles is formulated into a viscous ink for high‐resolution, high‐repeatability screen printing. A single RIJ process is performed to selectively dispense an acid‐based oxide etching agent onto the screen‐printed zinc ink to significantly improve its electrical conductivity, up to 4 × 10 4 S m −1 . The RIJ process enables precise control of the amount of deposited etching agent, allowing control of conductivity and avoiding damage caused by excessive acid exposure. The RIJ process deposits the etching agent selectively on the screen‐printed, water‐soluble zinc patterns, thus preserving the print fidelity by avoiding ink smearing that can occur when using a blanket treatment such as submersion. A printed biodegradable antenna with a minimum feature size of 500 μm for use with a batteryless radio frequency identification (RFID) chip is fabricated as demonstration. Due to the higher ink conductivity and improved pattern fidelity, the antenna fabricated by the RIJ process shows a ≈2.2× increase in reading distance compared with a similar antenna that is screen printed and activated using a drop‐casting process.

Sui, Yongkun↗

All-Solid-State Synaptic Transistor with Ultralow Conductance for Neuromorphic Computing

Electronic synaptic devices are important building blocks for neuromorphic computational systems that can go beyond the constraints of von Neumann architecture. Although two-terminal memristive devices are demonstrated to be possible candidates, they suffer from several shortcomings related to the filament formation mechanism including nonlinear switching, write noise, and high device conductance, all of which limit the accuracy and energy efficiency. Electrochemical three-terminal transistors, in which the channel conductance can be tuned without filament formation provide an alternative platform for synaptic electronics. In this work, an all-solid-state electrochemical transistor made with Li ion–based solid dielectric and 2D α-phase molybdenum oxide (α-MoO 3 ) nanosheets as the channel is demonstrated. These devices achieve nonvolatile conductance modulation in an ultralow conductance regime (<75 nS) by reversible intercalation of Li ions into the α-MoO 3 lattice. Based on this operating mechanism, the essential functionalities of synapses, such as short- and long-term synaptic plasticity and bidirectional near-linear analog weight update are demonstrated. Simulations using the handwritten digit data sets demonstrate high recognition accuracy (94.1%) of the synaptic transistor arrays. These results provide an insight into the application of 2D oxides for large-scale, energy-efficient neuromorphic computing networks.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Thermal Conductivity and Phonon Scattering Processes of ALD Grown PbTe–PbSe Thermoelectric Thin Films

Abstract This work studies the thermal conductivity and phonon scattering processes in a series of n‐type lead telluride‐lead selenide (PbTe–PbSe) nanostructured thin films grown by atomic layer deposition (ALD). The ALD growth of the PbTe–PbSe samples in this work results in nonepitaxial films grown directly on native oxide/Si substrates, where the Volmer–Weber mode of growth promotes grains with a preferred columnar orientation. The ALD growth of these lead‐rich PbTe, PbSe, and PbTe–PbSe thin films results in secondary oxide phases, along with an increase microstructural quality with increased film thickness. The compositional variation and resulting point and planar defects in the PbTe–PbSe nanostructures give rise to additional phonon scattering events that reduce the thermal conductivity below that of the corresponding ALD‐grown control PbTe and PbSe films. Temperature‐dependent thermal conductivity measurements show that the phonon scattering in these ALD‐grown PbTe–PbSe nanostructured materials, along with ALD‐grown PbTe and PbSe thin films, are driven by extrinsic defect scattering processes as opposed to phonon–phonon scattering processes intrinsic to the PbTe or PbSe phonon spectra. The implication of this work is that polycrystalline, nanostructured ALD composites of thermoelectric PbTe–PbSe films are effective in reducing the phonon thermal conductivity, and represent a pathway for further improvement of the figure of merit ( ZT ), enhancing their thermoelectric application potential.

DeCoster, Mallory E.↗

Thermal Conductivity of HfTe 5 : A Critical Revisit

Hafnium pentatelluride (HfTe 5 ) has attracted extensive interest due to its exotic electronic, optical, and thermal properties. As a highly anisotropic crystal (layered structure with in-plane chains), it has highly anisotropic electrical-transport properties, but the anisotropy of its thermal-transport properties has not been established. Here, accurate experimental measurements and theoretical calculations are combined to resolve this issue. Time-domain thermoreflectance measurements find a highly anisotropic thermal conductivity, 28:1:8, with values of 11.3 ± 2.2, 0.41 ± 0.04, and 3.2 ± 2.0 W m -1 K -1 along the in-plane a-axis, through-plane b-axis, and in-plane c-axis, respectively. This anisotropy is even larger than what was recently established for ZrTe 5 (12:1:6), but the individual values are somewhat higher, even though Zr has a smaller atomic mass than Hf. Density-functional-theory calculations predict thermal conductivities in good agreement with the experimental data, provide comprehensive insights into the results, and reveal the origin of the apparent anomaly of the relative thermal conductivities of the two pentatellurides. These results establish that HfTe 5 and ZrTe 5 , and by implication their alloys, have highly anisotropic and ultralow through-plane thermal conductivities, which can provide guidance for the design of materials for new directional-heat-management applications and potentially other thermal functionalities.

36 MATERIALS SCIENCE↗

Balancing Ionic and Electronic Conduction for High‐Performance Organic Electrochemical Transistors

Abstract Conjugated polymers that support mixed (electronic and ionic) conduction are in demand for applications spanning from bioelectronics to energy harvesting and storage. To design polymer mixed conductors for high‐performance electrochemical devices, relationships between the chemical structure, charge transport, and morphology must be established. A polymer series bearing the same p‐type conjugated backbone with increasing percentage of hydrophilic, ethylene glycol side chains is synthesized, and their performance in aqueous electrolyte gated organic electrochemical transistors (OECTs) is studied. By using device physics principles and electrochemical analyses, a direct relationship is found between the OECT performance and the balanced mixed conduction. While hydrophilic side chains are required to facilitate ion transport—thus enabling OECT operation—swelling of the polymer is not de facto beneficial for balancing mixed conduction. It is shown that heterogeneous water uptake disrupts the electronic conductivity of the film, leading to OECTs with lower transconductance and slower response times. The combination of in situ electrochemical and structural techniques shown here contributes to the establishment of the structure–property relations necessary to improve the performance of polymer mixed conductors and subsequently of OECTs.

Savva, Achilleas↗

Open-Shell Donor–Acceptor Conjugated Polymers with High Electrical Conductivity

Conductive polymers largely derive their electronic functionality from chemical doping, processes by which redox and charge-transfer reactions form mobile carriers. While decades of research have demonstrated fundamentally new technologies that merge the unique functionality of these materials with the chemical versatility of macromolecules, doping and the resultant material properties are not ideal for many applications. Here, it is demonstrated that open-shell conjugated polymers comprised of alternating cyclopentadithiophene and thiadiazoloquinoxaline units can achieve high electrical conductivities in their native “undoped” form. Spectroscopic, electrochemical, electron paramagnetic resonance, and magnetic susceptibility measurements demonstrate that this donor–acceptor architecture promotes very narrow bandgaps, strong electronic correlations, high-spin ground states, and long-range π-delocalization. A comparative study of structural variants and processing methodologies demonstrates that the conductivity can be tuned up to 8.18 S cm -1 . This exceeds other neutral narrow bandgap conjugated polymers, many doped polymers, radical conductors, and is comparable to commercial grades of poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene). X-ray and morphological studies trace the high conductivity to rigid backbone conformations emanating from strong π-interactions and long-range ordered structures formed through self-organization that lead to a network of delocalized open-shell sites in electronic communication. The results offer a new platform for the transport of charge in molecular systems.

36 MATERIALS SCIENCE↗