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At least 811 records · Page 45

Fundamental studies of thermal and electrical transport in microporous metal-organic frameworks

In this work, we established porous metal-organic frameworks (MOFs) as designer conductors of electrons and ions relevant to fundamental research and technological applications. MOFs are porous, crystalline materials composed of organic linkers and inorganic nodes. While most MOFs are insulating with respect to ionic and electronic charge carriers, a number of exceptions have been reported in recent years. Electrically conductive MOFs are highly attractive for applications including electrical energy storage, chemiresistive sensing, and optoelectronics because of their high surface areas and tunable chemical properties. Ion-conducting MOFs are desirable for the synthetically tunable size, shape, and polarity of their pore environments, allowing for the tailored development of solid state electrolytes for metal-ion batteries. We developed systematic strategies for the design of MOFs that conduct ions and electrons. For each objective, we leveraged the versatile chemistry of these materials to obtain frameworks with targeted properties towards electronic or ionic charge carriers. We studied the factors that govern electrical transport in MOFs in order to gain fundamental knowledge of this emerging class of materials. We took several approaches to tackle this problem from multiple angles. Namely, we synthesized and characterized new frameworks, investigated post-synthetic modifications to enhance conductivity, and correlated theory and experiment to uncover new mechanistic findings. These results, which put forth new design principles for conductive MOFs, move the field toward one of the DOE Basic Energy Sciences Grand Challenges: to “design and perfect atom- and energy-efficient synthesis of revolutionary new forms of matter with tailored properties.” In addition to investigating the movement of electrons in MOFs, we also studied the movement of other charged species in MOFs, such as protons, lithium, and magnesium. Proton-conducting frameworks could be appealing materials for solid state electrolytes in fuel cells. In addition, they contain crystallographically defined proton-conducting channels, in contrast with state-of-the-art polymer membranes such as Nafion, which are amorphous. Controlling pore size and polarity in MOFs can thus shed light on proton and other ion transport mechanisms, ultimately enabling the design of more advanced electrolyte materials and potentially novel electrical energy storage materials.

36 MATERIALS SCIENCE↗

Bipolar Battery Using Conductive-Fiber Composite

Improved version of lead/sulfuric acid battery, electrically-conducting fiber/polymer composite substrates used in place of metallic substrates. Sealing and corrosion problems reduced. Benefits include halving of weight, increased energy and power densities, and lower gassing rate. Important for electric-vehicle development.

Rippel, Wally E.↗

Embedded Sensors for Measuring Surface Regression

The development and evaluation of new hybrid and solid rocket motors requires accurate characterization of the propellant surface regression as a function of key operational parameters. These characteristics establish the propellant flow rate and are prime design drivers affecting the propulsion system geometry, size, and overall performance. There is a similar need for the development of advanced ablative materials, and the use of conventional ablatives exposed to new operational environments. The Miniature Surface Regression Sensor (MSRS) was developed to serve these applications. It is designed to be cast or embedded in the material of interest and regresses along with it. During this process, the resistance of the sensor is related to its instantaneous length, allowing the real-time thickness of the host material to be established. The time derivative of this data reveals the instantaneous surface regression rate. The MSRS could also be adapted to perform similar measurements for a variety of other host materials when it is desired to monitor thicknesses and/or regression rate for purposes of safety, operational control, or research. For example, the sensor could be used to monitor the thicknesses of brake linings or racecar tires and indicate when they need to be replaced. At the time of this reporting, over 200 of these sensors have been installed into a variety of host materials. An MSRS can be made in either of two configurations, denoted ladder and continuous (see Figure 1). A ladder MSRS includes two highly electrically conductive legs, across which narrow strips of electrically resistive material are placed at small increments of length. These strips resemble the rungs of a ladder and are electrically equivalent to many tiny resistors connected in parallel. A substrate material provides structural support for the legs and rungs. The instantaneous sensor resistance is read by an external signal conditioner via wires attached to the conductive legs on the non-eroding end of the sensor. The sensor signal can be transmitted from inside a high-pressure chamber to the ambient environment, using commercially available feedthrough connectors. Miniaturized internal recorders or wireless data transmission could also potentially be employed to eliminate the need for producing penetrations in the chamber case. The rungs are designed so that as each successive rung is eroded away, the resistance changes by an amount that yields a readily measurable signal larger than the background noise. (In addition, signal-conditioning techniques are used in processing the resistance readings to mitigate the effect of noise.) Hence, each discrete change of resistance serves to indicate the arrival of the regressing host material front at the known depth of the affected resistor rung. The average rate of regression between two adjacent resistors can be calculated simply as the distance between the resistors divided by the time interval between their resistance jumps. Advanced data reduction techniques have also been developed to establish the instantaneous surface position and regression rate when the regressing front is between rungs.

Gramer, Daniel J.↗

Review of thermophysical property methods applied to fueled and un-fueled molten salts

Recent investigation into designs of molten salt reactors (MSR) requires accurate data of candidate salts. Review of the literature shows lacking thermophysical (TP) property data for coolants and fuel-bearing salts of Advanced High Temperature Reactors (AHTR). Measurement uncertainties of current data are even more deficient, and this affects ongoing research where MSR modeling and testing are being performed. Melting temperature, viscosity, density, specific heat capacity, and thermal and electrical conductivity measurements are often not arranged together or discussed in great detail, especially for fuel-bearing salts. Raw data from key findings spanning over 70 years for LiF, LiF-BeF 2 , LiF-NaF-KF, KCl-MgCl 2 , KF-ZrF 4 , and NaF-KF-MgF 2 have been organized and presented here. Brief description of methods used to obtain these results, in addition to the TP data of some of these salts as fuel carriers, has also been discussed. Thermal conductivity data are particularly weak due to older, high-error measurement techniques. More recent measurement systems to evaluate salt thermal conductivity show promise for obtaining consistent absolute values. This work concludes that measurement systems such as transient hot-wire method, forced Rayleigh scattering, and laser flash analysis provide the most promise to fill these data gaps and reduce current uncertainty in thermal conductivity measurements of both fueled and un-fueled molten salts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Experiments On Transparent Conductive Films For Spacecraft

Report describes experiments on thin, transparent, electrically conductive films made, variously, of indium tin oxide covered by magnesium fluoride (ITO/MgF2), aluminum-doped zinc oxide (AZO), or pure zinc oxide (ZnO). Films are candidates for application to such spacecraft components, including various optoelectronic devices and window surfaces that must be protected against buildup of static electric charge. On Earth, such films useful on heat mirrors, optoelectronic devices, gas sensors, and automotive and aircraft windows.

Perez-Davis, Marla E.↗

Two-Dimensional Conductive Ni-HAB as a Catalyst for the Electrochemical Oxygen Reduction Reaction

Catalytic systems whose properties can be systematically tuned via changes in synthesis conditions are highly desirable for the next-generation catalyst design and optimization. Herein, we present a two-dimensional (2D) conductive metal–organic framework consisting of M-N 4 units (M = Ni, Cu) and a hexaaminobenzene (HAB) linker as a catalyst for the oxygen reduction reaction. By varying synthetic conditions, we prepared two Ni-HAB catalysts with different crystallinities, resulting in catalytic systems with different electric conductivities, electrochemical activity, and stability. We show that crystallinity has a positive impact on conductivity and demonstrate that this improved crystallinity/conductivity improves the catalytic performance of our model system. Additionally, density functional theory simulations were performed to probe the origin of M-HAB’s catalytic activity, and they suggest that M-HAB’s organic linker acts as the active site with the role of the metal being to modulate the linker sites’ binding strength.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In-plane thermal conductivity and the applicability of the Wiedemann–Franz law in dilute AlCu thin films

The Wiedemann–Franz (WF) law correlates heat and charge transport in metals. However, the validity of this correlation remains an open-ended question, especially in the context of inelastic scattering at room temperature. To address this gap in knowledge, we perform independent measurements of the in-plane thermal and electrical conductivities across four AlCu (0.5% Cu) films [thickness (⁠h⁠) ≈ 174, 98, 53, and 24 nm] using optical pump–probe metrologies and four-point probe techniques, respectively. For in-plane thermal conductivity measurements, we utilize time-domain thermoreflectance, in both concentric and beam-offset configurations, and the time-resolved magneto-optic Kerr effect. Our results show that the WF law overpredicts the thermal conductivity by at least ∼10% in all films, thus demonstrating modest deviations in predicted thermal conductivity when applying the WF law to dilute AlCu films. Using infrared variable angle spectroscopic ellipsometry, we demonstrate increased electron scattering rates in the thinnest film (⁠⁠h⁠ ≈ 24 nm), indicating electron-boundary scattering drives the reduction in in-plane thermal conductivity. Furthermore, this is generally an elastic scattering process, which is supported by our thermal conductivity measurements and analysis.

Electrical conductivity↗

The influence of boundary and edge-plasma modeling in computations of axisymmetric vertical displacement

A number of previously published studies apply extended-MHD computations to model macroscopic dynamics of tokamak vertical displacement events (VDEs). The characteristic plasma-wall contact and resistive-wall diffusion imply sensitivity to boundary conditions in a general sense, but which conditions have significant influence depends on how the plasma is modeled. This work examines these dependencies by comparing results of axisymmetric extended-MHD computations with different sets of boundary conditions, plasma thermal-conduction models, and wall resistivity values. The geometry and plasma parameters of the computations represent a modest-sized tokamak. The forced-displacement scenario and computational setup are similar to those used in previous 3D computations. The results show that for a given wall resistivity, the VDE time-scale is most sensitive to variations in the boundary and thermal-conduction parameters that affect electron thermal transport. The electrical conductivity depends on electron temperature, and the dependence on thermal transport stems from its influence on the electrical circuit that includes the open-field halo current. Lastly, conditions that lead to hotter, broader halo regions slow the evolution. Significant sensitivity to the boundary condition on plasma flow-velocity exists when electron thermal conduction is restricted and electron energy loss is convective, which is expected for conditions at the entrance of the magnetic presheath.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Thermodynamic and electron transport properties of Ca 3 Ru 2 O 7 from first-principles phonon calculations and Boltzmann transport theory

Here, this work demonstrates a first-principles-based approach to obtaining finite temperature thermal and electronic transport properties which can be employed to model and understand mesoscale structural evolution during electronic, magnetic, and structural phase transitions. A computationally tractable model was introduced to estimate electron relaxation time and its temperature dependence. The model is applied to Ca 3 Ru 2 O 7 with a focus on understanding its electrical resistivity across the electronic phase transition at 48 K. A quasiharmonic phonon approach to the lattice vibrations was employed to account for thermal expansion while the Boltzmann transport theory including spin-orbit coupling was used to calculate the electron-transport properties, including the temperature dependence of electrical conductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A code-to-code benchmark for magneto-convection in a horizontal duct

Liquid metals and magnetic fields are used in many technical applications such as metallurgy, crystal growth and nuclear fusion reactors. When an electrically conducting fluid moves in a magnetic environment, electric currents and electromagnetic forces are generated that affect velocity and pressure losses in the flow. These magnetohydrodynamic (MHD) interactions have to be investigated to optimize the engineering processes. The characteristics of MHD flows depend on the geometrical configuration, the strength of the applied magnetic field, the electrical properties of fluid and structural materials and the thermal conditions. In the so-called blankets for fusion reactors, where liquid metals are used to breed the plasma fuel component tritium and to extract the generated heat, magneto-convective flows play a crucial role in determining heat and mass transfer. Therefore, the availability of numerical codes to simulate this type of flow is mandatory and their validation is a necessary step to guarantee the reliability of the results. For that reason, a benchmark problem has been defined to simulate liquid metal flows in a horizontal rectangular duct heated from below and exposed to a non-uniform magnetic field. Results obtained by five research groups using different codes are compared.

benchmark↗

Field-dependent nonelectronic contributions to thermal conductivity in a metallic ferromagnet with low Gilbert damping

Heat conduction in metals is typically dominated by electron transport since electrons carry both charge and heat. In magnetic metals magnons, or spin waves, excitations of the magnetic order can be used to transport information. Heat conduction via magnons has been previously shown mostly for insulating magnets with low Gilbert damping and resulting long spin-wave lifetimes where conduction electrons cannot contribute. Here we show that thin films of properly optimized metallic ferromagnetic (FM) alloys show significant nonelectronic contributions to heat conduction, which furthermore depend on the direction of an applied magnetic field. These measurements are enabled by micromachined thermal isolation platforms optimized for thermal conductivity measurements of thin-film systems. Electrical conductivity measurements on exactly the same samples allow application of the Wiedemann-Franz relation, which shows large nonelectronic contributions to thermal conductivity for the cobalt-iron alloy with 25% Co. This composition has been shown to have exceptionally low damping for a metallic FM. The thermal conductivity of a 75-nm-thick film of the 25% Co alloy changes by more than 20% at some temperatures, while a reference sample with 50% cobalt that has much higher damping shows no field-direction dependence. Our measurements indicate that applied magnetic fields alter the magnon lifetimes in these films and that these magnons contribute to thermal conductivity in this metallic magnetic alloy with low Gilbert damping.

36 MATERIALS SCIENCE↗

Electrodynamic induction flowmeter

Device determines velocity and electrical conductivity of a moving fluid of high electrical resistance by imposing a transverse electro-quasistatic field on the fluid. Position changes of charge accumulations induced within the fluid by the field are sensed by relative movement between fluid and sensor.

Melcher, J. A.↗

A quasi-static model of global atmospheric electricity. II - Electrical coupling between the upper and lower atmosphere

The paper presents a model of global atmospheric electricity used to examine the effect of upper atmospheric generators on the global electrical circuit. The model represents thunderstorms as dipole current generators randomly distributed in areas of known thunderstorm frequency; the electrical conductivity in the model increases with altitude, and electrical effects are coupled with a passive magnetosphere along geomagnetic field lines. The large horizontal-scale potential differences at ionospheric heights map downward into the lower atmosphere where the perturbations in the ground electric field are superimposed on the diurnal variation. Finally, changes in the upper atmospheric conductivity due to solar flares, polar cap absorptions, and Forbush decreases are shown to alter the downward mapping of the high-latitude potential pattern and the global distribution of fields and currents.

Roble, R. G.↗

Carbon Fibers Conductivity Studies

In an attempt to understand the process of electrical conduction in polyacrylonitrile (PAN)-based carbon fibers, calculations were carried out on cluster models of the fiber consisting of carbon, nitrogen, and hydrogen atoms using the modified intermediate neglect of differential overlap (MINDO) molecular orbital (MO) method. The models were developed based on the assumption that PAN carbon fibers obtained with heat treatment temperatures (HTT) below 1000 C retain nitrogen in a graphite-like lattice. For clusters modeling an edge nitrogen site, analysis of the occupied MO's indicated an electron distribution similar to that of graphite. A similar analysis for the somewhat less stable interior nitrogen site revealed a partially localized II electron distribution around the nitrogen atom. The differences in bonding trends and structural stability between edge and interior nitrogen clusters led to a two-step process proposed for nitrogen evolution with increasing HTT.

Yang, C. Y.↗

Doubly diffusive magnetic buoyancy instability in the solar interior

An investigation of the buoyancy of diffuse magnetic fields has shown that in the presence of rotation, static equilibrium configurations of the toroidal magnetic field and ambient plasma can exist. In that case, the escape of toroidal magnetic flux from the solar interior may be determined by the growth of instabilities which the equilibrium configuration may be subject to. In connection with the present investigation, it is assumed that in the region of toroidal magnetic flux amplification, the magnetic field has not as yet filamented into flux ropes, and is therefore 'diffuse'. A study is conducted of the MHD stability of an electrically conducting and differentially rotating gas in the presence of a toroidal magnetic field, an external constant gravitational field, and radiance pressure. The full dispersion relation for the magnetic buoyancy problem is developed, and the solutions of the dispersion relation are discussed.

Schmitt, J. H. M. M.↗

Preliminary investigation of the electrodynamics of a conducting tether

An introductory study of the properties of an electrically conducting tether flown from the shuttle is presented. Only a single configuration is considered: a vertical conductor moving normally across the Earth's field, connecting the shuttle to a large conducting balloon that passively extracts electrons from the ionosphere. The distortions in the plasma at maximum current collection are described, as are the local and distant wakes. Numerical values are given.

Thompson, W. B.↗

Spontaneous formation of electric current sheets and the origin of solar flares

It is demonstrated that the continuous boundary motion of a sheared magnetic field in a tenuous plasma with an infinite electrical conductivity can induce the formation of multiple electric current sheets in the interior plasma. In response to specific footpoint displacements, the quadrupolar magnetic field considered is shown to require the formation of multiple electric current sheets as it achieves a force-free state. Some of the current sheets are found to be of finite length, running along separatrix lines of force which separate lobes of magnetic flux. It is suggested that current sheets in the form of infinitely thin magnetic shear layers may be unstable to resistive tearing, a process which may have application to solar flares.

Low, B. C.↗