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At least 793 records · Page 44

An Effect of Chemical Modification of Surface of Carbon Nanotubes on Their Thermal Conductivity

An effect of partial chemical modification of the surface of a single-walled carbon nanotube on its thermal conductivity is studied. Numerical simulation of heat transfer showed that partial hydrogenation (fluorination) of a nanotube (addition of hydrogen and fluorine atoms from its outer side) can lead to more than a tenfold decrease in thermal conductivity. When the length of the nanotube increases, its thermal conductivity increases in proportion to the logarithm of the length, whereas the proportionality coefficient decreases with an increase in density of hydrogen or fluorine atoms attached. A thermal conductivity reduction coefficient does not depend on the length of the nanotube, but depends on temperature (the lower the temperature, the stronger the decrease) and density of the attached atoms p. When p < 0.25, an increase in density monotonically decreases the thermal conductivity. A decrease is maximum, when density p is 0.25. If only one half of the nanotube is hydrogenated, this half has a lower thermal conductivity. Such a nanotube becomes anisotropic and can be used as a heat transfer rectifier with no more than two percent rectification efficiency.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

An Investigation of LSF-YSZ Conductive Scaffolds for Infiltrated SOFC Cathodes

Porous composites of Sr-doped LaFeO 3 (LSF) and yttria-stabilized zirconia (YSZ) were investigated as conductive scaffolds for infiltrated SOFC cathodes with the goal of producing scaffolds for which only a few perovskite infiltration steps are required to achieve sufficient conductivity. While no new phases form when LSF-YSZ composites are calcined to 1623 K, shifts in the lattice parameters indicate Zr can enter the perovskite phase. Measurements on dense, LSF-YSZ composites show that the level of Zr doping depends on the Sr:La ratio. Because conductivity of undoped LSF increases with Sr content while both the ionic and electronic conductivities of Zr-doped LSF decrease with the level of Zr in the perovskite phase, there is an optimum initial Sr content corresponding to La 0.9 Sr 0.1 FeO 3 (LSF91). Although scaffolds made with 100% LSF had a higher conductivity than scaffolds made with 50:50 LSF-YSZ mixtures, the 50:50 mixture provides the optimal interfacial structure with the electrolyte and sufficient conductivity, providing the best cathode performance upon infiltration of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF).

36 MATERIALS SCIENCE↗

Using data-science approaches to unravel insights for enhanced transport of lithium ions in single-ion conducting polymer electrolyte

Solid polymer electrolytes have yet to achieve the an ionic conductivity > 1 mS/cm at room temperature for realistic applications. This target implies the need to reduce the effective energy barriers of ion transport in polymer electrolytes to around 20 kJ/mol. In this work, we combine information extracted from existing experimental results with theoretical calculations to provide insights into ion transport in single-ion conductors (SICs) with a focus on lithium ion SICs. Through the analysis of temperature-dependent ionic conductivity data obtained from the literature, we evaluate different methods of extracting energy barriers for lithium transport. The traditional Arrhenius fit to the temperature-dependent ionic conductivity data indicates that the Meyer-Neldel rule holds for SICs. However, the values of the fitting parameters remain unphysical. Our modified approach based on recent work (Macromolecules, 56, 15, 6051(2023)), which incorporates a fixed pre-exponential factor, reveals that the energy barriers exhibit temperature dependence over a wide range of temperatures. Using this approach, we identify a series of anions leading to the energy barriers less than 30 kJ/mol, which include trifluoromethane sulfonimide (TFSI), fluoromethane sulfonimide (FSI), and boron-based organic anions. In our efforts to design the next generation of anions, which can exhibit the energy barriers less than 20 kJ/mol, we focused on boron-containing SICs, and performed density functional theory (DFT) based calculations to connect the chemical structures via the binding energy of cation (lithium)-anion pairs with the experimentally derived effective energy barriers for ion transport. Not only have we identified a correlation between the binding energy and the energy barriers, but we also propose a strategy to design new boron-based anions by using the correlation. This combined approach involving experiments and theoretical calculations is capable of facilitating the identification of promising new anions, which can exhibit ionic conductivity $> 1$ mS/cm near room temperature, thereby expediting the development of novel superionic single-ion conducting polymer electrolytes. The published datasets include all the temperature-dependent ionic conductivity collected from the literature with literature DOIs, DFT calculated binding energies, and python scripts to analyze data, construct statistical models, and generate plots.

36 MATERIALS SCIENCE↗

The thermal conductivity of mixed fuel U x Pu 1-x O 2 : molecular dynamics simulations

Mixed oxides (MOX), in the context of nuclear fuels, are a mixture of the oxides of heavy actinide elements such as uranium, plutonium and thorium. The interest in the UO 2 -PuO 2 system arises from the fact that these oxides are used both in fast breeder reactors (FBRs) as well as in pressurized water reactors (PWRs). The thermal conductivity of UO 2 fuel is an important material property that affects fuel performance since it is the key parameter determining the temperature distribution in the fuel, thus governing, e.g., dimensional changes due to thermal expansion, fission gas release rates, etc. For this reason it is important to understand the thermal conductivity of MOX fuel and how it differs from UO 2 . Here, molecular dynamics (MD) simulations are carried out to determine quantitatively, the effect of mixing on the thermal conductivity of U x Pu 1-x O 2 , as a function of PuO 2 concentrations, for a range of temperatures, 300 – 1500 K. The results will be used to develop enhanced continuum thermal conductivity models for MARMOT and BISON by INL. These models express the thermal conductivity as a function of microstructure state-variables, thus enabling thermal conductivity models with closer connection to the physical state of the fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NSUF RTE completion report for 23-4780: Microstructural Defect Induced Thermal Conductivity Reduction in Uranium Nitride and Thorium Nitride

Uranium nitride (UN) is known to have a higher thermal conductivity than traditional oxide fuels, which could lead to a more efficient energy transport and lower local temperature during its lifetime. But the thermal transport performance of UN in extreme environments has not been systematic studied. This study investigated the irradiation induced microstructural defects in UN and the impacts on thermal conductivity. The samples were produced by spark plasma sintering at University of Texas-San Antonio (UTSA), Los Alamos National Laboratory (LANL), and Idaho National Laboratory (INL). Thermal conductivity of UN before and after 2MeV proton irradiation were measured by using laser metrology at INL in a temperature range of 77-295K. Thermal conductivity measurements in this wide, cryogenic temperature range is critical to understand the phonon scattering mechanisms between the thermal energy carrier, phonons, and different types of irradiation-induced defects. In order to ensure the measurements were conducted in the same grains and minimize the impact of the local heterogeneities, the measurement locations were highlighted by fiducial marks using the focused ion beam (FIB) with grain orientation identified using the electron backscatter diffraction (EBSD) at the Center of Advanced Energy Studies (CAES). Irradiation experiment was conducted at the Ion Beam Laboratory at Texas A&M University (TAMU). A total of 6 samples were irradiated with different irradiation doses and temperatures. After irradiation, the microstructure was characterized by using Transmission Electron Microscope (TEM) at CAES (also in the FIB marks).

36 - MATERIALS SCIENCE↗

The Evaporation and Survival of Cluster Galaxy Coronae. I. The Effectiveness of Isotropic Thermal Conduction Including Saturation

We simulate the evolution of cluster galaxy hot interstellar medium (ISM) gas that is a result of the effects of ram pressure and thermal conduction in the intracluster medium (ICM). At the density and temperature of the ICM, the mean free paths of ICM electrons are comparable to the sizes of galaxies, therefore electrons can efficiently transport heat that is due to thermal conduction from the hot ICM to the cooler ISM. Galaxies consisting of dark matter halos and hot gas coronae are embedded in an ICM-like “wind tunnel” in our simulations. In this paper, we assume that thermal conduction is isotropic and include the effects of saturation. We find that as heat is transferred from the ICM to the ISM, the cooler denser ISM expands and evaporates. This process is significantly faster than gas loss due to ram pressure stripping; for our standard model galaxy, the evaporation time is 160 Myr, while the ram pressure stripping timescale is 2.5 Gyr. Thermal conduction also suppresses the formation of shear instabilities, and there are no stripped ISM tails since the ISM evaporates before tails can form. Observations of long-lived X-ray emitting coronae and ram pressure stripped X-ray tails in galaxies in group and cluster environments therefore require that thermal conduction is suppressed or offset by some additional physical process. The most likely process is anisotropic thermal conduction that is due to magnetic fields in the ISM and ICM, which we simulate and study in the next paper in this series.

79 ASTRONOMY AND ASTROPHYSICS↗

The Evaporation and Survival of Cluster Galaxies’ Coronae. II. The Effectiveness of Anisotropic Thermal Conduction and Survival of Stripped Galactic Tails

We simulate anisotropic thermal conduction between the intracluster medium (ICM) and the hot coronal interstellar medium (ISM) gas in cluster galaxies. In Paper I, we simulated the evaporation of the hot ISM due to isotropic (possibly saturated) conduction between the ISM and ICM. We found that hot coronae evaporate on ∼10{sup 2} Myr timescales, significantly shorter than the ∼10{sup 3} Myr gas loss times due to ram pressure stripping. No tails of stripped gas are formed. This is in tension with the observed ubiquity and implied longevity of compact X-ray coronae and stripped ISM tails, and requires the suppression of evaporation, possibly due to magnetic fields and anisotropic conduction. We perform a series of wind tunnel simulations similar to that in Paper I, now including ISM and ICM magnetic fields. We simulate the effect of anisotropic conduction for a range of extreme magnetic field configurations: parallel and perpendicular to the ICM wind, and continuous and completely disjointed between the ISM and ICM. We find that when conduction is anisotropic, gas loss due to evaporation is severely reduced; the overall gas loss rates with and without anisotropic conduction do not differ by more than 10%–20%. Magnetic fields also prevent stripped tails from evaporating in the ICM by shielding, and providing few pathways for heat transport between the ICM and ISM. The morphology of stripped tails and magnetic fields in the tails and wakes of galaxies are sensitive to the initial magnetic field configuration.

79 ASTRONOMY AND ASTROPHYSICS↗

RF Characterization of a Photocurable PEDOT:PSS:PEGDA Conductive Biomaterial for 3D-Printing Implantable Antennas

In this work, we demonstrate photocurable PEDOT:PSS:PEGDA biomaterial as a promising candidate for intracorporeal 3D printing. Intracorporeal 3D printing offers a less invasive method which offer flexibility to tailor the form factor of printed structures. Previous work has demonstrated the feasibility of a robotic probe to 3D-print biological tissues intracorporeally via a minor incision. This same probe could also 3D-print implantable antennas as long as a suitable conductive material is identified in terms of conductivity, biocompatibility, and ability to cure at room/body temperature for safety purposes. We assess the frequency-dependent conductivity of this biomaterial and explore the Radio-Frequency (RF) performance of resulting antennas operating in free-space and inside tissue-emulating phantoms. Results show that PEDOT:PSS biomaterial with 21% and 30% PEGDA content exhibit a conductivity of ~10 4 S/m up to 5 GHz, suitable for wireless implants. Comparing the two, 21% PEGDA content exhibits poorer curing abilities, while 30% PEGDA exhibits slightly lower conductivity. Measurements for 2.4 GHz free-space dipoles conducted in an anechoic chamber reveal only ~0.8 dB and ~1 dB lower gain for PEDOT:PSS:21%PEGDA and PEDOT:PSS:30%PEGDA biomaterial, respectively, as compared to their copper counterpart. For a 5 mm-deep implanted patch antenna, these two biomaterials exhibit 3.05 dB and 3.84 dB higher transmission loss than copper, respectively. If deemed necessary, this performance degradation can be overcome by increasing the overall antenna size since the printing process is now minimally invasive and miniaturization requirements can be relaxed.

3D-printing↗

Status Report on Separate Effects Testing of Thermal Conductivity of U-Zr Alloy

Phases by definition in an alloy system have distinct physical and chemical properties, including thermal conductivity. The goal of this multi-year study is to show that the different phases present in the U-Zr system indeed do have different thermal conductivities. This study will provide meso-scale (10-100 µm) experimental observations using the Thermal Conductivity Microscope (TCM) of phase dependent thermal conductivity. The results of this study may indicate the need to reconsider the application of homogeneous medium assumption for metallic nuclear fuel that is currently used in fuel performance modeling, and could provide input for improving such model using a heterogeneous phase dependent assessment of thermal properties. The local thermal conductivity values from the TCM will be compared to the bulk measurements to validate this work. Twelve alloy samples with varying Zr compositions and heat treatments were fabricated for the initial phase of this study to characterize the individual phases present in the U-Zr system. The gamma body-centered cubic (BCC) phase was successfully identified in the appropriate size for TCM measurement. Next steps in this work will include identification of remaining phases in the U-Zr alloy system. Thermal conductivity will be measured in those phase areas of the materials and used to assess fuel performance codes for improvements.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Controlled Hysteresis of Conductance in Molecular Tunneling Junctions

The problem this paper addresses is the origin of the hysteretic behavior in two-terminal molecular junctions made from an EGaIn electrode and self-assembled monolayers of alkanethiolates terminated in chelates (transition metal dichlorides complexed with 2,2'-bipyridine; BIPY-MCl 2 ). The hysteresis of conductance displayed by these BIPY-MCl 2 junctions changes in magnitude depending on the identity of the metal ion (M) and the window of the applied voltage across the junction. The hysteretic behavior of conductance in these junctions appears only in an incoherent (Fowler–Nordheim) tunneling regime. When the complexed metal ion is Mn(II), Fe(II), Co(II), or Ni(II), both incoherent tunneling and hysteresis are observed for a voltage range between +1.0 V and –1.0 V. When the metal ion is Cr(II) or Cu(II), however, only resonant (one-step) tunneling is observed, and the junctions exhibit no hysteresis and do not enter the incoherent tunneling regime. Using this correlation, the conductance characteristics of BIPY-MCl 2 junctions can be controlled. Furthermore, this voltage-induced change of conductance demonstrates a simple, fast, and reversible way (i.e., by changing the applied voltage) to modulate conductance in molecular tunneling junctions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Conductivity and Electron-Transfer Validation in an n-Type Fluoride-Anion-Doped Polymer for Thermoelectrics in Air

Air-stable and soluble tetrabutylammonium fluoride (TBAF) is demonstrated as an efficient n-type dopant for the conjugated polymer ClBDPPV. Electron transfer from F - anions to the π-electron-deficient ClBDPPV through anion–π electronic interactions is strongly corroborated by the combined results of electron spin resonance, UV–vis–NIR, and ultraviolet photoelectron spectroscopy. Doping of ClBDPPV with 25 mol% TBAF boosts electrical conductivity to up to 0.62 S cm -1 , among the highest conductivities that have been reported for solution-processed n-type conjugated polymers, with a thermoelectric power factor of 0.63 µW m -1 K -2 in air. Importantly, the Seebeck coefficient agrees with recently published correlations to conductivity. Moreover, the F - -doped ClBDPPV shows significant air stability, maintaining the conductivity of over 0.1 S cm -1 in a thick film after exposure to air for one week, to the best of our knowledge the first report of an air-stable solution-processable n-doped conductive polymer with this level of conductivity. The result shows that using solution-processable small-anion salts such as TBAF as an n-dopant of organic conjugated polymers possessing lower LUMO (lowest unoccupied molecular orbital), less than -4.2 eV) can open new opportunities toward high-performance air-stable solution-processable n-type thermoelectric (TE) conjugated polymers.

36 MATERIALS SCIENCE↗

Revisiting the Role of Conductivity and Polarity of Host Materials for Long-Life Lithium–Sulfur Battery

Despite their high theoretical energy density and low cost, lithium-sulfur batteries (LSBs) suffer from poor cycle life and low energy efficiency owing to the polysulfides shuttle and the electronic insulating nature of sulfur. Conductivity and polarity are two critical parameters for the search of optimal sulfur host materials. However, their role in immobilizing polysulfides and enhancing redox kinetics for long-life LSBs are not fully understood. In this work we have conducted an evaluation on the role of polarity over conductivity by using a polar but nonconductive platelet ordered mesoporous silica (pOMS) and its replica platelet ordered mesoporous carbon (pOMC), which is conductive but nonpolar. It is found that the polar pOMS/S cathode with a sulfur mass fraction of 80 wt% demonstrates outstanding long-term cycle stability for 2000 cycles even at a high current density of 2C. Furthermore, the pOMS/S cathode with a high sulfur loading of 6.5 mg cm -2 illustrates high areal and volumetric capacities with high capacity retention. Complementary physical and electrochemical probes clearly show that surface polarity and structure are more dominant factors for sulfur utilization efficiency and long-life, while the conductivity can be compensated by the conductive agent involved as a required electrode material during electrode preparation. The present findings shed new light on the design principles of sulfur hosts towards long-life and highly efficient LSBs.

25 ENERGY STORAGE↗

Silicon Wafers with Facet-Dependent Electrical Conductivity Properties

By breaking intrinsic Si (100) and (111) wafers to expose sharp {111} and {112} facets, electrical conductivity measurements on single and different silicon crystal faces were performed through contacts with two tungsten probes. While Si {100} and {110} faces are barely conductive at low applied voltages, as expected, the Si {112} surface is highly conductive and Si {111} surface also shows good conductivity. Asymmetrical I–V curves have been recorded for the {111}/{112}, {111}/{110}, and {112}/{110} facet combinations because of different degrees of conduction band bending at these crystal surfaces presenting different barrier heights to current flow. In particular, the {111}/{110} and {112}/{110} facet combinations give I–V curves resembling those of p–n junctions, suggesting a novel field effect transistor design is possible capitalizing on the pronounced facet-dependent electrical conductivity properties of silicon.

36 MATERIALS SCIENCE↗

Impacts of the Conductive Networks on Solid‐State Battery Operation

The micromorphology of composite cathodes is known to play a vital role in determining all-solid-state battery (ASSB) performance. However, much of our current understanding is derived from empirical observations, lacking a deeper mechanistic foundation. The “rocking chair” concept of battery chemistry requires maintaining charge neutrality, emphasizing the necessity of examining electrode micromorphology from the perspective of conductive networks. This study systematically investigates the microscopic electrochemical impacts of conductive network micromorphology by varying the Li + -to-e − channel ratio in cathodes comprising LiNbO 3 -coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 , Li 6 PS 5 Cl, and carbon fibers. Utilizing multiscale synchrotron-based spectro-microscopy, we unravel that unbalanced Li + and e − conducting channels intensify charge polarization within active cathode particles and accelerate their degradation. A further model system with X-ray nano-tomography resolved e − and Li + channels indicates that spatially uniform and well-paired Li + and e − conducting channels are highly desirable as they could promote more uniform lithiation/delithiation, mitigating microscopic electrochemical polarization. Electrode-scale X-ray holotomography analysis reveals that the impact of conductive networks is particle-size-dependent, with smaller cathode particles being more significantly affected. These findings provide mechanistic insights into the interplay between conductive networks and all-solid-state battery operation, laying the groundwork for rational design and optimization of cathode architectures in future solid-state battery technologies.

36 MATERIALS SCIENCE↗

Magnetic Field Effects on Optical Conductivity of Doped Armchair Graphene Nanoribbon

We address the optical conductivity of armchair graphene nanoribbon within tight-binding model Hamiltonian using Green’s function approach. The possible effects of ribbon width, magnetic field, and chemical potential on optical absorption are investigated. We have also found the dependence of the optical conductivity for various ribbon widths and chemical potentials. Our results show a peak appears in the frequency dependence of optical conductivity of graphene nanoribbon. Upon increasing ribbon width, the height of the optical conductivity at frequency of peak increases. Also, applying the magnetic field causes an increase of the optical conductivity. However, upon more increase of the magnetic field leads to a decrease of the optical conductivity. Moreover, we study the effects of chemical potentials on frequency behavior of optical absorption of graphene nanoribbon for both metallic and insulator cases.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

An Integrated Numerical Method to Predict the Strain Sensing Behavior of Flexible Conductive Fibers under Electric–Thermal Conditions

Flexible conductive textiles have attracted an increasing amount of attention due to being flexible and stretchable with multi-functions, in addition to the strain sensing function. In this paper, an integrated numerical method is established to predict the strain sensing behavior of PPy-coated flexible conductive fibers. Based on our previous investigation on the strain sensing behavior of the PPy-coated elastic conductive fibers, it has been known that the main strain sensing mechanisms of the conductive fibers are micro-cracks opening under stretching and closing under unloading. Therefore, in the numerical approach, extended finite element method is used to simulate the multi-crack initiation and propagation. Then, by establishing a representative element model including a single crack, the resistance variation with the increase in crack width/depth can be obtained using the electric–thermal package in ABAQUS software. Combining the relationship between crack width and strain, the relationship between fractional increment in resistance (ΔR/R{sub 0}) and the strain can be obtained. The prediction of the fractional increment in resistance (ΔR/R{sub 0}) versus strain is consistent with the experimental results of PPy-coated Lycra fibers. The new integrated method is further verified by experimental results of PPy-coated XLA fibers, showing that the integrated numerical approach can capture the complicated strain sensing mechanisms of PPy-coated elastic fibers and predict the strain sensing behavior of flexible conductive fibers. This approach will make it possible to shorten the period, and reduce the cost in R&D of the PPy-coated electrically conductive fibers, comparing with the corresponding experimental work.

36 MATERIALS SCIENCE↗

Duality of the Interfacial Thermal Conductance in Graphene-based Nanocomposites

The thermal conductance of graphene-matrix interfaces plays a key role in controlling the thermal transport properties of graphene-based nanocomposites. Using classical molecular dynamics simulations, we found that the interfacial thermal conductance depends strongly on the mode of heat transfer at the graphene-matrix interfaces: if heat enters graphene from one side of its basal plane and immediately leaves the graphene through the other side, the corresponding interfacial thermal conductance, G(across), is large; if heat enters graphene from both sides of its basal plane and leaves the graphene at a position far away on its basal plane, the corresponding interfacial thermal conductance, G(non-across), is small. For a single-layer graphene immersed in liquid octane, G(across) is ~150 MW/m2K while Gnon-across is ~5 MW/m2K. G(across) decreases with increasing multi-layer graphene thickness (i.e., number of layers in graphene) and approaches an asymptotic value of 100 MW/m2K for 7-layer graphenes. G(non-across) increases only marginally as the graphene sheet thickness increases. Such a duality of the interface thermal conductance for different probing methods and its dependence on graphene sheet thickness can be traced ultimately to the unique physical and chemical structure of graphene materials. The ramifications of these results in areas such as experimental measurement of thermal conductivity of graphene and the design of graphene-based thermal nanocomposites are discussed.

Liu, Ying↗

Characterization of ultralow thermal conductivity in anisotropic pyrolytic carbon coating for thermal management applications

Pyrolytic carbon (PyC) is an important material used in many applications including thermal management of electronic devices and structural stability of ceramic composites. Accurate measurement of physical properties of structures containing textured PyC layers with few-micrometer thickness poses new challenges. Here a laser-based thermoreflectance technique is used to measure thermal conductivity in a 30-μm-thick textured PyC layer deposited using chemical vapor deposition on the surface of spherical zirconia particles. Raman spectroscopy is used to confirm the graphitic nature and characterize microstructure of the deposited layer. Room temperature radial and circumferential thermal conductivities are found to be 0.28 W m –1 K –1 and 11.5 W m –1 K –1 , corresponding to cross-plane and in-plane conductivities of graphite. While the anisotropic ratio of the in-plane to cross-plane conductivities is smaller than previous results, the magnitude of the smallest conductivity is noticeably smaller than previously reported values for carbon materials and offers opportunities in thermal management applications. Very low in-plane and cross-plane thermal conductivities are attributed to strong grain boundary scattering, high defect concentration, and small inter-laminar porosity. Lastly, experimental results agree with the prediction of thermal transport model informed by the microstructure information revealed by Raman spectroscopy.

36 MATERIALS SCIENCE↗