Electrical conductivity of Colorado oil shale to 900 °C

Electrical conductivity of oil shale from the Anvil Points Mine, Colorado was measured to temperatures > 900 °C with conductance bridges operating at frequencies from 100 to 100 000 Hz. The conductivity of low, intermediate and high grade oil shales (15,124,233 ml kg^?1, respectively) is dependent on water content up to ≈ 100 °C. At ≈ 120 °C, values of conductivity at ≈ 10^?7 S m^?1 are observed for all grades. A strong, time-dependent, increase in conductivity, beginning at ≈400 °C, marks the loss of light hydrocarbons and the formation of a conductive char. The frequency dependence of conductivity-slightly less than a decade increase in conductivity per decade increase in frequency over the temperature range 100–400 °C-vanishes at temperatures near 500 °C. At 600–800 °C, the conductivity of these oil shales reaches a maximum value which is as much as 10⁸ times larger than the conductivity near 250 °C.     

Thermogravimetry and decomposition kinetics of British Kimmeridge Clay oil shale

The characteristics of volatile matter evolution and the kinetics of thermal decomposition of British Kimmeridge Clay oil shale have been examined by thermogravimetry. TG has provided an alternative to the Fischer assay for shale grade estimation. The following relation has been derived relating TG % volatiles yield to the shale gravimetric oil yield: oil yield (g kg^?1) = (TG volatiles, % × 5.82) ? 28.1 ± 14.5 g kg^?1. A relationship has also been established for volumetric oil yield estimation: oil yield (cm³ kg^?1) = (TG volatiles, % × 4.97) – 5.43. TG is considered to give a satisfactory estimation of shale oil yield except in certain circumstances. It is found to be less reliable for low yield shales producing <≈40 cm³ kg^?1 of oil (≈10 gal ton^?1) where oil content of the TG volatiles is low: volumetric yield estimation accuracy is affected by variations in shale oil specific gravity. First order rate constants, k = 4.82 × 10^?5s^?1 (346.3 cm³ kg^?1shale) and k = 6.78 × 10^?5s^?1 (44.6cm³ kg^?1shale) have been obtained for the devolatilization of two Kimmeridge oil shales at 280 °C using isothermal TG. Using published pre-exponential frequency factors, an activation energy of ≈57.9 kJ mol^?1 is calculated for the decomposition. Preliminary kinetic studies using temperature programmed TG suggest at least a two stage process in the thermal decomposition, with two maxima in the volatiles evolution rate at ≈450 and 325 °C being obtained for some samples. Use of published pre-exponential frequency factors gives activation energies of ≈212 and 43 kJ mol^?1 for these two stages in the decomposition.     

Thermal properties of Cf/HfC and Cf/HfC-SiC composites prepared by precursor infiltration and pyrolysis

Ultra-high temperature ceramic infiltrated carbon-fibre composites were prepared by precursor infiltration and pyrolysis (PIP) using a laboratory synthesized precursor. Microstructures and thermal properties including thermal expansion, thermal diffusivity, specific heat capacity and oxidative stability are correlated. XRD reveals the presence of C_f-HfC and C_f-HfC-SiC phases without formation of oxides. The CTE observed at 1200?°C is slightly higher for C_f-HfC (3.36?×?10^?6?K^?1) compared to C_f-HfC-SiC (2.95?×?10^?6?K^?1) composites. Lower thermal diffusivity of the C_f-HfC-SiC compared to C_f-HfC composites is attributed to a thermal barrier effect and cracks in the composites which formed due to the CTE mismatch between carbon fibre and the matrix as well as CO generated during graphitization. The thermal conductivity of C_f-HfC (4.18?±?0.14?Wm^?1?K^?1) is higher than that of C_f-HfC-SiC composite (3.33?±?0.42?Wm^?1?K^?1). Composites microstructures were coarse with some protruding particles (5?μm) with a homogeneous dense (～70%) matrix (HfC and HfC-SiC) for both composites.     

Thermal expansivity and conductivity of pure and silicon-alloyed pyrocarbons

Measurements were made of the thermal expansivity (22°–1000°C) and the thermal conductivity (22°–800°C) of isotropic pyrocarbons deposited in fluidized beds and containing up to 34 wt% silicon in the form of β-silicon carbide particles. The thermal expansivity of the pure carbons was proportional to their density, while that of the silicon-alloyed carbons decreased with increasing silicon content, falling from 6·3 × 10^?°C^?1 for material containing 4 wt% silicon to 4·6 × 10^?6°C^?1 for material with 34 wt% silicon. The thermal conductivity of both pure and silicon-alloyed pyrocarbons increased with increasing temperature up to about 500°C. The room-temperature thermal conductivity of the pure carbons increased with increasing apparent crystallite height (L_c), and the conductivity of the silicon-alloyed carbons was significantly lower than that of pure pyrocarbon with the same L_c. The results suggest that silicon entering substitutionally into the carbon lattice may reduce the conductivity.     

Poly(vinyl alcohol) tissue phantoms as a robust in vitro model for heat transfer

Glutaraldehyde-crosslinked poly(vinyl alcohol) (PVA) was used to create pourable, volume-stable hydrogel tissue phantoms that demonstrate several advantages over traditional poly(acrylamide) phantoms. The crosslinker concentration, curing time, and curing temperature were tuned to produce a tissue phantom whose volume varied by <0.2% over a 25-day span. The thermal conductivity of the PVA phantoms was tuned across the physiological range from 0.475 to 0.795 W m^?1°C^?1 by incorporating inert particle fillers. Experimental thermal diffusivity trials demonstrated the method’s utility for creating reliable, versatile tissue phantoms for the in vitro study of heat transfer in biologically relevant scenarios.     

Thermal diffusivity and thermal conductivity of pyrolytic graphite from 300 to 2700° K

The thermal diffusivity and thermal conductivity of as-deposited, annealed, and stress-annealed pyrolytic graphite have been measured at room temperature and over the range 1500–2700°K. Values of the thermal conductivity parallel to the plane of deposition compare reasonably well with published results on similar materials, as do the values in the perpendicular direction at room temperature. The conductivity in the perpendicular direction for the annealed and stress-annealed materials is the first reported for such highly oriented materials at temperatures above 900°K, and they follow approximately a T^?n dependence with $\text{n ?}\text{1}\text{2}$ over the temperature range 1500–2700°K, where the conductivity is two-to-three times larger than expected from a T^?1 extrapolation from room temperature.     

Kinetics of tetralin extraction of Jordan oil shale

Isothermal kinetic data are obtained for the dissolution of Jordan oil shale in a hydrogen-donating solvent (1,2,3,4-tetrahydronaphthalene) in the temperature range 229–315 °C for untreated (as received mf) shale and 230–360 °C for the decarbonated shales. Preheating time was not accounted for in the treatment. For the untreated shale, the first-order plots have two distinct slopes at the lower temperature. For the higher temperatures, the plots fitted a single first-order expression. The activation energies were 42.6 and 85.6 kJ mol^?1 respectively. The data for the decarbonated shale fit a first-order expression with one low activation energy (E_a = 37.6 kJ mol^?1), suggesting a physical control of the dissolution process. Particle size variation showed a maximum yield at 200 mesh and smaller, although tests using large particles were hampered by settling. Solvent to shale ratios variation showed an optimum at about 180 g shale to 550 ml solvent. No effects of pressure of N₂ and H₂ upon the shale slurry yield were found. A reaction mechanism explaining the kinetic data is postulated.     

Synthesis,characterization, and thermo‐optical properties of azobenzene polyurethane containing chiral units

An optically active levoazobenzene polyurethane (PU) was synthesized and was based on the chromophore 4‐(4′‐nitrophenylazo) phenylamine, the chiral reagent L (?)‐tartaric acid, and toluene diisocyanate. The chemical structure and thermal properties were characterized by ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, and differential scanning calorimetry. The PU had high number‐ and weight‐average molecular weights up to 52 300, a large glass‐transition temperature of 235.7°C, and an optical rotation of ?18.06°, The optical parameters, including the refractive index (n) and thermo‐optic coefficient (dn/dT); the dielectric constant (?) and its variation with temperature; and the thermal volume expansion coefficient and its variation with temperature of PU were obtained. The dn/dT and ? values for the polymer were in the range ?4.1200 to 3.6257 × 10^?4 °C^?1 and 2.00 ± 0.11, respectively. The dn/dT values were one order of magnitude larger than those of inorganic glasses, such as zinc silicate glass (5.5 × 10^?6 °C^?1) and borosilicate glass (4.1 × 10^?6 °C^?1), and were larger than organic materials, such as polystyrene (?1.23 × 10^?4 °C^?1) and poly(methyl methacrylate) (?1.20 × 10^?4 °C^?1). The ? values were lower than that of alicyclic polyimide and semiaromatic polyimide. The obtained PU is expected to be useful for optical switching and optical waveguide areas. The conclusion has a little significance for the development of a new digital optical switch. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Potential thermal barrier coating materials: RE3NbO7 (RE=La, Nd,Sm, Eu,Gd, Dy) ceramics

In this work, RE₃NbO₇ ceramics are synthesized via solid‐state reaction and the phase structure is characterized by X‐ray diffraction and Raman spectroscopy. The relationship between crystal structure and thermophysical properties is determined. Except Sm₃NbO₇, each RE₃NbO₇ exhibits excellent high‐temperature phase stability. The thermal expansion coefficients increase with the decreasing RE³⁺ ionic radius, which depends on the decreasing crystal lattice energy and the maximum value reaches 11.0 × 10^?6 K^?1 at 1200°C. The minimum thermal conductivity of RE₃NbO₇ reaches 1.0 W m^?1 K^?1 and the glass‐like thermal conductivity of Dy₃NbO₇ is dominant by the high concentration of oxygen vacancy and the local structural order. The outstanding thermophysical properties pronounce that RE₃NbO₇ ceramics are potential thermal barrier coating materials.     

Microwave dielectric properties of flexible butyl rubber–strontium cerium titanate composites

Butyl rubber–strontium cerium titanate (BS) composites have been prepared by hot pressing. The tensile tests show that the BS composites are flexible. The dielectric properties of the composites have been investigated at 1 MHz and 5 GHz as a function of ceramic contents. The composite with volume fraction 0.43 of ceramic filler has a dielectric constant (ε_r) of 11.9 and dielectric loss (tan δ) 1.8 × 10^?3 at 5 GHz. The measured values of ε_r are compared with the effective values calculated using different theoretical models. The thermal conductivity of the composites is found to increase with ceramic contents and reaches a value of 4.5 Wm^?1 K^?1 for maximum filler loading 0.43 volume fraction. The coefficient of thermal expansion of the composites decreases gradually with filler loading and reaches a minimum value of 30.2 ppm °C^?1 at a volume fraction 0.43. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal properties of La2Zr2O7 double-layer thermal barrier coatings

La₂Zr₂O₇ is a promising thermal barrier coating (TBC) material. In this work, La₂Zr₂O₇ and 8YSZ-layered TBC systems were fabricated. Thermal properties such as thermal conductivity and coefficient of thermal expansion were investigated. Furnace heat treatment and jet engine thermal shock (JETS) tests were also conducted. The thermal conductivities of porous La₂Zr₂O₇ single-layer coatings are 0.50–0.66?W?m^?1?°C^?1 at the temperature range from 100 to 900°C, which are 30–40% lower than the 8YSZ coatings. The coefficients of thermal expansion of La₂Zr₂O₇ coatings are about 9–10?×?10^?6?°C^?1 at the temperature range from 200 to 1200°C, which are close to those of 8YSZ at low temperature range and about 10% lower than 8YSZ at high temperature range. Double-layer porous 8YSZ plus La₂Zr₂O₇ coatings show a better performance in thermal cycling experiments. It is likely because porous 8YSZ serves as a buffer layer to release stress.     

Thermal properties of polytetrafluoroethylene/Sr2Ce2Ti5O16 polymer/ceramic composites

Polytetrafluoroethylene (PTFE) composites filled with Sr₂Ce₂Ti₅O₁₆ ceramic were prepared by a powder processing technique. The structures and microstructures of the composites were investigated by X‐ray diffraction and scanning electron microscopy techniques. Differential scanning calorimetry showed that the ceramic filler had no effect on the melting point of the PTFE. The effect of the Sr₂Ce₂Ti₅O₁₆ ceramic content [0–0.6 volume fraction (vf)] on the thermal conductivity, coefficient of thermal expansion (CTE), specific heat capacity, and thermal diffusivity were investigated. As the vf of the Sr₂Ce₂Ti₅O₁₆ ceramic increased, the thermal conductivity of the specimen increased, and the CTE decreased. The thermal conductivity and thermal expansion of the PTFE/Sr₂Ce₂Ti₅O₁₆ composites were improved to 1.7 W m^?1 °C^?1 and 34 ppm/°C, respectively for 0.6 vf of the ceramics. The experimental thermal conductivity and CTE were compared with different theoretical models. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Multiscale thermal modeling of cured cycloaliphatic epoxy/carbon fiber composites

Cycloaliphatic epoxies (CEs) are commonly used for structural applications requiring improved resistance to elevated temperatures, UV radiation, and moisture relative to other epoxy materials. Accurate and efficient computational models can greatly facilitate the development of CE‐based composite materials for applications such as Aluminum Conductor Composite Core high‐voltage power lines. In this study, a new multiscale modeling method is developed for CE resins and composite materials to efficiently predict thermal properties (glass‐transition temperature, thermal expansion coefficient, and thermal conductivity). The predictions are compared to experimental data, and the results indicate that the multiscale modeling method can accurately predict thermal properties for CE‐based materials. For 85% crosslink densities, the predicted glass‐transition temperature, thermal expansion coefficient, and thermal conductivity are 279 °C, 109 ppm °C^?1, 0.24 W m^?1 K^?1, respectively. Thus, this multiscale modeling method can be used for the future development of improved CE composite materials for thermal applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46371.     

Thermal Properties of (Zr,TM)B2 Solid Solutions with TM = Hf,Nb, W,Ti, and Y

The thermal properties were investigated for hot‐pressed zirconium diboride—transition‐metal boride solid solutions. The transition‐metal additives included hafnium, niobium, tungsten, titanium, and yttrium. The nominal additions were equivalent to 3 at.% of each metal with respect to zirconium. Powders were hot‐pressed to nearly full density at 2150°C using 0.5 wt% carbon as a sintering aid. Thermal diffusivity was measured using the laser flash method. Thermal conductivity was calculated from the thermal diffusivity results using temperature‐dependent values for density and heat capacity. At 25°C, the thermal conductivity ranged from 88 to 34 W·(m·K)^?1 for specimens with various additives. Electrical resistivity measurements and the Wiedemann–Franz law were used to calculate the electron contribution of the thermal conductivity and revealed that thermal conductivity was dominated by the electron contribution. The decrease in thermal conductivity correlated with a decrease in unit cell volume, indicating that lattice strain may affect both phonon and electron transport in ZrB₂.     

Study on highly thermostable low-k polymer films based on fluorene-containing polyetherimides

Highly thermostable low-k polymer films with potential applications as dielectric materials in microelectronic industry were synthesized starting from 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride and various diamines. A polyetherimide/silica nanocomposite film was obtained using methyltriethoxysilane as precursor of inorganic phase. The chemical structure was confirmed by FTIR and ¹H NMR spectroscopy. Water vapor's sorption capacity, thermal stability, glass transition temperature, thermal diffusivity, specific heat, thermal conductivity, and dielectric characteristics of the films were determined. All the films exhibited excellent thermal stability, with an initial decomposition temperature in the range of 500–530°C. They showed low dielectric constant of 1.98–2.86 and low dielectric loss of 0.0037–0.011, at a frequency of 1 Hz and room temperature. The subglass γ- and β-relaxations, primary α-relaxation, and conductivity relaxation processes were discussed according to the chemical structure of the samples. Quantitative structure–property relationship (QSPR) study was conducted, and linear regression models were formulated to describe the causal relationships between different parameters and polyetherimide properties.     

Effects of oxidation curing and sintering temperature on the microstructure formation and heat transfer performance of freestanding polymer-derived SiC films for high-power LEDs

Effects of oxidation cross-linking and sintering temperature on the microstructure evolution, thermal conductivity and electrical resistivity of continuous freestanding polymer-derived SiC films were investigated. The as-received films consisting of β-SiC nanocrystals embedded in amorphous SiO_xC_y and free carbon nanosheets were fabricated via melt spinning of polycarbosilane (PCS) precursors and cured for 3 h/10 h followed by pyrolysis from 900 °C to 1200 °C. Results reveal that nanoscale structure (β-SiC/SiO_xC_y/C_free) provides an ingenious strategy for constructing highly thermal conductive, highly insulating and highly flexible complexes. In particular, the 3 h-cured films sintered at 1200 °C with satisfying thermal conductivity (46.8 W m^?1 K^?1) and electrical resistivity (2.1 × 10⁸ Ω m) are suitable for the realization of high-performance substrates. A remarkable synergistic effect (lattice vibration of β-SiC nanocrystals and close-packed SiO_xC_y, free-electron heat conduction of β-SiC and free carbon, and supporting role of oxygen vacancy) contributing to thermal conductivity improvement is proposed based on the analysis of microstructure, intrinsic properties and simulations. Eventually, the SiC films without additional dielectric layers are directly silk-screen printed with high-temperature silver paste and used as heat dissipation substrates for high-power LED devices via chip-on-board (COB) package. The final devices can emit bright light with low-junction temperature (52.6 °C) and good flexibility owing to the mono-layer SiC substrate with low thermal resistance and desirable mechanical properties. This work offers an effective approach to design and fabricate flexible heat dissipation ceramic substrates for thermal management in advanced electronic packaging fields.     

Measurement of thermal conductivity of Green River oil shales by a thermal comparator technique

A thermal comparator method has been developed for the measurement of the thermal conductivity of oil shales from the Green River formation. Oil shales from two locations in the above formation were studied. Measurements were carried out in the temperature range 25–350 °C on oil shales assaying between 28.3 and 333.0 ml/kg (6.8 and 79.9 U.S. gal/short ton). Predictive equations showing the variation of thermal conductivity with temperature and shale grade are presented. A simple model is proposed to explain the anisotropic effects observed in the thermal-conductivity values for heat flowing in directions parallel and perpendicular to the shale bedding planes. The relative merits of the thermal comparator technique are discussed in the light of techniques previously employed for the measurement of thermal-conductivity factors of Green River oil shales.     

An Evaluation of the Thermophysical Properties of Stoichiometric CeO2 in Comparison to UO2 and PuO2

The thermal conductivity of stoichiometric CeO₂ was determined through measurement of thermal expansion from 313 to 1723 K, thermal diffusivity from 298 to 1473 K, and specific heat capacity from 313 to 1373 K. The thermal conductivity was then calculated as the product of the density, thermal diffusivity, and specific heat capacity. The thermal conductivity was found to obey an (A + BT)^?1 relationship with A = 6.776×10^?2 m·K·W^?1 and B = 2.793 × 10^?4 m·W^?1. Extrapolations of applied models were made to provide suggested data for the specific heat capacity, thermal diffusivity, and thermal conductivity data up to 1723 K. Results of thermal expansion and heat capacity measurements agreed well with the limited low‐temperature data available in the literature. The thermal conductivity values provided in the current study are significantly higher than the only high‐temperature data located for CeO₂. This is attributed to the tendency of CeO₂ to rapidly reduce at elevated temperatures given the available partial pressure of O₂ in air at ambient pressure. The CeO₂ data are compared to literature values for UO₂ and PuO₂ to evaluate its suitability as a surrogate in nuclear fuel systems where thermal transport is a primary criterion for performance     

Effect of γ-radiation on the thermal conductivity of polypropylene

The effect of ⁶⁰Co γ-radiation on the thermal conductivity of polypropylene (PP) has been studied over the temperature range 0–160°C. for radiation doses of 600 and 1800 Mrad. The conductivity of unirradiated specimens rises from 4.5 × 10^?4 cgs units (cal./cm.-sec.-°C.) at 0°C. to 4.8 × 10^?4cgs units at 80°C. and subsequently decreases with temperature to a value of about 3.1 × 10^?4cgs units at 160°C. Upon irradiation to 600 Mrad the thermal conductivity is lowered over the 0–150°C. temperature range. Above 90°C. the conductivity decreases with temperature and becomes relatively constant at 3.4 × 10^?4 cgs units from 120 to 160°C. Differential scanning calorimeter (DCS) measurements from 30 to 200°C. show that irradiation to 600 Mrad lowers the energy associated with crystalline melting and shifts the endotherm melting peak from about 160 to 105°C. Irradiation to 1800 Mrad results in additional lowering of the thermal conductivity over the 50–160°C. range, a further decrease in area of the endothermic peak and a shift of its maximum peak position to about 75°C. The effects of radiation on the thermal conductivity of polypropylene are compared and correlated with the observed effects of radiation on the dynamic mechanical behavior.     

Improved electrical and thermal conductivities of polysiloxane-derived silicon oxycarbide ceramics by barium addition

The electrical and thermal conductivities of bulk barium-added silicon oxycarbide (SiOC-Ba) ceramics are investigated. The SiOC-Ba ceramics exhibited improved electrical and thermal conductivities upon increasing the sintering temperature from 1450 °C to 1650 °C. Precipitation of graphitic carbon clusters observed by Raman spectroscopy and high-resolution transmission electron microscopy is attributed to the phase separation during the fabrication process. The increase in the electrical conductivity can be rationalized in terms of an increase in the density of the sp² CC bonds within the carbon clusters. The increase in the thermal conductivity is mainly attributed to the formation of interconnected graphitic clusters in the SiOC matrix and SiC embedded in the clusters. The electrical and thermal conductivities of the SiOC-Ba ceramics sintered at 1650 °C are 14.0 Ω^?1 cm^?1 and 5.6 W/m K, respectively, at room temperature. The electrical conductivity of SiOC-Ba sintered at 1550 °C is 5.3 Ω^?1 cm^?1 and 7.0 Ω^?1 cm^?1 at 2 and 300 K, respectively.