Specific features in the behavior of electrical resistivity of the pine biocarbon preform/copper composite

The electrical resistivity ρ(T) of the novel type of composites prepared by infiltrating melted copper in vacuum in empty sap channels of white pine high-porosity biocarbon preforms has been measured in the temperature range 5–300 K. Biocarbon preforms have been prepared by pyrolysis of tree wood in an argon flow at two carbonization temperatures, 1000 and 2400°C. The electrical resistivity of the composites has been found to vary relatively weakly with temperature and to pass through a characteristic minimum near 40–50 K, which can be ascribed to iron and manganese impurities penetrating into copper from the carbon preform when liquid copper is infiltrated into it. It has been shown that the electrical resistivity ρ(T) of the composites is governed primarily by the specific microstructure of the preform, which is made up of parallel channels with an average diameter of about 50 μm interrupted by systems of thin capillaries. The small cross section of the copper-filled capillaries accounts for these regions providing the major contribution to the electrical resistivity of the composites. An increase in the wood carbonization temperature brings about a noticeable increase in the effective capillary cross section and a decrease in the electrical resistivity ρ(T) of the composite.     

Thermal conductivity of the pine-biocarbon-preform/copper composite

The thermal conductivity of composites of a new type prepared by infiltration under vacuum of melted copper into empty sap channels (aligned with the sample length) of high-porosity biocarbon preforms of white pine tree wood has been studied in the temperature range 5–300 K. The biocarbon preforms have been prepared by pyrolysis of tree wood in an argon flow at two carbonization temperatures of 1000 and 2400°C. From the experimental values of the composite thermal conductivities, the fraction due to the thermal conductivity of the embedded copper is isolated and found to be substantially lower than that of the original copper used in preparation of the composites. The decrease in the thermal conductivity of copper in the composite is assigned to defects in its structure, namely, breaks in the copper filling the sap channels, as well as the radial ones, also filled by copper. A possibility of decreasing the thermal conductivity of copper in a composite due to its doping by the impurities present in the carbon preform is discussed.     

Thermal conductivity of high-porosity cellular-pore biocarbon prepared from sapele wood

This paper reports on measurements (in the temperature range T = 5–300 K) of the thermal conductivity κ(T) and electrical conductivity σ(T) of the high-porosity (～63 vol %) amorphous biocarbon preform with cellular pores, prepared by pyrolysis of sapele wood at the carbonization temperature 1000°C. The preform at 300 K was characterized using X-ray diffraction analysis. Nanocrystallites 11–30 Å in ize were shown to participate in the formation of the carbon network of sapele wood preforms. The dependences κ(T) and σ(T) were measured for the samples cut across and along empty cellular pore channels, which are aligned with the tree growth direction. Thermal conductivity measurements performed on the biocarbon sapele wood preform revealed a temperature dependence of the phonon thermal conductivity that is not typical of amorphous (and X-ray amorphous) materials. The electrical conductivity σ was found to increase with the temperature increasing from 5 to 300 K. The results obtained were analyzed.     

Heat capacity of the white pine biocarbon preform and the related biocarbon/copper composite

This paper reports on measurements in the 80–300-K temperature interval of the heat capacity at constant pressure C _p (T) of high-porosity amorphous white pine carbon preforms (biocarbon) prepared by pyrolysis (carbonization) at T _carb = 1000 and 2400°C in an argon flow. The dependences C _p (T) for biocarbon/copper composites based on the carbon preforms obtained have also been determined. It is shown that the mixture rule holds for the composites, i.e., that C _p (T) of the composite is a sum of the heat capacities of the constituent materials taken in the corresponding ratios. Phonon mean free paths for the white pine carbon preforms prepared at T _carb = 1000 and 2400°C have been calculated and used to estimate the size of the nanocrystallites contributing to formation of the carbon frameworks of these preforms.     

Thermopower of beech wood biocarbon

This paper reports on measurements of the thermopower S of high-porosity samples of beech wood biocarbon with micron-sized sap pores aligned with the tree growth direction. The measurements have been performed in the temperature range 5–300 K. The samples have been fabricated by pyrolysis of beech wood in an argon flow at different carbonization temperatures (T _carb). The thermopower S has been measured both along and across the sap pores, thus offering a possibility of assessing its anisotropy. The curves S(T _carb) have revealed a noticeable increase of S for T _carb < 1000°C for all the measurement temperatures. This finding fits to the published data obtained for other physical parameters, including the electrical conductivity of these biocarbons, which suggests that for T _carb ∼ 1000°C they undergo a phase transition of the insulator-(at T _carb < 1000°C)-metal-(at T _carb > 1000°C) type. The existence of this transition is attested also by the character of the temperature dependences S(T) of beech wood biocarbon samples prepared at T _carb above and below 1000°C.     

Heat capacity and thermopower coefficient of the carbon preform of sapele wood

This paper reports on measurements of the heat capacity at constant pressure C _p in the 80–300-K temperature interval and the thermopower coefficient S at 5–300 K of the carbon preform of sapele wood, which was prepared at the carbonization temperature of 1000°C. Measurements of C _p (T), our previous data on the phonon thermal conductivity, and literature information on the sound velocity have been used to calculate the phonon mean free path l(T) for this material. It has been shown that within the temperature interval 200–300 K, l is constant and equal to 11 Å, a figure matching the size of the nanocrystallites (“graphite fragments”) making up the carbon framework of the sapele carbon preform. The high-temperature parts of S(T) have been found to follow a linear course characteristic of diffusive thermopower for the degenerate state of charge carriers, with only one type of charge carriers present. The anisotropy of the thermopower coefficient has been estimated.     

Thermal conductivity of high-porosity biocarbon preforms of beech wood

This paper reports on measurements performed in the temperature range 5–300 K for the thermal conductivity κ and electrical resistivity ρ of high-porosity (cellular pores) biocarbon preforms prepared by pyrolysis (carbonization) of beech wood in an argon flow at carbonization temperatures of 1000 and 2400°C. X-ray structure analysis of the samples has been performed at 300 K. The samples have revealed the presence of nanocrystallites making up the carbon matrices of these biocarbon preforms. Their size has been determined. For samples prepared at T _carb = 1000 and 2400°C, the nanocrystallite sizes are found to be in the ranges 12–25 and 28–60 κ(T) are determined for the samples cut along and across the tree growth direction. The thermal conductivity κ increases with increasing carbonization temperature and nanocrystallite size in the carbon matrix of the sample. Thermal conductivity measurements conducted on samples of both types have revealed an unusual temperature dependence of the phonon thermal conductivity for amorphous materials. As the temperature increases from 5 to 300 K, it first increases in proportion to T, to transfer subsequently to ∼T ^1.5 scaling. The results obtained are analyzed.     

Electrical and galvanomagnetic properties of biocarbon preforms of white pine wood

The electrical and galvanomagnetic properties of high-porosity biocarbon preforms prepared from white pine wood by pyrolysis at carbonization temperatures T _carb = 1000 and 2400°C have been studied. Measurements have been made of the behavior with temperature of the electrical resistivity, as well as of magnetoresistance and the Hall coefficient in the 1.8–300-K temperature interval and magnetic fields of up to 28 kOe. It has been shown that samples of both types (with T _carb = 1000 and 2400°C) are characterized by high carrier (hole) concentrations of 6.3 × 10²⁰ and 3.6 × 10²⁰ cm⁻³, respectively. While these figures approach the metallic concentration, the electrical resistivity of the biocarbon materials studied, unlike that of normal metals, grows with decreasing temperature. Increasing T _carb brings about a decrease in electrical resistivity by a factor 1.5–2 within the 1.8–300-K temperature range. The magnetoresistance also follows a qualitatively different pattern at low (1.8–4.2 K) temperatures: it is negative for T _carb = 2400°C and positive for T _carb = 1000°C. An analysis of experimental data has revealed that the specific features in the conductivity and magnetoresistance of these samples are described by quantum corrections associated inherently with structural characteristics of the biocarbon samples studied, more specifically with the difference between the fractions of the quasi-amorphous and nanocrystalline phases, as well as with the fine structure of the latter phase forming at the two different T _carb.     

Thermal conductivity of the amorphous and nanocrystalline phases of the beech wood biocarbon nanocomposite

Natural composites (biocarbons) obtained by carbonization of beech wood at different carbonization temperatures T _carb in the range of 800–2400°C have been studied using X-ray diffraction. The composites consist of an amorphous matrix and nanocrystallites of graphite and graphene. The volume fractions of the amorphous and nanocrystalline phases as functions of T _carb have been determined. Temperature dependences of the phonon thermal conductivity κ(T) of the biocarbons with different temperatures T _carb (1000 and 2400°C) have been analyzed in the range of 5–300 K. It has been shown that the behavior of κ(T) of the biocarbon with T _carb = 1000°C is controlled by the amorphous phase in the range of 5–50 K and by the nanocrystalline phase in the range of 100–300 K. The character of κ(T) of the biocarbon with T _carb = 2400°C is determined by the heat transfer (scattering) in the nanocrystalline phase over the entire temperature range of 5–300 K.     

Thermal conductivity of high-porosity biocarbon precursors of white pine wood

This paper reports on measurements of the thermal conductivity κ and the electrical conductivity σ of high-porosity (cellular pores) biocarbon precursors of white pine tree wood in the temperature range 5–300 K, which were prepared by pyrolysis of the wood at carbonization temperatures (T _carb) of 1000 and 2400°C. The x-ray structural analysis has permitted the determination of the sizes of the nanocrystallites contained in the carbon framework of the biocarbon precursors. The sizes of the nanocrystallites revealed in the samples prepared at T _carb = 1000 and 2400°C are within the ranges 12–35 and 25–70 Å, respectively. The dependences κ(T) and σ(T) are obtained for samples cut along the tree growth direction. As follows from σ(T) measurements, the biocarbon precursors studied are semiconducting. The values of κ and σ increase with increasing carbonization temperature of the samples. Thermal conductivity measurements have revealed that samples of both types exhibit a temperature dependence of the phonon thermal conductivity κ_ph, which is not typical of amorphous (and amorphous to x-rays) materials. As the temperature increases, κ_ph first varies proportional to T, to scale subsequently as ～T ^1.7. The results obtained are analyzed.     

Thermopower of biomorphic silicon carbide

The thermopower coefficients of cubic bio-SiC, a high-porosity semiconductor with cellular pores prepared from the biocarbon template of white eucalyptus wood, and single-crystal β-SiC taken as a reference are measured in the temperature range 5–280 K. It is revealed that, in the low-temperature range, the samples are characterized by a thermopower contribution associated with the electron drag by phonons. The thermopower of the bio-SiC samples is measured both along and across the empty pore channels and is found to be anisotropic. Two models are proposed to account for the anisotropy of the thermopower in cubic bio-SiC.     

Heat capacity of a white-eucalyptus biocarbon template for SiC/Si ecoceramics

The heat capacity C _p of a biocarbon template based on white eucalyptus wood is measured at a constant pressure in the temperature range T = 3.5–300 K. The phonon mean free path l for a white-eucalyptus biocarbon template is calculated from the measured dependence C _p (T) and data available in the literature on the phonon thermal conductivity and velocity of sound. It is established that, in the range 100–300 K, the phonon mean free path l is nearly constant and equal to ～13 Å. This value is close to the smallest size of graphite-like crystallites (～12 Å), which was derived earlier from x-ray diffraction data for a quasi-amorphous biocarbon template.     

The influence of magnetic and structural heterogeneity on thermopower,magnetothermopower, electrical resistivity,and magnetoresistivity of Nd<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> manganite

The thermopower, S, magnetothermopower, ΔS/S, resistivity, ρ, and magnetoresistivity, Δρ/ρ, depending on the temperature T and magnetic field H, have been studied in an Nd_0.5Sr_0.5MnO₃ single crystal consisting of three types of clusters: an antiferromagnetic CE-type with charge-orbital ordering (below the Neel temperature T_NCE ~ 145 K) and an A-type with T_NA ~ 220 K; a ferromagnetic at 234 ≤ T ≤ 252 K, and a ferromagnetic metal phase below the Curie temperature T_C = 248 K. The thermopower was found to be negative, indicating the dominance of the electronic type of conductivity. In the S(T) curves, a sharp minimum is observed in the temperature range of 100 K ≤ T ≤ 133 K, close to T_NCE, where the absolute S value attains 53 μV/K. With a further increase in temperature, the absolute S value decreases rapidly; at 200 K it is equal to 7 μV/K. It then slightly increases, reaching its maximum value of 15 μV/K at a temperature of 254 K, which is close to T_C. The absolute thermopower decreased under the influence of the magnetic field; i.e., a negative magnetothermopower occurs. In {ΔS/S}(T) curves, a sharp minimum is observed at T = 130 K close to T_NCE, where the magnetothermopower reaches a huge value of ~45% at H = 13.23 kOe. A broad minimum in the {ΔS/S}(T) curves is observed near the Curie temperature and its value is also high, viz., ~15% in the maximum measuring magnetic field of 13.23 kOe. The extremely high magnetothermopower values mean that the charge-orbital ordered nanoclusters or ferron type make the main contribution to the thermopower of the entire sample. The behavior of the ρ(T) and {Δρ/ρ}(T) curves is similar to that of the S(T) and {ΔS/S}(T) dependencies, which is in agreement with this conclusion.     

Anisotropy of the thermal conductivity and electrical resistivity of the SiC/Si biomorphic composite based on a white-eucalyptus biocarbon template

The thermal conductivity κ and electrical resistivity ρ of a cellular ecoceramic, namely, the SiC/Si biomorphic composite, are measured in the temperature range 5–300 K. The SiC/Si biomorphic composite is fabricated using a cellular biocarbon template prepared from white eucalyptus wood by pyrolysis in an argon atmosphere with subsequent infiltration of molten silicon into empty through cellular channels of the template. The temperature dependences κ(T) and ρ(T) of the 3C-SiC/Si biomorphic composite at a silicon content of ～30 vol % are measured for samples cut out parallel and perpendicular to the direction of tree growth. Data on the anisotropy of the thermal conductivity κ are presented. The behavior of the dependences κ(T) and ρ(T) of the SiC/Si biomorphic composite at different silicon contents is discussed in terms of the results obtained and data available in the literature.     

Thermal conductivity of partially graphitized biocarbon obtained by carbonization of medium-density fiberboard in the presence of a Ni-based catalyst

The thermal conductivity k and resistivity ρ of biocarbon matrices, prepared by carbonizing medium-density fiberboard at T _carb = 850 and 1500°C in the presence of a Ni-based catalyst (samples MDF-C( Ni)) and without a catalyst (samples MDF-C), have been measured for the first time in the temperature range of 5–300 K. X-ray diffraction analysis has revealed that the bulk graphite phase arises only at T _carb = 1500°C. It has been shown that the temperature dependences of the thermal conductivity of samples MDFC- 850 and MDF-C-850(Ni) in the range of 80–300 K are to each other and follow the law of k(T) ～ T ^1.65, but the use of the Ni-catalyst leads to an increase in the thermal conductivity by a factor of approximately 1.5, due to the formation of a greater fraction of the nanocrystalline phase in the presence of the Ni-catalyst at T _carb = 850°C. In biocarbon MDF-C-1500 prepared without a catalyst, the dependence is k(T) ～ T ^1.65, and it is controlled by the nanocrystalline phase. In MDF-C-1500(Ni), the bulk graphite phase formed increases the thermal conductivity by a factor of 1.5–2 compared to the thermal conductivity of MDF-C-1500 in the entire temperature range of 5–300 K; k(T = 300 K) reaches the values of ～10 W m^–1 K^–1, characteristic of biocarbon obtained without a catalyst only at high temperatures of T _carb = 2400°C. It has been shown that MDF-C-1500(Ni) in the temperature range of 40?300 K is characterized by the dependence, k(T) ～ T ^1.3, which can be described in terms of the model of partially graphitized biocarbon as a composite of an amorphous matrix with spherical inclusions of the graphite phase.     

Anomalous thermopower in heavy-fermion compounds CeB<Subscript>6</Subscript>, CeAl<Subscript>3</Subscript>, and CeCu<Subscript>6 − <Emphasis Type="Italic">x</Emphasis></Subscript>Au<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

High-precision measurements of thermopower have been performed in a wide temperature range (2–300 K) for a series of cerium-based heavy-fermion compounds, including CeB₆, CeAl₃, CeCu₆, and substitutional solid solutions of the CeCu_{6 ? x} Au _x system (x = 0.1, 0.2). All compounds exhibit an unusual (logarithmic) asymptotic behavior of the temperature dependence of the Seebeck coefficient: S ∝ ?lnT. In the case of cerium hexaboride, this anomalous behavior of S(T) is accompanied by the appearance of weak-carrier-localization-mode asymptotics in the conductivity (σ(T) ∝ T ^0.39), while the paramagnetic susceptibility χ(T) and the effective mass of charge carriers m _eff(T) vary according to a power law (χ(T), m _eff(T) ∝ T ^?0.8) in the temperature interval T = 10–80 K. This behavior corresponds to renormalization of the density of states at the Fermi level. The observed anomalous behavior of thermopower in CeB₆ and other cerium-based intermetallic compounds is attributed to the formation of heavy fermions (many-body states in the metal matrix) at low temperatures.     

Kinetic phenomena in zero-gap semiconductors CuFeS<Subscript>2</Subscript> and CuFeTe<Subscript>2</Subscript>: Effect of pressure and heat treatment

Electrical resistivity ρ and Hal coefficient R are measured as a function of the temperature (T = 1.7−310 K) and the magnetic field (up to H = 28 kOe) in zero-gap semiconductor CuFeS₂ samples subjected to hydrostatic compression and under various heat-treatment conditions. At low temperatures, anomalies are observed in the kinetic effects related to the presence of ferromagnetic clusters: the magnetoresistance at T = 4.2 K and T = 20.4 K acquires a hysteretic character and thermopower α changes its sign at T < 15 K. The temperature dependence of conduction-electron concentration n in CuFeS₂ has a power form in the temperature range T = 14−300 K, which is characteristic of the intrinsic conductivity in zero-gap semiconductors. In CuFeS₂, we have n(T) ∝ T ^1.2; in isoelectron compound Cu_1.13Fe_1.22Te₂, we have n(T) ∝ T ^1.93. Heat treatment is found to affect the intrinsic conductivity of CuFeS₂, as the action of hydrostatic compression (carrier concentration changes); that is, the carrier concentration changes. However, a power form of the n(T) and ρ(T) dependences is retained.     

Thermoelectric power of heavy-fermion compounds

We calculate the diffusion thermopower of the Anderson lattice as a model for heavyfermion compounds in a semi-phenomenological theory. In this theory, the thermopower is expressed by the dynamical susceptibility which describes spin fluctuations and can be measured by neutron scattering. The Kondo effect is taken into account for a singlef-electron spin which is coupled to all other spins and to the conduction electrons. This approach neglects multiple intesite-scattering of the conduction electrons. We obtain a Kondo termS ₍₁₎ ^d (T) (in which the thermopower of non-interacting spins is multiplied by a factor which describes the spin dynamics) and a resonance termS ₍₂₎ ^d (T) of opposite sign which vanishes for vanishing interactions. The superposition of both terms leads to a broad maximum of the thermopower roughly at the Kondo temperatureT _K and to an additional minimum belowT _K . ForT0 the termS ₍₁₎ ^d vanishes asT ² and the termS ₍₂₎ ^d becomes proportional toT. We also show that the Sommerfeld expansion leads to an incorrect result for the low temperature resistivity of the Anderson lattice and that the Gorter-Nordheim relation does not hold at low temperatures.     

Thermopower of composites containing metallic cobalt nanoparticles embedded in the Al<Subscript>2</Subscript>O<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> dielectric matrix

The concentration and temperature dependences of the thermopower of composites containing Co nanoparticles embedded in the Al₂O _n dielectric matrix are investigated. Below the percolation threshold, i.e., in the tunneling conduction region, the absolute values of the thermopower of the composites under investigation are less than those above the percolation threshold. It is revealed that, in the tunneling conduction region, the slope of the temperature dependences of the thermopower changes at a temperature of ～205 K. This can indicate that the thermopower is sensitive to a change in the mechanism of conduction from the Mott law ln(σ) ∝ (1/T)^1/4 to a power relation that corresponds to the model of inelastic resonant tunneling through a chain of localized states in the dielectric matrix. The introduction of oxygen in the course of sputtering brings about a decrease in the absolute values of the thermopower; however, the character of variation in the concentration and temperature dependences of the thermopower remains unchanged.     

Synthesis and physical characterization of superconductivity-magnetism crossover compound RuSr2EuCeCu2O10−δ

We carefully studied the nonsuperconducting sample of the magneto-superconducting RuSr₂(Eu_1−xCe_x)Cu₂O_10−δ series with composition RuSr₂EuCeCu₂O_10−δ. This compound seems to exhibit a complex magnetic state as revealed by host of techniques like resistivity, thermopower, magnetic susceptibility, and MR measurements. The studied compound exhibited ferromagnetic like M(H) loops at 5, 20, and 50 K, and semiconductor like electrical conduction down to 5 K, with −MR^7 T of up to 4% at low temperatures. The −MR^7 T decreases fast above 150 K and monotonically becomes close to zero above say 230 K. Below, 150 K −MR^7 T decreases to around 3% monotonically down to 75 K, with further increase to 4% at around 30 K and lastly having a slight decrease below this temperature. The thermopower S(T) behavior closely followed the −MR^7 T steps in terms of d(S/T)/dT slopes. Further, both MR^7 T steps and d(S/T)/dT slopes are found in close vicinity to various magnetic ordering temperatures (T_mag) of this compound.