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.     

Polytherms of the Wetting Angles of Pb-Ni (0.3 at %) Melt on Nickel Substrates

Polytherms of the wetting angle of Pb-Ni (0.3 at %) melt on pressed nickel substrates and substrates cut from a plate of nickel of grade NP-2 are studied in the temperature range from the melting point to 850°C by the sessile drop method in a vacuum chamber with a residual pressure of 10^-2 Pa. The wettability thresholds are found. The wetting of both pressed substrates and NP-2 nickel begins at a temperature of 500°C or higher. After crystallization, the morphology of the droplet surface and the zones near it is studied using scanning electron microscopy. Pb _n Ni _m intermetallides of pyramidal form are detected, and zones where the melt spreads along the grain boundaries followed by the crystallization and formation of fibrous structures are found.     

Microstructure,elastic, and inelastic properties of biomorphic carbons carbonized using a Fe-containing catalyst

The microstructure and amplitude dependences of the Young’s modulus E and internal friction (logarithmic decrement δ), and microplastic properties of biocarbon matrices BE-C(Fe) obtained by beech tree carbonization at temperatures T _carb = 850–1600°C in the presence of an iron-containing catalyst are studied. By X-ray diffraction analysis and transmission electron microscopy, it is shown that the use of Fe-catalyst during carbonization with T _carb ≥ 1000°C leads to the appearance of a bulk graphite phase in the form of nanoscale bulk graphite inclusions in a quasi-amorphous matrix, whose volume fraction and size increase with T _carb. The correlation of the obtained dependences E(Т _carb) and δ(T _carb) with microstructure evolution with increasing Т _carb is revealed. It is found that E is mainly defined by a crystalline phase fraction in the amorphous matrix, i.e., a nanocrystalline phase at Т _carb < 1150°C and a bulk graphite phase at T _carb > 1300°C. Maximum values E = 10–12 GPa are achieved for samples with Т _carb ≈ 1150 and 1600°C. It is shown that the microplasticity manifest itself only in biocarbons with T _carb ≥ 1300°C (upon reaching a significant volume of the graphite phase); in this case, the conditional microyield stress decreases with increasing total volume of introduced mesoporosity (free surface area).     

Specific features of electrical properties of porous biocarbons prepared from beech wood and wood artificial fiberboards

This paper reports on comparative investigations of the structural and electrical properties of biomorphic carbons prepared from natural beech wood, as well as medium-density and high-density fiberboards, by means of carbonization at different temperatures T _carb in the range 650–1000°C. It has been demonstrated using X-ray diffraction analysis that biocarbons prepared from medium-density and high-density fiberboards at all temperatures T _carb contain a nanocrystalline graphite component, namely, three-dimensional crystallites 11–14 Å in size. An increase in the carbonization temperature T _carb to 1000°C leads to the appearance of a noticeable fraction of two-dimensional graphene particles with the same sizes. The temperature dependences of the electrical resistivity ρ of the biomorphic carbons have been measured and analyzed in the temperature range 1.8–300 K. For all types of carbons under investigation, an increase in the carbonization temperature T _carb from 600 to 900°C leads to a change in the electrical resistivity at T = 300 K by five or six orders of magnitude. The dependences ρ(T) for these materials are adequately described by the Mott law for the variable-range hopping conduction. It has been revealed that the temperature dependence of the electrical resistivity exhibits a hysteresis, which has been attributed to thermomechanical stresses in an inhomogeneous structure of the biocarbon prepared at a low carbonization temperature T _carb. The crossover to the conductivity characteristic of disordered metal systems is observed at T _carb ? 1000°C.     

Fluorescence induction changes in bean leaves after heat treatment

The regularities in the alterations of chlorophyll a fluorescence induction curves of bean leaves after short (15 min) heating in the range of temperatures from 24 to 45°C were determined. A dramatic decrease in the relative f luorescence quenching (F_P–F_T)/F_T, as well as the F_v/_Fm ratio, were observed after heating at temperatures above 38°C, which indicates a decrease in the photochemical activity of photosystem II. The effect of an increase in the resistance of the photosynthetic apparatus to the temperature of 43°C after preheating at 37°C was demonstrated.     

Optical properties and mechanisms of current flow in Cu<Subscript>2</Subscript>ZnSnS<Subscript>4</Subscript> films prepared by spray pyrolysis

Thin films Cu₂ZnSnS₄ (up to 0.9 μm thick) with p-type conductivity and band gap E_g = 1.54 eV have been prepared by the spray pyrolysis of 0.1 M aqueous solutions of the salts CuCl₂ · 2H₂O, ZnCl₂ · 2H₂O, SnCl₄ · 5H₂O, and (NH₂)₂CS at a temperature T_S = 290°C. The electrophysical properties of the films have been analyzed using the model for polycrystalline materials with electrically active grain boundaries. The energy and geometric parameters of the grain boundaries have been determined as follows: the height of the barriers is E_b ≈ 0.045–0.048 eV, and the thickness of the depletion region is δ ≈ 3.25 nm. The effective concentrations of charge carriers p₀ = 3.16 × 10¹⁸ cm^–3 and their mobilities in crystallites μ_p = 85 cm²/(V s) have been found using the technique for determining the kinetic parameters from the absorption spectra of thin films at a photon energy hν ≈ E_g. The density of states at grain boundaries N_t = 9.57 × 10¹¹ cm^–2 has been estimated.     

Changes in the electronic,optical, and magnetic properties of LaSrMnO films upon transition from the rhombohedral phase to the orthorhombic phase

The properties of LaSrMnO films are investigated in the temperature range of the transition from the rhombohedral phase to the orthorhombic phase (600–650° C). It is shown that, with a variation in the growth temperature T_s, the change in the film properties is governed by the interaction of Mn-O metallic (ferromagnetic) clusters in the dielectric (antiferromagnetic) matrix. At T_s≤600°C, the low density of e _g states and the dielectric gap (E _g =0.3–0.5 eV) are responsible for the following features: (i) the optical transparency in the range ?ω=0.5–2 eV, (ii) the difference between the FC and ZFC magnetizations M(T), (iii) the high resistance, and (iv) the appearance of the portions R(T) ≈ const in the dependence R(T) due to the transformation of clusters into a system of tunnel-coupled quantum dots. At T_s≥650°C, the local increase in the atomic and electronic densities leads to a decrease in the optical transmission and the resistance by three to nine orders of magnitude, the appearance of a maximum and a minimum in the dependences R(T) of the LaSrMnO films, and an increase in the magnetization M(10 K) by one order of magnitude. The inference is drawn that magnetic ordering of the system of tunnel-coupled clusters encourages an increase in the cluster size and in the content of the metallic (ferromagnetic) phase.     

Mechanisms of interaction of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript> <Emphasis Type="Italic">y</Emphasis> </Subscript> with water vapor at low-temperature annealing

Abstract—The interaction of YBa₂Cu₃O_y (123) with water vapor at temperatures T ≤ 150° has been studied. It has been shown that, with an increase in temperature, the mechanism of its interaction with water changes. Near room temperature, the main process is hydrolytic decomposition. At T ~ 100°C, the absorption of water is significantly reduced, because the role of hydrolysis becomes less important and water penetrates the structure weakly and is incorporated into oxygen vacancies mainly in the form of OH–-groups, which leads to the transition of YBa₂Cu₃O_y from the tetragonal to orthorhombic phase. With an increase in temperature to 150°C, the absorption of water increases again. In this case, the main mechanism is the penetration of water to the 123 structure, which leads to splitting of Cu–O chains and a phase transition from the 123 to pseudo-124 structure. The role of different mechanisms of interaction with water essentially depends on the oxygen content in the 123 structure. At a low oxygen index (y = 6.3), the role of hydrolysis is more important, and, at y ≥ 6.5, the incorporation of water into the structure prevails. It has been revealed that, at T = 150°C, after absorption of water, YBa₂Cu₃O_6.96 becomes a proton conductor.     

Dielectric Spectroscopy of Strongly Correlated Electronic States of Vanadium Dioxide

The thermal evolution of the conductivity of a VO₂ film and database-obtained band gap E_g of film nanocrystallites is traced in the temperature range of –196°C < T < 100°C (77 K < T < 273 K); the level position of donor impurity centers is determined to be E_d = 0.04 eV. It is shown that energy E_g decreases from 0.8 to ～0 eV with an increase in temperature in the range of 273 K < T < 300 K, which is caused by the narrowing of the energy gap due to correlation effects and considered as the temperature-extended Mott “insulator–metal” electron phase transition with the monoclinic lattice symmetry retained. The subsequent jump in the symmetry from monoclinic to tetragonal with a further increase in temperature is considered as the Peierls structural phase transition, the temperature of which is in the vicinity of 340 K and determined by the size effects, nonstoichiometry of VO₂ film nanocrystallites, and degree of their adhesion to the substrate.     

Multiscale model of deformed polycrystals. Hall-Petch problem

The paper puts forward a multiscale model of deformed polycrystals according to which the basis for self-consistent deformation of grains is rotational wave flows of planar structural transformations at their boundaries. Computer-aided engineering of grain boundaries reveals two types of rotational wave flows defined by the misorientation angle of adjacent grains. Grain boundary flows of the first type develop at low-angle boundaries and feature low curvature. These flows generate dislocations in the grain bulk and the Hall-Petch equation for them has the form σ=σ₀+kd^?1/2. Grain boundary flows of the second type develop at high-angle boundaries and feature high curvature. These flows generate curvature bands in near-boundary zones and inject them into the grain bulk, resulting in fragmentation of grains and breakdown of translation invariance. For such self-consistency of grains in a polycrystal, the Hall-Petch equation has the form σ=σ₀+kd^?1. Experimental data in support of the proposed multiscale model are presented.     

Structure and dielectric response of (1–<Emphasis Type="Italic">x</Emphasis>)NaNO<Subscript>2</Subscript> + <Emphasis Type="Italic">x</Emphasis>BaTiO<Subscript>3</Subscript> composites at <Emphasis Type="Italic">x</Emphasis> = 0.05 and 0.1

The (1–x)NaNO₂ + xBaTiO₃ composites of two compositions (x = 0.05 and 0.1) have been studied by powder neutron diffraction and broadband dielectric spectroscopy (frequency region 10^–1–10⁷ Hz). The temperature dependences of the ferroelectric order parameter of NaNO₂ in the composites and pure NaNO₂ have been measured. The frequency dependences of the real and imaginary parts of the permittivities of the composites and pure NaNO₂ have been analyzed in the temperature range 25–187°C. The anomaly of the dielectric response observed at T ~ 147°C is assumed to be related to the processes of accumulation and “resolution” of charges at the BaTiO₃ particle boundaries.     

Electrical characterization of porous La-doped BaSnO<Subscript>3</Subscript> using impedance spectroscopy

A few compositions in the system Ba_1???x La _x SnO₃ (x?=?0.00, 0.01, 0.05, and 0.10) have been synthesized via the solid state ceramic route. The synthesized powders have been characterized using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, Raman spectroscopy, Fourier transformation infrared, thermogravimetrical analysis, and differential thermal analysis techniques. The powder X-ray diffraction pattern of the samples confirms the formation of a single-phase solid solution only up to 0.50?≤?x. It was found that all the samples have a cubic crystal structure. The electrical properties of La-modified BaSnO₃ were studied using ac impedance spectroscopy technique over a wide range of temperatures (50–650 °C) in the frequency range of 10 Hz–13 MHz. The complex impedance plots above 300 °C show that total impedance is due to the contributions of grain and grain boundaries. The resistance of these contributions has been determined. Variation of these resistances with temperature shows the presence of two different regions with different slopes. The nature of the variation of conductivity of the grain and grain boundaries is different in different regions. Based on the value of activation energy, it is proposed that conduction via hopping of doubly ionized oxygen vacancies (V_O ^??) is taking place in the temperature region of 300–450 °C, whereas in the temperature region of 450–650 °C, it is due to proton, i.e., OH^? ions, hopping.     

Thermodynamic characteristics of the thermal polymerization of perfluoropropylvinyl ether at high pressures

The limiting polymerization temperatures of PFPVE at pressures 5.28–10.56 kbar (T _c = 200°C at 7.04 kbar and T _c = 240°C at 10.56 kbar) are measured. The volume of reaction ΔV and enthalpy of polymerization ΔH are determined.     

Paramagnetische Relaxation von CeCl3

The paramagnetic relaxation in CeCl₃ was investigated in the temperature interval between 1.07°K and 4.21°K using a mutual inductance bridge at frequencies between 3 Hz and 3200 Hz. The dependence of the complex susceptibility on temperature below theλ point is given by a Debye function. Above this temperature, however, deviations occur. The temperature dependence of the relaxation time forT<T _λ can be described byτ～T ^?n where 1.82≦n≦2.35 for 470 Oe≦H≦3360 Oe. At the highest temperatures Orbach Processes occur over the first excited crystal field component which according to these measurements lies atE _II=k(56±10)°K. In the entire temperature range the relaxation processes are determined by further relaxation mechanisms in addition to the spin lattice relaxation. The nature of these could not, however, be determined.     

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.     

Hall-Petch analysis for temperature and strain rate dependent deformation of polycrystalline lead

A dislocation pile-up analysis of the Hall-Petch constant k _ε for the tensile deformation of polycrystalline lead over a wide range of temperature T and at two strain rates has been made. The predicted and experimental Hall-Petch dependencies k _ε ² = f (T) are in good agreement. Lower than predicted k _ε values at very low temperatures are attributed to the high curvature of grain boundaries which experience high localized plasticity and consequent shear banding.     

Heat capacity and thermodynamic properties of HoMnO<Subscript>3</Subscript> in the range of 364–1046 K

The temperature dependence of the molar heat capacity of HoMnO₃ has been measured by differential scanning calorimetry. The experimental data have been used to calculate the thermodynamic properties of the oxide compound (changes in the enthalpy H°(T)–H°(364 K), entropy S°(T)–S°(364 K), and reduced Gibbs energy Φ°(T)). The data on the heat capacity of HoMnO₃ have been generalized in the range of 40–1000 K.     

A study of the microstructure,thermal properties and wetting kinetics of Sn–3Ag–<Emphasis Type="Italic">x</Emphasis>Zn lead-free solders

Microstructure, thermal properties and wetting kinetics of Sn–3Ag–xZn solders (x = 0.4, 0.6, 0.8, 1, 2 and 4 wt%) were systematically investigated. The results indicate that a small amount of Zn (Zn wt% ≤ 1 wt%) has a rather moderate effect on the microstructure morphology of the Sn–3Ag–xZn solders. The microstructures are composed of a β-Sn phase and the mixture of Ag₃Sn and ζ-AgZn particles. However, the β-Sn phase reduces its volume fraction in the entire microstructure and the intermetallic compounds population increases with the increasing of Zn content. The microstructure is dramatically changed with a further increase in the Zn content. The γ-AgZn phase is formed in a Sn–3Ag–2Zn solder. The ε-AgZn phase is formed in a Sn–3Ag–4Zn solder. The melting temperature and the undercooling of the Sn–3Ag–xZn solder alloys decrease with the increase in Zn content, reach to a minimum value when the content of Zn is 1 wt%, and then increase with further increase in Zn content. The Sn–3Ag–1Zn demonstrates the minimum value of 228.13 °C in the melting temperature and 13.87 °C in undercooling. The wetting kinetics of the main spreading stage features the power law of R ⁿ  ~ t (n = 1), which is controlled by chemical reactions at the triple line.     

Phase states and dielectric properties of sodium-potassium niobate solid solutions

The temperature dependence of dielectric constant ? for single crystals of Na_1?xK_xNbO₃ (0.04?x?0.15) is studied for the first time. From the shape of the ?(T) anomalies corresponding to rotational phase transitions, the type of interaction between the order parameters and the polarization is determined. A phenomenological model is developed which adequately describes the experimentally observed sequence of high-temperature (T>300°C) phase transitions, the dielectric anomalies associated with these transitions, and the changes in the phase states under the action of external factors (pressure, electric field).     

The influence of phase transitions in the Rb<Subscript>2</Subscript>CdI<Subscript>4</Subscript> ferroelastic on the exciton absorption spectrum

The parameters of the long-wavelength exciton band for Rb₂CdI₄ films are investigated in the temperature range 90–410 K. It is found that the Rb₂CdI₄ films undergo a sequence of phase transitions at temperatures T_c1=380 K (paraphase → incommensurate phase), T_c2=290 K (incommensurate phase → ferroelastic phase I), and T_c3 = 210 K (ferroelastic phase I → ferroelastic phase II). The parameters of the exciton band (such as the spectral position and the half-width) measured during heating and cooling of the Rb₂CdI₄ film differ significantly. This is especially true for the incommensurate phase. Upon heating of the incommensurate phase, the domain boundaries become frozen, whereas the cooling of this phase is accompanied by the generation of solitons and their pinning, which, in turn, results in a first-order phase transition at the temperature T_c2. It is revealed that the oscillator strength of the exciton band anomalously increases in the range of existence of commensurate phase I (T_c3<-T<-T_c2) due to ordering of the Rb₂CdI₄ crystal lattice.