Non-adiabatic small-polaron hopping conduction in VN–PbO–TeO2 glasses

The dc conductivity of VN–PbO–TeO₂ glasses with different mole percentages of VN, PbO and TeO₂ has been measured in the temperature range 125–450?K. The conductivity of the glasses increases with increasing VN content for a fixed mole percentage of PbO. Neither Mott's variable-range hopping (VRH) model at low temperatures (T<Θ_D/4, where Θ_D is the Debye temperature) nor Greaves’ VRH model at intermediate temperatures (Θ_D/?4<T<Θ_D/2) describe the dc conductivity data for these glasses. Multiphonon tunnelling transport of strongly coupled electrons is also unable to account for the carrier transport. However, at high temperatures (T?>?Θ_D/2), conduction is shown to be due to small-polaron hopping in the non-adiabatic regime. Alteration of the VN content causes a change in the model parameters achieved from best-fitting curves for the glasses. Modulated differential scanning calorimetry analysis shows that the glass transition temperatures T _g in this system vary from 269 to 302°C.     

The heat capacity of the layer compound tetrachlorobis (methylammonium) manganese—II (CH3NH3)2MnCl4, from 10 to 300k

The heat capacity of the layer compound, tetrachlorobis (methylammonium) manganese II, (CH₃NH₃)₂MnCl₄, has been measured over the range 10K <T<300K. In this region, two structural phase transitions have been observed previously by other techniques: one transition is from a monoclinic low temperature (MLT) phase to a tetragonal low temperature (TLT) phase, and the other is from TLT to an orthorhombic room temperature (ORT) phase. The present experiments have shown that the lower transition (MLT→TLT) occurs at T = 94.37±0.05K with ΔH_t = 727±5 J mol^?1 and ΔS_t = 7.76±0.05 J K^?1 mol^?1, and the upper transition (TLT→ORT) takes place at T = 257.02±0.07K with ΔH_t = 116±1J mol^?1 and ΔS_t = 0.451±0.004 J K^?1mol^?1. These results are discussed in the light of recent measurements on (CH₃NH₃)₂CdCl₄, and also with regard to a recent theoretical model of the structural phase transitions in compounds of this type.In addition to the structural phase transitions, (CH₃NH₃)₂MnCl₄ also undergoes magnetic ordering at T < 150K. The magnetic component to the heat capacity, as deduced from a corresponding states comparison of the heat capacity of the present compound with that of the Cd compound, is shown to be consistent with the behaviour expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Structural Phase Transition and the Dielectric Permittivity of the Model Lipid Bilayer [(CH2)12(NH3)2]CuCl4

Structural phase transitions in the lipid-like bilayer material [(CH₂)₁₂(NH₃)₂]CuCl₄ have been observed using differential thermal scanning. The compound shows an irreversible thermochromic transition at ? 465 K and three reversible transitions at T ₁ = 433 ± 4 K and T ₂ = 411 ± 2 K and T ₃ = 358 K. The transition at 350 K is ascribed to chain melting. The other two correspond to crystalline phase transformation.

Phase (IV) T₃ = 358 ± 2K Phase (III) T₂ = 411 ± 2K Phase (II) T₁ = 433 ± 4K Phase (I)

Dielectric permittivity is studied as a function of temperature in the range 300-440 K and frequency, range (60 Hz-100 kHz). It confirms the observed transitions. The dielectric permittivity reflects rotational and conformational transitions for the compound. The variation of the real part of the conductivity with temperature is thermally activated in the temperature range above 350 K, with frequency-dependent activation energy, the values of activation energy lie in the range of ionic hopping. The dependence of the conductivity on frequency follows the universal power law σ = σ₀ + A(T) ω ^{s ( T )} with 0<s<1. Comparison of this material with other members of the series is discussed     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Electrocaloric response in a relaxor ferroelectric polymer at temperatures far below the dielectric maximum

ABSTRACT

Relaxor ferroelectric polymer poly(vinylidene fluoride–trifluoroethylene–chlorofluoroethylene) (P(VDF-TrFE-CFE)) and its blends have been shown to exhibit a giant electrocaloric effect (ECE) over a broad temperature range, e.g. from 0 to 50 °C. Here, a special calorimeter was designed to directly characterize the heat absorbed Q_ECE due to ECE cooling of the blend of P(VDF-TrFE-CFE) with P(VDF-TrFE) 65/35 mol% copolymer down to ?15 °C, which covers the temperature range for many refrigeration applications. From Q_ECE, the isothermal entropy change ΔS and adiabatic temperature change ΔT are deduced. The data reveal that at ?15 °C the relaxor terpolymer/copolymer blend generates ΔS = 23.0J kg^?1 K^?1 and ΔT = 5.1K under 100 MV/m, which are still more than 65% of the ECE at room temperature. This temperature is far below the dielectric peak temperature of the relaxor blend and the results reveal the promise of the relaxor polymers for a broad range of EC cooling applications.     

Phase transitions in oxyfluoride (NH4)2WO2F4

(NH₄)₂WO₂F₄ single crystals are grown, and their polarization-optical, calorimetric, and birefringence properties are studied in the temperature range 90–350 K. A first-order structural phase transition is found to occur at T ₀₁↑ = 202 K with thermal hysteresis of ΔT ₀₁ ≈ 6–12 K. The phase transition is accompanied by twinning and modification of the symmetry . An additional weak anomaly in the differential scanning calorimeter signal is found at T ₀₂ ≈ 170 K. The total thermal effect of both anomalies is ∑ΔH _i = 3200 ± 400 J/mol and ∑ΔS _i = 16.5 ± 2.0 J/mol K. The phase transition at T ₀₁ is of the order-disorder type.     

Lattice thermal conductivity of compounds with inhomogeneous intermediate rare-earth ion valence

The thermal conductivity κ (within the range 4–300 K) and electrical conductivity σ (from 80 to 300 K) of polycrystalline Sm₃S₄ with the lattice parameter a=8.505 Å (with a slight off-stoichiometry toward Sm₂S₃) are measured. For T>95 K, charge transfer is shown to occur, as in stoichiometric Sm₃S₄ samples, by the hopping mechanism (σ ～ exp(?ΔE/kT) with ΔE ～ 0.13 eV). At low temperatures [up to the maximum in the lattice thermal conductivity κ_ph(T)], κ_ph ～ T ^2.6; in the range 20–50 K, κ_ph ～ T ^?1.2; and for T>95 K, where the hopping charge-transfer mechanism sets in, κ_ph ～ T ^?0.3 and a noticeable residual thermal resistivity is observed. It is concluded that in compounds with inhomogeneous intermediate rare-earthion valence, to which Sm₃S₄ belongs, electron hopping from Sm²⁺ (ion with a larger radius) to Sm³⁺ (ion with a smaller radius) and back generates local stresses in the crystal lattice which bring about a change in the thermal conductivity scaling of κ_ph from T ^?1.2 to T ^?0.3 and the formation of an appreciable residual thermal resistivity.     

Thermoelectric power of potassium doped lanthanum manganites at low temperatures

The temperature-dependent resistivity and thermoelectric power of monovalent (K) doped La_1−xK_xMnO₃ polycrystalline pellets (x=0.05, 0.10 and 0.15) between 50 and 300 K are reported. K substitution enhances the conductivity of this system. Curie temperature (T_C) also increases from 260 to 309 K with increasing K content. In the paramagnetic region (T>T_C), the electrical resistivity is well represented by adiabatic polaron hopping, while in the ferromagnetic region (T<T_C), the resistivity data show a nearly perfect fit for all the samples to an expression containing, the residual resistivity, spin-wave and two-magnon scattering and the term associated with small-polaron metallic conduction, which involves a relaxation time due to a soft optical phonon mode. Small polaron hopping mechanism is found to fit well to the thermoelectric power (S) data for T>T_C whereas at low temperatures (T<T_C) in ferromagnetic region (S_FM), S_FM is well explained with the spin-wave fluctuation and electron–magnon scattering. Both, resistivity and thermopower data over the entire temperature range (50–300 K) are also examined in light of a two-phase model based on an effective medium approximation.     

High-temperature phase transitions in the improper ferroelectric KIO3

The ac conductivity (σ_ac) and dielectric permittivity (?) are determined in the temperature range 300?K?T3 compound. The results indicated that the compound behaves as an improper ferroelectric and undergoes a ferroelectric phase transition from a high temperature rhombohedral phase I to a low temperature monoclinic phase II at T _c?=?(486?±?1)?K. A second structural phase transition was observed around 345?K. The conductivity varies with temperature range and for T?>?428?K intrinsic conduction prevails. Different activation energies in the different temperature regions were calculated. The frequency dependence of σ(ω) was found to follow the universal dynamic response [σ(ω)∝(ω) ^s(T)]. The thermal behaviour of the frequency exponent s(T) suggests the hopping over the barrier model rather than the quantum mechanical tunneling model for the conduction mechanism.     

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.     

Mechanisms of charge transfer and magnetoresistance in CuInSe<Subscript>2</Subscript>

The electrical conductivity and magnetoresistance effect of n and p types of CuInSe₂ single crystals were studied within the temperature range of 4.2–300 K and within magnetic fields of up to 6 T. It was found that the hopping mechanism of conductivity dominates in the temperature range of 4.2–100 K. A peculiarity of electrical conductivity behavior, accompanied by a change in the magnetoresistance sign in the vicinity of T ≈ 60 K, was revealed.     

Field-induced structural transition and the related magnetic entropy change in Ni43Mn43Co3Sn11 alloy

Magnetic properties and magnetic entropy change ΔS were investigated in Heusler alloy Ni₄₃Mn₄₃Co₃Sn₁₁. With decreasing temperature this alloy undergoes a martensitic structural transition at T_M=188 K. The incorporation of Co atoms enhances ferromagnetic exchange for parent phases. Austenitic phase with cubic structure shows strong ferromagnetic behaviors with Curie temperature T_C^A at 346 K, while martensitic phase shows weak ferromagnetic properties. An external magnetic field can shift T_M to a lower temperature at a rate of 4.4 K/T, and a field-induced structural transition from martensitic to austenitic state takes place at temperatures near but below T_M. As a result, a great magnetic entropy change with positive sign appears. The size of ΔS reaches 33 J/kg K under 5 T magnetic field. More important is that the ΔS displays a table-like peak under 5 T, which is favorable for Ericsson-type refrigerators.     

Low temperature electrical conductivity and magnetoconductivity of Fe39Ni39Mo4Si6B12 and Co58Ni10Fe5Si11B16 metallic glass alloys

A detailed study on the weak localization phenomenon vis-a-vis electron-electron interaction effects in magnetic metallic glasses has been carried out. We measured the electrical conductivity and magnetoconductivity within the temperature range 1.8≤T≤300K. A maximum on the conductivity versus temperature curve exists atT=T _m. The conductivity was observed to follow aT ^1/2 law forT<T _m andT ² law forT>T _m. Magnetoconductivity data of these alloys indicate the prominence of electron-electron interaction at low temperatures. The authors have determined the inelastic scattering field and spin-orbit scattering field from the magnetoconductivity data. The inelastic scattering field obeys aT ^p law (p=2) at low temperatures.     

Phase transitions and electrical conduction in thermal energy storage compound (n-C12H25NH3)2CdCl4

Differential scanning calorimetry (DSC) and differential thermal analysis (DTA) are performed for the compound (n-C₁₂H₂₅NH₃)₂CdCl₄. The ac conductivity σ_(ω,T), and the complex dielectric permittivity ?*_(ω,T) are measured as a function of temperature (100 K < T < 375 K) and at some selected frequencies (3 → 100 kHz). Two structural phase transitions are detected at T = (330 ± 1) K and T = (343 ± 1) K as minor and major transitions, respectively. The analysis of the measured electrical parameters reveals that the frequency-dependent conductivity obeys the power law, and the quantum mechanical tunneling (QMT) model is the main conduction mechanism in the low-temperature phase (LTP; phase III). The role of hydrogen bond N–H…Cl as a trigger force for phase transitions has been discussed. While the LTP is of the order–disorder type, the high-temperature phase (HTP) or phase I seems to be conformational and represents the main transition.     

Chirality and the thermophysical properties of molecular solid phases under pressure: (+)- and (±)-camphor

Thermal conductivity λ, heat capacity per unit volume pc_P and P-T phase diagrams are investigated for both (+)- and (±)-camphor. The transient hotwire method is used at temperatures in the range 100–430 K and at pressures up to 1·75 GPa. We detect solid phases I-IV for (+)-camphor and I′-V′ for (±)-camphor. We conclude that λ is independent of enantiomeric composition for plastic-crystal phase pairs I-I′, II-II′ and IV-IV′. Phase V′ also appears to be a plastic-crystal phase. Non-plastic phases III and III′ show a variation of λ with T that differ considerably from that expected for a simple crystal, with the greatest such difference being observed for the racemic compound III′. An unannealed specimen of the racemic compound III′ is probably chirally disordered and shows a variation of λ with T for T < 130 K, which may indicate phonon-assisted fracton hopping.     

Double magnetic entropy change peaks and high refrigerant capacity in Gd1-xHoxNi compounds in the melt-spun form

Gd_1-xHo_xNi melt-spun ribbons were fabricated by a single-roller melt spinning method. All the compounds crystallize in an orthorhombic CrB-type structure. The Curie temperature (T_C) was tuned between 46 and 99 K by varying the concentration of Gd and Ho. A spin reorientation (SRO) transition is observed around 13 K. Different from T_C, the SRO transition temperature is almost invariable for all compounds. Two peaks of magnetic entropy change (ΔS_M) were found. One at the higher temperature range was originated from the paramagnet-ferromagnet phase transition and the other at the lower temperature range was caused by the SRO transition. The maximum of ΔS_M around T_C is almost same. The other maximum of ΔS_M around SRO transition, however, had significantly positive relationship with x. It reached a maximum about 8.2 J kg⁻¹ K⁻¹ for x = 0.8. Thus double large ΔS_M peaks were obtained in Gd_1-xHo_xNi melt-spun ribbons with the high Ho concentration. And the refrigerant capacity power reached a maximum of 622 J kg⁻¹ for x = 0.6. Gd_1-xHo_xNi ribbons could be good candidate for magnetic refrigerant working in the low temperature especially near the liquid nitrogen temperature range.     

Hopping conductance in electron irradiated n-type GaAs

A.c. conductivity is studied in n-type electron irradiated GaAs at helium temperatures. For T < 25 K variable range hopping $\text{[σ∝exp(-b/T}{}^{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{)]}$ is observed. The experimentally observed low values of $\text{b(K}{}^{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{)}$ are discussed. At T > 30 K the conductivity exhibits an activation energy of 0.5 meV which is attributed to excitation into an upper band. The frequency dependence of hopping conductance is σ ∝ ω^S with S=1.8 and S=0.9 depending on the degree of radiation induced damage.     

Phonon coupled cooperative low-spin 1A1high-spin 5T2 transition in [Fe(phen)2(NCS)2] and [Fe(phen)2(NCSe)2] crystals

Heat capacities of [Fe(phen)₂(NCS)₂] and [Fe(phen)₂(NCSe)₂] were measured between 13⁵ and 375 K. A heat capacity anomaly due to the spin-transition from low-spin ¹A₁ to high-spin π₂ electronic ground state was found at 176·29 K for the SCN-compound and at 231·26 K for the SeCN-compound, respectively. Enthalpy and entropy of transition were determined to be ΔH = 8·60 ± 0·14 kJ mol^?1 and ΔS = 48·78 ± 0·71 J K^?1 mol^?1 for the SCN-compound and ΔH = 11·60 ± 0·44 kJ mol^?1 and ΔS = 51·22 ± 2·33 J K^?1 mol^?1 for the SeCN-compound. To account for much larger value of ΔS compared with the magnetic contribution, we suggest that there is significant coupling between electronic state and phonon system. We also present a phenomenological theory based on heterophase fluctuation. Gross aspects of magnetic, spectroscopic, and thermal behaviors were satisfactorily accounted for by this model. To examine closely the transition process, infrared spectra were recorded as a function of temperature in the range 4000 ? 30 cm^?1. The spectra revealed clearly the coexistence of the ¹A₁, and the ⁵T₂ ground states around T_c.