ac conductivity of anhydrous pellicular zirconium phosphate in hydrogen form

Aqueous suspensions of delaminated zirconium phosphate have been recently obtained in our laboratory by a suitable intercalation-deintercalation of alkylamines. By filtering these suspensions thin and flexible sheets or pellicles of lamellar α-zirconium phosphate, with the most part of the layers oriented parallel to the pellicle surface, can be easily prepared. ac conductivity measurements have been carried out, in the temperature range 150–300°C, on pellets made of α-Zr(HPO₄)₂ pressed pellicles, oriented both parallel and perpendicular to the electric field. Independently of the pellet orientation, a slope variation was observed in the Arrhenius plot at about 220°C. As already found for the α-Zr(HPO₄)₂ powder, this is associated with a phase transition at this temperature, which causes a discontinuous change of the interlayer distance from 7.4 Å to 6.8 Å. The conductivity of samples oriented parallel to the electric field ($\text{～10}{}^{\mathrm{?4}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}\text{at}\text{300°}\text{C}$) is about two orders higher than the conductivity of the anhydrous microcrystalline powder, which, in turn, is higher than that of perpendicularly oriented samples ($\text{～3 × 10}{}^{\mathrm{?7}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}\text{at}\text{300°}\text{C}$).     

Chemical diffusion in CoO

Equilibration kinetics of CoO have been studied over the range 1–10^?5 atm oxygen pressure and 900–1300°C by both thermogravimetric and electrical conductivity techniques. The former technique gives excellent agreement with theory based on bulk diffusion and results in a chemical diffusion coefficient given by, $\text{D}\text{?}\text{= 4.8×10}{}^{\mathrm{?3}}\text{exp (?22,500/RT)}$ cm${}^2\text{sec}$. The defect diffusion coefficient (Dinvinco) is equal to $\text{i}\text{?}\text{tD}\text{2}$. No dependence of ?tD on defect concentration was observed. The electrical conductivity technique qualitatively supports these results.     

Electrical transport and magnetic properties of Nd2(WO4)3

Measurements of the molar magnetic susceptibility (X_m) of a powdered sample of Nd₂(WO₄)₃ in the temperature range 300–900 K, and the electrical conductivity (σ) and dielectric constant (?$\text{)}\text{?}$ of pressed pellets of the compound in the temperature range 4.2–1180 K are reported. X_m obeys the Curie-Weiss law with a Curie constant C= 3.13 K/mole, a paramagnetic Curie temperature θ= ?60 K and a moment of Bohr magnetons, p= 3.49 for the Nd³⁺ ion. The electrical conductivity data can be explained in terms of the usual band model and impurity levels. Both the σ and ?$\text{\$}\text{?}$data indicate some sort of phase transition round 1025 K. The conductivity follows Mott's law $\text{σ = A exp (?B/T}{}^{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{)}$ in the temperature range $\text{200 < T < 3000}\text{K with}\text{B = 45.00 (}\text{K}\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{and}\text{A = 1.38 × 10}{}^{\mathrm{?5}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$. The dielectric constant increases slowly up to 600 K, as is usual for ionic solids. The increase becomes much faster above 600 K, which is attributed to space-charge polarization of thermally generated charge carriers.     

The ground state of methane 12CH4 through the forbidden lines of the ν3 band

High resolution spectra of the ν₃ band of methane, ¹²CH₄, were recorded by using a “third generation vacuum Fourier interferometer”; a large pressure range (from 0.009 to 10 Torr) with a sample path fixed at eight meters was used, enabling observation of transitions with intensity ratios as low as $\text{1}\text{10 000}$. More than 350 forbidden transitions of the ν₃ band, including about 125 transitions of the Q⁺ branch, were unambiguously identified. Of the 277 transitions retained for computations, one-hundred have 11 ≤ J ≤ 16. From combination difference relations using pairs of transitions having the same upper state energy level (forbidden-allowed and forbidden-forbidden pairs were used), 276 independent differences between ground state energy levels could be determined with uncertainties of about 0.001 cm^?1.These data yielded the following values for the ground state structure constants of ¹²CH₄ along with their standard deviations (in cm^?1): $\text{β}{}^{\mathrm{o}}\text{hc}\text{=5.2410356±0.0000096}$, $\text{γ}{}^{\mathrm{o}}\text{hc}\text{=(?1±0.00074) 10}{}^{\mathrm{?4}}$, $\text{π}{}^{\mathrm{o}}\text{hc}\text{=(5.78±0.18) 10}{}^{\mathrm{?9}}$, $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(?1.4485±0.0023) 10}{}^{\mathrm{?6}}$, $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(1.768±0.126) 10}{}^{\mathrm{?10}}$, $\text{ξ}{}^{\mathrm{o}}\text{hc}\text{=(?1.602±0.067) 10}{}^{\mathrm{?11}}$, Thus, for the first time, the scalar constant π⁰ has been evaluated and ir values have been obtained for the two tetrahedral constants ?⁰ and ξ⁰; furthermore, these values are in very good agreement with the ones recently determined from radiofrequency data, i.e., in cm^?1: $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(?1.45061±0.00014) 10}{}^{\mathrm{?6}}$, $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(1.7634±0.0068) 10}{}^{\mathrm{?10}}$, $\text{ξ}{}^{\mathrm{o}}\text{hc}\text{=(?1.5432±0.0040) 10}{}^{\mathrm{?11}}$ From these values, the 276 differences can be reproduced with an overall rms deviation equal to 0.0009 cm^?1.Finally, the ground state energies of ¹²CH₄ have been calculated for J ≤ 16.     

Determination of the fermi surface of monoclinic SrAs3 by Shubnikov dehaas effect

The electronic properties of single crystals of monoclinic SrAs₃ have been studied by investigating the temperature dependence of electrical conductivity, Hall effect and Shubnikov de Haas (SdH) oscillations. At 4.2 K, SrAs₃ is predominantly p-conducting with a typical hole concentration of 6 × 10¹⁷cm^-3. The Hall coefficient changes its sign near 80 K. The angular dependence of the SdH oscillations was used to map out the shape of the Fermi-surface of holes. Two asymmetric, quasi-ellipsoidal Fermi-bodies are located in the first Brillouin zone. The cyclotron effective masses $\text{m}{}^1$ for two crystallographic directions were calculated from the temperature dependence of the amplitude of the oscillations: $\text{m}{}^1\text{(B6a)=(0.70± 0.002)m}{}_0$and $\text{m}{}^1\text{(B6c}{}^1\text{)=(0.095±0.003)m}{}_0$, respectively. There are indications for a third Fermi-surface which is attributed to electrons.     

Pressure dependence of superconductivity in the pseudo-one-dimensional compound Tl2Mo6Se6

Measurements of the temperature and pressure dependences of the resistivity of the pseudo-one-dimensional ternary compound Tl₂Mo₆Se₆ are presented. We find that the conductivity parallel to the highly conducting c-axis is enhanced by pressure and the superconducting transition temperature T_c is suppressed by pressure at a rate $\text{?T}{}_{\mathrm{c}}\text{?P}\text{=?7.6×10}{}^{\mathrm{?5}}$ kbar^?1. These results are discussed in relation to the current models of transport in one-dimensional conductors.     

Electrical conductivity of the system Y2O3CeO2

The electrical conductivity of the system Y₂O₃CeO₂ was measured in the temperature range 500–1100°C and P_o2 range 10^–7?10^?1 atm. Possible defect models were suggested on the basis of conductivity data, which were investigated as a function of temperature and of P_o2. The observed activation energies were 0.40 eV and 1.79 eV in the low- and high-temperature regions, respectively. The observed conductivity dependences on P_o2 were in the temperature range 500–750°C and at temperatures from 750–1100°C. It is suggested that the system Y₂O₃CeO₂ shows a mixed ionic plus hole conduction due to an O^″_i defect and an electronic hole conduction due to a V^'''_Y defect in the low- and high-temperature regions, respectively.     

Thermodynamics and mobility of copper in bornite (Cu5FeS4)

The thermodynamics and kinetics of copper transport in bornite (Cu₅FeS₄) have been investigated. Coulometric titration experiments on single-crystal and hot-pressed polycrystalline materials indicated a restricted range of composition for substoichiometric single-phase bornite, with materials of copper contents less than Cu_4.95FeS₄ existing as a two-phase mixture of bornite and a chalcopyrite-type phase (Cu₃FeS₄). For the polycrystalline material the van der Pauw technique was used to obtain the electronic conductivity (σ_e) as a function of temperature and a six-point cell was used to measure the ionic conductivity (σ_i) as a function of composition. Typical results obtained at 170°C were $\text{σ}{}_{\mathrm{e}}\text{=230 Ω}{}^{\mathrm{?1}}\text{m}{}^{\mathrm{?1}}$, $\text{σ}{}_{\mathrm{i}}\text{= 11 Ω}{}^{\mathrm{?1}}\text{m}{}^{\mathrm{?1}}$, activation energy for electronic conduction = 15 kJ mol^?1. The transient behaviour of the electronic and ionic probe voltages during the six-point cell experiments have been tentatively interpreted in terms of the chemistry of the copper-iron sulphides.     

Hopping conductivity in amorphous carbon films

The electrical resistivity of amorphous carbon films getter-sputtered at 95°K is well fitted between 300 and 20°K by the relation $\text{? = ?}{}_0\text{exp}\text{[(T}{}_0\text{/T)}{}^{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{]}$ with T₀ ? 7 × 10⁷K. This behavior suggests a hopping conductivity very similar to that found in other amorphous semiconductors.     

Diffusion and ionic conductivity in sodium beta alumina

Measurements of sodium tracer diffusion (D_t) and ionic conductivity (σ) have been made on the same single crystals of sodium beta-alumina of composition 1.23 Na₂0.11 Al₂O₃. The σ- measurements were made over the temperature 390–660 K using reversible (liquid sodium) electrodes. A fit to the conductivity data gives $\text{σT = 2470}\text{exp}\text{(?0.142}\text{eV}\text{kT}\text{)Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}\text{K}$. The D_t, measurements employed two techniques, i.e. nondestructive profiling over the temperature range 210–750 K and cation exchange over the temperature range 505–970 K. The results of the two techniques were in close agreement and can be expressed as $\text{D = 2.12 ×10}{}^{\mathrm{?4}}\text{exp}\text{(?0.169}\text{eV}\text{kT}\text{)}\text{cm}{}^2\text{sec}{}^{\mathrm{?1}}$ for T>520K and $\text{D = 2.45 × 10}{}^{\mathrm{?4}}\text{exp}\text{(?0.164}\text{eV}\text{kT}\text{)}\text{cm}{}^2\text{sec}\text{470}\text{K}$. The “transition” region between 470 and 520 K is not observed in the conductivity measurements. Silver cation exchange was used to determine the number of mobile sodium ions. A comparison of D_t and σ data yielded a Haven ratio that is temperature dependent, ranging in value from 0.45 at 870 K to 0.35 at 370 K.     

Anomalous ionic conduction in AgBrAgI mixed crystals and multiphase systems

Ionic conductivity, σ, of the AgBrAgI system has been studied as a function of composition and temperature. The maximum conductivity of $\text{3 × 10}{}^{-4}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$ at 25°C is obtained for a AgI-20 mole% AgBr two-phase mixture which is $\text{\$}\text{?}$3 orders of magnitude larger than that predicted by the classical theories of Lord Rayleigh and Maxwell. On the other hand, the substitution of so-called homovalent ions, e.g. Br^? in AgI and I^? in AgBr one phase solid solutions leads to anomalously large increase in the ionic conductivity that cannot be explained in terms of the charge compensation (doping) mechanism, and is attributed to purely elastic displacements (lattice distortion) due to the very “wrong” size of the substituted ions. A quadratic dependence of conductivity on the concentration of substituents is substantiated. An important consequence of the latter anomaly is that AgBr + 30 mole% AgI exhibits σ $\text{\$}\text{?}$7 Ω^?1 cm^?1 at 380°C which is $\text{\$}\text{?}$170% higher than that of α-AgI, the best known superionic conductor, at its melting point (557°C).     

Structure,vibrational study and conductivity of the trihydrated uranyl bis(dihydrogenophosphate): UO2(H2PO4)2·3H2O

The X-ray structure (293 K) of UO₂(H₂PO₄)₂·3H₂O has been refined (R = 0.062): M_r = 518g, space group: P2₁/c (Z = 4); $\text{a = 10.816(1)}\text{A}\text{?}$, $\text{b = 13.896(2)}\text{A}\text{?}$, $\text{c = 7.481(1)}\text{A}\text{?}$, β = 105.65(1)^°, $\text{V = 1082.7(2)}\text{A}\text{?}{}^3$; D_c = 3.17 Mg m^?3. The structure consists of infinite chains along the (101) axis with U atoms bridged by two H₂PO₄ groups. The U atom is surrounded by a pentagonal bipyramid of oxygen atoms, one of them being an equatorial water molecule. The cohesion between the chains is ensured by hydrogen bonds involving the two last water molecules. An assignment of IR and Raman bands with isotopic substitution spectra is proposed. A phase transition at 128 K was made evident by DSC and spectroscopy. The room-temperature phase is characterized by a high disorder of the OH bond orientation while in the low-temperature phase H₂O and POH species appear well oriented. The conductivity seems to occur by proton transfer and protonic-species rotation at the POH-water molecular interface between the chains. ac conductivity has been determined by means of the complex-impedance method ($\text{σ}{}_{\mathrm{<mtext>RT</mtext>}}\text{～ (3?12) × 10}{}^{\mathrm{?5}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$; E ～ 0.20 eV).     

Electrical conductivity and chemical diffusion coefficient measurements in single crystalline nickel oxide at high temperatures

Electrical conductivity measurements on nickel oxide have been performed at high temperatures (1273 K<T< 1673 K) and in partial pressures of oxygen ranging from Po₂ = 1.89 × 10^?4 atm to Po₂ = 1 atm. The $\text{po}{}_2{}^{\mathrm{<mtext>1</mtext><mtext>n</mtext>}}$ dependence of the conductivity decreases from about $\text{1}\text{4}$ for Po₂ = 1 atm to smaller values for lower partial pressures of oxygen. The activation enthalpy for conduction increases for decreasing oxygen partial pressures (from 22.5 kcal mol^?1 at Po₂ = 1 atm to 26.0 kcal mol^?1 for Po₂ = 1.89 × 10^?4 atm). This behaviour can be explained by the simultaneous presence of singly and doubly ionized nickel vacancies, with different energies of formation.Furthermore, chemical diffusion coefficient measurements have been performed in the same temperature range, using the conductivity technique, and leading to the result:

$\text{D}\text{?}\text{= 0.244 exp (?}\text{36,600}\text{RT}\text{) cm}{}^2\text{s}{}^{\mathrm{?1}}$

.     

Iron diffusion and electrical conductivity in magnesio-wüstite solid solutions (Mg,Fe)O

Diffusion of ⁵⁹Fe and electrical conductivity in magnesio-wüstite solid solution (Mg_xFe_1?x)O with x = 0.26 and 0.5 have been measured as a function of temperature and oxygen partial pressure. For both solid solutions, the results show that at 1100°C the diffusivity D of ⁵⁹Fe is directly proportional to $\text{p}{}_{\mathrm{o2}}{}^{\mathrm{<mtext>1</mtext><mtext>6</mtext>}}$, whereas the electrical conductivity σ is directly proportional to $\text{p}{}_{\mathrm{o2}}{}^{\mathrm{<mtext>1</mtext><mtext>3.4</mtext>}}$. At a given temperature and oxygen partial pressure, the value of D decreases with an increase in MgO concentration in the solid solution. The results are discussed in terms of the coexistence of variously ionized cation vacancies and their change in concentration with MgO additions.     

Analysis of the Ã1A″ ← X̃1A′ electronic transition in thiocarbonyl chlorofluoride

The visible absorption spectrum of thiocarbonyl chlorofluoride, ClFCS, in the region 5000 to 3000 Å has been observed under conditions of high resolution in the vapor phase and has been assigned to the $\text{A}\text{?}{}^1\text{A″(nπ}{}^1\text{) ←}\text{X}\text{?}{}^1\text{A′}$ and $\text{a}\text{?}{}^8\text{A″(n, π}{}^1\text{) ←}\text{X}\text{?}{}^1\text{A′}$ electronic transitions. All six fundamental modes have been assigned for both the upper and lower singlet electronic states. From the observed splittings of the even-odd quanta of ν₆′ in the spectrum the barrier to inversion in the $\text{A}\text{?}{}^1\text{A″}$ state has been evaluated to be 1556.0 ± 45 cm^?1.     

Ω− produced in K−p reactions at 4.2 GeV/c

Forty $\text{Ω}{}^{\mathrm{?}}$ events have been observed in a large (133 events/βb) experiment at 4.2 GeV/c incident K^? momentum. Thirty nine of the events come from the three-body reaction $\text{K}{}^{\mathrm{?}}\text{p}\text{→Ω}{}^{\mathrm{?}}\text{K}{}^{\mathrm{+}}\text{K}{}^0$. The $\text{Ω}{}^{\mathrm{?}}$ is mainly produced in the forward hemisphere (direction of the incident K^?). The lifetime is measured to be τ = (0.75 _+0.14?0.11 × 10^?10 sec substantially less than the Particle Data Group value of (1.3 _?0.3^+0.2) × 10^?10 sec. The mass is determined to be 1671.7 ± 0.6 MeV, in good agreement with other determinations. The decay asymmetry parameter α (for the decay mode $\text{Ω}{}^{\mathrm{?}}\text{→ Λ}\text{K}{}^{\mathrm{?}}$) is found to be ?0.2 ± 0.4.     

Thermal conductivity and heat capacity of cyclohexane under pressure

The transient hot-wire technique was used to determine the thermal conductivity, λ, and the specific heat capacity per unit volume, pc_p, of cyclohexane up to 1.5 GPa in the range 120–340 K. The measurements were carried out in a piston-cylinder apparatus, 45 mm in internal diameter, cooled by liquid nitrogen. There is only a small (6%) increase in λ on freezing, while there is an increase by a factor of two corresponding to the plastic→ normal crystal transition. The variation of λ with temperature (T) at P = 0.03 GPa is $\text{d(lnλ)}\text{dT}\text{= ?2.2×10}{}^{\mathrm{?3}}\text{K}{}^{\mathrm{?1}}$ for the liquid and $\text{d(ln λ)}\text{dT}\text{= ?0.9× 10}{}^{\mathrm{?3}}\text{K}{}^{\mathrm{?1}}$ for the plastic crystalline phase. In the norm crystal phase an approximate T^?1 dependence is observed. Within each of the phases λ increases linearly with pressure, and the slope of λ (P) is smallest in the plastic crystal phase. The existence of a recently reported new high pressure phase is evident from conductivity data. Qualitative ρC_p -results are reported.     

Analysis of the Raman spectrum of SF6

The Raman active fundamentals ν₁(A1g), ν₂(Eg), ν₅(F2g), and the overtone 2ν₆ of SF₆ have been investigated with a higher resolution and the band origins were estimated to be: ν₁ = 774.53 cm^?1, ν₂ = 643.35 cm^?1, ν₅ = 523.5 cm^?1, and 2ν₆ = 693.8 cm^?1. Raman and infrared data have been combined for estimation of several anharmonicity constants. The ν₆ fundamental frequency is calculated as 347.0 cm^?1. From the analysis of the ν₂ Raman band, the following rotational constants of both the ground and upper states have been calculated:

$\text{B}{}_0\text{= 0.09111 ± 0.00005}\text{cm}{}^{\mathrm{?1}}\text{; D}{}_0\text{= (0.16±0.08)10}{}^{\mathrm{?7}}\text{cm}{}^{\mathrm{?1}}$

;

$\text{B}{}_2\text{= 0.09116 ± 0.00005}\text{cm}{}^{\mathrm{?1}}\text{; D}{}_2\text{= (0.18±0.04)10}{}^{\mathrm{?7}}\text{cm}{}^{\mathrm{?1}}$

.     

Electrical and structural properties of iron-doped β-alumina

β-alumina containing 50 w/o Fe exhibits high electronic conductivity when sintered in air but Mössbauer studies have shown the presence of Fe₃O₄. Single-phase β-alumina containing 50 w/o Fe could be prepared by sintering at 1400°C for 4–4.5 h followed by annealing at 1300°C for 96 h encapsulated with coarse β-alumina powder enriched with Na₂CO₃. Mössbauer spectroscopy indicated that all iron was present as Fe(III). Complex-plane impedance data showed a maximum bulk $\text{σ}{}_{\mathrm{25°C}}\text{= 5.56 × 10}{}^{-4}\text{(Ω cm)}{}^{-1}$ with little electronic conductivity. Reduction treatments on Fe-doped β-alumina utilizing H₂:N₂ gas were successful in producing a mixed conductor containing Fe(II) and Fe(III) but also produced a distorted β-alumina lattice. This material exhibited an electronic conductivity $\text{σ}{}_{\mathrm{e,25°C}}\text{= 2 × 10}{}^{-4}\text{(Ω cm)}{}^{-1}$ and a bulk ionic conductivity $\text{σ}{}_{\mathrm{b,25°C}}\text{= 1.35 × 10}{}^{-4}\text{(Ω cm)}{}^{-1}$.