Electrical conductivity study of oxidation process in manganese-substituted magnetites

During oxidation in air of finely-grained manganese-substituted magnetites (Mn _0.8x ²⁺ Fe _1–0.8x ³⁺ )_A– (Fe _1+0.6x ³⁺ Fe _1–0.8x ²⁺ Mn _0.2x ³⁺ )_BO ₄ ^2– (A=tetrahedral, B=octahedral) the temperature dependence of the electrical conductivity over a temperature range of 100 to 700° C was investigated. Below 500° C the evolution of electrical conductivity might be closely associated with the position and nature of cations in the spinel lattice. The profile of the =f(t) curves show that the mechanism of electrical conduction in the temperature range 150 to 300° C can be explained in terms of the oxidation of Fe²⁺ to Fe³⁺ ions at octahedral sites. For the temperature range 300 to 400° C the conductivity involves the hopping of electrons from tetrahedral-site Mn²⁺ ions to tetrahedral-site Mn³⁺ ions. Above 500° C the oxidation of Mn²⁺ ions leads to an increase in conductivity with the generation of new phases of -Fe₂O₃, Mn₂O₃ and -(MnFe)₂O₃.     

Mössbauer studies of Li0.5Fe2.5-xGaxO4 system: canted spin alignment and cation distribution

Based on⁵⁷Fe Mössbauer effect studies conducted at 4.2 K with and without an external magnetic field of 40 kG, the exact distribution of Fe³⁺ between the octahedral and tetrahedral sites has been determined for the Li_0.5Fe_2.5-x Ga _x O₄ system for 0.0 x 1.1. Gallium ions show a slight preference for tetrahedral sites. The values of canting angle _yk have been determined for octahedral Fe³⁺ ions using both relative intensity of different peaks and hyperfine field values. The effect of sintering on the values of hyperfine field, cation distribution and canting angle has been studied for Li_0.5Fe_1.4Ga_1.1O₄. The effect of gallium substitution on the values of hyperfine interaction parameters and the occurrence of a magnetically collapsed doublet is also discussed.     

Effect of magnesium content on the stress exponent and effective stress in the steady state creep of Al-Mg alloys

The stress exponent of steady state creep,n, and the internal ( _i) and effective stresses ( _e) have been determined using the strain transient dip test for a series of polycrystalline Al-Mg alloys creep tested at 300° C and compared with previously published data. The internal or dislocation back stress, _i, varied with applied stress,, but was insensitive to magnesium content of the alloy, being represented by the empirical equation _i=1.084 ^1.802. Such an applied stress dependence of _i can be explained by using an equation for _i of the form _i (dislocation density)^1/2 and published values for the stress dependence of dislocation density. Values of the friction stress, _f, derived using the equation _e/=(1–c) (1– _f/), indicate that _f is not dependent on the magnesium content. A constant value of _f can best be rationalized by postulating that the creep dislocation structure is relatively insensitive to the magnesium content of the alloy.On leave from Engineering Materials Department, University of Windsor, Windsor, Ontario N9B 3P4, Canada.     

Interfacial debonding and fibre pull-out stresses

Based on a theoretical model developed previously by the authors in Part II of this series for a single fibre pull-out test, a methodology for the evaluation of interfacial properties of fibre-matrix composites is presented to determine the interfacial fracture toughness G _c, the friction coefficient , the radial residual clamping stress q _o and the critical bonded fibre length z _max. An important parameter, the stress drop , which is defined as the difference between the maximum debond stress _d ^* and the initial frictional pull-out stress _fr, is introduced to characterize the interfacial debonding and fibre pull-out behaviour. The maximum logarithmic stress drop, In(), is obtained when the embedded fibre length L is equal to the critical bonded fibre length z _max. The slope of the In()-L curve for L bigger than z _max is found to be a constant that is related to the interfacial friction coefficient . The effect of fibre anisotropy on fibre debonding and fibre pull-out is also included in this analysis. Published experimental data for several fibre-matrix composites are chosen to evaluate their interfacial properties by using the present methodology.On leave at the Department of Mechanical Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong.     

Magnetic Microstructure and Electrical Properties of Ferrimagnetic Oxide Epilayers

Data are presented on the correlations between the angle the magnetization vector makes with the normal to the surface () and the surface conductivity (_s) and activation energy for conduction in Mn _p Mg _q Fe_{3 – p – q} O_{4 +} epilayers. The orientation of the magnetic moment and the effective magnetic fields at Fe nuclei on tetrahedral and octahedral sites were determined by Mössbauer spectroscopy. It is shown that increases with _s and, according to x-ray diffraction data, depends on the density of misfit dislocations. The revealed correlations are interpreted in terms of epilayer microstructure, electronic–ionic disordering, lattice mismatch, and Jahn–Teller effect. The development of uniaxial anisotropy in the layers studied is due to the presence of the Jahn–Teller ion Mn³⁺, rather than Fe²⁺.     

On internal stress and activation volume in polymers

The two-site model is developed for the analysis of stress relaxation data. It is shown that the product of d In (– )/d and (- _i) is constant where is the applied stress, _i is the (deformation-induced) internal stress and = d/dt. The quantity d In ( )/d is often presented in the literature as the (experimental) activation volume, and there are many examples in which the above relationship with (- _i) holds true. This is in apparent contradiction to the arguments that lead to the association of the quantity d In (– )/d with the activation volume, since these normally start with the premise that the activation volume is independent of stress. In the modified theory presented here the source of this anomaly is apparent. Similar anomalies arise in the estimation of activation volume from creep or constant strain rate tests and these are also examined from the standpoint of the site model theory. In the derivation presented here full account is taken of the site population distribution and this is the major difference compared to most other analyses. The predicted behaviour is identical to that obtained with the standard linear solid. Consideration is also given to the orientation-dependence of stress-aided activation.     

Mössbauer Study of Tetragonal ZrO2–Y2O3–Fe2O3 Solid Solutions

Tetragonal Zr_0.886Y_0.057Fe_0.057O_{2 –} solid solutions prepared by calcining coprecipitated and successively precipitated hydroxide mixtures were studied by Mössbauer spectroscopy immediately after calcination and after long-term storage. The results indicate that the solid solutions prepared via coprecipitation and successive precipitation contain Fe³⁺ in two (octahedral coordination) and three (octahedral, fivefold, and tetrahedral coordinations) inequivalent sites, respectively. Partial Fe³⁺ substitution for Y³⁺ is shown to prevent or substantially slow down the low-temperature structural degradation of stabilized zirconia.     

On the effects of microstress on macroscopic diffusion processes

Summary The effects of internal microstress fields are neglected in a usual simulation of the diffusion of a small solute trough solid heterogeneous media. However, when a heterogeneous material is used in a structure undergoing external mechanical loading, highly nonuniform stress fields can arise locally due to the variable microstructure. In this paper a simple quasi-Fickian model is studied which employs a spatially variable stress-dependent diffusivity,D . The structure ofD stems from an assumption that the stresses nonuniformly open and close the pores of the material microstructure, thus providing preferential sites for accumulation of the diffusing solute. When =0, the usual stress-free Fickian diffusivity,D ⁰, is recovered. Because of the highly oscillatory stress fields on the micro level, when employing numerical methods, such as the finite element or finite difference method, the distance between discretization nodes must be far smaller than the microstructural oscillations to obtain accurate simulations. This fact makes direct numerical simulations involvingD virtually impossible without computationally intensive, and complicated, special techniques. In this paper upper bounds are developed for the difference between solutions produced when usingD and alternativelyD ⁰ in the body under analysis. The general case, whenD ⁰, and consequentlyD , are spatially variable, is considered. The bounds are a function of onlyD ⁰ and and do not require any knowledge of the stress-dependent solution, and can thus be used as an a-priori check to determine whether potentially expensive computations are necessary.Dedicated to Prof. Dr. Peter Haupt on the occasion of his 60th birthday     

Electrical conductivity in hot-pressed nitrogen ceramics

The a.c. and d.c. electrical conductivities of some hot-pressed polycrystalline nitrogen ceramics have been measured between 400 and 1000° C. The materials examined were Si₃N₄, 5.0% MgO/Si₃N₄ and two sialons, Si_(6–z) · Al _z · O _z · N_(8–z) having z 3.2 and z 4.0 respectively. The electrical behaviour of all the materials showed similar general features. The d.c. conductivities were about 10^{–10 –1} cm^–1 at 400° C and rose to between 10^–6 and 10^{–5 –1} cm^–1 at 1000° C. The a.c. Data, taken over the frequency range 15 Hz to 5 kHz showed that below about 500° C the a.c. conductivity ( _a.c.) varied with frequency as _a.c. ^s where 0.7 _d.c.) agreed well with the relation _d.c. = A exp(–B/T ^1/4). Above 700° C both the a.c. and d.c. conductivities followed log T ^–1. Hall effect and thermoelectric power measurements enabled the Hall mobility to be estimated as less than 10^–4 cm² V^–1 sec^–1 at 400° C and showed that the materials were all p-type below 900° C and n-type above 900° C. The electrical properties of all four materials are consistent with the presence of a glassy phase.     

Frequency and temperature dependence of the millimeter wave conductivity of epitaxial YBa2Cu3O7 films

A millimeter wave spectrometer for frequencies between 100 and 350 GHz consisting of continuously tunable backward wave oscillators as sources and a quasioptical interferometer in the Mach-Zehnder configuration was used to measure the transmittivity in phase and amplitude of YBa₂Cu₃O₇ thin films on NdGaO₃ substrates. From the measured spectra we derived the real and imaginary part of the dynamic conductivity= ₁+i ₂ in the superconducting state as a function of temperature. The ₁(T) and ₂(T) values at 300 GHz were compared to corresponding values at 19 GHz determined by surface impedance measurements of the same films using a shielded dielectric resonator. Our observed frequency dependence of both ₁(T) and ₂(T) is consistent with a strong reduction of the quasiparticle scattering rate ^–1(T) with decreasing temperature belowT _c .     

Examining the temperature dependence of the mechanical properties for materials in large-diameter tubes

Measurements have been made on the mechanical properties of largediameter tubes made of 09G2S, 14G2SAF, and 17G1S steels and on welded joints in them at strain rates of 200 sec^–1 and 113–293 K. Fivefold microspecimens 1.2 mm in diameter have been employed. The parameters have been determined in the temperature-rate dependence of the Yaroshevich yield point, lower brittleness temperature, and fracture resistance as affected by the ferrite diameter. A method is proposed for predicting the brittleness range from the dependence of the notch bottom narrowing B on the generalized parameter = S_f/_y — _t/_i for a Menaget specimen.Translated from Problemy Prochnosti, No. 4, pp. 43–50, April, 1994.     

Methodology for the determination of the interfacial properties of brittle matrix composites

The interfacial properties of a glass-ceramic matrix composite (SiC/CAS) were determined from single-fibre push-out tests using the interfacial test system. The coefficient of friction, , the residual clamping stress, _c, and fibre axial residual stress, _z , were extracted by fitting the experimental stress versus fibre-end displacement curves using the models of Hsueh, and Kerans and Parthasarathy. Using Hsueh's model, the intrinsic interfacial frictional stress (=_c) was found to be 11.1±3.2 MPa, whereas by using Kerans-Parthasarathy's model it was found to be 8.2±1.5 MPa. Comparisons between these models are included, together with a discussion of data analysis techniques.Nomenclature _z Axial fibre residual stress (Pa) - ^* Effective clamping stress (Pa) - _c Residual clamping stress (Pa) - _p Poisson's effect-induced clamping stress (Pa) - _d ⁰ Debond stress in the absence of residual stresses (Pa) - _d Experimental debond stress (Pa) - Compressive applied stress (Pa) - Interfacial shear stress (Pa) - u Fibre-end displacement (m) - h Debond length (m) - r Fibre radius (m) - E _f Fibre Young's modulus (Pa) - E _m Matrix Young's modulus (Pa) - v _f Fibre Poisson's ratio (dimensionless) - v _m Matrix Poisson's ratio (dimensionless) - f Fibre volume fraction (dimensionless) - k Parameter (dimensionless) - D Parameter (dimensionless) - Interfacial coefficient of friction (dimensionless) - G _i Interface toughness (J m^–2) - C _m Load-train compliance (m N^–1)     

Pyramidal yield criteria for epoxides

The tensile, compressive and shear yield strengths of two epoxides were measured under superposed hydrostatic pressure extending to 300 MN m^–2. For both materials, the ratio of the moduli of the tensile, _T, to compressive, _C, yield stress at atmospheric pressure was approximately 34, as has been reported previously for a number of thermoplastics. The ₂= ₃ envelope in stress space was plotted according to these two-parameter ( _C and _T) yield criteria: conical, paraboloidal and pyramidal; the best correlation was with the last. The experimental tensile and compressive data for tests under pressure, however, fit slightly better two straight lines which are consistent with a three-parameter single hexagonal pyramidal yield surface. For plane stress and shear under pressure yield envelopes of these surfaces, the correlation with experimental data is again best for the pyramidal criteria, except for biaxial or triaxial tension when these resins are brittle. The third independent parameter employed in the pyramidal criterion was the equi-biaxial compressive yield stress, determined by tensile experiments under appropriate superposed hydrostatic pressure; alternatively plane strain compressive yield stress, _PC, may be used.     

Molar heat capacity at constant volume of difluoromethane (R32) and pentafluoroethane (R125) from the triple-point temperature to 345 K at pressures to 35 MPa

Molar heat capacities at constant volume (C _v) of dill uoromethane (R32) and pentalluoroethane (R125) were measured with an adiabatic calorimeter. Temperatures ranged from their triple points to 345 K, and pressures up to 35 MPa. Measurements were conducted on the liquid in equilibrium with its vapor and on compressed liquid samples. The samples were of a high purity, verified by chemical analysis of each fluid. For the samples, calorimetric results were obtained for two-phase (C _v ⁽²⁾ ), saturated liquid (C orC _x ), and singlephase (C _v) molar heat capacities. TheC data were used to estimate vapor pressures for values less than 0.3 MPa by applying a thermodynamic relationship between the saturated liquid heat capacity and the temperature derivatives of the vapor pressure. The triple-point temperature (T _tr) and the enthalpy of fusion (_fus H) were also measured for each substance. The principal sources of uncertainty are the temperature rise measurement and the change-ofvolume work adjustment. The expanded uncertainty (at the two-sigma level) forC _v is estimated to be 0.7%, forC _v ⁽²⁾ it is 0.5%, and forC it is 0.7%.     

Electrical conduction in γ-irradiated and unirradiated zinc-iron ferrites

The electrical conductivity of -irradiated and unirradiated finely-divided spinels of composition (Zn _x ²⁺ Fe _1–x ²⁺ Fe ₂ ³⁺ )O ₄ ^2– was studied in a nitrogen atmosphere as a function of temperature. The results of both -irradiated and unirradiated ferrites with compositions x 0.79 showed that the electrical conduction occurred by fast electron exchange amongst Fe²⁺ and Fe³⁺ ions situated on octahedral sites in the spinel lattice, by a hopping mechanism. For composition x > 0.79 it was found that the transition of the charge carriers through cation vacancies is the predominant mechanism. Some breaks in the conductivity-temperature curves were found near the Curie points. Seebeck voltage measurements showed that -irradiated and unirradiated spinels behave as n-type semiconductors. The effect of -irradiation on the conductivity, activation energy, charge carriers and the conduction mechanism is discussed.     

Cu2+ ions in sodium fluoride-sodium borate glasses studied by EPR and optical absorption techniques

Electron paramagnetic resonance (EPR) and optical absorption spectra of Cu²⁺ ions in 80Na₂B₄O₇-(20 – x)NaF – xCuO (NFNB) glass system with 0 x 6 mol% have been studied. EPR spectra of all the glass samples exhibit resonance signals characteristic of Cu²⁺ ions. The values of spin-Hamiltonian parameters indicate that the Cu²⁺ ions in sodium fluoride-sodium borate (NFNB) glasses were present in octahedral sites with tetragonal distortion. The number of spins (N) participating in resonance was calculated as a function of temperature for NFNB glass sample containing 1 mol% of Cu²⁺ ions and the activation energy was calculated. From the EPR data, the paramagnetic susceptibility () was calculated at various temperatures and the Curie constant was calculated from the 1/ – T graph. The optical absorption spectra of these samples show a broad absorption band centered at 13280 cm^–1 which is assigned to the ² B _1g ² B _2g transition of Cu²⁺ ions in distorted octahedral sites. The optical band gap energy (E _opt) and Urbach energy (E) are calculated from their ultraviolet edges. It is observed that as the copper ion concentration increases, E _opt decreases while E increases. This has been explained as due to the creation of additional localized states by CuO, which overlap and extend in the mobility gap of the matrix. By correlating the EPR and optical data, the molecular orbital coefficients have been evaluated.     

Convection in a shallow laterally heated cavity with conducting boundaries

Shallow cavity flows driven by horizontal temperature gradients are analysed over a range of Rayleigh numbersR and Prandtl numbers , whereR is comparable in size to the aspect ratioL(1). Eigenvalue calculations show the existence of a critical Prandtl number R > R _c (), below which the parallel core-flow structure is destroyed for Rayleigh numbersR>R _c(). For other Rayleigh numbers and Prandtl numbers the horizontal scale of influence of the end walls of the cavity is determined.     

Structure parameters of metal-fiber heat pipe wicks

The results of an experimental investigation of local and average values of permeability and effective pore diameter for metal-fiber wicks, using a laser-Doppler velocity measurement, are presented and discussed.Notation K permeability coefficient, m² - V filtration rate, m/sec - viscosity, N·sec/m² - dp/dx pressure gradient - rms deviation - f_i probability density distribution,m^–1 - D pore diameter,m - E excess - A asymmetry The 50-Year Anniversary of the Great October Socialist Revolution Kiev Polytechnic Institute.Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 35, No. 5, pp. 777–781, November, 1978.     

Cation distribution of the system CuAlxFe2−xO4 by X-rays and Mossbauer studies

The structural and Mossbauer spectroscopy studies have been performed on the spinel solid solution series CuAl _x Fe_2–x O₄ (0.0 x 1.0). All the compounds with 0.0 x 1.0 crystallised with cubic spinel structure. Lattice constant values calculated from XRD analysis were found to decrease on increasing x, linearly obeying Vegard's law. The X-ray intensity calculations indicated that Cu²⁺ prefers to occupy octahedral (B) site, where as Al³⁺ ions replace Fe³⁺ ions from both tetrahedral (A) and octahedral (B) sites. Mossbauer spectra at room temperature display magnetic sextets corresponding to A and B-sites superimposed on each other. The data shows that Al-possesses greater preference for B-site compared to A-site, and iron exists in high spin ferric Fe³⁺ state. The hyperfine fields for both A and B-sites decrease with increasing x. The cation distribution calculated from X-ray intensity data agrees with the Mossbauer results.     

Transport results from untwinned YBCO: Washboard frequency of the vortex lattice,and the quasiparticle mean free path

The washboard frequency of the moving vortex lattice in untwinned YBa₂ Cu₃ O_6.93 may be observed through mode-locking to an externally applied ac current of frequency _ext. The interference between and _ext results in jumps in the dc current-voltage characteristics when and _ext are harmonically related¹. The interference effect disappears in the vortex liquid state. The Hall conductivity _xy below T_c in YBCO contains contributions² from a positive quasiparticle (qp) term (H) and a negative vortex term (1/H). The qp term is surprisingly large well below T_c and implies a large gap anisotropy and a long qp mean free path (mfp). The thermal Hall effect³ _xy is closely related to the qp _xy; _xy is produced by asymmetric scattering of qp by pinned vortices. The qp mfp at H = 0, extracted from _xy and extended to low T by _xy, increases remarkably from 90 Å at T_c to more than 0.5m at 22 K.