Dielectric and thermodynamic behaviour of binary mixtures of anisole with o-chlorophenol and with o-cresol

The molecular interactions in binary mixtures of anisole with o-chlorophenol and o-cresol have been studied at three different temperatures using dielectric measurements. The static permittivity and the permittivity at optical frequency have also been determined and used to obtain the Kirkwood correlation factors, the Bruggeman parameter, the excess permittivity and the excess free energy for different concentrations of two binary mixtures, namely (1) anisole + o-chlorophenol and (2) anisole + o-cresol. Using the effective Kirkwood correlation factor, parallel and anti-parallel alignments among the dipoles are identified. The corrective Kirkwood correlation factor, the excess permittivity and the Bruggeman parameter are used to explain the interaction between unlike molecules. The temperature dependences of the above parameters are also reported. The investigation shows systematic changes in the dielectric behaviour with variations in concentration and temperature.     

Dielectric relaxation study of mixtures of alkyl methacrylates and 1-alcohols using time-domain reflectometry

Dielectric relaxation measurements on alkyl methacrylates (methyl methacrylate, ethyl methacrylate and butyl methacrylate) with 1-alcohols (1-propanol, 1-pentanol, 1-heptanol, 1-octanol and 1-decanol) have been carried out using time-domain reflectometry (TDR) over the frequency range 10?MHz to 20?GHz at 303?K for different concentrations of alcohols. The dielectric parameters, namely the static dielectric constant (ε ₀), the dielectric constant at microwave frequencies (ε _∞) and the relaxation time (τ) were determined. The Kirkwood correlation factor, which contains information regarding solute–solvent interaction and corresponding structural information, the excess permittivity and the excess inverse relaxation time were also determined. The values of the static dielectric constant and the relaxation time increase with the percentage of alkyl methacrylates in the alcohol, whereas the static dielectric constant decreases and the relaxation time increases with an increase in the alkyl chain length of both the methacrylates and the alcohols.     

Dielectric relaxation in ternary systems of alcohols and nitriles in benzene at microwave frequency

The permittivity and the dielectric loss of ternary mixtures of equimolar concentrations of m-cresol, o-cresol with acetonitrile, acrylonitrile and benzonitrile in benzene have been measured at 8.33 GHz and 308 K. The distribution parameter α, the most probable relaxation time τ, the relaxation time for overall rotation of the molecule τ(1), the relaxation time for group rotation τ(2), and the excess dipole moment for various systems have been calculated by the Cole-Cole and Higasi methods. Data has been analyzed in terms of two-relaxation processes: overall rotation and group rotation.     

A new type of defect on {1120} planes in ß-Si3N4 produced by neutron irradiation

Measurements of static permittivity, refractive index and density have been carried out to study possible H-bonded complexes in solutions of anisole diluted by benzene together with high-static-permittivity alcohols, i.e. cyclohexanol, n-butanol, tert-butanol, isopropyl alcohol and 1-hexanol. The experiments were performed at 303 K. Dipole moments of the mixtures are calculated from the experimental data and these are used to obtain dipolar increments. The concentration ratio of proton donor to proton acceptor is plotted against a parameter, Ω_B, which is determined from experimental data. From the plot, the dipole moment of the mixture and that of the component B are determined. The order of the complex can be obtained from the nature of the graph. The investigation shows that the interaction between the two components arises solely from a polarization effect.     

Frequency-temperature dependent dynamics of dielectrics in ferric oxoborate Fe3BO6 of cocktail structure of nanorods

Oxoborates have both dielectric and magnetic properties useful for magnetodielectric devices, sensors, or biological tools. Such compounds Fe₂BO₄, Fe₃BO₅, or Fe₃BO₆ are known to grow easily as single crystals in a liquid flux. A polycrystalline phase forms only on controlled conditions of a solid state reaction of the basic oxides. In this study, we report highly dielectric Fe₃BO₆ when grown in a specific shape of nanorods (～200?nm diameter and 50–100?µm length) from an iron borate glass, which offers devisable shapes of sheets, discs, and fibers. Frequency (f)-temperature reliant dynamics of dielectric constant ε_r is studied over 25–300°C at 0.1–10^3?kHz frequencies. At low frequency such as 100?Hz, a large ε_r -value 40,000, better than most of high ε_r -value ferroelectrics, incurs at room temperature. At f?≥?50?kHz, although only an order of diminished ε_r -value lasts, it increases steadily with temperature, possibly due to increasing electrical conductivity in a specific resistor–capacitor network. Suppressed dielectric relaxation and spin-flops share a merely weak spin-reorientation transition near 160°C. A stable power loss ≤0.5 lasts at f?>?10?kHz useful for possible applications of magnetodielectric materials.     

Differential Method of Characterizing Gait Strategies From Step Lengths and Frequencies: Strategy of Velocity Modulation

The differential method consists of the analysis of the variation of gait parameters length, frequency, and velocity with respect to their mean values, respectively, ΔL = L — L_m , Δf = f — f_m , and Δv = v – v_m , where L_m , f_m , and v_m represent the mean values of those parameters. Assuming that the strategy of modulation of velocity implies that L and f are functions of v and that statistical analyses of ratios ΔL/Δv and Δf/Δv have established that there is a very significant linear correlation, close to 1, between those ratios, the mathematical procedure allows one to determine the equation of step length, L = a · f + b · v + K, where a and b are the slope and the intercept of the linear regression and K is close to L_m . The equation was experimentally tested on 140 gait sequences performed by 6 participants and for gait velocities ranging from 0.6 to 2.2 m/s and was found to be very representative of all individual values. The differential method provides another way of using the derivative of velocity, v = L·f, to characterize the strategy of velocity modulation, which then permits one to determine the linear equation of velocity, v = f · L_m + L · f_m — L_m · f_m , and to show that the respective parts played by each parameter in the progression velocity are approximately equal. The author establishes the uniqueness of the different linear adjustments and discusses the differential method's own modes of use, that is, interindividually or globally.     

Static dielectric constants of the binary mixtures of N-methylformamide with water,ethyl alcohol,ethylene glycol,dimethylsulphoxide, acetone and 1,4-dioxane

The static dielectric constants of binary mixtures of N-methylformamide (NMF), used as a solute with the solvents water (W), ethyl alcohol (EA), ethylene glycol (EG), dimethyl sulphoxide (DMSO), acetone (Ac) and 1,4-dioxane (Dx), have been measured over the entire concentration range at 30°C. The negative values of excess dielectric constant and less-than-unity values of the corrective Kirkwood correlation factor of these binary mixtures are used to analyse the formation of H-bond complexes and molar ratio of the stable adduct. In these systems, the unassociated mixture constituents, DMSO, Ac and Dx, act as structure-breakers for self-associated linear structures of NMF, whereas, both the self-associated mixture constituents (W, EA and EG mixtures with NMF) act as structure-breakers to each other during the complexations. It is found that the large variations in the strength of H-bond complexation and the effective number of parallel aligned dipoles in the mixtures are governed by the dielectric constant of the solvents.     

Ternary eutectic growth during directional solidification of Ag–Cu–Sb alloy

The directional solidification process of ternary Ag_42.4Cu_21.6Sb₃₆ eutectic alloy within a wide growth rate range from 2 to 60 μm/s was accomplished at a constant temperature gradient of 50 K/cm. As growth rate increases, the ternary (θ(Cu₂Sb) + ε(Ag₃Sb) + Sb) eutectic morphology evolves from “lamellar (θ + ε) plus fibrous (Sb)” structure into “(θ + Sb) fibres in continuous ε matrix” structure. The θ and (Sb) phase spacings decrease with the increase of growth rate according to power functions with exponent values of 0.55 and 0.56, respectively. It is also found that the microhardness of directionally solidified Ag_42.4Cu_21.6Sb₃₆ alloy samples is enhanced with the increase of growth rate, and the decrease of θ and (Sb) phase spacings.     

Transcending Lindemann's predictions for the melting temperatures of metals and for the long-wavelength limit of their liquid structure factors

Lindemann's melting criterion remains useful. However, one prediction it makes for liquid metals (our focus here) is that the long-wavelength limit of the structure factor S(q) at freezing, S _{T m} (0), where T _m is the melting temperature, is a universal constant. For 34 metals we have calculated S _{T m} (0) from input data, which is essentially the measured T _m and the surface thickness L, defined near freezing as the product of isothermal compressibility and surface tension. To complete the characterization of S _{T m} (0) we fit to one metal, chosen as Rb, for which S _{T m} (0) is well established experimentally. For a wide variety of metals considered, S _{T m} (0) is then found to vary by a factor of 10.     

Numerical treatment of electron-energy-loss spectra and determination of optical constants

Electron-energy-loss spectra in the reflexion mode (REELS) have been obtained for palladium and silicon oxide and the data treated numerically in order to derive their optical constants ε₁ and ε₂. The numerical method consists of obtaining the loss function Im(?1/ε) from the experimental REELS spectra, and then, through a second step of numerical integration, accessing the real part of (?1/ε) by Kramers–Krönig analysis.     

A mixture model for distributions of correlation coefficients

An old problem in personnel psychology is to characterize distributions of test validity correlation coefficients. The proposed model views histograms of correlation coefficients as observations from a mixture distribution which, for a fixed sample sizen, is a conditional mixture distributionh(r|n) = _{j j} h(r; _j ,n), whereR is the correlation coefficient, _j are population correlation coefficients and _j are the mixing weights. The associated marginal distribution ofR is regarded as the parent distribution underlying histograms of empirical correlation coefficients. Maximum likelihood estimates of the parameters _j and _j can be obtained with an EM algorithm solution and tests for the number of componentst are achieved after the (one-component) density ofR is replaced with a tractable modeling densityh(r; _j ,n). Two illustrative examples are provided.     

Morphological and magnetic response of copper-substituted nickel ferrite nanoparticles

Ferrite nanoparticles are interesting materials owing to their unique physical and chemical properties. The metal-doped ferrites have well-defined structures and magnetic response, such as high permeability for a specific frequency range. In this study, copper-substituted nickel ferrite (Ni_1?xCu_xFe₂O₄) nanoparticles with a compositional range of 0?≤?x?≤?0.3 were synthesised through a co-precipitation technique. Metal chlorides were used as precursors and NaOH as a precipitating agent for the growth of ferrite nanoparticles. To minimise the internal stresses and maximise the magnetic response, ferrite nanoparticles were annealed in a furnace at 700°C for 6 h. The structural and magnetic response of Ni_1?xCu_xFe₂O₄ ferrite with different values of x were investigated using Scanning Electron Microscopy (SEM), Fourier Transform Infrared spectroscopy (FT-IR), Vibrating Sample Magnetometer (VSM) and X-ray Diffraction (XRD) techniques. XRD analysis confirmed the formation of cubic spinel structure of single phase for all the compositions. The lattice constant decreased with increase in the value of x. FT-IR study showed two main metal oxygen bonds in the range 500–700 cm^?1 confirming the formation of a single-phase cubic inverse structure of Cu-substituted Ni ferrite. VSM results revealed the formation of ferrimagnetic nanoparticles. The optical and magnetic response of the ferrite nanoparticles changed with Cu content.     

Comparing dependent robust correlations

Let r₁ and r₂ be two dependent estimates of Pearson's correlation. There is a substantial literature on testing H₀ : ρ₁ = ρ₂, the hypothesis that the population correlation coefficients are equal. However, it is well known that Pearson's correlation is not robust. Even a single outlier can have a substantial impact on Pearson's correlation, resulting in a misleading understanding about the strength of the association among the bulk of the points. A way of mitigating this concern is to use a correlation coefficient that guards against outliers, many of which have been proposed. But apparently there are no results on how to compare dependent robust correlation coefficients when there is heteroscedasicity. Extant results suggest that a basic percentile bootstrap will perform reasonably well. This paper reports simulation results indicating the extent to which this is true when using Spearman's rho, a Winsorized correlation or a skipped correlation.     

In situ simultaneous measurements of photodarkening and photoinduced defect creation in amorphous As2Se3 films

To understand the direct correlation between photodarkening (PD) and photoinduced defect creation (PDC) observed in amorphous chalcogenides, in situ simultaneous measurements of PD and photocurrent (PC) have been performed on amorphous As₂Se₃ films. The time evolution of PD and PDC during light excitations are empirically described by a stretched exponential function; 1 ??exp[?(t/τ) ^β ], where τ is the effective response time and β the dispersion parameter. The value of τ for the PDC is very much smaller than that for the PD, suggesting that there is no direct correlation between the two.     

Formation of yittrium oxide in cemented carbides

Rare-earth (RE) elements are helpful in improving the mechanical properties of cemented carbides. In this work, the formation of Y₂O₃ in functionally graded cemented carbides is investigated using transmission electron microscopy. The results indicate that Y₂O₃ can stabilize the Co phase with the face-centred cubic structure (α-Co), since it has a cubic structure similar to the high-temperature Co phase. The α-Co phase has a higher plasticity than ε-Co, and this suggests a possible mechanism for the role of RE elements in toughening cemented carbides.     

A new rank correlation coefficient with application to the consensus ranking problem

The consensus ranking problem has received much attention in the statistical literature. Given m rankings of n objects the objective is to determine a consensus ranking. The input rankings may contain ties, be incomplete, and may be weighted. Two solution concepts are discussed, the first maximizing the average weighted rank correlation of the solution ranking with the input rankings and the second minimizing the average weighted Kemeny–Snell distance. A new rank correlation coefficient called τ_x is presented which is shown to be the unique rank correlation coefficient which is equivalent to the Kemeny‐Snell distance metric. The new rank correlation coefficient is closely related to Kendall's tau but differs from it in the way ties are handled. It will be demonstrated that Kendall's τ_b is flawed as a measure of agreement between weak orderings and should no longer be used as a rank correlation coefficient. The use of τ_x in the consensus ranking problem provides a more mathematically tractable solution than the Kemeny–Snell distance metric because all the ranking information can be summarized in a single matrix. The methods described in this paper allow analysts to accommodate the fully general consensus ranking problem with weights, ties, and partial inputs. Copyright © 2002 John Wiley & Sons, Ltd.     

Recent Trends in the Nordic Doctrine

A review is provided of methods that estimate the magnitude of effects within experimental designs. Intraclass correlation type procedures are appropriate with any ANOVA model. Friedman's r _m and Cohen's power analysis apply to many non-ANOVA type situations, but only to the Fixed Effects ANOVA design. The Gaito utility procedure has two advantages over other intraclass correlation type measures: the coefficients sum to unity (or to 100%), and coefficients for error components are obtained.     

Thermophysical properties of undercooled liquid cobalt

The surface tension of undercooled liquid cobalt has been measured by the oscillating-drop technique combined with electromagnetic levitation. The accuracy of the method was verified by measurements of the surface tension of liquid nickel. The liquid cobalt was undercooled by up to 231K (0.13T _m), and its surface tension determined to be σ_Co =1875 0.348(T-T _m)mNm^-1. From this result, the viscosity, self-diffusion coefficient, density and thermal diffusivity of undercooled liquid cobalt were derived. Using these thermophysical parameters, the growth velocity of cobalt dendrite is calculated and shown to agree well with experimental results. Furthermore, the Marangoni number and the Rayleigh number are calculated; these increase slowly with increasing degree of undercooling.     

Experimental evidence of relaxation arising from the motion of geometrical kinks on screw dislocations in iron

Abstract

Internal friction measurements with a superimposed bias stress have provided evidence for geometrical kink migration on screw dislocations in iron. This intrinsic process causes a relaxation phenomenon in internal friction which has been identified with the occurrence of a subpeak (below 20 K) of the α-peak. The effect of different bias stress has allowed us to evaluate the kink migration energy, E ^m _k ? 0·001eV.     

Structural evolution during crystal nucleation in supercooled liquids with icosahedral short-range order

The structural evolution during crystal nucleation in supercooled Lennard–Jones liquids at a supercooling of 0.3T _m (T _m is the melting temperature) has been studied by molecular dynamic simulations. The icosahedral clusters are observed to compete with crystalline clusters in space, and rearrange before crystal nucleation. Both the stable face-centered-cubic and hexagonal-close-packed (hcp) structures and metastable body-centered-cubic (bcc) structures nucleate simultaneously, resulting in the formation of an incomplete bcc meso-layer in the nuclei. The nuclei form twinned crystal with five-fold axes through a successive twinning process bounded by planes with hcp atoms.