Viscosity of nonelectrolyte liquid mixtures. IV. Binary mixtures containingp-Dioxane

Measurements of the viscosity and densityp are reported for eight binary mixtures ofp-dioxane with methylcyclohexane, l-chlorohexane, l-bromohexane, p-xylene, propylbenzene, methyl acetate, butyl acetate. anyl acetate at 303.15 K. The viscosity data haw been correlated with the equations of Grunbeng Nissan. of McAllister, and of Auslaendcr. The relation among the excess viscosity In, excess Gibbs energy of activationG* ^E of viscous flow. and intermolecular interaction in these mixtures is discussed.     

Viscosity of biniary mixtures. III. Tri-n-butylamine with alkanes and monoalkylamines at 303.15 and 313.15 K

Viscosities of seven binary systems of n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-hexane, n-octane, and isoctane (2,2,4-trimethylpentane) with tributylamine have been measured at 303.15 and 313.15 K with an Ubbelohde suspended-level viscometer. Based on Eyring's theory, values of excess Gibbs energy of activation G ^*E of viscous flow have been calculated. Deviations of viscosities from linear dependence on the mole fraction and values of G ^*E are attributed to the H-bonding and to the size of alkylamine and alkane molecules. The free volume theory of Prigogine-Flory-Patterson in combination with work by Bloomfield-Dewan has been used to estimate the excess viscosity ln and the terms corresponding to enthalpy, entropy, and free volume contributions for the present binary mixtures.     

Viscosity of binary mixtures. I. mono-, di-, and tri-n-butyl and -n-octylamine with cyclohexane

Viscosities for six binary mixtures of n-butylamine, di-n-butylamine, tri-n-butylamine, n-octylamine, di-n-octylamine, and tri-n-octylamine with cyclohexane have been measured at 303.15 K with an Ubbelohde suspendedlevel viscometer. Deviations of viscosities from a rectilinear dependence on mole fraction are attributed to H-bonding and to the size of alkylamine compounds. The application of the Eyring's theory of activation energy is examined. The free volume theory of Prigogine-Flory-Patterson (PFP) and the experimental excess enthalpy have been used to estimate excess viscosity ln = (ln / ₁ ⁰ – x ₂ ln ₂ ⁰ / ₁ ⁰ ) and corresponding free volume, enthalpy, and entropy contributions for five binary mixtures of tri-n-alkylamine: triethyl, tripropyl, tributyl, trihexyl, and trioctylamine with cyclohexane. A comparison of experimental and theoretical excess viscosities indicates a failure of the PFP theory when two components of the mixture differ considerably in size. The size difference contribution to excess viscosity is related to (V ₂ ^*1/2 – V ₁ ^*1/2 ), where V ₁ ^* and V ₂ ^* are hard-core volumes of two components of the mixture.     

Coupling of order parameter collective modes to spin density in3He-B

We derive a general expression for the dynamic spin susceptibility of³He-B which is valid for all magnetic fields. The coupling of real and imaginary modes by particle-hole asymmetry is taken into account. Then we calculate the contribution of the mode at frequency =2 – 1/4 ( is the effective Larmor frequency) to the transverse susceptibility. The spectral weight of this mode in magnetic resonance absorption is proportional to (/)^1/2 (–)², where and are particle-hole asymmetry parameters. From the experimental coupling strength of the real squashing mode to sound we estimate (–)²10^–4. The dynamic susceptibility satisfies the sum rules of Leggett. Finally we point out the difficulties in calculating the transverse NMR frequency of³He-B. These difficulties arise from theS _z =0 Cooper pairs and from the coupling ofJ _z =±1 modes forJ=1 andJ=2.     

Viscosity of nonelectrolyte liquid mixtures. III Binary mixtures of methyl methacrylate with hydrocarbons,haloalkanes, and alkylamines

Measurements of the viscosity and the density are reported for 14 binary mixtures of methyl methacrylate (MMA) with hydrocarbons, haloalkanes, and alkylamines at 303.15 K. The viscosity data have been correlated with equations of Grunberg and Nissan, of McAllister, and of Auslaender. Furthermore, excess viscosity In and excess Gibbs energy of activationG* ^E of viscous flow have been calculated and have been used to predict molecular interactions occurring in present binary mixtures. The results show the existence of specific interactions in MMA + aromatic hydrocarbons, MMA + haloalkanes, and MMA + primary amines.     

Shear viscosity of liquid4He and3He-4He mixtures,especially near the superfluid transition

High-resolution measurements of are reported for liquid⁴He and³He-⁴He mixtures at saturated vapor pressures between 1.2 and 4.2 K with particular emphasis on the superfluid transition. Here is the mass density, the shear viscosity, and in the superfluid phase both and are the contributions from the normal component of the fluid ( _n and _n ). The experiments were performed with a torsional oscillator operating at 151 Hz. The mole fraction X of³He in the mixtures ranged from 0.03 to 0.65. New data for the total density and data for _n by various authors led to the calculation of . For⁴He, the results for are compared with published ones, both in the normal and superfluid phases, and also with predictions in the normal phase both over a broad range and close to T. The behavior of and of in mixtures if presented. The sloped/dT near T and its change at the superfluid transition are found to decrease with increasing³He concentration. Measurements at one temperature of versus pressure indicate a decreasing dependence of on molar volume asX(³He) increases. Comparison of at T, the minimum of _n in the superfluid phase and the temperature of this minimum is made with previous measurements. Thermal conductivity measurements in the mixtures, carried out simultaneously with those of , revealed no difference in the recorded superfluid transition, contrary to earlier work. In the appendices, we present data from new measurements of the total density for the same mixtures used in viscosity experiments. Furthermore, we discuss the data for _n determined for⁴He and for³He-⁴He mixtures, and which are used in the analysis of the data.     

Viscoelastic and rheological behavior of concentrated colloidal suspensions

Molecular approaches are discussed to the density (), viscoeleastic (), and rheological () behavior of the viscosity(,,) of concentrated colloidal suspensions with 0.3 < < 0.6, where, is the volume fraction, the applied frequency, and ; the shear rate. These theories are based on the calculation of the pair distribution functionP ₂(r,,), wherer is the relative position of a pair of colloidal particles. The linear viscoelastic behavior(,,=0) follows from an equation forP ₂(r,,) derived from the Smoluchowski equation for small, generalized to large by introducing the spatial ordering and (cage) diffusion typical for concentrated suspensions. The rheological behavior(,,=0) follows from an equation forP ₂(r,) of a dense hard-sphere fluid derived from the Liouville equation. This leads to a hard-sphere viscosity^hs(,) which yields the colloidal one(,) by the scaling relation(,) ₀=^hs(,) _B, where ₀ is the solvent viscosity. _B is the dilute hard-sphere (Boltzmann ) viscosity and the's are appropriately scaled,(,) and(,) agree well with experiment. A unified theore for(,,) is clearly needed and pursued.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994. Boulder, Colorado, U.S.A.     

Shear viscosity measurements of liquid 3He-4He mixtures above 0.5 K

Simultaneous measurements of () and of the molar volume are reported for liquid mixtures of ³He in ⁴He over the temperature range between 0.5 and 2.5 K. Here is the shear viscosity and is the mass density. In the superfluid phase, the product of the normal components, _n and _n , is measured. The mixtures with ³He molefractions 0.30 < X < 0.80 are studied with emphasis on the region near the superfluid transition T and near the phase-separation curve. Along the latter, they are compared with data by Lai and Kitchens. For X > 0.5, the viscosity singularity near T becomes a faint peak, which however fades into the temperature-dependent background viscosity as X tends to the tricritical concentration X _t. Likewise, no singularity in is apparent when T _t is approached along the phase separation branches _– and ₊. Furthermore, viscosity data are reported for ³He and compared with previous work. Finally, for dilute mixtures with 0.01 X 0.05, the results for are compared with previous data and with predictions.     

Shear viscosity measurements of liquid 4He and 3He-4He mixtures near the tricritical point

A torsional oscillator cell is described, by means of which simultaneous precision measurements of () and of the molar volume can be made in liquid ⁴He-⁴He mixtures over the temperature range between 0.5 and 3 K. Here is the mass density, the shear viscosity and in the superfluid phase they become the contributions _n and _n of the normal component. The results of for ⁴He near the superfluid transition are compared with the predictions by Schloms, Pankert and Dohm, and by Ferrell. Measurements of () are reported for mixtures with 0.64X0.74, where X is the ³He mole fraction. Those for X = 0.67 and 0.70 are compared with data by Lai and Kitchens. The viscosity experiments show no evidence of a weak singularity at the tricritical point.     

Effect of annealing upon decomposition of electrodeposited iron-zinc alloy coatings

As-deposited electrodeposited iron-zinc alloy coatings containing phase, decompose upon heating through a sequence of metastable phases. The h c p phase transforms to b c c G, or -like phase via a rapid diffusional phase transformation in the vicinity of 150 °C. For bulk iron contents of 8–13 wt%, transforms to 100% G phase. The G phase subsequently transforms at 240 °C to phase, which in turn transforms to or ₁ phase near 300 °C by depletion of iron from the surrounding matrix. The decomposition process may be driven by supersaturation of with iron.     

Measuring of contact gaps by the absolute interference method

Summary The accidental error which is introduced by the measuring contacts is contained in the variations of readings on the gage scale, and requires no special investigation.Systematic errors introduced by the measuring contacts must be calculated or measured for each type of measurement and taken into account during the accurate determination of dimensions in precision measurements.In measuring gage blocks (OST 85,000-39) on the contact devices, the optimum results were obtained with spherical corundum tips with R 14 mm, operating with loads of up to 300 g. In these cases the contact pressures for gage blocks are only a third to a fifth of the permissible values, while the contact gaps are so small and constant that the measurements can be made with the utmost precision.The measurements of showed that for best contacts=0 when the lengths of these gages is determined by the method of comparison, and=0.06 when it is determined by the absolute method.     

The viscosity and some related properties of liquid3He at the melting curve between 1 and 100 mK

The viscosity of liquid ³ He has been measured along the melting curve from 1 to 100 mK by means of a vibrating wire viscometer. In the normal Fermiliquid region we find 1/T² = 1.17–3.10T, where is in P and T in K. At the transition temperature T _A = 2.6 mK a rapid decrease occurs in _n , the viscosity of the normal component. Within 0.3 mK below T _A , _n decreases to about 25% of _A, but then becomes essentially constant. In the B phase _n first decreases to 20% of _A and then seems to increase below 1.4 mK. Data on _n , the density of the normal component, are also presented in the A and B phases. The results show that viscous flow is accompanied by a flow of zero dissipation, thus proving superfluidity in the A and B phases. The viscosity data at magnetic fields up to 0.9T have been related to theoretical calculations of the energy gap of superfluid ³ He near T _A . The splitting of the A transition and the suppression of the B phase in an external field were also measured.     

Excess thermodynamic properties of mixtures of alkyl benzoates withn-heptane

The paper reportsh ^E values at 298.15 K andv ^E and values at various temperatures for binary mixtures of propyl or butyl benzoate andn-heptane. The excess Gibbs energy of viscous flow,g ^*E, and the thermodynamic activation properties were calculated from these values. The results are compared with those for similar mixtures and interpreted on the basis of the characteristic dipole-dipole interactions of alkyl esters.Nomenclature A _i Parameters in Eq. (2) - dg ^*E Gibbs free energy of viscous flow (J · mol^–l) - dg Activation free energy (kJ · mol^–1) - K Parameter in Eq. (2) - h Planck constant - h ^E Excess enthalpy (J · mol^–1) - h Activation enthalpy (kJ · mol^–1) - N Avogadro number - R Universal gas constant (J · K^–1 · mol^–1) - s Standard deviation - s Activation entropy (J · K^–1 · mol^–1) - T Temperature (K) - v Molar volume of pure component (m³ · mol^–1) - v ^E Excess volume (m³ · mol^–1) - x _i Mole fraction of componenti Greek Letters Expansion coefficient (K^–1) - Density (kg · m^–1 ) - Viscosity (mPa · s ) - Apparent excess viscosity (mPa · s)     

Fermi liquid behaviour of the viscosity of3He-4He mixtures

We have investigated³He-⁴He mixtures at³He-concentrations 0.98%x9.5% by the vibrating wire technique in the temperature range 1 mKT 100 mK and at pressures 0 bar p 20 bar. In the degenerate regime of the mixtures the Landau theory of Fermi liquids predicts a temperature dependence of the viscosity proportionalT ^–2. We report on the first observation of this behaviour at 3 mKT 10 mK for all investigated concentrations and pressures. At temperatures below about 20 mK slip corrections had to be taken into account due to the increase of the quasiparticle mean free path at very low temperatures. The low-temperature cut-off in T ² = constant indicates the transition into the ballistic regime of the mixtures, where the mean free path of the quasiparticles exceeds the radius of the vibrating wire. Our results for the pressure dependence of the viscosity as well as for its magnitude show substantial differences from predictions based on pseudopotential theory. However, a calculation of with the quasiparticle interaction potential of recent solubility measurements in mixtures agrees well with our experimental data, in particular the pressure independence of .     

Viscosity and Density at High Pressures in an Associative Ternary

The dynamic viscosity and the density of the associative ternary mixture water+diacetone alcohol+2-propanol have been measured as a function of temperature T (303.15, 323.15, and 343.15 K) and pressure P (100 MPa). The experimental results correspond to 698 values of and . With reference to the 54 values previously published on pure substances and 486 values for three corresponding binaries, the system is globally described by 1188 experimental values for various values of P, T and composition. The results for are discussed in terms of excess activation energy of viscous flow.     

Shear viscosity of the B phase of superfluid3He

The shear viscosity (T) in the Balian-Werthamer (BW) state of superfluid ³ He is calculated variationally throughout the region 0t 1(t=T/T _c) from the transport equation for Bogoliubov quasiparticles. Coherence factors are treated exactly in the calculation of the collision integral. The numerical result for =_s= _s(T)/_n(T_c) agree very well with experiment in the range 0.8t1.0. Analytic expressions = 0.577 (1–1.0008t) and =1–(23/64) [=(T)/k _B T] are obtained in the low-temperature region and in the vicinity ofT _c, respectively. From the numerical analysis it is shown that the latter equation is valid only in the temperature range 0.9997t1.0.Supported by the Research Institute for Fundamental Physics, Kyoto University.     

Nonequilibrium Molecular Dynamics Simulations of Shear Viscosity: Isoamyl Alcohol, n-Butyl Acetate, and Their Mixtures

Nonequilibrium, NVT, molecular dynamics (NEMD) simulations were used to obtain the shear viscosity, , of isoamyl alcohol, n-butyl acetate, and their binary mixtures at 35°C and 0.1 MPa. The fluids were modeled using rigid bonds, rigid bond angles, appropriate torsional potentials, pairwise-additive Lennard–Jones dispersion interactions between united-atom sites, and partial point charges located at atomic centers. Simulations were performed at different shear rates, , and values obtained at =0 are compared to experimental values. Two methods are commonly used to extrapolate pure-fluid simulated data to zero shear, (0). The applicability of these two methods to mixtures of polar fluids was examined in this study. It was found that linear extrapolation with respect to ^1/2 can lead to ambiguous (0) results for some mixtures because of a curvature in the data that shows no observably distinct change in rheology. On the other hand, a log–log plot of () versus is consistently very linear with a distinct change from shear-thinning to Newtonian rheology at lower shear rates. The latter method is recommended for consistency sake, even though agreement between experiment and (0) values was better with the former method. This agreement was 12 and 21% for the two methods, respectively. A negative bias in the simulated values is attributable to the united-atom model.     

Texture and hydrodynamics of a thin slab of superfluid3He-A in a torsional oscillator. II. Experiment

Experiments on a torsional oscillator containing a slab of liquid³He of thickness 105 µm and diameter 8.38 mm are described. Normal phase experiments confirm the theory of the oscillator dynamics but an apparent descrase in the measured value of T ² at lowT casts doubt on the existing slip theory. Measurements for the uniform texture for the A phase give values of _s and ₄₄. The _s measurements suggest that the A-phase energy gap is enhanced by a factor 1.24 over the BCS value. Distortion of the uniform texture by a magnetic field perpendicular to the slab occurs at a threshold field slightly smaller than predicted. Measurements for fields at different angles to the slab enable accurate values to be deduced for the superfluid density anisotropy and two other viscosity coefficients. The remaining two viscosity coefficients are only poorly determined. Flow alignment of the orbital texture was achieved by increasing the oscillator amplitude. A different texture obtained on some occasions after warming from the B phase was investigated but is not understood.     

Separable functions in load separation for the ηpl and ηpl CMOD plastic factors estimation

The objective of this paper is to develop the load separation method for evaluating the _pl and _pl ^CMOD plastic factors used in the J estimation approach based on load versus displacement records. Appropriate forms for the geometry and deformation functions have been suggested from the EPRI Handbook solutions to produce the separable form for the load. The obtained functions are applied to evaluate the _pl and _pl ^CMOD plastic factors for center cracked tension specimen. The present load separation method gave results which are somewhat different from the estimated values of _pl given in the literature. For shallow cracks, the _pl and ^CMOD _pl plastic factors show considerable variation with crack size and the strain hardening exponent. For a deeply cracked CCT specimen, the ^CMOD _pl factor tends to the _pl factor and equals approximately unity. Abbreviations: CCT – center cracked specimen; CMOD – Crack Mouth Opening Displacement; EPRI – Electric Power Research Institute; FEM – Finite Element Method; LLD – Load Line Displacement.     

Band-theoretical calculation for the anomalous resistivity of Ni near the Curie temperature

The anomalous resistivity of nickel near the Curie temperature T _c is investigated using the itinerant model of the magnetic electron. The 3d-band wave functions are used to calculate the form factor. The temperature derivative of resistivity diverges positively when T approaches T _c from below and negatively when it approaches from above. The calculation of the correlation function shows that both short-range and long-range orders exist. The critical exponents = 1/2 and = 0 are equal to the Ornstein—Zernike values in the paramagnetic region, but in the ferromagnetic region in addition to these values ₁ = 1/2 and ₁ = 0 there is simultaneously a second set of values ₂ = and ₂ = –1.