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 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.     

The Viscosity Surfaces of Propane in the Form of Multilayer Feed Forward Neural Networks

The present work focuses on the development of a viscosity equation =(,T) for propane through a multilayer feedforward neural network (MLFN) technique. Having been successfully applied to a variety of fluids so far, the proposed technique can be regarded as a general approach to viscosity modeling. The MLFN viscosity equation has been based on the available experimental data for propane: validation on the 969 primary data shows an average absolute deviation (AAD) of 0.29% in the temperature, pressure, and density range of applicability, i.e., 90 to 630 K, 0 to 60 MPa, and 0 to 730 kgm^–3. This result is very promising, especially when compared with experimental data uncertainty. The minimum amount of required data for setting up the MLFN has been investigated, to explore the minimum cost of the model. Comparisons with other viscosity models are presented regarding amount of input data, claimed accuracy, and range of applicability, with the aim of providing a guideline when viscosity has to be calculated for engineering purposes. A high accuracy equation of state for the conversion of variables from experimental P,T to operative ,T has to be provided. To overcome this requirement, two viscosity explicit equations in the form =(P,T) are also developed, for the liquid and for the vapor phases. The respective AADs are 0.58 and 0.22%, comparable with those of the former =(,T) equation. Finally, the trend of the experimental viscosity second virial coefficient is reproduced and compared with that obtained from the MLFN.     

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.     

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.     

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.     

Temperature-, concentration- and pressure-dependence of the viscosity of liquid3He-4He mixtures at low temperatures

We have investigated the viscosity of liquid³He-⁴He mixtures at various³He - concentrations (0.98%x9.5%) in the temperature range1 mK T 100 mK and at pressures 0 bar P 20 bar. At T10 mK the Fermi-liquid behaviour T² = const. as well as x^4/3 could be confirmed. However, there are significant deviations from theoretical predictions for the magnitude of the viscosity as well as for its pressure dependence.     

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.     

The behavior of the4He viscosity near the superfluid transition

Measurements of the shear viscosity at saturated vapor pressure through the lambda transition indicate a singular behavior of the form |1 – (/)|=A ^x , (where =|1–(T/T )|, with equal values for the critical exponent on both sides of the transition.Work sponsored by Consiglio Nazionale delle Ricerche, Rome (Italy).     

Ageing characteristics of cast Zn-Al based alloy (ZnAl7Cu3)

Microstructure and ageing characteristics of a cast Zn-Al based alloy (ZnAl7Cu3) were studied using X-ray diffraction, electron scanning microscopy and back-scattered diffraction techniques. Two stages of phase transformation, i.e., decomposition of zinc rich phase and four phase transformation, + T + , were detected during ageing at 150°C. Electron back-scattered diffraction technique was applied in distinguishing both zinc rich and phases.     

Phase decomposition in extruded Zn-Al based alloy

Ageing characteristics of an extruded eutectoid Zn-Al based alloy were investigated using X-ray diffraction and scanning electron microscopy techniques. The extruded alloy consisted of Al rich phase and Zn rich _E and phases. The original cast eutectoid Zn-Al alloy was extruded at 250 °C. Both supersaturated _s and _s phase decomposed during extrusion and appeared as fine and coarse lamellar structures. The _E and phases particles formed in the original interdendritic region. It was found that two Zn rich phases _E and decomposed sequentially during ageing at 170, 140 °C. The decomposition of the _E phase occurred as a discontinuous precipitation in the early stage of ageing and the decomposition of the phase took place in a four phase transformation: + T + in the prolonged ageing. Two typical morphologies of the decomposition of the Zn rich phases _E and were distinctive in back-scattered scanning electron microscopy.     

Effects of non-steady state nucleation in the kinetics of crystallization of the amorphous alloy Fe80B20

The existence of non-steady state nucleation in the isothermal crystallization of the amorphous alloy Fe₈₀B₂₀ is shown. The incubation time ₀ of isothermal volume crystallization of the alloy is investigated in a wide range as a function of temperature. From these data an equation for the temperature dependence of the viscosity = (T) is derived: = 6.62 exp (2526.97T) × exp [836.52/(T – 530)].[/p]     

Viscosity of steam in the critical region

The shear viscosity of fluids exhibits an anomalous enhancement in the close vicinity of the critical point. A detailed experimental study of the viscosity of steam in the critical region has been reported by Rivkin and collaborators. A reanalysis of the experimental data indicates that the behavior of the viscosity of steam near the critical point is similar to that observed for other fluids near the critical point. An interpolating equation for the viscosity of water and steam is presented that incorporates the critical viscosity enhancement.Nomenclature a critical region equation of state parameter - a _k coefficients in equation for ₀ - a _ij coefficients in equation for ¯ - b critical region equation of state parameter - c _p specific heat at constant pressure - c _v specific heat at constant volume - k critical region equation of state parameter - k _B Boltzmann constant - P pressure - P _r 22.115 MPa - P ^* P/P _r - P _c critical pressure - P _i coefficients in critical region equation of state - R~P (P-P _c )/P _c - q parameter in equation for critical viscosity enhancement - r parametric variable in critical region equation of state - T temperature in K (IPTS-48) - T _r 647.27 K - T ^* T/T _r - T _c critical temperature - T (T–T _c )/T _c - V volume - critical exponent of specific heat - critical exponent of coexistence curve - critical exponent of compressibility - critical exponent of chemical potential at T=T _c - dynamic viscosity - ₀ lim ₀ - ¯ normal viscosity - critical viscosity enhancement - ¯ thermal conductivity - normal thermal conductivity - critical thermal conductivity enhancement - parametric variable in critical region equation of state - correlation length - ₀ correlation length amplitude above T _c at = _c - critical exponent of correlation length - density - _r 317.763 kg/m³ - ^* / _r - _c critical density - (– _c )/ _c - _p estimated error of pressure - _T estimated error of temperature - estimated error of viscosity - exponent of critical viscosity enhancement - _t (/P) _T symmetrized compressibility - _T ^* _T P _r / _r ² - _{t t} P _c / _c ²     

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.     

Mixing displacement of viscoplastic fluids feom a channel with a rectangular cavity

Different mixing displacement regimes for viscoplastic fluids are investigated theoretically and experimentally.Notation x and y Cartesian coordinates - h half-width of the gap - H, L dimensionless depth and length of the cavity - v_x, v_y velocity components - density - _ik components of the viscous stress tensor - e_ik components of the deformation rate tensor - dynamic viscosity - dynamic viscosity for infinitely high displacement velocity - ₀ analog of the limiting shear stress in Bingham's fluid - W parameter in Williamson's model - =/gh dimensionless viscosity - stream function - vorticity - ₀, ₀ distributions of and at the inlet - r,a, b, and c auxiliary constants - C concentration of the displacing fluid - D diffusion coefficient - Pe Peclet's number Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 40, No. 3, pp. 432–439, March, 1981.     

Correlation of dense fluid self-diffusion,shear viscosity,and thermal conductivity coefficients

A general procedure has been developed for simultaneously fitting any two of the self-diffusion coefficient, the viscosity (as the fluidity), and the thermal conductivity (as its reciprocal) as Dymond reduced coefficients, (D*,*,*), to a simple function of the volume and the temperature for dense fluids. For example,D*=₁+₂ V _r/(1+₃,/V _r), whereV _r=V[1-₁(T–T _r)-₂(T–T _r)²].T _r is any convenient temperature, here 273.15 K. AsV _r is common to the two properties, only eight coefficients, _j and _k are required. Such reduced transport-coefficient curves are geometrically similar for members of groups of closely related compounds. The procedure has been extended to give family curves for such groups by fitting a pair of transport properties for three substances from the group in a single regression. Overall, fewer coefficients are required than for other schemes in the literature, and the fitting functions used are simpler. The curves so constructed can be used for the correlation of data obtained from different sources, as well as interpolation and, to a limited extent, extrapolation. A comparison is made for a number of compotmd groups between simultaneous fits of the pairs (D– ), (D–), and (–)Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

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 .     

Measuring Turbidity in a Near-Critical, Liquid–Liquid System: A Precise, Automated Experiment

A ground based (1g) experiment is in progress that measures the turbidity of the density-matched, binary fluid mixture methanol–cyclohexane extremely close to its liquid–liquid critical point. By covering the range of reduced temperatures t (T–T _c)/T _c from 10^–8 to 10^–2, the turbidity measurements should allow the Green–Fisher critical exponent to be determined. This paper reports measurements showing ±0.1 % precision of the transmitted and reference intensities, and ±4K temperature control near the critical temperature of 320 K. Preliminary turbidity data show a nonzero consistent with theoretical predictions. No experiment has precisely determined a value of the critical exponent , yet its value is significant to theorists in critical phenomena. Relatively simple critical phenomena, as in the liquid–liquid system studied here, serve as model systems for more complex behavior near a critical point.     

Correlation of high-pressure thermal conductivity,viscosity, and diffusion coefficients for n-alkanes

Thermal conductivity, viscosity, and self-diffusion coefficient data for liquid n-alkanes are satisfactorily correlated simultaneously by a method based on the hard-sphere theory of transport properties. Universal curves are developed for the reduced transport properties ^*, ^*, and D ^* as a function of the reduced volume. A consistent set of equations is derived for the characteristic volume and for the parameters R , R , and R _D, introduced to account for the nonsphericity and roughness of the molecules. The temperature range of the above scheme extends from 110 to 370 K, and the pressure range up to 650 MPa.     

Density and Viscosity of the 1-Methylnaphthalene+2,2,4,4,6,8,8-Heptamethylnonane System from 293.15 to 353.15 K at Pressures up to 100 MPa

The dynamic viscosity of the binary mixture 1-methylnaphthalene+2,2,4,4,6,8,8-heptamethylnonane was measured in the temperature range 293.15 to 353.15K (in progressive 10K steps) at pressures of 0.1, 20, 40, 60, 80, and 100MPa. The composition of the system is described by nine molar fractions (0 to 1 in 0.125 progressive steps). The density was measured at pressures from 0.1 to 60MPa in progressive 5 MPa steps. The measurements of are used to determine the excess viscosity ^E and the excess activation energy of flow G ^E as a function of pressure, temperature, and composition. Some models have been used to represent the viscosity of this binary mixture.