Sound attenuation, shear viscosity, and mutual diffusivity behavior in the nitroethane-cyclohexane critical mixture

The shear viscosity eta(s), mutual diffusion coefficient D, and ultrasonic attenuation spectra of the nitroethane-cyclohexane mixture of critical composition have been measured at various temperatures near the critical temperature T(c). The relaxation rate of order parameter fluctuations resulting from a combined evaluation of the eta(s) and D data follows power law behavior with the theoretical exponent and with the large amplitude Gamma(o)=(156+/-2)x10(9) s(-1). The ultrasonic spectra have been evaluated in terms of a critical contribution and a noncritical background contribution. The amplitude of the former exhibits a temperature dependence, in conformity with a temperature dependence in the adiabatic coupling constant (|g| = 0.064 near T(c) and 0.1 at T-T(c)=3 K). If the variation of the critical amplitude with T is taken into account the experimental attenuation coefficient data display a scaling function which nicely fits to the theoretical prediction from the Bhattacharjee-Ferrell dynamic scaling model [R. A. Ferrell and J. K. Bhattacharjee, Phys. Rev. A 31, 1788 (1985)].     

Critical dynamics of the binary system nitroethane/3-methylpentane: relaxation rate and scaling function

Shear viscosity and dynamic light scattering measurements as well as ultrasonic spectrometry studies of the nitroethane/3-methylpentane mixture of critical composition have been performed at various temperatures near the critical temperature, T(c). A combined evaluation of the shear viscosity and mutual diffusion coefficient data yielded the amplitude, xi(0), of the fluctuation correlation length, xi, assumed to follow power law, and the relaxation rate, Gamma, or order parameter fluctuations. The latter was found to follow power law with the theoretical universal exponent. The amplitudes xi(0) = 0.23 +/- 0.02 nm and Gamma(0) = (125 +/- 5) x 10(9) s(-1) nicely agree with literature values. Using the relaxation rates resulting from the viscosity and diffusion coefficient data, the scaling function has been calculated assuming the ultrasonic spectra to be composed of a critical part and a noncritical background contribution. The experimental scaling function fits well to the predictions of the Bhattacharjee-Ferrell dynamic scaling model with scaled half-attenuation frequency, Omega(BF)1/2= 2.1. The amplitude of the sonic spectra yields the amount |g| = 0.26 of the adiabatic coupling constant, g, in fair agreement with -0.29 from another thermodynamic relation.     

Critical fluctuations near the consolute point of n-pentanol-nitromethane. An ultrasonic spectrometry, dynamic light scattering, and shear viscosity study

Ultrasonic attenuation spectra, the shear viscosity, and the mutual diffusion coefficient of the n-pentanol-nitromethane mixture of critical composition have been measured at different temperatures near the critical temperature. The noncritical background contribution, proportional to frequency, to the acoustical attenuation-per-wavelength spectra has been determined and subtracted from the total attenuation to yield the critical contribution. When plotted versus the reduced frequency, with the relaxation rate of order-parameter fluctuations from the shear viscosity and diffusion coefficient measurements, the critical part in the sonic attenuation coefficient displays a scaling function which nicely fits to the data for the critical system 3-methylpentane-nitromethane and also to the empirical scaling function of the Bhattacharjee-Ferrell dynamic scaling theory. The scaled half-attenuation frequency follows from the experimental data as Omega(1/2)emp= 1.8+/-0.1. The relaxation rate of order-parameter fluctuation shows power-law behavior with the theoretically predicted universal exponent and the extraordinary high amplitude Gammao= (187+/-2) x 10(9) s(-1). The amount of the adiabatic coupling constant /g/= 0.03, as estimated from the amplitude of the critical contribution to the acoustical spectra, is unusually small.     

Dynamic scaling of the critical binary mixture methanol-hexane

Acoustical attenuation spectrometry, dynamic light scattering, shear viscosity, density, and heat capacity measurements of the methanol/n-hexane mixture of critical composition have been performed. The critical part in the sonic attenuation coefficients nicely fits to the empirical scaling function of the Bhattacharjee-Ferrell [Phys. Rev. A 24, 1643 (1981)] dynamic scaling model if the theoretically predicted scaled half-attenuation frequency Omega(12) (BF)=2.1 is used. The relaxation rates of order parameter fluctuations, as resulting from the acoustical spectra, within the limits of experimental error agree with those from a combined evaluation of the light scattering and shear viscosity measurements. Both series of data display power law with amplitude Gamma(0)=44x10(9) s(-1). The amplitude of the fluctuation correlation length follows as xi(0)=0.33 nm from the light scattering data and as xi(0)=0.32 nm from the amplitude of the singular part of the heat capacity if the two-scale factor universality relation is used. The adiabatic coupling constant g=0.11 results from the amplitude of the critical contribution to the acoustical spectrum near the critical point, in conformity with g=0.12 as following from the variation of the critical temperature with pressure along the critical line and the thermal expansion coefficient.     

Critical fluctuations of the micellar triethylene glycol monoheptyl ether-water system

Using the equal volume criterion and also the pseudospinodal conception the critical demixing point of the triethylene glycol monoheptyl ether/water system (C7E3H2O) has been determined as Ycrit=0.1 and Tcrit=296.46 K (Y, mass fraction of surfactant). From density measurements the critical micelle concentration (cmc) followed as Ycmc=0.007 at 288.15 K and Ycmc=0.0066 at 298.15 K. The (static) shear viscosity etas and the mutual diffusion coefficient D of the C7E3H2O mixture of critical composition have been evaluated to yield their singular and background parts. From a combined treatment of both quantities the relaxation rate Gamma of order parameter fluctuations has been derived. Gamma follows power law with universal critical exponent and amplitude Gamma0=3.1 x 10(9) s(-1). Broadband ultrasonic spectra of C7E3H2O mixtures exhibit a noncritical relaxation, reflecting the monomer exchange between micelles and the suspending phase, and a critical term due to concentration fluctuations. The former is subject to a relaxation time distribution that broadens when approaching the critical temperature. The latter can be well represented with the aid of the dynamic scaling model by Bhattacharjee and Ferrell (BF) [Phys. Rev. A. 31, 1788 (1985)]. The half-attenuation frequency in the scaling function of the latter model is noticeably smaller (Omega12 (BF) approximately 1) than the theoretically predicted value Omega12 (BF)=2.1. This result has been taken as an indication of a coupling between the fluctuations in the local concentration and the kinetics of micelle formation, in correspondence with the idea of a fluctuation controlled monomer exchange [T. Telgmann and U. Kaatze, Langmuir 18, 3068 (2002)].     

Assessment of phenomenological models for viscosity of liquids based on nonequilibrium atomistic simulations of copper

The shear viscosity of liquid copper is studied using nonequilibrium molecular-dynamics simulations under planar shear flow conditions. We examined variation of viscosity as function of shear rate at a range of pressures (ca. 0 - 40 GPa). We analyzed these results using eight different phenomenological models and find that the observed non-Newtonian behavior is best described by the Powell-Eyring (PE) model: eta(gamma) = (eta(0)-eta(infinity))sinh(-1)(taugamma)(taugamma) + eta(infinity), where gamma is the shear rate. Here eta(0) (the zero-shear-rate viscosity) extracted from the PE fit is in excellent agreement with available experimental data. The relaxation time tau from the PE fit describes the shear response to an applied stress. This provides the framework for interpreting the shear flow phenomena in complex systems, such as liquid metal and amorphous metal alloys.     

The influence of potential softness on the transport coefficients of simple fluids

This study explores the effects of interaction softness on the transport properties of simple fluids. The transport coefficients of soft-sphere fluids in which the particles interact via the potential, phi(r)=epsilon(rsigma)(-n), with n in the range from 6 to 1152, have been calculated by molecular-dynamics computer simulation. The self-diffusion coefficient D shear viscosity eta(s), bulk viscosity eta(b), and thermal conductivity lambda were computed over a wide packing fraction range. It was found that the Batschinski-Hildebrand expressions, in which D, eta(s) (-1), eta(b) (-1), and lambda(-1) are assumed to have a linear dependence on the molar volume, represent the data quite well for all n, although least well for the thermal conductivity. The density for which, on extrapolation, each of these quantities is zero, increases with the softness of the interaction (or approximately n(-1)), suggesting that the effective hard-sphere diameter decreases with increasing softness in the small n limit. This treatment leads to simple empirical formulas for the effect of density and n on the effective hard-sphere diameter and packing fraction (in an intermediate range) and the four transport coefficients of these fluids.     

Turbidity determination of the critical exponent eta in the liquid-liquid mixture methanol and cyclohexane

The turbidity of the liquid-liquid mixture methanol-cyclohexane has been measured very near its critical point and used to test competing theoretical predictions and to determine the critical correlation-correction exponent eta. By measuring the ratio of the transmitted to incident light intensities over five decades in reduced temperature, we are able to determine that Ferrell's theoretical prediction for the turbidity explains the data with the correlation length amplitude xi0=0.330+/-0.003 nm and critical exponents eta=0.041+/-0.005 and nu=0.632+/-0.002. These values are consistent with the values measured before for xi0 in this system and with the exponents predicted by theory. The data allow five different theoretical expressions to be tested and to select two as being equivalent when very close to the critical point.     

Structural, topographical, and shear characteristics of milk protein and monoglyceride monolayers spread at the air-water interface

In this contribution we are concerned with the study of structure, topography, and surface rheological characteristics under shear conditions of monoglyceride (monopalmitin and monoolein) and milk protein (beta-casein, kappa-casein, caseinate, and WPI) spread monolayers at the air-water interface. Combined surface chemistry (surface film balance and surface shear rheometry) and microscopy (Brewster angle microscopy: BAM) techniques have been applied in this study to pure emulsifiers (proteins and monoglycerides) spread at the air-water interface. To study the shear characteristics of spread films, a homemade canal viscometer was used. The experiments have demonstrated the sensitivity of the surface shear viscosity (eta(s)) of protein and monoglyceride films at the air-water interface, as a function of surface pressure (or surface density). The surface shear viscosity was higher for proteins than for monoglycerides. In addition, eta(s) was higher for the globular WPI than for disordered beta-casein and caseinate due to the strong forces acting on spread globular proteins. This technique makes it possible to distinguish between beta-casein and caseinate spread films, with the higher eta(s) values for the later due to the presence of kappa-casein. The eta(s) value varies greatly with the surface pressure (or surface density). In general, the greater the surface pressure, the greater the values of eta(s). Finally, the eta(s) value is also sensitive to the monolayer structure, as was observed for monoglycerides with a rich structural polymorphism (i.e., monopalmitin).     

从聚丙烯流动曲线估算分子量分布

聚丙烯的控制降解技术由于能够带来很好的经济效益，国内外都在进行研究．其中分子量分布是一个重要数据，它对于聚丙烯的注塑、纺丝、薄膜等加工过程都有重要的影响．分子量分布一般用重均分子量Mw和数均分子量Mn之比D=Mw/Mn来表征，称为分子量分布指数．它可以     

Rheological Behavior of Titanium Dioxide Suspensions

The rheological properties of titanium dioxide dispersed in water are measured over a wide range of powder concentrations, temperatures, and pH values. The value of intrinsic viscosity of titanium dioxide measured with an Ubbelohde capillary viscometer is 3.55, which is useful for determining the shape and aggregation property of the particles. The yield stress and steady shear viscosity of titanium dioxide with broad and narrow particle size distributions were measured over a wide range of solid volume fractions on a Brabender rheometer. It is observed that the rheological properties of the suspensions are quite different due to the difference in particle size distributions. Quemada, Casson, and Zhou's models were used to fit the experimental data and useful parameters were obtained. Calculated data are also in good agreement with the experimental data. As expected, the shear viscosity and yield stress decrease with increasing temperature. But when the temperature is around 50 degrees C, yield stress increases with increasing temperature while shear viscosity exhibits a complex behavior. The phenomena are very interesting and special. The Peclet number was used to analyze the shear thickening behavior. Models were also used to describe the shear viscosity under different temperatures and the master plots of the reduced variables eta/eta(infinity) vs t(c)gamma; at different temperatures are superimposed, which means the agreement is fair and the models are suitable to describe the rheological properties of titanium dioxide suspensions. pH effects were investigated on a Rheometrics RFS-II rheometer and it was found that pH can change the surface charge of the particles, which also affects the rheological behavior. The pH at which maximum shear viscosity and yield stress occur is in concordance with the isoelectric point. Copyright 2001 Academic Press.     

Translational diffusion in sucrose benzoate near the glass transition: probe size dependence in the breakdown of the Stokes-Einstein equation

The translational diffusion coefficient D(trans) for rubrene, 9,10-bis(phenylethynyl)anthracene (BPEA), and tetracene in the fragile molecular glass-former sucrose benzoate (SB) (Tg=337 K) was studied as a function of temperature from Tg+3 K to Tg+71 K by use of the holographic fluorescence recovery after photobleaching technique. The values of D(trans) vary by five to six orders of magnitude in this temperature range. Contrary to the predictions of the Stokes-Einstein equation, the temperature dependence of probe diffusion in SB over the temperature range of the measurements is weaker than that of T/eta, where eta is the shear viscosity. In going from the crossover temperature Tx approximately 1.2Tg to Tg, D(trans)eta/T increases by factors of 2.4+/-0.2 decades for rubrene, 3.4+/-0.2 decades for BPEA, and 3.8+/-0.4 decades for tetracene. The decoupling between probe diffusion in SB and viscosity is characterized by the scaling law D(trans) approximately T/eta(xi), with xi=0.621 for tetracene, 0.654 for BPEA, and 0.722 for rubrene. Data for probe diffusion in SB are combined with data from the literature for probe diffusion in ortho-terphenyl and alphaalphabeta-tris(naphthyl)benzene in a plot of enhancement versus the relative probe size parameter rho(m)=(m(p)m(h))(1/3), where m(p) and m(h) are, respectively, the molecular weights of the probe and host solvent. The plot clearly shows a sharp increase in enhancement of translational diffusion at rho(m) approximately 1. By applying temperature shifts, D(trans) for probe diffusion in SB and the dielectric relaxation time tau(D) can be superimposed on a single master curve based on the Williams-Landel-Ferry equation. This suggests that the dynamics of probe diffusion in SB is described by the scaling relationship D(trans) approximately 1/tau(D)(T+DeltaT), where tau(D)(T+DeltaT) is the temperature-shifted dielectric relaxation time. The results from this study are discussed within the context of dynamic heterogeneity in glass-forming liquids.     

Fluidity of water confined down to subnanometer films

A surface force balance with extremely high sensitivity and resolution for measuring shear forces across thin films has been used to investigate directly the dynamic properties of salt-free water (so-called conductivity water) in a gap between two atomically smooth solid surfaces. Our results reveal that no shear stress can be sustained by water (within our resolution and shear rates) down to films of thickness D = D0 = 0.0 +/- 0.3 nm. At short range (D < 3.5 +/- 1 nm), an attractive van der Waals (vdW) force between the surfaces causes a jump into a flat adhesive contact at D0, at which the surfaces rigidly couple. Analysis of the jump behavior reveals that the viscosity of water remains within a factor of 3 or so of its bulk value down to D0. This contrasts sharply with the case of confined nonassociating liquids, whose effective viscosity increases by many orders of magnitude at film thicknesses lower than about five to eight monolayers. We attribute this to the fundamentally different mechanisms of solidification of organic liquids and of water. In the former case, the density increase induced in the films by the confinement promotes solidification, while, in the case of water, such densification (due to vdW attraction between the liquid molecules and the confining walls), in agreement with bulk behavior, suppresses the tendency of the water to solidify.     

Characterization of high molecular weight polyethylenes using high temperature asymmetrical flow field-flow fractionation with on-line infrared, light scattering, and viscometry detection

High temperature asymmetrical flow field-flow fractionation (HTAF4) coupled to infrared (IR), multi-angle light scattering (MALS), and viscometry (Visc) detection is introduced as a tool for the characterization of high molecular weight polyethylenes. The high molecular weight fraction strongly affects the rheological behaviour and processability of polyethylene materials and can often not be accurately resolved by current technology such as high temperature size-exclusion chromatography (HTSEC). Molecular weight (M), radius of gyration (Rg), and intrinsic viscosity [eta] of linear high density polyethylene (HDPE) and branched low density polyethylene (LDPE) samples are studied in detail by HTAF4 and are compared to HTSEC. HTAF4 showed a better separation and mass recovery than HTSEC for very high molecular weight fractions in HDPE and LDPE samples. As no stationary phase is present in an HTAF4 channel, the technique does not show the typical drawbacks associated with HTSEC analysis of high molecular weight polyethylenes, such as, exclusion effects, shear degradation, and anomalous late elution of highly branched material. HTAF4 is applied to study the relation between the molecular weight and the zero shear viscosity eta0 for high molecular weight HDPE. It was found that the zero shear viscosity values predicted from HTAF4 results are in good qualitative agreement with measured values obtained from dynamic mechanical spectroscopy (DMS) experiments, whereas eta0 values predicted from HTSEC do not show a strong correlation. The low molecular weight cutoff of HTAF4 is approximately 5x10(4) as a result of relatively large pores in the HTAF4 channel membrane. HTAF4 is, therefore, currently not suited to analyze low molecular weight materials.     

Shear viscosity of molten alkali halides from equilibrium and nonequilibrium molecular-dynamics simulations

The shear viscosity of molten NaCl and KCl was calculated through equilibrium (EMD) and nonequilibrium molecular-dynamics (NEMD) simulations in the canonical (N,V,T) ensemble. Two rigid-ion potentials were investigated, namely, the Born-Mayer-Huggins-Tosi-Fumi potential and the Michielsen-Woerlee-Graaf-Ketelaar potential with the parameters proposed by Ladd. The NEMD simulations were performed using the SLLOD equations of motion [D. J. Evans and G. P. Morriss, Phys. Rev. A 30, 1528 (1984)] with a Gaussian isokinetic thermostat and the results are compared with those obtained from Green-Kubo EMD (N,V,T) simulations and experimental shear viscosity data. The NEMD zero strain rate shear viscosity, eta(0), was obtained by fitting a simplified Carreau-type equation and by application of mode-coupling theory, i.e., a eta-gamma(1/2) linear relationship. The values obtained from the first method are found to be significantly lower than those predicted by the second. The agreement between the EMD and NEMD results with experimental data is satisfactory for the two potentials investigated. The ion-ion radial distribution functions obtained with the two rigid-ion potentials for both molten salts are discussed in terms of the differences between the two models.     

Alternative view of self-diffusion and shear viscosity

By performing an elementary transformation, the conventional velocity autocorrelation function expression for the temperature and density dependent self-diffusion constant D(T,rho) has been reformulated to emphasize how initial particle momentum biases final mean displacement. Using collective flow variables, an analogous expression has been derived for 1/eta(T,rho), the inverse of shear viscosity. The Stokes-Einstein relation for liquids declares that D and T/eta should have a fixed ratio as T and rho vary, but experiment reveals substantial violations for deeply supercooled liquids. Upon analyzing the self-diffusion and viscous flow processes in terms of configuration space inherent structures and kinetic transitions between their basins, one possible mechanism for this violation emerges. This stems from the fact that interbasin transitions become increasingly Markovian as T declines, and though self-diffusion is possible in a purely Markovian regime, shear viscosity in the present formulation intrinsically relies on successive correlated transitions.     

Shear thinning and shear dilatancy of liquid n-hexadecane via equilibrium and nonequilibrium molecular dynamics simulations: Temperature, pressure, and density effects

Equilibrium and nonequilibrium molecular dynamics (MD) simulations have been performed in both isochoric-isothermal (NVT) and isobaric-isothermal (NPT) ensemble systems. Under steady state shearing conditions, thermodynamic states and rheological properties of liquid n-hexadecane molecules have been studied. Between equilibrium and nonequilibrium states, it is important to understand how shear rates (gamma) affect the thermodynamic state variables of temperature, pressure, and density. At lower shear rates of gamma<1 x 10(11) s(-1), the relationships between the thermodynamic variables at nonequilibrium states closely approximate those at equilibrium states, namely, the liquid is very near its Newtonian fluid regime. Conversely, at extreme shear rates of gamma>1 x 10(11) s(-1), specific behavior of shear dilatancy is observed in the variations of nonequilibrium thermodynamic states. Significantly, by analyzing the effects of changes in temperature, pressure, and density on shear flow system, we report a variety of rheological properties including the shear thinning relationship between viscosity and shear rate, zero-shear-rate viscosity, rotational relaxation time, and critical shear rate. In addition, the flow activation energy and the pressure-viscosity coefficient determined through Arrhenius and Barus equations acceptably agree with the related experimental and MD simulation results.     

Collective and self-diffusion coefficients in an ionic critical mixture: 3-methylpyridine+water+NaBr

The dynamics of concentration fluctuations of three critical samples of the 3-methylpyridine (3MP)+water+NaBr system have been measured by photon correlation spectroscopy. The collective-diffusion coefficient D shows the usual Ising behavior near the critical temperature T(c). However, as |T-T(c)| increases, the dynamic correlation length calculated from D, xi, takes values higher than the correlation length of the critical fluctuations calculated from static light scattering, xi(s). At the largest |T-T(c)| measured, xi approaches the value, xi(0,d) approximately equal to 1.13 nm, while the amplitude of xi(s) is xi(0,s)=0.38 nm. Pulsed-gradient NMR spectroscopy points out the existence of two dynamic contributions. One of them is consistent with the existence of molecular entities of hydrodynamic radius 0.31 nm, while the other one indicates the existence of aggregates rich in 3MP of radius 1.16 nm. The existence of the aggregates may explain the apparent anomalous behavior of the dynamic light scattering experiments for this system far from the critical point.     

Study on laminar viscosity and zero shear viscosity of latex systems

The flowing nature and rheological properties of polymethyl methacrylate latex systems in a coaxial cylinder viscometer were studied on the basis of laminar shear flow model and rheological experimental data. The physical meaning of laminar viscosity (eta(i,j)) and zero shear viscosity (eta(0)) were described. We assumed that laminar shear flows depended on position and shear time, so microrheological parameters were the function of position and shear time. eta(i,j) was the viscosity of any shear sheet i between two neighboring laminar shear flows at time t; j was denoted as j=t/Deltat; and Deltat was the interacting time of two particles or two laminar shear flows. tau(i,j) and gamma(i,j) were shear stress and shear rate of any shear sheet i at j moment. According to Newton regulation tau(i,j)=eta(i,j)gamma(i,j), apparent viscosity eta(a) should be a statistically mean value of j shear sheets laminar viscosity at j moment, i.e., eta(a)= summation operator(i=j)eta(i,j)gamma(i,j)/ summation operator(i=j)gamma(i,j). eta(0) was defined as shear viscosity between a laminar shear flow and a still fluid surface, i.e., eta(0)=(tau(i,j)/gamma(i,j))(j-i-->0). These new ideas described above may be helpful in the study of the micromechanisms of latex particle systems and worthy of more research.     

Calculation of the transport and relaxation properties of methane. I. Shear viscosity, viscomagnetic effects, and self-diffusion

Transport properties of pure methane gas have been calculated in the rigid-rotor approximation using the recently proposed intermolecular potential energy hypersurface [R. Hellmann et al., J. Chem. Phys. 128, 214303 (2008)] and the classical-trajectory method. Results are reported in the dilute-gas limit for shear viscosity, viscomagnetic coefficients, and self-diffusion in the temperature range of 80-1500 K. Compared with the best measurements, the calculated viscosity values are about 0.5% too high at room temperature, although the temperature dependence of the calculated values is in very good agreement with experiment between 210 and 390 K. For the shear viscosity, the calculations indicate that the corrections in the second-order approximation and those due to the angular-momentum polarization are small, less than 0.7%, in the temperature range considered. The very good agreement of the calculated values with the experimental viscosity data suggests that the rigid-rotor approximation should be very reasonable for the three properties considered. In general, the agreement for the other measured properties is within the experimental error.