Time-temperature superposition and relaxational behavior in polymeric glasses

It is shown that a free-volume treatment of the relaxational behavior of a polymer can be extended into the glassy region. A modified form of the WLF equation is derived in which the temperature is replaced by T_e, a parameter related to the “frozen” free volume in the glass and defined such that Te = T at equilibrium. Measurements of the isothermal volume contraction of polystyrene and poly(methyl methacrylate) between ?20 and + 95°C are used to estimate the “frozen” free volume and to calculate the temperature dependence of log(a_T) below Tg. The calculated shift factors are compared to experimental values for the glassy state, and good agreement is obtained by selecting an arbitrary, but reasonable, equilibrium glass volume-temperature curve. The slope of this equilibrium glass curve is smaller than the experimental volume curve at some finite cooling rate. The data indicate that the glass is not an “iso-free volume” state and that the relaxation mechanisms in the glass are controlled primarily by the free volume, at least in the vicinity of Tg. A quantitative definition of the role of free volume in the glassy state requires evaluation of the quantities ? log a_T/?V)_T,P and (? log a_T/?T)_v,p; sufficient data of this type are not presently available.     

Minimal model for Beta relaxation in viscous liquids

Contrasts between beta relaxation in equilibrium viscous liquids and glasses are rationalized in terms of a double-well potential model with structure-dependent asymmetry, assuming structure is described by a single order parameter. The model is tested for tripropylene glycol where it accounts for the hysteresis of the dielectric beta loss peak frequency and magnitude during cooling and reheating through the glass transition.     

Simple micro engines for transport in viscous liquids

A comparative theoretical analysis of micro engine models that have appeared in recent years is performed. A new model surpassing the considered ones in efficiency and convenience of implementation is proposed.     

Differential criterion of a bubble collapse in viscous liquids

The present work is devoted to a model of bubble collapse in a Newtonian viscous liquid caused by an initial bubble wall motion. The obtained bubble dynamics described by an analytic solution significantly depends on the liquid and bubble parameters. The theory gives two types of bubble behavior: collapse and viscous damping. This results in a general collapse condition proposed as the sufficient differential criterion. The suggested criterion is discussed and successfully applied to the analysis of the void and gas bubble collapse.     

Interphase stability of stratified viscous liquids in Couette flow

An exact long-wavelength asymptotic solution is constructed for the problem of interphase stability in the Couette flow of a two-layer system of Newtonian liquids with different viscosities and with shallow depths. It is shown that the dispersion relation for the complex velocity of a wave of disturbances can be represented as an expansion in fractional powers of the wave number which are multiples of 1/3. New stability criteria, different from those obtained previously, are found. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 5, 330–334 (10 September 1996)     

Studies of blends of poly(phenylene sulfide) and a liquid crystalline polymer: Time-temperature superposition

Polymer blends containing poly(phenylene sulfide) (PPS) and liquid crystalline polymer (LCP) of varying compositions were injection molded and tested. Three-point bending tests were carried out on annealed and unannealed samples at various temperatures and strain rates. The time–temperature master curves were constructed by shifting the experimental modulus data at each point of the curves. The increase in bending modulus and reduction of bending strength with increasing LCP content were attributed to the skincore morphology. The time-temperature curves revealed that the bending modulus of the blends can be superimposed over a wide range of temperatures and strain rates.     

Electrically forced microthreading of highly viscous dielectric liquids

The behaviour of three high viscosity (4875, 12 125 and 58 560 mPa s), dielectric liquids was investigated at flow rates of 10⁻¹⁰, 10⁻¹² and 10⁻¹⁴ m³ s⁻¹ and the applied voltage range 6–15 kV. In these experiments, due to the low electrical conductivity of the liquids (10⁻¹³ S m⁻¹) and therefore the ensuing high electrical relaxation time, classical electrohydrodynamic atomization conditions are not satisfied. Only dripping and unstable jetting were observed at 4875 mPa s. A transition from no jetting to stable microthreading was observed for the 12 125 and 58 560 mPa s samples. The relics accompanying the transition were found to change from discrete droplets to a continuous filament. Stable microthreading, which generates uniform filaments, was obtained for the 12 125 mPa s sample at flow rates 10⁻¹⁰ and 10⁻¹² m³ s⁻¹ and in the case of the 58 560 mPa s sample at all the flow rates investigated. The high viscosity assisted stable microthreading with the filament diameter decreasing with increasing applied voltage and more dramatically decreasing with reducing flow rate.     

A scaling law in the hydrodynamics of anisotropic viscous liquids

Summary We show that 1) the stationary flow of an isotropic liquid in a given viscosimeter is described by the same equations valid for a wellaligned nematic liquid crystal, having suitable values of the five viscosity coefficients, flowing in a viscosimeter like the previous one, but whose dimensions along the average molecular directionň are contracted; 2) a similar equivalence exists for a nematic flowing in a suitably chosen viscosimeter in two experiments which differ only for the direction ofň. This equivalence allows us to exactly compensate boundary effects in the measurement of the ratio between two of the Miesowicz viscosity coefficients. Furtherly a new particularly simple derivation of the Rayleigh dissipation function for nematics is given. To speed up publication, the author of this paper has agreed to not receive the proofs for correction.     

Solidity of viscous liquids. II. Anisotropic flow events

Recent findings on displacements in the surroundings of isotropic flow events in viscous liquids [Phys. Rev. E 59, 2458 (1999)] are generalized to the anisotropic case. Also, it is shown that a flow event is characterized by a dimensionless number reflecting the degree of anisotropy.     

Investigation of the spectra of depolarized light scattering in two viscous liquids

The fine structure of the Rayleigh line wing was studied experimentally in a broad temperature range in the viscous guaiacol liquid. The propagation velocity and the absorption coefficient of the transverse hypersound were determined by the Rayleigh line wing spectra at temperatures from ?27 to ?85°C. The transverse hypersound absorption is shown to pass through its maximum at a temperature of ?34°C. The experimental data for two vitrifying viscous liquids, namely, guaiacol and salol were analyzed. The limiting elastic bulk moduli were found to intersect at the crystallization temperature and the limiting shear modulus to vanish at this temperature. These and other specific features of the guaiacol and salol behavior at the crystallization temperature, revealed in this and previous our studies, point to the possibility of the existence of two phases in a liquid.     

On the dynamics of liquids in their viscous regime approaching the glass transition

Recently, Mallamace et al. (Eur. Phys. J. E 34, 94 (2011)) proposed a crossover temperature, T(×), and claimed that the dynamics of many supercooled liquids follow an Arrhenius-type temperature dependence between T(×) and the glass transition temperature T(g). The opposite, namely super-Arrhenius behavior in this viscous regime, has been demonstrated repeatedly for molecular glass-former, for polymers, and for the majority of the exhaustively studied inorganic glasses of technological interest. Therefore, we subject the molecular systems of the Mallamace et al. study to a "residuals" analysis and include not only viscosity data but also the more precise data available from dielectric relaxation experiments over the same temperature range. Although many viscosity data sets are inconclusive due to their noise level, we find that Arrhenius behavior is not a general feature of viscosity in the T(g) to T(×) range. Moreover, the residuals of dielectric relaxation times with respect to an Arrhenius law clearly reveal systematic curvature consistent with super-Arrhenius behavior being an endemic feature of transport properties in this viscous regime. We also observe a common pattern of how dielectric relaxation times decouple slightly from viscosity.     

Dynamic viscosity of macromolecular liquids for a superposition of static and oscillating velocity gradients

Two coupled, inhomogeneous relaxation equations for the friction pressure tensor and the alignment tensor are derived within the framework of irreversible thermodynamics. These equations are solved for a specific geometry, viz. flow between flat plates, and for a velocity gradient of the form $\text{Γ}{}_0\text{+ Γ}{}_1\text{cos Ωt}$ with small Γ₁. From the resulting relation between the (time-dependent) friction pressure tensor and the velocity gradient, the dynamic viscosity and the normal pressure can be inferred. The frequency dependence of the relevant viscosity coefficients is discussed. If Г₀, the magnitude of the static part of the velocity gradient is large enough, a type of resonance behavior is found with the resonance frequency $\text{Ω}{}_{\mathrm{res}}\text{≈(1 + ξ)}{}^{-1}\text{Γ}{}_0$ where ξ is the ratio between the relation times of the friction pressure tensor and of the alignment tensor.     

Transformation of a Taylor cone into a frustum upon discharge in viscous dielectric liquids

Technical Physics - The specifics of behavior of viscous electrolytes (exemplified by glycerol) subjected to spark discharges with direct connection of electrodes and in the induced charge mode...     

Numerical simulation of 3D bubbles rising in viscous liquids using a front tracking method

The rise of bubbles in viscous liquids is not only a very common process in many industrial applications, but also an important fundamental problem in fluid physics. An improved numerical algorithm based on the front tracking method, originally proposed by Tryggvason and his co-workers, has been validated against experiments over a wide range of intermediate Reynolds and Bond numbers using an axisymmetric model [J. Hua, J. Lou, Numerical simulation of bubble rising in viscous liquid, J. Comput. Phys. 22 (2007) 769–795]. In the current paper, this numerical algorithm is further extended to simulate 3D bubbles rising in viscous liquids with high Reynolds and Bond numbers and with large density and viscosity ratios representative of the common air–water two-phase flow system. To facilitate the 3D front tracking simulation, mesh adaptation is implemented for both the front mesh on the bubble surface and the background mesh. On the latter mesh, the governing Navier–Stokes equations for incompressible, Newtonian flow are solved in a moving reference frame attached to the rising bubble. Specifically, the equations are solved using a finite volume scheme based on the Semi-Implicit Method for Pressure-Linked Equations (SIMPLE) algorithm, and it appears to be robust even for high Reynolds numbers and high density and viscosity ratios. The 3D bubble surface is tracked explicitly using an adaptive, unstructured triangular mesh. The numerical model is integrated with the software package PARAMESH, a block-based adaptive mesh refinement (AMR) tool developed for parallel computing. PARAMESH allows background mesh adaptation as well as the solution of the governing equations in parallel on a supercomputer. Further, Peskin distribution function is applied to interpolate the variable values between the front and the background meshes. Detailed sensitivity analysis about the numerical modeling algorithm has been performed. The current model has also been applied to simulate a number of cases of 3D gas bubbles rising in viscous liquids, e.g. air bubbles rising in water. Simulation results are compared with experimental observations both in aspect of terminal bubble shapes and terminal bubble velocities. In addition, we applied this model to simulate the interaction between two bubbles rising in a liquid, which illustrated the model’s capability in predicting the interaction dynamics of rising bubbles.     

Effect of static pressure on acoustic energy radiated by cavitation bubbles in viscous liquids under ultrasound

The effect of static pressure on acoustic emissions including shock-wave emissions from cavitation bubbles in viscous liquids under ultrasound has been studied by numerical simulations in order to investigate the effect of static pressure on dispersion of nano-particles in liquids by ultrasound. The results of the numerical simulations for bubbles of 5 μm in equilibrium radius at 20 kHz have indicated that the optimal static pressure which maximizes the energy of acoustic waves radiated by a bubble per acoustic cycle increases as the acoustic pressure amplitude increases or the viscosity of the solution decreases. It qualitatively agrees with the experimental results by Sauter et al. [Ultrason. Sonochem. 15, 517 (2008)]. In liquids with relatively high viscosity (～200 mPa s), a bubble collapses more violently than in pure water when the acoustic pressure amplitude is relatively large (～20 bar). In a mixture of bubbles of different equilibrium radius (3 and 5 μm), the acoustic energy radiated by a 5 μm bubble is much larger than that by a 3 μm bubble due to the interaction with bubbles of different equilibrium radius. The acoustic energy radiated by a 5 μm bubble is substantially increased by the interaction with 3 μm bubbles.     

Acoustic waves emitted by radial oscillations of a spherical bubble in viscous compressible heat conductive liquids

Czechoslovak Journal of Physics - The relations have been derived which characterize the speed distribution υ(r, t) of density ϱ′(r, t) and pressure p′ir, t) of a viscous...     

Influence of ultrasound on mixing on the molecular scale for water and viscous liquids

Micromixing has a decisive action on the yield of fast reactions such as combustions, polymerizations, neutralizations and precipitations. The aim of this study was to test the possible effect of ultrasound on micromixing, through the phenomenon of acoustic cavitation. To evaluate the local state of micromixing, we used a system of parallel competing reactions involving the Dushman reaction between iodide and iodate, coupled with a neutralization. At first, we studied the effects of the acoustic frequency on micromixing (20-540-1000 kHz). It was found that micromixing through acoustic cavitation and acoustic streaming was more important at 20 kHz than at 540 kHz or 1 MHz. At high and low frequency, it was shown that the injection must be located near the ultrasonic emitter. The influence of the acoustic intensity proved to be predominant mostly for low intensities; for an acoustic intensity of 10 W cm(-2), a characteristic micromixing time of about 0.015 s has been obtained. Viscous media have been studied and experiments showed that micromixing is more difficult to achieve than in aqueous media, but that ultrasound may be as effective as classic stirring.     

Instability of a charged interface of two immiscible viscous liquids with charge relaxation taken into account

On the basis of an analysis of a derived dispersion relation, it is demonstrated that there can be two different types of instability relative to the free charge of a charged, planar interface between two viscous immiscible liquids with finite electrical conductivity in a gravitational field. For large values of the surface charge density, depending on the viscosities and ratio of conductivities of the media, one can observe either an aperiodic (of the Tonks-Frenkel type) or oscillatory instability of the interface. Increasing the viscosity of the lower liquid leads to a substantial drop in the increments of the mentioned instability types and alters the critical conditions for manifestation of the oscillatory instability, whereas varying the viscosity of the upper surface has only a very weak effect on these characteristics. Zh. Tekh. Fiz. 68, 13–19 (September 1998)     

Study of viscous liquids by spin micro- and macroprobe methods at 2-mm wave band EPR

The possibility of combined application of spin microprobe and macroprobe methods at 2-mm wave band EPR in determining the viscosity of a model system is demonstrated. Such an approach widens the range of dynamic viscosity EPR measurement in condensed systems and gives one the possibility to study separately various dynamic processes in a matrix.