Complex liquids, relaxation time

Various theoretical and empirical models have been derived expressing either charge density or charging current in terms of flow characteristics such as pipe diameter d (m) and flow velocity v (m/s). Liquid dielectric and physical properties appear in more complex models. The application of theoretical models is often limited by the nonavailability or inaccuracy of parameters needed to solve the equations. Empirical models are adequate in most cases. For turbulent flow of nonconductive liquid through a given pipe under conditions where the residence time is long compared with the relaxation time, it is found that the volumetric charge density Qy attains a steady-state value which is directly proportional to flow velocity... 

Contrary to the phase separation curve, the sol/gel transition is very sensitive to the temperature more cations are required to get a gel phase when the temperature increases and thus the extension of the gel phase decreases [8]. The sol/gel transition as determined above is well reproducible but overestimates the real amount of cation at the transition. Gelation is a transition from liquid to solid during which the polymeric systems suffers dramatic modifications on their macroscopic viscoelastic behavior. The whole phenomenon can be thus followed by the evolution of the mechanical properties through dynamic experiments. The behaviour of the complex shear modulus G (o)) reflects the distribution of the relaxation time of the growing clusters. At the gel point the broad distribution of... 

This most simple model for the relaxation time spectrum of materials near the liquid-solid transition is good for relating critical exponents (see Eq. 1-9), but it cannot be considered quantitatively correct. A detailed study of the evolution of the relaxation time spectrum from liquid to solid state is in progress [70], Preliminary results on vulcanizing polybutadienes indicate that the relaxation spectrum near the gel point is more complex than the simple spectrum presented in Eq. 3-6. In particular, the relation exponent n is not independent of the extent of reaction but decreases with increasing p. 

The answer to our question at the beginning of this summary therefore has to be as follows. When you want to locate the glass transition of a polymer melt, find the temperature at which a change in dynamics occurs. You will be able to observe a developing time-scale separation between short-time, vibrational dynamics and structural relaxation in the vicinity of this temperature. Below this crossover temperature, one will find that the temperature dependence of relaxation times assumes an Arrhenius law. Whether MCT is the final answer to describe this process in complex liquids like polymers may be a point of debate, but this crossover temperature is the temperature at which the glass transition occurs. 

G. R. Fleming In simple liquids such as methanol and ethanol there is no evidence for relaxation times slower than expected from dielectric measurements. Glasses at room temperature clearly show time scales that are infinite on our measurement time scale. In complex liquids such as glycerol-water mixtures and ethylene glycol, we may observe time scales that are longer than dielectric relaxation, but further studies are required to confirm this. 

As a second example, we consider liquid fluoromethane CH3F, which is a typical strongly absorbing nonassociated liquid. For our study we choose the temperature T 133 K near the triple point, which is equal to 131 K. The relevant experimental data [43] were summarized in Table IV. As we see in Table VIII, which presents the fitted parameters of the model, the angle p is rather small. At this temperature the density p of the liquid, the maximum dielectric loss and the Debye relaxation time rD are substantially larger than they would be, for example, near the critical temperature (at 293 K). At such small (5 the theory given here for the hat-curved model holds. For calculation of the complex permittivity s (v) and absorption a(v), we use the same formulas as for water. 

It is now realized that OH and RO radicals in liquid solution have an extremely short relaxation time due to various strong perturbations of the ir-levels (129). Their spectra are therefore too broad for detection, and this fact should be kept in mind when analyzing a complex ESR spectrum produced by the peroxide photolysis technique. Liquid photolysis of organic amines and hydrazines and the reaction of NC>2 with liquid olefins are known to produce nitrogen radicals. However, there is often a... 

The conformational orientation between the excited CNA and CHD should be restricted very much to produce a photocycloadduct in the collision complex indicated in the scheme 1. In the fluid solvents like hexane, the rotational relaxation times of the solute molecules are rather fast compared to the reaction rate, which increases the escape probability of the reactants from the solvent cavity due to the large value of ko. On the other hand, the transit time in the reactive conformation, probably symmetrical face to face, may be longer in the liquid paraffin. This means that the observed kR may be expressed as a function of the mutual rotational relaxation time of reactants and the real reaction rate in the face-to-face conformation. In this sense, it is very important to make precise time-dependent measurements in the course of geminate recombination reaction indicated in Scheme 2, because the initial conformation after photodecomposition of cycloadduct is considered to be close to the face-to-face conformation. The studies on the geminate processes of the system in solution by the time resolved spectroscopy are now progress in our laboratory. 

In addition to the more usual application to solids, dielectric relaxation or dispersion measurements are also used on solutions (and pure liquids). Cook (425) related the relaxation mechanism in water-dioxane mixtures to the rupture of H bonds. Hasted and co-workers (890) found that water-dioxane mixtures had longer relaxation times as the dioxane proportion increased or the temperature was lowered. Both trends are explained by formation of a H bonded complex. Yasumi (2219) found similar effects when large amounts of hexane... 

Perhaps the most important distinction between classical solids and classical liquids is that the latter quickly shape themselves to the container in which they reside, while the former maintain their shape indefinitely. Many complex fluids are intermediate between solid and liquid in that while they maintain their shape for a time, they eventually flowr They are solids at short times and liquids at long times hence, they are viscoelastic. The characteristic time required for them to change from solid to liquid varies from fractions of a second to days, or even years, depending on the fluid. Examples of complex fluids with long structural or molecular relaxation times include glass-forming liquids, polymer melts and solutions, and micellar solutions. 

A dimensionless quantity called the Deborah number, De, is defined as the fluid s characteristic relaxation time t divided by a time constant tf characterizing the flow (Reiner 1964). Thus, De = t///. In an oscillatory shearing flow, for example, we might take tf to be the inverse of the oscillation frequency (o, and then De = xo). At high Deborah number, the flow is fast compared to the fluid s ability to relax, and the fluid will respond like a solid, to some extent. Thus, in an oscillatory shearing flow, when De = cur 3> 1 the complex modulus is solid-like, while when De = 1 a liquid-like terminal behavior is... 

The dielectric constant is a natural choice of order parameter to study freezing of dipolar liquids, because of the large change in the orientational polarizability between the liquid and solid phases. The dielectric relaxation time was calculated by fitting the dispersion spectrum of the complex permittivity near resonance to the Debye model of orientational relaxation. In the Debye dispersion relation (equation (3)), ij is the frequency of the applied potential and t is the orientational (rotational) relaxation time of a dipolar molecule. The subscript s refers to static permittivity (low frequency limit, when the dipoles have sufficient time to be in phase with the applied field). The subscript oo refers to the optical permittivity (high frequency limit) and is a measure of the induced component of the permittivity. 

Figure 1 shows the dielectric relaxation properties of the Tween microemulsions plotted on the complex permittivity plane (from Foster et al ( 1). The mean relaxation frequency (corresponding to the peak of each semicircle) decreases gradually from 20 GHz for pure water at 25°C to ca. 2 GHz for a concentrated microemulsion containing 20% water. Since the permittivity of the suspended oil/ emulsifier is 6 or less at frequencies above 1 GHz, this relaxation principally arises from the dipolar relaxation of the water in the system. Therefore, the data shown in Figure 1 clearly show that the dielectric relaxation times of the water in the microemulsions are slower on the average than those of the pure liquid. The depressed semicircles indicate a distribution of relaxation times (9), and were analyzed assuming the presence of two water components (free and hydration) in our previous studies. 

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