Newtonian determinism

Boltzmann s tombstone in Vienna bears the famous formula 5 = k log W (W = Wahrscheinlichkeit—probability) that was a signature of his audacious concepts. The alternative formula (13.69) (which reduces to Boltzmann s in the limit of equal a priori probabilities pa) was ultimately developed by Gibbs, Shannon, and others in a more general and productive way (see Sidebar 13.4), but the key step of employing probability to trump Newtonian determinism was his. Boltzmann was long identified with efforts to establish the //-theorem and Boltzmann equation within the context of classical mechanics, but each such effort to justify the second law (or existence of atoms) in the strict framework of Newtonian dynamics proved futile. Boltzmann s deep intuition to elevate probability to a primary physical principle therefore played a key role in efforts to find improved foundation for atomic and molecular concepts in the pre-quantum era. 

The friction coefficient determines the strength of the viscous drag felt by atoms as they move through the medium its magnitude is related to the diffusion coefficient, D, through the relation Y= kgT/mD. Because the value of y is related to the rate of decay of velocity correlations in the medium, its numerical value determines the relative importance of the systematic dynamic and stochastic elements of the Langevin equation. At low values of the friction coefficient, the dynamical aspects dominate and Newtonian mechanics is recovered as y —> 0. At high values of y, the random collisions dominate and the motion is diffusion-like. 

Of the models Hsted in Table 1, the Newtonian is the simplest. It fits water, solvents, and many polymer solutions over a wide strain rate range. The plastic or Bingham body model predicts constant plastic viscosity above a yield stress. This model works for a number of dispersions, including some pigment pastes. Yield stress, Tq, and plastic (Bingham) viscosity, = (t — Tq )/7, may be determined from the intercept and the slope beyond the intercept, respectively, of a shear stress vs shear rate plot. 

Polymer melts are frequendy non-Newtonian. In this case the earlier expression given for the shear rate at the capillary wall does not hold. A correction factor (3n + 1)/4n, called the Rabinowitsch correction, must be appHed in such a way that equation 21 appHes, where 7 is the tme shear rate at the wall and nis 2l power law factor (eq. 22) determined from the slope of a log—log plot of the tme shear stress at the wad, T, vs 7. For a Newtonian hquid, n = 1. A tme apparent viscosity, Tj, can be calculated from equation 23. 

A constant is often determined from measurements with a Newtonian oil, particularly when the caUbrations are suppHed by the manufacturer. This constant is vaUd only for Newtonian specimens if used with non-Newtonian fluids, it gives a viscosity based on an inaccurate shear rate. However, for relative measurements this value can be useful. Employment of an instmment constant can save a great deal of time and effort and increase accuracy because end and edge effects, sHppage, turbulent interferences, etc, are included. 

Controlled stress viscometers are useful for determining the presence and the value of a yield stress. The stmcture can be estabUshed from creep measurements, and the elasticity from the amount of recovery after creep. The viscosity can be determined at very low shear rates, often ia a Newtonian region. This 2ero-shear viscosity, T q, is related directly to the molecular weight of polymer melts and concentrated polymer solutions. 

OtherRota.tiona.1 Viscometers. Some rotational viscometers employ a disk as the inner member or bob, eg, the Brookfield and Mooney viscometers others use paddles (a geometry of the Stormer). These nonstandard geometries are difficult to analy2e, particularly for an infinite bath, as is usually employed with the Brookfield and the Stormer. The Brookfield disk has been analy2ed for Newtonian and non-Newtonian fluids and shear rate corrections have been developed (22). Other nonstandard geometries are best handled by determining iastmment constants by caUbration with standard fluids. 

Viscosity can also be determined from the rising rate of an air bubble through a Hquid. This simple technique is widely used for routine viscosity measurements of Newtonian fluids. A bubble tube viscometer consists of a glass tube of a certain size to which Hquid is added until a small air space remains at the top. The tube is then capped. When it is inverted, the air bubble rises through the Hquid. The rise time in seconds may be taken as a measure of viscosity, or an approximate viscosity in mm /s may be calculated from it. In an older method that is commonly used, the rate of rise is matched to that of a member of a series of standards, eg, with that of the Gardner-Holdt bubble tubes. Unfortunately, this technique employs a nonlinear scale of letter designations and may be difficult to interpret. 

Laminar and Turbulent Flow, Reynolds Number These terms refer to two distinct types of flow. In laminar flow, there are smooth streamlines and the fuiid velocity components vary smoothly with position, and with time if the flow is unsteady. The flow described in reference to Fig. 6-1 is laminar. In turbulent flow, there are no smooth streamlines, and the velocity shows chaotic fluctuations in time and space. Velocities in turbulent flow may be reported as the sum of a time-averaged velocity and a velocity fluctuation from the average. For any given flow geometry, a dimensionless Reynolds number may be defined for a Newtonian fluid as Re = LU p/ I where L is a characteristic length. Below a critical value of Re the flow is laminar, while above the critical value a transition to turbulent flow occurs. The geometry-dependent critical Reynolds number is determined experimentally. 

The following analysis can be used to determine economic pipe diameters for the turbulent flow of Newtonian fluids. The working expression that can be used is ... 

To constitute the We number, characteristic values such as the drop diameter, d, and particularly the interfacial tension, w, must be experimentally determined. However, the We number can also be obtained by deduction from mathematical analysis of droplet deforma-tional properties assuming a realistic model of the system. For a shear flow that is still dominant in the case of injection molding, Cox [25] derived an expression that for Newtonian fluids at not too high deformation has been proven to be valid ... 

Concrete calculations carried out via formula (10) for different values of constant have shown that it reflects the behavior of flow curves quite really. However, a series doubt remains for such a system (with a yield stress) it is not obvious how to determine the initial Newtonian viscosity (is it necessary to determine it and does it exist ). 

The branch of science which is concerned with the flow of both simple (Newtonian) and complex (non-Newtonian) fluids is known as rheology. The flow characteristics are represented by a rheogram, which is a plot of shear stress against rate of shear, and normally consists of a collection of experimentally determined points through which a curve may be drawn. If an equation can be fitted to the curve, it facilitates calculation of the behaviour of the fluid. It must be borne in mind, however, that such equations are approximations to the actual behaviour of the fluid and should not be used outside the range of conditions (particularly shear rates) for which they were determined. 

As indicated in Section 3.7.9, this definition of ReMR may be used to determine the limit of stable streamline flow. The transition value (R ur)c is approximately the same as for a Newtonian fluid, but there is some evidence that, for moderately shear-thinning fluids, streamline flow may persist to somewhat higher values. Putting n = 1 in equation 3,140 leads to the standard definition of the Reynolds number. 

Eor a dilnte aqneons solntion the mass average velocity is determined from the equation of motion for a Newtonian flnid, the Navier-Stokes eqnation,... 

The rheological characteristics of AB cements are complex. Mostly, the unset cement paste behaves as a plastic or plastoelastic body, rather than as a Newtonian or viscoelastic substance. In other words, it does not flow unless the applied stress exceeds a certain value known as the yield point. Below the yield point a plastoelastic body behaves as an elastic solid and above the yield point it behaves as a viscoelastic one (Andrade, 1947). This makes a mathematical treatment complicated, and although the theories of viscoelasticity are well developed, as are those of an ideal plastic (Bingham body), plastoelasticity has received much less attention. In many AB cements, yield stress appears to be more important than viscosity in determining the stiffness of a paste. 

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