Viscosity empirical

Finally a phenomenon should be mentioned which polymer solutions show more often than polymer melts viz. a second Newtonian region. This means that with increasing shear rate the viscosity at first decreases, but finally approaches to another constant value. As the first Newtonian viscosity is denoted by rjor the symbol // x, is generally used for the second Newtonian viscosity. Empirical equations as those presented in Chap. 15 now need an extra term r oo to account for this second Newtonian region. This leads to ... 

Melt viscosity Dynamic or steady-state viscosity Empirical correlation of viscosity and Mw - ... 

The viscosity index is an empirical number, determined from the kinematic viscosities at 40 and 100°C it indicates the variation in viscosity with temperature. 

Incorporation of viscosity variations in non-elastic generalized Newtonian flow models is based on using empirical rheological relationships such as the power law or Carreau equation, described in Chapter 1. In these relationships fluid viscosity is given as a function of shear rate and material parameters. Therefore in the application of finite element schemes to non-Newtonian flow, shear rate at the elemental level should be calculated and used to update the fluid viscosity. The shear rale is defined as the second invariant of the rate of deformation tensor as (Bird et at.., 1977)... 

Figure 2.5 shows some actual experimental data for versus 7, measured on a sample of polyethylene at 126°C. Note that the data are plotted on log-log coordinates. In spite of the different coordinates. Fig. 2.5 is clearly an example of pseudoplastic behavior as defined in Fig. 2.2. In this and the next several sections, we discuss shear-dependent viscosity. In this section the approach is strictly empirical, and its main application is in correcting viscosities measured...

When m = 1.0, as in Fig. 2.5, the exponent becomes zero and the viscosity is independent of 7 when m = 0.7, a factor of 10 change in 7 results in a decrease of viscosity by a factor of 2. This is approximately the case for the data in Fig. 2.5 for 7 values between 10" and 10" sec". Equation (2.14) and its variations are called power laws. Relationships of this sort are valuable empirical tools for extrapolating either F/A or t over modest ranges of 7. In such an application, the exponent m - 1 and the proportionality constant are... 

Figure 2.5 reveals that polymer viscosity approaches Newtonian behavior for sufficiently low rates of shear. From an empirical point of view, this simply means that m 1 as 7 0. From a molecular point of view, in the region of... 

A basic theme throughout this book is that the long-chain character of polymers is what makes them different from their low molecular weight counterparts. Although this notion was implied in several aspects of the discussion of the shear dependence of viscosity, it never emerged explicitly as a variable to be investi-tated. It makes sense to us intuitively that longer chains should experience higher resistance to flow. Our next task is to examine this expectation quantitatively, first from an empirical viewpoint and then in terms of a model for molecular motion. 

Inspection of Fig. 3.9 suggests that for polyisobutylene at 25°C, Ti is about lO hr. Use Eq. (3.101) to estimate the viscosity of this polymer, remembering that M = 1.56 X 10. As a check on the value obtained, use the Debye viscosity equation, as modified here, to evaluate M., the threshold for entanglements, if it is known that f = 4.47 X 10 kg sec at this temperature. Both the Debye theory and the Rouse theory assume the absence of entanglements. As a semi-empirical correction, multiply f by (M/M. ) to account for entanglements. Since the Debye equation predicts a first-power dependence of r) on M, inclusion of this factor brings the total dependence of 77 on M to the 3.4 power as observed. 

In discussing Fig. 4.1 we noted that the apparent location of Tg is dependent on the time allowed for the specific volume measurements. Volume contractions occur for a long time below Tg The lower the temperature, the longer it takes to reach an equilibrium volume. It is the equilibrium volume which should be used in the representation summarized by Fig. 4.15. In actual practice, what is often done is to allow a convenient and standardized time between changing the temperature and reading the volume. Instead of directly tackling the rate of collapse of free volume, we shall approach this subject empirically, using a property which we have previously described in terms of free volume, namely, viscosity. 

The viscosity of a polymer solution is one of its most distinctive properties. Only a minimum amount of research is needed to establish the fact that [77] increases with M for those polymers which interact with the solvent to form a random coil in solution. In the next section we shall consider the theoretical foundations for the molecular weight dependence of [77], but for now we approach this topic from a purely empirical point of view. 

Rheology. Flow properties of latices are important during processing and in many latex appHcations such as dipped goods, paint, inks (qv), and fabric coatings. For dilute, nonionic latices, the relative latex viscosity is a power—law expansion of the particle volume fraction. The terms in the expansion account for flow around the particles and particle—particle interactions. For ionic latices, electrostatic contributions to the flow around the diffuse double layer and enhanced particle—particle interactions must be considered (92). A relative viscosity relationship for concentrated latices was first presented in 1972 (93). A review of empirical relative viscosity models is available (92). In practice, latex viscosity measurements are carried out with rotational viscometers (see Rpleologicalmeasurement). 

APHA color (269) is usually one of the specifications of PTMEG, sometimes viscosity is another (270). Melt viscosity at 40°C is often used as a rough measure of the molecular weight distribution within a narrow molecular weight range. Sometimes an empirical molecular weight ratio,... 

A viscoelastic material also possesses a complex dynamic viscosity, rj = rj - - iv( and it can be shown that r = G jiuj-, rj = G juj and rj = G ju), where CO is the angular frequency. The parameter Tj is useful for many viscoelastic fluids in that a plot of its absolute value Tj vs angular frequency in radians/s is often numerically similar to a plot of shear viscosity Tj vs shear rate. This correspondence is known as the Cox-Merz empirical relationship. The parameter Tj is called the dynamic viscosity and is related to G the loss modulus the parameter Tj does not deal with viscosity, but is a measure of elasticity. 

Spray Correlations. One of the most important aspects of spray characterization is the development of meaningful correlations between spray parameters and atomizer performance. The parameters can be presented as mathematical expressions that involve Hquid properties, physical dimensions of the atomizer, as well as operating and ambient conditions that are likely to affect the nature of the dispersion. Empirical correlations provide useful information for designing and assessing the performance of atomizers. Dimensional analysis has been widely used to determine nondimensional parameters that are useful in describing sprays. The most common variables affecting spray characteristics include a characteristic dimension of atomizer, d Hquid density, Pjj Hquid dynamic viscosity, ]ljj, surface tension. O pressure, AP Hquid velocity, V gas density, p and gas velocity, V. ... 

This equation is based on the approximation that the penetration is 800 at the softening point, but the approximation fails appreciably when a complex flow is present (80,81). However, the penetration index has been, and continues to be, used for the general characteristics of asphalt for example asphalts with a P/less than —2 are considered to be the pitch type, from —2 to +2, the sol type, and above +2, the gel or blown type (2). Other empirical relations that have been used to express the rheological-temperature relation are fluidity factor a Furol viscosity P, at 135°C and penetration P, at 25°C, relation of (H—P)P/100 and penetration viscosity number PVN again relating the penetration at 25°C and kinematic viscosity at 135 °C (82,83). 

EmpiricalEfficieny Prediction Methods. Numerous empirical methods for predicting plate efficiency have been proposed. Probably the most widely used method correlates overall column efficiency as a function of feed viscosity and relative volatiHty (64). A statistical correlation of efficiency and system variables has been developed from numerous plate efficiency data (65). 

Ertl and DuUien [ibid.] found that Hildebrand s equation could not fit their data with B as a constant. They modified it by applying an empirical exponent n (a constant greater than unity) to the volumetric ratio. The new equation is not generally useful, however, since there is no means for predicting /i. The theory does identify the free volume as an important physical variable, since n > for most hquids implies that diffusion is more stronglv dependent on free volume than is viscosity. 

Additives can alter the rate of wet ball milling by changing the slurry viscosity or by altering the location of particles with respect to the balls. These effects are discussed under Tumbhng Mills. In conclusion, there is still no theoretical way to select the most effective additive. Empirical investigation, guided by the principles discussed earlier, is the only recourse. There are a number of commercially available grinding aids that may be tried. Also, a Idt of 450 surfactants that can be used for systematic trials (Model SU-450, Chem Service... 

Using the Stokes-Einstein equation for the viscosity, which is unexpectedly useful for a range of liquids as an approximate relation between diffusion and viscosity, explains a resulting empirical expression for the rate of formation of nuclei of the critical size for metals... 

As in die case of die diffusion properties, die viscous properties of die molten salts and slags, which play an important role in die movement of bulk phases, are also very stiiicture-seiisitive, and will be refeiTed to in specific examples. For example, die viscosity of liquid silicates are in die range 1-100 poise. The viscosities of molten metals are very similar from one metal to anodier, but die numerical value is usually in die range 1-10 centipoise. This range should be compared widi die familiar case of water at room temperature, which has a viscosity of one centipoise. An empirical relationship which has been proposed for die temperature dependence of die viscosity of liquids as an AiTlienius expression is... 

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