Out-of-phase viscosity

Note 2 See Definition 5.22, note 6 rf = Mica may be used to evaluate the out-of-phase viscosity. 

Note 5 The complex viscosity is related to the dynamic and out-of-phase viscosities through the relationships... 

Equation 6.73 can be rewritten in yet a different form by introducing an in-phase viscosity t and out-of-phase viscosity t ". The real part t, the dynamic viscosity, represents the viscous contribution associated with energy dissipation. The imaginary part ti" represents the elastic contribution associated with energy storage. The shear stress can be written as a function of t and ti" as follows ... 

The imaginary component, "(f), is the dilational viscosity modulus. This arises when the demulsifier in the monolayer is sufficiently soluble in the bulk liquid, so that the tension gradient created by an area compression/expansion can be short circuited by a transfer of demulsifiers to and from the surface. It is 90° out of phase with the area change. 

Here t is the resulting shear stress, 6 is the phase shift often represented as tan(d), and (O is the frequency. The term 6 is often referred to as the loss angle. The in-phase elastic portion of the stress is To(cosd)sin(wt), and the out-of-phase viscous portion of the stress is To(sind)cos(complex modulus and viscosity, which can be used to extend the range of the data using the cone and plate rheometer [6] ... 

Figure 3.15 The frequency-dependent in-phase and out-of-phase components of the dynamic viscosity, rj and rj in small-amplitude oscillatory shear, along with the shear-rate dependence of the first normal stress coefficient hi (y) for a 0.05 wt% solution of polystyrene of molecular weight 2.25 X 10 in a solvent of oligomeric styrene. The lines through the data show the predictions of the Zimm theory for r and 2r)"f(o and the Zimm theory for hi(y) modified to account for finite extensibility, as discussed in Section 3.6.2.2.I. The dashed lines are the contributions of the individual Zimm relaxation modes to 2rj"((o) /

Through use of classical network theories of macromolecules, G has been shown to be proportional to crosslink density by G = nKT -i- Gen, where n is the nnmber density of crosslinkers, K is the Boltzmann s constant, T is the absolnte temperature, and Gen is the contribution to the modulus because of polymer chain entanglement (Knoll and Prud Homme, 1987). The loss modulus (G") gives information abont the viscous properties of the fluid. The stress response for a viscous Newtonian fluid would be 90 degrees out-of-phase with the displacement but in-phase with the shear rate. So, for an elastic material, all the information is in the storage modulus, G, and for a viscous material, aU the information is in the loss modulus, G". Refer to Eigure 6.2, the dynamic viscosities p and iT are defined as... 

The behavior of viscoelastic materials subjected to oscillatory perturbations may also be treated by generalizing the concept of viscosity (rather than modulus) and separating it into in-phase and out-of-phase components. Thus Newton s law for viscous fluids in shear, defined in equation (3-4) in Chapter 3, Section A, becomes... 

In these cases the relative velocity of the shearing plates is not constant but varies in a sinusoidal manner so that the shear strain and the rate of shear strain are both cyclic, and the shear stress is also sinusoidal. For non-Newtonian fluids, the stress is out of phase with the rate of strain. In this situation a measured complex viscosity (rf) contains both the shear viscosity, or dynamic viscosity (t] ), related to the ordinary steady-state viscosity that measures the rate of energy dissipation, and an elastic component (the imaginary viscosity ij" that measures an elasticity or stored energy) ... 

Out-of-phase component of complex viscosity Shear stress growth coefficient Shear stress decay coefficient Tensile stress growth coefficient Tensile stress decay coefficient... 

Pig. 1. (a) When a sample is subjected to a sinusoidal oscillating stress, it responds in a similar strain wave, provided the material stays within its elastic limits. When the material responds to the applied wave perfectly elastically, an in-phase, storage, or elastic response is seen (b), while a viscous response gives an out-of-phase, loss, or viscous response (c). Viscoelastic materials fall in between these two extremes as shown in (d). For the real sample in (d), the phase angle S and the amplitude at peak k are the values used for the calculation of modulus, viscosity, damping, and other properties. 

Most adsorbed surfactant and polymer coils at the oil-water (0/W) interface show non-Newtonian rheological behavior. The surface shear viscosity Pg depends on the applied shear rate, showing shear thinning at high shear rates. Some films also show Bingham plastic behavior with a measurable yield stress. Many adsorbed polymers and proteins show viscoelastic behavior and one can measure viscous and elastic components using sinusoidally oscillating surface dilation. For example the complex dilational modulus c obtained can be split into an in-phase (the elastic component e ) and an out-of-phase (the viscous component e") components. Creep and stress relaxation methods can be applied to study viscoelasticity. 

If the sample behaves as an ideal elastic solid, then the resulting stress is proportional to the strain amplitude (Hooke s Law), and the stress and strain signals are in phase. The coefficient of proportionality is called the shear modulus G. (7(f) = G 70 cos cot) If the sample behaves as an ideal fluid, then the stress is proportional to the strain rate, or the first derivative of the strain (Newton s Law). In this case, the stress signal is out of phase with the strain, leading it by 90f. The coefficient of proportionality is the viscosity tj. cr t) = tjcojo cos tot + n/2)... 

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