The Rheology Handbook. Thomas Mezger
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Название: The Rheology Handbook
Автор: Thomas Mezger
Издательство: Readbox publishing GmbH
Жанр: Химия
isbn: 9783866305366
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| Table 3.3: Regeneration of two coatings in terms of η(t) and in % (after a high-shear interval) | ||||
| Coating 1 | Coating 2 | |||
| η [Pas] | Reg. [%] | η [Pas] | Reg. [%] | |
| at the end of the first interval, at low-shear conditions; the reference value of the viscosity-at-rest | 15 | 100 | 30 | 100 |
| at the end of the second interval, at high-shear conditions | 0.5 | (3) | 1.0 | (3) |
| regeneration in the third intervalafter t = 30 safter t = 60 safter t = 120 s | 131415 | 8793100 | 41015 | 133350 |
Figure 3.42: Preset of a time-dependent shear rate profile consisting of three test intervals: upward ramp, high-shear phase, and downward ramp
3.4.2.2.7b) Flow curves and hysteresis area (for evaluating thixotropic behavior)
This testing and analysis method for determining thixotropic and rheopectic behavior is now outdated (DIN 53214 of 1982, meanwhile withdrawn). Nevertheless, it is still used in many industrial laboratories to carry out simple QC tests.
Preset
1 With controlled shear rate (CSR): profile γ ̇ (t), see Figure 3.42
2 With controlled shear stress (CSS): profile τ(t), similar to Figure 3.42
3.4.2.2.8Example 1: Preset of the shear rate
1st interval (shear rate ramp upwards, in t = 120 s): with γ ̇ = 0 to 1000 s-1
2nd interval (high-shear phase, for t = 60 s): at γ ̇ = 1000 s-1 = const
3rd interval (shear rate ramp downwards, in t = 120 s): with γ ̇ = 1000 to 0 s -1
Therefore here, the total test duration is t = 300 s.
Figure 3.43: Flow curves obtained when controlling the shear rate, showing a hysteresis area:
(1) with decreasing, and (2) with increasing structural strength when shearing
Figure 3.44: Flow curves obtained when controlling the shear stress, showing a hysteresis area: (1) with decreasing, and (2) with increasing structural strength when shearing
3.4.2.2.9Example 2: Preset of the shear stress
1st interval (shear stress ramp upwards, in t = 120 s): with τ = 0 to 2000 Pa
2nd interval (high-shear phase, for t = 60 s): at τ = 2000 Pa = const
3rd interval (shear stress ramp downwards, in t = 120 s): with τ = 2000 to 0 Pa
3.4.2.2.10Measuring result
1 With CSR: Flow curves τ( γ ̇ ) showing a hysteresis area, see Figure 3.43
2 With CSS: Flow curves γ ̇ (τ) showing a hysteresis area, see Figure 3.44
The area between the upward and downward curves in Figures 3.43 and 3.44 is called hysteresis area. Hysteros is a Greek word meaning later, and hysteresis literally is the dependence of a (physical) state on previous states [3.65]. In this case, we can interpret this term as a time-dependent loop or a loop which is influenced by time-dependent behavior. In the past, the terms thixotropic area or rheopectic area, respectively, were used. The thixotropic value was determined by the following procedure.
1 When presetting the shear rate, determination of the difference of the first area between the upward curve and the γ ̇ -axis, and the second area between the downward curve and the γ ̇ -axis: Samples for which a positive value of resulting area is obtained are termed thixotropic (no. 1), and those with a negative value are called rheopectic (no. 2).
2 When presetting the shear stress, evaluation of the difference of the first area between the downward curve and the τ-axis, and the second area between the upward curve and the τ-axis: Samples for which a positive area value is obtained are referred to as thixotropic (no. 1), and those with a negative value are named rheopectic (no. 2).
Note 1: Hysteresis area and shearing power
The shearing power which corresponds to the thixotropic structural decomposition, can be calculated as the product of the total amount of the area between the two measured flow curves and the sheared volume of the sample [3.69]:
P = [(τ ⋅ γ ̇ )1 – (τ ⋅ γ ̇ )2] ⋅ V
with τ [Pa], γ ̇ [s-1] and V [m3]. The resulting unit is 1 (Pa ⋅ m3) / s = 1 Nm/s = 1 J/s
It is, however, very optimistic to assume that all parts of the whole sample are sheared homogeneously, and therefore at a constant shear load or shearing power.
Comment: No undisturbed structure regeneration
Using the hysteresis area method, flow behavior is only determined in a state of motion, and thus, only in the phase of structural decomposition. This method does not reveal any information about structural regeneration at rest, since a state of rest is not part of the test method at all. This is why in current literature the analyzed hysteresis area no longer is referred to as the thixotropic area or rheopectic area, respectively. However, in most cases it is just the phase of regeneration which is important for practical users if leveling and sagging behavior after an application process of a coating has to be evaluated. As a consequence, it is therefore better to use the step test here, as explained above in Chapter 3.4.2.2a to determine thixotropic behavior [3.80].
Note 2: Hysteresis area, and different structural changes for ramps with increasing and decreasing shear rates
Suspensions may show different morphologies, not only depending on the shear rate, but also on the direction of the shear rate ramp. Example: (1) Ramp with increasing shear rates: Initially at rest or at low shear rates, the sample showed a homogeneous structure, and therefore, relatively high viscosity values. At intermediate shear rates a flocculated structure was produced, thus, loosely bound flocs and water-rich voids reduced the overall viscosity. (2) Ramp with decreasing shear rates: After reaching again the range of low shear rates, the flocculated structure differs from the initial structure showing relatively lower viscosity values now.
Example: Dependent on the shear rate range, micro- and nano-fibrillated cellulose materials (MFC, NFC), displayed alternating hysteresis areas with СКАЧАТЬ