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Rheology PDF
Rheology PDF
Rheology PDF
Miller et al 2005
Colloidal dispersions
~ 1 nm 10 m particles dispersed in a medium, typically a liquid Brownian motion
Uses of colloids
Phase behavior, dynamics and transport
Paints Coatings Polish Cosmetics Foods Carpet backing Inks Adhesives Films
A. P. Gast
A. van Blaaderen
Colloidal interactions
u(r)/kT
20 20
10
salt
2 3 4
10
0 2 3 4
r/a
-10
-10
-20
-20
Interactions among particles strongly affect macroscopic properties, like the rheology Can be used to tune the flow properties in a rational way!
Instrumentation
Rheometer Geometries
parallel plate
cone-plate
Couette
ex te ns io n
co m
pure rotation
pure strain
pr es s
io n
Flow curves
Newtons equation of viscosity
(linear) constitutive equation (all gases and most simple liquids)
. =
constant
water 1 mPa s
We use Newtons equation of viscosity but then the viscosity is a function of or Could try =1+2 +3 +...
.2
.3
. . =()
Flow curves
Newtonian plateau Shear thinning Typical flow curve for a colloidal dispersion
Pclet number
Two important mechanisms: displacement owing to Brownian motion and shear flow
time a2/D0 L
. .
= 60a3/kT
Pe is a dimensionless shear rate that gauges the importance of Brownian motion relative to shear forces
Pclet number
Example: effect of different solvents =0.5
I. Krieger
Pe takes care of the main effects of particle size, solvent viscosity, and temperature But, size, solvent, and temperature can produce additional effects through the interaction In general ... Pe1 Brownian motion dominates, close to equilibrium Pe1 Flow forces dominate, far from equilibrium
Pclet number
Example: effect of different solvents =0.5 /0
I. Krieger
60a3/kT Pe takes care of the main effects of particle size, solvent viscosity, and temperature But, size, solvent, and temperature can produce additional effects through the interaction In general ... Pe1 Brownian motion dominates, close to equilibrium Pe1 Flow forces dominate, far from equilibrium
Pclet number
Example: effect of different solvents
Pe takes care of the main effects of particle size, solvent viscosity, and temperature But, size, solvent, and temperature can produce additional effects through the interaction In general ... Pe1 Brownian motion dominates, close to equilibrium Pe1 Flow forces dominate, far from equilibrium
Shear thinning
Hard spheres
Foss and Brady, J. Fluid Mech (2000)
The arrangement of particles depends on Pe! It is very different at large Pe! Hydrodynamic interactions are important! Shear thinning is caused by particles adopting a more flow-oriented arrangement, very different from the equilibrium arrangement Total Brownian /0
The (relative) importance of Brownian motion decreases with increasing Pe, and it shows up in the viscosity as shear thinning Hydrodynamic
Pe
Shear thickening
Squeezing of thin solvent film, Force~1/(r-2a) To delay onset of shear thickening try keeping particles separated, e.g., by polymer grafting
Co mp res sio n
no hydrodynamic interaction Pe
Foss and Brady, J. Fluid Mech (2000)
Zero-shear viscosity
Hard spheres
/0
Low-shear viscosity
Newtonian plateau disappears! Viscosity (Pa s) Estimate for time scale of relaxation by Brownian motion, time a2/D0, is terribly poor at high concentration! Should be, time a2/Dcage, but Dcage the glass transition! 0 at
If we redefine Pe as, . (a2/Dcage)/ -1, then Pe remains very large . even if is small
Cage effect
Yield stress
Newtonian plateau disappears! Viscosity (Pa s)
. -1 ~
A yield stress can be defined at the glass transition, where the viscosity diverges and system becomes solid The dilemma: But what if we could measure at even lower shear rates? Would we find a Newtonian plateau?
Thixotropy
t amount of deformation
Gulik-Krzywicki et al. (1996) Bergenholtz & Wagner (1996)