Hydrogel Rheology
1
© Robert Pelton
References
Anseth, K. S.; Bowman, C. N.; Brannon Peppas, L.,
Mechanical properties of hydrogels and their experimental
determination. Biomaterials 1996, 17, (17), 1647-1657.
2
© Robert Pelton
Wh Gel Rheology
Why Rheolog
Classify gels
Identify gel point – characterizing gel formation
Compare
p gel
g strengths
g
3
© Robert Pelton
Rheological Meas
Measurements
rements
Cone-and-plate geometry
g y
– Uniform shear field across sample
– Small sample volumes
– Constant and oscillatory rotation
Major experimental controlled variables
– Rotational speed for steady flow
– Frequency and amplitude for oscillatory flow
Measure parameter – force on rotor or stator
Other issues
– Must control temperature
– Must worry about evaporation
– Must know area of contact
4
© Robert Pelton
E perimental Issues
Experimental Iss es With Gels
Weak gels can be destroyed by the measurement – a
destructive test.
Strong gels do not flow.
Usual approach – small amplitude oscillatory flow
– Gives both shear and storage modulus (explained later)
– May not destroy weak gels
5
© Robert Pelton
Viscosit Definitions
Viscosity
dυ υ top
t plate
l t velocity,
l it m/s
/
γ& = γ& shear rate, s-1
dx σ force on bottom plate/area, Pa
σ η viscosity,
η≡ i it Pa.s
P
γ&
η −ηo ηsp specific
η sp ≡
ifi viscosity
i it
ηo viscosity of water
η [η] intrinsic viscosity, m3/kg
⎛ η sp ⎞
[η ] ≡ limc→0 ⎜⎜ ⎟⎟
⎝ c ⎠
6
© Robert Pelton
Ideal Cases – 1.
1 The Ne
Newtonian
tonian Liquid
Liq id
σ Viscosity is independent of shear rate
η≡
γ&
Force is proportional to the rate of extension (shear
rate)
7
© Robert Pelton
Ideal Cases – 2.
2 The Ideal Elastic Solid
A F x − xo
σ= = E
x A xo
E elastic modulus,
mod l s Pa
F is force, N
area m2
A cross section area,
xo length at 0 force
F
Force is proportional to extension
8
© Robert Pelton
Ideal Cases – 3 The Hard Sphere
S
Suspension
i
Einstein Equation
Viscosity independent of particle size
and shape
η = η o (1+ 2.5φ )
Exercise – which is more viscous, at
50% (b
(by volume)
l ) suspension
i off bl
blood
d
cells or a 50% (by volume)
suspension of air bubbles?
ηo viscosity
iscosit of water
ater
φ volume fraction of
dispersed particles
9
© Robert Pelton
Interpreting Oscillatory
Oscillator Measurements
Meas rements
σ = γ o [G ' (ω )sin (ωt ) + G" (ω ) cos(ωt )]
σ =F/A shear stress,
stress Pa
For ideal
F id l solid:
lid
γo is maximum amplitude
(strain) – G’ = Go and G” =0
G’ storage (elastic) modulus,
G For Newtonian liquid;
Pa
Go elastic modulus of ideal – G’= 0, G”= ωη
(Hooke’s Law) solid
G’’ loss (viscous) modulus, Pa
ω Frequency
t time
10
© Robert Pelton
Pol mer Solutions
Polymer Sol tions vs
s Gels
Polymer Solution
– At low frequency:
o the chains have time to move and untangle
o Viscous dissipation more important
Polymer
Solution – At high frequency
o Entangled chains act as network connection
o Elastic forces dominate
Gel
– Elastic contribution greatest at all frequencies
Cross-linked
Gel
Ross-Murphy 1995
11
© Robert Pelton
E ample H
Example Hydroxypropyl
dro prop l Guar
G ar (HPG)
CH2 CH3
HO
O
OH
Water soluble, linear mannose
HO
O
OH
HO
OH
O
chains with single galactose
CH2 CH3
OH
HO O
OH HO
O
O branches
OH
O O O
O
OH HO
O O
OH HO
O
OH HO
O O
OH HO O O
O
High molecular weight – gives
CH2 CH3 viscous solutions
OH
Used in many products
including
c ud g for
o tertiary
te t a y oil
o recovery
eco e y
Hydroxypropyl groups added to
prevent spontaneous gel
formation
12
© Robert Pelton
HPG Steady
Stead Shear Behavior
Beha ior
100
Varying HPG Concentration
10
Viscosity increases with polymer
η s (Pas)
concentration
1
Viscosity constant a low shear rates
0.1
0.4 wt% 0.5 wt% (N t i b
(Newtonian behavior)
h i )
0.6 wt% 0.7 wt%
0.8 wt% 0.9 wt% Shear thinning
0.01 Can extrapolate to zero shear
0.001 0.01 0.1
shear rate (1/s)
1 10 100
viscosity ηo
viscosity,
10
0.6
0.4
Ln ( η 0) (Pas)
0.2
0
-0.2
-0.4
Varying Temperature
-0.6
-0.8
0.36 0.38 0.4 0.42 0.44 The higher the T,
T the lower the
η s (Pas)
1000/(RT) (mol/kJ)
1 viscosity.
Can fit to an Arrhenius expression
15 C
25 C
20 C
30 C
to get an activation energy
35 C 40 C
45 C 50 C
0.1
0.01 0.1 1 10 100 13
© Robert Pelton
shear rate (1/s)
HPG Oscillatory
Oscillator Behavior
Beha ior
10
Moduli decrease with
increasing temperature
1
1
G’ < G” typical of
G', G" (Pa)
G’ G” polymer solution
0.1 15 C 15 C
20 C 20 C
25 C 25 C
30 C 30 C
35 C 35 C
40 C 40 C
0.01
0 0 45 C 45 C
50 C 50 C
2
0.001
0.1 1 10 100
ω (rad/s)
14
© Robert Pelton
Cross linking HPG
Cross-linking HPGuar
ar with
ith Borate
HO
HO
O
Borate ion, B(OH)4- forms ester with
OH
O
HO
galactose units, forming a crosslink
A gel will be produced if enough cross-
- links form.
HO O
B O
HO O
OH
HO O
HO O
OH
O
O B O
O
O
- O
OH
HO O 15
© Robert Pelton
HG ar/Bora Gel - Temperature
HGuar/Borax Temperat re
100
15 C
20 C
25 C
10 30 C
35 C
At low T, G’ is ~ constant and
G' (Pa)
40 C
45 C
G’ >> G” – typical of a gel
1
50 C
Gel strength decreases with
G’
increasing temperature –
0.1 borate bonds are weak
0.1 1 10 100
10 ω (rad/s)
Exercise – why only oscillatory
15 C
20 C
measurements – why y not
25 C steady flow as well
G" (Pa)
1 30 C
35 C
40 C
G” 45 C
50 C
0.1
0.1 1 10 100
16
© Robert Pelton
ω (rad/s)
Borate Chemistry
Chemistr is Sensitive
Sensiti e to pH
pKa = 9.2 - Active
OH- + BOH3 <
<=>
> BOH4
Species
Borate is a buffer, at pH 9.2 half of boron species are borate.
At low pH concentration of borate is very low
17
© Robert Pelton
HPG ar/Borate – pH
HPGuar/Borate
100
7.95
8 08
8.08
10
8.31 Go is the high frequency limit
8.62
9.16 of G’
9.78
G' (Pa)
1 10.72 At high pH, G’>10 Pa, strong
G
1 11 46
11.46
12.17
12.42
gel
0.1
G’ 12.64
12.81
At pH 8, G’ is similar to HPG
2 13.09
alone, not a gel
0.01
0.1 1 10 100
25
25 C
ω (rad/s) We can tune gel properties
35 C
20
40 C by
y varying
y gp pH.
15
G0 (Pa)
10
5 Go
0
6 8 10 12 14 18
© Robert Pelton
pH
Rheolog of Microgel Suspensions
Rheology S spensions
Cone and p
plate geometry
g y
Uniform, controllable shear rates
Small sample volumes (1.2mL)
Factors affecting viscosity of microgel suspensions gel point
Volume fraction of particles
η
– Below gelation point – Einstein equation
– Above gelation point – interparticle lattice forces
φ
Drainage of liquid through particle (hard vs. soft colloids)
Shear rate of viscosity measurement
Low Shear High Shear
High friction to flow Particles ordered
through disordered parallel to flow
suspension 19
© Robert Pelton
E ample PNIPAM Microgel Rheology
Example Rheolog
ηo Batchelor eqn can be used to measure
= 1 + 2.5φ + 5.9φ 2 volume fraction and thus the degree of
ηw swelling
Valid up to 10% volume fraction
ηo zero shear viscosity
ηw viscosity
i it off water
t
Gels are shear thinning
Cross equation can be used to
calculate the zero shear viscosity, ηo
Senff, H.; Richtering, W., Temperature sensitive microgel suspensions: Colloidal phase behavior and rheology of soft spheres.
20
Journal of Chemical Physics 1999, 111, (4), 1705-1711. © Robert Pelton
C
Comparison
i with
ith Hard
H d Sphere
S h Suspensions
S i
Up to 45% microgels appear as hard
spheres
At very high volume fractions we
see the effect of deformable
particles
Senff, H.; Richtering, W., Temperature sensitive
microgel suspensions: Colloidal phase behavior and
rheology of soft spheres
spheres. Journal of Chemical Physics
1999, 111, (4), 1705-1711.
21
© Robert Pelton
S mmar – Gel Rheology
Summary Rheolog
Macrogels
– Oscillatory measurements give gel strength
– Can ggive the onset set off gelation
g
Microgels
– Behave as hard spheres until very high concentrations
– Good method to determine volume fraction which can be used to
calculate the degree of swelling
22
© Robert Pelton
http //
[Link]
papersci mcmaster ca
That’s It!
23
© Robert Pelton
***Peeling – Energy
Energ Analysis
Anal sis
24
© Robert Pelton
