11 - Latex Rheology

Latex Rheology
Professor José M. Asua
POLYMAT, University of the Basque Country UPV/EHU

Donostia-San Sebastián, Spain
September 10, 2014
Emulsion Polymerization Processes Course

September 2014, Donostia-San Sebastián
EASE 2005– Exciting And Simple Experiments, GRC (2005)

Coordinator: Dr Dieter Urban, BASF

shear stress : σ =
F
[Pa]
A
D
strain : γ =
H
shear rate : γ& =

D time v
H
=
H
[s ]
−1

Shear thickenning
σ21 Newtonian
(shear stress)
Shear thinning
η (viscosity)
• Concentrated slurries
• Concentrated starch suspensions
γ21 (shear rate)
• • Concentrated large particle size
monodispersed latexes
η
Shear thickenning
Newtonian • water
• milk
Shear thinning • latexes (paints, adhesives)

•γ • shampoo
21 • fruit juice concentrates

Bingham
σ21
Viscoplastic material
σ0
•γ
21

Thixotropy
•γ
21
η time
time
Time-dependent viscosity
These materials present three dimensional structure that breaks under shear rate
(yoghurt, mayonnaise, cottage cheese, drilling mud, some clays)

Thixotropy
thixotropic
Viscosity is lower because the fluid

is less structured and had no time to
rebuild the structure

Viscoelasticity
σ
Shear modulus
σ
time G (t ) =
γ
γ
time time

Modeling Viscoelasticity
Maxwell model
Spring (elastic)
Dashpot (viscous)

Modeling Viscoelasticity
Maxwell model
Spring (elastic)
Dashpot (viscous)


Solution vs. Dispersion
Solution viscosity Dispersion viscosity
• Concentration • Concentration
• Molecular weight • Particle size and size distribution
• Backbone stiffness • Particle shape
• Electrical charges • Electrical charges

• Adsorbed surface layer
• Shear rate • Shear rate
• Higher viscosity for a given polymer

volume fraction

Influence of the polymer volume fraction
1000
Relative viscosity
100
γ& = constant
10
1
0.1 0.2 0.3 0.4 0.5 0.6 0.7
Volume fraction
Exponential increase of the viscosity after reaching a critical

volume fraction. This limits the solids content attainable

Influence of the particle size distribution
1000
dp1=232 nm L1
dp2= 34 nm
100
L1/L2= 77/23 wt/wt
10
1
0.4 0.45 0.5 0.55 0.6 0.65
Volume Fraction
The small particles fill up the space between the large particles

Influence of the particle size distribution


Influence of the electrical charges
[Ionic species]
η
Less interaction between particles. Smaller
effective volume
E.J. Schaller, A. E. Humphrey, J. Colloid Interf. Sci. 22, 573 (1966)

Influence of the electrical charges
Ionic strength
Electrical double layer

(electrostatic potential)

Latexes containing carboxylic groups
Na+
Na+
Na+
COO-
-OOC
COOH COO-
HOOC Na+ Na+
+ NaOH
COOH
HOOC -OOC
COO-
COOH COO-
COOH Na+
HOOC
-OOC
COOH COO-
HOOC Na+
COOH COO-
Na+
Na+
Na+
Particles swelling is a function of:

• Acid content and distribution of the acid groups
• Degree of neutralization (pH)
• Crosslinking density
• Time

280
MA - 15
260 MA - 9
MA - 3
Particle size (nm)
240
220
200
180
2 4 6 8 10 12 14
pH
Polystyrene latexes with a MAA shell (wt%)
J. Sarobe, PhD dissertation, University of the Basque Country (2000)

Influence of the adsorbed layer


Particle size
Polystyrene latexes with nonionic surfactant.

Open symbols: raw data
Closed symbols: volume fraction adjusted for a 4.5 nm thick layer
Woods and Krieger, J. Colloid Int. Sci., 34, 91 (1970)

Influence of the particle shape
C.S. Chou et al., J. Coat. Tech. 59, 93 (1987)
Nonspherical particles might increase the effective volume fraction, leading to

to an increase in the viscosity in a rather broad range of shearing conditions

Influence of the particle shape
C.S. Chou et al., J. Coat. Tech. 59, 93 (1987)
For some applications, nonspherical particles allow the reduction in the level of thickener
required to adjust the viscosity.

Influence of aggregation
Aggregation of polymer particles might increase the viscosity by trapping water between
aggregated particles, increasing ϕ by transferring volume from the aqueous phase to the
dispersed phase.
1000
Relative viscosity
100
10
0.35 0.4 0.45 0.5 0.55 0.6 0.65

Volume fraction
V.M. Starov, V.G. Zhdanov XIII International Congress on Rheology, Cambridge, 2000.
On the other hand, limited particle flocculation might decrease the viscosity due to the formation
of bimodal PSDs.

Influence of solids content and shear rate
2EHA/MMA/AA 88/10/2 wt/wt

Influence of the shear rate and PSD
S-20% L-80%
S-50% L-50%
S-80% L-20% dp
0,02
Viscosity (Pa.s)
0,01
0,009
0,008 dp
0,007
500 1000 1500 2000 2500 3000
Shear rate (1/ s) f
dp

Influence of the solids content, shear rate and PSD

Influence of ionic strength and shear rate
E.J. Schaller, A. E. Humphrey, J. Colloid Interf. Sci. 22, 573 (1966)

Influence of the shear rate
0.07
0.018
Viscosity (Pa.s)
Viscosity (Pa.s)
Regular latex
0.05 0.017
Monodisperse
large particles
0.016
0.03 0.015
500 1000 1500 2000 2500 3000
Shear Rate (1/ s)
ϕ>50%) monodisperse latexes with large particle size often show

Concentrated (ϕ
a shear thickening behavior.
M.K. Chow, C.F. Zukoski, J. Rheology 39, 15 (1995)


η = f (ϕ , PDS , shear rate, emulsifier , pH , ionic strength )
Can all these effects be quantified?
Yes !, but using empirical equations

Accounting for the effect of the volume fraction
η = η0 (1 + 2.5ϕ )
Only very low solids
Einstein ηo: viscosity of the continuous
phase
− [η ]ϕ n
 ϕ  [η]: intrinsic viscosity
Krieger-Dougherty η = η 0 1 −
  ϕn: maximum volume fraction for
 ϕn
a given latex (packing fraction)

 
 
ϕ
Mooney η = η 0 exp [η] 
 ϕ 
 1 − 
 ϕn 

Intrinsic viscosity:: [η ] = limϕ →0 η r − 1

ϕ
1000
Relative viscosity
100
Packing fraction:
10
ϕn
Monodispersed latex:
1 ϕn = 0.63 random packing
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 ϕn = 0.68 body centered cubic
Volume fraction

Accounting for the effect of the volume fraction
1000 Experimental
Einstein
Krieger-Dougherty
Relative viscosity
Mooney
100
10
1
0.1 0.2 0.3 0.4 0.5 0.6
Volume fraction

Effective volume fraction
Particle size
∆
6∆
ϕ neff = ϕ n (1 + )
dp
− [η ]ϕ neff
 ϕ 

η = η 0 1 − 

 ϕ neff 

Accounting for the effect of the volume fraction and PSD
Krieger-Dougherty equation represents quite well the effect of the volume fraction
on the viscosity measured at a given shear rate for any PSD, provided that the value of ϕn
is estimated for that particular latex.
This limits its usefulness. Thus, it cannot be used to estimate the increase in viscosity during
a semicontinuous emulsion polymerization because both the solids content and the PSD
vary during the process.
Sudduth (R.D. Sudduth, J. Appl. Polym. Sci. 48, 25 (1993); 48, 37 (1993)) proposed an approach to
overcome this limitation.

− [η ]ϕ n
 
 
 ϕ  ϕ
η = η 0 1 −  η = η 0 exp [η] 
 ϕ 
 ϕn   1− 
 ϕn 
Krieger - Dougherty Mooney
dη
= [η ](1 − κϕ ) dϕ
−σ
η
Interaction coefficient
 η   [η ]ϕ n   ϕ n − ϕ 
1−σ
 
ln  =     − 1
 η0   σ − 1   ϕ n   Packing fraction
R.D. Sudduth, JAPS, 43, 37 (1993)

Packing fraction
 η   [η ]ϕ n   ϕ n − ϕ 
1−σ
 
ln  =     − 1
η
 0  σ − 1   ϕ n  
Random packing of spheres
ϕn.ult
Packing fraction
ϕm
1 Polydispersity

0.85
0.8 R=3.44
dp large
Packing fraction, ϕn
R=4.769
R=6.526 R=
0.75
R=11.27
R=16.53
dp small
0.7
0.65
0.6
0 20 40 60 80 100
Volume fraction of small particles
R.D. Sudduth, J. Appl. Polym. Sci. 48, 37 (1993)

0.9
0.85
Maximum packing fraction
  D5 
ϕ n = ϕ n ,ult − (ϕ n ,ult − ϕ m )exp α 1 −
0.8
0.75

  D1 
0.7
∑
0.65 x
ND
Dx = i i
0.6
10 20 30 40 50 60 70 80
Ratio of large to small diameter particles (R)
∑N D i i
x −1
α= 0.247
ϕm=0.639
ϕn,ult=0.857

Particle interaction coefficient
 η   [η ]ϕ n   ϕ n − ϕ 
1−σ

ln  =     − 1
 η0   σ − 1   ϕ n  
σ PC
Sudduth empirical equation: σ= + σs
D1
The smaller the particles the higher
the interaction
The distance between particles (h) decreases as dp decreases:
 ϕ  13 
h =  n  − 1 dp
 ϕ  
 

Assessment of the Sudduth equation using latexes of different sizes, PSDs and stabilized
with different surfactants
 η   [η ]ϕ n   ϕ n − ϕ 
1−σ
 1000
ln  =     − 1
RM14_01+RM05_01
RM14_01
 η0   σ − 1   ϕ n  
Relative Viscosity
100
1000 10
RM12_01
Relative Viscosity
RM12_01+RM05_01
100 0.4 0.45 0.5 0.55 0.6 0.65
Volume fraction
1000
10
RM23_01+RM05_01
RM23_01
Relative Viscosity
0.36 0.4 0.44 0.48 0.52 0.56 0.6 0.64 100
Volume fraction
10
M. do Amaral, S. van Es, J.M. Asua
J. Polym. Sci. A. Polym. Chem. 42, 3936 (2004)
36 40 44 48 52 56 60 64 68
Volume (%)

−1
2,2
−1
σ = 1,4849 + 13,719D R= 0,99379 σ = 1,6354 + 21,937D R= 0,99027
1 1
1,9 RM15_01 2,15
+RM05_01
RM22_01
2,1 +RM05_01
1,8 RM14_01
SIGMA
+RM05_01
SIGMA
2,05
1,7 2 RM22_01
+RM16_01
+RM05_01
RM15_01
1,95
1,6
RM22_01
1,9 +RM16_01
RM14_01 +RM05_01
1,5 1,85
0,005 0,01 0,015 0,02 0,025 0,03 0,012 0,016 0,02 0,024
-1 -1 -1 -1
D1 (nm ) D1 (nm )
σ PC
σ= + σs
D1 Formulation σpc (nm-1)
Intercept: σs Slope: σpc Non-ionic, anionic surfactant 7.4
Anionic surfactant 13.7

M. do Amaral, S. van Es, J.M. Asua
J. Polym. Sci. A. Polym. Chem. 42, 3936 (2004) Higher superficial [AA] 22.0
M. do Amaral,, J.M. Asua
Macromol Rapid Commun.25, 1883, (2004) Polymeric surfactant 75.3

Relative
Relative Viscosity ds (nm)
Viscosity ds (nm)
dl (nm)
dl (nm)
Volume fraction: 0.7 Volume fraction: 0.7

Weight proportion Large/Small: 95/5 Weight proportion Large/Small: 90/10
Relative
Viscosity ds (nm)
Volume fraction: 0.7

Weight proportion Large/Small: 80/20
dl (nm)

Polymerization model Viscosity equation
RM32_01/2 Simulation of the evolution RM32_01/2 - Simulation Results

time (min)
of the large and small particle size 0 50 100 150 200 250
650
140
Viscosity X TSC
640 120 Viscosity X time
Small seed (nm)
Relative Vis cosity

Large seed (nm)
100
630 100
80
620
60
610 10
40
600 20
0 50 100 150 200 250 45 50 55 60 65
time (min) Solids content (%)
M. do Amaral, S. van Es, J.M. Asua, Macromol. Theor. Simul., 13, 107 (2004)

Large Small
miniemulsion/dispersion miniemulsion/dispersion
Solids (wt %) Viscosity (mPa.s)
65.5 4300
67.7 150
70.4 2850

Is Sudduth equation enough?
Short answer: NO!

Accounting for the influence of the solids content and shear rate
ηr 0
η r 0 − η r∞
η r∞ ηr = ηr 0 +
1 + bσ r
log σ r
Limitations:
ηdp 3γ& η r 0 and η r∞
σr =
volume fraction dependence of
PSD not considered
kT
I.M. Krieger Adv. Colloid Interface Sci., 3, 111 (1972).

Accounting for the influence of the solids content and shear rate
2
 
ηγ& =0  
 1 + (τγ& )
p 
ηγ& =∞ η = η∞  0.5

  ηγ& =∞  
  + (τγ& ) 
p
  ηγ& =o  
γ&   
ηγ& =o = η0 (1 − 0.5koϕ )−2

τ, p, k o , k ∞ are parameters of the model
ηγ& =∞ = η 0 (1 − 0.5k∞ϕ )−2
Limitations: PDS not considered
Quemada D, Flaud P, Jezequel PH.. Chem. Eng. Commun. 1985;32:61-83

Accounting for the influence of the solids content, shear rate and PSD
Modified Sudduth equation
 η   [η ]ϕ n   ϕ n − ϕ 
1−σ

ln  =     − 1
 η0   σ − 1   ϕ n  
  D5 
ϕ n = 0.857 − (0.857 − 0.639) exp 0.2471 − 
  D1 
[ ] h ∝ [ϕ n − ϕ ] 3 D1
1
σ = k1 exp − k 2 hγ& k3

Accounting for the influence of the solids content, shear rate and PSD
A. Arevalillo et al. Ind. Eng. Chem Res. 45, 3280 (2006).

PVOH stabilized latexes
Effect of solids content
k1=2.34
k1=2.58
k2=1.0x10-2 and k3=0.45


Effect of PVOH concentration
10
9
η (mPas)
7
0
5
6 8 10 12 14 16 18 20 22
PVOH (phm)
k2=1.0x10-2 and k3=0.45

Effect of temperature
3,5
η (mPas)
2,5
0
1,5
0,5
0
10 15 20 25 30 35 40
T (ºC)
k2=1.0x10-2 and k3=0.45

Rheology modifiers
Commercial formulations (paints, inks, …) often require adjustment of viscosity or rheology

profile for suitable application properties.
Different shear rates
Conflicting requirements
sagging leveling brush marks
This adjustment is done by modifying the viscosity of the continuous medium by means
of rheology modifiers (thickeners).

Thickeners
Naturally derived
• Hydrophobically-modified cellulose ether (HMHEC)
Synthetic polymers
• Nonionic urethanes and polyols (HEUR)
• Hydrophobically-modified alkali soluble (HASE)
Hydrophobic part

Non-associative thickeners
Naturally derived
• Cellulose ethers (HEC, CMC, etc.)
• Other polysaccharides (alginates, guar, etc.)
Synthetic polymers
• Alkali soluble or swellable (usually acrylics)
• Nonionic (PVOH, PEO, etc.)
2.8
2.4
VAc/ BuA/ AA - 55% TSC - dp: 340 nm
2
Viscosity (Pa.s)
BuA/ St/ AA - 35% TSC - dp: 165 nm
1.6
1.2
0.8
0.4
0 0.04 0.08 0.12 0.16

kg of HEC/ kg of latex
R.E. Salazar, PhD dissertation, The University of the Basque Country (2002)

Latex Rheology – Selected references
General references
E. J. Schaller, In Emulsion Polymerization and Emulsion Polymers, M.S. El-Aasser, P.A. Lovell (Ed), John Wiley and
Sons, NY, (1997), Chapter 13
P.C. Hiemenz, R. Rajagolopan, Principles of Colloid and Surface Chemistry, Marcel Dekker Inc, NY, (1997), Chapter
4
R.M. Fitch, Polymer Colloids, Academic Press, San Diego, (1997) Chapter 10.
Viscosity equations, packing fraction

R.D. Sudduth, J. Appl. Polym. Sci. 48,
48 25 (1993); 48,
48 37 (1993)
I.M. Krieger, T.J. Dougherty, Trans. Soc. Rheol. 3, 137 (1959)
D.I. Lee, J. Paint Tech. 42, 579 (1970)
R.J. Farris, Trans. Soc. Rheol. 12, 281 (1968)
R.L. Hoffman, J. Rheol. 36, 947 (1992)
M. do Amaral, S. van Es, J.M. Asua, J. Polym. Sci. A. Polym. Chem. 42, 3936 (2004)
A. Arevalillo et al. Ind. Eng. Chem Res. 45, 3280 (2006).
Rheology of concentrated emulsions

D. Quemada, Prog. Colloid Poylm. Sci. 79, 112 (1989)
Viscosity of emulsions
Heyes, D.M.; Sigurgeirsson, H. J. Rheol.48, 223 (2004)
New techniques for the study of rheological behavior of emulsions

M. Wilhelm, Macromol. Mater. Eng. 287, 83 (2002)
Thickening of acid-containing polymer latexes

C.J. Vergrugge, J. Appl. Polym. Sci. 14, 897 (1970), 14, 911 (1970)


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Latex Rheology

Professor José M. Asua

POLYMAT, University of the Basque Country UPV/EHU

September 10, 2014

Emulsion Polymerization Processes Course

EASE 2005– Exciting And Simple Experiments, GRC (2005)

Emulsion Polymerization Processes Course

shear rate : γ& =

Emulsion Polymerization Processes Course

Shear thinning • latexes (paints, adhesives)

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Viscosity is lower because the fluid

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

EASE 2005– Exciting And Simple Experiments, GRC (2005)

Emulsion Polymerization Processes Course

Solution viscosity Dispersion viscosity

• Molecular weight • Particle size and size distribution

• Backbone stiffness • Particle shape

• Electrical charges • Electrical charges

• Shear rate • Shear rate

• Higher viscosity for a given polymer

Emulsion Polymerization Processes Course

Influence of the polymer volume fraction

Exponential increase of the viscosity after reaching a critical

Emulsion Polymerization Processes Course

L1/L2= 77/23 wt/wt

Emulsion Polymerization Processes Course

Influence of the particle size distribution

EASE 2003– Exciting And Simple Experiments, GRC (2003)

Emulsion Polymerization Processes Course

E.J. Schaller, A. E. Humphrey, J. Colloid Interf. Sci. 22, 573 (1966)

Emulsion Polymerization Processes Course

Influence of the electrical charges

Electrical double layer

Emulsion Polymerization Processes Course

Particles swelling is a function of:

Emulsion Polymerization Processes Course

J. Sarobe, PhD dissertation, University of the Basque Country (2000)

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Influence of the adsorbed layer

Emulsion Polymerization Processes Course

Polystyrene latexes with nonionic surfactant.

Woods and Krieger, J. Colloid Int. Sci., 34, 91 (1970)

Emulsion Polymerization Processes Course

Influence of the particle shape

C.S. Chou et al., J. Coat. Tech. 59, 93 (1987)

Nonspherical particles might increase the effective volume fraction, leading to

Emulsion Polymerization Processes Course

C.S. Chou et al., J. Coat. Tech. 59, 93 (1987)

Emulsion Polymerization Processes Course

0.35 0.4 0.45 0.5 0.55 0.6 0.65

Emulsion Polymerization Processes Course

Influence of solids content and shear rate

2EHA/MMA/AA 88/10/2 wt/wt

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Influence of the solids content, shear rate and PSD