Rheology of Aqueous Clay

Suspensions

William M. Carty, Ph.D.

New York State College of Ceramics
at Alfred University

Whiteware Research Center

Oil Sands Extraction Fundamentals and Process Water Workshop
Canadian Oil Sands Network for Research and Development
May 8, 2001
 5 Factors Controlling
Suspension Rheology
v Particle-Particle Interactions
Colloidal Behavior
v Particle Concentration (Water Content)
v Particle Size and Distribution
v Particle Morphology
v Rheology of the Suspension Medium
 Outline
• Colloidal Nature of Kaolinite

• Dispersants with Kaolinite

ζ-Potential Measurements

• Behavior of 2:1 Sheet Silicates

• Ionic Strength Affects

 The Colloidal Nature of
Kaolinite
• 1:1 Sheet silicate

• Primary component of commercial clays

(Ball clays, kaolins, china clays)

• Formed from the decomposition of feldspar

• Variable degree of crystallization

 Historical View of a Kaolinite Particle
the “famous” gold particle experiments
P. A. Thiessen, "Wechselseitige Adsorption von Kolloiden,"
Ztachr. Elektrochem, 48 [12], 675-81 (1942).

“…it seems rather obvious

that the preferred edge
attachment of the gold
particles is the result of
mutual flocculation of the
negative gold particles
and the positive kaolinite
edges.”
H. van Olphen
 Prevailing Perspective
• Basal planes are similarly charged;
Edges are oppositely charged.
• Na+ is a dispersant
(folklore – particle surface is negative)

• Not consistent with mineralogy and

dispersant demand.
Mineralogy of
the common
sheet silicates
XRD results

Quartz
confirm

Kaolinite
mineralogy

Relative Intensity

Quartz
Montmorillonite
Mica
Ball Clay

D. M. Moore & R. C.
Reynolds, X-Ray Kaolin
Diffraction and the
Identification and
Analysis of Clay English Kaolin
Minerals, 2nd Ed., 5 10 15 20 25 30 35 40 45 50
Oxford University
Press. 2θ
 Morphology & Charge Distribution

Silica-like
basal plane
Isoelectric Points (IEP)
2L
8Alumina: 8.5-10.4
8Silica: 2.0-3.5
h
8Kaolinite: 3.0-5.0
Edge Alumina-like
basal plane

"Silica-like" surface
-
- - - - - - - - - - - - -+
+ Edge
-
- (neutral?)
+
+ + + + + + + + + + + + +
"Alumina-like" surface
Well-Crystallized Georgia Kaolin

2L

h
h=0.10(2L)
Surface Area of a Hexagonal Platelet
Total area

3 3 2 
A tot = A edge + 2A basal = 6hL + 2 (L )
 2 

Fraction of edge to basal plane surface area

A edge 12x h
f edge = = Where: x =
A tot 12 x + 3 3 2L

For fedge = 0.5 èè h = 0.866L

 Edge Surface Area Ratio

0.8
Edge Area:Total Surface Area

0.6

0.4

0.2

0.0
10-2 10-1 100
Aspect Ratio (h/2L)
Particle Dimensions: 2L
50% Edge & 50%
Basal Surfaces h
h=0.10(2L)

h=0.433(2L)
Basal-Plane Surface Area Ratios
0.6
One Basal Plane Surface Area/

0.5
Total Surface Area

0.4

0.3

0.2

0.1

0.0
10-2 10-1 100
Aspect Ratio (h/2L)
Results of SEM Measurements

Thickness, h 103 nm (±30nm)

Width, 2L 1.1 µm (±430nm)

Aspect ratio 0.095

fbasal 41%
Viscosity of Na-PAA on Kaolin and Alumina
(Corrected for SSA & pH)
Apparent Viscosity (1.0s-1; Pa·s)

101
Kaolin

100
Alumina

pH=8.5
10-1
0.0 0.2 0.4 0.6 0.8 1.0
Dispersant Level (mg/m2)
 Adsorption of Na-PAA
Na-PAA added (mg/m ) 0.4
pH=9.0
2

100% Adsorption
0.3

0.2
Al2O3

0.1
Kaolin
0.0 SiO2

0.0 0.2 0.4 0.6 0.8

PAA adsorbed (mg/m2)

 Adsorption of Na-PAA
Na-PAA added (mg/m ) 0.8
pH=6.0
2

0.6 100% Adsorption

0.4 Al2O3

0.2
Kaolin
0.0 SiO2

0.0 0.2 0.4 0.6 0.8 1.0 1.2

PAA adsorbed (mg/m2)

The surface area ratios
• Aspect ratio: 0.095 (roughly 1:10)
• Basal plane surface area = 82%
(41% for each surface)
• Edge surface area = 18%
pH=9.0 pH=6.0
Kaolin 0.066 (0.014) 0.167 (0.017)
Al2O3 0.161 (0.014) 0.400 (0.042)

Ratio 0.411 0.418

 Summary
• Kaolin adsorbs approximately 41% of
the amount of dispersant
compared to alumina.
• For an aspect ratio 1:10, the amount
of dispersant corresponds to the
coating of one basal plane.

There are two different basal plane

surfaces on Kaolinite.
Dispersants with Kaolinite

Dispersant Chemical Formula Abbreviation

Na-Poly Acrylic Acid H-(NaC3O2H3)n-H Na-PAA

Na-Poly Methacrylic Acid H-(NaC4O2H5)n-H Na-PMAA

Na-Hexametaphosphate (NaPO3)6 Na-HMP

Na-Silicate (x=0.22) xNa2O•(1-x)SiO2 Na-silicate

Na-Ash Na2CO3•10H2O Na-ash

Na-Silicate:Na-Ash Blend (1:1) as noted above 1:1

 Experimental Specifics
• Stock suspension diluted to appropriate
level with dispersant + water additions.
• pH measured but not adjusted.
• Viscosity measured in Stress-Controlled
rheometer (SR-200, Rheometrics Scientific).
• Measured from high rate to low rate.
Behavior of Commercial Dispersants

Apparent Viscosity (1.0 s-1, Pa•s) 40 vol.% Porcelain Batch

102

101
Na2CO3

PMAA
100
PAA

10-1
Na2SiO3 Na-HMP

10-2
0.0 0.1 0.2 0.3 0.4 0.5 0.6
2
Concentration of Dispersant (mg/m )
 ζ-Potential Measurements
• Acoustophoretic Mobility on kaolin
suspensions (not the porcelain batch).
• 5 v/o suspensions
• pH not adjusted, only measured as a
function of dispersant addition.
ζ-potential 0

versus pH -10

-20

Zeta Potential (mV)

-30 Na-Silicate

-40
Na-Ash
-50

-60 Na-PAA

-70
5 6 7 8 9 10
pH
 0
ζ-potential B.
-10
versus
[dispersant] -20

Zeta Potential (mV)

-30

-40 Na-Silicate

-50
Na-Ash
-60 Na-PAA
-70
0.0 0.2 0.4 0.6 0.8 1.0
2
Dispersant Concentration (mg/m )
1:1 versus 2:1 Sheet Silicates
• Seven commercial clays
Veegum T (90.26 m2/g) 3.0 v/o
VanGel (49.33 m2/g) 4.5 v/o
Wyoming Bentonite (31.74 m2/g) 4.5 v/o
Bentolite L (95.85 m2/g) 25 v/o
101 Ball Clay (15.61 m2/g) 26 v/o
401 Ball Clay (14.68 m2/g) 26 v/o
Marshall (24.01 m2/g) 26 v/o
• Effect of clay concentration
Target Viscosity at 1.0 s-1: 100 Pa·s
• Effect of dispersants
Na-PAA and Na-HMP
VeeGum T (Mg-Montmorillonite?)
Normalized Apparent Viscosity 101

Na+- PAA
100 Na-HMP

10-1

10-2

10-3
2
Specific Surface Area: 90.26 m /g
Solids Loading: ~ 3 vol.%
10-4
0.0 0.2 0.4 0.6 0.8 1.0
Dispersant Level (mg/m2)
Montmorillonite and Bentonite
Normalized Apparent Viscosity 101

100

10-1

10-2

Veegum T
10-3 Van Gel B
Wyoming Bentonite

10-4
0.0 0.2 0.4 0.6 0.8 1.0
Na+- Poly Acrylic Acid (mg/m2)
Bentonite (Bentolite L)
103
Normalized Apparent Viscosity
Specific Surface Area: 95.85 m2/g
Na+- PAA Solids Loading: ~ 25 vol.%
Na-HMP
102

101

100

10-1
0.0 0.2 0.4 0.6 0.8 1.0

Dispersant (mg/m 2)
Kaolin-Illite Mixtures (Indiana ball clays)
Normalized Apparent Viscosity 101

101 Clay
100 401 Clay
Marshall

10-1

10-2

10-3

10-4
0.0 0.2 0.4 0.6 0.8 1.0

Na+- Poly Acrylic Acid (mg/m2)

Kaolin-Illite Mixtures (Indiana ball clays)
101
Normalized Apparent Viscosity

101 Clay
100 401 Clay
Marshall

10-1

10-2

10-3

10-4
0.0 0.2 0.4 0.6 0.8 1.0

Sodium Hexametaphosphate (mg/m 2)

Effects of Ionic Strength
• Six salts were evaluated:
NaCl, CaCl2, MgCl2,
Na2SO4, CaSO4, MgSO4
• Salts were always added as
saturated solutions
• Porcelain Batch; 3 Dispersant levels
 105

CaCl2 Suspension: 30 vol% (distilled water)

Salt: CaCl2

APPARENT VISCOSITY (1.0 s , mPa·s)

2
0.00 mg/m
104

-1
2
0.02 mg/m
2
0.05 mg/m

103

102
Kaolin: 29.0 wt.%
Ball Clay: 7.0 wt.%
Quartz: 29.5 wt.%
Alumina: 12.5 wt.%
Neph. Syen.: 22.0 wt.%
101
10-2 10 -1 100 101 102 103
CATION CONCENTRATION (mMol/L)
Cation 105
Suspension: 30 vol% (distilled water)
Dispersion Level: 0.05 mg/m2

affects

APPARENT VISCOSITY (1.0 s , mPa·s)

CaCl2

only 104

-1
CaSO4

103

CaCl2
CaSO4 102
Kaolin: 29.0 wt.%
Ball Clay: 7.0 wt.%
Quartz: 29.5 wt.%
Alumina: 12.5 wt.%
Neph. Syen.: 22.0 wt.%
101
10-2 10-1 100 101 102 103
CATION CONCENTRATION (mMol/L)
 Divalent 105
Suspension: 30 vol% (distilled water)
2

8x Dispersion Level: 0.02 mg/m

APPARENT VISCOSITY (1.0 s , mPa·s)

NaCl
Monovalent 104

-1
MgCl2

CaCl2

103

102
Kaolin: 29.0 wt.%
Ball Clay: 7.0 wt.%
Quartz: 29.5 wt.%
Alumina: 12.5 wt.%
Neph. Syen.: 22.0 wt.%
101
10 -2 10-1 100 101 10 2 103
CATION CONCENTRATION (mMol/L)
 Coagulation occurs at a specific
double-layer thickness
(no significant specific adsorption of cations)
102

Apparent Viscosity (1.0 s , Pa·s)

Viscosity
-1
101
versus
Double- 100 NaCl
Layer MgSO4
CaSO4
Thickness 10-1

(via Debye-Hückel)
10-2
10-1 100 101 102
Double-Layer Thickness (nm)
 Summary and Conclusions
§ Kaolinite has oppositely charged basal
planes + neutral/positive edges.
§ Kaolin/Typical Porcelain Suspension
Anion species responsible for dispersion.
Na+, Ca+2, & Mg+2 cause coagulation.

§ ζ-potential does not always correlate

with dispersion. (Needs further study.)
 Acknowledgements

Hyojin Lee, Chris Caughel,

Mike Brumbach, Katherine Rossington,
Brian Sundlof, Pete Kupinski
Michele Hluchy
Whiteware Research Center