School of Engineering

Swansea University

VISCOSITY OF COLLOIDAL SILICA SOLUTIONS

Report Written By:__________

Summary Written By:___________
Date of Experiment: 10th January 2010

SUMMARY
Knowledge of how the viscosity of colloidal solutions varies with concentration is important
for many industrial and medical applications. In this report the viscosity of charged colloidal
silica (surface charge = -76 mV) in a 0.03M NaCl electrolyte solution at pH 9.0 at various
solution concentrations was investigated. The viscosity was measured using a capillary flow
method. The capillary flow method is still the most frequently employed method for
measuring viscosities. In order to use the capillary flow method, density measurements of the
dispersions used were also required. The experiments showed that the density of the colloid
solution could be related to the volume fraction of silica particles present by the following
equation:
o (1 0.8046)

where is the density of the dispersion, o is the density of the pure solvent and the volume
fraction of silica particles present.

The measured viscosity was found to conform to the Kreiger-Doherty equation:

1
o m

[ ] m

where is the viscosity of the dispersion, o is the viscosity of the pure solvent, [] is the
intrinsic viscosity and m is the maximum packing fraction.
For uncharged hard spheres, [] = 2.5 and m is 0.74, however for the charged silica spheres
used here [] = 7.9965 and m was 0.1468. This shows that the surface charge has a big effect
on the viscosity of colloidal solutions.

TABLE OF CONTENTS
Page

SUMMARY

TABLE OF CONTENTS

LIST OF FIGURES

LIST OF TABLES

1.0 INTRODUCTION

1.1 Aims

2.0 THEORY
2.1 Deviations away from Einsteins Law

9
10

2.1.1 Effect of particle concentration

10

2.1.2 Effect of particle-particle interactions

11

3.0 MATERIALS AND METHODS

13

3.1 Materials

13

3.2 Solution Density Measurement

13

3.3 Solution Viscosity Measurement

14

4.0 RESULTS

18

4.1 Silica Stock Solution Concentration

18

4.2 Density Measurements

18

4.3 Viscosity Measurements

20

5.0 DISCUSSION

23

5.1 Silica Stock Solution Concentration

23

5.2 Density Measurements

24

5.3 Viscosity Measurements

25

6.0 CONCLUSIONS

27

7.0 NOMENCLATURE

28

8.0 REFERENCES

29

APPENDIX 1

30

APPENDIX 2

31

LIST OF FIGURES
Figure No.

Title

Page

2.1

The effect of concentration on viscosity

11

2.2

Measured viscosity for concentrated charged silica spheres

12

3.1

Pyknometer for measuring solution density

14

3.2

Schematic diagram of Viscometer Bath

15

3.3

U-tube viscometers for direct flow (BS 188 (1977))

16

4.1

Dispersion density versus volume fraction for silica dispersions

at pH 9 in 0.03M NaCl
Plot to determine the intrinsic viscosity of the silica dispersion at
pH 9.0 in 0.03M NaCl
Plot to determine the maximum packing fraction of the silica
dispersion at pH 9.0 in 0.03M NaCl

20

4.2
4.3

21
22

LIST OF TABLES
Table No.

Title

Page

4.1

Experimental data for the concentration of stock silica solution

18

4.2

Fixed parameters for density measurements

18

4.3

19

5.1

Experimental determination of the density of colloidal silica

solutions
Experimental determination of the viscosity of colloidal silica
solutions
Error on Weight %.

5.2

Error in viscosity measurements at 25C

25

Relationship between concentration, weight % and volume

fraction
Experimental determination of the viscosity of colloidal silica
solutions

30

4.4

A1.1
A2.1

20
24

31

1.0 INTRODUCTION
Rheology is the science of the deformation of flow of matter. It is a subject of tremendous
and increasing technological importance being involved in processing operations in industry
and medicine e.g. rubber, plastics, food, paint, textiles, heamatology, blood. The rheological
behaviour of process streams and dispersions determines (Shaw, 1992):
the pumping and transportation costs,
the ease of mixing operations in reactors
the quality of the final product in many cases
Materials in a colloidal state (size range 1 nm 1 m) are frequently preferred in industrial
processing because their large surface areas per unit volume enhance chemical reactivity,
adsorptive capacity, heat transfer rate etc. (Hunter, 1993). Therefore, one cannot overlook the
importance of the flow behaviour and properties of colloids since they exert a significant
influence on the performance, efficiency and economy of the process, some examples of this
include ceramic processing, electrophoretic display devices and food colloids (chocolate). In
addition, one often uses the flow properties and behaviour of the products as measures of
(Hunter, 1993):
the microstructure (or morphology) of the products
as a means of quality control (e.g. printing inks, toners, paints, skin cream, blood
substitutes, gels used as drug delivery systems etc.)
even to ensure consumer appeal and marketability of the products

Rheology is also one of the factors that determine the esthetic and sensual appeal of certain
products, especially in the case of food and cosmetics. Differences in the feel of a face lotion
or skin cream or the consistency of a ketchup can make or break the market for a product
(Hunter, 1993).

From a technical standpoint colloids display a wide range of rheological behaviour. The most
straightforward rheological behaviour is exhibited by Newtonian viscous fluids and by
Hookean elastic solids. However, most materials, particularly those of a colloidal nature,

exhibit mechanical behaviour which is intermediate between these two extremes, with both
viscous and elastic characteristics in evidence, such materials are termed viscoelastic.

1.1 Aims
The aims of the experiment are as follows:

(i)

To measure the viscosity of dispersions of colloidal silica at various

concentrations

(ii)

To measure the density of the same dispersions

(iii)

To fit the data to established correlations to obtain the appropriate parameters to

describe the viscosity for these dispersions

2.0 THEORY
The first derivation for an expression for the viscosity of a dilute dispersion of solid spheres
was published by Einstein (1906). The initial theory contained errors that were corrected in a
subsequent paper (Einstein, 1911). The Einstein derivation was based on the following
assumptions:

and for the fluid are constant

the flow velocity is low

the concentration of particles is low

no slippage of liquid at the surface of the particles occurs

the size of the particles >> size of the solvent molecules

the particles are identical, non-interacting, rigid, spheres

there is no ordering in the system

The hydrodynamic calculation relating to the disturbance of flow lines when identical, noninteracting, rigid, spherical particles are dispersed in a liquid medium resulted in (Einstein,
1906, 1911):

1 / 2

1 (1 2 ) 2
o (1 ) 2 2

(2.1)

where is the viscosity of the dispersion, o is the viscosity of the pure solvent and is the
volume fraction of particles in the dispersion.
If no term higher than the first order in are retained, then Equation (2.1) becomes:

1 2.5
o

(2.2)

Thus plotting /o versus for low values of (i.e. < 0.1) will result in a straight line with
a gradient of 2.5. The coefficient 2.5 is termed the intrinsic viscosity and is given the symbol
(Barnes et al. 1989)

2.1 Deviations away from Einsteins Law

The rheological behaviour of colloidal dispersions depends on many factors including
(Barnes et al. 1989):

Viscosity of the dispersion medium

Particle concentration

Particle size and shape

Particle-particle and particle-dispersion medium interactions

Particle swelling due to solvation

The general expression for Einsteins Law is:

1 []
o

(2.3)

Deviations away from Equation (2.3) will occur due to (Barnes et al. 1989):

1. An increase in particle concentration (the law was formulated for dilute systems)
2. A change in particle shape (the law was formulated for spherical particles)
3. Particle-particle and particle-dispersion medium interactions (the law was formulated
for uncharged particles)

2.1.1 Effect of particle concentration

Einsteins Law (Equation (2.3)) only applies at low volume fractions (i.e. < 0.1). For higher
volume fractions recourse has been made to empirical fits to data measured at these higher
concentrations. The first expression tried was an expansion of Einsteins Law which takes
into account higher order values of (Hiemenz, P.C. and Rajagopalan R., 1997):

1 2.5 k1 2
o

(2.4)

This equation is adequate but still does not give good agreement at high . However, in spite
of many recent works, including theoretical, experimental and numerical approaches, the

10

prediction of the viscosity of concentrated suspensions is still poorly achieved (Allain,

Cloitre, Lacoste & Marsone, 1994). Hence, correlations have been used to describe the
viscosity of concentrated hard spheres, the most commonly accepted being that of Krieger
and Dougherty (Krieger, 1972),

1
o m

[ ] m

(2.5)

For hard sphere systems: [] = 2.5, and m = 0.74 (for face centred cubic (f.c.c) packing).

Figure 2.1: The effect of concentration on viscosity. The dotted line is Einsteins Law
(Equation (2.2)) and the points are experimental data (taken from Hunter (1993)).

2.1.2 Effect of particle-particle interactions

For hard spheres the value of the intrinsic viscosity is precisely calculated as 2.5 (Krieger,
1972). Most substances, in general develop a surface charge when placed in an aqueous
solution (Hunter, 1993). The presence of electrical charges on the particles causes an
augmentation of the intrinsic viscosity. This effect can be calculated theoretically (the
currently accepted theoretical model being that of Booth (1950)), but it may also be
determined experimentally by measuring the viscosity of a range of dilute solutions and
11

plotting a graph of o - 1 versus . This results in a straight line passing through the origin
with a gradient which is equal to the intrinsic viscosity.

Figure 2.2: Measured viscosity for concentrated charged silica spheres. The fitting
parameters here are [] = 3.17 and m = 0.631, using the Krieger-Dougherty Equation,
(taken from Hunter (1993)).

From Figure 2.2, it can be seen that the electrostatic interactions in this case have altered both
the intrinsic viscosity ([] has changed from 2.5 for hard spheres to 3.17) and the maximum
packing fraction (m has changed from 0.74 for hard spheres to 0.631).

12

3.0 MATERIALS AND METHODS

3.1 Materials
Sodium chloride electrolyte solutions were made by dissolving a weighed amount of sodium
chloride, obtained from Fisher Scientific Equipment (Grade:- Fisher AR), in high purity
water (produced by reverse osmosis, ion exchange, carbon adsorption and then
microfiltration) to make a solution of ionic strength 0.2M. This solution was kept as a stock
solution, from which sodium chloride solutions of varying ionic strength could be obtained
by dilution with more high purity water.

The colloid used was LUDOX SM-30 colloidal silica (purchased from Sigma Chemical Co.).
This came as a liquid dispersion with the following properties: concentration 30 % by
weight, dispersion medium 0.03M NaCl solution at pH 9.0, particle diameter 22 nm,
particle surface potential -76mV. The exact concentration of this stock solution was
determined in the following manner. Five petri dishes were taken and weighed using an
electronic balance (Mettler Toledo P303 Delta Range, accurate to 0.001g). A known
amount of the stock silica solution was then added to each petri dish. The dishes were then
placed in an oven set at 120C and left over night to dry. The dishes were then weighed again
the following day and the difference between this new weight and the clean petri dish weight
was found. This corresponds to the mass of dry silica in the solution. The weight % was then
found by dividing the weight of dry silica by the total solution weight. Finally, the average
value of the five measurements was taken and used subsequently as the concentration of the
stock silica solution. Dilutions of this stock solution were made by adding known amounts of
0.03M NaCl at pH 9.0 to a known mass of the stock solution.

3.2 Solution Density Measurement

The density of a solution can be determined by using the method described in BS 4522
(1988). The recommendation is made that the bath and thermometers used for determination
of kinematic viscosity (see Section 3.3) should also be used for the determination of density.

A clean dry pyknometer flask with its stopper (see Figure 3.1) was weighed to the nearest
0.001 g using the balance described in Section 3.1. The flask was then filled with high purity
water and the mass of the flask plus the contents was determined, after previously being

13

brought to 25 0,1 C in the water bath. The flask was then cleaned and dried and filled with
the sample to be tested. This was again weighed to determine its mass after being brought
again to 25 0,1 C. The density of the sample was then calculated using:

m A
o
1
m2 A

(3.1)

where m1 is the apparent mass, in grams, of sample required to fill the flask at 25 C, m2 is
the apparent mass, in grams, of water required to fill the flask at 25 C, o is the density of
water at 25 C (= 0.9970 g/mL) and A is the buoyancy correction given by
A = a m2

(3.2)

where a is the density of air at 25 C (= 0.00118 g/mL). The final density, , is calculated to
four decimal places.

Figure 3.1: Pyknometer for measuring solution density.

3.3 Viscosity Measurement

A brief description of the method for measuring the viscosity of solutions is given below, but
a full description of the method can be found in BS 188 (1977). The apparatus used for
measuring the viscosity of a solution/dispersion is shown schematically in Figure 3.2. This

14

apparatus consists of a glass capillary tube viscometer, a viscometer holder (to keep the
viscometer vertical), a temperature measuring device and controller accurate to 0.1 C and a
thermostatic bath (which includes a heater/cooler and a stirrer). The capillary flow method is
probably still the most frequently employed method for measuring viscosities.

Motor

Temperature

Viscometer

Control

TC

Thermostatic

Heater

bath

Stirrer

Figure 3.2: Schematic diagram of Viscometer Bath.

Initially the thermostatic bath was heated to the required temperature, which was 25 0.1C
in these experiments. A sufficient amount of the colloidal dispersion of known concentration
was then introduced into the viscometer, via a long pipette (to minimize any wetting of the
tube above the mark G) until the dispersion reached the line at G (see Figure 3.3). The
viscometer was then placed into the thermostatic bath, with care being taken that the
viscometer was vertical, and allowed to come into thermal equilibrium with the liquid in the
bath. This usually took about 10 minutes.

15

Once thermal equilibrium was reached, suction was applied to draw the dispersion up the
right-hand limb of the viscometer until it was about 5 mm above level E. The suction was
then removed and the time taken for the dispersion to drop from level E to level F was
measured using a stopwatch accurate to 0.01 seconds. This procedure was repeated at least
five times so a suitable average time could be recorded.

Figure 3.3: U-tube viscometers for direct flow (BS 188 (1977)).
From this time, the kinematic viscosity, , of the dispersion was calculated using:
= Ct

(3.3)

16

where t is the mean flow time (in s) and C is the factor for the viscometer given in its
calibration certificate (usually in mm2 s-2). The result is usually expressed in mm2/s (BS 188
(1977)). Two different viscometers were used in this experiment. The viscometer which was
used depended on the concentration of the dispersion being measured. For concentrations less
than 10g/L the viscometer used had a C value of 3.26 10-3 mm2 s-2, whereas for
concentrations greater than this value the viscometer had a C value of 2.71 10-3 mm2 s-2.
The dynamic viscosity, , of the dispersion can be calculated from the kinematic viscosity, ,
using:
=

(3.4)

where is the density of the dispersion (in g/mL). That is why it was also necessary to
measure the density of the colloidal dispersion. Using the units stated, the final units of the
dynamic viscosity are then given in mPa s or cP (BS 188 (1977)). These experiments were
repeated for numerous concentrations of the silica dispersions.

17

4.0 RESULTS
4.1 Silica Stock Solution Concentration
Mass of

Mass of Stock

Mass of Dish + dry

Mass of dry

Weight %

Dish

Solution Added

solid

solid

100 x gSi/gstock

41.105

4.443

42.542

1.437

32.34

43.225

4.583

44.710

1.485

32.40

42.216

3.977

43.508

1.292

32.49

45.243

4.838

46.814

1.571

32.47

44.521

8.171

47.164

2.643

32.35
32.39 0.10

Table 4.1: Experimental data for the concentration of stock silica solution. All masses are
accurate to 0.001g.

Table 4.1 shows the results obtained for calculating the stock solution concentration. Table
4.1 shows that the average stock solution concentration in terms of weight % is 32.39 0.10
wt%. Note that this is calculated by taking the mass of solid divided by the total mass of the
stock solution and multiplying the result by 100. Appendix I shows how the weight % is
related to the dispersion concentration and volume fraction.

4.2 Density Measurements

Mass of Empty Pyknometer

18.547 g

Mass of Pyknometer + water 61.899 g

M2, Mass of Water

43.352 g

o, Density of Water

0.9970 g/mL

a, Density of Air

0.00118 g/mL

Table 4.2: Fixed parameters for density measurements. All these values are given for a
temperature of 25C and all masses are accurate to 0.001g.

18

Table 4.2 shows the fixed parameters used in Equations (3.1) and (3.2) for calculating the
density of colloidal silica solutions. The density of air and the density of water at 25 C were
obtained from standard Steam Tables whilst the other values were determined by
experimentation.

Dispersion
Concentration
g/L
1.0
2.5
5.0
7.5
10.0
50.0
100.0
150.0
200.0
250.0
286.5

Mass of Pyknometer
+ Dispersion
g
61.973
61.979
62.023
62.047
62.079
62.597
63.376
64.161
64.989
65.941
66.555

Mass of Dispersion
m1
g
43.426
43.432
43.476
43.500
43.532
44.050
44.829
45.614
46.442
47.394
48.008

Density of Dispersion
g/mL
0.9987
0.9988
0.9998
1.0004
1.0011
1.0130
1.0309
1.0490
1.0680
1.0898
1.1040

Table 4.3: Experimental determination of the density of colloidal silica solutions. All values
are given for a temperature of 25C and all masses are accurate to 0.001g.

Table 4.3 shows the density obtained for silica dispersions at different concentrations. A
sample calculation for row 1 is shown below:
43.426 (43.352 0.00118)
0.9970

43.352 (43.352 0.00118)
0.9987 g/mL

(4.1)

From Table 4.3, illustrates that as the concentration of silica in the dispersion increases, the
density of the dispersion increases. This data can be plotted versus volume fraction as shown
in Figure 4.1. From this data a correlation for the dispersion density versus volume fraction is
obtained:
o (1 0.8046)

(4.2)

This correlation has an accuracy of 0.26 % (see Section 5).

19

1.12
Experimental Data
Regression: = o (1 + 0.8046 )

1.10

/ (g mL-1)

1.08

1.06

1.04

1.02

1.00

0.98
0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

Figure 4.1: Dispersion density versus volume fraction for silica dispersions at pH 9 in 0.03M
NaCl.

4.3 Viscosity Measurements

Concentration
g mL-1
1.0
2.5
5.0
7.5
10.0
50.0
100.0
150.0
200.0
250.0
286.5

Average Time
s
275.60 2.09
278.93 1.74
277.98 0.98
281.07 0.42
281.64 0.21
381.23 1.12
522.40 13.41
651.49 13.45
1048.28 81.52
1995.19 40.37
3091.46 154.80

C
mm2 s-2
0.00326
0.00326
0.00326
0.00326
0.00326
0.00271
0.00271
0.00271
0.00271
0.00271
0.00271

=tC
mm s-1
0.8985
0.9093
0.9062
0.9163
0.9181
1.0331
1.4157
1.7655
2.8408
5.4070
8.3779

g mL-1
0.9987
0.9988
0.9998
1.0004
1.0011
1.0130
1.0309
1.0490
1.0680
1.0898
1.1040

=r
mPa s
0.8973
0.9082
0.9060
0.9167
0.9192
1.0466
1.4594
1.8520
3.0340
5.8925
9.2492

Table 4.4: Experimental determination of the viscosity of colloidal silica solutions. All values
are given for a temperature of 25C.
20

Table 4.4 shows the average flow times obtained for each of the different concentrations. The
full range of experimental data plus sample calculations are shown in Appendix 2. The flow
times are converted into kinematic, , and dynamic, , viscosities by using Equations (3.3)
and (3.4). The data in Table 4 can be used to determine the intrinsic viscosity [] and the
maximum packing fraction m.

By using the dilute limit data from Table 4.4 (i.e. the data for solutions of 10 g/L and below)
and plotting

1 versus (where o = 0.8906 g/mL for NaCl at 25 C, see also Equation

o

(2.3)), a straight line graph should be obtained with a slope which is equal to the intrinsic
viscosity [].

0.04
Experimental Data
Regression: ( / o - 1) = 7.9965

/ o -1

0.03

0.02

0.01

0.00
0.000

0.001

0.002

0.003

0.004

0.005

Figure 4.2: Plot to determine the intrinsic viscosity of the silica dispersion at pH 9.0 in
0.03M NaCl.

Figure 4.2 shows that the intrinsic viscosity for this system is 7.9965.
21

The rest of the data in Table 4.4 is now fitted to the Kreiger-Doherty equation (see Equation
(2.5)) in order to obtain the maximum packing fraction fm for this silica dispersion.

10
Experimental Data
Fit to data: = o (1 - /m)-[] m
8

where [] = 7.9965 and m = 0.1486

/ (mPa s)

Hard sphere equation:

[] = 2.5 and m = 0.74
6

0
0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

Figure 4.3: Plot to determine the maximum packing fraction of the silica dispersion at pH
9.0 in 0.03M NaCl.

The maximum packing fraction obtained from the data in Figure 4.3 is 0.1468. This value
was obtained by fitting Equation (2.5) to the data using SigmaPlot 2001.

22

5.0 DISCUSSION
5.1 Silica Stock Solution Concentration
The concentration of the stock silica solution was determined by weighing the samples. This
introduces an error into the determination of the overall concentration as the scales were only
accurate to 0.001 g. However, the influence of this error is very small as illustrated by the
sample calculation below:

Looking at Row 1 in Table 4.1:

Mass of dish = 41.105 0.001 g

(5.1)

Mass of dish + dry solid = 42.542 0.001 g

(5.2)

Taking the extreme values in either case:

Maximum Mass of dry solid = 42.543 41.104 = 1.439 g

(5.3)

Minimum Mass of dry solid = 42.541 41.106 = 1.435 g

(5.4)

Average mass of dry solid = 1.437 0.002 g

(5.5)

Therefore,

Again from row 1 in Table 4.1,

Mass of stock solution added = 4.443 0.001 g

(5.6)

Therefore the maximum and minimum weight percentages can be calculated as:

Maximum weight % = 100 (1.439/4.442) = 32.40 %

(5.7)

Minimum weight % = 100 (1.435/4.444) = 32.29 %

(5.8)

These values differ from the average value of 32.34 % by:

Difference using maximum value = 32.40-32.34 = +0.06%

(5.9)

Difference using minimum value = 32.29 32.34 = -0.05%

(5.10)
23

Using the maximum difference then

Weight % = 32.34 0.06 %

(5.11)

Performing these calculations for each row gives:

Weight %

100 x gSi/gstock
32.34 0.06
32.40 0.05
32.49 0.06
32.47 0.05
32.35 0.03

Table 5.1: Error on Weight %.

5.2 Density Measurements

Again the density measurements were determined by weighing the samples, but as before the
influence of this error are very small as illustrated by the sample calculation below.

Taking row 1 from Table 4.2 as an example, the maximum deviation in density is obtained
when:
m1 = 43.428 g (= 61.974 18.546)

(5.12)

m2 = 43.352 g (= 61.898 18.546)

(5.13)

43.428 (43.352 0.00118)

0.9970

43.352 (43.352 0.00118)
0.9987 g/mL

(5.14)

Therefore

24

This gives the same value as before. If these calculations are repeated for all the data, the
maximum error in the density is 0.0002 g/mL which is insignificant and will not even show
up on a graph as shown by Figure 4.2.

5.3 Viscosity Measurements

The viscosity measurements also have an error associated with them This is due to the flow
time being an average value of five measurements. The error can be carried through the
viscosity calculation in the following manner. Using the value of the flow time from row 1 in
Table 4.4;

t = 275.60 2.09 s

(5.15)

The kinematic viscosity, , may be calculated using Equation (3.3) and a C value of 3.26
10-3 mm2 s-2:

= (275.60 2.09) 3.26 10-3 = 0.8985 0.0068 mm s-1

(5.16)

The dynamic viscosity is then calculated using Equation (3.4) as;

= (0.8985 0.0068) 0.9987 = 0.8973 0.0068 g/mL

(5.17)

This calculation can be repeated for all the data giving the following results:
Concentration
Average Time
=r
g mL-1
s
mPa s
1.0
275.60 2.09
0.8973 0.0068
2.5
278.93 1.74
0.9082 0.0057
5.0
277.98 0.98
0.9060 0.0032
7.5
281.07 0.42
0.9167 0.0014
10.0
281.64 0.21
0.9192 0.0007
50.0
381.23 1.12
1.0466 0.0031
100.0
522.40 13.41
1.4594 0.0375
150.0
651.49 13.45
1.8520 0.0382
200.0
1048.28 81.52
3.0340 0.2359
250.0
1995.19 40.37
5.8925 0.1192
286.5
3091.46 154.80 9.2492 0.4631
Table 5.2: Error in viscosity measurements at 25C.

25

The data in Table 5.2 has been used in plotting Figures 4.2 and 4.3.

Figure 4.2 enables the calculation of the intrinsic viscosity for silica dispersions at pH 9 in
0.03M NaCl. The intrinsic viscosity in this case was 7.9965. By comparison with Einsteins
value of 2.5 for spherical particles, it can be seen that the viscosity of this colloidal silica
dispersion is much enhanced. Figure 4.3 confirms this as the value for the maximum packing
fraction becomes 0.1486 compared to the hard sphere value of 0.74. Figure 4.3 also shows a
comparison between the hard sphere Kreiger-Doherty equation and the equation with the
parameters for colloidal silica. It can be seen that the surface charge has greatly increased the
dispersion viscosity over that for uncharged spheres.

26

6.0 CONCLUSIONS
The effect of concentration on the density and viscosity for charged colloidal silica
dispersions (surface charge = -76 mV) in a 0.03M NaCl electrolyte solution at pH 9.0 was
investigated. The density has been shown to follow the following equation:
o (1 0.8046)

(6.1)

where is the density of the dispersion, o is the density of the pure solvent and the volume
fraction of silica particles present.

The measured viscosity was found to conform to the following Kreiger-Doherty equation:

7.99650.1468

(6.2)

where is the viscosity of the dispersion, o is the viscosity of the pure solvent and is the
volume fraction.

This equation differs significantly from the uncharged hard sphere equation:

2.50.74

(6.3)

and demonstrates that the charge on the particle has a significant influence on both the
intrinsic viscosity and maximum packing fraction. This also demonstrates the need for
measuring the viscosity of concentrated charged colloidal solutions.

27

7.0 NOMENCLATURE
Symbol

Definition

Units

Buoyancy correction

Factor for the viscometer given in its calibration certificate

k1

Constant in polynomial viscosity equation

m1

Apparent mass of sample required to fill the flask at 25 C

m2

Apparent mass of water required to fill the flask at 25 C

Mean flow time

Volume fraction of particles in the dispersion

Maximum packing fraction

Intrinsic viscosity

mm2 s-2

Dynamic viscosity of the dispersion at 25 C

mPa s

Dynamic viscosity of the pure solvent at 25 C (= 0.8906 mPa s)

mPa s

Density of the dispersion at 25 C

g/mL

Density of air at 25 C (= 0.00118 g/mL)

g/mL

Density of water at 25 C (= 0.9970 g/mL)

g/mL

Kinematic viscosity

mm2/s

28

8.0 REFERENCES
Allain, C., Cloitre, M., Lacoste, B. & Marsone, I., (1994). Viscosity renormalization in
colloidal suspensions. Journal of Chemical Physics, 100(6), 4537 4542.

Barnes, H.A., Hutton, J.F. and Walters, K. (1989). An introduction to rheology. Elsevier,
Amsterdam.

Booth, F., (1950). The electroviscous effect for suspensions of solid spherical particles.
Proceedings of the Royal Society (London), Series A, 203, 533 551.

BS 188, (1977). Methods for Determination of the viscosity of liquids.

BS 4522, (1988). Method for Determination of absolute density at 20 C of liquid chemical

products for industrial use.

Einstein, A., (1906). Eine neue Bestimmung der Molekldimensionen. Annalen de Physik,
19, 289 306
Einstein, A., (1911). Berichtigung zu meiner Arbeit: Eine neue Bestimmung der
Molekldimensionen. Annalen de Physik, 24, 591 592
Hiemenz, P.C. and Rajagopalan R., (1997). Principles of colloid and surface chemistry (3rd
Edition). Marcel Dekker, New York.

Hunter, R.J., (1993). Introduction to modern colloid science. Oxford University Press,
Oxford; New York.

Krieger, I.M., (1972). Rheology of monodisperse latices. Advances in Colloid and Interface
Science, 3, 111 136.
Shaw, D.J., (1992). Introduction to colloid and surface chemistry (4th Edition). ButterworthHeinemann, ISBN:0750611820.

29

APPENDIX 1
Initially the concentration was measured in terms of weight %, the following data and
equations may be used to convert between weight %, g/L and volume fraction:
Sil = 2.2 g/cm3

o = 1 g/cm3

For weight% to concentration (g/L):

c (in g/L) 1000

wt%
wt% (100 - wt%)

o
Sil

(A1.1)

For concentration (in g/L) to weight%:

wt%

220 c
2200 1.2 c

(A1.2)

For weight % to volume fraction:

wt%

Sil

wt% (100 - wt%)

o
Sil

Dispersion Concentration
g/L
1.0
2.5
5.0
7.5
10.0
50.0
100.0
150.0
200.0
250.0
286.5

Weight %
100 x gSi/gstock
0.0999
0.2497
0.4986
0.7469
0.9946
4.8673
9.4828
13.8655
18.0328
22.0000
24.7779

(A1.3)

0.00045
0.00114
0.00227
0.00341
0.00455
0.02273
0.04545
0.06818
0.09091
0.11364
0.13023

Table A1.1: Relationship between concentration, weight % and volume fraction.

30

APPENDIX 2
The data shown in Table A2.1 is the raw data measured for each of the capillary flow
experiments. An average flow time for each of the dispersion concentrations used is
calculated along with the standard deviation.
Dispersion Concn (g/L)

1.0

2.5

5.0

7.5

10.0

50.0

t1 (s)

278.59

277.60

279.40

280.93

282.00

380.59

t2 (s)

275.12

277.00

277.03

280.75

281.68

380.28

t3 (s)

273.22

279.34

278.19

280.85

281.50

380.56

t4 (s)

276.69

281.44

277.06

281.81

281.56

381.81

t5 (s)

274.37

279.28

278.22

281.03

281.48

382.93

Average t (s)

275.60

278.93

277.98

281.07

281.64

381.23

(st dev)

2.09

1.74

0.98

0.42

0.21

1.12

Dispersion Concn (g/L)

100.0

150.0

200.0

250.0

286.5

t1 (s)

507.68

646.23

978.53

2010.52

3082.43

t2 (s)

531.50

634.75

1038.78

2024.15

3000.60

t3 (s)

528.59

671.00

1172.69

1932.46

3318.92

t4 (s)

508.31

648.72

1076.33

2030.3

2910.10

t5 (s)

535.93

656.77

975.06

1978.53

3145.23

Average t (s)

522.40

651.49

1048.28

1995.19

3091.46

(st dev)

13.41

13.45

81.52

40.37

154.80

Table A2.1: Experimental determination of the viscosity of colloidal silica solutions.

31