International Seminar on Paste and Thickened Tailings

Paste and Thickened Tailings Paste 2004

31 March 2 April 2004, Cape Town, South Africa

Know Your Chemistry Suspension and Compaction

Behaviour of Paste

Andrew Vietti
De Beers Consolidated Mines Limited
Abstract
An attempted is made to provide an explanation for the observed suspension and compaction
behaviours of kimberlitic clay slurries based on three mechanisms affecting clay colloidal
properties. In addition, three models are proposed which allow for the prediction of both the
suspension and compaction behaviours based on an understanding of the slurry system
parameters.
1.

Introduction

Current diamond winning metallurgical processing relies heavily on water as a process

medium. Throughout the kimberlitic ore treatment phases, process slurries are generated
which contain a variety of suspended minerals. Since water recovery and re-use is paramount
to the operation of the treatment plant, considerable attention has been paid to the slurry
thickening and tailings disposal processes, principally through the adoption of new
technologies such as Paste and Thickened Tailings Disposal (P&TTD).
Enhanced water recoveries are achieved by P&TTD systems, by concentrating the suspended
solids within so-called low-density slurries through novel high compression thickening
processes. These high-density tailings are then transported hydraulically to a surface disposal
site where they are deposited.
The operation of the P& TTD thickening and pumping processes are themselves critically
dependant on the settling and rheological behaviours of the clay slurries. For instance, the
thickening process requires that the suspended clays be in a colloidally unstable state for
solid/liquid separation to take place and the subsequent compaction to a high-density state. It
is equally important that the rheological behaviour of the high-density slurry be such that
hydraulic transport is possible.
The suspension and subsequent rheological behaviours of both low and high-density clay
slurries are dependant on a number of ore and water related parameters which affect the
colloidal properties of the suspended clays. This paper attempts to explain the mechanisms
affecting kimberlitic clay slurry suspension and compaction behaviour.

2.

Saline Agricultural Soils

It would appear that processed kimberlitic ores (slimes), in general, bear a striking similarity
to the behavioural characteristics of a class of agriculturally problematic soils known as the
saline and alkali soils. These soils can be further grouped into:

Saline soils
Saline-alkali soils
Non saline-alkali soils

Three criteria are used to classify the soils (Richards 1969):

1) The conductivity of an extract taken from a saturated soil sample provides a measure
of the water-soluble cations within the soil (i.e. the salinity of the soil).
2) The Exchangeable Sodium Percentage (ESP) provides a measure of the amount of
sodium ions bound to the clay fraction in the soil (i.e. the sodicity of the soil).
3) The pH of the saturated soil.
2.1

Saline Soils

These soils have high conductivity; the ESP and pH values are low. Because of the
high soluble salt content, the soils are in a flocculated state and will form settling
slurries if suspended in water.
2.2

Saline-Alkali Soils

The ESP of these soils are high, however, these soils behave either as saline soils or
non-saline-alkali soils depending on the amount of soluble salts present (i.e. their
conductivity). If the conductivity of the soils is high, and the pH of the soil is low the
soils remains in a flocculated state. If however, the soluble salts are leached out of
the soil, the properties of the soil change and they begin to behave as non-saline-alkali
soils.
2.3

Non-saline-Alkali Soils

The conductivity of these soils are low, the ESP and the pH values are usually high.
The ESP has a profound effect on the chemical characteristics of the soil. The higher
the ESP, the higher the pH and the more the soils tend to disperse. Typically,
problematic processed kimberlite ores show behavioural characteristics similar to this
category of soil.
3.

Alkalisation of Soils

Most importantly to the process of alkalisation, is the fact that it is the clay fraction in the soil,
which is able to adsorb and exchange cations (notably sodium, calcium and magnesium) from
the surrounding aqueous medium by ion exchange mechanisms. Normally, calcium and
magnesium are the principle ions found in a saturated soil extract, however, under certain
conditions, the sodium ion can become the dominant ion if the salts become concentrated
through evaporation. In this case, the saturation limit of various salts (e.g. calcium/magnesium

sulphates or carbonates) is exceeded and they are precipitated out of solution, increasing the
relative proportion of sodium ion. Under such conditions, sodium replaces the original
exchangeable calcium and magnesium cations on the clay surfaces, the ESP of the soil
increases and the soils become alkali.
4.

The Effect of Water

Another factor, which plays a vital role in determining the ion exchanged nature of the clays,
is the chemical quality of the water, which contacts the soil.
The alkali hazard potential of a water used for irrigation is determined by the absolute and
relative concentrations of the cations in the water. If the proportion of sodium in the water is
high, the alkali hazard is high and conversely if calcium and magnesium predominate, the
hazard is low. An easy to remember rule of thumb is hard water makes soft land and soft
water makes hard land (Richards 1969).
A unit which is used to determine whether a water quality is likely to create clays, which are
highly sodium ion exchanged is know as the Sodium Adsorption Ratio (SAR) value of the
water. The SAR is the ratio of sodium ions to calcium and magnesium ions in solution and the
figures are derived from a normal chemical analysis of the water (in meq/l):
Na +
SAR =
(Ca 2+ + Mg 2+ ) / 2

Since there is a fairly good correlation between the SAR value for a water and the ESP value
of a suspended clay, the ESP value of the clays in the irrigated soil can be estimated if the
SAR of the irrigating water is known (Richards 1969).
5.

Kimberlitic Clay Characteristics

Kimberlite ore is an ultrabasic igneous rock consisting of a matrix of cementing material in

which mineral inclusions of various crystal elements such as diamond are found. In most
cases, the cementing matrix is composed of a range of clay minerals, of which those from the
smectite group are dominant, comprising anywhere from 50% to 90% of the clay mineral
fraction (-2 micron). The Montmorillonite clays are thought to be the major clay species.
In order to understand the behaviour and interaction of clays in slurries (or soils), it is
essential to understand their structure. Smectites are classified as 2:1 type clays as a
consequence of the particular arrangement of the clay particle crystal lattice (Van Olphen
1977). The crystal lattice is composed of a single octahedral gibbsite layer (if the central
atom is Al3+) which is sandwiched between two silicon tetrahedral layers (Hurlbut & Klein
1977) (Figure 1).

Figure 1: Crystal Lattice Structure of a Typical 2:1 Clay Mineral (Hurlbut & Klein 1977)
These crystal lattice layers are however, not uniform with respect to the chemical nature of
their central atoms. Often, isomorphus substitution of the existing atom by an atom with a
lower valance can take place (for example Mg2+ for Al3+ in the octahedral layer) that results in
an excess negative charge, which is distributed at the tetrahedral surfaces. The excess negative
charge is compensated for by the adsorption of cations onto the outer surfaces of the clay
crystal lattice structure. These cations are present even in the dehydrated forms of the clay,
however, in the presence of water, the compensating cations may be exchanged by other
cations in solution depending on how strongly they are bound to the clay surface. For this
reason, they are known as exchange cations and their concentrations can be used as a measure
of the amount of lattice charge or cation exchange capacity of the clay (Van Olphen 1977).
Smectite clay surface charge accounts for about 80% of the total cation exchange capacity
while the remainder is accounted for by the clay particle edges. It is generally concluded that
under aqueous conditions, hydroxyl (OH-) groups will attach to the exposed silicon
tetrahedral and metal ion octahedral atoms at the clay edges (Svarovsky 1981). As a
consequence, the pH of the surrounding environment will have a profound effect on the
crystal lattice edge charge. Under acidic conditions, the OH- bearing groups will become
protonated to carry an overall positive charge. As the pH is increased, the OH- groups will
become deprotonated until a point of overall edge neutrality is achieved. This pH is known as
the Point of Zero Charge (PZC) of the clay crystal edge. Further increases in pH will result in
total deprotonation of the OH- groups until an overall negative edge charge dominates (Figure
2).

Zeta Potential (mV)

- -- - - -- - - -- +- - + -- - + -- - + + +++ +
--- +
2

10

12

pH

PZC

Figure 2: Surface Electrical Charge Characteristics of a 2:1 Clay With Respect to pH

Finally, all members of the smectite group of clays share one common feature, in that they
have the ability in the presence of moisture to absorb water and other polar molecules
between the particle unit layers and cause swelling of the matrix hence the term swelling
clays. Two forms of swelling mechanism are known which depend on the moisture content
to which the clays are exposed.
Firstly under low moisture content conditions a limited step-wise expansion of the unit layers
known as Interlayer (or Type I) swelling occurs. As more water molecules are drawn between
adjacent clay platelets up to three layers of water molecules are covalently bonded to the
tetrahedral surfaces and in a semi-crystalline structure that resembles that of ice. This mode of
swelling leads to at most a doubling in the volume of the dry clay (Grimm 1968).
The second form of swelling occurs at high moisture contents and can lead to an unlimited or
complete separation of individual layers and is known as Osmotic (or Type II) swelling.
Under this condition, the exchange cations dissociate from the clay surface and move to the
hydrated region between clay particles and as such they are regarded as being in solution
and hence lower the activity of the water between the particles. This allows more water from
the surrounding to move into the interlayer region by osmotic forces thereby increasing the
interlayer swelling. This form of swelling may continue indefinitely until normal electrical
double layers separate the individual clay particles (Figure 3).

Interplanar
Spacing
()

C -1/2
Figure 3: Change in Layer Spacing of a 2:1 Clay with Increasing NaCl Concentration (Sequet
et al. 1975).
(Type I swelling is step-wise and limited while Type II swelling is linear and unlimited)
The degree of osmotic swelling of a particular clay depends largely on the nature and
concentration of the cations in the contacting water and the degree of octahedral substitution
of the clay type. Monovalent cations (such as Na+) in solution tend to cause unlimited
swelling since they are small and are able to dissolve more easily in the semi-crystalline
water layers which surround the clay particles thereby drawing more water between the
adjacent particles by osmotic action. Divalent cations (such as Ca2+ and Mg2+) on the other
hand tend not to cause unlimited swelling since they have a disruptive effect on the water
layer structure and as they are able to provide links between charged sites on adjacent silicate
sheets (Sequet et al. 1975; Mering 1946).
6.

Kimberlite Ore Processing and Clays

Conventional kimberlitic ore processing practices (particularly in the water recovery and
tailings disposal circuits) are undergoing rapid change. The concept of Paste and Thickened
Tailings Disposal (P&TTD) is gaining acceptance within the minerals industry, primarily as a
means of reducing water consumption, as well as improving disposal site stability and safety
(Robinsky 1999; Paterson et al. 1999). However, the technique is more sensitive to the
variability in the behavioural characteristics of clay suspensions than are the conventional
water recovery and tailings disposal circuits.
Within a typical kimberlite processing circuit, ore is crushed and scrubbed before being
screened and processed further. Scrubbing represents the first contact between the ore and the
plant process water and may be critical in determining the behavioural characteristics of the
subsequent low-density tailings stream. Should a P&TTD circuit be installed, this stream
would typically be routed to a high compression thickener where the solid/liquid separation
would take place and the solids would be compacted to a high-density underflow product,

which would have certain unique non-Newtonian rheological characteristics. These

characteristics would determine the pump and pipeline design requirements and subsequently
the disposal site sizing requirements.
7.

Paste Behavioural Models

As stated, low-density kimberlitic tailings slurries (1.5 mm) would typically constitute the
feed to a high compression thickening unit. The slurry is generally classified into two
fractions according to particle size, namely the +75 micron 1.5 mm grits fraction (which is
easily settlable) and the 75 micron slimes fraction containing the clay minerals. The most
important parameter affecting the thickener performance would be the suspension or settling
behaviour of the slimes fraction within the slurry.
Three mechanisms affect the colloidal properties of clay slurries.
1. Ion exchanged nature of the suspended clays:- increasing the sodium ion exchanged
nature of the clays will lead to increased dispersion behaviour of a clay slurry suspension.
2. pH of the suspension:- as alluded to earlier, the pH of the suspension greatly affects the
charge associated with the clay particle edges. Below the clay edge PZC, edge-to-face
particle interactions take place, resulting in particle aggregation and settling under gravity.
At suspension pH values above the PZC, clay slurries will tend to remain dispersed as a
consequence of negative particle repulsive forces (Figure 4).

10

12

10

12

Figure 4: Clarity Profiles of a Sodium Exchanged Clay Suspension (left) and a Calcium
Exchanged Clay Suspension (right) with pH.
3. Ionic concentration of the suspension:- A third and overriding mechanism affecting the
colloidal properties of clay suspensions is the absolute ionic concentration of the
suspension. The electrical double layer surrounding individual clay particles becomes
progressively compressed at high ionic concentrations, reducing interparticle distances
and allowing particles to interact. An ionic concentration is reached, known as the Critical
Coagulation Concentration (CCC) at which, the forces of attraction between adjacent
particles become greater than the repulsion forces and particle aggregation and settling
can occur.

Integration of the three mechanisms can provide visualisation models to explain the
suspension and compaction behavioural observations of kimberlitic clay slurries.
Typically, particle colloidal potential would increase with increasing clay ESP due to the
increasing dispersive nature of the clay, however, this trend is only truly expressed in a
narrow band between approximately pH 8 and 11. At lower pH values, clay particle edge-toface interactions take place and hence settling can occur even at high ESP values. Also at pH
values greater than 11, settling is once again observed at high ESP values simply due to the
CCC of the suspension being exceeded (Figure 5).

Solids in Suspension After 90 hours

Solids in Suspension After 90 hours

(Plan view)

(Isometric view)
0.0 %
0.2 %
0.4 %
0.6 %
0.8 %
1.0 %
1.2 %

11

10

1.4

(%)

12

1.2

Solids Concentration

Slurry pH

1.0

0.8
0.6
0.4
0.2
0.0
20

ES
5
20

40

60

ESP (%)

80

100

11

40

P(

%)

10
9

60

8
80

7
100

6
5

Slu

p
rry

Figure 5: Model for Describing the Suspension Behaviour of Naturally Settling Low-Density
Kimberlitic Clay Slurries
Observing and describing the suspended portion of a slurry provides one view of the
behaviour of clay particles within such a slurry. Another view, which would be more useful to
the hydraulic transport and deposition characteristics of the slurry, would be to describe the
behaviour of the settled or compacted portion of the slurry under the same conditions as
described in Figure 5.
In this case, it would appear that two compaction zones (or clay particle interaction zones)
exist a zone of relatively poor compaction surrounding a zone of high compaction which
corresponds to the region of maximum clay dispersion (Figure 6). Indeed, the degree of solids
consolidation in the compaction zone is significant, up to 60% solids by mass (Figure 7).

12

Mud Bed Compaction After 90 hrs

Mud Bed Compaction After 90 hrs

(Plan View)

(Isometric View)

12
0.02 m
0.04 m
0.06 m
0.08 m
0.10 m

10

0.10
0.08
0.06

0.04
0.02
0.00

7
20

ES

40

(%
)

60
80

5
20

40

60

80

100

100

ESP (%)

12

11

10

H
ry p
Slur

Figure 6: Model for Describing the Compaction Behaviour of Naturally Settled Low-Density
Kimberlitic Clay Slurries
Solids Content in Settled Bed After 90 hours

Solids Content in Settled Bed After 90 hours

(Plan view)
12

10 %
20 %
30 %
40 %
50 %
60 %

11

(Isometric view)

70

10

n (%)
Solids Concentratio

60

Slurry pH

Slurry pH

0.12

Mud bed Height (m)

11

50

40
30
20
12

10

11

10
0

9
20

8
40

5
20

40

60

ESP (%)

80

100

ES P

60

(%)

ry
ur
Sl

80
100

Figure 7: Solids Content of the Settled Bed of Naturally Settled Low-Density Kimberlitic
Clay Slurries
Initially, these observations may appear to be contradictory, i.e. a colloidal condition exists in
which maximum clay particle dispersion is allowed and in which maximum slurry
consolidation and compaction of any settled solids to take place.

pH

In order to explain this seemingly contradictory behaviour, the orientation of the clay particles
in the settled bed was investigated and visualised using a cryogenic Scanning Electron
Microscope technique.
Figures 8 and 9 represent two micrographs describing similar clay mineral suspensions with
differing colloidal properties. Figure 8 describes the clay particle orientation within a slurry in
which the colloidal properties allow particle interaction to take place (i.e. within the particle
interaction zone as described by the compaction model). It is noted that significant edge to
face interactions are allowed with the accompanied presence of a significantly high void
ratio and low compaction density.

Figure 8. Scanning Electron Micrograph Describing Clay Particle Orientation Associated with
a Slurry in which the Colloidal Properties allow for Particle Interaction
Figure 9 describes the clay particle orientation of a slurry in which the colloidal conditions are
such that particle interaction is not allowed. In this case, a high degree of compaction of the
solids is achieved. It is noted that almost exclusively face to face interactions are allowed
with the accompanied presence of a significantly low void ratio and high compaction density.

Figure 9. Scanning Electron Micrograph Describing Clay Particle Orientation Associated with
a Slurry in which the Colloidal Properties do not allow for Particle Interaction
8.

Colloidal Properties and Paste Rheological Behaviour

The rheological behaviour of a paste, are determined by a number of slurry related

parameters. Very often, particle size and slurry solids content are regarded as the prime
contributors to the strength and flow behaviour of the paste. On occasion, however,
rheological behaviours are observed which appear puzzling and which can not be explained
on the basis of particle size and slurry density alone for instance a low density paste may
exhibit a higher yield strength than a similar paste at much higher density.
The effects which slurry colloidal properties have on clay particle association and hence paste
rheology are clearly demonstrated in Figure 10 in which a wide range of rheological
behaviours are expressed by a single thickened kimberlitic clay mineral paste. In this case,
under certain colloidal conditions, the slurry (d50 of 2 micron) was shown to have no yield
strength at solids contents as high as 47% solids by mass, while in other conditions, it was
shown to develop significant strength at comparatively low solids contents (30% solids by
mass).
These rheological observations, when simply related to the solids content within the paste
provide no explanation of this apparently aberrant behaviour, however, if the same data is
expressed as a function of slurry colloidal properties such as ESP and pH they can be
explained clearly (Figure 11).

300

Shear Yield Strength (Pa)

250

200

150

100

50

0
0

10

20

30

40

50

60

Solids Content (% by mass)

Figure 10: The Effect of Slurry Colloidal Properties on the Rheological Behaviour of a Single
Kimberlitic Clay Mineral Suspension and Expressed as a Function of Solids Content.

500

0
100
200
300
400
500

Yield Strength (Pa)

400

300

200

100

0
20

ES

40

(%
)

11

60

10
9

80

8
100

7
6

pH

Figure 11: The Effect of Solids Content on the Rheological Behaviour of a Single Kimberlitic
Clay Mineral Suspension (at 41% solids content by mass) Expressed as a Function of Slurry
Colloidal Properties.

9.

Conclusion

As the minerals industry strives towards adopting Sustainable Development principles,

possibly one of the most far-reaching process improvements has been the development of the
Paste and Thickened Tailings Disposal system. As both the reliability and the understanding
of the system improves, it is envisaged that these systems will become a commonly accepted
alternative to conventional disposal techniques within minerals and other industries.
However, as will all processes, pushing the boundaries of a technique requires greater
attention to detail. With regard to P&TTD systems, the detail appears to be at the level of the
surface chemistry characteristics of the suspended clay minerals.
As demonstrated, the colloidal properties of a slurry can have a profound effect on the
settling; compaction and rheological behaviour of many mineral tailings and particularly
those containing clay minerals. In these slurries, the effects of slurry density appear to play a
sub-ordinate role to the colloidal properties in determining the rheological behaviour of the
paste.
A complete understanding of the tailings suspension characteristics (i.e. both the mineral and
aqueous components) as well as the mechanisms which affect the clay surface charge
characteristics are required in order to manipulate process conditions to match the process
needs and to ultimately master the P&TTD system.
Based on the above and on visual observations, two models have been proposed in order to
predict the suspension and compaction behaviours for kimberlitic clay mineral suspensions.
Reference
Richards, L.A. (ed.) (1969) Diagnosis and improvement of saline and alkali soils, US Dept
Agriculture Handbook No. 60.
Van Olphen, H. (1977) An introduction to clay colloidal chemistry, John Wiley & Sons,
New York.
Klein, C. and Hurlbut, C. S. (1993) Manual of Mineralogy (21st ed), John Wiley & Sons,
New York.
Svarovsky, L. (ed.) (1981) Solid-liquid separation (2nd ed), Butterworths, London.
Grimm, R. E. (1968) Clay mineralogy (2nd ed), McGraw Hill,
Sequet, H.; De La Calle, C. and Pezerat, H. (1975) Swelling and structural organisation of
saponite, Clays and Clay Minerals, Vol 23, Pages 1-9.
Mering, J. (1946) The hydration of Montmorillonite, Trans. Faraday Soc., Vol 42, Pages
205-219.
Robinsky, E. I. (1999) Thickened tailings disposal in the mining industry, E. I. Robionsky
& Associates, Toronto.

Paterson, A.J.C., Vietti, A.J., Derammelaere, R.R. and Hester, H. (1999) Future Trends:
Waste Disposal of High Concentration Kimberlite Tailings, 101st Annual General Meeting of
Canadian Institute of Mines, Calgary, May 1999.