Powder Technology 105 Ž1999.

430–435
www.elsevier.comrlocaterpowtec

The selection of wet grinding chemical additives based on slurry

rheology control 1
a,b,)
R.R. Klimpel
a
RK Ass., Midland, MI, USA
b
UniÕersity of Florida, GainesÕille, FL, USA

Abstract

The wet grinding of materials in most industrial grinding devices can be significantly influenced by controlled changes in slurry
rheology. Thus, pulp density, the level of fines present, and the pulp chemistry conditions are all very important to maximizing
throughput. This paper will present a brief summary of what grinding studies involving slurry rheology control have shown industrially
followed by a summary of the nature of dispersant chemical adsorption behavior for different materials. Finally, a summary of the
attributes of various chemical families used industrially as wet grinding additives is given to assist industrial practitioners. q 1999
Elsevier Science S.A. All rights reserved.

Keywords: Slurry rheology control; Chemical additives; Wet grinding

1. Introduction using rheology control from the viewpoint of the industrial

It has been recognized for many years by industrial
plant operators, that controlling the slurry flow character-
istics is important in developing improved wet grinding
operating procedures including maximizing throughput.
One of the first scientific studies to characterize rheologi-
cal slurry behavior and its associated breakage character-
istics was conducted by this author in the period of 1976–
1985 w1–3x. The original motivation of this work was to
prepare plant design data for dense coal–water slurry
grinding as a precursor to building a large scale gasifica-
tion unit w1x. Shortly afterwards, the same technology
trends were found to be useful in the wet grinding of
minerals and materials such as ceramics and pigments
w2,3x. Since 1980, there have been hundreds of industrial
grinding plants that have or are using careful rheology
control to increase throughput. Industrial experiences in
)
Cro Prof. B.M. Moudgil, Engineering Research, Center for Particle
Science and Technology, University of Florida, Gainesville, FL 32611,
USA. Tel.: q 352-846-1194; fax: q 352-846-1196; E-mail:
bmaud@eng.ufl.edu
1
To the memory of R.R. Klimpel. The organizers of the 9th European
Symposium on Comminution would like to pay tribute to R.R. Klimpel
who tragically died on November 4, 1998.
operator have been recently summarized w4x. The purpose
of this paper is to summarize some of the author’s experi-
ences in selecting appropriate grinding aid chemicals.
The results of the laboratory scale grinding characteriza-
tion tests will now be briefly described. It has been well
recognized since the 1960s that optimal wet grinding in
most grinding machines is associated with the instanta-
neous first-order disappearance of each size over time.
Thus, if one were to trace any given size in the feed and
then follow the disappearance of traced particles over time,
a plot of the log fraction remaining of this traced material
vs. linear time of grinding will give a straight line. The
slope of this line is proportional to the specific rate con-
stant of breakage for that size.
Those operating conditions that cause slower non-first
order breakage to occur need to be avoided in industrial
operations if possible. Carefully performed laboratory stud-
ies w1x have shown that the appearance of non-first order
breakage starts with the occurrence of a rheological yield
value measured on the same slurry. Too high a percent
solids loading and the presence of excessive fines are two
of the primary factors leading to the development of a
slurry yield value. An example of this effect is shown in
Fig. 1 with the first order decay plot shown for a particular
test along with the simultaneous slurry rheology testing.

0032-5910r99r$ - see front matter q 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 0 3 2 - 5 9 1 0 Ž 9 9 . 0 0 1 6 9 - 2
 R.R. Klimpelr Powder Technology 105 (1999) 430–435
Fig. 1. Rate of breakage plot and associated slurry rheology for a feed of 250 = 300 mm coal ground at 57.1% volume solids.
The appearance of slower non-first order breakage with the
occurrence of a yield value is apparent.
The role of the chemical grinding aids Ždispersants. is
primarily to eliminate or reduce the slurry yield value. All
of this author’s work has shown that the optimal through-
put possible Žthe highest specific rate of breakage. with
tumbling media and stirred media mills is when the slurry
is as thick as possible but still not exhibiting a yield value.
Operating with this philosophy generally gives 5–20%
more throughput w4x. This optimal condition is rheologi-
cally characterized as a pseudoplastic slurry. Thus, there is
a need to thicken the slurried being ground beyond a thin
slurry exhibiting dilatant rheology but not so much as to
create a yield value slurry. The role of the grinding aid or
dispersant is one of simply minimizing the magnitude of
the yield value or totally eliminating the yield value.
The other major influence on the rheology behavior of
slurries is the progeny fragment distribution produced by
breakage of any given material. This fragment distribution
Fig. 2. The influence of the material property g on rheology as a function
of % solids.
431
is a material property and is generally characterized by the
cumulative breakage distribution function Ž Bi j , a plot of
the log of the cumulative weight fraction less than size vs.
log size for a short D t time of grinding of a narrow size
fraction of feed.. The ending slope of the log–log curve
can be described by the parameter g . The larger the g
value the narrower the progeny size distribution. Con-
versely, the smaller the value of g , the broader the size
distribution Žthe greater the amount of fines being pro-
duced.. Fig. 2 shows some recent data collected on how
important the characteristic material property described by
g is to the location of rheological regimes with changes in
slurry density.
2. Dispersant adsorption mechanisms
With regard to selecting an appropriate dispersant w5–8x
for a given slurry, it is important to have some knowledge
of the type and magnitude of electrical charge existing on
the surfaces of particles in the slurry. The concept of an
electrical double layer is widely used to explain and
quantify this electrical nature. The electrical double layer
develops w9,10x when a particle is immersed in the continu-
ous fluid Ži.e., water.. Once immersion has taken place,
charged species will begin to migrate across the
solidrliquid interface until an equilibrium is reached. An
example of an electrical double layer for a negatively
charged particle surface is shown in Fig. 3. Ions that give
rise directly to the charge on the particle surfaces are
called potential determining ions and are unique to each
type of particle system. With many types of solid particles,
especially those that are oxides, the potential determining
ions are Hq and OHy. In this situation, simply changing
the pH of the liquid phase can cause a change in the
particle surface charge. Thus as pH is increased, the OHy
concentration increases and the particle surface charge will
go from positive to negative with the point of zero charge
432 R.R. Klimpelr Powder Technology 105 (1999) 430–435
Fig. 3. The concept of the electrical potential of a particle surface.
ŽPZC. being that pH value for which the surface charge is
neutral.
The concept of dispersibility is defined as the ease with
which particles are distributed into the liquid phase and
when they no longer make permanent contact with the
other particles present. The yield value associated with
thick slurries comes about when the particles are locked
into fixed geometric patterns and hence are not dispersed.
There are several mechanisms by which particles can be
dispersed including electrostatic repulsion of particles
where all particles have the same charge and are repelled
from each other, solvation forces arising from water
molecules around particles thus preventing close contact,
and steric stabilization of particles caused by the use of
adsorbed chemicals w9,10,5x. Steric stabilization involving
polymers and surfactants is the primary mechanism in-
volved with chemical grinding aids. The repulsion is caused
by the interference of adsorbed chemical molecules as they
come into close contact with each other. Fig. 4 gives a
simple illustration of steric repulsion of particles by ad-
sorbed polymers.
Fig. 5 illustrates five common conditions for which a
polymeric dispersant Žincluding simple organic monomers.
can attach to a solid surface leading to steric stabilization.
These are: Ža and b. the electrostatic bonding which is the
attraction of oppositely charged materials leading to charge
neutralization; Žc. hydrophobic bonding which occurs when
the hydrocarbon backbone of a dispersant associates with
the particle surface Žthus allowing for a chemical and a
solid of similar charge to associate.; Žd. hydrogen bonding
which is common on solids having a near-neutral surface
charge with chemicals having no charge Žnon-ionic.; and
Že. chelation bonding of a chemical with a metal atom on
the particle surface. Normally electrostatic bonding is pre-
ferred and is the easiest to control in plant practice but
chemicals based on hydrophobic bonding are also quite
commonly used in industrial practice.
The other important factor that needs to be discussed is
the nature of how anionic and cationic chemicals develop
their charge with changes in pH. Non-ionic chemicals
Žusually containing –O– and –OH functionality. are rela-
tively insensitive to pH but are most effective as disper-
sants on near-neutral particle surfaces. By far the most
common negatively charged Žanionic. dispersants contain
carboxylic acids Žor their salts.. Such organic acids disso-
ciate in aqueous solution into negatively charged carboxyl-
ate ions,
RCOOH Ž aqueous. ™ Hqq RCOOy
at a pH of 5 or 6 and above. Thus, such materials are not
generally effective as dispersants at pH’s less than 5 or 6.
With carboxylic acids, the presence of multivalent ions
Ži.e., Ca2q . from hard water or lime being added as part of
the slurry is quite detrimental as insoluble carboxylic salts
are formed. Therefore grinding under such conditions can
cause high uneconomical levels of dispersant to be used as
much of the initial dosage is being used to remove the
water hardness. Sulfonic acid based dispersants,
RSŽ5O. 2 OH, are often used as dispersants for lower pH
ranges as they dissociate at a pH of approximately 2.
With regard to positively charged Žcationic. dispersants,
the chemicals used are generally amines. Amines ionize in
aqueous solution by protonation,
RNH 2 Ž aqueous. q H 2 O ™ RNHq y
3 q OH .
The actual form of the amines used can be quite
variable and includes primary, secondary, tertiary, and
Fig. 4. Steric stabilization of particles due to adsorption of polymeric
dispersants.
 R.R. Klimpelr Powder Technology 105 (1999) 430–435 433

Fig. 5. Common types of polymer attachment configurations on particle surfaces in aqueous slurries.

quaternary forms. Quaternary amines are strong bases so dent. Typically for a primary amine, the ionization starts to
are ionized over essentially the complete range of pH, fall off in the range of pH 10 or greater thus defining the
while the ionization of the remaining forms is pH depen- practical use window as being less than pH 10. Cationic

Table 1
Some simple inorganic and organic grinding aids
Caustic NaOH A surprisingly general dispersant for slurries especially those
containing some oxide materials. The major challenge is whether the
slurry pH associated with the effective dosages required can be tolerated
Sodium silicate Na x Si yOz Sometimes used as a combination dispersant and depressant
in complex mineral systems.
It is sensitive to pH and has some unusual solubility properties
which can make effective usage difficult leading to excessive
dosages being required. These high dosages can cause difficulties in some
downstream applications. Generally not an economical grinding aid
Sodium metaphosphate Na x PyOz An effective dispersant for some specific types
of grinding applications.
Primary problem in large scale applications is the
environmental aspect associated with water userrecycle.
In some applications, these materials can cause adverse downstream effects
Alkanol amines H n NŽC 2 H 4 OH. 3yn , An effective dispersant for slurries containing some silica
n s 0,1,2 and silicate minerals at pH’s less than 10.
Care has to be taken as particle surfaces can be blocked from adsorbing other
chemicals in downstream operations.
Use generally not economical except in specialized applications
Citric acid C 6 H 8 O 7 Ža mono- A surprisingly effective general purpose dispersant for a wide variety
hydroxy tri- of slurries in grinding applications at pH’s greater than 6.
carboxylic acid. The major use problem is the tendency to associate with metal atoms
including Ca2q to form insoluble salts thereby cutting down the dosage effectiveness.
Citric acid is often a good component to have in a blended dispersant system and
is economical to use. Generally does not cause downstream slurry usage problems
Titanates TiŽOR.4 Useful in the grinding of some hydrophilic materials such as pigments
in an organic or hydrocarbon based slurry.
Usually very application specific and use is not economical
for general applications
434 R.R. Klimpelr Powder Technology 105 (1999) 430–435
Table 2
Lignon sulfonic acid used as a grinding aid
chemicals are generally much more expensive than anionic
dispersants which is why the hydrophobic bonding ap-
proach using anionic or non-ionic dispersants with nega-
tively charged particles in slurries is used.
3. Some industrially used dispersants as wet grinding
additives based on slurry rheology control
The general selection guidelines of choosing dispersants
for control of slurry flow behavior have been well docu-
Table 3
Common water soluble polymers used as grinding aids
mented w5–8x. This experience base has been dominated by
industrial and consumer product formulations involving
pigments, ceramics, industrial minerals, foods, and phar-
maceuticals. From the viewpoint of using dispersants for
controlling slurry rheology behavior in grinding applica-
tions involving high shear, often elevated temperatures,
and often hard water conditions, the guidelines are much
less clear. Most of the industrial experiences in the use of
dispersants in wet grinding is unpublished or exists in
publications not widely available and is often considered
proprietary by individual companies. The primary pub-
lished reference in the open literature on the design and
selection aspects of rheology control chemicals for grind-
ing is a paper by Klimpel and Hansen w11x. Even this paper
is not complete because it addresses primarily water solu-
ble polymeric dispersants. For this reason, this section will
list, based on this author’s various industrial experiences,
some of the more commonly used dispersants for assisting
wet grinding processes.
In Table 1, some simple inorganic and organic disper-
sants used as grinding aids are listed along with some
usage comments. In Table 2, the chemical structure of
lignon sulfonic acid Žor its salts. is given. This class of
dispersants is derived from sulfonating lignon to achieve
different extents of sulfonic acid functionality. Lignon is a
naturally occurring polymer Žbased on phenyl propane as
the underlying monomer. produced as a by-product of
 R.R. Klimpelr Powder Technology 105 (1999) 430–435
paper making processes. These dispersants are still the
most commonly used industrial grinding aid dispersant due
to their low cost. Typically, there are between 0.2 and 1.0
sulfite groups added per phenyl propane unit and molecu-
lar weights can vary from several thousand to 100,000.
Generally, lignon sulfonates of higher sulfonation are ef-
fective in grinding applications due to their ability to resist
degradation under shear while sulfonates of lower sulfona-
tion tend to be more effective in the grinding of particles
that are more hydrophobic such as coals.
In Table 3, some of the more common designed water
soluble polymers are listed that have been evaluated and
used in studies conducted by this author. The advantage of
using designed water soluble polymers as grinding aids is
the specificity that can be achieved for any given slurry.
Thus selecting an optimal dispersant can mean optimizing
molecular weight, the hydrocarbon content, the charge and
charge density, pH, water chemistry, and the chemical
dosage. It is not uncommon for polymeric dispersants to be
used at a dosage of 1r10 or less than those chemicals
listed in Tables 1 and 2. Since such polymers typically cost
two to five times as much on a comparable activity basis,
the economics of using polymeric dispersants can be quite
favorable. Also, it is common to see polymeric dispersants
used in combination with the aids of Table 1.
Probably, the most widely used chemical as a grinding
aid from Table 3 is polyacrylic acid Žand its salts.. Molecu-
lar weights in the region of 5000–20,000 appear to be
optimal depending on the application. Polyacrylic acid,
like any other carboxylic acid containing material reacts
with cations such as Ca2q to form insoluble salts, therefore
increasing the dosage required to be an effective grinding
aid in hard water and slurries containing lime. Also,
carboxylic acid dispersants are most effective when used at
a pH of 6 or above. Generally any sulfonic acid based
dispersant such as lignon sulfonic acid or sulfonated
polystyrene offers lower pH operating flexibility and
sometimes lower dosages in hard water than carboxylics.
Since most minerals and other materials are negatively
charged at a pH of 6 or greater and most grinding applica-
tions are also performed at pH of 6 or higher to avoid
excessive corrosion, some special application ‘‘tricks’’ can
be utilized to get the cheaper negatively charged disper-
sants to associate with the negatively charged particles.
One of the ways of doing this is to increase the hydrocar-
435
bon content of the dispersant andror to lower the charge
density including going all the way to an non-ionic chemi-
cal. To do this type of testing, obviously requires a user to
have a variety of reasonably well characterized chemicals
to test.
Another common way of handling this like charge
situation, is to carefully add cationic coagulants to the
slurry before any polymer is added. Examples of such
coagulants would be inorganic salts containing Ca2q,
Mg 2q, Al 3q, Fe 3q, etc. Adding these cationic materials
reduces the magnitude of the negative particle surface
charges towards neutrality making it easier for hydropho-
bic bonding andror hydrogen bonding to occur on the
particle surfaces. The challenge here is to add only enough
cations to act as a coagulant and not so much cations that
the excess can react with the carboxylic acid type disper-
sants when they are added. Ca2q, by itself in the form of
lime, for example, is basically an anti-grinding aid due to
its coagulation tendency leading to aggregate formation
followed by a yield value. Non-ionic dispersants such as
polyvinyl alcohol, polyacrylamide, and polyethylene oxide
work best on slurries where the particles are not highly
charged. Polyphosphoric acid and polyvinyl amine are
useful only in rather specialized grinding applications as
the cost of their use can be relatively high.
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