Advanced Powder Technology 20 (2009) 350–354

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Advanced Powder Technology

journal homepage: www.elsevier.com/locate/apt

Original Paper

Effect of grinding aids on the kinetics of fine grinding energy consumed of

calcite powders by a stirred ball mill
Heekyu Choi a,*, Woong Lee a, Seongsoo Kim b
a
School of Nano and Advanced Materials Engineering, Changwon National University, 9 Sarim-Dong, Changwon, Gyeongnam 641-773, Republic of Korea
b
Department of Precision and Mechanical Engineering and Eco-Friendly Heat and Cooling Energy, Mechanical Research Team, BK21, Gyeongsang National University,
445 Inpyeong-Dong, Tongyoung, Gyeongnam 650-160, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: An experimental investigation was carried out on the ultra-fine grinding of inorganic powders using a
Received 11 September 2008 stirred ball mill. The power consumed in the grinding process was measured, and the comminution coef-
Received in revised form 13 January 2009 ficient, K, in the grinding kinetics equation was examined, based on an analysis of the relationship
Accepted 20 January 2009
between the experimental specific surface area and the particle-size distribution of ground products.
The effect of grinding aids on the comminution coefficient, K, was also investigated. It was demonstrated
that the grinding rate for calcite could be improved by the addition of grinding aids. When using grinding
Keywords:
aids, K improved by 16.0% and 34.2% for 60 wt% and 70 wt% slurry concentrations, respectively. Thus
Ultra-fine grinding
Comminution coefficient
grinding aids are very effective in the submicron range grinding process.
Grinding kinetics Ó 2009 The Society of Powder Technology Japan. Published by Elsevier BV and The Society of Powder
Grinding energy consumption Technology Japan. All rights reserved.
Stirred ball mill
Grinding aids

1. Introduction
Ultra-fine grinding in the sub-micron range has recently drawn
attention in the wake of the development of new functional mate-
rials, such as new ceramics and electronic materials, in various
industrial fields. Stirred ball mills have been used in recent years
for grinding particles to sub-micron sizes due to their easier oper-
ation, simpler construction, higher grinding rate and lower energy
consumption compared with other fine-grinding machines [1–4].
The grinding-energy efficiency is an important parameter that af-
fects the amount of energy used during grinding. It is affected by
the mechanical energy transition, the breakage mode, and the en-
ergy lost in elastic and permanent deformation when the solid par-
ticles are broken. High energy consumption and inefficiency in the
comminution of materials such as minerals, cement, pigments,
chemicals and food have long been regarded as major problems
to be overcome, especially for producing sub-micrometer-sized
particles [5,6].
Gao et al. [7] found that increasing the power consumed during
grinding accelerated the size reduction dramatically, with only a
small change in the energy efficiency of the process. In an experi-
ment using a stirred ball mill and grinding aids, Paramasivam and
Vedaraman [8] studied the effect of the physical properties of li-
* Corresponding author.
E-mail address: hkchoi99@changwon.ac.kr (H. Choi).
quid additives on dry grinding and found that additives increased
the fineness of the ground particles and the powder flow. Fuerste-
nau [9] and Hasegawa et al. [10] reviewed the use of chemical
additives for improving the efficiency of both wet and dry pulver-
ization. The effect of grinding aids, i.e. dispersants or additives, on
grinding has been explained mainly by two mechanisms. One is the
alteration of the surface and mechanical properties of individual
particles, such as a reduction of surface energy, and the other is
the change in arrangement of particles and their flow in suspen-
sions [11–14].
Experimental work so far suggests that the grinding efficiency is
related to the grinding behavior of particles. Hence, it would be
practically useful if the grinding behavior could be quantitatively
correlated with the grinding efficiency. In this context, the grinding
rate per specific consumption of grinding energy in the sub-micron
particle size range can be expressed as a comminution coefficient,
K, based on the grinding kinetics. Work so far has shown that K is
related to the mechanical experimental conditions [15]. However,
the relationship between the addition of grinding aids and K is
not yet known. In this study, the behavior of inorganic powders
being ground into sub-micron particles in a wet-grinding process
in a stirred ball mill has been investigated by examining the grind-
ing rate, which is the main parameter affected by the grinding aids
and slurry concentration. The specific grinding energy based on the
measured power and the increase of the specific surface area of
ground products is discussed. And the effect of grinding aids on

0921-8831/$ - see front matter Ó 2009 The Society of Powder Technology Japan. Published by Elsevier BV and The Society of Powder Technology Japan. All rights reserved.
doi:10.1016/j.apt.2009.01.002
 H. Choi et al. / Advanced Powder Technology 20 (2009) 350–354 351

Nomenclature

Caids grinding aids concentration based on weight (wt%) q3 frequency percent under particle size (%/lm)
Cs slurry concentration based on weight (wt%) Sw specific surface area based on weight (m2/g)
dB grinding ball diameter (mm) S1 Limit Specific surface area based on weight in this
D[3,2] mean volume–surface diameter or Sauter diameter experimental range (m2/g)
(lm) t grinding time (min or h)
Em grinding energy consumed (MJ) Vi relative volumes in size class i (m3)
J ball filling ratio (–) Ws weight of the test sample (g)
K comminution coefficient (kg/MJ) x particle diameter (lm)
n rotation speed of stirrer (–) x50 median diameter (lm)
P power consumed to grinding (W) qp density of particle (g/m3)

the comminution coefficient, K, [16] is investigated. The values of K
with or without grinding aids are compared under various experi-
mental conditions.
2. Experimental procedure
All the grinding experiments were carried out in a vertical stir-
red ball mill as in previous work [5,16]. The mill consists of a grind-
ing chamber and a stirrer as schematically illustrated in Fig. 1,
which also shows the dimensions. The grinding chamber holds a
centrally positioned rotating stirrer system with four arms. The
cylindrical pins of 10 mm diameter of and 78.0 mm length are ar-
ranged at right angles to each other. The net inner volume of the
milling chamber is 0.95 l. Alumina balls (purity 99.9%, diameter
u = 1.0 mm (1.41/+0.84), density 3600 kg cm3) were used as
the grinding medium. The consumed energy was measured using
an automatic voltage regulator and an in-house detection circuit,
while the stirrer torque was measured with an A/D converter.
The particle-size distribution of ground products was analyzed
by a Mastersizer microplus (Malvern Instruments, Ltd., UK), based
on the laser diffraction and scattering method. A US-300T homog-
enizer was used as the dispersion device. Calcite powder
(x50 = 6.42 lm, density = 2720 kg cm3) was chosen as the material
to be ground. Grinding aids were based on poly-acrylic acid
(CH2CHCOOH)n.
When the stirrer started to rotate, measurement of the grinding
power consumed with an on-line computer system was started.
The measuring devices for consumed energy consist of the auto-
matic voltage regulator of GPA 100SS AVR (Sung Sin Electronic.
Co., Ltd., Korea) and the detection circuit made by our laboratory.
The torque of stirrer was measured A/D converter (AX5210, Axiom
Technology Inc., Taiwan) and Interface card (ACL-8112PG, AD Link
Technology Inc. UK) with PC on-line.
The total charged weights of balls for each value of the ball-fill-
ing ratio, J, was 1.38 kg for J = 0.7. The slurry concentration was
changed between 60.0 and 70.0 wt%. The grinding experiment
was carried out via a batch process of sampling from the pot at
determined intervals of the grinding time. The amount of grinding
aid was 1.2 wt% of the charged sample. Table 1 shows the amounts
of grinding aids for various slurry concentrations.
Slurry of the sample, including 0.2 wt% grinding aids, was
ground during an initial stage of 13 min and then 1.0 wt% was
fed continuously into the grinding chamber from 14 to 73 min.
During the last 2 min, the grinding operation took place without
feeding grinding aids. The particle-size distribution of the samples
was measured without any dispersion agent. Prior to the measure-
ment of particle size distribution, the homogenizer was used to
disperse particles for 90 s. At the end of each test, all the media
and ground samples were removed from the mill, and the media
were separated from the products by sieving. In order to investi-
gate the effects of slurry concentration on the particle-size distri-
bution of the products for different grinding times, a series of
experiments was carried out. The grinding power consumed was
recorded every 2 min within 30 min or 5 min after that by Excel
software. And we did not consider the power consumed of empty
mill chamber. When the stirrer started rotating, the measuring of
grinding power consumed was started with a computer on-line
system. The calibration of the computer program was performed
by taking 10 measurements by multi-meter [16].

3. Results and discussion

Fig. 2 shows the frequency particle-size distribution of the

products obtained after various grinding times without [Fig. 2a]

Table 1
Composition of the grinding samples.

Cs (wt%) Sample (g) Water (ml) Grinding aids (1.2 wt% of sample, g)
Dispersant Diluent (water)
(40 wt%, g) (60 wt%, g)
60 246 164 7.38
2.95 4.43
70 320 137 9.60
3.84 5.76
Fig. 1. Dimensions and shape of grinding mill pot of experimental stirred ball mill.
352 H. Choi et al. / Advanced Powder Technology 20 (2009) 350–354
Fig. 2. The frequency particle size distribution of feed and ground products for experimental conditions: n = 700 rpm, J = 0.7 (–), dB = 1.0 mm, Cs = 60 wt%. (a) Without
grinding aids and (b) with grinding aids.
and with grinding aids [Fig. 2b]. It is seen that increasing the grind-
ing time not only produces finer products but also narrows the par-
ticle-size distribution by reducing the size and fraction of coarse
particles. The particle-size distribution of the raw material (t = 0)
was broadly bimodal with a fine mode of 0.42 lm and a coarse
mode of 19.31 lm. As the grinding time was increased from
7.5 min to 30 min, the gap between the fine and coarse modes of
the bimodal distribution became gradually narrower, the fine-
mode peak is increasing and the coarse-mode peak is decreasing.
After a sufficient grinding time, 30 min in the current case, the
peak of the coarse mode disappeared and the particle-size distribu-
tion of the ground products became narrow and mono-modal.
Whether grinding aids were added or not, the tendencies of
changes in particle-size distribution were similar to those shown
in Fig. 2. However, the addition of grinding aids resulted in differ-
ences in the size of the final product. It is known that grinding aids
are absorbed on the particle surfaces, and then prevent or reduce
the agglomeration of fine particles due to van der Waals forces
or cold welding [10,11,17–19]. In the absence of agglomeration,
grinding can proceed to a finer state, since the limit of grinding
is shifted towards the finer region as shown in Fig. 2.
Having confirmed the positive effect of a grinding aid, the com-
bined effect of the slurry concentration on the grinding behavior
was investigated. Fig. 3 shows the relationship between grinding
energy consumed and median diameter for each combination of
slurry concentration Cs and the use of grinding aids. The median
diameter of the ground products decreased with increasing grind-
Fig. 3. The relationship between grinding energy consumed and grinding for
experimental conditions: n = 700 rpm, J = 0.7 (–), dB = 1.0 mm.
ing energy consumed for two levels of slurry concentration, 60 and
70 wt%, and was smaller when 1.2 wt% of grinding aid was added
compared to the case without grinding aids. The rate of reduction
of the median diameter, i.e. the slope of the curve in Fig. 3, was lar-
ger up to the grinding energy consumed of about 1 MJ/kg, and then
decreased gradually with the grinding energy consumed. In Fig. 3,
in addition to the beneficial effect of the grinding aids, it is also
seen that the median diameter of the ground products is depen-
dent on the slurry concentration. In the present case, a lower slurry
concentration, i.e. Cs = 60 wt%, results in more finely ground parti-
cles for the given experimental conditions.
In general, the penetration of water and grinding aids into a
crack within a particle could promote propagation of the crack,
resulting in easier breakage of the particle. Hence, the grinding en-
ergy consumed at which the particle-size distribution reached the
grinding limit was shortened with a lower slurry concentration.
With the beneficial role of the grinding aids in preventing agglom-
eration of the particles and the lower slurry concentrations accel-
erating particle breakage, the combination of lower slurry
concentrations and addition of grinding aids should provide opti-
mal conditions for fine grinding for a given consumption of grind-
ing energy.
The effects of the grinding aid and the slurry concentration on
the grinding behavior are now explored in terms of the grinding
kinetics. The grinding behavior is often explained in terms of the
specific surface area of powders and the energy consumed during
grinding. The specific surface area is one of the basic properties
of a powder and is generally represented by the total surface area
of the particles contained in a unit mass of powder. If the distribu-
tion of particle sizes and the shape of a powder sample are known,
the surface area of the powder can be calculated, where the shape
of the ground product particles are assumed to be spherical accord-
ing to the following equation,
P Vi
6 6
Sw ¼ P di ¼ ð1Þ
qp V i qp D½3; 2
Here, Sw is the specific surface area based on weight, Vi is the rela-
tive volumes in the size class i, di is the mean size class diameter
and qp is the particle density, D[3,2] is the surface weighted, or Sau-
ter, mean diameter, that is used from results of particle size ana-
lyzer. Garcia et al. and Cho et al. show a direct comparison of the
BET method and particle size analysis on the specific surface area.
The linear relationship which can be seen for grinding times
increasing suggests that the particle size analysis is reliable for
grounding products [21,22].
 H. Choi et al. / Advanced Powder Technology 20 (2009) 350–354
The specific grinding energy Em is the summation of the grind-
ing power per unit weight of the test sample during the grinding
process, and can be calculated by
Z t
1
Em ¼ PðtÞdt
Ws 0
where Ws is the weight of the test sample and P(t) is the power con-
sumed in grinding for a given grinding time. Since Em is a function
of t, which is related to the ground particle size as shown in Fig. 3.
Thus, using Eq. (2) the specific energy consumed in grinding
was estimated; the relation between the specific surface area and
the specific energy consumed is plotted in Fig. 4. Rittinger sug-
gested that the energy consumed in reducing the size of a solid
was proportional to the new surface produced [19,20]. In the pres-
ent experiment, the increase of the specific surface area was pro-
portional to the specific grinding energy at the initial stage of
grinding without grinding aids. However, Rittinger’s law is applica-
ble only during the first stage where Em is very low, i.e.
Em < 1.2 MJ kg1 in the present case. Besides, the specific surface
area did not reach the grinding limit when grinding aids were used.
For the region of higher Em, the limit theory of grinding fineness
proposed by Tanaka [15] could be applied.
It was confirmed that the limit theory of grinding fineness pro-
posed by Tanaka could be applied to the data obtained within this
experimental range. Following this grinding-limit theory, the pres-
ent grinding behavior can be expressed as [15]
dSw
¼ KðSw1Sw Þ
dt
where K is the comminution coefficient, t is the grinding time and
Sw1 is the specific surface area for t = 1. In this study, we supposed
that the value of the specific surface area Sw1 is the largest in this
experimental range. The specific surface area of powder is one of
the basic properties of the powder and is generally represented
by the surface area of total particles contained in a unit mass of
powder [23,24]. Eq. (3) can be solved using the initial conditions
Sw = Sw0 for t = 0 to give
Sw1  Sw
¼ expðKtÞ
Sw1  Sw0
Denoting DSw ¼ Sw  Sw0 and DSw1 ¼ Sw1  Sw0 and rearranging Eq.
(4) gives
DSw ¼ DSw1 ½1  expðKtÞ
The use of Eq. (5) allows K to be estimated via DSw and t.
Fig. 4. The relationship between the specific surface area and grinding energy
consumed for experimental conditions; sample: calcite, n = 700, J = 0.7 [–], dB =
1.0 mm, Caids = 1.2 wt%
353
ð2Þ
Fig. 5. Change value of specific surface area and grinding energy consumed for
experimental conditions; sample: calcite, exp. conds.: n = 700 rpm, J = 0.7 [–],
dB = 1.0 mm.
Fig. 5 shows the relationship between the change in the specific
surface area and the grinding energy consumed in a semi-log plot.
As can be seen, Sw depends linearly on t, i.e. the slopes K are con-
stant for the given experimental conditions. As the slopes in
Fig. 5 vary with the experimental conditions, it is obvious that K
is dependent upon the addition of grinding aids and the slurry
concentration.
From the slopes in Fig. 5, the comminution coefficient, K, were
estimated for each combination of experimental conditions and
ð3Þ
the results are shown in Fig. 6. It can be seen that comminution
coefficient, K, increases with the use of a grinding aid. For
Cs = 60 wt%, K is improved by 16.0% with the use of a grinding
aid, whereas it is improved by 34.2% with the use of a grinding
aid when Cs = 70 wt%. Therefore, it is suggested that grinding aids
have an important effect on increasing the grinding rate, especially
when the slurry concentration is high. These results show that the
main beneficial effect of grinding aids for a high slurry concentra-
tion is to permit full utilization of the grinding medium inside the
mill through a reduction of slurry viscosity in wet-grinding pro-
cesses. Grinding aids appear to serve the function of preventing
ð4Þ
re-agglomeration by adsorbing on the external particle surface
[23–27]. Some more points about the role of grinding aids can be
drawn from the results of this study. Reduction in the attractive
forces causes better dispersion of the fine particles, which subse-
ð5Þ quently results in easier particle flow, and reduction or prevention
of the coating of the balls and the chamber wall with powder. Fur-
ther, it should be noted that the specific surface area did not reach
the grinding limit when grinding aids were used. Therefore, it is
Fig. 6. The comminution coefficient K and slurry concentration for experimental
conditions; sample: calcite, exp. conds.: n = 700, J = 0.7 [–], dB = 1.0 mm, Caids =
1.2 wt%.
354 H. Choi et al. / Advanced Powder Technology 20 (2009) 350–354
confirmed that grinding aids are very effective in the range of sub-
micron grinding.
4. Conclusions
A series of wet-grinding experiments using inorganic powders
has been carried out in a vertical stirred ball mill. The effects of
grinding aids on the particle-size distribution, grinding efficiency,
particle size, and the comminution coefficient K by the surface area
of total particles contained in a unit mass of powder were
examined.
The comminution coefficient K based on the particle-size distri-
bution with grinding aids was increased by 16.0% and 34.2% for 60
and 70 wt% slurry concentrations, respectively, compared with
those without the addition of grinding aids. When grinding aids
were used, the median diameter decreased in a shorter grinding
energy consumed. Thus, it is confirmed that the comminution coef-
ficient improved with the addition of grinding aids, and that they
are very effective in the range of fine grinding.
Acknowledgement
The authors wish to thank an emeritus professor Woosik Choi of
interdisciplinary program powder technology in Pusan National
University for advising of this study.
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