Powder Technology 105 Ž1999.

374–381
www.elsevier.comrlocaterpowtec

Comminution of ceramics in stirred media mills and wear of grinding

beads 1
M. Becker ) , J. Schwedes
Institute of Mechanical Process Engineering, Technical UniÕersity of Braunschweig, Volkmaroder Str. 4 r 5, D-38104, Brunswick, Germany

Abstract

Experimental investigations on the comminution of fused corundum and silicon carbide show that comminution and wear behaviour of
ceramic grinding beads are affected by the structural constitution of grinding beads. For grinding beads composed of large primary
particles, the achievable product fineness seems to be limited by the size of the primary particles. For the grinding beads composed of
small primary particles, the product fineness is not limited by the size of the primary particles. The relation between specific energy
requirement and product fineness is essentially affected by the amount of grinding bead wear. The wear of grinding beads is determined
by the structure and the hardness of beads as well as by the hardness and the shape of the feed particles.

´ ´
Resume

´
Les essais experimentaux ´
relatifs au broyage de corindon fondu et de carbure de silicium montrent que le broyage et la resistance a`
´
l’usure des corps de broyage en ceramique ´ par la composition structurale des corps de broyage. Pour les corps de broyage
sont influences
´ de grosses particules primaires, on peut atteindre une certaine finesse de produit mais elle semble limitee
formes ´ par la taille des
particules primaires. Pour les corps de broyage formes ´ de petites particules primaires, la finesse du produit n’est pas limitee´ par la taille
´
des particules primaires. Le rapport entre le besoin en energie ´
specifique ´
et la finesse du produit depend surtout de l’importance de l’usure
´
des corps de broyage. L’usure des corps de broyage est determinee ´ par la texture et la durete´ des corps, ainsi que la durete´ du materiau
´ a`
broyer. q 1999 Elsevier Science S.A. All rights reserved.

Keywords: Stirred media mill; Wear of grinding beads; Comminution of ceramics

1. Introduction Thus, stirred media mills are increasingly used for the
comminution of ceramics. They show a higher power
The requirements for raw ceramic materials and struc- density than ball mills, and are generally more favourable
tural parts for industrial applications are constantly grow- with regard to energy requirement than other mills in the
ing. Among others, the properties of structural parts de- demanded particle size range.
pend on the different processing steps during production. For the comminution of hard ceramic materials, the
An important step in the production is the comminution of selection of suitable grinding beads is very important.
the raw materials down to the required product fineness, Besides the costs of grinding beads and the contamination
frequently below 1 mm for engineering ceramics. The of the product with abraded particles, the grinding bead
comminution of hard ceramics such as fused corundum wear causes a higher specific energy consumption. The
and silicon carbide is difficult because these materials investigations show that different properties of grinding
present a high resistance to comminution. Dry comminu- beads and feed affect the relation between product fineness
tion processes with jet mills or roller mills are hardly and specific energy as well as the relation between energy
suitable for the comminution of these materials to submi- consumption and grinding beads wear.
cron sizes and also comminution in ball mills has its limits.

) 2. Experimental setup
Corresponding author. Du Pont Central Research and Development,
Experimental Station, Wilmington, DE 19880-0304, USA
1
Extended version of the presentation at the 9th European Symposium Fused corundum ŽAl 2 O 3 . and silicon carbide ŽSiC. are
on Comminution, September 8–10, 1998, Albi, France. comminuted with grinding beads of aluminium oxide Žfive

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 1 - 8
 M. Becker, J. Schwedesr Powder Technology 105 (1999) 374–381 375

Fig. 1. Grinding chamber of laboratory stirred media mill.

different types., zirconium oxide Ž2., mixed oxide Ž2., grinding bead size: d gb s 1.3 mm; grinding bead density:
silicon nitride, steatite, titanium oxide and steel in a labora- rgb s 2700–6000 kgrm3.
tory stirred media mill. The median particle sizes of fused The moduli of elasticity of the grinding beads were
corundum Ž x 50 f 33 mm. and silicon carbide Ž x 50 f 40 determined by compression tests and have values in the
mm. are measured with a laser diffraction spectrometer range of 101–410 GPa. The comminution tests were termi-
ŽSympatec, Helos.. Fig. 1 shows the grinding chamber of nated after 1, 2, 4, 8, 15, 20 and 40 passages and the
the laboratory stirred media mill with a grinding chamber samples were analysed with a laser diffraction spectrome-
volume of 0.58 l. The stirrer shaft is fitted with four ter ŽSympatec. for particle size analysis.
perforated discs. The filling ratio of grinding beads is In numerous tests on comminution of limestone in
wgb s 80% and the remaining free volume is filled with a stirred media mills, Stehr and Schwedes w1x and Weit et al.
waterrproduct suspension. w2x have ascertained that the comminution result for the
Since comminution of hard ceramic materials not only comminution in stirred media mills essentially depends on
causes grinding beads wear but also considerable wear of the specific energy. The specific energy is the energy input
stirrer discs and grinding chamber wall, stirrer discs made into the grinding chamber related to the mass of stressed
of wear-resistant polyurethane and a grinding chamber particles m p . During the tests, the torque T and the number
coated with polyurethane are used. The heat conductivity of revolutions n were measured at the stirrer shaft. Con-
of polyurethane is relatively low so that the cooling of the sidering the idling torque T0 and the comminution time t,
grinding chamber is not sufficient to dissipate the heat the specific energy Em can be determined as follows:
arisen in the grinding chamber during the comminution t
process. Thus, the waterrproduct suspension is pumped H0 Ž T Ž t . y T . 2p ndt
0
repeatedly through the grinding chamber in passage opera- Em s . Ž 1.
tion and the heat is dissipated in an external cooler. The mp
volume flow rate is adjusted to 25 lrh. Since the external
suspension volume is kept small Ž0.3 l, no stirrer tank., the
comminution result corresponds to a discontinuous test for 3. Comminution results
a sufficient number of passages. The following operating
parameters are chosen: solids mass concentration: c m,0 s The comminution results for the comminution of fused
0.2; circumferential velocity of stirrer discs: Õt s 12 mrs; corundum with different grinding beads are presented as a
376 M. Becker, J. Schwedesr Powder Technology 105 (1999) 374–381

function of specific energy in Fig. 2. For the tests, all silicon nitride. It can be seen that the specific energy
operating parameters were kept constant. It can be seen requirement for the production of a certain fineness is
that for steel beads the specific energy required for the different for the different types of grinding beads. For
production of a certain fineness is higher than for ceramic instance, for producing a median particle size of 1 mm
beads for a median particle size coarser than 1.5 mm. with grinding beads made of steatite, about 50% more
During the comminution process, small wear particles with specific energy is required than for grinding beads made of
a high specific surface are removed from the surface of the silicon nitride.
grinding beads. If steel beads are used a very reactive For the other group of grinding beads, the curves level
surface is produced so that steel and water are transformed off early. In Fig. 2, the two aluminium oxide grinding bead
into Fe 2 O 3 and H 2 Žgaseous. in a chemical reaction. That types with an Al 2 O 3-content of 99.7% and 92% belong to
means that part of the grinding chamber volume is perma- this group. The achievable product fineness seems to be
nently filled with gas. Hence, the motion of grinding beads limited for grinding beads of this group. In spite of an
in the grinding chamber differs from that without gas. increasing specific energy, it is not possible with grinding
Besides, the surface of steel beads can be plastically beads of this group to comminute as finely as with grin-
deformed during a stress event. The energy that is used for ding beads of the other group. The reasons for this can be
plastic deformation of the surface of the steel beads cannot found in the structural constitution of the grinding beads.
be used for the comminution of the feed particles. In The surfaces of two grinding bead types of different
contrast, the plastic deformability of the surface of ceramic groups which were already used in comminution tests are
beads is negligible. Therefore, the energy utilisation for compared in Fig. 3. The presented structure of the bead
steel beads is lower than for ceramic beads. The hindered surface is obtained after comminution times less than
motion of the grinding beads due to the gas in the grinding 1 min. Thereafter, the principal structure of the bead
chamber and the lower energy utilisation due to plastic surface does not change any more. The grinding beads
deformability of the bead surface are the reasons for the with an Al 2 O 3-content of 99.7% are composed of rela-
higher specific energy requirement of steel beads com- tively large primary particles Žabout 5–10 mm.. The struc-
pared to ceramic beads. ture of the surface shows that whole primary particles are
Considering only the comminution results for the com- broken out of the grinding bead surface during the com-
minution with ceramic beads in Fig. 2, two groups of minution process. Thus, the product is constantly contami-
grinding bead types can be distinguished. The one group is nated with abraded particles of the size of the primary
distinguished by a constant comminution progress with particles of the grinding beads Ž5–10 mm.. The achievable
increasing specific energy. In Fig. 2, this group includes product fineness is limited due to the constant supply of
grinding beads made of aluminium oxide Ž86.5%., steatite, the product with these large particles. The smaller the
mixed oxide 2, zirconium oxide ŽY2 O 3-stabilized. and primary particles of which the grinding beads are com-

Fig. 2. Comminution results for comminution of fused corundum with different grinding beads.
 M. Becker, J. Schwedesr Powder Technology 105 (1999) 374–381 377

Fig. 3. Surface of two grinding beads types with different wear behaviour. Žleft: Aluminium Oxide Ž99.7%., right: Aluminium Oxide Ž86.5%..

posed, the higher is the achievable product fineness for this of the product particles plus half of the mass of the
group of grinding beads. grinding bead wear m gb,w :
In contrast to the grinding beads with a high Al 2 O 3
t
content, the aluminium oxide grinding beads ŽFig. 3. with
an Al 2 O 3-content of 86.5% belong to the group of grind-
Em ,w s H0 Ž T Ž t . y T . 2p ndt
0
. Ž 2.
ing beads which are characterized by a constant increase in m p q 0.5m gb ,w
product fineness for increasing specific energy supply. The
grinding beads of this group are composed of considerably Since the stirrer discs are made out of wear-resistant
smaller primary particles Žup to approximately 1.5 mm.. polyurethane and the grinding chamber is coated with
For these grinding beads, another wear mechanism can be polyurethane the wear of stirrer discs and of the grinding
recognized. It can be seen in Fig. 3 that no whole primary chamber wall is very much lower than the wear of grin-
particles are broken out of the grinding bead surface but ding beads. Thus, the wear of stirrer discs and grinding
small particles are ground off from the primary particles. chamber wall needs not to be taken into account for the
These abraded particles are considerably smaller than the calculation of the specific energy. In Fig. 4, the median
primary particles and thus cannot limit the product fine- particle size x 50 is presented as a function of the specific
ness in the investigated particle size range. energy Em,w for the comminution of fused corundum with
Due to the wear of grinding beads, the solids concentra- different grinding beads. Only those results are shown,
tion of the suspension increases during comminution. The which were obtained by tests with grinding beads that
energy input into the grinding chamber is not only con- show no limitation of the achievable product fineness by
sumed for the comminution of the product particles but the primary particles size. Except the grinding bead types,
also for the comminution of the abraded particles of the all other operating parameters are kept constant. In contrast
grinding beads. At the start of a test, no grinding bead to Fig. 2, the comminution results for the different types of
wear has yet occurred, whereas at the end of the test the grinding beads presented in Fig. 4 can be described in a
entire mass of grinding bead wear m gb,w is present in the first approximation by a fitted curve. The width of the
grinding chamber. On average, the total energy input into particle size distribution is not affected by the type of
the grinding chamber must therefore be applied for the grinding beads. For a constant specific energy Em,w diffe-
comminution of the product mass and half of the mass of rent grinding bead materials with different wear rates
grinding bead wear. The specific energy Em,w is the produce almost the same product fineness when all other
energy input into the grinding chamber related to the mass operating parameters are maintained constant. The higher
378 M. Becker, J. Schwedesr Powder Technology 105 (1999) 374–381

Fig. 4. Effect of grinding bead wear on relation between specific energy and product fineness for the comminution of fused corundum.

the grinding bead wear, the more total energy input into According to Joost and Schwedes w4x, the grinding bead
the grinding chamber is required to obtain the same spe- wear essentially depends on the energy related to the
cific energy Em,w ŽEq. Ž2... The part of the energy that is grinding chamber volume Vgc :
used for the comminution of the wear particles cannot be
used for the comminution of the actual product. To keep Etot
Ev ,gc s Ž 4.
this part as low as possible and to minimize contamination Vgc
of the product, wear resistant grinding beads should be
used. Etot is the total energy input in the grinding chamber. In
For a more precise consideration, deviations of the Fig. 5, the dimensionless wear value for different types of
measured values from the fitted curves can be recognized. grinding beads is plotted vs. the energy related to the
Since all other operating parameters were kept constant, grinding chamber volume. The measured values can well
these deviations must be caused by different grinding bead be described by straight lines in a log–log scale. The two
densities. Among other, the effect of grinding bead density groups of grinding bead types which show different com-
on the relation between specific energy consumption and minution behaviour can also be distinguished concerning
product fineness was investigated by Kwade et al. w3x for wear behaviour. In Fig. 5, the two groups of grinding bead
the first time for the comminution of limestone in a stirred types differ with regard to the gradient of the straight lines.
media mill. For the first group, the gradient is equal to 1, while it is
less than 1 for the other group. A gradient less than 1 in a
log–log scale means that the curves correspond to a power
4. Grinding bead wear function with degressive behaviour. The wear of grinding
Comminution in stirred media mills basically takes beads decreases with increasing comminution progress and
place between the grinding beads. During the stress event, thus with decreasing product particle size. Comparable to a
not only the product particles are comminuted but also the grinding process, large product particles are able to remove
surface of the grinding beads is stressed and damaged. Due relatively large wear particles from the surface of the
to abrasion and breaking of primary particles out of the grinding beads due to their geometric dimensions, while
surface of the grinding beads, the mass of grinding beads small product particles only can abrade small wear parti-
decreases during comminution. The mass of grinding beads cles. Thereby, a smoothly ground surface is produced ŽFig.
is weighed before and after each test and the mass diffe- 3, at right.. Due to the structural constitution of these
rence is the grinding bead wear D m gb . A dimensionless grinding beads out of relatively small primary particles, the
wear value is obtained by relating the loss of grinding bead wear mechanism is characterized by abrasion of small
mass D m gb to the mass of grinding beads at the start of a parts of the primary particles.
test m gb : For the group of grinding beads with a gradient of 1,
D m gb the grinding bead wear is constant during the comminution
. Ž 3. process, independently of the product fineness. The struc-
m gb
ture of these grinding beads of relatively large primary
 M. Becker, J. Schwedesr Powder Technology 105 (1999) 374–381 379

Fig. 5. Grinding bead wear as function of energy related to grinding chamber volume.

particles Ž5–10 mm. leads to the number of contact points With those grinding beads, which consist of small
per unit volume between the primary particles being lower primary particles Ž- 1.5 mm., fused corundum Žpyramid
than for a structure of smaller primary particles. Therefore, hardness: 2200 HV., silicon carbide Ž2650 HV. as well as
the strength between the primary particles is reduced so quartz Ž1500 HV. were comminuted. For the comminution
that permanently whole primary particles are removed of silicon carbide and quartz, similar relations between
from the grinding bead surface ŽFig. 3. independent of the grinding bead wear and volume related energy can be
product fineness. For this group of grinding beads, the found as for the comminution of fused corundum. The
wear of grinding beads is higher the larger the primary hardness of the products are taken from the manufacturers
particles are. specifications whereas the hardness of grinding beads are

Fig. 6. Effect of hardness of grinding beads and product particles on grinding bead wear.
380 M. Becker, J. Schwedesr Powder Technology 105 (1999) 374–381

further properties of the grinding beads andror the product

that affect the grinding bead wear. It is expected that the
shape of the product particles has an effect on the wear of
grinding beads. To investigate this, SEM images are taken
of the particles and the shape factor SF proposed by
Pentland w6x is determined. This shape factor is defined as
the relation of the area of the particle image to the area of
the smallest circle that surrounds the particle ŽFig. 7.:
Ap
SF s . Ž 5.
Ac

A shape factor of 1 means that a particle is circular. The

investigations show that the shape factors of fused corun-
dum, silicon carbide as well as quartz are independent of
the product fineness. The mean values of the shape factors
Fig. 7. Area of particle and circle. of about 70–100 particles of each product are determined:
silicon carbide: SF s 0.52, quartz: SF s 0.56, fused corun-
dum: SF s 0.62. The highest shape factor is obtained for
measured by the pyramid method. The measured hardness fused corundum. Consequently, the fused corundum parti-
of the grinding beads are in the range of 505 HV Žsteatite. cles are rounder than the others. For a constant hardness
and 1571 HV Žaluminium oxide, 95%.. ratio, the grinding bead wear is lower the rounder the
To determine the effect of grinding bead hardness on product particles are. Therefore, the wear for the comminu-
the wear of grinding beads, the dimensionless wear values tion of fused corundum is lower than for quartz and silicon
are plotted vs. the ratio of hardness of grinding beads carbide, as can be seen in Fig. 6. In Fig. 8, the wear of
ŽHVgb . to hardness of the product ŽHVp . for a constant grinding beads is plotted vs. the product of the hardness
volume related energy Em,w of 1000 Jrcm3 in Fig. 6. The ratio and the shape factor for a constant volume related
grinding bead wear decreases with increasing hardness of energy Em,w of 1000 Jrcm3. In this figure, the dimension-
grinding bead material. From various tribological systems, less wear values for all products coincide. That means that
it is well known that the wear of a sample depends on the for the group of grinding beads which consist of small
ratio of the hardness of the stressed material to the hard- primary particles the volume related energy, the hardness
ness of the abrasive material w5x. Thus, it was expected that of the grinding beads, the hardness of the product particles
the curves in Fig. 6 for fused corundum and silicon carbide as well as the shape factor of the product particles are the
would coincide. Since this is not the case, there have to be main influencing parameters on the wear of grinding beads

Fig. 8. Effect of hardness of grinding beads, hardness of product particles and shape of product particles on grinding bead wear.
 M. Becker, J. Schwedesr Powder Technology 105 (1999) 374–381 381

in stirred media mills. The higher the hardness of the essentially depends on the hardness of the beads as well as
product particles is the higher is the wear of grinding on the hardness and the shape of the product particles.
beads. The grinding bead wear decreases with increasing Therefore, to minimize the specific energy requirement
hardness of the grinding beads and increasing shape factor and the contamination of the product, grinding beads which
of the product particles. A lot of shape factors are defined are composed of small primary particles Ž- 1.5 mm. and
by different authors in the literature. If the shape factors have a high hardness as well, should be used.
proposed by Tickel w7x and Wadell w8x, for instance, are
used instead of the shape factor of Pentland, similar results
are obtained in principle.
The shape and hardness of the product particles cannot References
usually be changed. Thus, to keep the grinding bead wear
as low as possible, grinding beads should have a high w1x N. Stehr, J. Schwedes, Investigation of the grinding behaviour of a
hardness and should be composed of primary particles stirred ball mill, Ger. Chem. Eng. 6 Ž1983. 337–343.
smaller than 1.5 mm. w2x H. Weit, J. Schwedes, N. Stehr, Comminution and Transport Beha-
vior of Agitated Ball Mills, Preprints: 1. World Congress Particle
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Technology, Part II, Nurnberg, 1986, pp. 709–724.
w3x A. Kwade, L. Blecher, J. Schwedes, Motion and stress intensity of
5. Conclusions grinding beads in a stirred media mill: Part II. Stress intensity and its
effect on comminution, Powder Technol. 86 Ž1996. 69–76.
The experimental investigations on comminution of w4x B. Joost, J. Schwedes, Comminution of white fused alumina and wear
fused corundum and silicon carbide in a stirred media mill of grinding beads in stirred media mills: Part II. Effect of operational
parameters, grinding chamber geometry and beads hardness on the
show that the comminution behaviour as well as the wear wear of grinding beads, Ceram. Forum Int. 73 Ž1996. 69–76.
behaviour is affected by the size of the primary particles of w5x H. Uetz ŽEd.., Abrasion und Erosion, Grundlagen, Betriebliche Er-
which the grinding beads consist. The energy input into the fahrungen, Verminderung, Carl Hanser Verlag, Wien, 1986.
grinding chamber is not only used for the comminution of w6x A. Pentland, A method of measuring the angularity of sands, R. Soc.
the product particles but also for the comminution of the Can. Proc. Trans. 3 Ž21. Ž1927. 93.
w7x F.G. Tickel, The Examination of Fragmental Rocks, Stanford Univ.
wear particles. Press, 1931, pp. 6–7.
If the size of the primary particles of the grinding beads w8x H. Wadell, Volume, shape and roundness of quartz particles, J. Geol.
is relatively small Ž- 1.5 mm. the grinding bead wear 43 Ž1935. 250–280.