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Selecting Ceramic Grinding Media: Part 1 – Theory

Article  in  Chemical Engineering & Technology · November 2012

DOI: 10.1002/ceat.201200122

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 Fine grinding 2051

Hanlie Kotzé Research Article

Consensi Consulting, Mtunzini,
South Africa.
Selecting Ceramic Grinding Media:
Part 1 – Theory
In the mining industry where large volumes of grinding media per mill are re-
quired, media wear versus cost is a key optimization consideration. Quantifica-
tion of in-plant media wear is, however, often problematic. It can be done indir-
ectly via small-scale laboratory mill tests or potentially via measurement of the
physical and mechanical properties of the media: size, density, sphericity, hard-
ness, toughness, etc. While some of these parameters are easily quantifiable, hard-
ness and toughness as indicators of media wear are not as straightforward. The
importance of hardness and toughness of grinding media in the stirred-mill
environment are explained as well as the considerations that should be borne in
mind when using these measurements as quality parameters. These considera-
tions are given against the background of the various manufacturing methods of
ceramic grinding media and the influence thereof on media quality.

Keywords: Ceramic grinding media, Fine grinding, Modulus of elasticity

Received: February 29, 2012; revised: April 30, 2012; accepted: May 10, 2012
DOI: 10.1002/ceat.201200122

1 Introduction
As with other inert grinding media, ceramic media leave clean
mineral surfaces, leading to substantially improved mineral re-
coveries in downstream hydrometallurgical processes [1, 2]. In
addition to the advantages ceramic media have over conven-
tional steel grinding media, they also have advantages over the
other inert media types [3]. One study found them to have
four times lower wear rates than sand, while no fine SiO2 par-
ticles are generated that can cause sliming in downstream ben-
eficiation. These benefits do come at a price. Hence, the total
cost of use must be calculated to enable an informed decision
on the most economically viable media type – the lowest me-
dia wear rate combined with the highest metallurgical benefit,
for the best price.
Factors that directly influence the total cost of media are the
purchase price and the media wear rate. Other factors that in-
directly influence the user cost are: consequential maintenance,
e.g., to what extent the mill lining and disc or pin life are
affected by the choice of media, energy efficiency, i.e., the re-
quired energy input to reach a given reduction ratio, and the
positive or negative effects of the media on downstream recov-
ery processes.
– must be understood. The first part of this paper is a brief
Correspondence: Dr. H. Kotzé (hanlie.k@consensi.co.za), Metallurgical
Engineering, Consensi Consulting, P.O. Box 106, Mtunzini, 3867
KwaZulu-Natal, South Africa.
Of the above direct and indirect cost factors, only the pur-
chase price is readily determinable. In theory, the wear rate of
media should also be easily determinable; however, the reality
is that industrial plants on occasion need to dump entire mill
charges and/or experience media losses via outgoing streams.
These and similar occurrences typical of an industrial-scale op-
eration prohibit the accurate measurement of media wear via a
mass balance method. Although wear measurement via image
analyses has been reported [4], representative sample selection
could be a problem. Where comparative wear rates are mea-
sured on large-scale plants, scientific principles need to be
maintained to ensure comparable results, i.e., keeping all other
outcome-determining variables constant while varying the me-
dia type.
A viable alternative to the measurement of plant wear is
comparative laboratory wear tests – provided such wear tests
are of similar energy intensity to the specific plant. Quantifica-
tion of the stress energies [5, 6] of the industrial mill and labo-
ratory- or bench-scale tests is helpful in this regard. Examples
of representative laboratory test methods for stirred detritor
mills (SMD) [7] and IsaMills [8–10] are described in the litera-
ture.
This paper focuses on the roles of physical properties of
media on the wear mechanism. In order to correctly interpret
the mechanical properties of ceramic materials, the methods
with which ceramic micro-grinding media are manufactured
description of manufacturing methods and is aimed at those
consumers of grinding media who are usually not trained cera-
micists.

Chem. Eng. Technol. 2012, 35, No. 11, 2051–2057 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
2052 H. Kotzé

2 Manufacturing Methods Table 1. Theoretical densities of some typical industrial chemicals used in the
manufacturing of ceramic grinding media. Densities of common grinding media
manufactured from such industrial chemicals are also shown.
Two prevalent perceptions exist around ceramics,
namely, that all ceramics are similar and that ce- Raw Raw material Grinding media Grinding
ramic micro-milling media are too expensive to be material density [g cm–3] media density
considered for the large volumes of grinding media [21] [g cm–3]
required in fine milling applications in the mining
Alumina 3.99 Alumina media 3.78–3.81
industry. In the preceding paragraphs, it was ex-
plained that the total cost of use must incorporate Zircon 4.7 Zirconium silicate – sintered [14] 4.1
the media price including delivery to site, the wear
Zirconium silicate – fused [14] 3.8
rate, consequential maintenance and metallurgical
benefits in the downstream processes. The follow- Zirconia 5.7–6.1 Zirconia – Y stabilized [14] 6.0–6.1
ing paragraphs address the second perception by Silica 2.65 Ceramic glass [21] 2.3–3.1
explaining why ceramic materials can differ sub-
stantially in quality.

on an industrial scale with densities equal to the theoretical

2.1 Raw Material Selection and Preparation
Although ceramic grinding media like zircon, porcelain, glass
and sand media are made from natural raw materials, the more
advanced media are manufactured from refined industrial
chemicals such as alumina (Al2O3), zirconia (ZrO2), silicon
carbide (SiC) and silica (SiO2) [11, 12]. The processing steps
in manufacturing advanced ceramic materials are well illustrat-
ed by the photographs shown in Fig. 1 of a polycrystalline,
multi-component magnetic garnet material [11]. Though this
raw material – magnetic garnet – is not relevant to ceramic
grinding media, the general manufacturing steps are similar
and well illustrated by these microstructures.
The selection of type and quality of raw materials used in
the manufacturing of ceramic media is determined by the de-
sired properties of the final product. Using the density of
grinding media as an example, the theoretical densities of a
few relevant raw materials are listed in Tab. 1, together with
the densities of some grinding media manufactured from these
raw materials. The difference in the theoretical densities of the
raw material and those of the grinding media is attributed to
two primary reasons. Firstly, ceramic products are often
named after the major constituent, e.g. an alumina ceramic
can contain 80–99 % Al2O3. Two or more sources of, e.g., alu-
mina grinding media can therefore not be compared directly
without knowledge of their compositions. Secondly, it is very
difficult to manufacture large volumes of a ceramic material
density of the compositional materials. The reasons for this
will become evident during the next paragraphs regarding the
manufacturing steps.
Selected raw materials of the desired size range are thor-
oughly mixed (Fig. 1, left) before being heat treated to form a
uniformly phased material consisting of agglomerated crystals
(Fig. 1, middle). If required, this uniform material is then
milled to the desired size range before being formed. The size
of the primary particle of a ceramic final product is determin-
ing in its final mechanical properties, especially its wear behav-
ior [4, 13]. Wear losses are less for grinding media composed
of smaller primary particles.
2.2 Forming
There are three forming methods for grinding media [14]: the
sol–gel process, granulation and pressing. With the sol–gel
process, the prepared raw material is mixed with water to
form a slurry. Rheology modifiers are added to enable the slur-
ry to be cast as droplets, which gel when coming into contact
with a saline solution. The as-cast drops are subsequently dried
before being sintered. Provided slurry preparation and the
casting and drying processes are well controlled, the sol–gel
process delivers a spherical green bead (the freshly formed
bead still with little mechanical strength) with a homogeneous
structure containing few if any flaws. The process is limited

Figure 1. Microstructures along the manufacturing steps of a magnetic garnet ceramic: (left) raw materials in powder being prepared for
forming; (middle) the mixture after homogenisation at elevated temperatures; (right) ceramic material after high-temperature sintering
[11].

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to the production of small bead diameters – usually less than
5 mm.
During granulation, the processed raw materials are added
in powder form to small seed granules contained within a ro-
tating drum. By adding controlled amounts of water and
sometimes binder material, the seed granules grow in size by
progressively accumulating layers of powder while new seeds
form. When within the desired size range, the granules are re-
moved from the rotating drum and sintered. This forming
method has a wider size range application, but the onion-
layered effect could be a source of flaws within the sintered
product.
A pressed bead is formed by filling a die cavity with pro-
cessed, normally spray-dried, powder and compacting it at
high pressure. Provided the raw material is free flowing and
other quality control measures are in place, the subsequent
green form has a uniform, flaw-free structure. This method is
usually employed when making larger ceramic balls, i.e.,
10 mm and larger. The economic viability of the method di-
minishes with smaller media sizes.
2.3 Sintering
Subsequent to the forming step, the green product has little or
no mechanical strength and has a bulk density of around 45–
60 % of the theoretical one (Fig. 1, middle). It will reach the
desired density and physical properties through sintering. Sin-
tering temperatures range from 1300 to 1750 °C, depending on
the composition. At such elevated temperatures, ions or atoms
are mobilised to allow diffusion across grain boundaries, lead-
ing to pore elimination resulting in a dense material (Fig. 1,
right). Grain growth, which will lead to inferior wear resistance
in grinding media, can also occur during prolonged sintering.
Successful sintering is a fine balance between densification and
flaw elimination on the one hand and contained grain growth
on the other.
As an alternative to the above forming and sintering pro-
cesses, the fusion process melts the raw material(s) at elevated
temperatures – up to 2000 °C [14]. Droplets are generated
from the molten material and sprayed or granulated into the
atmosphere. During their travel path, they cool down and soli-
dify into stable beads. Beads thus produced are reported to
tend to create micropores due to rapid cooling, air entrapment
within the droplets, two or more beads sintering together after
colliding in mid-air and/or inhomogenization of the bead dur-
ing cooling [14].
It is evident that the manufacturing processes of micro-ce-
ramic grinding media pose several opportunities for the crea-
tion of microstructural flaws within the bead. Unlike metals
where a microscopic flaw can be accommodated by local plas-
tic flow to contain crack progression, the brittle nature of
ceramic materials does not allow for much local plastic defor-
mation. The strength of ceramic materials is determined by the
presence or not of microscopic flaws, whereas the toughness of
ceramic materials was found to be related to the average mi-
crostructure [11] – for example grain size.
In summary, there is a wide range of ceramic materials avail-
able. This is also true for ceramic micro-grinding media. With-
Chem. Eng. Technol. 2012, 35, No. 11, 2051–2057 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Fine grinding 2053
in any given type of ceramic material, large variations of physi-
cal properties can exist due to different raw material properties
and different manufacturing methods.
3 The Mechanism of Wear
The wear mechanism of ceramics is a combination of two
types of surface events: plastic ploughing and fracturing [12].
In this context, fracturing is interpreted as both macro-frac-
tures (where the media fragments lead to increased wear on
the mill lining etc., due to sharp edges) and micro-cracks
forming on the bead surface, leading to progressive wear from
the bead surface. Lower wear rates resulting from plastic sur-
face flow is hence the preferred wear mechanism for grinding
media. Which mechanism dominates is determined by the
stress intensity within the mill environment and the relative
physical properties of the grinding media and ore.
Apart from hardness and toughness, other parameters im-
portant for the wear rate are the size of the primary particles
constituting the media, the hardness of the ore relative to that
of the grinding media, the smoothness of the media surface,
the sphericity of the media and the chemical environment
within the milled slurry [4, 13, 15]. Media size and density play
a determining role in wear via the mill stress energy. From
Eq. (1), the stress energy SE (N m) is proportional to the media
size dGM1) (m), the media density qGM (kg m–3) and the mill
tip speed tt (m s–1) [6]. For harder, crystalline product materi-
al, the moduli of elasticity of the product EP (GPa) and the
media particles EGM (GPa) are included in the equation.
For softer product particles:
SE / dGM
3
qGM t2t (1a)
For harder product particles:
! 1
EP
SE / dGM qGM tt 1 ‡
3 2
(1b)
EGM
Theoretically, higher stress energies are thus imposed by
using larger and denser media with all other parameters being
constant. Bearing the interplay between dominant wear mech-
anisms in mind, grinding media can thus be their own worst
enemy. In an optimal mill environment, the stress energy and
thus media size and density are selected to minimize the spe-
cific energy required to mill the feed material [6].
The importance of hardness and toughness in the mecha-
nism of grinding media wear and their use as quality parame-
ters warrants further discussion in the following sections.
3.1 Media Hardness
Hardness is a measure of the resistance of a material against
plastic deformation. Hardness is determined via indentation
–
1) List of symbols at the end of the paper.
www.cet-journal.com
2054
techniques, namely the Vickers, Rockwell or Knoop tests [12].
As an indicator of media quality, hardness is important from
two aspects: (i) its role in determining the wear mechanism
and (ii) as an indicator of the whole-bead quality, i.e., the
hardness along the cross-section of a bead.
3.1.1 The Role of Media Hardness in Determining the Wear
Mechanism
Media wear is reported to increase as the ratio of media hard-
ness to particle hardness decreases [13], i.e., the harder the ore,
the harder the media must be to minimize wear. When com-
paring the absolute hardness of materials, the statement that
harder materials will have lower wear than the softer ones
holds true only for materials with substantially different hard-
ness numbers. Smaller differences in hardness do not necessar-
ily imply different wear rates: For example, the Vickers hard-
ness (HV0.15) for hot-pressed alumina is 1400–1700 kg mm–2
while that of high-alumina ceramics is 1200–1550 kg mm–2.
Despite the small overlap in hardness numbers, their respective
wear rates were found to overlap extensively [12].
Hence, though the hardness of grinding media plays an im-
portant role in deciding their dominant wear mechanism, as a
standalone property it is not a predictor of wear, especially
where the hardness values of comparative media types do not
differ substantially.
3.1.2 Consistency of the Hardness Property throughout the
Media Particle
Besides having a direct influence on particle wear, hardness
measurements along cross-sections of media particles are in-
dicative of media life within the mill. An example of Vickers
hardness measurements taken at ten points along the cross-
sections of two 3.5-mm alumina beads are shown in Fig. 2
Figure 2. Vickers hardness measurements (HV1) on two types of 3.5-mm alumi-
na beads taken along their cross-sections [16].
www.cet-journal.com © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
H. Kotzé
[16]. The variation in hardness measurements is characteristic
of ceramic materials; both materials show consistent hardness
throughout.
On occasion, beads are found with a hard shell but substan-
tially softer core. This is thought to be due to layered inconsis-
tent densities formed during granulation, or possibly due to
incorrect sintering steps. Such flawed beads show low wear
rates for as long as the outer shell is intact. When the hard out-
er shell is worn away, the remainder of the bead disintegrates
in the harsh mill environment. In laboratory-/bench-scale test-
ing, this quality defect can go undetected if the energy applied
is too low to wear away the outer shell. An example of such re-
sults is shown in Fig. 3 where the cumulative mass loss of beads
is plotted against the milling energy. These tests were con-
ducted in an M4 horizontal Netzsch mill lined with polyure-
thane and with an effective volume of 3.4 L. The initial bead
volume was 2 L (60 % fill ratio) and the agitator rotational
speed was 2100 rpm; water was used as medium and was circu-
lated at 2.6 L min–1. The mill’s energy consumption was mea-
sured before and after each pass. The total test duration was
8 h. After every 2 h, the mill was drained and the beads cap-
tured and dried. The mass loss after each pass was calculated
as the percentage of the dry media mass charged into the mill
at the start of each pass. Bead B showed good wear rates after
2 h, but during the second pass the beads disintegrated to a
mass loss of almost 25 % – an order of a magnitude more than
the 2.5 % average mass loss of the other beads.
For Bead B to show its true quality, the test energy had to
surpass a minimum level. The test energy can be increased,
amongst others, by increasing the test duration and/or increas-
ing the fill ratio. Thorough quality testing of media can be a
time-consuming exercise. This is problematic for both media
consumers and manufacturers: The simpler and less time con-
suming a quality test, the more frequently it can be applied;
hence, smaller batches can be checked. More time-consuming
quality tests require less frequent sampling and composite
samples and/or batches not being tested. Quality information
hence becomes either less representative of the me-
dia or more averaged out between batches. For a
manufacturer, fast feedback from a quality test is
required to enable fast corrective reaction.
Having a representative and fast quality test that
measures a media property or properties, which,
on its own or in combination, accurately predicts
wear performance is therefore the ideal. The Vick-
ers hardness measurement is ideal from a test
duration point of view, but likely not sensitive
enough.
3.2 Media Fracture Toughness
The toughness of grinding media is a measure of
their resistance to fracture. Though the correctness
of fracture toughness measurements on ceramic
materials via indentation techniques is contested
[17], the small volume of a micro-ceramic grinding
bead necessitates the use of indentation techniques.
Indentation techniques and calculation models are
Chem. Eng. Technol. 2012, 35, No. 11, 2051–2057
 Fine grinding 2055

In the case of sample B, a lower hardness corre-

sponded with a lower toughness measurement.
However, as seen from samples D and E, this is not
a consistent correlation: Samples D and E mea-
sured similar toughness measurements, but with
different hardness measurements. In fact, the high-
est toughness measurement – sample F – was
found to correspond with the lowest hardness.
Since media wear is a combination of surface
plastic deformation, i.e. hardness, and surface mi-
cro-fracture, i.e. toughness, mechanisms predicting
the media wear from hardness and toughness
measurements requires a model quantifying the
contributions of hardness and toughness and, per
implication, elasticity. From Figs. 4 and 5, this is
Figure 3. Cumulative mass loss of various types of grinding media after being obviously not a linear model. Though the accuracy
milled in an M4 Netzsch horizontal-disc mill with water as medium for four
–1 of fracture toughness values measured via
passes. Each pass lasted for 2 h. The mill disc tip speed was 11 m s and the
water flow rate was 2.6 L min–1. indentation techniques is reported to be as little as
30 % [12], the combination of hardness and
toughness measurements does have potential as a
extensively reported on in the literature [18–20] and, when in- quality assurance tool. Provided the measurement method,
terpreted as comparative results, they are valuable. e.g., sample preparation, indentation technique, crack mea-
One such model is given by Eq. (2) [21] where fracture surement, calculation model and measurement of the modulus
toughness is quantified by K1C, the stress intensity factor. The of elasticity, is standardized on, hardness and toughness mea-
subscripts 1 and C respectively denote crack initiation under a surements could potentially be used as a wider indicator of
tension normal to the crack plane (an opening crack as op-
posed to a shearing crack) and conditions for critical stress, i.e.
unstable crack growth. K1C (MPa m1/2) is calculated from the
average dimensions of the indentation a (lm), and the crack
length c (lm). The shorter the crack(s) forming at the corners
of the indent, the tougher is the material. In Eq. (2), E (GPa)
and H (GPa) represent the Young’s modulus of elasticity and
hardness, respectively, while F (N) is the indentation force.
The Young’s modulus is a material property and therefore
representative of a flawless material. However, as already ex-
plained, the measured strength of ceramic materials is flaw
dependent. For this reason, a measured modulus of elasticity
instead of the Young’s modulus is more correct for ceramic
materials and minerals.
Figure 4. Hardness measurements on six zirconia-toughened
!0:4 ! 1 alumina grinding media under progressively changing sintering
p E c 2
F conditions. Error bars are sized to one standard deviation.
K1c ˆ 0:018H a 1 where H ˆ 0:47 (2)
H a a2

Six zirconia-toughened alumina grinding media samples

(samples A–F) were collected from batches sintered under pro-
gressively changing conditions. These samples were mounted
in a resin, ground and polished to create smooth cross-sec-
tional areas. Hardness and toughness measurements were
made using a Vickers indentation instrument. The load force
was 30 kg and the dwelling time was 30 s. The hardness and
toughness was calculated utilising Eq. (2). In the absence of a
measured modulus of elasticity and not detecting visible flaws
within the bead cross-sections under magnification, a Young’s
modulus for zirconia-toughened alumina of 360 GPa [22, 23]
was used. The measured hardness numbers are in agreement
with typical numbers for good-quality ceramic grinding Figure 5. Indentation toughness of zirconia-toughened alumina
media, while the toughness measurements correspond to the grinding media as calculated from Eq. (2) and hardness num-
higher end of the scale reported for wear-resistant materials. bers as given in Fig. 4. Error bars are for one standard deviation.

Chem. Eng. Technol. 2012, 35, No. 11, 2051–2057 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
2056 H. Kotzé

grinding media quality. However, accurate measurement of E [MPa] Young’s modulus of elasticity
crack lengths when trying to distinguish crack tips between EGM [GPa] modulus of elasticity of grinding
other microstructural features is difficult and open to interpre- media
tation. Further work to correlate the wear in test and industrial EP [GPa] modulus of elasticity of ground
applications with hardness and toughness data is required. particles
Measurement of the modulus of elasticity of a non-spherical H [–] indentation hardness
bead – which is typical of grinding media produced at high K1C [MPa m1/2] stress intensity factor (fracture
volumes – also requires further investigative studies. toughness)
SI [kJ kg–1] stress intensity

4 Conclusion Greek symbols

qGM [kg m–3] grinding media specific density
A wide range of ceramic micro-grinding media with hugely
tt [m s–1] tip speed of mill pin/disc
varying compositional and quality properties is available on
circumference
the market. Selecting media with physical properties best suit-
ed for a given mill environment will contribute immensely to
optimize the metallurgical benefit and to minimize media and References
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the theory is incomplete. Media selection and comparison will
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[2] S. Grano, Miner. Eng. 2009, 22, 386.
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 Fine grinding 2057

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