Chemical Engineering Science 207 (2019) 69–78

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Chemical Engineering Science

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

Tailoring product formulation properties to reduce grinding media wear

Frederik Flach ⇑, Sandra Breitung-Faes, Arno Kwade
Institute for Particle Technology, Technische Universität Braunschweig, Volkmaroder Straße 5, 38104 Braunschweig, Germany

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Formulation variables show a high

impact on the generation of grinding
media wear.

Both solids concentration and
agglomerate size affect the
generation of wear.

The effective stress intensity was
identified as key parameter for
process optimization.

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

Article history: The generation of grinding media wear during wet stirred media milling of organic particles was studied
Received 28 September 2018 in dependence of product formulation parameters. It was shown that targeted product formulation leads
Received in revised form 7 April 2019 to the reduction of ceramic grinding media wear for a certain product quality. Solids concentration and
Accepted 7 June 2019
agglomerate size of product particles were identified as key parameters. Both influence the effective
Available online 13 June 2019
stress intensity of grinding media which has a significant impact on the generation of grinding media
wear. Moreover, the reduction of grinding media wear can be attributed to the damping properties of
Keywords:
comparatively soft organic particles. Their potential to protect ceramic grinding media from abrasion
Stirred media milling
Colloidal stability
can be increased by tailoring formulation properties. Therefore, especially the increase of solids concen-
Grinding media wear tration was identified as most practical formulation variable which affects also grinding efficiency and
Organic particles production capacity.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction pharmaceutical preparation is generally strictly regulated to a lim-

Stirred media milling is applied for mechanical production of
submicron particles. Especially, the production of fine ground
organic particles increased during the last years. Applications can
be found in many fields of industry, such as pharma, food, pigment
and ink, electronics, agrochemicals or chemicals. Most of these
applications require high standards of purity, e.g. the brilliance of
printing inks can be affected by impurities or the approval of a
⇑ Corresponding author.
E-mail address: f.flach@tu-braunschweig.de (F. Flach).
ited contamination. Regarding the process of stirred media milling
it is not possible to avoid contamination from grinding media wear.
There are only a few lab-scale developments based on different
mill principles, e.g. planetary ball mills, which use special grinding
media made from water or dry ice (Juhnke, 2006; Sugimoto et al.,
2012), but these are not suitable for the production-scale. Basically,
the generation of grinding media wear has to be reduced by pro-
cess optimization (Breitung-Faes and Kwade, 2014; Flach et al.,
2016a).
The wear mechanism inside stirred media mills can be classified
according the tribological system as three body abrasive wear

https://doi.org/10.1016/j.ces.2019.06.007
0009-2509/Ó 2019 Elsevier Ltd. All rights reserved.
70 F. Flach et al. / Chemical Engineering Science 207 (2019) 69–78
Nomenclature
Symbol
cm solids mass concentration
cv solids volume concentration
d diameter [m]
Em mass specific energy input [kJ kg1]
Ev grinding chamber volume specific energy input [J cm3]
H separation distance [m]
i ionic strength [mol L1]
m mass [kg]
Np,stressed number of stressed product particles [–]
P power consumption [W]
P0 no load power consumption [W]
r wear rate [k J1]
SE stress energy [J]
SI stress intensity [N m2]
t time [s]
T temperature [K]
V volume [m3]
VGM,act active volume between two grinding media [m3]
Vi interaction energy [J]
where a product particle is stressed between two surfaces, i.e. two
approaching grinding media (Yamamoto et al., 1994). Many studies
on grinding media wear inside stirred media mills were focused on
minerals or ceramics. These products can lead to excessive
grinding media wear due to their abrasive properties, the wear
generation is strongly influenced by operational parameters
(Breitung-Faes and Kwade, 2011, 2008; Kotzé and Bedesi, 2015;
Mende et al., 2004). Especially, the quality of the applied grinding
media and the hardness ratio between product and grinding media
were identified as significant influencing parameters on the result-
ing grinding media wear (Joost and Schwedes, 1996; Becker and
Schwedes, 1999). Joost and Schwedes divided the hardness ratio
in different regimes, excessive grinding media wear is expected
when the product particles are much harder than the grinding
media, moderate wear when both have similar hardness values
and low grinding media wear when the product particles have a
much lower hardness compared to the grinding media (Joost and
Schwedes, 1996). Another general result was, that the generation
of grinding media wear is proportional to the energy input into
the mill (Joost and Schwedes, 1996). Studies with substantial focus
on the stressing conditions and the energy efficiency of grinding
revealed that the generation of grinding media wear is propor-
tional to the applied stress energy (Breitung-Faes and Kwade,
2014; Stender et al., 2001). It was shown that the energy transfer
from the grinding media to the product particles plays a major
role; this characteristic can be derived from the younǵs moduli
of grinding media and product particles (Stender et al., 2001).
Moreover, Breitung-Faes showed that the minimum of grinding
media wear corresponds to optimum stressing conditions
(Breitung-Faes and Kwade, 2014). Farber et al. propagated that also
the friction of grinding media has a significant impact on the
resulting grinding media wear (Farber et al., 2009).
There were also studies on the generation of grinding media
wear resulting from fine grinding of organic particles. Different
studies showed that the product contamination from grinding
media can be reduced by the optimization of process parameters
(Flach et al., 2016a; Hennart et al., 2010; Li et al., 2015; Steiner
et al., 2016). Juhnke et al. found a strong impact of the applied
operation parameters and highlighted the importance of the grind-
ing media quality (Juhnke et al., 2012). Further investigations,
regarding the grinding media material, have shown that the
vt stirrer tip speed [m s1]
w relative grinding media wear [–]
x particle size [m]
Greek letters
g viscosity [Pa s]
j Boltzmann constant [J K1]
m energy transfer coefficient [–]
q density [kg m3]
Indices
A attractive
eff effective
GC grinding chamber
GM grinding media
g grinding
P product
R repulsive
S steric
T total
W water
hardness of grinding media has a significant impact on the result-
ing product contamination. In contrast to ceramics, grinding media
with lower hardness lead to reduced grinding media wear (Flach
et al., 2016a, 2016b).
Organic particles do not have abrasive properties, it can be
assumed that they provide a potential to protect grinding media
from abrasion. A systematic study with varying formulation prop-
erties was performed in order to evaluate the potential of grinding
media wear reduction by organic product particles. Especially, the
variation of solids concentration and targeted particle stabilization
were investigated.
2. Materials and methods
2.1. Materials
The polycyclic aromatic hydrocarbon Anthraquinone (Sigma
Aldrich, Germany) was used as feed material. The crystalline parti-
cles had an initial median particle size x50,3 of 25 mm (Flach et al.,
2016b), the material density is 1440 kg m3 (IARC, 2013). The poly-
mer KollidonÒ VA 64 (KVA 64, BASF, Germany) and the ionic sur-
factant sodium dodecyl sulfate (SDS, Sigma Aldrich, Germany)
were employed as stabilizing additives. All materials were used
as received.
2.2. Particle stabilization
Additives were required to ensure colloidal stability of fine
ground Anthraquinone in water. Particles were stabilized by an
electrosteric barrier against agglomeration. The barrier results
from a steric layer which is provided by adsorption of the nonionic
polymer Kollidon KVA 64 and an additional electrostatic charge.
The electrostatic force can be applied by two different mecha-
nisms: On the one hand the ionic surfactant SDS can be added
which adsorbs together with the polymer onto the particle surface
(Flach et al., 2016a; Konnerth et al., 2016) and on the other hand it
is possible to adjust the pH in order to create a surface charge of
polymer grafted Anthraquinone particles resulting from hydroxyl
ion association towards the particle surface. Several studies on
interfacial properties of hydrophobic materials in water, e.g. of
 F. Flach et al. / Chemical Engineering Science 207 (2019) 69–78
oil in water emulsions, reported the formation of a negatively
charged surrounding layer around the disperse phase due to the
association of hydroxyl ions (Marinova et al., 1996; Elworthy
et al., 1971; Zimmermann et al., 2001; Kudin and Car, 2008). The
Anthraquinone surface is assumed to behave similar like
hydrophobic oil droplets in water, thus a negative surface charge
is resulting from increasing hydroxyl ion concentrations. Electro-
static repulsion can be characterized by the zeta-potential, Fig. 1
shows the zeta-potentials of two different electrostatically stabi-
lized Anthraquinone suspensions as a function of pH. As reported
before, the combination of SDS and KVA 64 showed an almost
pH independent zeta-potential in the magnitude of <30 mV
(Flach et al., 2017). In contrast, the formulation without SDS
showed a decreasing zeta-potential with increasing pH, this can
be attributed towards the aforementioned assembly of hydroxyl
ions towards hydrophobic surfaces in water. The polymer KVA 64
does not carry any pH sensitive groups, thus, it is assumed to pro-
vide only a steric contribution to colloidal stability. The polymer
concentrations of both suspensions were set to 6.25 g L1 KVA 64
and the concentration of SDS was set to 1.25 g L1, pH-changes
were adjusted by adding hydrochloric acid (HCl) or caustic soda
solution (NaOH).
2.3. Milling setup
Experiments were conducted with a 600 mL lab scale stirred
media mill (PML 2, Buehler, Switzerland). The mill was equipped
with a horizontally operated CentexÒ disc stirrer. Both, chamber
lining and stirrer were made of wear resistant silicon doted silicon
carbide. The mill was operated in recirculation mode at a constant
volume flow of 30 L h1. The process temperature was set to
20 ± 2 °C and the operating parameters were kept constant. A stir-
rer tip speed of 8 m s1 was applied and 515 mm yttrium stabilized
zirconia beads (Sigmund Lindner, Germany) were employed as
grinding media. The grinding media filling ratio was kept constant
at 0.8. The electrical power draw, P, of the mill was recorded from
the variable-frequency drive in order to calculate the grinding
chamber volume specific and the product mass specific energy
input according to Eqs. (1) and (2), respectively. No load power,
P0, measurements were performed after each grinding experiment
in order to calculate the net power input.
R tg
ðP  P0 Þdt
0
Ev ¼ ð1Þ
V GC
Fig. 1. Zeta-potentials of different product formulations as a function of the pH.
71
R tg
ðP  P0 Þdt
Em ¼ 0
ð2Þ
mp
2.4. Particle size analysis
Particle size analysis of ground suspensions was performed in
dependence on the product fineness. Particle size distributions in
the micron range (>1 mm) were measured by laser diffraction and
smaller size distributions in the submicron range (<1 mm) were
analyzed by dynamic light scattering. Laser diffraction measure-
ments were carried out with a Helos diffractometer (Sympatec,
Germany). Suspensions were diluted with Anthraquinone satu-
rated water according to the detector signal of the measurement
device. Submicron particle size distributions were analyzed by
using a Nanophox dynamic light scattering system (Sympatec, Ger-
many). Sample preparation was similar, the suspensions were also
diluted with Anthraquinone saturated water according to the
detector signal.
2.5. Grinding media wear analysis
Collisions between grinding media are assumed to represent
the main source of wear generation at grinding operations with
suspensions containing organic particles. Wear is mainly generated
by collisions of the media itself and to some extent by collisions
with mill internals. A comparison of the surface areas demon-
strates the dimensions which determine the probability of contact
events. The grinding media filling of 515 mm beads has a total sur-
face area of 4.19 m2 and the mill internals of the used disc stirrer
geometry (rotor + stator) have a surface area of about 0.1 m2. In
addition, the mill internals were made of silicon doted silicon car-
bide which has a much higher hardness compared to the yttrium
stabilized zirconia grinding media (Becker and Schwedes, 1999).
From tribologic investigations it is known that the hardness ratio
between two materials determines the extent of abrasion of the
materials in contact (Yamamoto et al., 1994). As the grinding
media is known to have a lower hardness, a higher degree of grind-
ing media abrasion can be assumed for collisions of grinding media
with mill internals. Overall it can be stated that the main parts of
wear originate from the grinding media itself. In addition, previous
spectroscopic investigations proved that the residue was mainly
zirconia resulting from grinding media abrasion (Flach et al.,
2017); thus, the wear can be described as grinding media wear.
The ground suspensions were analyzed by a gravimetric procedure.
Liquid and organic substances were removed by thermal treatment
at 600 °C and the residue was determined by weighing. Each sam-
ple was analyzed three times. The wear can be expressed in terms
of relative grinding media wear, w or product contamination, wp
according to Eqs. (3) and (4).
DmGM
w¼ ð3Þ
mGM
DmGM
wp ¼ ð4Þ
mp
2.6. Rheological characterization
Significant information on suspension properties were gener-
ated by rheological characterization. The rotational viscometer
Bohlin Gemini 2 (Malvern Instruments, UK) was used, measure-
ments were performed with a cylindrical gap cell at 20 °C. A shear
rate controlled test was performed. The shear rate was varied in a
logarithmic sequence from 10 to 100 s1.
72 F. Flach et al. / Chemical Engineering Science 207 (2019) 69–78
3. Results and discussion
3.1. Influence of particle stabilization on grinding media wear
Grinding experiments with targeted particle stabilization were
performed in order to control agglomerate sizes, this was realized
by pH-adjustment in the presence of KVA 64. The colloidal stability
can be described by calculating the total interaction energy, V T
between two particles according to the DLVO theory including
the potential of steric repulsion (Derjaguin and Landau, 1941;
Verwey and Overbeek, 1948; Einarson and Berg, 1993).
VT ¼ VR þ VA þ VS
The total interaction energy is derived from the sum of interac-
tions given in Eq. (5), such as attractive (Van-der-Waals), repulsive
(electrostatic) and steric forces.
Fig. 2 presents the calculated total interaction energies of
Anthraquinone particles in water as function of the particle separa-
tion distance at different pH. The interaction energies were calcu-
lated for a particle size of 200 nm according to a previous shown
procedure (Flach et al., 2017). Colloidal stability is characterized
by the height of the energy barrier which keeps the particles at a
certain distance to prevent agglomeration. The calculations show
that the height of the energy barrier is a function of pH. At pH 5
the potential barrier does not exceed 10 kT, thus, particles are
expected to agglomerate. The energy barrier increases with
increasing pH. A maximum value in the range of 25 kT was calcu-
lated at pH 7, limited colloidal stability is expected at this pH. Even
higher maximum values were calculated at pH 9 and 11, energies
in the magnitude of 40 kT and higher are reached. Therefore, espe-
cially in the alkaline regime, colloidal stability is expected.
These theoretical considerations were verified by grinding
experiments at different pH with suspensions containing a solids
concentration of 0.05 Anthraquinone. Fig. 3 depicts the evolution
of the median particle sizes as function of the specific energy input,
resulting from grinding experiments at pH 5, 7, 9 and 11, respec-
tively. The particle sizes, measured either by static light scattering
(x50,3 > 1 mm) or dynamic light scattering (x50,3 < 1 mm), represent
agglomerate sizes which give a measure for colloidal stability. In
the alkaline regime particle sizes smaller than 350 nm were mea-
sured, colloidal stability was assured by increased electrostatic
repulsion forces. Zeta-potentials in the magnitude of 20 mV
proved these observations. The experiments at pH 9 and 11
showed similar results, both were stabilized well against agglom-
eration. Rather strong agglomeration was observed at pH 5 and
Fig. 2. Interaction energy between Anthraquinone particles at different pH-values
as function of the separation distance.
ð5Þ
Fig. 3. Grinding experiments at different pH: median particle sizes plotted as
function of specific energy input.
7, measured particles sizes were in the micron range. Even higher
degrees of agglomeration were observed with increasing specific
energy input because the breakage of primary particles led to an
increase of specific surface area. The equilibrium agglomerate sizes
were shifted towards higher degrees of agglomeration to minimize
the excess of surface free energy. A steady state median agglomer-
ate size of around 2.2 mm was reached at pH 5 and the experiment
performed at pH 7 showed still a continuous increase of the med-
ian agglomerate size. In both cases the electrosteric barrier was not
high enough to ensure colloidal stability. Related investigations
with electrostatic stabilized alumina particles were performed by
Mende et al. who showed that particles can be ground in the
agglomerated state and stabilized afterwards by shifting the pH
(Mende et al., 2003). The same principle was applied to electros-
teric stabilized Anthraquinone particles, a pH shift from 5 to 11
was realized after 5 h of grinding. Afterwards the product suspen-
sion was processed several minutes in order to disperse agglomer-
ates. A significant zeta-potential shift was detected and a median
particle size of 170 nm was measured by dynamic light scattering.
These findings proved that the principle of grinding and subse-
quent particle stabilization can be also applied to suspensions con-
taining organic particles. Moreover, obviously no strong
agglomerates with solid bonds are formed during the process.
It has to be noted that the mill power draws of the different
experiments were almost constant, this can be attributed to the
flow behavior of the suspensions. Table 1 summarizes viscosity
measurement data at shear rates of 10 and 100 s1.
Significant differences between stabilized and non-stabilized
suspensions can be identified. Suspensions at pH 9 and 11 showed
almost newtonian flow behavior. In contrast, the agglomerated
suspensions at pH 5 and 7 showed distinct shear thinning charac-
teristics, viscosities at 100 s1 were significantly lower compared
to 10 s1. This is advantageous for milling, because the effective
shear rates inside stirred media mills were estimated to magni-
tudes of 104 s1 and higher (Blecher et al., 1996; Theuerkauf and
Table 1
Viscosities of suspensions milled at different pH-values (Em: 100.000 kJ kg1) for
different shear rates, values and standard deviations given in Pa s.
10 s1 100 s1
pH 5 0.048 ± 0.00860 0.0072 ± 0.0009
pH 7 0.036 ± 0.00745 0.0066 ± 0.00044
pH 9 0.0014 ± 0.00009 0.0016 ± 0.00004
pH 11 0.0013 ± 0.00004 0.0014 ± 0.00002
 F. Flach et al. / Chemical Engineering Science 207 (2019) 69–78
Schwedes, 1999; Gers et al., 2010; Breitung-Faes, 2017). Thus, the
viscosity changes resulting from particle agglomeration had only a
minor influence on net power draw and grinding efficiency.
The main objective of the present study focuses on the investi-
gation of grinding media wear generation. Fig. 4 shows significant
differences in the resulting relative grinding media wear. Obvi-
ously, the extent of grinding media wear was influenced by the
degree of particle agglomeration. The experiment conducted at
pH 5 led to the lowest values of grinding media wear. With increas-
ing pH an increase of relative grinding media wear was detected
for constant volume specific energy inputs. A similar observation
was made by Mende et al. who detected a lower degree of grinding
media wear resulting from a grinding experiment of alumina with
subsequent particle stabilization, but a further explanation was not
given within their study (Mende et al., 2003).
In case of fine grinding organic particles it is assumed that the
feed material has potential to protect grinding media from abra-
sion (Juhnke et al., 2012). Comparatively soft product particles do
not cause abrasion and provide a certain damping capacity to
absorb collision energy of grinding media. It is assumed that the
damping potential is linked to the stress intensity which is a func-
tion of the particle size and the stress energy of grinding media,
SEGM (Kwade et al., 1996).
SEGM / dGM  qGM  v 2t
3
ð6Þ
Kwade derived the stress energy of grinding media from the
kinetic energy of two approaching beads (Kwade, 2003). The stress
energy is proportional to the mass of one grinding bead and to the
square of stirrer tip speed (Eq. (6)). All experiments of this study
were performed at constant process parameters, i.e. stirrer tip
speed, size and type of grinding media were not changed. That
means the applied stress energy of grinding media was kept con-
stant. Therefore, it is more appropriate to express the energy of a
stress event in terms of stress intensity in order to describe the
impact on product particles. The stress intensity is a specific value
related to the volume of stressed particles. Former investigations
on wet media milling have shown that it is rather difficult to deter-
mine this value exactly. In the submicron range it is likely that
multiple product particles are stressed within one stressing event
(Mende et al., 2004; Kwade, 1996). In the following, the number
of stressed product particles, NP,stressed was estimated based on
the active volume between two grinding media, V GM;act (Eq. (8))
(Kwade et al., 1996), the solids volume concentration, cv and the
apparent median product particle size, x according to Eq. (7).
Fig. 4. Relative grinding media wear resulting from milling experiments at different
pH as a function of the volume specific energy input.
73
V GM;act  cv
NP;stressed / ð7Þ
x3
p
V GM;act /  x2  dGM ð8Þ
4
Therewith, the resulting stress intensity can be expressed in
proportion to the volume of stressed product particles according
to Eq. (9).
SE SE
SI /  / ð9Þ
x3 
V GM;act cv V GM;act  cv
x3
Based on the scheme given in Fig. 5 it can be imaginated that
the extent of agglomeration has a high impact on the resulting
stress intensity. The higher the extent of agglomeration the lower
the resulting stress intensity at constant operating parameters.
Regarding the organic Anthraquinone particles which are relatively
soft compared to the ceramic grinding media a mechanism of
shielding by product particles might be proposed. Due to the lower
hardness and the higher degree of elasticity compared to the grind-
ing media, especially agglomerates of organic particles may protect
the grinding media from abrasion. It can be assumed that collisions
of approaching grinding media were damped when product parti-
cles, in particular agglomerates, were captured and stressed.
In addition to the degree of agglomeration, other suspension
properties have to be considered. Especially, the viscosity has a
strong impact on the kinetic energy of colliding grinding media
and the frequency of grinding media collisions. In particular at high
suspension viscosities the energy dissipation due to fluid displace-
ment leads to a significant decrease of the stress energy of grinding
media. Former investigations of Knieke et al. have shown the exis-
tence of a critical viscosity which represents a limiting value for
comminution. Their definition is based on the Stokes number of
grinding media as a measure for the energy dissipation due to fluid
displacement. It is assumed that no further grinding is possible
when high suspension viscosities prevent the contact of grinding
media surfaces (Knieke et al., 2010). In the present study this
approach was proved to be not applicable. Due to the distinct shear
thinning flow behavior of product suspensions it was not possible
to estimate a correct value for describing the viscosity. Inside the
grinding chamber a shear rate dependent distribution, compared
to the distribution of grinding media velocities, can be assumed
(Blecher et al., 1996; Theuerkauf and Schwedes, 1999). In this case
it seemed to be more applicable to balance the dissipation by fluid
displacement according to the approach of Breitung-Faes. Her
approach is based on the assumption that the energy dissipation
by fluid displacement is minimized when the mill is operated with
pure water (Breitung-Faes, 2017).

ðP P0 ÞW
mg /  ð10Þ
ðP P0 ÞP
The energy dissipation due to fluid displacement inside a given
mill can be described by a so–called energy transfer coefficient mg
(Eq. (10)). It is calculated from the net power consumption when
pure water is processed with the same set of operating parameters
related to the experimental net power consumption.
SIeff / SI  mg ð11Þ
Finally, the so-called effective stress intensity can be calculated
according to Eq. (11). It provides a measure to describe the impact
of operation and formulation parameters. Thus, especially the
influences of particle size, solids concentration and fluid viscosity
were considered by this approach.
The influence of the effective stress intensity on the generation
of grinding media wear is reflected in Fig. 6 which refers to the
74 F. Flach et al. / Chemical Engineering Science 207 (2019) 69–78
Fig. 5. Schematic view to describe normal stressing events of stabilized particles and agglomerates.
wear rate of grinding media. This characteristic value is calculated
from the relative grinding media wear and the net energy input
according to Eq. (12).
w and deviations can be mainly attributed to this approximation.
r ¼ Rt
ðP  P0 Þdt
0
It has to be recognized that the stress energy of grinding media
was kept constant, the variation of effective stress intensities was a
result of changing agglomerate sizes, which obviously have an
impact on the wear rate. It has to be noted that the stress intensi-
ties were calculated based on median values from at-line particle
Fig. 6. Impact of effective stress intensity on the wear rate.
size analysis. Inside the grinding chamber there are much higher
dispersion forces affecting the agglomerate sizes. Hence, the mea-
sured values enable only a rough estimation of the stress intensity
ð12Þ Nevertheless, this proves that agglomerates from organic particles
have the capability to reduce wear effects. On the one hand it can
be assumed that the effective stress intensity was closer to the
optimum one, which results in a reduction of grinding media wear
generation (Breitung-Faes and Kwade, 2014). And on the other
hand it is assumed that agglomerates absorb a higher extent of
stress energy by elastic and plastic deformation. According to the
findings of Stender et al., the wear rate depends strongly on the
degree of energy which remains in the grinding media after a
stressing event (Stender et al., 2001). This degree of energy can
be characterized by the so called wear energy of grinding media,
which decreases strongly with decreasing younǵs modulus of the
product particles (Stender et al., 2001). Thus, it is likely that a
higher elasticity of product particles, i.e. of agglomerates, leads to
reduced wear rates.
3.2. Influence of solids concentration on the effective stress intensity
and resulting grinding media wear
According to the definition of the effective stress intensity it can
be assumed that also the grinding efficiency and the extent of wear
are influenced by the variation of the solids concentration. There-
fore, grinding experiments with varying solids concentrations of
Anthraquinone in the range of 0.05–0.6 were performed in order
to evaluate the potential of this formulation principle. According
to the material density of Anthraquinone this corresponds to a vol-
umetric concentration range, cv from 0.035 to 0.42.
Fig. 7 depicts the median particle sizes x50,3 as function of the
specific energy input resulting from grinding experiments with
 F. Flach et al. / Chemical Engineering Science 207 (2019) 69–78
varying solids concentrations. It can be seen that the grinding effi-
ciency is strongly dependent on solids concentration and product
fineness. Similar effects were observed from the comminution of
ceramics (Knieke et al., 2010). The worst grinding performance
resulted from the grinding experiment with the lowest solids con-
centration of 0.05. Increasing solids concentrations led to increas-
ing grinding efficiencies. The experiment at 0.15 mass load
Anthraquinone showed a three times higher energy efficiency
compared to the experiment at 0.05, because the net power con-
sumption remained almost constant. Even a further increase of
solids concentration to 0.375 led to a more efficient comminution.
These observations can be mainly attributed to the increasing
number of particles being catched and stressed between approach-
ing grinding media (Kwade, 1996). A further increase of solids con-
centration to values 0.45 showed a different behavior. In this
concentration range the efficiency is strongly dependent on the
product fineness. At the beginning of the grinding process high
concentrations were more efficient, but with increasing fineness
the efficiency shifted towards median solids concentrations. This
effect can be attributed to increasing suspension viscosities with
increasing volume fractions and numbers of product particles
(Knieke et al., 2010; Bernhardt et al., 1999). From these observa-
tions it gets obvious that there is an optimum solids concentration
for reaching a certain product fineness. Fig. 8 shows exemplary for
a target particle size of 180 nm that this dependency can be
described well by the effective stress intensity.
In Fig. 8 a minimum of specific energy requirement can be iden-
tified at effective stress intensities in the range of 9  1012 Nm2.
This minimum is a result of varying stressing and energy transfer
conditions due to the different solids concentrations. With increas-
ing solids concentrations there are more particles inside the sus-
pension which can be captured and stressed between two
approaching grinding media. This leads to a higher extent of colli-
sions where particles are sufficiently stressed and thus, more
kinetic energy is transferred from the grinding media to the pro-
duct particles. In addition, the stress intensity decreases with
increasing number of particles captured and stressed per stress
event which results in a higher energy utilization. Most efficient
grinding is assumed to take place at the optimum stress intensity.
A further increase of the solids concentration leads to lower stress
intensities at which the stress intensity gets too small to break a
sufficient number of particles or even to break particles at all
Fig. 7. Median particle size x50,3 as function of the specific energy input at varying
solids concentrations.
75
Fig. 8. Specific energy to obtain a target particle size of 180 nm as function of the
effective stress intensity for different solids concentrations.
(Kwade, 2003). Additional impact on the kinetic energy of grinding
media and therewith on the effective stress intensity is given by
the suspension viscosity, which is strongly affected by increasing
particle volume fractions and decreasing particle sizes. Higher sus-
pension viscosities lead to increased dissipation by fluid displace-
ment of the grinding media. This effect was intensely studied by
Knieke et al. who found a critical suspension viscosity which rep-
resents a process limit for real comminution of ceramics (Knieke
et al., 2010). However, a critical viscosity which represents a limit
of grinding was not found for the organic product particles. A chal-
lenge might be given by the particle stabilization against agglom-
eration at high solids concentrations. It can be assumed that
reduced distances between single particles at high volume frac-
tions may led to bridging effects and the formation of agglomerates
(Tadros, 2010). This can be seen as a limiting condition of particle
stabilization.
Overall, it can be seen that the increase of solids concentration
provides a high potential to increase the energy efficiency of grind-
ing. It can be assumed, that as well the generation of grinding
media wear is being affected.
Fig. 9 shows the relative grinding media wear as function of the
volume specific energy input resulting from the variation of solids
concentration. It can be seen that the different concentrations
show different wear characteristics. The increase in wear as func-
tion of the volume related energy input was more pronounced
for low solids concentrations. Towards the grinding process of
ceramics, this operation can be classified into the lower shelf of
hardness ratio between product and grinding media (Joost and
Schwedes, 1996). The organic product particles have a much lower
hardness compared to the grinding media, thus, they have the abil-
ity to protect grinding media from abrasion. The more particles are
present inside the suspension, the more are captured between two
approaching grinding media, this leads to a higher extent of kinetic
energy which is transferred from the grinding media to the product
particles. At the same time the process is influenced by the
increase of the suspension viscosity with increasing solids concen-
tration. The effective stress intensity is lowered by energy dissipa-
tion due to fluid displacement at high solids concentrations. The
objective of grinding is usually defined by a certain target particle
size, therefore the resulting grinding media wear has to be evalu-
ated in relation to the fineness. Similar to the required specific
energy, the relative grinding media wear generated to achieve a
target particle size of 180 nm is plotted in Fig. 10 as a function of
the effective stress intensity for different solids concentrations.
76 F. Flach et al. / Chemical Engineering Science 207 (2019) 69–78
Fig. 9. Relative grinding media wear at different solids concentrations as function
of the volume specific energy input.
Fig. 10 depicts that a minimum of wear can be identified at an
effective stress intensity of 7  1012 Nm2, which is close to the
effective stress intensity for the minimum of required specific
energy to achieve a product fineness of 180 nm (see Fig. 8). It is
assumed that most efficient grinding conditions are linked to the
minimum of wear (Flach et al., 2016a). Deviations can be attribu-
ted to simplifications of the calculation procedure, measurement
deviations in particle size and wear analysis as well as slightly
changing wear characteristics of grinding media over time
(Stender et al., 2001). Therefore, it can be concluded that optimiza-
tion of grinding conditions by means of the effective stress inten-
sity enables both the reduction of grinding media wear and the
minimization of specific energy input. It has to be noted that also
the stress energy of grinding media has to be taken into account,
in this case it was kept constant to show the impact of formulation
variables. In former studies it was proven that wear is a function of
the stress energy of grinding media which can be described by the
relative wear per wear event (Stender et al., 2001). Therefore,
further investigations on the impact of varying mill operating
Fig. 10. Relative grinding media wear related to a target particle size of 180 nm,
resulting from grinding at different solids concentrations as function of the effective
stress intensity.
parameters and the stress energy of grinding media in combination
with changing solids concentrations are required.
Other important measures related to the vairation of the solids
concentration are the production capacity and the product con-
tamination. The production capacity can be calculated by rearrang-
ing Eq. (2). In general the maximum production capacity, for a
specified product fineness, is reached when the specific energy
input is minimized and the net power input is maximized
(Kwade, 2004). From Fig. 11 it can be clearly seen that the produc-
tion capacity increases significantly with increasing solids concen-
tration until a maximum value is reached. This can be explained by
the increasing power draw of the mill and the decreasing specific
energy input. It should be noted that optimum grinding conditions
regarding specific energy consumption and maximum production
capacity do not match each other. The required specific energy
input increases by exceeding the minimum at solids concentra-
tions in the range of 0.45 (see Fig. 8), but the maximum production
capacity is reached at a solids concentration of 0.525, because the
decrease in energy efficiency is compensated by the high increase
of power draw. However, at the maximum solids concentration of
0.6 grinding is less efficient, thus the production capacity
decreases. Usually, a further increase of the production capacity
can be achieved by increasing the net power input at optimum
stressing conditions, most likely by increasing the stirrer tip speed
and decreasing the grinding media diameter (Kwade, 2004).
For many applications the product contamination which is
affected by the solids concentration gives a relevant measure to rate
the product quality. Fig. 11 shows also the resulting product con-
taminations as function of the solids concentration. Due to the dif-
ferent wear characteristics and product mass concentrations high
differences in the resulting product contaminations can be identi-
fied. By changing the solids concentration a reduction of almost fac-
tor 10 is possible. The lowest product contamination was reached at
a solids concentration of 0.45 at which also the optimum effective
stress energy is reached, but there is only a marginal difference
compared to the resulting contaminations at higher solids concen-
trations. In this range of high solids concentrations the increasing
amount of wear is compensated by the increasing product mass.
According to practical considerations it would be recommended
to operate the mill at a solids concentration of 0.5 in order to obtain
the maximum production capacity at a low contamination level and
relatively low specific energy consumption.
Fig. 11. Production capacity and resulting product contamination for a target
particle size of 180 nm as function of the solids content.
 F. Flach et al. / Chemical Engineering Science 207 (2019) 69–78
4. Conclusions
The wear resulting from ceramic grinding media abrasion dur-
ing stirred media milling can be lowered by targeted product for-
mulation of suspensions containing organic particles. It was
shown that product particles have the ability to protect the grind-
ing media from abrasion. Especially, the increase of solids concen-
tration represents a suitable strategy to reduce grinding media
wear and increase productivity. The effect can be mainly ascribed
to a change of the effective stress intensity because more particles
are captured and stressed between colliding grinding media. More
energy is transferred to the comparatively soft product particles,
this leads to the reduction of wear. The increase of solids concen-
tration is a suitable formulation principle, as long as the suspen-
sion viscosity does not limit the grinding process. Hence, there is
an optimum solids concentration corresponding to the minimum
of grinding media wear for a given target fineness. Additionally,
it was shown that organic particles can be ground in the agglomer-
ated state and dispersed by subsequent stabilizer addition. This
strategy was proved to result in a lower relative grinding media
wear because stressing of agglomerates leads to lower effective
stress intensities. The question arises if the increase of solids con-
centration and the strategy of targeted stabilization can be com-
bined. Experiments have shown that milling of non-stabilized
suspensions at elevated solids concentrations lead to a significant
increase in viscosity which increases the risk of blocking the mill
or the circulation system. Thus, the applicability of this strategy,
i.e. the stabilization of the suspension at the end of the milling pro-
cess, is limited to low solids concentrations. An increase of the
solids concentration without proper stabilization is restricted due
to a critical viscosity. Ideally, starting with the optimum solids con-
centration without stabilizer the viscosity has to be controlled by
adding stabilizer during almost the entire milling process. How-
ever, since such a strategy is difficult and expensive to realize, it
can be concluded from a practical point of view, that the increase
of solids concentration to an optimum value with initial stabiliza-
tion is the most appropriate formulation principle to reduce grind-
ing media wear.
In summary, it was shown that changes of the product formula-
tion provide a high potential to reduce ceramic grinding media
wear. Most practical relevance is given by the increase of solids
concentration which provides a high potential to increase the
grinding efficiency. The specific energy input can be significantly
reduced by optimizing the solids concentration, this has a strong
impact on the production capacity and the resulting product con-
tamination. Finally, the production capacity can be maximized by
increasing the solids concentration to a certain value, which corre-
sponds almost to the minimum product contamination.
Declaration of Competing Interest
The authors declared that there is no conflict of interest.
Acknowledgement
The Deutsche Forschungsgemeinschaft (DFG) is gratefully
acknowledged for funding this research work (grant: KW 9/18).
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