ROHSTOFFE UND ANWENDUNGEN

RAW MATERIALS AND APPLICATIONS

Raw material parameter variations

Mixing
Compound quality variations

Carbon black clusters
In the present paper the influence of
the carbon black quality parameter
fines content was investigated with
respect to the mixing process and the
compound properties. It was found
that the carbon black fines content
influences the mixing process of the
sulphur cured and EPDM based recipe
to less extend. However, small variations of the specific mixing energy
correlate with the macro-dispersion of
the carbon black and the Mooney
viscosity. In contrast to these results,
the compression set, the die swell and
the mechanical compound properties
are significantly affected by the carbon
black fines content, which can be explained by the existance of carbon
black clusters. Furthermore, the cure
rate of the compound is reduced by
about 50% when the fines content
increases, which is confirmed by variations of the sulphur dispersion.

Der Einflu von Rohmaterial

Parameterschwankungen im
Mischsaal: Feinanteil von Ru
Teil 1
Rohmaterial Parameterschwankungen
Mischen
Qualitatsschwankungen der Mischungen
Rucluster
In dem vorliegenden Bericht wurde
der Einflu des Ru Qualitatsparameters Feinanteil hinsichtlich seiner
Auswirkung auf den Mischproze
und die Mischungseigenschaften
untersucht. Es wurde festgestellt,
da Feinanteil des Rues den
Mischproze der schwefelvernetzten und EPDM basierten Mischung
kaum beeinflusst. Trotzdem korrelieren kleine Abweichungen der
spezifischen Mischenergie mit der
Makrodispersion des Rues und der
Mooney Viskositat. Demgegenuber
wirkt sich der Feinanteil des Rues
merklich auf den Druckverformungsrest, das Dusenschwellen und
die mechanischen Mischungseigenschaften aus, was durch die Existenz
von Ruclustern erklart werden
kann. Weiterhin sank die Vernetzungsgeschwindigkeit um 50% ab,
was mit der Dispersion des Schwefels
korreliert.

250

The Influence of Raw Material

Parameter Variations in the
1
Mixing Room
Carbon Black Fines Content Part 1

Nowadays the rubber industry is exposed

to both an increasing economical pressure
and higher quality requirements. Following
the chain of added value from raw material
acceptance to end products one can define four influencing fields which have impact on quality: The raw materials and
their deviation range, the raw material
storage, the compounding process and
the processing of end articles.
In the present paper the field of raw material parameter variations will be studied.
Looking at raw material acceptance test
procedures in the todays rubber processing industry it must be stated that not
much work is done at all. The reason for
this is that most of the suppliers are certified according to ISO 9000/9001 or similar
standards. In addition such testing would
mean that one needs all the corresponding
facilities and manpower due to the high
number of ingredients. Furthermore one
should realize that rubber compounds
are rather complex mixtures: It is really difficult to get an overview of the meaning of
all kind of raw material parameters in combination to their impact to the mixing process and the end article properties. Of
course, mutual dependencies do also exist
among the ingredients. Therefore quality
agreements are made between suppliers
and processors.
In most recipes carbon black and polymers
are the important ingredients in terms of
mass content. For this reason raw material
parameter variations of these ingredients
can be expected to have an impact on
compounding, further processing and
the end article properties. The study described in this paper deals with variations

Presented at a meeting of the Rubber Division,

American Chemistry Society, April 4th, 2000 in Dallas.

in the fines content of carbon blacks.

The term fines sums up all carbon black
particle sizes smaller than 125 lm which
may arise for example due to transport
or conveying processes.
The carbon black fines content is quite low
at the delivery by the suppliers. At rubber
processors the carbon black is normally
stored in silos and conveyed pneumatically
from there to the hopper above the mixer.
The conveyance from the lorry to the silo
and from the silo to the hopper is often
problematical. In dependence of the conveyance system, different amounts of fines
contents may be generated [1]. In cases
where high air velocities are applied, values
of 60% fines content or even higher can
be reached at the entrance of the mixer.
If such systems are in use the conveyance
process itself is already very problematical.
With increasing fines contents the risk of
pressure variations in the pipes due to formations of plugs rises. The conveyance
process becomes discontinuous and resulting problems are extended feeding times
of the carbon black into the mixer and
weighing inaccuracies. Depending on
the type of carbon black sticking effects
may also occur in the pipes. In an earlier
study the pneumatic conveyance process
was investigated and it was found that
the fines content of low structured carbon
blacks sticks to the pipes, which leads to a
reduced cross section of the pipe. For this
reason the air velocity is increased further
on and the problems are intensified [2].
As the mixing process is concerned, resulting problems can be seen in the sense of a
reduced bulk density, which is due to the
fineness of the material. Therefore the

A. Limper, H. Keuter,
and C. Ruter, Paderborn

KGK Kautschuk Gummi Kunststoffe 56. Jahrgang, Nr. 5/2003

fill factor of the mixer may be influenced at

the beginning of the mixing process. Variations of the fill factor may lead to dispersion problems [3]. Further problems may
arise if the polymer and the carbon black
are not compatible and slip effects may appear. In those cases the power input into
the batch might be not very effective, resulting in bad dispersion of the carbon
black.
For this study, carbon black was produced
having variations of the fines content up to
40%. The carbon black fines have then
been exchanged in an sulphur cured and
EPDM based recipe, being used in the field
of household appliance seals. The effects
of different fines content were studied
with respect to the mixing process and
the compound properties. Compound
properties have been determined with
standard testing methods and more sophisticated methods like RELMA and the
RPA.

Experimental results
Ingredients
The carbon black N 650 was conveyed in a
pneumatic conveying system to obtain different amounts of fines content. About
500 kg each was conveyed several times
in the system in every experiment to
achieve different values of fines content.
Since the material had to be delivered in
bags to the mixing line, a small deviation
to the original process had to be accepted:
In a normal production set up the carbon
black is added to the mixer using air with
an adjustable velocity between 5 and
40 m/s. Usually this ends up in some degree of fluidisation of the carbon black resulting in an impaired carbon black incorporation. In our case, an intermediate
packaging step for the carbon black was
used.
The compound formulation (Table 1) is typical for household appliance seals. An oil
extended amorphous EPDM type having
a Mooney viscosity of 48 MU (at 100 8C),
an ethylene content of 56 wt.% and an
ENB content of 4.1 wt.% was used.

Mixing equipment
The mixing experiments were done on a
Werner & Pfleiderer GK 90 E internal mixer
with a chamber volume of 90 L and intermeshing rotor geometry (PES 3). The mixer
was cooled by a water system of different
circuits for the rotors and the chamber. The

Table 1. Recipe to study the effects of different carbon black fines contents.
Ingredients

Density/(kg/dm3)

Parts/(phr)

Polymer: EPDM, 50 wt% oil extended

Carbon Black N 650; Fines Contents: 14.9%,
25.2%, 40.6%
Paraffinic Oil
Sulphur
Chemicals

0,880
1,800

150 (100)
115

0,881

31 (81)
2
16

Total

314

Table 2. Mixing Procedure.

Step

Rotor Speed/rpm

Time/s

1. Feeding Polymer
2. Polymer Crumbling
3. Feeding Carbon Black, Sulphur,
Oil and Chemicals
4. Mixing
5. Cleaning
6. Mixing
7. Dumping

35
35
25

20
20
20
40

180
10
60
10

mixer was operated at a fill factor of 63%

and maximum ram pressure. The fill factor
chosen for the experiments was optimal
with respect to quality aspects and mixing
efficiency. After the mixing step a roll-mill
and a strip-cooling unit followed. The specific mixing energy in the respective mixing
cycles was calculated by integrating the
current consumption as a function of
time. The results were divided by the corresponding batch weight. The crumbling
energy was subtracted in order to focus
the effective mixing phase only.
The mixer was equipped with a data processing unit able to record the current consumption, the batch temperature, the rotor speed, the ram position and the ram
pressure.

Mixing procedure
A one step mixing procedure was applied
(Table 2). Every carbon black adjustment
was mixed 3 times. The third batch of
each set was examined. The mixer was
heated up with two batches before the actual experiment started. The data presented in this paper exists of mean values,
gained from 3 repeat tests.

Characterization of compounds
The characterization of the compound
quality was performed using standard
methods such as: Rheometer MDR 2000
(at 0.58 strain, 180 8C) according to ISO
6502; Mooney viscosity ML (1 4)
100 8C according to ISO 289; Mooney
Scorch (at 145 8C); hardness Shore A; density; tensile strength; tear strength, elonga-

KGK Kautschuk Gummi Kunststoffe 56. Jahrgang, Nr. 5/2003

Temperature/ 8C

40
110
122

tion at break; stress-strain behavior (Modulus M 100); compression set (70 h/100 8C)
and 22 h, 25% according to ISO 815.
More sophisticated methods like e.g. the
RELMA method and the Rubber Processing
Analyzer (RPA) [4] were employed also. The
carbon black macro-dispersion was determined optically [5] and mechanically [6]. In
addition the Garvey Die test was used to
characterize the extrusion behaviour of
compounds. The RELMA method, which
is usually not applied in the rubber mixing
room, will be introduced as follows:
A pulsed laser beam produces a plasma on
the surface of a sample. The material is ablated from the surface and enters a plasma
cloud. The electrons of the outer orbits are
brought to a higher energy level, which is
an unstable condition. Going back to a
lower energy level, specific radiation is
emitted which can be attributed to chemical elements. This radiation can be detected with spectroscopic methods. As
the measuring time is quite short, the system can work with a frequency of 25 Hz.
By scanning the surface, the content of
chemical elements at each measured
spot can be indicated. By statistical methods the distribution of the elements in the
surface can be determined [7].

Results and discussion

In Figure 1 and 2 the current consumption
of the mixer and the batch temperature are
shown in dependence of the carbon black
fines content. No significant differences
can be observed. The deviation range of
the curves can be addressed to normal pro-

251

Fig. 1. Current consumption during the mixing cycle as a function of the

mixing time and the carbon black fines content.

Fig. 2. Batch temperature during the mixing cycle in dependence of mixing time and the parameter carbon black fines content.

Fig. 3. Specific Mixing energy in dependence of the carbon black fines

content.

Fig. 4. Dispersion in dependence of the carbon black fines content

[5, 6] 2).

cess variations. A slight shift of about 10

seconds in the current consumption curves
at the time of feeding carbon black and
chemicals is related to the handling of
these materials.
The free flowing of the carbon black having high fines content is disturbed, because the adhesive forces of the particles
are increased with decreased particle sizes.
Due to the transportation of the material in
bags, the effect of building up plugs is similar to those, which occur in the pipes of
pneumatic conveyance systems described
before. As a consequence, processors often react by dividing the carbon black
feeding process into different steps. Of
course, such a procedure is time consuming and leads to time losses of the mixing
cycle.

252

The temperature curves (Fig. 2) do not

show any differences at all. It can be
seen that the temperature of the mixing
chamber at the beginning of every mixing
cycle is in fact almost the same. Therefore,
any variations of compound properties to
be observed are not caused by different
boundary conditions of the mixing cycle.
The results of the specific energy input are
shown in Fig. 3. The batch containing
25.2% fines content got less energy input.
However, almost no trend can be observed, which can be attributed to variations of the carbon black fines content.
Therefore the present variations have to
be addressed to normal process deviations
of the production.
From the literature it is known that the specific mixing energy correlates to the carbon
black dispersion [8]. However, the devia-

tion range of the methods applied is in

such a small range that no clear conclusion
can be drawn (Fig. 4). Furthermore, it must
be mentioned that the methods deliver information about the macro-dispersion
only.
In Figure 5 the Mooney viscosity is plotted
as a function of the carbon black fines content. It can be seen that the deviation
range is once more very small, but the single values are correlating to the previous
results nicely.
It can be concluded that the variations of
the results presented in Figure 1 5 would
have not been noticed during a normal

1 DI was plotted in order to have the trendlines of

both methods pointing in the same direction and not
to cunfuse the reader.

KGK Kautschuk Gummi Kunststoffe 56. Jahrgang, Nr. 5/2003

Fig. 5. Mooney ML (1 4), 100 8C, in dependence of the carbon black

fines content.

Fig. 6. MH ML and cure rate (MH ML)/(t90 t10 ) at 20 minutes measuring time, 170 8C and 0.5% strain in dependence of the carbon black
fines content.

Fig. 7. Compression set at 70 8C and 100 8C, 22 hours, 25% compression

in dependence of the carbon black fines content.

Fig. 8. Tensile strength and tear resistance in dependence of the carbon

black fines content.

production process, because the deviation

range would be settled within the limits of
the production accuracy respectively within the accuracy of the testing methods.
In Fig. 6 the torque difference MH ML
and the cure rate are shown. The torque
difference MH ML is usually interpreted
as the crosslink density. It can be seen
that MH ML is nearly unaffected,
although it is increased from the lowest
to the highest carbon black fines content.
The cure rate is decreased to a big extend
of about 28%. This is due to a strong increase of t90 while t10 stays almost constant. It must be pointed out however,
that the effect would probably not have
been noticed if the standard measuring

time of 10 minutes would have been applied.

The results of the compression set measurements are shown in Fig. 7. It can be
seen that a strong dependency of the compression set to the carbon black fines content was received at the test temperature
of 100 8C. In contrast to that result, nearly
no influence of the carbon black fines content was found at the testing temperature
of 70 8C.
The reason for the strong dependency can
be attributed to a worse carbon black dispersion at increased fines content. If it is
assumed, that in addition to the macro-dispersion, being only a little poorer at increased fines content and being caused

KGK Kautschuk Gummi Kunststoffe 56. Jahrgang, Nr. 5/2003

by variations of the specific mixing energy

(see Figure 4), more carbon black clusters
do exist at higher fine contents. The polymer matrix contains sections with higher
concentrations of carbon black and others,
having smaller carbon black concentrations. Due to the compression of the sample, the polymer flow at sections of less
carbon black concentration is comparable
high. The permanent deformation is therefore higher. The effect only appears at the
testing temperature of 100 8C because the
polymer is soft enough to show dispersion
problems. At the lower testing temperature of 70 8C the curve is unaffected because the polymer still has a high modulus.
The origin and a definition of carbon black

253

Fig. 9. Elongation at break and modulus at 100% strain in dependence

on the carbon black fines content.

clusters will be given in the chapter Interpretation of the Results.

From the literature it is known that the dispersion level has no influence to the compression set of EPDM compounds but the
crosslink efficiency is an important factor
[9]. As seen in Fig. 6, MH ML, if interpreted by the crosslink density, does not
show significant differences and the trend
is opposite. Therefore, the effect of increased compression set values at increasing fine contents can not be explained with
the cross-link density in this case, which
can be a result of non-polymer influences.
The reason for the statement in [9] must be
seen in the measuring temperature: In that
case the compression set was measured at
room temperature. Obviously this result is
only valid at low temperatures.
In the following, the physical properties
such as tensile strength, tear resistance,
elongation at break and the modulus
M100 are shown in Fig. 8 and Fig. 9.
The mechanical properties are becoming
worse by increasing fines content. The tensile strength, tear resistance, and the modulus M100 are decreased by 10% from the
lowest to the highest fines content. The
elongation at break is decreased to an
higher extend, which is about 15%. The
results can be explained again with the
worse carbon black dispersion at higher
fines contents, being intensified by the carbon black cluster effect. The tensile
strength for example is known to depend
on the crosslink density and to indicate
poor dispersion [10]. The analysis of the
tear resistance is more problematical, be-

254

Fig. 10. Storage modulus G 0 and viscous modulus G 00 in dependence of

the frequency and the parameter carbon black fines content, 100 8C, 0.58
strain (7%).

cause the scattering range is known to

be high. On the other hand the results
of this study are nicely pointing in the
same direction as the previous results.
Here, it can also be seen that the influence
of less specific mixing energy into the compound having 25.2% fines is still visible.
The elongation at break, being decreased
at increasing fine contents, can be explained with carbon black agglomerates,
acting like artificial weakening points.
The polymer chains can be departed
more easily as long as the sample is tested
in the milling direction. The modulus M100
fits to the results because up to strain rates
of 100%, the presence of a carbon black
network can be assumed.
The frequency sweeps of the RPA are
shown in Fig. 10. The storage modulus
G 0 and the viscous modulus G 00 are plotted
as a function of the carbon black fines content. It can be seen that only the fines content of 40,6% leads to doubled values at
low frequencies. The Payne effect might
be responsible for this behavior [11]. The
problem of this interpretation must be
seen in the fact that the calculation of
G 0 and G 00 from the measured complex
torque (G*) values is only strictly valid in
the linear viscoelastic region. Therefore
an exact interpretation is difficult. On the
other hand the RPA results fit nicely to
the other results presented in this paper.
The results of the die swell of the compound which was determined by the implementation of the Garvey Die test are
shown in Fig. 11. Once more, a difference
of about 10% was found at increased fines

content. The highest die swell was found

at the highest fines content. The data point
at 25% fines, which, at first, does not fit
very well to the trend line, correlates nicely
to the specific mixing energy and the
roughness, shown in Figure 4. In general,
die swelling is known to be an entropy related relaxation phenomenon. Furthermore, it is known that the die swell, among
others, depends on the morphology of the
compound, the carbon black content, the
oil content and the mixing time [12].
If the morphology of the compound
changes, e.g. caused by variations of the
carbon black dispersion, the observation
can be explained as follows. With decreased dispersion levels less polymer is occluded in the voids of the carbon black aggregates. For that reason, the polymer will
relax to higher extends than in case of ideal
dispersed carbon black, where the polymer
chains are occluded in the primary aggregates to an higher extend. In that case the
blocked polymer cannot take part at relaxation processes [13, 14].
It must be noticed, that the tests were
done at a screw speed of 30 rpm and
50 rpm but only the latter one shows
the effect described above. At 30 rpm,
the die swell was not affected at all as a
function of fines content. Obviously, the
time for relaxation processes in the die
was long enough to equalize the effect
of the entrance flow into the die.
In Figure 12 the results of the RELMA
method are shown [7, 15]. The mean values of intensity ratio and the variation
coefficient for the elements zinc and sul-

KGK Kautschuk Gummi Kunststoffe 56. Jahrgang, Nr. 5/2003

Fig. 11. Die swell at 50 rpm in dependence of the carbon black fines content.

phur are displayed in dependence of the

carbon black fines content. The samples
were taken directly from the batch and
analysed in an uncured condition.
The mean values of intensity ratios are a
measure of the feeding accuracy of the
corresponding chemical elements. It can
be seen that the contents of sulphurand zinc are almost constant in the different batches. Herewith it is proved that the
feeding of the curing chemicals was done
very accurate. Remarkable differences of
the crosslink density should therefore not
be related to this parameter. This is an important fact because the crosslink density,
among others, depends on the starting
concentration of the curing chemicals [16].
The variation coefficient is a measure of
the distribution of the chemical elements
in the sample, which is known to be accurate below values of 5%. From Figure 12 it
can be concluded that zinc is dispersed
quite well and the dispersion of sulphur
is worse. In Figure 12 only mean values
are shown. The mean values of intensity
ratios and the variation coefficients were
calculated by the data gained of analysing
5 rows of 40 spots, shot by the laser beam
and existing of 15 measured shots each
per spot (3000 measured values per data
point in Figure 12). By this it is obvious
that the results are based on enough
data to regard the results as statistically secured.
The results of the different variation coefficients between sulphur and zinc show, that
the dispersion of sulphur must have been
more complicated. The comparison can

Fig. 12. Mean values of intensity ratio and variation coefficient between
the analyt (zinc and sulphur) and reference elements (carbon) in dependence of the carbon black fines content, determined with the RELMA
method.

be drawn because both ingredients were

added into the mixer at the same time. It
can also be observed that the sulphur distribution in the compound becomes worse
at increasing fines content. The variation
coefficient is about 50% higher at the highest fines content. This result clarifies that
dispersion problems must exist.
Coming back to earlier results of this paper, the increased conversion time t90,
shown in Figure 5, can be explained in a
better way: The reactivity of the curing system depends of the absolute surface,
which is placed at disposal by the sulphur.
If the sulphur dispersion becomes worse,
the corresponding surface is less. Therefore the conversion time t90 increases.
Knowing the fact of a worse sulphur dispersion one should expect a decrease of
MH ML at increasing fine contents, because the crosslink density should locally
be poorer, but the opposite trend was
found. Obviously, carbon black dispersion
problems, caused by variations of the specific mixing energy and carbon black clusters, seem to be dominant here.
It looks like the effect of worse sulphur dispersion, assumed to decrease the torque
difference at increased fines content compensates the effect of carbon black dispersion.

Interpretion of results
The results presented before can be interpreted as dispersion problems in most
cases. The consistency of the mechanical
properties, the compression set, the die

KGK Kautschuk Gummi Kunststoffe 56. Jahrgang, Nr. 5/2003

swell and the RPA examination are evident

with respect to the carbon black dispersion. On the other hand, some results
like the Mooney viscosity and the macrodispersion were found in a very small variation range. Furthermore, a significant decrease of the cure rate was determined
with the MDR. This result was confirmed
by the RELMA method. At the same
time, MH ML, which can be interpreted
as the crosslink density, increases slightly
with increasing fines content. This, at first,
is a contradiction to the course of the cure
rate, because of locally lacking network
connections. Consequently, it can be assumed that there are two effects, which
are competing with each other: On the
one hand, there is the poor sulphur distribution, which in fact leads to the reduced
cure rate, but should lead to a decreased
crosslink density at the same time. On
the other hand, the carbon black dispersion was found to vary in a very small
range, correlating with the specific mixing
energy but irrespective of the fines content. Therefore, the results of the compression set, the mechanical properties, the die
swell and the RPA can assumed to be
caused by the formation of carbon black
clusters. Herewith, the compensation of
the torque difference can be explained,
too. The origin of both effects, able to explain the results of this study, will be discussed below.
At first, the sophisticated raw material carbon black and its behaviour during the
mixing process will be introduced, as described in the literature:

255

Fig. 13. a) carbon black pellet fragments forming bigger agglomerates; b) compression and break
down of the agglomerates, caused by the mixing process; c) formation of carbon black clusters
during the dispersion process.

It is well known that carbon black consists

of aggregates which are the smallest,
stable and independent units of the finished carbon black [12]. The aggregates
in turn combine to form loose agglomerates. The agglomerates are pelletized for
handling reasons by the help of processing
agents [10].
During the mixing process the pellets must
be destroyed again. In ideal case, the carbon black will be reduced to an aggregate
structure [17]. The final condition of carbon black dispersion mainly depends on
the type of carbon black, the nature of
the polymer, the viscosity of the compound
and the mixing conditions.
The difference between carbon blacks having high and low contents of fines is the
particle size at the beginning of the mixing
process when it is added to the mixer. Undestroyed carbon black pellets have got a
particle size distribution on the whole between 0.25 mm and 1 mm [2]. In this case
the content of fines can be almost neglected. If the fines content increases significantly due to pneumatic conveyance or
similar processes, the carbon black is dominated by particles sizes being smaller than
125 lm. The carbon black fines content in
this case consists of pellet fragments. In
such fine materials the probability of forming bigger agglomerates increases again,
because the Van der Waals forces are influenced by the particle diameter, the distance between the particles and the number of contact points.
At the beginning of the effective mixing
process, when the polymer is crumbled
and all ingredients are fed, there is a multi-phase system in the mixer consisting of
polymer, disperse solids like the carbon
black fines content or the sulphur, oil
and others.
It can be assumed that the fines content of
the carbon black and the sulphur in this
phase of the mixing process tend to
form weak agglomerates. It is probable,

256

that the formation of such agglomerates

is intensified by the presence of the oil,
due to capillary forces and sticky agglomerates come into being, consisting of carbon black fragments, being smaller than
125 lm, sulphur and other dispersed solids, too. If these sticky agglomerates are
forced through the rotor gap or the region
between rotor flight and the chamber wall,
they will be compressed. It can be assumed
that the pellet fragments of the carbon
black are being further compacted by
the compression. This procedure could
lead to agglomerates, being more stable
in comparison to the original pellets. The
procedure takes place at the beginning
of the mixing process, when the ram just
closed. An additional stage is taking place
before the conventional carbon black dispersion process described in [18] starts.
Figure 1 confirms this statement. There,
it was visible that the feeding time of
the carbon black having higher fines compacted was extended, due to sticking effects. It was more difficult to get the material out of the bags, because the fine material builds up plugs already in the bags,
which confirms the theory discussed here.
In the further mixing process it will be more
difficult to break down such agglomerates
in comparison to original pellets. It will
take longer until the dispersion of the carbon black is finished. In general, agglomerates are known to cause problems during the dispersion process, because more
mixing energy must be spent in order to
disconnect the Van der Waals based particle-particle forces [18]. Another problem
enhancing the difficulty of carbon black
dispersion can be seen in the inclusion
of such agglomerates or pellet fragments
by the polymer [19]. Therefore, the carbon
black dispersion process will not overcome
the phase of coherent sections of the carbon black in the compound here. Of
course the same is valid for the sulphur
in this case, because the sulphur was in-

cluded to the compressed agglomerates

as well. This was in fact clarified by the results of the RELMA method. So, the compound will contain sections, having higher
carbon black and sulphur concentrations,
and sections, having less ones. Sections
of high carbon black concentrations are referred to as carbon black clusters. These
carbon black clusters are not accessible
to the dispersion measurement methods,
applied in this study. The model concept
of the procedure of forming carbon black
clusters is illustrated in Figure 13 schematically.
The question, why the coherent sections
are not overcome, can be answered as follows: If clusters consisting of polymer, carbon black and sulphur are imposed to
shear- or elongation stresses in the mixer,
the sections of lower carbon black and sulphur concentration will flow more easily.
The clusters will be consequently conveyed
through the compound in a more or less
stable condition. This effect is caused by
the extended time to reach the coherent
phase of the clusters, due to the sticky agglomerates at the beginning of the mixing
process. It must be taken into account that
the viscosity reduces during mixing irrespective of the procedure of forming clusters. This means, that the batch viscosity at
the time of the coherent phase is already
lower if the carbon black contains fines
than in case of no fines.
The particle sizes forming the carbon black
clusters are supposed to be in the range
between the carbon black aggregate size
and about 2 lm. The upper limit of the
particle sizes in clusters is caused by the resolution of the dispersion measurement
methods applied in this study, which is
2 lm. The medium size of N650 aggregates is about 0.5 lm in the longest extension and 0.1 lm respectively 0.05 lm in
the other directions [20]. The lower limit
is given by the fact that low structured carbon blacks will usually not be destroyed
during the mixing process [10]. Only
high structured carbon black aggregates
may break down in dependence of the
mixing conditions to a certain extend
[21 23]. So fractures of aggregates can almost be excluded for the carbon black
N650 applied here.

Acknowledgment
The results were obtained in the Mini Derucom project, which was financially supported by European Commission, whom

KGK Kautschuk Gummi Kunststoffe 56. Jahrgang, Nr. 5/2003

we would like to thank very much. We

would also like to forward special thanks
to the project partners Codan Gummi A/
S; Trelleborg Industri AB; Thona SA; Lusorol; LIsolante s.r.l.; DSM Elastomers; Volkswagen; University of Pierre & Marie Curie
Paris (LRMOP); Degussa AG; Buhler GmbH.

References
[1] K.-H. Freitag, Schuttgut 1 (1995) Nr. 1, 115.
[2] H. Keuter, A. Limper, A. Wehmeier, T. Riedemann
and K.H. Freitag, Schuttgut 6 (2000) 385.
[3] H.M. Schmid, KGK 35 (1982) 674.
[4] J.L. Leblanc and C. de la Chapelle, ACS Meeting,
Cleveland, 2001 USA.
[5] H. Geisler, VDI-K Seminar Mischungsherstellung
fur Elastomere Workshop mit praktischen Versuchen.
[6] A. Wehmeier, Diplomarbeit Fachhochschule
Munster, (1998).
[7] H. Keuter, D. Ackfeld and A. Limper, KGK 53
(2000) 566.
[8] W.M. Hess, R.A. Swor and E.J. Micek, Rubber
Chem. Technol. 57 (1984) 959.
[9] J.W.M. Noordermeer and M.J.M. Wilms, KGK 7
(1991), 679.
[10] M.L. Studebaker in Reinforcement of Elastomers; Intersc. Publ. (1965), chapter 12.
[11] A.R. Payne, Journal of Applied Polymer Science 9
(1965) 3245.
[12] R.H. Schuster, Interner Bericht W.d.K. (1989).
[13] A.J. Medalia and J. Coll. Interface Sci. 32 (1979)
115.
[14] A.J. Medalia and F.A. Heckmann, Carbon 7 (1969)
567.
[15] W. Hader and C.-J. Lorenzen, Technische Mitteilungen Krupp 2/1992.
[16] S. Wolff, KGK 23 (1970) 7.
[17] S. Shiga and M. Furuta, Rubber Chem. Techn. 58
(1985) 22.
[18] G. Kraus, Rubber Chem. Techn. 38 (1965) 1070.
[19] B.B. Boonstra and A.J. Medalia, Rubber Age (N.Y.)
92 (1963) 892.
[20] W.M. Hess, ACS Meeting, Rubber Division, New
Orleans, 1975, USA.
[21] A.M. Gessler, Rubber Chem. Techn. 43 (1973)
943.
[22] A.J. Medalia and G.J. Horniek, Pattern Recognition 4 (1972) 1955.
[23] W.M. Hess, V.E. Chirico and K.A. Burgess, KGK 26
(1973) 344.

Authors
Prof. Dr.-Ing. Andreas Limper is a Professor at the
University of Paderborn. Dipl.-Ing. Harald Keuter,
is working as a scientific co-worker at the Institut
fur Kunststofftechnik of the University in Paderborn. Dipl.-Ing. Carsten Ruter, is a technical manager of Thona SA.
Corresponding author
Prof. Dr. A. Limper
Institut fur Kunststofftechnik
Pohlweg 47 49
33098 Paderborn

KGK Kautschuk Gummi Kunststoffe 56. Jahrgang, Nr. 5/2003

257