MASCHINEN UND ANLAGEN
MACHINERY AND EQUIPMENTS
Mixing quality · rubber compound ·
internal mixer · fingerprint diagram ·
filler dispersion
The aim of this study is the evaluation
of the mixing quality of rubber com-
pounds already during the disconti-
nuous internal batch mixing process by
means of an alternative assessment of
the process data. For this, the logarithm
of torque as a function of the reciprocal
mixing temperature is used. The results
show that once the requested com-
pound quality is attained, a linear rela-
tionship between the above mentioned
process data can be observed. Thus po-
tentials such as a potential mixing time
reduction can be recorded online during
production, something that is not pos-
sible using conventional fingerprint dia-
grams.
Neuartige Methode zur
Bewertung der Kautschuk-
mischungsqualität durch
alternative Darstellung des
Fingerprint-Diagramms
Mischungsqualität · Kautschuk-
mischung · Innenmischer · Fingerprint-
Diagramm · Füllstoffdispersion
Ziel dieser Studie ist es, durch eine al-
ternative neue Auswertung bekannter
Prozessdaten die Mischungsqualität ei-
nes Batches bereits während der Her-
stellung im diskontinuierlichen Innen-
mischer-Mischprozess bewerten zu
können. Dazu wird das logarithmierte
Drehmoment über dem Reziprokwert
der vom Thermoelement des Innenmi-
schers detektierten Mischguttempera-
tur unabhängig von der Mischzeit auf-
getragen. Die Ergebnisse zeigen, dass
bei Erreichen der geforderten Mi-
schungsqualität ein linearer Zusam-
menhang zwischen diesen Prozessda-
ten besteht. Somit können Potentiale
zur Prozessoptimierung wie z. B. zur
Mischzeitreduzierung online erfasst
werden, was mit den üblichen
„Fingerprint“-Diagrammen nicht mög-
lich ist.
Figures and tables:
By a kind approval of the authors.
www.kgk-rubberpoint.de
New Method for Evaluating
Rubber Mixing Quality by means
of alternative Representation of
the Fingerprint Chart
A so-called fingerprint diagram, recorded
for each individual mixing cycle, is used
consistently nowadays for production
monitoring of the internal mixer com-
pounding process [1-3]. This diagram
shows the course over time of certain
process variables such as output or
torque, temperature, ram position and
energy input. The fingerprint of the indi-
vidual compounding cycle is compared
with those of previous cycles or with an
earlier diagram that has been defined as
reference. This makes it possible to ob-
serve fluctuations in the key process pa-
rameters from batch to batch, to identify
in a compounding cycle deviating from
the reference the occurrence of possible
inhomogeneities, and to quarantine this
„charge“ to prevent further production
processing of it. However, many compa-
nies in the rubber processing industry
currently lack a suitable method for pro-
cess optimization and for generation of
an ejection criterion with which the sta-
tus of the compound with regard to ho-
mogeneity/quality can already be predic-
ted online during production.
The following can be said with regard
to the basic problem of compounding
process optimization: The development of
new rubber compounds initially involves
trials conducted on laboratory mixers. For
the subsequent scale-up, there is no get-
ting around further trials on mixers actu-
ally used in production; this is necessary
due to the continued lack of reliable scale-
up methods. To minimize the expense in-
volved in terms of time and effort, reliable
information on the „state“ of the com-
pound is required. This information can
already be obtained on the basis of the
process data generated and is of conside-
rable economic interest for industry.
In industry there are just a few well-
founded rules for compounding process
optimization, e.g. for the sequence in
which the individual compound ingre-
dients are added and the most effective
possible filler contents defined [3; 4]. The-
re is also a very broad „practitioner exper-
tise“ as regards the characteristic shapes
of the performance curve and the ram
setting time for the purpose of evaluating
the incorporation of fillers (black incorpo-
ration time = BIT) [5; 6]. For optimization
of the rubber internal mixer‘s compound-
ing process, there is, however, no method
in general use for analyzing process data
to predict the compounding quality that
will be achieved. Evaluation of the effici-
ency of the compounding process always
requires subsequent time-consuming ge-
neration of key physical values. The
measuring expense involved is considera-
ble and can be realized only at a certain
time lag vis-à-vis compounding.
The approach for online evaluation of
compound quality and for generation of
an ejection criterion presented here below
exhibits considerable potential for opti-
mizing the compounding process. Its no-
vel type of analysis draws on process data
usually generated during the compound-
ing process. This means that no additional
measuring expense is entailed.
Theoretical context
The course of rotor torque during the
compounding cycle is one of the most
important process variables allowing for
a statement as to the momentary in-
process state of the compound in terms
of energy input. In combination with ram
setting time, moreover, torque is a good
Authors
B. Klie, S. Teich, E. Haberstroh,
U. Giese, Hannover
Corresponding authors:
Benjamin Klie; Ulrich Giese
Deutsches Institut für Kautschuk-
technologie e. V.
Eupener Str. 33
D-30519 Hannover
Germany
Benjamin.Klie@DIKautschuk.de
Ulrich.Giese@DIKautschuk.de
Ph.: +49(0)511/84201-0
KGK · 10 2015 31
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 MASCHINEN UND ANLAGEN
MACHINERY AND EQUIPMENTS
1 τ
Temperature [°C]
2000
Torque [Nm]
1000
150
100
50
0 5
0 100
Mixing time [s]
Fig. 1: Internal mixer‘s process data in the fingerprint diagram (left) and in the new repre-
sentation form (right), (Upside-down mixing process of an EPDM formula on the GK 5 E).
way to observe, for example, the process
of filler incorporation. Once the BIT is
exceeded, homogenization processes are
triggered. This is evident from the typical
slight drop in torque curve towards the
end of the compounding process. Repre-
sentation of process data in the regular
fingerprint diagram cannot, on the other
hand, identify an exact point in time bey-
ond which further prolongation of com-
pounding is no longer of any use in up-
ping the dispersive and distributive mi-
xing quality.
In extensive studies, a new way of
describing the course of the process was
developed. Here, torque is no longer re-
presented as a function of time but
rather as a function of the temperature
of the mix. The change in viscosity as a
result of the rise in temperature during
the compounding process was used to
establish a correlation between rotor
torque and the reciprocal value of the
batch temperature (Figure 1, right). A
simple formula based on the basis of
physical correlations results.
For a better understanding of this
new theoretical approach, it is necessa-
ry to first take a look at the torque curve
in the usual fingerprint diagram as a
function of mixing time (Figure 1, left).
Once the BIT is exceeded towards the
end of the homogenization phase, it can
be assumed that the microscopic struc-
ture of the compound will not change
anymore as of a specific point in time.
Filler particles are incorporated into the
polymer and the agglomerates are well
dispersed. At this point in time, the ho-
mogeneous distribution of all ingre-
dients must also be regarded as having
been concluded. It can thus be expected
that as of this point in time, the com-
pound exhibits rheological behavior
that can easily be described. This means
that viscosity depends solely on tempe-
32 KGK · 10 2015
8
7 Shear stress is proportional to the inter-
Ram position [mm]
In Torque
6
100
50
0 4
200 0,0022 0,0024 0,0026 0,0028 0,0030 0,0032
T-1 [1/K]
rature and on shear and strain rate du-
ring compounding. At a constant rotor
speed, this rate remains constant, how-
ever. The temperature continues to rise
due to the uninterrupted impact of
shear energy and there is thus a drop in
torque due to decreasing viscosity.
For this reason, it is possible to descri-
be the compound viscosity‘s dependency
on temperature in accordance with the
Arrhenius approach [7]. In chemical kine-
tics, the latter describes the tempera-
ture-dependency of the velocity constant
k, which, as proportionality factor, re-
flects a correlation between the reaction
rate and the concentrations of two reac-
tion partners in a chemical reaction [8]. A
temperature dependency of this kind
prevails during the compounding pro-
cess for the viscosity of the rubber com-
pound as well. Depending on the rotor
speed setting, the shear forces introdu-
ced and the energy thus dissipated lead
to a rise in the temperature of the rubber
compound, with changes in viscosity. The
Arrhenius relationship can thus be car-
ried over into the following initial func-
tion that takes into account the tempera-
ture dependency of the compound‘s vis-
cosity:
DP
G = P ∗ ; −BML @ → ∆η(L) = ηFIE ∗ ; −BML @
In reference to the mixing process, the
exponential prefactor A, referred to in
chemistry as the frequency pre-exponen-
tial factor, is replaced by the prefactor
ηmin, indicating the rubber compound‘s
theoretically attainable minimal com-
pound viscosity at the rotor speed set-
ting. The activation energy EA and the
universal gas constant R are interpreted
together here as one constant. Viscosity,
shear rate and shear stress are in a
straightforward relationship to one ano-
ther (definition of shear viscosity):
η=
γ!
(2)
nal mixer‘s rotor torque M:
τ ≅M (3)
For the internal mixer‘s torque, the Ar-
rhenius function thus yields the fol-
lowing mathematical relation:
DP
? = ?FIE ∗ ; −BML @ (4)
By means of logarithmic calculus, this
can be represented in the following form,
thereby corresponding to a linear equati-
on of the so-called „target line“ ZG.
Mmin describes the theoretically mini-
mum torque applied during the com-
pounding process at the point in time
of the rubber compound‘s minimum vis-
cosity:
(5)
1
"target line": =A(: = ) = < + F ∗ :
L
(6)
The two process variables (torque and
melt temperature) are continuously
available throughout the compounding
operation so that the plotting of the log-
arithmized torque is possible online via
the reciprocal, absolute temperature.
Contingent on validity of the derivated
formula, this representation of torque
and temperature yields a linear relation-
ship that can be described via the linear
equation generated in equation 5. The
formula is not valid until no further note-
worthy changes in viscosity occur due to
progressive dispersion of the filler partic-
les or incorporation of the filler into the
polymer matrix. As a consequence, a li-
near progression („home stretch“) indi-
cates constant material properties, on
DP
the basis of which a criterion for ejection
(1) can be derived. This point is not identifi-
able with the procedural method cur-
rently in common use—i.e. plotting of
torque over time and compound tempe-
rature over time. This is because torque
changes in the course of compounding
and usually shows an exponentially dec-
lining progression.
The relationship between rotor torque
and temperature opens up not only the
possibility of a new description of the
mixing process but might also be usable
online as a new quality control tool or as
a new kind of ejection criterion at termi-
nation of the compounding process.
www.kgk-rubberpoint.de

Experiments
Raw materials and compounding formula
The formula is based on „Buna SB 1500“
(Styron Synthetic Rubber), an emulsion
SBR with a styrene content of 23.5 % and
a Mooney viscosity ML (1+4) at 100 °C of
50 MU. „Corax N 550“, with an STSA of
39 m2/g and an OAN of 121 ml/100 g
(Orion Engineered Carbons) is used as
filler. Other compound additives for acti-
vation of the crosslinking reaction are
„Edenor ST 4 A“, (Emery Oleochemicals
GmbH), a stearic acid, and a zinc oxide of
the Rotsiegel type (Grillo-Werke AG).
„Vulkacit NZ“ TBBS (Lanxess AG) is used
as accelerator and ground sulfur with a
purity of > 99.9 % (Solvay) as crosslinking
agent. Table 1 shows the complete com-
position of the compound formula.
Compounding process
The compound is manufactured in ac-
cordance with ASTM D 3191 in a two-
stage mixing process. The GK 5 E (Werner
& Pfleiderer) laboratory mixer, with an
intermeshing rotor system (PES 3 geo-
metry) and a feed volume of 70 %, is em-
ployed. The rotor speed setting was
40 rpm, with the rotors, mixing chamber
and drop door tempered at 32 °C. The
accelerator was subsequently incorpora-
ted into the compound on a double roll
mill at a mill temperature of 50 °C and
with a roller nip of 4 mm. Table 2 shows
the exact mixing cycle.
Characterization
Mooney viscosity
The viscosity of the rubber compound is
determined to Mooney ML (1+4) at
100 °C by means of a Monsanto „MV
2000 E“ viscometer. It is measured with
the large rotor, at a preheating time of 1
minute and a testing time of 4 minutes.
Dynamic-mechanical analysis of the
non-vulcanized material
An Alpha Technologies rubber process
analyzer of type „RPA 2000“ was emplo-
yed for the dynamic-mechanical analysis
to determine the Payne effect on the
rubber compound. For this purpose, con-
trols are effected for the non-vulcanized
compounds at 80 °C and a frequency of
1 Hz with amplitudes of strain of bet-
ween 0.02° and 32°.
Vulcanization
The compound‘s vulcanization proper-
ties are measured with a Monsanto
www.kgk-rubberpoint.de
„MDR 2000 E“ rheometer at 160 °C. The
compounds are then vulcanized in a la-
boratory autoclave at 280 bar and 160 °C,
corresponding to the respective t90 time.
The vulcanized slabs measure 180 x 80 x
2 mm (length x width x thickness).
Filler dispersion
For determination of the macrodispersion
of the filler particles the „dispersion index
analysis system“ (DIAS), a Zeiss/Jena
„Jenavaert“ research microscope was
used. The microscope works with 125-fold
enlargement, generating an image that is
then recorded by means of a digital came-
ra and evaluated using a Kontron „KS
400“ image processing system. A fresh
razor-edge cut of the crosslinked material
serves as test specimen. Analysis takes
into account the mean dispersion index
from 10 individual measurements and
the particle size distribution detected.
Dynamic tear propagation
For the analysis of dynamic tear propaga-
tion, vulcanized strip specimens notched
on one side are subjected at room tem-
perature to frequency-dependent tensile
fatigue stress using a Bayer Coesfeld
„Tear Analyzer“. The dynamic load on the
notched test specimen to the tearing
point is conducted with elongation of
15/20/25/30 % at a frequency of 10 Hz
and a pulse width of 50 ms. With the
help of a CCD camera, tear propagation
and the contour of the tear is determi-
ned in equidistant intervals and saved. A
quantitative correlation is then establis-
hed between tear propagation and the
mechanical parameters during stressing.
Physical parameters
The tensile test on the vulcanizates is
2 Cycle times for the two-stage mixing process
Mixing time [s] Action
Stage 1 (Internal mixer)
0 Admixture of polymer, ZnO
15 s Ram lowered
60 s Ram raised; Admixture of carbon black, stearic acid, sulfur
75 s Ram lowered
150 s Ram raised; aeration/ turn
165 s Ram lowered
Var. mixing time after the
Ejection of master batch
aeration step
Stage 2 (Double roll mill)
0 Admixture of master batch
60 s Admixture of TBBS
210 s Upturning (6x)
300 s Drop off sheet
MASCHINEN UND ANLAGEN
MACHINERY AND EQUIPMENTS
1 SBR formula
Ingredients Phr
E-SBR 100
N 550 50
ZnO (Rotsiegel) 3
Stearic acid (Edenor ST 4 A) 1
TBBS 1
Sulfur 1.8
Total 156.8
carried out to DIN 53504 employing a
Zwick Z010 tensile testing machine. The
multiple-hysteresis tests are conducted
at an initial load of 0.1 N and a testing
speed of 40 mm/min. Controls are car-
ried out for elongation amplitudes of 30,
70 and 120 %, with three cycles for each
amplitude. The Shore A hardness of the
vulcanized test specimens is measured
to DIN 53505.
Dielectric
The vulcanizate‘s dielectric properties
are measured at room temperature in
the 0.1 Hz to 10 MHz frequency range
using a Novocontrol „BDS 40“ broadband
dielectric spectrometer. The measuring
instrument consists of a multilayer dis-
coidal capacitor with a diameter of 30
mm, with the two-mm-thick specimen
being placed between two gold-plated
electrodes. The surfaces of the specimen
were likewise provided with a thin gold
coating to ensure the electric contact to
the electrodes.
Results
Mixing
For determination of the „target line“, it
is necessary to first conduct a prelimina-
ry test to unambiguously identify the li-
KGK · 10 2015 33
 MASCHINEN UND ANLAGEN
MACHINERY AND EQUIPMENTS

2 the two are congruent. Carried over into

7
3 the new method of analysis, the point of
Temperature [°C]

400
Torque [Nm]

6 3
300
1 2 4 4
2 intersection coincides with the beginning
200 5 of the „target line“. According to the afore-

Ram position [mm]

4 mentioned hypothesis, the same com-

In Torque
100
0 3 pound properties can be assumed from
100
2 this point on, for which reason prolonging
50 1 the mixing time beyond this point would
1
0 0 not yield any further change in compound
0 100 200 300 400 25 30 35
properties.
Mixing time [s] 1/T [1/K*10000]
1
=A K: = > = 2208,5: − 0,0349
L
(7)
Fig. 2: Process data of the preliminary test in the fingerprint diagram (left) and the
new representation form (right).
Targeted variation of post-aeration-step
mixing times (between 45 s and 180 s) is
3 to make possible manufacture of rubber
Beginning of linear range 8 Torque_calculated
7 compounds allowing for a subsequent
Torque_measured

Difference in torque values [-]

7
7 Difference characterization and verification of rele-
6
6 vant material parameters. The point of
6
5
5 providing proof of constant material pa-
5
4 rameters in the „target line“ measuring
In Torque

In Torque

4
3
2 2
1
0
25
1/T [1/K*10000]
Fig. 3: Determination of the „target line“ and the appurtenant starting point.
near relationship of the process data in
the constant compound homogeneity
range in the internal mixing process on
the basis of the new method of analysis.
For this purpose, an explicitly long mi-
xing time of 180 s was stipulated in the
final mixing phase following the aerati-
on step. Figure 2 shows the process data
in both the regular and the new repre-
sentation form, making clear that it is
possible to plot torque—and thus the
process run— in both diagram forms. It is
to be noted that in the new method of
analysis, the reciprocal value is plotted
along the x-axis; in the diagram, a rise in
temperature over time in the course of
uninterrupted mixing is always connec-
ted to a progression of the measured va-
lues in the direction of the origin of the
axis. In the regular fingerprint, it is clear
from the ram position that there is not
enough mixing time between the admix-
ture of black carbon (2) and the aeration
step (3) to fully incorporate the filler. At
this point in the mixing process, a non-
homogeneous batch can still be assu-
med. The additional mixing time bet-
ween the aeration step and ejection (4) is
thus necessary to conclude incorporation
and to „maximize“ compound homo-
geneity by means of subsequent disper-
4
3 substantiation, for practical purposes, of
2 the theoretical projection that analysis
209 s
1 1
30 35 0 0
0 100 200
Mixing time [s]
sion operations and distributive mixing
effects. In the regular fingerprint, this
range is characterized by a steady decline
in torque over mixing time. The length of
this effective mixing time for homogeni-
zation of the batch cannot, however, be
determined on the basis of the progressi-
on of the curve.
On the basis of the new method of
analysis, it is, on the other hand, possible
to clearly identify a range in which there is
a linear relationship between torque and
temperature (Figure 3, left) and which
could thus be used as ejection criterion. To
make it possible to describe this range
mathematically, a linear fit of the measu-
red values is carried out for this segment.
It yields the linear equation cited in Equa-
tion 6, which very well describes the
course of „torque as a function of tempe-
rature“ in the new method of analysis. By
inserting into the linear equation melt
temperature as a function of mixing time
during the compounding process, it is pos-
sible to calculate torque as a function of
temperature and compare it with the
torque actually generated during the mi-
xing cycle. For a mixing time of 209 s (Figu-
re 3, right), the difference between the
two torque curves results in an intersec-
tion of both curves from which point on
3
range is to allow for verification and
of the temperature-dependent torque
can be used to determine an ejection
300 400
criterion. Here, the mixing times are se-
lected in such a way as to image as many
mutually deviating measuring points as
possible along the „target line“. This also
involves mixing batches that are ejected
well before the „target line“ is reached.
Up to commencement of the „target
line“, prolongation of mixing time would
have to result in an improvement in ma-
terial parameters, whereas along the
„target line“, constant material parame-
ters must prevail irrespective of mixing
time.
It is evident from the results in Figure
4 that the process data in the fingerprint
diagram show curves of comparable
shapes. Consequently, all curves in the
new method of analysis adhere to the
generated „target line“, pointing to good
compounding reproducibility. It is solely
in the case of the mixing trial with a
post-aeration-step runtime of 75 s that
there is a temperature rise of just a few
degrees Celsius in the regular fingerprint
diagram, with a higher ejection tempera-
ture than for the other compounds. As a
result, in the new method of analysis,
the aeration step has the curve shifting
slightly to the left in the direction of hig-
her temperatures for this compound;
because of comparable torque, this does
not, however, have any effect on energy
input. The energy input values for the six
compounds are constant through to the
aeration step and then vary due to the
different mixing times (Table 4), so that

34 KGK · 10 2015 www.kgk-rubberpoint.de

 MASCHINEN UND ANLAGEN
MACHINERY AND EQUIPMENTS

the maximum energy input increases 4

with mixing time. The consistency of the 400
7

Temperature [°C]
torque curve progression allows for the 300 6

Torque [Nm]
200
assumption of constant mixing condi- 5
45 s

Ram position [mm]

100
tions in the mixing chamber during the

In Torque
4 60 s
0 75 s
process. Taking the „target line“ determi- 3
90 s
100
ned in the preliminary trial into account, 2 150 s
180 s
it is evident that already as of a post-ae- 50 1
ration-step mixing time of approx. 70 s, 0 0
0 100 200 300 400 25 30 35
all curves progress in adherence to the Mixing time [s] 1/T [1/K*10000]
linear torque-temperature relationship,
meaning they would have to result in the
Fig. 4: Process data with variation of post-aeration-step mixing time, shown in both repre-
same material parameters. It is now a
sentation forms.
matter of substantiating this by charac-
terizing physical and dynamic-mechani-
cal parameters. 3 Energy inputs as a function of mixing time
Mixing time after aeration step [s] 45 s 60 s 75 s 90 s 150 s 180 s
Vulcanization and Mooney viscosity
Specific Energy [Wh/kg] 178 199 252 263 327 377
First the parameters for the unvulca-
nized rubber compound are determined.
In so doing, it becomes clear that the ef- RPA measurements on unvulcanized material properties along the „target
fectiveness of the compounding process material line“ set forth at the outset.
does not influence crosslinking reaction To be able to draw initial conclusions as
kinetics, as can be inferred from the mea- to the activity of the filler network and Dispersion analysis with microscopy
sured vulcanization times (Figure 5, left). thus with regard to the effectiveness of To validate this hypothesis, the
Crosslinking density—measured on the filler dispersion, the Payne effect is deter- vulcanizate‘s filler macrodispersion is
basis of the difference between the rheo- mined as the change in the storage mo- then determined on the basis of the dis-
meter curve‘s maximum and minimum dulus ΔG´ as a function of post-aeration- persion index and particle size distributi-
torque—is independent of post-aerati- step mixing time. In principle: The grea- on (Figure 7). Prolongation of post-aerati-
on-step mixing time. The shape of the ter the change in the storage modulus in on-step mixing time is initially shown to
Mooney viscosity curve as a function of the detected amplitude range, the less improve filler dispersion. Already as of a
post-aeration-step mixing time points effective filler dispersion is during the post-aeration-step mixing time of 75 s,
up the anticipated straightforward rheo- mixing process. This is due to the enhan- however, the parameters show constant
logical relationship between torque and ced filler network activity in poor mixed values. This is reflected both in the mean
temperature along the „target line“ and compounds, in particular in the low am- dispersion index and in the variation coef-
the compound viscosity attained. With plitude range, and the concomitant grea- ficient. What is more, for the compounds
longer mixing time, the specific energy ter filler-filler interactions. manufactured, the number of particles
expended during mixing rises and the In the case of the mixing trials carried remains constant in the range of magni-
measured Mooney viscosity decreases out here, reduction in the Payne effect tude critical for tear initiation. This is evi-
(Figure 5, right). As of a post-aeration- begins to stagnate already at a post-ae- dent from the torque curve, which at this
step mixing time of 75 s, Mooney viscosi- ration-step mixing time of 75 s, with the point in time already adheres to the linear
ty no longer experiences any further no- measured values plateauing (Figure 6). course of the „target line“. If the process
teworthy change of note, however (so- This can be seen as an indication that parameters remain unchanged as set,
lely 5 MU when the post-aeration-step further prolongation of mixing time maximum filler distribution can be assu-
mixing time is extended from 75 s to 180 would not bring about any improvement med for the rotor speed selected. Without
s); at the same time, the measured melt in the effectiveness of filler dispersion. a corresponding adjustment of the inter-
temperature stagnates. This confirms the hypothesis of constant nal mixer‘s system parameters (e.g. an

5 Fig: 5: Vulcaniza-
18 40 94 160 tion properties
t90 (left) and Mooney
determined with inserting

16
Vulcanizing times [min]

92 140
ML (1+4) at 100°C [MUC]

viscosity (right) as
S′max - S′min [Nm]

Ejection temperature

14 30
thermometer [°C]

120
12 90 a function of mi-
S′max - S′min 100 xing time after
10 88
8
20 80 the aeration step
86
60 (means from
6
10 84 5 MU 40
three individual
4
82
measurements
2 t5 20
per batch).
0 0 80 0
0 50 100 150 200 0 50 100 150 200
Post-aeration-step mixing time [s] Post-aeration-step mixing time [s]

www.kgk-rubberpoint.de KGK · 10 2015 35

 MASCHINEN UND ANLAGEN
MACHINERY AND EQUIPMENTS
6 cal sizes (see Figure 7). At the same time,
Fig. 6: Change in the storage modulus ΔG´ as a function of post-aeration-step mixing time
(Payne Effect).
7 The effect of stress-strain curve softe-
Number of measurements = 10/formula
Dispersion index [%] (mean)
Variation coefficient of dispersion index
Number of particles measured > 50 µm
Fig. 7: Dispersion index as a function of post-aeration-step mixing time.
increase in rotor speed), prolonging mi-
xing time (longer than 75 s after the aera-
tion step) cannot effect any further im-
provement in filler particle dispersion.
Reaching the „target line“ can thus be
regarded as a criterion beyond which fil-
ler macrodispersion attains the mixing
process‘s maximum value for the process
parameters set.
Physical parameters - tensile test
On the other hand, regardless of whe-
ther the „target line“ is reached or not,
8 higher energy dissipation recorded for the
Fig. 8: Results of the tensile test conducted on vulcanized S2 bars as a function of mixing
time after the aeration step (mean from ten individual measurements per batch).
36 KGK · 10 2015
expanding the measuring range (a grea-
ter number of individual measurements
per batch) would increase the likelihood
that the defect causing the tear also is
within the test volume and thus detec-
ted. That leads to the conclusion that for
the number of test series carried out, it is
only in the case of the batch with a post-
aeration-step mixing time of 45 s that a
number of detected particles multiplied
by a factor of ten is sufficient for a statis-
tically significant influencing of the ten-
sile test parameters.
ning (Mullins effect) in the case of an
elastomer under quasi-static cyclical de-
formation is a well-known phenomenon
frequently described in the literature [9;
10]. Due to material changes, the stress-
strain curve of the hitherto unloaded ma-
terial (1st cycle) runs above the curve of
the 2nd and all further cycles. This effect is
more prominent in black-carbon-filled
200 µm materials than in unfilled systems. Along-
side processes like the tearing of network
Post-aeration-step mixing time [s]
chains, the destruction of weak physical
45 s 60 s 75 s 90 s 150 s 180 s
bonds and further reversible and irreversi-
74,8 86,8 94,2 93,3 94,1 95,6
ble processes occurring in the material, it
4,1 3,1 0,7 1,2 1,1 1,3
is above all the breakup of black carbon
107 35 10 5 7 11
agglomerates that can be further cited as
causing stress softening [11]. In the case
of smaller elongations, the larger filler
clusters in the carbon black network are
the effects on the physical parameters of destroyed first. With increasing stress am-
the tensile test are minimal. Solely a plitude, these are broken up into ever-
post-aeration-step mixing time of 45 s smaller clusters [12-16]. In the example
shows a reduced mean tensile strength. shown in Figure 9 (left), the dissipatively
Along the „target line“, no significant transformed energy in connection with
improvement is discernible, either in this process is visible as hysteresis. Figure
terms of tensile strength or in terms of 9 (right) shows the difference in the dissi-
elongation at break (Figure 8). The rea- pative energy densities of the first and
son for this is the increasing likelihood of third cycles for 30 % elongation (right). As
poor filler particle dispersion resulting in it was already possible to show in dyna-
premature tear of the S2 test bar, a likeli- mic-mechanical studies, only a slight
hood which grows with an increasing change in energy transformation per unit
number of documented particles of criti- of volume is still recordable as of a post-
aeration-step mixing time of 75 s. The
material mixed 45 or 60 s after the aerati-
on step can be explained by the higher
number of non-dispersed or insufficiently
dispersed carbon black agglomerates
with a diameter of over 50 µm.
Physical parameters - hardness
Determination of Shore A hardness, on
the other hand, shows no noteworthy
influence of the mixing process on the
parameters (Figure 10). Constant de-
grees of hardness were detected irres-
pective of the mixing time.
www.kgk-rubberpoint.de
 MASCHINEN UND ANLAGEN
MACHINERY AND EQUIPMENTS

9 Fig. 9: Exemplary re-

Difference in dissipated energy density

presentation of a mul-

between 1 and 3 cycle (ε = 30%) [J/m3]

5 30% Strain 1. cycle
3,00 x 104
30% Strain 2. cycle
45 s tiple hysteresis cycle
60 s
4
30% Strain 3. cycle
70% Strain 1. cycle 75 s and dissipated energy
2,75 x 104
70% Strain 2. cycle 90 s density at 30 % elon-
Stress [MPa]

70% Strain 3. cycle 150 s

3 120% Strain 1. cycle 180 s gation amplitude as a
120% Strain 2. cycle
120% Strain 3. cycle
2,50 x 104 function of post-aera-
2 tion-step mixing time.
2,25 x 104
1

0 2,00 x 104
0 25 50 75 100 125 0 40 80 120 160 200
Strain [%] Post-aeration-step mixing time [s]

10 Fig. 10: Hardness test pound properties, any further improve-

100
to Shore A as a func- ment actually occurs beyond the identi-
80 45 tion of post-aeration- fied post-aeration-step mixing time of
step mixing time approx. 75 s, or whether actually existing
Hardness [Shore A]

60
60
75
90
40
150
20 180
0 assumed.
0 50 100 150 200
Post-aeration-step mixing time [s]
Physical parameters - tear propagation significant difference among the com-
Tear propagation passes through three pounds mixed for 45, 60 and 180 se-
phases in tear analyzer testing: the initi- conds after the aeration step. Analogous
al phase of stable tear propagation in to the tensile testing, it becomes evident
which the evaluation of this test method in this case as well that the investigation
also takes place; the follow-up instable of tear propagation as a means of quan-
phase with tear propagation that is no tifying dispersion quality does not lead
longer linear; and finally, the catastro- anywhere in the case of test specimens
phic phase [17]. It is quite evident in the with a volume in the magnitude of an S2
example shown in Figure 11 (left) that tensile bar. Despite a tenfold higher
the amplitude of stress has a major influ- number of particles with a diameter of
ence on the physical life of the test speci- over 50 µm, materials mixed for 45 and
mens. With increasing amplitude, tear 60 seconds show no tendency to „run
propagation passes over into the catast- short“. This is presumably due to the low
rophic phase much earlier. Observation test volume.
of the change in tear propagation per On the basis of what has been learnt
cycle as a function of energy density in so far, the question posed is whether in
Figure 11 (right) does not point up any terms of compound quality and com-
(mean derived from differences cannot be represented due to
five individual measu-
inadequate sensitivity in the case of the
rements per batch).
measuring systems. Accordingly, approp-
riate processes have to be found that are
sensitive enough to depict the effects
Dielectric measurements
Measuring the dielectric properties, as
described in [15; 16], lends itself for this
purpose. Theory teaches that at constant
filler concentration, greater mixing pro-
cess effectiveness leads to lower conduc-
tivity insofar as concentrations below
the percolation threshold are involved
(above a critical black carbon concentra-
tion, the rubber compound is again con-
ductive) [15; 18]. The uniform distributi-
on of well-dispersed filler particles then
leads to a lesser degree of filler-filler in-
teractions due to the larger spacing bet-
ween particles. The result is reduced con-
ductivity. This is apparently the case in
the test series carried out. The longer
mixing time along the „target line” has
been proven to lead to lower conductivi-
ty (Figure 12). That this is so is due to
improved filler microdispersion, which it

11 Fig. 11: Change in tear

14
Strain amplitude:
0,0 propagation per cycle
12 15 mm over energy density as
180 s
a function of post-ae-
log dc/dn / µm/cycle

20 mm
Crack length [mm]

10 25 mm
30 mm
-1,0 60 s ration-step mixing
8 45 s time.
6
-2,0
4

0 -3,0
-1,10 -1,00 -0,90 -0,80 -0,70 -0,60 -0,50
0 1 x 105 2 x 105 3 x 105
Number of cycles [‒] log Wtot / MPa

www.kgk-rubberpoint.de KGK · 10 2015 37

 MASCHINEN UND ANLAGEN
MACHINERY AND EQUIPMENTS

12 Fig. 12: Dielectric

10-3 100,0 properties as a func-
45 s 60 s 100 45 s
75 s 90 s 60 s tion of post-aerati-

normalized conductivity
150 s 180 s 75 s on-step mixing time
Conductivity [S/cm]

10-4 80
90 s (mean from three in-

at 100 Hz [%]
150 s
60 dividual measure-
10-5 180 s
47,0 ments per batch).
40
10-6
20 15,3
6,2
1,2 0,5
10-7 0
10-2 10-1 100 101 102 103 104 105 106 107 108 45 60 75 90 150 180
Frequency [Hz] Post-aeration-step mixing time [s]

was hitherto not possible to identify be- whether the temperature-sensitive [9] Mullins, L.; Tobin, N.R.; Theoretical model for
cause of the limited resolution capability torque method presented is universally the elastic behavior of filled-reinforced vulca-
of the optical microscopy method (DIAS); valid and applicable. nized rubbers; Rubber Chemistry and Tech-
it does not, furthermore, have any signi- nology; Issue 30; 1957; p. 555 ff.
ficant influence on the other parameters Acknowledgment [10] Klüppel, M.; Schramm, J.; A Molecular-Stati-
measured. We owe thanks to the German Federati- stical Approach to Hyperelasticity of Elasto-
on of Industrial Research Associations mer Materials; DIK publication 105; Confe-
Summary „Otto von Guericke“ e.V. (AiF) and its rence Proceedings of the Fall Rubber Collo-
The aim of this study to use the process member associations DKG and VDMA for quium 1998.
data generated during compounding in the financial support provided for the [11] Kreiselmaier, A.; Wie elastisch ist Gummi?
the internal mixer to characterize online work on the IGF project 18244 N, funded – Definition von Mullins und Payne Effekt;
the state of the compound in terms of by the Federal Ministry for Economic Af- Kautschuk Gummi Kunststoffe; Volume 67;
the compound‘s attained dispersive fairs and Energy (BMWi). Dr.-Ing. F. Kurzi- No. 4; 2014; pp. 16.
and distributive mixing quality. To this dim (formerly research staffer at DIK) is [12] Harwood, J.A.C.; Mullins, L.; Payne, A.R.;
end, the new method of analysis— deserving of special thanks for pointing Stress softening in Natural Rubber Vulcani-
“temperature-sensitive torque“—was the way to the innovative rendering of zates. Part II. Stress softening effects in pure
applied, in which the logarithm of torque process parameters. gum and filler loaded rubbers; Journal of
is plotted against the reciprocal value of Applied Polymer Science; Issue 9; 1965; pp.
the melt temperature irrespective of the Bibliography 3011.
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The curve progression of the process a laboratory internal mixer; Kautschuk Gum- reifens; Physikalische Blätter 57; No. 6;
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shown that once a given mixing time is 467. [14] Heinrich, G.; Klüppel, M.; Vilgis, T.; Rein-
exceeded, a straightforward rheological [2] Pohl, J.; Limper, A.; Gummi-Mischtechnik, Alt- forcement Theories; Physical Properties of
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with the Arrhenius approach materiali- Gummi Fasern Kunststoffe; No. 45; 9, 1992, 599.
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Along this so-called „target line“, the [3] Limper, A., editor; Mixing of Rubber Com- working in Elastomers Monitored by Dyna-
compound properties remain constant pounds; Hanser Verlag, 2012 . mic Mechanical and Dielectric Spectrosco-
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was possible to confirm this hypothesis mierungsmöglichkeiten bei der Herstellung ring; Issue 293; 2008; pp. 12.
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pound properties and compound para- scher; Dissertation RWTH Aachen; 1992. Reinforcement of Elastomers on Various
meters conducted both on the com- [5] Dizon, E.S.; Papazian, L.A.; The Processing of Length Scales; Advances in Polymer Sci-
pound as well as on the vulcanizate. The Filler reinforced Rubber; Rubber Chemistry ence; Issue 164; 2003; pp. 1-86.
„temperature-sensitive torque“ method and Technology; Issue 50, No. 4, pp. 765, [17] Schröder, A.; Früh, T.; May, K.; Ruppelt, D.;
of analysis thus harbors considerable 1977. Alshuth, T.; Very Fine Dispersable Polymer
potential for reducing mixing time [6] Cotten, G.R.; Mixing of Carbon Black with Bound Additives; Kautschuk Gummi Kunst-
through online forecasting of the com- Rubber II – Mechanism of Carbon Black In- stoffe; Volume 61; No. 11; 2008; pp. 584.
pound quality of the respective batch. It corporation; Rubber Chemistry and Techno- [18] Le, H.H.; Ilisch, S.; Jakob, B.; Radusch, H.-J.;
should be pointed out here that the vali- logy Issue 58, No. 4, 1985, pp. 774. Online Characterization of the Effect of Mi-
dity of the method of analysis presented [7] Arrhenius, S.; Über die Reaktionsgeschwin- xing Parameters on Carbon Black Dispersi-
for describing the mixing process has digkeit bei der Inversion von Rohrzucker on in Rubber Compounds Using Electrical
been discussed solely on the basis of the durch Säuren; Zeitschrift für physikalische Conductivity; Rubber Chemistry and Tech-
formula used here. In view of the wide Chemie; No. 4; 1889; pp. 226. nology; Issue 77; No. 1; 2004; pp. 147.
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38 KGK · 10 2015 www.kgk-rubberpoint.de