VOL.

65

1at nonaffine
cross linking
noftrapped

1 magnitude THE DISPERSION OF CARBON BLACK IN RUBBER PART I.

is rejoinder, RAPID METHOD FOR ASSESSING QUALITY OF DISPERSION*
he fact that
rsing strain A. Y. CORANt
ms into the MONSANTO CHEMICAL COMPANY, 260 SPRINGSIDE DRIVE, AKRON, Omo 44333
11 ostensibly
r polymeric AND
•ered on the
J.-B. DONNET
responsible
tilibrium or CENTRE DE RECHERCHES SUR LA PHYSICO-CHEMIE DES SURFACES SOLID ES,

viscoelastic 24 AVENUE DU KENNEDY, 68200 MULHOUSE, FRANCE

>equence of
~sing defor- ABSTRACT
Carbon black is the most important reinforcing filler for rubbers. The incorporation of carbon black into rubber
vulcanizates generally gives improved strength, extensibility, fatigue resistance, abrasion resistance, etc. In order to
exert its beneficial influence on the properties of rubber vulcanizates, the carbon black must be sufficiently dispersed
therein. Indeed, poor dispersion can, in itself, give rise to detrimental effects (e.g. reduced product life, poor performance
in service, poor product appearance, poor processing characteristics, poor product uniformity, raw-material waste,
1 and Dr. L. high finished-product rejection rates, and excessive energy usage). These inadequacies are generally the result of the
rson of Bell presence of rather large, undispersed agglomerates.
Ll Research. The present work was initiated in order to develop an improved understanding of the carbon-black dispersion
Laboratory process including the understanding of factors which affect the kinetics of dispersion. The work described here is
focused on methodology for reproducibly mixing carbon black with rubber in the laboratory, and reproducibility, but
rapidly and easily estimating the degree of dispersion of the carbon black into the rubber as a function of mixing time.
Procedures were developed for introducing rubber, filler, and other ingredients into a small, laboratory internal mixer
and for mixing the batches for various periods of time. Also, an improved, simple-to-use, reproducible method for
determining the degree of carbon black dispersion in rubber has been adapted. The extent of dispersion was correlated
with various measures of tensile strength and with other performance-related properties.

INTRODUCTION
Carbon black is the most important reinforcing filler for rubbers. In many, if not most
applications, the utility of rubber would be indeed limited were it not reinforced by the in-
corporation of carbon black. The incorporation of carbon black into rubber vulcanizates gen-
erally gives improved strength, extensibility, fatigue resistance, abrasion resistance, etc. 1- 4 •
In order to exert its beneficial influence on the properties of rubber vulcanizates, the
carbon black must be sufficiently dispersed therein. In addition, poor dispersion can in itself
give rise to certain detrimental effects. These can be summarized as follows 5 : (i) reduced
.. Jaffee, Eds.,
product life, (ii) poor performance in service, (iii) poor product appearance, (iv) poor pro-
cessing characteristics, (v) poor product uniformity, (vi) raw-material waste and high fin-
ished-product rejection rates, and (vii) excessive energy usage. These inadequacies are gen-
erally the result of the presence of rather large, undispersed agglomerates.
Large agglomerates can give rise to poor mechanical properties3 •6 • It is possible that the
large agglomerates act as failure-initiating flaws. If this is the case, one might expect that
agglomerates larger than the inherent flaw size for the rubber 7 would be responsible for
decreases in mechanical properties such as ultimate tensile strength, energy to break, tearing
energy, fatigue resistance, etc. The inherent flaw size, for natural rubber is of the order, 10
µm; thus, a magnification of 50 X was used in our work to easily observe agglomerates which
are 5-10 µm or greater in diameter. It should be noted that most optical microscopic techniques
used by others focus on agglomerates of similar dimensions.
The present work was initiated in order to develop an improved understanding of the
carbon-black dispersion process including the understanding of factors which affect the
•Received February 24, 1992; revised April 20, 1992.
t Present address: The Institute of Polymer Engineering, The University of Akron, Akron, Ohio 44325-0301.

973
974 RUBBER CHEMISTRY AND TECHNOLOGY

kinetics of dispersion. These factors include such parameters as mixing conditions, carbon-
black type, elastomer type, etc. The kinetics of carbon-black dispersion will be considered
in the next paper of this series.
The work described in this first paper of this series is focused on methodology for re- Mis les!
producibly mixing carbon black with rubber in the laboratory, and reproducibly, but rapidly mmonly
and easily estimating the degree of dispersion of the carbon black into the rubber as a Technic
function of mixing time. For the purposes here, dispersion is defined as the reduction in the 7ears2s-ao a
amount of carbon black present as undispersed agglomerates of average diameter greater '•photomet
than about 5 µm. {surfaces.
In order to reproducibly disperse the carbon black into the natural rubber, procedures In addH
were developed for introducing the rubber, filler, and other ingredients into a small internal
mixer and for mixing the batches for various periods of time. Also, an improved, simple-to-
use, reproducible method for determining the degree of carbon black dispersion in rubber
has been adapted. In addition, the extent of dispersion was correlated with various measures
of tensile strength.
Because of the importance of the effects of dispersion on the properties of carbon-black
filled vulcanizates, many methods for its characterization or estimation have been used.
These have been reviewed by Hess5.
Work in the field of filler dispersion started early in this century. Ditmar reported the
use of microtome sectioning in 19098 to prepare samples which were examined by trans-
mission light microscopy. In 1913, Loewen pressed pieces of uncured, raw rubber to prepare can be use1
thin specimens for examination9 • Improvements were made during the 1920s with the first Other ii
use of cryosectioning for the preparation of thin sections by Depew and Ruby 10 • Cryosec- " tical extinc
tioning techniques were further improved with contributions from Tidmus and Parkinson For the
in 1937 11 and Leigh-Dugmore in 1956 12 .
Methods based on the visual examination were also used. In 1926, Wiegand examined
the surfaces of torn vulcanizates by using a hand-held lens 13 . In 1933, Roninger developed reasons: (i
the so-called "ebonite" method in which a test stock was soaked overnight in molten sulfur
and essentially converted to filled ebonite which was cut and polished 14 . Examination by
incident light provided images of undispersed agglomerates on the basis of changes in re-
fractive indices associated with the degree of dispersion.
Cutting and tearing are the most extensively used techniques for preparing sample sur- is the sam1
faces for examination of dispersion quality. Such a technique is based on the principle that In this
filler agglomerates divert cutting or tearing paths to cause the formation of bumps or depres-
sions in the cut or torn surface. Indeed, the bumps and depressions are easily observable
under incident light by using an optical microscope typically at 30-50 X. Schweitzer and
co-workers developed a tearing procedure which has become Test Method A of ASTM Stan- reproducit
15 (as in the
dard D 2663-89 ·16 • Stumpe and Railsback developed a razor-cutting technique in which a
single edged razor blade is forced through the filled rubber sample by using a lever arrange- field optic~
ment to keep the blade normal to a molded surface of a vulcanized spe~imen as it cuts estimated
straight through the specimen 17 .
Another example of surface examination is the use of a stylus 18- 20 . With this method, a
fine stylus is tracked over a cut rubber surface to measure its roughness. This procedure is
now part of ASTM Standard D 2663-89, Test Method C. As the stylus is caused to move
across a cut surface, its position is recorded. From an analysis of the recorded stylus trace,
the surface roughness can be quantified. This quantification has been related to dispersion
quality.
Transmission electron microscopy (TEM) was first used for determining the degree of In this
carbon-black dispersion in rubber by Von Ardenne and Beisher in 1940 21 . Ladd used TEM
to examine smeared out raw rubber films and replicated fractured surfaces in 1944 22 . Ford
23
and Gessler and then Dannenberg 24 examined dried films of diluted suspensions of filled
elastomer. In other work, Chappuis, Polley, and Schulz examined rubber which had been
swollen with a methacrylate monomer which was then polymerized, and finally thinly
 VOL. 65 DISPERSION OF CARBON BLACK 975
25
litions, carbon- microtomed to produce TEM specimens. The First cryosectioning of carbon-black filled
l be considered rubber for TEM examination was reported by Chappuis and Robblee 26 •
Scanning electron microscopy (SEM) was introduced during the late 1960s. Analysis by
:>dology for re- SEM is less complicated than TEM because of the simplicity of sample preparation5 • It is
>ly, but rapidly commonly used in combination with energy dispersive x-ray analysis (EDAX) 27 •
1e rubber as a Techniques of image analysis have been applied to TEM and SEM during the last 15-20
2
eduction in the years s-so and more recently, Ebell and Hemsley 2 and Mutagahywa and Hemsley31 have applied
ameter greater a photometric image analysis to dark-field light microscopic examination of cut filled rubber
surfaces.
'er, procedures In addition to the above, assessments of dispersion quality have been made on the basis
. small internal of indirect measurements. The measurement of electrical conductivity has been used as an
ved, simple-to- indirect measure of carbon-black dispersion 32 •33 • Electrical conductivity can be viewed as an
·sion in rubber inverse function of the degree of separation of individual carbon-black aggregates.
rious measures Cembrola has compared resistivity measurements to cut-surface roughness 34 . He pointed
out that the surface roughness measurements relate to undispersed agglomerates whereas
f carbon-black resistivity is a measure of microdispersion at dimensions well below those of the agglomerates.
Lve been used. However, assessment of dispersion quality on the basis of conductivity measurements cannot
be used universally. This is because of the fact that compounding variables, heat history,
r reported the and other factors in addition to dispersion quality can greatly affect electrical conductivity.
ined by trans- Nevertheless under properly controlled conditions, measurements of electrical conductivity
1ber to prepare can be used to assess dispersion quality.
1 with the first Other indirect measures of carbon-black dispersion, such as rheological properties35 , op-
by 10 • Cryosec- tical extinction36 or vulcanizate ultimate properties5 •37 have been used.
md Parkinson For the experimental research described in this series of reports, a direct, rapid method
for estimating the quality of dispersion as a function of mixing time was desired. Also, the
and examined method should be applicable to unvulcanized as well as vulcanized stocks. This is for two
ger developed reasons: (i) If unvulcanized stocks could be assessed for dispersion quality, it would not be
molten sulfur necessary to masticate the rubber and carbon black in the presence of curing system com-
rnmination by ponents such as sulfur, organic accelerator or peroxide which could have effects on the rate
changes in re- of carbon black dispersion in addition to those effects one wished to study. (ii) If unvulcanized
stocks could be assessed, one would not be required to assume that the dispersion quality
1g sample sur- is the same after vulcanization as before vulcanization.
principle that In this work we have developed a method of determining a dispersion rating (DR) with
nps or depres- respect to both vulcanized and unvulcanized stocks containing carbon black dispersed to
lly observable varying degrees. It was adapted from a combination of methods reported by Stumpe and
17
~hweitzer and Railsback and by Ebell and Hemsley 2 •31 • The method of Stumpe and Railsback for making
>f ASTM Stan- reproducible razor cuts has been improved and instead of the use of side-angle illumination
ue in which a (as in the Stumpe-Railsback microscope setup), the cut surfaces were examined by dark-
lever arrange- field optical microscopy as in the method of Ebell and Hemsley. The dispersion ratings were
[len as it cuts estimated by visual comparisons similar to those of Stumpe and Railsback. In addition a
special tensile strength specimen has been devised. The object was to produce a test piece
.his method, a which would be particularly susceptible to compositional inhomogeneities associated with
s procedure is poor carbon-black dispersion. Tensile strength values were correlated with dispersion ratings.
used to move Other performance-related properties were also correlated with dispersion quality.
l stylus trace,
to dispersion EXPERIMENT AL

the degree of In this work, the extents of dispersion of type N330 carbon black and of type N326
~dd used TEM carbon black into natural rubber (SMR 5CV) were investigated. In each case, the freshly
22
l 1944 • Ford mixed composition was press-cured, razor-cut and microscopically examined to visually es-
sions of filled timate the degree of carbon-black dispersion as expressed by a dispersion rating DR. Cured
Lich had been sheets of each composition were also tested with respect to ultimate tensile strength and
finally thinly other performance-related properties. The test recipes are given in Table I.
 976 RUBBER CHEMISTRY AND TECHNOLOGY

TABLE I
back-out and 1
TEST RECIPE greatly reduc1
Ingredient 8. Aftertl
Recipe Batch a
with the mixi.
Natural rubber 100 44.84 the stud bolts
Carbon black 45 20.18 9. Immedii
Zinc oxide 5 2.24 (to 100°C)
Stearic acid 2 0.90 poly(ethy lene1
Santoflex® 13 b 1.5 0.67 from the presi
Santocure® NSc 0.6 0.27 evaluated wit]
Sulfur 2.0 0.90
Totals form of an ap]
156.l 70.00

aBatch weights in g.
bAntidegradant manufactured by Mon-
As stated a
santo Chemical Company.
be applied to 4
c Accelerator manufactured by Monsanto
Chemical Company. be vulcanized,
approximate i
from each cir4
MIXING
characteristic:
curing charac1
Batches, each weighing 70.00 g, were mixed in a Brabender mixer-measuring head (catalog The square
number 02-17-P02, capacity of 60 to 85 mL, electrically heated (1300 watt], blade speed ratio slabs 15.2 cm
drive-to-driven 3: 2, air cooled, with stock temperature thermocouple, fitted with cam-type the curing ch~
rotors) at 40 rpm, with the temperature set points adjusted to 100°C. The mixer-measuring the vulcaniza1
head was coupled to a Brabender type EPL-V5501 (catalog number 01-17-000) electronic From each vul,
torque rheometer. of carbon blac
In order to reproduce the results of this work, it is necessary to follow closely the detailed
procedure for charging the mixer and for mixing. The detailed procedure which has been
developed by trial and error is as follows:
The <lisper
1. Adjust the temperature set points of the mixer to l00°C, and let the indicated tem-
razor-cut surf:
perature stabilize. Then start the mixer rotors and adjust the speed to 40 rpm. Run through
the torque calibration procedures with the rotors in motion. Preparatio
2. Add the rubber and let it be masticated for two minutes. razor-blade he
built to hold s
3. Run the rotors in the reverse direction (reverse jog) to remove 10 g ± 0.2 g of the
sufficient qual
rubber. This sample is put aside in a paper cup to keep it relatively warm for re-addition a
little later in the procedure. (Schick Plus P
or other irreg
4. With the mixer not running, add all of the carbon black with the rest of the ingredients
designed a cut1
to the hopper of the mixer. Prior to addition of the carbon black to the mixer the other
edged blades.
ingredients should be placed on top of the carbon black, which had been weighed into a
The purprn
paper cup. The paper cup is ideal for the addition of these ingredients because it can be
blade straight
easily crimped such that it has a lip to aid in directing the ingredients into the hopper of
thereof, witho
the mixer, and it can be deformed by hand, more-or-less rhythmically, as the ingredients
flow into the mixer hopper as they are poured from the paper cup. which was ma
5. Restart the mixer rotors in the normal direction, again at 40 rpm.
j base upon whi,
; through the UJ
6. After the carbon black and other ingredients have been essentially completely taken
· between the UJ
into the mixer (this generally takes about 45 to 60 seconds), the clock is started and the ram
is dropped into place. of the lever tli
tolerances bet
7. Mixing is continued for 30 seconds after which the batch is rapidly backed out of the
· appreciably a1
mixer by using the reverse-jog mode (80 rpm, 10 seconds). The mixture is immediately re-
held between 1
charged into the mixer along with the 10 g of masticated rubber which had been removed
dicular to the
earlier (to make room for the bulky carbon black). The ram is then immediately dropped
are held togetl
again into place. The recharging is done by using the normal forward-direction mixing mode
' position of the
at 40 rpm, and very little time is taken for backing-out and recharging. The reason for the
· is maintained •
 VOL. 65 DISPERSION OF CARBON BLACK 977

back-out and recharge is to obtain reproducible mixing results and to minimize or, at least,
greatly reduce the presence of unincorporated, free-powder carbon black.
8. After the desired mixing time, the batch is removed from the mixer. This is best done
with the mixing head disassembled (or opened up after the removal of the wing nuts from
the stud bolts of the mixer).
9. Immediately after removal from the mixing head, each batch is pressed between heated
(to 100°C) platens to a thickness of 2.3 mm between two pieces of Mylar
poly(ethyleneterephthalate) film. The batch is held in the press for 4.0 minutes then removed
from the press and left on the bench top to cool and later, if desired, to be press cured and
evaluated with respect to dispersion characteristics. At this point, the entire batch is in the
form of an approximate disc.

PREPARATION OF CURED SHEETS

As stated above, the present method for determining carbon-black dispersion quality can
be applied to either unvulcanized or vulcanized stocks. In cases when the samples were to
be vulcanized, each pressed disc-like sheet (2.3 mm thick) of uncured mix was cut into an
approximate square (about 15 cm on a side). From the pieces (excess material) removed
from each circular sheet, a sample was taken for characterization with respect to curing
characteristics at 153°C by using the Monsanto moving-die rheometer (MDR 2000). The
curing characteristics are given in Table II.
ng head (catalog The square sheets were then vulcanized for 12.0 minutes at 153°C in a press to give test
>lade speed ratio slabs 15.2 cm by 15.2 cm by approximately 2 mm thick. According to the MDR 2000 data,
l with cam-type the curing characteristics of all of the batches were similar. A choice of 12.0 minutes for
tixer-measuring the vulcanization time for all of the batches was taken as a compromise of convenience.
·000) electronic From each vulcanized sheet, a small amount was taken and kept for evaluation of the quality
of carbon black dispersion.
ely the detailed
DETERMINING THE DEGREE OF DISPERSION
ivhich has been
The dispersion ratings, DRs, were determined by microscopic examination of freshly
indicated tem- razor-cut surfaces of the vulcanizates.
n. Run through Preparation of the vulcanizate surface for examination.-First we attempted to use the
razor-blade holder and cutting device described by Stumpe and Railsback 17 • Their jig was
built to hold single-edged razor blades. Currently we could find no single-edged blades of
± 0.2 g of the sufficient quality to give good cut surfaces. We could find excellent double-edged blades
r re-addition a (Schick Plus Platinum). It should be noted that these blades are essentially free from nicks
or other irregularities visible when viewed under a light microscope at 50 X. Thus, we
;he ingredients designed a cutting apparatus based on the use of the currently available high-quality double-
ixer the other edged blades.
~eighed into a The purpose of the apparatus was to provide a means to move the cutting edge of the
ause it can be blade straight through the vulcanizate sheet in a direction normal to the molded surface
the hopper of thereof, without letting the thin blade be deflected to either side. A drawing of the apparatus
le ingredients which was made from a moderately hard wood (maple) is given in Figure 1. It comprises a
base upon which is mounted upright elements to support a lever arm when a pin is positioned
through the upright elements and the lever arm to form a fulcrum. The lever arm is placed
tpletely taken between the upright elements so that the pin passes through it near one of its ends. The end
:land the ram of the lever through which the pin passes is expanded in area so that, with slightly loose
tolerances between. the upright elements and the lever arm, the lever arm cannot rotate
ced out of the appreciably around its longest axis. Near the opposite end (away from the pin) the blade is
mediately re- held between the two mirror-image halves of the lever arm. Thus, the blade is held perpen-
•een removed dicular to the upper surface of the cutting block. The mirror-image halves of the lever arm
tely dropped are held together by a single nut and thumb screw which also holds the blade tightly. The
mixing mode position of the blade is stabilized by the two blade-positioning pins so that its cutting edge
~ason for the is maintained parallel to the cutting block positioned beneath it.
978 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 65

1.0 cm BOLT WI TH NUT

APPROXIMATE
rro HOLD ILADE ANO LEVEll-AllM A66EMILV TOtJETHElll
However, in some c~
SCALE H by Figure 2. The un
and the strain is m~
vulcanized rubber v
essary for soft unc
rubber is strained, 1
the leading edge of
Uncured specim1
REMOVABLE PIN Otherwise, the poly1
DOUBLE-EDGED required for visuali
LEVER ARM RAZOR BLADE " Microscopic exa
.~---!'---.
by using dark-field
@ ,-
' $ A Nikon Optiphot I
fitted with a Nikon
··--·-
' CUTTING 8LOCK '\.
'
a Polaroid 4 X 5 La:
Photomicrograp
: : compared to "stan<
preparation of the
time, small sample~
25 cm
mold. (The press-c1
FIG. !.-Cutter for carbon-black dispersion measurements. photomicrographs '
the micro-cavity-m~
4a and 4b. The star
In order to cut the surface of a vulcanizate sample, a small piece of it (approximately 5 Generally, wher
mm by 5 mm by 2.3 mm) was placed on the block below the lower cutting edge of the blade. photomicrographs <
The arm which holds the blade was then pushed down, gently but steadily, through the a dispersion rating
rubber sample. Thus, in each case, a high-quality surface for examination was created. A apparent dispersim
new portion of blade was used for each cut and when the lower cutting edge of the blade dispersion rating va
was "used-up", the pin was pulled from the pivot and the lever arm and blade were turned of Figures 4a and 4
over (rotated 180 degrees around the longest axis of the lever arm) to make available a new DR is chosen by int
lower cutting edge. Of course, when both edges of a blade were completely used, the blade
was replaced by a new one.
The apparatus described for preparing a surface for microscopic examination of vulcan-
izates can also be used to prepare good surfaces for the examination of unvulcanized rubber.

LEVER-ARM
ASSEMBLY - SE
STRAINED SILV1
,/ RUBBER MIR

DEVIi
REFLE.
8E1

RUBBER STRAINED BEFORE CUTTING

(ABOUT 10 %)
FIG. 2.-Preparation of fresh-cut surfaces of uncured rubber.
 VOL. 65 DISPERSION OF CARBON BLACK 979

However, in some cases, a slight modification in the technique is required. This is illustrated
'HEif/
by Figure 2. The unvulcanized rubber sample is slightly strained just prior to its being cut
and the strain is maintained as the blade passes through the specimen. Otherwise, the un-
vulcanized rubber would be smeared as the blade passed through it. This technique is nec-
essary for soft uncured stocks, especially when a noncrystallizing rubber is used. If the
rubber is strained, the rubber is essentially immediately removed away from the blade as
the leading edge of the blade passes through the sample.
Uncured specimens must be examined very soon after the fresh-cut surface is prepared.
Otherwise, the polymer can slowly flow and at least partially obscure the surface irregularities
required for visualization of the agglomerates.
Microscopic examination of the freshly-cut vulcanizate. -The surfaces were examined
by using dark-field illumination from directly above, at a magnification of 50 X (Figure 3).
A Nikon Optiphot Biological Microscope was used with a Nikon Universal EPl-Illuminator
fitted with a Nikon Microflex AFX-11 Photomicrographic attachment having there attached
a Polaroid 4 X 5 Land Film Holder #545. Polaroid type 53 coaterless film was used.
Photomicrographs of the prepared surfaces of all of the mixes were obtained. These were
compared to "standard" photomicrographs which had been previously obtained. For the
preparation of the standards, a single batch was mixed. After various periods of mixing
time, small samples (approximately 0.22 g) were taken and press-cured in a micro-cavity
mold; (The press-cured samples measured about 7 mm X 7 mm X 3.2 mm.) The standard
photomicrographs were obtained by microscopic examination of the razor-cut surfaces of
the micro-cavity-molded samples. The standards for comparison are represented by Figure
4 17 34
4a and 4b. The standards are very similar to those used by others • • •
t (approximately 5 Generally, when assigning dispersion ratings to compositions which were to be studied,
g edge of the blade. photomicrographs of about 25 samples were obtained before any of the group was assigned
iadily, through the a dispersion rating. Then the photomicrographs were visually arranged in order of their
;ion was created. A apparent dispersion quality, from the poorest quality to the best quality of the group. Then
g edge of the blade dispersion rating values were assigned by making comparisons with the standard photographs
I blade were turned of Figures 4a and 4b. In each case the unknown was matched with a standard or a value of
tke available a new DR is chosen by interpolation between adjacent standards. The reason for prearranging the
;ely used, the blade

mination of vulcan-
wulcanized rubber.

lAINED
SEMI-
SILVERED 0 LIGHT
-SOURCE
rsBER MIRROR

:> OBJECTIVE LENS

?
::::::::::>
DEVIATED
REFLECTED
BEAM
....._ INCIDENT BEAM

SAMPLE
Fm. 3.-Schematic diagram of optical dark field microscopy.
980 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 65

D.R.• 2.2 I- 1.0 mm -I D.R.= 4.5 I- 1.0 mm -I

Fm. 4a.-Standard photomicrographs for dispersion rating. Rating
increasing top to bottom in each column; DR = 0.5 to 4.5.
 VOL. 65 DISPERSION OF CARBON BLACK 981

-1 D.R.• 6.5 I- 1.0 mm -I D.R.= 8.5 I- 1.0 mm -I

FIG. 4b.-Standard photomicrographs for dispersion rating. Rating
increasing top to bottom in each column; DR = 5.0 to 8.5.
982 RUBBER CHEMISTRY AND TECHNOLOGY VOL.65

experim~n~al photomicrographs was to maintain consistency within the group; whereas the tance was measurE
comparisons with the standard photomicrographs maintains consistency between groups. by the Monsanto F
set were measure
DETERMINATIONS OF TENSILE STRENGTH

Three British Standard dumbbell-type tensile test specimens and 8 or 9 specially designed
tensile test specimens were died out from the cured test slabs. The specially designed test
specimen is shown in Figure 5. The object of the design was to give a tensile-test specimen
which would be especially sensitive to the types of flaws which would form as the result of
During mixing,
undispersed carbon black agglomerates. It is expected that weakness of a specimen would
of mixing time. Fe
result from a large agglomerate (greater than 5 micrometers in diameter) at or near an edge
torque profiles w
of the specimen. Thus the specimen was made long and narrow. The length was limited by
mixing torque thE
the limit of the jaw separation in the tensile tester and the width was made as small as
lustrated by Figm
practical for maintaining an easily measurable cross sectional area. The idea was to obtain
extended butadie:
the most edge per test-specimen volume. For comparisons, the relatively small British Stan-
two power peaks
dard specimen was used rather than those cut by the larger ASTM tensile die. This was
single peak and 1
because of limitations in the amounts of material which were available with each mix.
mixer. At any rat
The British Standard test specimens were tested by using a Monsanto Tensometer 10
discussed by Cott
tensile tester with a jaw separation rate of 50 cm/min whereas the special test specimens
An effect of in
were tested with a jaw separation rate of 100 cm/min since they were about twice as long
and thus its mixiI
as the British Standard specimens.
is to reduce the 1
DETERMINATION OF OTHER PERFORMANCE-RELATED PROPERTIES
increase in mixin
FOR CORRELATIONS WITH DISPERSION RATINGS
torque due to the
observed. This wa
In addition to the determination of tensile strength, other performance-related properties butadiene rubber
were determined. In this case, batches were larger than the 70 g batches discussed above. The same effe1
The larger batches were used so that there would be enough material for the dispersion power peak. In ac
ratings, the determination of vulcanization characteristics (by using the Monsanto moving
die rheometer MDR 2000), stress-strain properties, abrasion resistance, fatigue resistance,
and the properties measured by the Goodrich Rheometer (heat build-up and permanent set).
The recipe was changed slightly by the incorporation of the vulcanization retarder N- I
cyclohexylphthalimide to give increased scorch resistance. It was feared that the larger
batch might give higher mix temperatures and thus, that scorch might be a problem.
i
The larger batches, each weighing 275.35 g, were mixed in a Brabender Prep Mixer mea-
suring head (catalog number 02-23-000 capacity of 250-350 mL, electrically heated, air
cooled, with stock temperature thermocouple, fitted with Banbury-type rotors) at 40 rpm.

l
The mixer-measuring head was coupled to a Brabender type EPL-V7752 electronic torque
rheometer. The start-up procedure was similar to that used with the smaller mixing head;
however, the amount of masticated rubber temporarily removed from the mixer (to make
room for the addition of the bulky carbon black) was scaled up from 10 g to 40 g.
Stress-strain properties were measured as before with the "long-die" tensile specimens
but this time only three specimens were used in order to conserve material. Abrasion resis- MIXING

uR·0.3
TORQUE

-0 r
I
0.30
I
1.5
I

10.0
13.0
(Dimensions in centimeters)
FIG. 5.-Specially designed tensile specimen for correlations between ultimate tensile strength and dispersion ratings.
 VOL.65 DISPERSION OF CARBON BLACK 983

!reasthe tance was measured by the Pico abrasion test (ASTM D 1630), fatigue resistance was measured
groups. by the Monsanto Fatigue-to-Failure Tester (ASTM D 4482), and heat build-up and permanent
set were measured by the Goodrich Flexometer (ASTM D623-A).

designed RESULTS AND DISCUSSION

~ned test
1pecimen MIXING CHARACTERISTICS
result of
During mixing, the mixing torque and temperature were measured and plotted as functions
m would
of mixing time. For both the N330 and N326 carbon blacks, similar temperature and mixing
·an edge
torque profiles were obtained. The mixing torque reaches a maximum very rapidly. The
mited by
mixing torque then drops continuously-at first rapidly, and then more slowly. This is il-
small as
lustrated by Figure 6. This type of behavior has been observed before 35 with respect to oil-
;o obtain
extended butadiene rubber. However, in that case and in other previously reported work,
ish Stan-
two power peaks (torque maxima) were observed. It is possible that we only observed a
rhis was
single peak and not the second peak because of the method which we use to charge the
mix.
mixer. At any rate there are probably several factors operating here. Some of these were
neter 10
discussed by Cotten35 •
>ecimens
An effect of incorporating of the carbon black into the rubber is to increase its viscosity
e as long
and thus its mixing torque. The effect of dispersing the carbon black after it is incorporated
is to reduce the viscosity and thus the mixing torque. Depending on the relative rate of
increase in mixing torque due to incorporation and the relative rate of decrease in mixing
torque due to the dispersion of the carbon black, a second power peak will or will not be
observed. This was the explanation for the so-called second power peak found in oil-extended
roperties butadiene rubber but which is not seen in the present work with natural rubber.
d above. The same effects could be operating here but not in the proportions to give the second
spersion power peak. In addition, the method of starting the mixing procedure is different here than
>moving
sistance,
tent set).
arder N- i
1e larger
m. I
xer mea-
ated, air
-··
.
......
PREVIOUS WORK I
.40 rpm. -. _{BR, SBR)
le torque I
ng head; ··--·--1
(to make
PRESENT WORK
(NR)
I
~ecimens
lon resis- MIXING
TORQUE

MIXING TIME - - - -...

;ion ratings. Fm. 6.-Mixing torque as a function of mixing time.
984 RUBBER CHEMISTRY AND TECHNOLOGY VOL.65

in other work. This might also explain the absence of the second power peak in the pres-
ent work.
In each case, temperature increased with mixing time until a maximum of about 117-
1190C was reached after about 2-3 minutes, then the temperatures slowly decreased in a
continuous manner. This temperature reduction is probably due to the above noted reduction c
in mixing torque which also occurs with increasing time.
N3
VULCANIZATION CHARACTERISTICS

The vulcanization characteristics of the variously mixed batches were measured. It was
observed that both minimum and maximum torque, measured by the MDR, decrease somewhat
with increasing time of mixing. Scorch time as measured by t 2 (vulcanization time required
for a small increase in the torque measured by the MDR 2000) decreases with increases in
mixing time. However, the effect of mixing time on t 90 , the time required for 90% of the
vulcanization to occur, is only slightly affected by changes in mixing time. Overall, the effects
of mixing time on vulcanization characteristics are relatively minor, with scorch resistance N3
being reduced somewhat by the use of very long mixing times (e.g. 20 minutes).

CARBON BLACK DISPERSION

Reproducibility of dispersion ratings (DRs) and effect of vulcanization. -The compo-

sitions of Table I were mixed for 5 minutes according to the mixing procedure given above.
A schematic drawing of a disc-shaped sample representing an entire batch is given in Figure
7. It shows the relative positions from which specimens were detached for razor cutting and
microscopic examination. Two types of specimens are illustrated: the central sample and
the edge samples. The flow histories of these two types differ somewhat because of the way
in which the batch was flattened in a press to form the disc. In the case of each of the five
specimens cut from each unvulcanized disc, a DR assignment was made. The rated pieces of The dif
the disc were then replaced in the disc and the disc was vulcanized under pressure for 12
minutes at 153°C. The pressure was limited so that only little flow occurred during the
molding-vulcanization process. After vulcanization, specimens were again cut in accordance
with Figure 7. The vulcanized specimens were then rated for dispersion quality.
Four discs were prepared, two of which contained N330 carbon black and two of which
contained N326 carbon black. Thus the reproducibility among equivalent specimens (edge
samples within a treatment of a disc) and the reproducibility between discs can be assessed.
Also the effect of carbon-black type can be observed as can the effect of vulcanization. The
results are given in Table II.

j
j
j
E
j

FIG. 7 .-Sampling from a 2.3 mm thick sheet of an entire batch.

 VOL. 65 DISPERSION OF CARBON BLACK 985

in the pres- TABLE II

THE EFFECT OF VULCANIZATION AND SAMPLE POSITION a
'about 117-
~creased in a Unvulcanized (Cl) Vulcanized (C2)
:ed reduction Carbon
black Run Edge, Dl Center, D2 Edge, Dl Center, D2

N330 (Al) Trial 1 (Bl) 4.6 4.8 5.0 4.8

4.6 5.0
mred. It was 4.0 5.0
sesomewhat 4.8 5.0
Trial 2 (B2) 5.0 5.0 4.8 4.7
lme required
4.6 4.7
increases in 4.6 4.7
· 90% of the 4.4 5.0
11, the effects
:h resistance N326 (A2) Trial 1 (Bl) 3.2 2.9 3.8 3.4
). 3.0 3.6
3.0 3.2
3.0 3.4
Trial 2 (B2) 2.9 3.0 3.0 3.2
-The compo- 3.0 3.2
given above. 3.0 3.0
fen in Figure 2.8 3.0
r cutting and a Values are dispersion ratings, DR.
, sample and
1eofthe way
:h of the five
ted pieces of The difference between averages and comparisons with the standard deviation of the
~ssure for 12 averages (calculated from the standard deviation of the measurements) of the observations
d during the are given in Table III. The standard deviation of the difference was taken as that of the
n accordance measurements (estimated from the replications of the DR values measured at the edges of
;y. the whole-batch-pressed samples) multiplied by [(m + n)/mn)°- 5 where m and n are the
;woof which
cimens (edge
1be assessed. TABLE III
1ization. The COMPARISON BETWEEN EFFECTS AND ERRORa

Diff. between
Effect averages p

N330 vs. N326 (A) 1.6531 27.033 <0.001

Trial 1 vs. Trial 2 (B) 0.0781 1.278
Unvulcanized vs. Vulcanized (C) -0.2031 -3.322 <0.01
Edge vs. Center (D) -0.0406 -0.886
CB Type/trial (AB) -0.0906 -1.482
CB Type/ Vulcanized vs. Unvulcanized (AC) 0.1156 1.891
CB Type/Center vs. Edge (AD) -0.0469 -0.767
Trial/Vulcanized (BC) -0.1594 -2.606 <0.05
/; Trial/Center vs. Edge (BD)
Vulcanized/Center vs. Edge (CD)
0.0781
-0.1031
1.278
-1.686
ABC -0.0031 -0.051
ABD -0.0406 -0.664
ACD -0.1344 -2.197 <0.05
BCD -0.0094 -0.153
ABCD -0.0031 -0.051

a Standard deviation of measurement= 0.1934.

'986 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 65

numbers of measurements used in the calculations of each of the two mean values whose
difference was considered. The value of t (of the Student t-test) is then the value of the
difference divided by the standard deviation of the difference.
From these data, one can conclude that the reproducibility of the observations is quite
good, the standard deviation of the measurements being less than 0.2 arbitrary units of DR.
The meaning of this can be understood by examining the standard photographs of Figures
4a and 4b. By the application of the Student t-test to the difference between averages, the
effects of carbon-black type, vulcanization, sampling position on the whole-batch-pressed
disc, batch-to-batch variation (trial 1 and trial 2), etc., were analyzed for statistical signif-
icance. These effects and their interactions are analyzed in Table III.
The differences between batch replications (trials 1 vs. trials 2, effect B of Table III) are
not very significant (P < 0.05). On the other hand, it is apparent that the dispersion of carbon
black in compositions prepared from N330 is significantly better than that in the case N326
(P < 0.001).
There is a small but highly significant difference due to the effect (C in Table III) of
vulcanization (P < 0.01). This might be explained as follows: If there is gas (air) trapped in
an undispersed agglomerate, it would be compressed somewhat during vulcanization (under
pressure) and forced to remain at least slightly compressed due to the crosslinking. This
could cause the agglomerates to appear somewhat smaller after vulcanization and thus it
could explain the small difference due to vulcanization. It should be pointed out, however,
that the difference is minor and that, in a practical sense, nearly the same result is obtained
with and without vulcanization. This suggests some justification for the assumption made
by others 6 that the state of dispersion does not appreciably change during vulcanization.
Dependance of dispersion rating on mixing time and carbon-black type selection. -Data
in Table IV give dispersion ratings (DRs) for vulcanized compositions which were mixed for
various lengths of time in the small mixer (70 g batches). The effects of mixing time on
-
>

~
dispersion quality with two types of carbon black are also given in Figures 8 and 9. The
general effect is the improvement of dispersion quality with increases in mixing time. Again,
there appears to be a slight improvement in dispersion quality due to vulcanization. There
is almost no exception to this.
The two different types of carbon black (types N330 and N326) are of similar surface
area (and of similar particle size in their primary aggregates); however, they differ in structure
as measured by the dibutyl phthalate-absorption method, with the N330 having the greater
degree of structure (having more "chain-like" character, the primary aggregates comprising
longer chains of primary particles). It has been known that carbon blacks which exhibit the
greater degree of structure are the more rapidly dispersable (all other factors being similar).
This greater rate of dispersion associated with higher-structure carbon blacks is consistent
with the present results.

CORRELATIONS BETWEEN ULTIMATE TENSILE STRENGTH MEASUREMENTS AND DISPERSION RATINGS

As stated above, it has long been known that poor dispersion of carbon black can give
rise to poor ultimate or failure properties 3 •5 •6 • However, most of the relationships between
dispersion quality and ultimate properties have been of a qualitative nature. Here, we have
attempted to find a quantitative relationship between the dispersion ratings DR and some
measure of ultimate tensile strength (UTS). To that end, the special tensile test specimen
shown in Figure 5 was designed.
The object of the design was to make the test piece as long and as narrow as practical.
The length limitation, as stated above, was determined by the maximum travel of the cross
head of the tensile tester (Monsanto Tensometer 10) in view of the expected maximum
ultimate elongation of the specimens tested in this work. The selection of width of the
specimen (0.30 cm) was based on our experience with specimens which have small cross
sections. If the die becomes too narrow with respect to the thickness of the rubber which it
is to cut, then the specimen cross section might tend toward a not-very-reproducible trap-
 s. ::i 00 §. :::!l- -~~~< ""~~ ~ 0.. =
-o;.:;~oi'6~o ;-~ ~ ::r ::i

~z
~UJ~V~<;;;: ::i "' 0
:::; ::i PJ ~- <"D 0 - ,..-.. - ·
~'P=~e;~
0 5· ~ s. e.
{!,I ("1-

""!i;::<....,g."":::;:J it b ::i:qg. g a' e;· ~ -· ~ ::r ~..... >-3

("1- ~
0: O" ~ ::r '< '"'" (D <
u;· ~. ::r ~ ~ ~ §"
t/l t/l
8,0"ro:::;:JeD~ E,; ~ oo ~. ~ ;:a. n S ~ i:: =' :=: E,l 0 >-3 ~ ~ ~ < 00 i:: 5· < ~
...... ......
0
~::tl~.o·~
(D
i::g'oo ..... Q..o~
oo~·!Doo:>::"'
(') ::::i
oCJQ><O::i"='~
('O (')rt-·:::.: c. ::;· ~ ::s ~· § ~ u;· _;+::rg.
(D
o;::>::SCJQs~ ..........
~ ~ c. '"'" ~
..... 0"'1,_.
n ::S O" ..... nroo::s::i
&;7~ ..... ;:;:00
~

i::
i::
c. ""! s ~ s ::::.' "O l:rj
>
..., ::s ~. ::r s (D 00 ""! ::s!'DO..n- .... ·• sog.o ::s::S~ro ~ 8, ib ...... "O (IQ '-:c.:I 00 u;· (D
(D
00
g::ae::r~::r"'1 "O::S:::;:JO"n
~. s0: "O (IQ q 00 ,,_(D ..... ><I'"'" ::s '"'":a '"'"(!Q,....., .... ...... 00 ... ro ..... o <
(D
~
::r ...... 0 ~. (D ~
;::r: ;· o~ '"'"i::
~ s ~ tt
~O..ro~~
..... 00 ::r .., ::i
~o
;::> ~ ~ (D «CJQ
zgs =
~ ~ ~ :::!. ~ ~ ~
~. ~ e- . . ,
•
1-3...-. Sro ..... ~~ ::r
::r ~ >-3 (D Q.. t:I § ~ 5· ~ ~ >-3 ::s ~
~ 5· ::r ~ O' ~ . Q..
i;::: ..... ......

Q..(D ~ ..... 8'. ~ ;: : · 0

c
('O

~ '-'
Z ....
00
(')

-
O" ~
:::::::
..... (D 00 (IQ ....,..0

~g;:..,.~be.
0

'"'"0
::r
: :;:J
...., ::r 0
r
a0~Eiti"'1~
(D '"'"
~ o n ..... N) 0 .... '"'"!D::i"ro::tin- 00 ~
'9;:;:g;g"sg;~ §~ ~ §~ • '" v~ ""! (D (D
ro.ro ....... ~ ro .n-00'"1 .... ..., ~ ::s (D ';°"Q..rooo. ro (1) (1) C]l

TABLE IV
CORRELATIONS BETWEEN DISPERSION RATINGS AND ULTIMATE TENSILE STRENGTH

Average ultimate tensile strengths and standard deviations, MPa

CB N=3 N=3 N = 9a
Mix dispsn Brit. standard die Long die
Mix Long die
CB time, index
no. type SF min. (DR) Median Mean STD Median Mean STD Median Mean STD
1
2
N330
N330
0
0
2
3
1
1.8
26.97
29.61
25.82
27.76
1.81
2.73
24.84
28.61
25.05
29.50
0.44
2.14
24.70
27.75
24.61
28.61
1.56
1.89
-t:I
r:n
"t1
t'j

-
3 N330 0 4 2.2 29.17 29.11 0.24 28.01 28.41 0.66 ~
28.40 28.65 0.96
4 N330 0 5 4 28.60 28.72 0.22 29.43 29.17 0.85
r:n
29.43 29.12 1.23
5
6
N330
N330
0
0
7
9
5.2
5.8
29.70
29.79
29.56
29.72
0.20 29.92 29.94 0.08 29.20 29.21 0.80 z0
0.55 29.01 27.86 1.81 28.84 28.34 1.43 0
7 N330 0 12 8 28.83 28.88 0.61 29.86 29.60 0.46 '-:c.:I
30.07 30.19 0.72
8 N326 1 2 1 27.02 27.30 0.44 22.95 22.03 3.87 25.69 0
24.07 3.18
9 N236 1 4 2.2 29.58 29.16 0.59 27.13 27.82 1.62 29.33 29.17 1.49
>
~
10 N326 1 6 2 27.97 28.04 0.15 28.28 27.18 1.55 to
28.18 27.65 1.10
11 N326 1 9 3.5 30.67 0
12 N326 1 12 4.7 31.51
30.75
31.92
1.18 31.14 31.19 0.61 30.34 30.49 0.70 z
0.63 30.87 30.12 1.17 30.70 30.52 0.81 to
13 N326 1 15 5 30.94 30.94 0.21 30.14 30.00 0.83 t"'
30.63 29.85 2.24
14 N326 1 25 6 29.47 29.45 0.78 30.28 30.73 0.32 30.28 30.37 0.40
>
0
RSq. = 0.645 0.773 0.209 0.864 :;:.:::
0.781 0.360 0.967 0.902 0.436
% Conf. = 99+ 99.9+ <90 99.9+ 99.9+ 95+ 99.9+ 99.9+ 98+
n= -1.84 -1.12 -0.16 -1.51 -2.06 -0.75 -1.33 -1.95 -1.75
Bo= 29.72 30.01 -1.68 30.46 29.99 -0.05 30.06 29.75 0.85
B1= 0.640 1.176 -0.368 0.179 -0.08 0.477 0.994 0.479 0.189
B2 = -3.057 -4.133 3.111 -6.66 -6.41 2.051 -5.38 -5.65 1.437
0
In two cases, N = 8 and the median was taken as the average of the two central values.
•SF is carbon black selection factor.

(D
00
~
988 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 65

DISPERSION RATING ezoid~

the er
I N-330 die is
8j As
narro1
would
glome:
6 piece
initiat
the te1
such fl
Ult
4
of reg1
(DR)"

2
where
equal 1
0 UNVULCANIZED X VULCANIZED
x Thi
with I
0 I

0 2 4 6 8 10 12 14 16 18 20
MIXING TIME, MINUTES
FIG. 8.-Dispersion rating of N330 carbon black-filled natural rubber as a function of mixing time.

from t
· pullin~
headec
DISPERSION RATING 't long-dl
6.s.-~~~~~~~~~~~~~~~~~~~~~~~~~- (poorly
\N-326 'the Ion

5.5 r
4.5 I i

3.5 I I

2.5 I
~i
1

1.5 I
I 0 UNVULCANIZED x VULCANIZED I I
o.s; I
0 2 4 6 8 10 12 14 16 18 20 22 24
MIXING TIME, MINUTES
FIG. 9.-Dispersion rating of N326 carbon black-filled natural rubber as a function of mixing time.
 VOL. 65 DISPERSION OF CARBON BLACK 989

ezoidal shape rather than the right-angled parallelogram required for readily determining
the cross-sectional area. This is due to the deformation of the rubber under the die as the
die is being forced through it.
As mentioned in the experimental section, the reason for the selection of such a long and
narrow test specimen was to increase the probability that a large carbon black agglomerate
would be at the edge of the specimen. Thus, for a given concentration of undispersed ag-
glomerates, the proportion of such agglomerates to be found near or at the edge of the test
piece would be greater, the longer the test piece. Such agglomerates could act as crack-
initiating flaws during the failure or rupture process while the rubber is stretched during
the tensile test. The narrower the specimen, the greater would become the concentration of
such flaws per unit volume of sample.
Ultimate tensile test results, Y, were correlated with the dispersion ratings DR. Results
of regression analyses for tensile test results vs. dispersion ratings raised to the n-th power
(DR)n are given in Table IV. The general equation was as follows:

(1)
where SF is the carbon-black selection factor equal to 0.00 for type N330 carbon black or
equal to 1.00 for type N326 carbon black.
The use of the function (DR)n, rather than the use of DR per se, was to let the relationship
with DR be either direct or reciprocal and to allow the relationship to be curvilinear. The
18 20 value of n was selected, in each case, by trial and error, such that the value of R squared
(correlation coefficient squared) would be maximized.
The correlations of tensile test results obtained by using the new die were compared
1ixing time.
with those obtained by using the British Standard tensile test die. For each mix, three British
Standard test specimens were pulled and eight or nine long-die specimens were pulled. Results
from the first three of the long-die specimens are compared with the results obtained by
pulling the three British Standard specimens. (Compare the two sets of three columns each,
headed by "N = 3" in Table IV.) As expected, overall the correlations were better with the
long-die than with the British Standard specimens. It is interesting to note that DR correlates
poorly with the standard deviation (STD) of ultimate tensile strength obtained with either
the long-die cut specimen or the shorter British-Standard-die cut specimen, whereas its cor-
relation with the mean or median of ultimate tensile strength is reasonably good for specimens
prepared by using either die.
In an effort to improve the correlation between the function of DR and ultimate tensile
strength, more long-die specimens were pulled. (These were the specimens which gave the
best correlation with DR.) The data collected as a result of pulling eight or nine long-die
specimens are given in Table IV under the three columns headed by "N = 9*". Here a re-
markable correlation was found between (DR)-1. 33 and the median ultimate tensile strength.
A regression analysis based on the mode value of ultimate tensile strength was also done.
In this case, the values of the mode value were determined by fitting data to a doubly ex-
ponential frequency distribution according to the method reported by May 38 • The correlation
was not quit as good as it was in the case of the median value, which of course is easier to
determine. Also note that the correlation with the arithmetic mean of the long-die ultimate
tensile strength is not as good as that obtained by using the median value. Nevertheless, the
correlations with all three types of averages obtained by using the long-die specimens were
quite good.
The best equation which we have found for relating ultimate tensile strength to dispersion
rating then is:

!2 24 median long-die UTS = 30.06 + 0.994(SF) - 5.38(DR)- 133 • (2)

By using this equation, the standard error for estimating UTS as a function of DR is only
icing time.
0.36 Mpa. The results of this regression analysis are illustrated by Figure 10.
99p RUBBER CHEMISTRY AND TECHNOLOGY VOL. 65

EXPERIMENTAL UTS, MPa UTS,

I: UTS • 30.06 - 5.38(DR) .
-133
+ 0.935(SF)
32--

31
r 2
IR = 96.7% 30 ~
I
29 ~ I
2a l

] 2e r-

24~)
1

I * N-330 0 N-326 I:.:

I
23---~-----'--~----'-~~-'-~~--'-~~~~~~~----~~--'-~~-' 22 L___
23 24 25 26 27 28 29 30 31 32 0
CALCULATED UTS, MPa
FIG. 10.-Median (of eight or nine specimens) "long-die" ultimate tensile strength as a function of dispersion rating
FIG. 11.-M·
and carbon black type (SF = selection factor = 1.00 for N326 or = 0.00 for N330).

EFFECTS OF DISPERSION QUALITY ON PERFORMANCE PROPERTIES

Compositions were prepared in a large laboratory mixer, for correlating dispersion quality, ULTll
as measured by values of DR, with performance-related properties of vulcanizates in which 575:-
the carbon black was dispersed to varying degrees. The mixing characteristics were quite 1
I
similar to those obtained for the batches described above which were one quarter the size I
of the batches used here (mixed in the smaller mixer). I
550 ;-
Values of ultimate tensile strength (UTS) and ultimate elongation (UE) are plotted as
/
functions of DR in Figures 11 and 12. In both cases, major effects are observed at lower
values of DR. Once a dispersion rating of about 4 to 5 is achieved, further increases in DR
give little improvement in either UTS or UE. This is the case with both the higher-structure 5251
(N330) and lower-structure (N326) carbon blacks. The results relating to ultimate tensile
strength are somewhat different than those obtained above with the smaller-batch mixes.
However, the qualitative conclusion is similar: poor carbon-black dispersion gives reduced
values of tensile strength. These results are similar to those observed by others, e.g. Hess
SOJ
et al., with respect to other elastomer-carbon black systems 19 .
The effects of dispersion quality on stress at 100% strain, 200% strain, and 300% strain
are given in Figures 13, 14, and 15. At the lower levels of strain (100%), the effect of poor
dispersion is to give apparently stiffer vulcanizates. The relatively high modulus (at 100%
475t
strain) associated with poor dispersion could be due to interference between large undispersed
agglomerates. This effect essentially disappears at the higher strains (200% and 300%).
The Pico abrasion-resistance data are given in Figure 16. Here, no strong effect can be
attributed to the quality of dispersion. Only the effect of carbon-black selection can be ob-
450[J
served with the higher-structure black (N330) giving the better resistance to abrasion. Car- 425--
bon-black dispersion quality, however, could have an important effect on tire-tread wear. 0
This would not be very surprising since the severity and mechanisms for tire-tread abrasion
could well be different than in the case of the Pico abrasion test. FIG. 12.-!
 VOL. 65
DISPERSION OF CARBON BLACK 991
UTS, MPa
32.~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

30 ~
N-326 0

I
I
28 ~

N-330
26 f-
l
24 l/¥
I

!
22'--~~-'--~~-'-~~-'--~~--'-~~--'-~~-'-~~--"-~~-'-~~----'
31 32 0 2 3 4 5 6 7 8 9
DR
of dispersion rating
0). FIG. 11.-Median (of three specimens) "long-die" ultimate tensile strength as function of dispersion rating.

persion quality,
ULTIMATE ELONGATION, %
tizates in which 575,
;tics were quite !
I
1uarter the size I
I
) are plotted as
550 i c
1erved at lower I N-326 0

mcreases in DR . 0
5251
igher-structure
1ltimate tensile *
~r-batch mixes.
1 gives reduced 50J *
thers, e.g. Hess
*
nd 300% strain
~ effect of poor
iulus (at 100%
475~ N-330

·ge undispersed '\ I

and 300%).
g effect can be
tion can be ob-
45l
abrasion. Car- 425
re-tread wear. 0 2 4 6 8 ·10
tread abrasion~ DR
FIG. 12.-Median (of three specimens) "long-die" ultimate elongation as function of dispersion rating.
992 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 65

STRESS AT 100% STRN, MPa

4.2~.~~~~~~~~~~~~~~~~~~~~~~~~

171
4 16.5

3.8 16

3.6 15.5
N-330
15
3.4r 14.5
3.2

3 * 14

~
~·:ir-
2.8

2.6 ~ n
1

2.4 r-
I 12.5
1
2.21_ _...J..__ _ . l __ ___!.._ _ ..____...;....__~_
12 -
0 1 2 3 4 5 6 7 8 9 0
DR
FIG. 13.-Stress at 100% strain as a function of vulcanizate dispersion rating.

STRESS AT 200% STRN, MPa A

9.Si~
1251

9 ~ N-330 ¥ * 120 rI
I
8.51 * * * 115
8

7.5

~ ~
7

" w w
6.5
N-326
6

5.5'--~--l-~~L--~-1.-~~L...-~__L_~--l~~-L-~--l~__J
0 1 2 3 4 5 6 7 8 9 0
DR
FIG. 14.-Stress at 200% strain as a function of vulcanizate dispersion rating.
 VOL. 65 DISPERSION OF CARBON BLACK 993

STRESS AT 300% STRN, MPa

17r--~~~~~~~~~~~~~~~~~~~~~~~~~---,

16.5

16

15.5 *
15 * *
14.5

14

'~·: ~
12.5 r
12'--~~-'--~~-'-~~-'-~~~'--~~~~~-'-~~-'-~~--'~~--'

8 9 0 1 2 3 4 5 6 7 8 9
DR
g. FIG. 15.-Stress at 300% as a function of vulcanizate dispersion rating.

ABRASION RESISTANCE RATING

125~~~~~~~~~~~~~~~~~~~~~~~~~~~~

I *
1201~~~-+~~~~-*~~~~_.;,.*~'~~~~~~~~
** 115
I*
L
N-330
*
110

105
0
N-326

8 9
1:: l
0 1
0

2
0

3
0

4 5 6
0

7 8 9
DR
;ing. FIG. 16.-Abrasion (Pico) resistance rating as a function of dispersion rating.
994 RUBBER CHEMISTRY AND TECHNOLOGY

PERM. SET, % The

2Qr-~~~~~~~~~~~~~~~~~~~~~~~~~

19

18

17

16

15

14

13
0
12 ,....,

11
io
r N-326
I I I
, * ' ' I
0 2 3 4 5 6 7 8 9
DR
FIG. 17.-Permanent set (Goodrich Flexometer) as a function of dispersion rating.

DELTA T,°C
35~~~~~~~~~~~~~~~~~~~~~~~~----,

*
30

25 *

20
!
r
0
15---~__.~~--'-~~-'-~~..__~--L.~~-l-~~....l.-~~J__~__J
* 1
7~
I.;

0 1 2 3 4 5 6 7 8 9
DR
Fm. 18.-Temperature rise (Goodrich Flexometer) as a function of dispersion rating.
 VOL. 65 DISPERSION OF CARBON BLACK 995

The effect of dispersion quality on permanent set and heat build-up measured by the
Goodrich Flexometer is given by Figures 17 and 18. Very poor dispersion of carbon black is
associated with poor permanent set (higher values). However, over most of the range of DR
measured, the effects on Goodrich Flexometer permanent set are quite small. On the other
hand, for both types of carbon black there appears to be an optimum degree of carbon black
corresponding to a DR value of about 3 to 5. The relatively high heat build-up associated
with poor dispersion could be due to intederence between large (about 5 to 150 µm in di-
ameter) undispersed agglomerates. The increased heat build-up associated with very good
dispersion of agglomerates could be the result of stronger interactions between rubber mol-
ecules and carbon-black aggregates or the result of associations between primary aggregates
at a very small scale (of the order of 0.01 to 0.1 µm).
With respect to the measurements of fatigue life, we obtained a multi-regression analysis
of values of the logarithm of fatigue life in kilocycles (Y) against carbon black type (X1
= 0.00 for type N330, or 1.00 for type N-326), logarithm of DR (X2), logarithm of tensile
strain, % (X3), and the second order factors: X.y( 2 , X.y(3, X 1X2, and X.y(3. The resulting

< equation is as follows:

Y = 41.277 - 0.2707X1 - l.422X2 - 35.86X3 - 0.1483X2X 2

:J 9
+ 8.042X3X3 + .3936X1X2 + 0.8884X2X 3.
The correlation coefficient, R squared, for the equation of 0.9689 with 28 degrees of freedom
(3)

for error. All of the coefficients of the equation are significant at least at the 95% confidence
level. From the equation, the curves of Figures 19 and 20 were calculated. From this analysis,
it is apparent that dispersion quality is an extremely important determinate of fatigue life
as measured by the Monsanto Fatigue-to-Failure Tester. This fatigue-resistance test is largely
a cut initiation test rather than a cut-growth test since no initiating cut or notch is made in

FATIGUE LIFE, kc
N-330 CARBON BLACK

O/SPEBSION
100 EMI1fil1

8.0
4.0
2.0
1.0
0.5
* 0.25
10
t
~
I
1 '--~~~~~~~~~~~-'--~~~~~~~~~~~-'-~~~__J

75 100 125
B 9
STRAIN AMPLITUDE, %
Fm. 19.-Fatigue life (Monsanto Fatigue-to-Failure Tester) as a function
of strain amplitude and dispersion rating for N330 carbon black.
'996 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 65

FATIGUE LIFE, kc N-326 CARBON BLACK

1 E. M. Danm
1, • P. C. Ebell 1

100
r
t
DISPERSION
B.liI.J1iJJ
a I. Pokluda 1
• A. I. Medali
Boston,
8.0
aw. M. Hess,
E 4.0
a B. B. Boons1
7
A. N. Gent,
a Ditmar, "A1
2.0 • H. Loewen,
10 H. A. Depe'
11 J. S. Tidmu:
1.0 12 C. H. Leigh·
1a W. B. Wieg1
10 1• F. H. Rllnin:
0.5
1a c. w. Sweit
1a c. w. Sweit
0.25 17 N. A. Stum1
1a P. c. Vegva
10 w. M. Hess,
ao P. C. Vegv111
11 M. von Ard1
nw. A. Ladd
1'--~~~~~~~~~......L~~~~~~~~~__j~~~__J aa F. P. Ford a
, "E. M. Danm
75 100 125 u M. M. Chap
STRAIN AMPLITUDE, % , 18 M. M. Chap
27 R. Fitzgeral
Fm. 20.-Fatigue life (Monsanto Fatigue-to-Failure Tester) as a function 18 w. M. Hess,
of strain amplitude and dispersion rating for N326 carbon black. •w. M. Hess
so R. Kandunc
11 B. M. Muta!
12 A. I. Medali
the specimen. It is not surprising then that poor dispersion gives poor fatigue life, as measured
aaB. B. Boons
by this test, since the rather large agglomerates associated with poor carbon-black dispersion "R. Cembroll
could well act as cut-initiating flaws. 86 G. R. Cotter

CONCLUSIONS
A small-scale (70 g batch size) laboratory mixing procedure for studying the dispersion
of carbon black in rubber has been developed. The method is characterized in that after the
mastication of the pure polymer, a portion of the rubber is removed from the mixer (to make
room for the carbon black). The carbon black is then added and after the carbon black is
taken into the mixer, the rubber which had been removed is added back. There is little or
no unmixed powder at the end of a mixing run.
Meaningful estimates of the degree of dispersion can be easily obtained by using a simple,
improved method for preparing surfaces of carbon-black filled rubber vulcanizates for dark-
field optical microscopic examination. The method can even be adapted to the preparation
of surfaces of unvulcanized stocks and masterbatches.
Dispersion ratings as determined by the present method correlate very well with ultimate
tensile strength values obtained by using a specially designed highly elongated test specimen.
In addition, the dispersion ratings can be correlated with performance-related properties
such as heat build-up measured by the Goodrich flexometer and mechanical fatigue resistance
as measured by the Monsanto Fatigue-to-Failure Test.

ACKNOWLEDGMENT
The assistance given by T. D. Reid and P. C. Smakula are greatly acknowledged by the
authors. Their careful work in carrying out much of the experimental work was very im-
portant.
 VOL. 65 DISPERSION OF CARBON BLACK 997

LACK REFERENCES
1 E. M. Dannenberg, Eur. Rubber J. 167(1), 25 (1985).
2 P. c. Ebell and D. A. Hemsley, RUBBER CHEM. TECHNOL. 54, 698 (1981).
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Boston, Mass., about 1970 .
• w. M. Hess, RUBBER CHEM. TECHNOL. 64, 386 (1991).
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7 A. N. Gent, in "Fracture," H. Liebowitz, Ed., Academic Press, New York, 1972.

8 Ditmar, "Analyses des Kautschuks," Hartben, Leipzig and Vienna, 1909.

• H. Loewen, Gummi-Ztg. 27, 1301 (1913).

10 H. A. Depew and I. R. Ruby, Ind. Eng. Chem. 12, 1156 (1920).

11 J. S. Tidmus and D. Parkinson, Trans. Inst. Rubber Ind. 13, 152 (1937).

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14 F. H. ROninger, Jr., Ind. Eng. Chem., Anal. Ed. 5, 251 (1933).

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17 N. A. Stumpe, Jr. and H. G. Railsback, Rubber World 151(3), 41 (1964).

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20 P. C. Vegvari, W. M. Hess, and V. E. Chirico (to Columbian Chemicals Company) U.S. 4,220,042, (September 2, 1980).
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22 W. A. Ladd, Ind. Eng. Chem. 16, 642, (1944).

23 F. P. Ford and A. M. Gessler, RUBBER CHEM. TECHNOL. 25, 858 (1952).

24 E. M. Dannenberg, Ind. Eng. Chem. 44, 813 (1952).

2 • M. M. Chappuis, M. H. Polley, and R. A. Schulz, RUBBER CHEM. TECHNOL. 28, 253 (1955).

26 M. M. Chappuis and L. S. Robblee, Rubber World 136, 391 (1957).

27 R. Fitzgerald, K. Keiland, and K. F. J. Heinrich, Science 159, 528 (1968).

28 w. M. Hess, G. c. McDonald, and E. Urban, RUBBER CHEM. TECHNOL. 46, 204 (1973).

29 w. M. Hess and G. c. McDonald, RUBBER CHEM. TECHNOL. 56, 892 (1983).

• 0 R. Kandunce, RUBBER CHEM. TECHNOL. 47, 469 (1974).

31 B. M. Mutagahywa and D. A. Hemsley, Plast. Rubber Process. Appl. 5, 219 (1985).

32 A. I. Medalia, RUBBER CHEM. TECHNOL. 59, 432 (1986).

:e, as measured 33 B. B. Boonstra, RUBBER CHEM. TECHNOL. 50, 194 (1977).

lack dispersion •• R. Cembrola, RUBBER CHEM. TECHNOL. 56, 233 (1983) .

•• G. R. Cotten, RUBBER CHEM. TECHNOL. 57, 118 (1984).
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38 w. May, Trans. Inst. Rubber Ind. 40, Tl09-22 (1964); RUBBER CHEM. TECHNOL. 37, 1134, (1964).

the dispersion
l that after the
mixer (to make
:arbon black is
here is little or

using a simple,
izates for dark-
he preparation

ll with ultimate
l test specimen.
ated properties
tigue resistance

wledged by the
k was very im-