Technical Paper


DuPont Advanced Fibers Systems

KEVLAR Engineered Elastomer

for Reinforcement of Rubber Roll Covers

by

C. W. Tsimpris
DuPont Advanced Fibers Systems
Richmond, Virginia

Based on a presentation given at the

Rubber Roller Group Meeting
Las Vegas, Nevada
May 6, 2003

H-89940 5/03

2003 E.I. du Pont de Nemours and Company. All rights reserved.

The DuPont oval logo, DuPont and KEVLAR are trademarks or registered trademarks of E. I. du Pont de Nemours and Company.

DuPont Advanced Fibers Systems ■ 5401 Jefferson Davis Highway ■ Richmond, VA 23234 ■ (800) 453-8527
 KEVLAR Engineered Elastomer
for Reinforcement of Rubber Roll Covers

ABSTRACT

KEVLAR engineered elastomer, a composite of KEVLAR pulp and elastomer,

enables incorporating high-surface-area para-aramid pulp reinforcement to rubber
compounds. It affords the rubber chemist opportunities to go beyond present limits in
designing rubber compounds. It not only provides a vehicle for aramid pulp
reinforcement of rubber compounds; but also, by its proprietary manufacturing process,
maximizes the effectiveness of aramid pulp reinforcement.

Engineered elastomer builds tensile and compressive modulus at low loadings allowing
compounds to be re-engineered to enhance properties. It is possible to obtain very high
modular anisotropy by extruding or milling a compound into a thin sheet. Tear
resistance can be increased, and tear propagation can be reduced. Compounds
reinforced with engineered elastomer have excellent dynamic properties. It enables
building modulus without significantly increasing hysteresis. It is also highly effective
as a processing aid by increasing compound green strength.

Rubber roll cover compounds reinforced with engineered elastomer have been
developed and are in routine use in several industries. Rolls covered with these
compounds have demonstrated reduced abrasion, better cut resistance, and lower cut
growth resistance – and thus a longer life in use.

INTRODUCTION

DuPont KEVLAR brand fiber was introduced in the 1970’s. KEVLAR, the world’s
first para-aramid fiber, is known for its high strength to weight ratio, high modulus, and
excellent chemical and thermal stability. Initially, it was offered in continuous filament
form, and soon found applications in tires, mechanical rubber goods, bullet resistant
vests, and composites. In the 1980’s, short forms of the fiber - staple, floc, and pulp -
were introduced and quickly found acceptance in cut-resistant protective apparel,
gaskets, and friction materials. Photographs of these three product forms are shown
in Figure 1.

DuPont and KEVLAR are trademarks and registered trademarks of E. I. du Pont de Nemours and Company
Once short forms of KEVLAR and Akzo’s (now Teijin Twaron’s) para-aramid
TWARON were introduced, they were evaluated for rubber reinforcement. Using
short fibers (such as cellulosics, cotton linters, cut scrap denim, polyester, and nylon) to
reinforce rubber is common in the rubber industry. They improve green strength,
provide dimensional stability prior to cure, and improve mechanical properties of the
vulcanizate. Compounders found that they could incorporate para-aramid floc (we
define floc as short uncrimped fiber less than 6 mm long) into rubber using an
internal mixer or a roll mill, often with difficulty. An electron photomicrograph
showing floc in a rubber compound may be found in Figure 2. Incorporating the
high-surface-area pulp product (Figure 3) proved to be exceedingly difficult. Para-
aramid pulp is a low bulk density, static-prone material that is hard to handle in a
rubber plant. A few people were able to adequately disperse pulp into a rubber
compound. Their work did demonstrate the superior reinforcement potential of
aramid pulp if the dispersion limitation were overcome. Compounds reinforced with
pulp had 3-5x higher modulus at a given loading than those reinforced with floc.
Pulp reinforced compounds also had lower heat build up in dynamic applications,
and they had had better processing characteristics. An electron photomicrograph
showing pulp in a rubber compound may be found in Figure 4.

The rubber industry frequently utilizes dispersion or masterbatch technology to

incorporate materials that are difficult to mix into a rubber compound. This was
quickly identified as the preferred method for incorporating aramid pulp into a
rubber compound.

DuPont initiated studies to define a method to disperse para-aramid pulp into

rubber, and this effort led to development of a unique new technology platform for
dispersing pulp into an elastomer matrix. Products produced via this technology
showed superior dispersion of aramid pulp in rubber compounds. Two samples of
rubber compound having identical compositions were analyzed using an ultrasonic
scanning technique that measures relative porosity; the two scans are shown in
Figure 5. In the sample on the left, the pulp was introduced using engineered
elastomer; in the sample on the right, the pulp was added directly into the rubber.
Both compounds were mixed using a laboratory scale internal mixer. A uniform
color indicates a homogenous mixture. The sample made by compounding pulp
directly into the rubber shows significant color differences indicating relatively poor
fiber dispersion; the sample prepared using engineered elastomer is nearly a
uniform color, demonstrating its excellent dispersion.

Product made via this new technology enabled dispersion of pulp into rubber so
well that it was given a new name, ‘KEVLAR engineered elastomer.’ Initial
evaluation in the rubber industry confirmed that engineered elastomer was far
easier to process than dry para-aramid pulp, and confirmed the improved
dispersability of pulp made possible by using this offering. Initial adoptions for
engineered elastomer were in power transmission belts. This industry had
experience with short-fibers, a common ingredient in belt formulations.

TWARON is a registered trademark of Teijin Twaron B. V.

 REINFORCMENT EFFICIENCY

One of the first rubber chemists who evaluated engineered elastomer found it highly
effective in rubber reinforcement. This person described the offering as having…
“an intimacy between the rubber and particle never before
reached via conventional compounding.”

We also learned that several other customers who had been able to achieve good
dispersion of dry para-aramid pulp in rubber found better reinforcement when using
engineered elastomer to introduce pulp into their compound. They obtained up to 20%
higher modulus at the same fiber content when using engineered elastomer rather than
using raw pulp. Internal DuPont data illustrating the improved reinforcement efficiency
is shown in Figure 6. The NR/SBR tire tread compound reinforced with engineered
elastomer had about an 8% higher modulus than an identical compound reinforced
with dry pulp.

We proposed a hypothesis to explain the basis for this improved reinforcement; the
hypothesis is based on:

• Superior dispersion of the fiber,

• Openness of the fiber, and
• The microstructure of para-aramid fiber.

The importance of good dispersion of fillers in a rubber compound is well known in the
rubber industry. Dispersing fibers into a rubber compound can be more challenging
than using traditional fillers. Fibers can form tangles (called neps in the fiber industry)
that are not likely to be removed in rubber mixing. It is also important that the
concentrate be well dispersed (mixed) into the final rubber compound. Both fiber neps
and undispersed concentrate can form defect sites that can lead to failure of the rubber
compound. An example of both tangles and undispersed concentrate in a compound
is shown in Figure 7. Eliminating defects like those shown in Figure 7 requires that the
technology used to prepare the concentrate treat the pulp in a manner to avoid forming
tangles, and that the rubber mixing technology subject the concentrate to sufficient
shear to blend the concentrate into the compound.

Our quality policy states that “The KEVLAR organization will be recognized as
providing superior value and continual improvement in all the customer services and
products supplied.” We strive for continual improvement in our engineered elastomer
product. All products are tested for dispersion of pulp into the concentrate. We have
reduced the number of apparent ‘defects’ in our product by over 30%. We have
changed the physical form of the offering to a more ‘user friendly’ form that more easily
incorporates into a rubber compound. We continually look for improvements in mixing
procedures to make the mixing process easier and suggest these improvements to our
customers.
Openness is also essential to maximize the reinforcement potential of aramid pulp.
Note the number of fine fibrils present in the electron micrograph of the pulp shown in
Figure 3. Having these fibrils ‘open’ and extended is essential. Photographs of two
compound samples illustrating openness of pulp are shown in Figure 8. The photo on
the right is of a compound reinforced with KEVLAR engineered elastomer. Note the
number of extended fibrils present in the photograph. An identical compound
formulation, mixed by the same procedure, is shown on the left. The aramid pulp was
incorporated using a concentrate prepared by a technology different from that used to
produce engineered elastomer. Note that the pulp is not as extended and, in some
cases, even appears somewhat compacted.

Openness is essential to achieve interaction between the fiber and rubber. The
polymer base for para-aramid is poly(p-phenylene terephthalamide); a rigid rod
molecule. When spun into fiber, the polymer becomes highly oriented and highly
crystalline. The high orientation allows extensive hydrogen bonding between the
carbonyl and ‘N-H’ functionality in the amide groups of adjacent polymer chains (Figure
9.) KEVLAR fiber is spun from highly concentrated sulphuric acid. Free SO3- in the
solvent sulphonates some of the aromatic rings, and studies within DuPont suggest
that the resulting sulphonic acid groups tend to be accessible at the fibril surface. Thus,
the pulp fibril surface contains polar groups (amide and sulphonic acid on the polymer
backbone as well as amine and carboxylic acid end groups) that can associate with a
group on an elastomer.

We believe that the well-dispersed, well-opened pulp fiber present in KEVLAR

engineered elastomer can associate with the elastomer matix. Evidence for this
association of the elastomer with charged groups on the fibril surface is provided by
gravimetric determination of fiber content of engineered elastomer. When engineered
elastomer grades in neoprene that contain 23% fiber on a weight basis are analyzed by
gravimetric analysis, they average about 26% fiber. Gravimetric analysis of ‘apparent’
fiber content of engineered elastomer in the more polar NBR matrix averages 29.1%
fiber, although the nominal fiber concentration is 23 weight percent. Non-fiber
containing controls, subjected to our process, show no fiber present.

We propose that the gravimetric analyses provide the evidence for ‘bound rubber’ in
engineered elastomer, similar to bound rubber in carbon black. Bound rubber theories
for carbon black assume that segments of elastomer molecules adhere to ‘active sites’
or ‘reactive sites’ on the filler particles. Leblanc describes this theory in a recent
publication (1). A similar mechanism could certainly be operative in engineered
elastomer.

(1) J. L. Leblanc, J. Applied Polymer Science, 66, 2257 (1997).

The key requirement for our hypothesis is high accessibility of the surface of the pulp to
the elastomer. The patented process used to prepare engineered elastomer presents
the pulp to the elastomer in a way that the fiber is fully open to allow the elastomer to
completely wet the fibrils. The engineered elastomer process maximizes the wetting of
the pulp allowing it to reinforce with maximum efficiency. If pulp is mixed directly in an
internal mixer or roll mill, or if a ‘masterbatch’ of pulp in rubber is made by other
technologies, the pulp can become compacted to some degree, and its reinforcing
potential can not be fully realized. The process by which engineered elastomer is
manufactured creates the intimacy between the rubber and particle. Engineered
elastomer is more than a simple masterbatch or dispersion of pulp in elastomer.

REQUIREMENTS IN ROLL COVERS

One ‘product need’ for a roll cover is that it has long life in service. Service life can
be affected by a number of factors. Certainly, the elastomer matrix is critical; the
elastomer must be stable to the chemical environment and temperature in which
the roll will operate. Other important considerations are the physical properties of
the compound; its hardness, abrasion resistance, tear resistance, compression set,
and dynamic properties.

There are many references that summarize the chemical and thermal resistance of
different elastomer matrixes, included the Rubber Roller Group Handbook, a
benefit of being a member of the Rubber Roller Group. KEVLAR pulp is a
remarkably chemically stable material. It is stable in most organic solvents, salt
solutions, petroleum products, and many dilute acids and bases over a broad
temperature range. Its limitations are primarily strong aqueous acids, bases and
bleach over long periods of time and at elevated temperatures.

Once the elastomer matrix for a roll cover is selected, the goal is often to maximize the
abrasion and tear resistance of the rubber compound. The dynamics of a roll cover are
complex; a schematic is shown in the Roller Group Handbook. A good discussion of a
possible mechanism for abrasion of a rubber covered roll is described in an article
published by Metlikovic and Meineke(2). Abrasion results from pressure on the working
roll, which causes a stress on the rubber covering. This stress leads to a strain, or
deformation of the rubber. The strain causes a bulge in the rubber as it approaches the
pressure point (roll nip.) The shape of the roll cover changes from the dotted line to the
solid line as shown in Figure 10.

(2) P. Metlikovic and E. Meineke, “Stesses, Slip and Abrasion of Rubber Covered Conveyor Rollers, A
Review”, Paper 66, ACS Rubber Division Meeting, Louisville, 1996.
The rubber moves rapidly in the entry bulge as the turning roll approaches the point of
maximum stress. The rubber is subjected to a tangential shear stress and a normal
friction stress. Since the shear stress is greater than the friction stress between points A
and B, the rubber slips in this region. This slipping under stress can lead to abrasion of
the roll cover. A similar situation exists in the exit bulge and slipping occurs between
points C and D. The theory presented in Melokovic and Meineke’s paper predicts that
abrasion is inversely proportional to compound modulus; abrasion resistance can be
improved by increasing compound modulus.

EFFECT OF ENGINEERED ELASTOMER

ON COMPOUND PROPERTIES

KEVLAR engineered elastomer builds compound modulus very efficiently. The effect
of aramid pulp on modulus in a SBR/BR treadstock is shown in Figure 11. Modulus
increases dramatically at low fiber loading.

Para-aramid pulp has a high L/D aspect ratio. This geometry makes possible an
orientation of the particle when sheared in processing. Calendering or extruding
compounds reinforced with aramid pulp leads to modular anisotropy – a difference in
modulus between the machine direction (MD) and cross machine direction (XMD.)
This modular anisotropy is illustrated in the data shown in Figure 11. MD modulus is
about 5X that of XMD modulus in 2-mm test pieces of this NR/SBR tire tread
compound. Samples calendered or extruded to thinner sheets will display even higher
anisotropy. Some users of engineered elastomer routinely achieve MD/XMD ratios
greater than 10.

Using engineered elastomer to reinforce a roll cover compound can help reduce wear due
to slipping and abrasion. By designing the roll so fibers are aligned in the circumferential
direction (a strip builder for rolls will achieve this orientation), the modulus or stiffness of
the compound can be increased in this direction. The strain at a given stress will be
reduced, so the entrance and exit bulge in a running roll will be reduced. However
because of the modular anisotropy possible with aramid pulp reinforcement, radial and
axial moduli are increased to a lesser extent.

The ability of engineered elastomer to efficiently build compound modulus was mentioned
previously. As seen in Figure 12, aramid pulp builds modulus about 3 to 5 times more
efficiently that short fibers or flocs that are often used in neoprene power transmission belt
compounds. Figure 13 illustrates the effect of adding both carbon black and pulp to a NR
tire compound. The lowest curve is a gum rubber compound. The next three stress-
strain curves show the increase in modulus by adding 30, 45 and 60 phr N330 carbon
black. The upper two curves show the dramatic increase in modulus achieved by adding
1 and 3 phr aramid pulp to the compound. Aramid pulp addition of only 1 phr gives a
greater increase in modulus than 15 parts of N330.
Increasing compound modulus using traditional stiffening agents typically results in an
increase in compound hardness. For a roll cover, an increase in hardness may mean a
sacrifice in roll grip since a harder roll may have less desirable frictional properties.
Engineering the rubber compound by balancing the relative content of aramid pulp and
other reinforcing agents allows for increased modulus without an increase in hardness.
This is illustrated in a NBR roll compound formulation in Figure 14. Compounds were
prepared at different loadings of silica and aramid pulp. The control (no fiber compound)
has a Shore ‘A’ durometer hardness of 81. A compound of 80 durometer was prepared
with >6X higher modulus (13.1 vs 2.1 MPa) by addition of 9 phr aramid pulp while
decreasing silica from 45 to 15 phr.

Additional data from this compound study are shown in Figure 15. Incorporating
engineered elastomer into the rubber compound enabled an improvement in both tear
and abrasion – two key properties for improved performance in a rubber covered roll.
Aramid pulp enables desirable improvements in modulus, tear and abrasion resistance
without affecting hardness or affecting processability. Mooney viscosity of these NBR roll
cover compounds is shown in Figure 16. The modulus increase in the neoprene power
transmission belt compounds (Figure 12) was accompanied by a lower increase in
Mooney viscosity than when using flocs.

Compounds reinforced with engineered elastomer display modular anisotropy, a great

increase in modulus in the machine direction, and a far smaller increase in modulus in the
cross-machine direction. In contrast, tear resistance increases in both the machine (MD)
and cross-machine (XMD) direction. Data from the SBR/BR heavy duty treadstock study
are shown in Figure 17 (trouser tear) and Figure 18 (Die C Tear.) We attribute the
isotropic increase in tear resistance in compounds reinforced with engineered elastomer
to the three dimensional nature of aramid pulp, and to the openness of the pulp which
results from our manufacturing process.

Compounds reinforced with engineered elastomer behave quite differently than their no-
fiber controls in tear testing. Control compounds will stretch in the tensile test machine,
and then suddenly fail. A compound reinforced with engineered elastomer will stretch as
it is pulled in the tensile tester; one or more ‘notches’ will form on one side as stretching
continues. Ultimately, the compound reinforced with engineered elastomer will fail – at a
higher tear strength than the no-fiber control. Photographs of a tear test are shown in
Figure 19. The photo on the left is of the control compound; this EPDM based roofing
compound failed at 183 lbs/inch. The photo on the right is of the same compound
reinforced with engineered elastomer. Note the notch that has developed. This
compound had a tear strength of 230 lbs/inch, a 26% improvement over the no-fiber
control.

In general, it is important to reformulate a compound to make best use of engineered

elastomer reinforcement. It is unlikely that one can achieve property goals by simply
dropping aramid pulp into an existing formulation.
Roll covers are a dynamic application. The rubber compound will see cyclic stress-
strain behavior in the end-use. We have conducted an extensive study to
determine the behavior of a compound reinforced with engineered elastomer in
cyclic, dynamic conditions.

The cyclic stress-strain behavior of para-aramid pulp reinforced NR compounds

was observed over 10 cycles up to 2.5, 10, and 50% strain. In these tests, the first
cycle was at the given strain, and subsequent cycles at the (constant) force
required to achieve this strain in the first cycle. Some of the test details are
described in Figure 20. Typical curves from the test at 10% ultimate strain are
shown in Figure 21; the curves for the first and tenth cycle are shown.

The energy loss fraction (fraction of energy dissipated in each cycle as shown in
Figure 22) was calculated from the stress-strain curves for each cycle (Figure 23.)
The energy loss fraction was:

• Nearly constant after the first cycle;

• Nearly the same in the machine and cross-machine direction, and
• Nearly independent of the fiber concentration in the compound (Figure 24.)

The stress-strain behavior of engineered elastomer reinforced compounds after

cycling was also measured. These tests were conducted at 10, 30, 50 and 100%
strain, and after 2, 10 and 100 cycles. Measurements were made in both the
machine and cross-machine direction (with and against fiber orientation.) A
description of the test is shown in Figure 25. The stress-strain curves in the
machine direction for the reference (no fiber compound) after 2, 10 and 100 cycles
at 10% strain and for the compound containing 1 phr para-aramid pulp are shown
in Figures 26 and 27. The effect of cycling on stress-strain behavior is nearly
identical for both compounds. Similar nearly identical results were obtained with
samples cycled to other strains, and those measured in the cross-machine
direction.

Short-term dynamic properties in compression were measured using plied-up

cylinders (disks.) The specimens were precompressed to 10%, and were
measured from 0.1% to 5% dynamic strain at 1, 10 and 100 Hz, and at 20° and
100°C.

Curves for compound containing 1 phr aramid are shown in Figure 28 (20° C) and
Figure 29 (100°C). Stiffness at 1 and 3 phr aramid content at 1% dynamic strain is
shown in Figure 30. Stiffness, as expected, increases with increasing fiber
content. Loss angle was almost totally independent of fiber content as shown in
Figure 31.

Short-term dynamic properties in tension were measured using molded strips

prestressed to 5%. Samples were measured at 0.1% to 5% dynamic strain at 1, 10
and 100 Hz, and at 20° and 100°C.
Results were quite similar to those of the short-term dynamic properties in
compression. Curves at 20° and 100°C are shown in Figure 32 and Figure 33.
Stiffness increased with increasing fiber content (Figure 34) while loss angle was
relatively independent of fiber content (Figure 35.)

Both dynamic tests, compression and tension, showed that loss angle was nearly
independent of fiber content. This is in contrast to carbon black reinforcement
where loss angle is quite dependent upon concentration (Figure 36.)

In general, engineered elastomer enables developing high modulus compounds

with reduced potential for heat generation. High modulus power transmission belt
compounds in neoprene were developed with lower tan delta than comparable
compounds reinforced with flocs (Figure 37.) The dynamic modulus of a NR/SBR
treadstock was increased by use of engineered elastomer with no increase in tan
delta over a broad frequency range (Figure 38.)

The stress-strain curves of compounds reinforced with para-aramid pulp are nearly
linear with ‘high modulus’ at low strain, and at again with ‘lower modulus’ at high
strain. Tensile modulus in the direction of fiber orientation (machine direction - MD)
is higher than that perpendicular to the direction of orientation (cross-machine
direction – XMD.) The MD/XMD modulus difference (anisotropy) of the
compounds peaks near 50% strain. Figure 39, shows the relationship between
modular anisotropy, strain and fiber content where anisotropy is calculated from the
absolute stress values at a given strain. Anisotropy peaks at about 60% strain for
the compound reinforced with 1 phr of para-aramid pulp, and at about 50% strain
for the compound with 3 phr reinforcement. Figure 40 shows an identical plot
where modular anisotropy is calculated by the tangential stiffness at a given strain.
Anisotropy peaks at about 40% for the compound with 1 phr of pulp, and at about
30% for the compound containing 3 phr pulp. The transition or inflection in the
stress-strain curve always occurs around 50% strain. Acoustic emission tests were
conducted on a number of compounds, both with and without engineered
elastomer reinforcement. Specimens were pulled at a constant rate of 2 inches per
minute, and the acoustic output monitored throughout. Key observations made
during the testing included:

• Each material (non-pulp-reinforced and pulp-reinforced) showed detectable

acoustic activity.
• The amount of acoustic activity, as measured by the total number of events,
was roughly proportional to the amount of pulp present (Figure 41).
• The amplitude (intensity) of the acoustic events was similar; that is, the fiber
compounds reinforced with pulp did not produce louder events, just more of
them.
The peak acoustic activity was determined by plotting the data as ‘hits’ per strain
interval (Figures 42 and 43.) We found that peak acoustic activity occurs in the
range 40-60% strain; this corresponds to the region where the stress-strain curve
changes slope. The onset and peak of acoustic activity for the three compounds is
summarized below:

Pulp concentration (phr) 0 1 3

Onset of acoustic activity

% Strain 14-38 26-36 24-37
Stress (lbs) <10 16-18 26-30

Peak of acoustic activity

% Strain 51-85 60 47-54
Stress (lbs) 8-15 22-23 38-40

We hypothesize that reinforcement of elastomers by para-aramid pulp involves

association between charged groups on the fibril surfaces and those in the
elastomer, a mechanism similar to bound rubber theories for carbon black. It is
our belief that acoustic emission testing is recording the disruption of the
association between the charged groups on fibrils and elastomers. We therefore
recommend that engineered elastomer be considered primarily in applications
where strain does not exceed 40 to 50%.

ROLL COVER PERFORMANCE

Engineered elastomer is used in a number of commercial roll cover applications.

Actual end-use performance data and case histories are, of course, proprietary to
each customer and can not be reported in this paper. However, in summary, the
following can be stated regarding performance of roll covers reinforced with
KEVLAR engineered elastomer:

• Roll life improvement ranged from 2x to 10x.

• Tear resistance was improved.
• Tear growth potential was reduced.

Engineered elastomer is available in a number of elastomer matrixes. A list is

included in Figure 44.
 CONCLUSIONS

• Engineered elastomer can be used to significantly reinforce rubber compounds

for roll cover applications.
• The reinforcement efficiency is significantly greater than that of other commonly
used reinforcing materials such as carbon black and silica.
• A high level of modular anisotropy can be introduced to a compound by
conventional processing techniques.
• Hysteretic properties are nearly unaffected by the concentration of engineered
elastomer pulp used in the compound.
• Stress-strain and acoustic emission data suggest that association between
elastomer and fiber exists up to 40-50% strain.
• Tear resistance can be improved by incorporation of engineered elastomer into
a compound.
• Tear growth resistance can be improved by incorporation of engineered
elastomer in a roll cover compound.
• KEVLAR engineered elastomer reinforcement should be considered for
demanding roll cover applications.

Product safety information is available upon request.

This information corresponds to our current knowledge on the subject. It is offered solely to provide
possible suggestions for your own experimentations. It is not intended, however, to substitute for any
testing you may need to conduct to determine for yourself the suitability of our products for your particular
purposes. This information may be subject to revision as new knowledge and experience becomes
available. Since we cannot anticipate all variations in actual end-use conditions, DUPONT MAKES NO
WARRANTIES AND ASSUMES NO LIABILITY IN CONNECTION WITH ANY USE OF THIS
INFORMATION. Nothing in this publication is to be considered as a license to operate under or a
recommendation to infringe any patent right.

H-89940 5/03
United States and South America:

DuPont Advanced Fibers Systems

Customer Inquiry Center
5401 Jefferson Davis Highway
Richmond, VA 23234
Tel: (800) 453-8527
(804) 383-4400
Fax: (800) 787-7086
(804) 383-4132
E-Mail: afscdt@usa.dupont.com

Europe: Canada:

DuPont Engineering Fibres DuPont Canada Inc.

P.O. Box 50 Advanced Fibers Systems
CH-1218 Le Grand-Saconnex P. O. Box 2200
Geneva, Switzerland Streetsville Postal Station
Tel. ++ 41-22-717 51 11 Mississauga, Ontario L5M 2H3
Fax: ++ 41-22-717 60 21 Tel. (905) 821-5193
Fax: (905) 821-5177

Asia: Japan:

DuPont (Thailand) Limited DuPont Toray Company, Inc.

6-7th Floor, M. Thai Tower, All Seasons Place 1-5-6 Nihonbashi-Honcho,
87 Wireless Road Chuo-ku, Tokyo 103
Lumpini, Phatumwan Japan
Bangkok 10330, Thailand Tel. 81-3-3245-5080
Tel: 662-6594060 Fax: 81-3-3242-3183
Fax: 662-6594002

Web Address: www.kevlar.com

 Figure 1
®
Commercial Forms of KEVLAR

Pulp
Filament

Staple
 Figure 2

Aramid Floc in Rubber

Staple on V-belt Staple in V-belt

surface compound
 Figure 3

Pulp Versus Floc Fiber Form

0.1-0.3 m2/g 7-9 m2/g

 Figure 4

Pulp Fiber in Rubber

 Figure 5

Fiber Dispersion and Uniformity with and without

use of KEVLAR® Engineered Elastomer
 Figure 6

Improved Reinforcement from

Engineered Elastomer vs Dry Pulp
MODULUS AT 20% ELONGATION

800

700

600
MODULUS, psi

500

400

300

200

100

0
NR/SBR 2 phr PULP via 2 phr DRY PULP 4 phr PULP via 4 phr DRY PULP
CONTROL EE EE
 Figure 7

Compound with Undispersed Concentrate

Tangled
Fiber
 Figure 8

Compound Samples Illustrating Degree of

Openness
 Figure 9

Chemical Structure of KEVLAR

C=O
C=O
C=O
Na-S-O3

C
O=C
O=C
N-H N-H
N-H

H-N
H-N
H-N
C=O
C=O
C=O
Fiber

S-O3-Na
 Figure 10

Roll Cover Dynamics

 Figure 11
Effect of Engineered Elastomer
On Compound Modulus
MODULUS AT 20% ELONGATION
CROSS MACHINE DIRECTION

MODULUS AT 20% ELONGATION

6
MACHINE DIRECTION
Modulus,
4
MPa
8
0.95 1.20 1.80
1.79
2
6.04
6 0.79 1.63 44

0 30 Parts per
hundred carbon
Modulus, 0.0 15 black
4 2.6
MPa 5.2
1.96 7.8
Parts per hundred
0.93 2.20 3.19 fiber
2
1.55
44
Parts per
0 30
hundred carbon
SBR/BR heavy duty tire tread
0.0
2.6 15 black compound
5.2
7.8
Parts per hundred
fiber
 Figure 12

Reinforcement and Mooney Comparison Between

Engineered Elastomer and Various Flocs

M25 (Mpa) Mooney ML 1+4 at 100 deg C

20 100

18 95

16 90

14 85

Mooney Viscosity....
12 80
M25 (MPa)...

10 75

8 70

6 65

4 60

2 55

0 50
l
ro 3.
0
7.
5 10 r1
0 10 10 10
nt oc le se
Co
Pu
lp
Pu
lp Fl ibe nim ap ulo
n F De St l l
E" E" tto po
ly n lon C e
"E "E Co m tto Ny
6
m Co n
m 6n
6m
Fiber Type and Loading (pphr)
 Figure 13
Comparison between carbon black and
p-aramid pulp reinforcement of NR

Static stress-strain curves

8
60phr black
3phr Kevlar fibre
7 60phr black
Effect of adding 1phr Kevlar fibre
KEVLAR fibers 60phr black
6 0phr Kevlar fibre
Stress (N/mm²)

45phr black

5 30phr black

0phr black
4

2 Effect of adding
N330 Carbon black
1

0
0 20 40 60 80 100 120
Strain (%)
 Figure 14

Effect of Engineered Elastomer on

Modulus and Hardness of a Roll Cover Compound
MODULUS AT 25% ELONGATION

16 15.0
15.1
14 12.3

12 13.1

10
6.4
Modulus, MPa 8

6 2.1 4.1
HARDNESS
4
3.0
2 45
0 30 Parts per hundred
0 15 silica 100
3 96
6
Parts per hundred 9 91
86 92
fiber
90
81

80
Hardness,
80
Shore A
80

70 71

45
60 30 Parts per hundred
0 silica
3 15
6
NBR Roll Cover Parts per hundred 9
fiber
 Figure 15

Effect of Engineered Elastomer on Tear and Abrasion

Resistance of a Roll Cover Compound
TEAR

120
105
93
100 98
77
64 91
80
67
TEAR, kN/M
60 59
(ISO 34 Method)
40
DIN ABRASION
20
45

0 30 Parts per hundred

34
0 15 silica
3 35
6 29
9
Parts per hundred
30 28
fiber 28
24 24
25 26

20 22
Weight loss,
-3
gms x 10 15

10

5
45

0 30 Parts per hundred

0
15
silica
3
NBR Roll Cover Parts per hundred
6
9

fiber
 Figure 16

Effect of Engineered Elastomer on

Mooney Viscosity of a Roll Cover Compound

MOONEY VISCOSITY

100

90
80
70
60
Mooney ML 1+4
o 50
at 100 C
40
30
20
10 45

0 30 Parts per hundred

0 15 silica
3
6
9
Parts per hundred
fiber
NBR Roll Cover
 Figure 17

Effect of Engineered Elastomer and

Carbon Black Loadings on Trouser Tear
TROUSER TEAR
CROSS MACHINE DIRECTION

TROUSER TEAR
MACHINE DIRECTION
100 93

80

Tear Strength,
60
99 ppi 53
100 30 32
50
40

80 70 28 44
20 30 Parts per
65 hundred carbon
Tear Strength, 0.0 15
60 2.6 black
ppi 39 5.2
7.8
54 Parts per hundred
40 fiber

29 44
20 30 Parts per
hundred carbon
0.0 15
2.6 black
5.2
7.8
Parts per hundred
fiber
 Figure 18

Effect of Engineered Elastomer and

Carbon Black Loadings on Die C Tear
'DIE C' TEAR
CROSS MACHINE DIRECTION

400
353
360
306
'DIE C' TEAR 320 303

MACHINE DIRECTION Tear Strength,

280 232
ppi
269
240

200
44
400 179
378 30 Parts per
160
hundred carbon
360 0.0 15
2.6 black
5.2
7.8
320 282 Parts per hundred
Tear Strength, 279 fiber
280 232
ppi
240

200 217 44
177
160 30 Parts per
hundred carbon
0.0 15
2.6 black
5.2
7.8
Parts per hundred
fiber
 Figure 19

Photographs of Die C Tear Test

 Figure 20
50

Cyclic Stress-strain 40

Conditions 30

Force (N )
20

• Pull Speed: 25mm/min

10

• Position: cross-head -10

0 20 40 60 80

displacement calibrated for pull Position (mm)

speed

P osition (mm)
80

• First Cycle at constant Strain 30

• Subsequent Cycles at constant -20

Force 50

• Test pieces: Bongos

Force (N )
30

(100 x 3.2 x 2 mm)

10

-10
 Figure 21

Cyclic stress-strain
Effect of fiber loading on 1st and 10th hysteresis cycles,
cycled up to 10% strain

12 12
1st cycle 10th cycle
10 10

8 8

6 6
Ref, MD
4 F1NR, MD
4 Ref, MD
F3NR, MD F1NR, MD
F3NR, MD
2 2

0 0
0 3 6 9 12 15 0 3 6 9 12 15
Displacement (mm) Displacement (mm)
 Figure 22

Definition of Energy Loss Fraction

Energy Loss Fraction = A1 / (A1+A2) =Hysteresis Energy / Stored Elastic Energy

50

40

30

A1
20

A2
10

0
0

Strain (%)
 Figure 23
Cyclic stress-strain
Effect of number of cycles upon Energy Loss Fraction

F1NR Compound – Cycles up to 10% Strain

30,00

25,00

20,00
[Nmm]

15,00
MD

10,00

XMD
5,00

0,00
0 2 4 6 8 10 12

Cycle Nb.
 Figure 24
Cyclic stress-strain Energy loss fraction vs. fiber loading
Cycled up to 10% strain

60 60
1st cycle
10th cycle MD
50 50 XMD

40 40

30 30
MD
20 XMD 20

10 10

0 0
0 1 2 3 4 0 1 2 3 4
Fibre Loading (phr) Fibre Loading (phr)
 Figure 25
Cycles Were Performed At Constant Force

7 Pull after cycling

6
6
Stress (N/mm²)

5 Original stress-strain
curve
5 Cycles 4

4 3
2
3
1 Stress-strain curve
2 after cycling
0
1 0 20 40 60 80 100

0 Strain (%)
0 50 100 150
Strain (%)
 Figure 26
Ref MD cycled at 10% for 2, 10 and 100 cycles

2 .5

1 .5

0 .5

0
0 10 20 30 40 50
D is p la c e m e n t ( m m )
 Figure 27
F1NR MD cycled at 10% for 2, 10 and 100 cycles

3.5

2.5

1.5

0.5

0
0 5 10 15 20 25 30 35 40 45 50
D ispla ce me nt (mm)
 Figure 28
Short-Term Dynamic Compression
F1NR Compound 20°C Plied Up Discs

600 18

500 15
100Hz 10Hz
Stiffness N/mm

400 12

Loss Angle °
1Hz

300 9
100Hz

200 6
10Hz

100 3
1Hz

0 0
0.1 1 10

Dynamic strain %
 Figure 29
Short-Term Dynamic Compression
F1NR Compound 100°C Plied Up Discs

300 12

10
1Hz
Stiffness N/mm

Loss Angle °
200 8
10Hz
100Hz
100Hz
6
10Hz
100 4
1Hz
2

0 0
0.1 1 10

Dynamic strain %
 Figure 30
Short-Term Dynamic Compression
Stiffness vs. Fiber Loading
Piled Up Discs 20°C and 100°C at 1% Dynamic Strain

220

340
2 0 °C 100°C
200
320

300 180
Stiffness [N/mm]

Stiffness [N/mm]
280
160

260

140
1Hz
240
10Hz
100Hz
120
220

200 100
0 1 2 3 4 0 1 2 3 4

F ib e r L o a d in g [p h r] Fiber Loading [phr]

 Figure 31
Short-Term Dynamic Compression
Loss Angle vs. Fiber Loading
Piled Up Discs 20°C and 100°C at 1% Dynamic Strain

12 12
20°C 100°C

10 10

8 8

Loss Angle °
Loss Angle °

6 6

4 1Hz 4
10Hz 1Hz
100Hz 10Hz
2 2
100Hz

0 0
0 1 2 3 0 1 2 3
Fiber Loading (phr) Fiber Loading (phr)
 Figure 32
Short-Term Dynamic Tension
F1NR Compound 20°C Moulded Strip

100 12
90 100Hz

80 10
Stiffness [ N/mm ]

10Hz

Loss Angle [ ° ]
70 1 Hz 8
60
50 6
40
30 4
20 2
10
0 0
0.1 1 10
Dynamic strain [ % ]
 Figure 33
Short-Term Dynamic Tension
F1NR Compound 100°C Moulded Strip

100 12
90
80 10
Stiffness [ N/mm ]

10 Hz

Loss Angle [ ° ]
70 8
60 100 Hz 1 Hz 100 Hz
50 10 Hz 6
40 1 Hz

30 4
20 2
10
0 0
0.1 1 10
Dynamic strain [ % ]
 Figure 34
Short-Term Dynamic Tension
Stiffness vs. Fiber Loading
Moulded strip at 1% Dynamic Strain

100 100

20 ° C 100 ° C
100 Hz
80 80
MD
Stiffness [N/mm]

Stiffness [N/mm]
10 Hz
1 Hz

60 100 Hz 60
10 Hz XMD
100 Hz
1 Hz 10 Hz MD
1Hz
40 40
100 Hz XMD
10 Hz
1Hz

20 20

0 0
0 1 2 3 4 0 1 2 3 4

Fiber Loading [phr] Fiber Loading [phr]

 Figure 35
Short-Term Dynamic Tension
Loss Angle vs. Fiber Loading (MD only)
Moulded strip at 1% Dynamic Strain

12 12
20 ° C 100 ° C
10 100 Hz 10
1,10 Hz

1 Hz
8

Loss Angle [°]

8
Loss Angle [°]

10 Hz
100 Hz

6 6

4 4

2 2

0 0
0 1 2 3 4 0 1 2 3 4

Fiber Loading [phr] Fiber Loading [phr]

 Figure 36
Comparison between effects of carbon black and
para-aramid fibers upon loss angle

Effect of N330 carbon black upon Effect of fibre loading on Loss Angle
Loss Angle Dynamic compression, Frequency
Dynamic Shear, Frequency 1Hz, 23°C 1Hz, 20°C

15 Reference compound in compression 15

12 0phr 12
15phr
30phr
9 45phr 9
60phr reference
6 6
F1NR
F3NR
3 3

0 0
0.1 1 10 100 0.1 1 10 100
Dynamic strain (%) Compressive strain (%)
Data from MRPRA, Engineering Data Sheets©
 Figure 37
Reinforcement and Tan Delta Comparison Between
Engineered Elastomer and Various Flocs
M25 (Mpa) Tan Delta at 121 C

20 0.2

18 0.18

16 0.16

14 0.14
M25 MD (MPa).…....

Tan Delta…..
12 0.12

10 0.1

8 0.08

6 0.06

4 0.04

2 0.02

0 0
10

10
l

10
0
10
0

5
tro

r1
7.
3.

im

le
on

se
oc

be
lp
lp

ap
en

lo
C

Fl
Pu
Pu

Fi

lu
St
D
n

ly

el
E"
E"

to

on
n
po

C
ot

to
"E

"E

yl
m
C

ot

N
m

n
m
6

6n
6m

Fiber Type and loading (pphr)

 Figure 38
Hardness, Modulus, Tear Balance
as affected by pulp and carbon black loadings
DYNAMIC MODULUS TAN DELTA
4000
0.2300

3500
0.2200

3000
0.2100

2500
0.2000
M O D UL US , p s i

Tan Delta
2000 NR/SBR CONTROL
0.1900 NR/SBR CONTROL
1F722 / 2 phr FIBER
1F722 / 4 phr FIBER 1F722 / 2 phr FIBER
1500 1F722 / 4 phr FIBER
0.1800

1000
0.1700

500
0.1600

0
0.1500
0 20 40 60 80 100 120 140 160
0 20 40 60 80 100 120 140 160
Frequency, Hertz
Frequency, Hertz

NR/SBR Tire Tread Compound

 Figure 39

Stress Ratio Anisotropy vs. Strain

Stress ratio anisotropy is the ratio of MD/XMD absolute
stress values at a given strain
2.5
F3NR

F1NR
1.5

1
Reference

0.5

0
0 20 40 60 80 100 120
Strain (%)
 Figure 40
Modular Anisotropy vs. strain
Modular anisotropy is ratio of MD/XMD tangential
stiffness at a given strain

F3NR
3.5

2.5 F1NR

1.5

1
Reference
0.5

0
0 20 40 60 80 100 120
Strain (%)
 Figure 41

Acoustic Emission Tests

Acoustic Events are proportional to Fiber Loading

3500

3000
Total Acoustic Events

2500

2000

1500

1000

500

0
0 1 2 3 4
Fiber Loading
 Figure 42

Acoustic Emission Tests

Acoustic Activity for F1NR

50
1phr Fiber Loading Total Hits 443
45

40
Acoustic Events per strain interval

Maximum Acoustic Activity 55 to 60 % strain

35

30

25

20

15

10

0
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160

Strain (%)
 Figure 43
Acoustic Emission Tests
Acoustic Activity for F3NR

250

3phr Fiber Loading Total Hits 1675

Acoustic Events per strain interval

200

Maximum Acoustic Activity 50 to 55 % strain

150

100

50

0
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160

Strain (%)
 Figure 44
K E V L A R  b r a n d e n g in e e r e d e la s to m e r
A n e la s t o m e r ic c o m p o s it e o f K E V L A R  b r a n d p u lp a n d e la s t o m e r

P ro d u c t N u m b e r 1F722 1F724 1F770 1K1239

P r o p e r t ie s

M a t r ix e la s t o m e r N a tu ra l SBR NBR ENGAGE

Rubber 1502 M ed ACN 8400
P u lp c o n c e n t r a t io n 23% 23% 23% 6 1 .5 %
S p e c if ic g r a v it y 1 .0 5 1 .0 5 1 .1 0 1 .2 2
P h y s ic a l f o r m nugget nugget nugget g r a n u le

P ro d u c t N u m b e r 1F723 1F1234 1F735 1F1168 1F819

P r o p e r t ie s

M a t r ix e la s t o m e r N e o p re n e N e o p re n e N e o p re n e N e o p re n e N e o p re n e
GW GW GRT GRT W RT
P u lp c o n c e n t r a t io n 23% 2 8 .6 % 23% 2 8 .6 % 23%
S p e c if ic g r a v it y 1 .2 8 1 .2 9 1 .2 8 1 .2 9 1 .2 8
P h y s ic a l f o r m nugget nugget nugget nugget nugget

G e n e r a l R e c o m m e n d a t io n s
K E V L A R  e n g in e e r e d e la s to m e r e n a b le s th e c o m p o u n d e r a n d d e s ig n e r to a c h ie v e p e rfo rm a n c e ,
p r o p e rtie s a n d d e s ig n s n o t p o s s ib le in th e p a s t. C o m p o u n d s h a v e b e e n e n g in e e re d to im p ro v e
w e a r a n d a b ra s io n , a c h ie v e b e tte r fr ic tio n a l p r o p e r tie s , im p r o v e te a r , im p r o v e s h e a r re s is ta n c e ,
r e p la c e r e in fo r c in g fa b ric , r e d u c e p a r t th ic k n e s s , o r lo w e r ro llin g r e s is ta n c e .

K E V L A R  is a r e g is te re d tra d e m a rk o f E . I. d u P o n t d e N e m o u r s a n d C o m p a n y
E N G A G E  is a r e g is te r e d tr a d e m a rk o f D u P o n t D o w E la s to m e r s L .L .C .