ITEC September 1996

"Evaluation of Filler Reinforcements to Improve Cutting and Chipping

Resistance of Tire Treads"

by

Martin L. Engelhardt, Ki Do Kim and Jung Ho Son

Hankook Tire

with

Krishna Baranwal and Robert Samples

Akron Rubber Development Laboratory

Abstract

Heavy duty truck and large off-road tires are often subjected to rough road conditions that
cause chipping and chunking of the tread surface. In these tires, chip/chunk is a source of
wear mechanism. Various technologies have been developed to improve the chip/chunk
resistance of tire treads. Most efforts have concentrated in developing new reinforcement
technologies. A range of carbon blacks, coupled and non-coupled silicas and several short
fibers were compared for chip/chunk resistance, as well as the impact on other physical
properties. Chip/chunk performance correlated with the hysteresis associated with
deforming the filler-filler network. All carbon black reinforced compounds had the highest
hysteresis and were best for chip/chunk resistance. Replacing silica with carbon bLack
lowered the hysteresis and the chip/chunk performance. The addition of silane coupling
to the silica-containing compounds further lowered the hysteresis and the chip/chunk
resistance.
 Introduction

Heavy duty truck and large off-road tires are often subjected to rough road conditions

that cause chipping and chunking of the tread surface. These tires are not only confined to

limited off-highway service or local construction sites. For example, in western Canada

pea gravel is commonly used on paved highways to provide traction, giving the result of

driving on unpaved roads’. Also, recent trends in highway radial medium truck tires to

reduce rolling resistance for improved fuel economy have sometimes resulted in treads

that are more prone to chipping and chunking even when exposed to seemingly little

gravel road service. In these tires, chip/chunk can be an important wear mechanism.

Rough roads or pea gravel on smooth roads cause repetitive, localized high pressure

pounding of the tread surface, resulting in a fatigue fracture2 mechanism that causes small

chips or chunks of tread material to come off the tire. Because of the relatively large

pieces, this wear mechanism is much faster than typical abrasion so tires in this type of

service get only a fraction of the mileage of tires in long-haul usage.

Because of the thick cross section in these tires heat build up or hysteresis of the tread

is important so typically all-natural rubber treads are used in this service, although several

authors have disclosed the invention of modified solution SBR3A. However, the intent of

the polymer modifications have been to allow the usage of reinforcement that is good for

chip/chunk and compensate for the usual increase in hysteresis. Most efforts to improve

the chip/chunk performance of on/off highway truck treads have concentrated on new

reinforcement technologies, including carbon blacks57, silicas83, silica/silane5’°" and

short fibers I 2-I 5

 Carbon blacks are typically characterized by surface area, as measured by either

nitrogen adsorption ASTM D3037 or iodine adsorption ASTM DISlO, and structure,

as measured by either n-Dibutyl Phthalate DBP absorption ASTM D2414 or crushed

DBP absorption ASTM D3493. Carbon blacks that are commonly used in on/off

highway treads have nitrogen absorption surface areas ranging from 100 to 150 m2/g and

DBP structure ranging from 100 to 140 cm3/100 g. N220 and NilO are commercial

examples of carbon blacks that have been used in this application. Reported

improvements in chip/chunk performance have come from somewhat higher surface areas

but there is some contradiction in the recommended direction to take in carbon black

structure67.

Silica can also be characterized by surface area and structure using the same test

methods as used for carbon black. Silica is often used in on/off highway treads because of

its ability to deflect and suppress cut propagation. Silicas used in on/off highway treads

have typical nitrogen surface areas ranging from 140 to 175 cm3/100 g and a fairly narrow

range of structure from 180 to 200 cm3/l00 g. Commercial examples of silicas for truck

treads are Hisil 210 from PPG and VN3 from Degussa. Recent developments in silica

technology have opened a wider range of available surface areas and structures.

Because of the importance of hysteresis for tire durability, some investigators5’°"

have advocated the use of silane coupling agents that are designed to bond silica to

unsaturated elastomers like NR and SBR. A similar idea1 is to use a modified elastomer

that has the silane built into the polymer during manufacture. The purpose of silane

bonding agent is to minimize the polymer-filler dewetting hysteresis mechanism’°’6 and

 thereby reduce heat build up. Another reported advantage of silane bonding is an

improvement in road abrasion resistance because the silica particles theoretically have less

tendency to come out of the polymer matrix when chemically bonded to it.

Short fibers are characterized by both chemical composition and physical form. The

type ofmaterial used to make the short fiber determines the tenacity or stiffness of the

fiber. Nylon fibers have low modulus; aramid fibers are very high in modulus. The

ability of the fiber to reinforce the elastomer matrix depends on the contact area so there is

a tendency to use small diameter, high surface area fibers. The ability ofa fiber to

reinforce can be further enhanced by surface treatment to improve bonding to the

elastomer. And finally, dispersion and orientation of the fiber are sometimes important’3,

depending on application.

Treated cellulose fiber pulp has been reported’2 to improve the chip/chunk

performance of tires operating in mining service. Syndiotactic- 1 ,2-polybutadiene flbrils

improved the chip/chunk resistance of radial medium truck tires’5. In these applications

the short fibers probably had a substantially random orientation.

Because of the wide range of reported technologies to improve chip/chunk

performance we decided to systematically compare the various ideas in a model truck

tread recipe.

Experimntal Design

Alternate reinforcement technologies were evaluated in the recipes shown in Table I.

 Table I

Carbon SilicW Short

Black Silica Silane Fiber SBR

Compound ID’s 1-8 9-12 13-16 17,18 19

1st Stage
NR 100.00 100.00 100.00 100.00 -

SBR - - - - 100.00
Variable C/B Typec 50.00 - - - -

N220 C/B 40.00 38.50 48.00 50.00

Variable Silica TypeC - 10.00 10.00 - -

X505 Degussa - - 3.00 - -

Variable Fiber Typec - -

- 2 -

ZnO 4 - - 4 4
StearicAcid 2 2 2 2 2
AgeriteResinD 1 1 1 1 1
6-ppd - - - - I

2nd Stage
ZnO - 4 4 - -

Final Stage
6-ppd 1 1 1 1 -

Sulfur 1,40 1.40 1.30 1.40 1.40

TBBS 1.00 1.20 1.10 1.00 1.00
MBTS - - - 0.30

Total 160.40 160.60 161.9 a,b - 160.40

.°

Notes: a. 161.14 phr when using 2.74 phr cellulose mastethatch with 74% fiber.
b. I 63.40 phr whcn using 5.00 phr aramid masterhatch with 40% fiber.
c. See table II for types of fillers used.

Eight different carbon black types were tested, all at 50 phr loading Table II. Four

different silica types were tested, all at 10 phr silica replacing 10 phr carbon black Table

II, with and without silane coupling. Two different types of short fibers were tested at 2

phr and an alternate polymer, SBR, was evaluated. Carbon black loading was reduced

when silica or fiber was added. Minor adjustments were made in the accelerators to try

to maintain crosslink density about the same. Zinc oxide was added in the second mix
 ______________

stage when silica was used.

The surface area and structure characterization data for the carbon blacks and silicas

used are listed in Table II, along with the source of supply, and shown graphically in

Figures 1-3.
Table II

Compound Filler N2 Surface Area DBP,

rn2/g Number Identification Suppjier cmiJ0Q&.

Carbon Black
1 N330 Cabot 83 102
2 N220 Cabot 119 114
3 N23l Cabot 117 92
4 CD2005 Columbian 121 175
5 N293 Cabot 130 100
6 N115 Cabot 145 113
7 ExpC/B2 Cabot 150 150
8 ExpCIBI Cabot 171 128

Silica
9 Hisil 315T-G PPG 120 142
10 Hisil 243-LD PPG 148 187
11 Hisil 255T-LD PPG 172 189
HisiI2000PPG 244 B.238
13-16 repeat 9-12 but with X5OS Si-69® silane coupling agent.

Two fibers in pulp form were also evaluated. Sanotweb® DX+ treated cellulose short

fiber pulp was supplied by Flexsys in masterbatch form: 74% treated cellulose pulp, 13%

oil, 9% SBR, 4% carbon black. The surface treatment is intended to improve

compatibility to elastomers. Twaron® aramid pulp, type 1095, was supplied by Akzo in

masterbatch form: 40% pulp, 40% N660 C/B, 20% Vestenamer® rubber compatibilizer.

All of the reinforcements were evaluated in a 100 MR model recipe truck tread recipe.

For comparison purposes, a 100 SBR recipe was also tested using 50 phr N220 carbon

black.
 .. 23°C

Propety Testing Physical

The compounds were mixed in a laboratory BR internal mixer using ASTM D 3182

procedure with three mixing stages. A simple remill was used for the second stage of the

recipes that did not have anything added in the second stage.

Chip/chunk performance was tested on the BFGoodrich Chip/Chunk tester’7 that has

demonstrated reasonable correlation to tire field performance. A round sample disk is

subjected to repeated pounding by an anvil mounted on an eccentric cam. Samples were

cured 50 minutes at 150°C, to simulate a large truck tire cure. Each compound was tested

in duplicate and average results were used for analysis. Both weight loss and diameter

reduction of the disk were measured.

Abrasion resistance was tested on a Lambourn abrader using J1S K6262 procedure and

conditions listed in Table IH.

Table IH
Variable Test Condition
Abrading Surface Speed 50 rn/mm
Load 50 N
Sample/Abrading Surface Slip Amount 25%
Temperature Room Temperature

Dynamic mechanical properties were measured at 60°C with an RPA2000® using the

test procedure outlined in Table IV.

Table IV

Ready Temperature 60°C

Cure 40’ @ 150°C, 0.7% strain, 1.67 Hz
Strain Sweep 1 60°C, 20 Hz, 1-25% strain
Strain Sweep 2 60°C, 20 Hz, 1-25% strain
Strain Sweep 3 60°C, 20 Hz, 1-25% strain
 Procedure

The first strain sweep is used to condition the sample. The data from the 2nd and

subsequent strain sweeps are very similar; the 3rd strain sweep is simply used to confirm

the results of the 2nd sweep. Dynamic properties reported and used for analysis are from

the 3rd strain sweep.

Other physical property tests are listed in Table V.

Table V

Property Tes
Cure Characteristics ASTM D 2084, ODR, 150°C, 1° arc
Stress-Strain ASTM D412, die C, 508 mm/mm
Hardness ASTM D 2240
Heat-Aged Properties ASTM D 573, 3 days @ 70°C
Cut Growth ASTM D 813 precut deMattia
Tear Resistance ASTM D 624, Constrained Path
molded groove

- BFG Chip/Chunk Results

During original development of the BFG chip/chunk test it was noted that volume

ratings or diameter loss correlated better with field performance than weight loss

measurements. In this study, Figure 4 shows there is a very close agreement between

weight loss and diameter loss ?= 0.97, F = 507 for the nineteen compounds, so

reported performance is based only on diameter loss rating with the N220 carbon black

sample set to an index of 100. Table VI lists the results from the BFG chip/chunk test,

ranked best to worst based on diameter loss.

The samples containing only carbon black are ranked highest, followed by silica

containing compounds. Addition of silane coupling agent lowered the silica compounds’

ranking further. Of the carbon blacks studied, Nl 15 performed the best for chip/chunk.
Of the silicas studied, Hisil 2000 performed the best. And of the fibers evaluated, aramid

fibers were better for chip/chunk resistance.

Table VI

Compound Feature - BFG Chip/Chunk RatingRPA tan 3 @ 60°C.10%,

dia. loss, N220 = 100 20Hz; 3rd strain sweep
6 N115 117 .213
7 ExpC’B2 110 .230
4 CD2005 106 .199
S Exp C/B 1 106 .230
3 N231 103 .215
5 N293 103 .196
1 N330 100 .163
2 N220 100 .186
12 SilicaHisil2000 97 .182
16 Silica Hisil 2000/Silane 89 .159
9 Silica Hisil 315T-G 87 .156
18 Twaron 1095 87 .161
10 Silica Hisil 243-LD 85 .155
11 Silica Hisil 255-LD 85 .163
17 Santoweb DX 83 .170
15 Silica Hisil 255-LD/Silane 79 .139
14 Silica Hisil 243-LD/Silane 77 .133
13 Silica Hisil 315T-G/Silane 72 .134
19 S1500 SBR N220 65 .207

As the type of reinforcement was varied within the model natural rubber tread, the

hysteresis also varied. Figure 5 shows that most of the variation in chip/chunk resistance

can be explained by changes in hysteresis as measured by RPA tan 6 at 60°C. As

hysteresis increases the chip/chunk resistance improves.

The correlation between tan 6 and chip/chunk performance depends on the level of

strain used to test the dynamic properties. The correlation coefficient improves

dramatically between 0.5% and 5% strain Figure 6 and reaches a maximum around 10%

strain amplitude. As the material is deformed from 0.5% to 10% the hysteresis is caused
 by the breakdown of the filler-filler network18.

The variation in tan 6 between the different compounds is caused by changes in the

amount of energy lost when the different filler networks are broken down and reformed.

The ‘Payne Effect"9 is used to quantify the filler-filler network breakdown and is defined

as the ratio of high-extension dynamic modulus to low-extension dynamic modulus.

Figure 7 shows how the Payne Effect is calculated from dynamic modulus data.

Dynamic Modulus @ 10% strain G’,o

1 PayneEffect= X 100 = X 100
Dynamic Modulus @ 1% strain

The Payne Effect is largely responsible for the hysteresis in these compounds Figure 8

and, therefore significantly impacts the chip/chunk performance Figure 9. A large filler-

filler interaction increases the hysteresis and improves the chip/chunk resistance.

For a tire, there is a general trade-off between chip/chunk performance and heat build

up. It is desirable to minimize the hysteresis increase when improving chip/chunk

performance. Carbon blacks NI 15 and N330 gave the best compromise between

chip/chunk performance and hysteresis.

- Lambourn Abrasion Results

Each compound was tested on a Lambourn lab abrader to estimate the wear

performance under less severe conditions than chip/chunk. The Lambourn results are

summarized in Table VII along with an Interaction Parameter, I’, similar to that developed

by Ayala2° to understand carbon black filler-filler and filler-polymer interactions.

 gp

M200
2 I’= X 100 X
C’1

Where M200 and M3 are moduli measured at 200 and 300% strain. The Interaction

Parameter attempts to characterize both filler-filler interactions, by the Payne effect, and

Table VII

Compound Feature Lamboum Abrasion Interaction Parameter, I’

N?Q=
4 CD2005 107 95
7 ExpC/B2 105 89
2 N220 100 114
6 N115 98 100
8 ExpC/B1 98 93
3 N231 91 105
S N293 91 100
19 S1500SBRN220 85 123
11 Silica Hisil 255-LD 84 125
I 19330 80 121
12 Silica Hisil 2000 79 128
14 Silica Hisil 243-LD/Silane 77 130
16 Silica Hisil 2000/Silane 77 134
15 Silica Hisil 255-LD/Silane 74 137
9 Silica Hisil 31ST-C 73 128
10 Silica Hisil 243-LD 73 128
13 Silica Hisil 315T-C/Silane 73 137
17 SantowebDX 71 114
Twaron 1095 68 18 111

filler-polymer interactions by a stress ratio at high extension.

Generally, the carbon blacks had the highest ratings for lab abrasion, followed by silica

and silica/silane. The addition of fibers to the model tread recipe resulted in significantly

poorer abrasion rating. The filler interaction parameter, I’, was found to be somewhat

useful in understanding variations in abrasion Figure 10 but could not be used for

compounds containing fibers or SBR. The Lambourn Abrasion results were plotted
 against the chip/chunk results Figure 11. There is a broad correlation between lab

abrasion and lab chip/chunk. Generally as one is improved, so is the other; but the

relationship is weak. Several carbon blacks were found to perform well for both abrasion

and chip/chunk Ni 15 and Experimental C/B 2.

Summary

1. A range of carbon blacks, silicas, both with and without silane coupling, and several
fibers were evaluated for BFC chip/chunk, Lambourn abrasion and static and dynamic
physical properties in a model natural rubber tread compound.

2. The lab chip/chunk performance depended on hysteresis, as measured by tan 3 at 10%

strain 20 Hz, 60°C used, which depends on filler-filler network formation as measured
by the ‘Payne effect’.

3. Of the reinforcements studied, carbon blacks were better for both chip/chunk and
abrasion resistance, compared to silica, silica/silane and short fibers.

4. Several carbon blacks 19115 and 19330 appear to be advantageous at improving the
strong trade-off between good chip/chunk and high hysteresis.

5. There is a weak relationship between chip/chunk and abrasion resistance; but generally
reinforcements that are good for chip/chunk also tend to be good for abrasion.

6. Samples containing only carbon black ranked highest for chip/chunk performance,
followed by silica-containing compounds, then silica/silane compounds, with fiber
loaded last.
References

‘Lloyd Stoyer, Modern Tire Dealer, October 1995.

2Y. Udagawa, ACS Rubber Division Meeting, May 1991.

3U. S. Patent 5 066 721.

"U. S. Patent 4914 147.

5U. S. Patent 5225011.

6U. S. Patent4 703 079.

7U. S. Patent 4 154 277.

8w. H. Waddell and J. R. Parker, Rub er World, 207, 29 1992.

9J. L. Ryba and B. Rogers, ACS Rubber Division Meeting, May 1993.
105
Wolff, Tire Sci. Technol., 4, 276 1987

" S. Wolff, Kaut. Gum i Kunst., 11, 969 1983.

‘2L. A. Walker and J. B. Harber, ACS Rubber Division Meeting, October 1984.

‘3L. deVos, H. van der Pol, B. Rijpkema, Rub er & PlasticsNews, Sept. 11, 1995.

14D C. Prevorsek, Y. D. Kwon, C. W. Beringer, J. J. Nelson, Rubbercon 1992.

‘5U. S. Patent 4257 468.

‘6A. R. Payne, J. Ap !. Poly. Sci.,6, 57 1962.

‘7J. R. Beatty and B. J. Miksch, RUBBER CHEM. TECHNOL. 55, 1531 1982.

‘8A. R. Payne, J. Ap l. Poly. Sci.,6, 57 1962

‘9M. L. Engelhardt, C. L. Day, R. Samples, K. C. Baranwal, ITEC ‘94 Proceedings

20j
A. Ayala, W. M. Hess, A. 0. Dotson, C. A. Joyce, RUBBER CHEM. TECHNOL.
63, 747 1990.
 Appendix 1 Recipes for Chip/Chunk Evaluation
1 2 3 4 5 6 1
N330 N220 N1231 CD2005 N293 N115ExpC/B
1st Stage:
1C20 100.00 100.00 100.00 100.00 100,00 100.00 100.00
5-1500
N330 50cC0
N220 50.00
N231 50.00
CD2005 50.00
N293 50.00
N115 50.00
Exp C/B 2 50.00
Exp C/B 1
Hisil 31 51-G
Hisil 243-LD
Hisil 255-LO
Hisil 2000
x50S
Sontoweb DX 73% pulp
Twaron 1095 Mosterbatch 40% pulp
ZnO 4.00 4.00 4.00 4.00 4.00 4.00 4.00
St Acid - 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Agerite Resin D_pply. hydroquinone 1.00 1.00 - 1.00 1.00 1.00 1.00 1.00
o-ppd

2nd Stage: Remill Remill Remill Remill Remlil Remill Remill

ZnO

Final 3rd Stage

6-ppd 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Sulfur 1.40 1.40 1.40 1.40 1.40 1.40 140
TBBS ith 1.00 1.00 i.bo 1.00 1.00 1.00
M BTS

Total phr 160.40 16040 160.40 160.40 16040 160.40 16040

1st Stage:
77 rpm, 70% Fill Factor
0’ Add 1/2 Rubber, C/B & pigments, 1/2 Rubber .______

45" Ram sweep

4’ Drop -

2nd Stage: .

77 rpm, 70% Fill Factor

0’ Add 1/2 Rubber, pigment, 1/2 Rubber
2’ Drop

Anal 3rd Stage

77 pm, 65% fill factor
0’ Add 1/2 Rubber pigments. 1/2 Rubber
45" Ram sweep
2’ Drop
 Appendix 1 Recipes for Chip/Chunk Evaluation
8 9 10 11 j_j2 13 14
Exp C/B 1 silica silica silica silica silica/silarie silica/silone
-

1C20 100.00 100.00 100.00 100.00 100.00 100.00 100.00

5- 1500
N330
N220 40.00 40.00 40.00 40.00 38.50 38.50
N23 1
CD2005
N293 .

N115
ExpC/B2
C/B1 - 5CLOO
Hisil 315T-G 10.00 10.00
Hisil 243-LD 10.00 10.00
Hisil 255-LD 10.00
Hisil 2000 10.00
X505 3.00 3.00
Sontoweb DX 73% pulp
Twaron 1095 Masterbatch 40% pulp
ZnO 4.00
St Acid 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Agerite Resin D poly. hydroquinone 1.00 1.00 1.00 1.00 1.00 1.00 1.00
6-ppd

2nd Stage: Remill

ZnO 4.00 4.00 4.00 4.00 4.00 4.00

And 3rd Stage

6-ppd 1.00 1.00 1.00 1.00 1W 1.00 1.00
Sulfur 1.40 1.40 1.40 1.40 1.40 1.30 1.30
1BBS 1.00 1.20 1.20 1.20 1.20 1.10 1.10
M BTS

Total phr 160.40 louoo 16U60 ioaoo 160.60 161.90 161.90

1st Stage:
77 rpm, 70% FiH Factor
0 Add 1/2 Rubber. C/B& piqme nts, 1/2 Ru bber
45" Ram sweep
4’ Drop

2nd Stage:
77 rpm, 70% Fill Factor
0’ Add 1/2 Rubber, pigment, 1/2 Rubber
2’ Drop

FInal 3rd Stage

77 rpm, 65% fill factor
0’ Add 1/2 Rubber, pigments, 1/2 Rubber
45’ Ram sweep
2’ Drop
 .

Appendix 1 Recipes for Chip/Chunk Evaluation

15 16 17 18 19
silica/shone silica/shone Cellulose Fibe Aramid Fiber SBR

TC2O 100.00 100.00 100.00 100.00

5-1500 100.00
N330
N220 38.50 38.50 48.00 48.00 50.00
N231
CD2005
N293
Ni 15
ExpC/B2
ExpC/B1 .

Hisil 315T-G
Hisil 243-LD
Hisil 255-LD 10.00
Hisil 2000 10.00
X5OS 3.00 3.00
Santoweb DX 73% pulp 2.74
Twaron 1095 Mosterbatch 40% pulp 5.00
ZnO 4.00 4.00 - 4.00
St Acid 2.00 2.00 2.00 2.00 2.00
Agerite Resin D poly, hydroquinone 1.00 1.00 - 1.00 1.00 - 1.00
6-ppd 1.00

2nd Stage: Remill -- Remill Remill

ZnO 4.00 4.00

Final 3rd Stag -___________

o-ppd 1.00 1.00 1.00 1.00

Sulfur 1.30 1.30 140 140 1.40
TBBS 1.10 1.10 1.00 1.00 1.00
METS -______ 0.30

Totolphr -____________ 161.90 161.90 161.14 163.40 160.40

1st Stage:
77 rpm, 70% Fill Factor
0’ Add 1/2 Rubber, C/B & pigme its, 1/2 Rubber
45" Ram sweep
4 Drop

2nd Stage:
77rpm, 70% Fill Factor
0’ Add 1/2 Rubber, pigment, 1/2 Rubber
2’ Drop

Final 3rd Stage -

77 rpm, 65% fill factor

YAdd 1/2 Rubber, pigments. 1/2 Rubber -__________

45" Ram sweep -__________________ --____

2’ Drop
 Appendix 2 Data Summary
1 2 3 4 5 6 7 8 9
N330 N220 N231 CD2005 N293 Ni 15 Exp C/B 2 Exp C/B 1 sil
BEG chip/chunk Test
ave. wt. loss,g 2.2594 2.2635 2.3103 2.2024 2.2842 2.1910 [ 2.2364 2.2394 2.4
1X 100 98 103 99 103 101 101 9
ave. dia. loss, mm 4.3 4.3 4.2 4.1 4.2 3.7 3.9 ‘ 4.1 5
Rcitingbyvolume 100 100 103 106 103 117 110 106 8

Lamborn Abrasion
ave. wt. loss, g 0.362 0.288 0.317 0.268 0.318 0.294 0.275 0.293 0.3

Hardness, Shore A 65 67 66 72 68 69 73 70 6

Stress-Strain Properties
Tensile, MPa 31.0 32.1 32.1 29.0 31.3 31.1 30.3 32.3 27
Elong.,% 558 569 581 420 579 583 451 543 4
BrkEnergy,J 26.0 26.0 26.8 18.4 26.4 27.9 20.3 28.2 1
ModlOO, MPa 2.9 2.7 2.6 4.1 2.7 2.7 3.7 2.9 2
Mod200, MPa 8.1 7.5 7.1 12.1 7.5 7.3 10.o 8.4 7
Mod300,MPa 15.1 14.6 13.7 20.8 14.1 13.9 19.3 15.9 1

82.0
Molded Groove Tear, kN/m :...-- 66.4 93.2 28.9 .0 57.1 36.1 48.7 5

deMattia cut growth

-

cycles for 10.7 mm growth 85l.x -

75000 isao 7500 15000 15000
.-_j___.±-. 8IXXJ 18 1&
slope dc/dn mm/RDJcycle 0.126 0.142 0.71 1 1.422 0.71 0.711 1.334 0.593 0.

Fifler Dispersion Image Analysis 96 97 98 98 99 98 96 97 9

RPA Data, 60°C, 20 Hz

G"@ 1%,kPa 2200 2614 2773 3639 2986 3076 4426 3554 20
G’@lO%,kpa 1429 1533 1495 2002 1573 1616 2160 1730 1
G’©20%,kPa 1274 1339 1296 1723 1355 1399 1842 1475 1

tandeffa@1% 0.130 0136 0159 0148 0.151 0.135 0.151 0173 0.

tan delta@ 10% 0.163 0.186 0.215 0.199 0.196 0.213 0.230 230 0.
tandelta@20% 0.148 0.166 0.180 0.187 0.179 0.180 0.198 207 0.
 Appendix 2 Data Summary
12 13 14 15 16 17 18
silica silica/silane silica/silane silica/silane silica/silane Cellulose Fibe Aramid Fib
BEG chip/chunk Test
ave. WI. loss, g 2,3565 2.9097 2.7235 2.7450 2.4799 2.6268 2.5019
Rating byweigh4 96 78 83 82 91 86 90
ave. dia. loss, mm 4.4 6.0 5.6 5.5 4.8 5.2 5.0
Rating by volume 97 72 77 79 89 83 87

Lambom Abrasion
ave. WI. loss, g 0.363 0.396 0.372 0.388 0.375 . 0.405 0.422

Hardness,ShoreA 64 64 66 65 65 68 71
1
Stress-Strain Properties
Tensile, MPa 27.3 28.4 29.3 29.1 26.9 29.4 27.9
Elong., % 517 486 497 498 483 517 487
BrkEnergy,J 20.8 17.9 20.8 18.8 18.9 21.9 2L9
ModlOO, MPa 2.4 2.8 3.0 2.8 2.6 3.0 4.3
Mod200,MPa 6.7 8.1 8.5 7.9 7.5 8.0 9.2
ModSQO, MPa 13.1 15.5 16.0 15.2 14.4 15.0 16.2

MoldedGrooveTear,kN/m 45.9 15.6 20.0 22.1 38.5 54.1 - 38.0

deMattia cut growth

cycles for 10.7 mm growth 105 650CC 15000 2503 45000 8000 IIXX0
slope dc/dn mm/l000cycle 0.102 0.164 0.711 0.427 0.237 1.334 1.067

Filler Dispersion Image Analvs 86 88 92 86 76 77 83

RPA Data, 60°C, 20 Hz

G@ 1%,kPa 2035 1940 2083 1950 2035 2529 2465
G’@ 10%,kPa 1330 1394 1431 1386 1415 1524 1555
G’ @ 20%, kPa 1175 1272 1295 1257 1272 1350 1370

tandelta@1% 0.146 0.fll 0.106 1109 0.121 1132 0.132

tan delta @ 10% 0.182 0.134 0.133 0.139 0.159 0.170 0.161
tandelta20% 0.174 0.128 0.135 0.133 0.148 1160 0.146
 Figure 1 Carbon Blacks Studied

190--
CL
C
o
CD2005
170 -

ExpC/B2
150’-

Pt

130-’ ExpC/
I
ci
N220 N115
C?
110
- N330
U
.
N293
90 - .. N231
I.
.4-
‘I

70- I I U

70 90 110 130 150 170

Nitrogen Surface Area sq-m/g
-
 Figure 2 Silicas Studied

240’
CL
C
C
Th
U
U

243-LD 255T-LD

Pt 180
4?
I.
cii 160
315T-G
U
U 140--
4?

.4-
Cl,
100 - I U I I
10 120 140 160 180 2X 220
Surface Area, sq-m/g - Measured by Nitrogen Absorption
 Figure 3 Carbon Blacks and Silicas Studied

CL 235 ‘‘

215--

Q 195
U

243-LD 255-LD
175-
.0 CD2Q35
-V
155 -
0
* ExpC/B2
135 - 315T-G
0
U ExpC/B1
C. ,i
L_ lU 0 0
3 N220 N115
U 0 0
E 95 -. N330 0 N293
N231
75 -
I

70 90 110 130 150 170 190 210

Nitrogen Surface Area sq-m/g
-
 Figure 4 BFG Chip/Chunk Test - Weight vs Diameter R

7.11-

6.50 -

6113 -

E
E 5.50 U
-
ri
ci
0
**
I 5.00 - -

C?
‘4-
C?
r-squa
E 4.50
Ct -
U

411 - -
U

3.50

3.00 - -
I I I U

2.cXXX 2.2X 2.4000 2.61K 2.80I 3.010

Weight Loss, g
 Figure 5 BFG Chip/Chunk vs. Hysteresis

120 -
6N115
S
115
C er
0
1
110-
II
C 4
N S
N 5
2: 105- 3
S
1 N330 2
100 -- S
12
CC

Ct
95. -

16
0 90
= 9
1=

U 11
0. 85- a
18
Pt z
x
80 -
015
U, o
1
*
75. - *
13
70 -

0.120 0.140 0.160 0.180 0.200 0.

RPA tan 3 60°C, 20 Hz, 10%

 Figure 6 Correlation between tan 6 and chip/chunk vs. Strain
0.85 -

0.80 -

eqI
0.75 -

C
C?
U
0.70 -

0.65--
C?
0
U
= 0.60 -.
0
.4-
Ct
C?
0.55 -

I
0 0.50
U
0.45 -

0.40-
0.00 5.00 10.00 15.00 20.00
Strain, %
 Figure 7 Payne Effect
5000- Compound 7

4500- large Payne effect

4000-

3500 -

3000 -

Ct
.4 2500 -
GUi
Compound 13
U,
2003 small Payne effedt

1500--

1..

Payne Effect = G’101G’1 X 100

500--

0
0.1 to 10.0
Strain %
 Figure 8 Hysteresis vs. Payne Effect

0.240

0.220 -

200 -.

0.180*

U
0 S
C

0.160 - x a
Cc
C
Ct
.4-

0.140 -

0
* carbon black
* N220, Silica
0.120 a N220, Silica/Silane
* N220, Fiber
Reg. Une
0.1Y I 4 I -

45 50 55 60 65
Payne Effect 1O0*GI1SG1
 Figure 9 Chip/Chunk Performance vs Payne Effect

115*

*
C
* *
II 105
* *
S *

:Ct 95--

.4
=
.0 *
U
- 85 * *
Pt *
U
C, S carbon black
N220, Silica
75 -
0 N220, Silica/Silane
S N220. Fiber
-Reg. Line

65- I U

40 45 50 55 60 65
Payne Effect 100 * G’io/G’i
 Figure 10 Abrasion Loss vs Interaction Parameter
l10*
S

105

C
C 100 S
S
II
C
N
ti 95.

CL S S
= 90-
Ct

I
Ct 85 -
C.

0
80 S
0
.0 S carbon black 0
ECt * N220. Silica
75
a N220, Silica/Silane I
- Reg. Line
70--

65
85 95 105 115 125
Filler Ineraction Parameter, F

Compounds 1-16 plotted. Compounds 17-19 Fibers. SBR not plotted.

 Figure 11 Lambourn Abrasion vs BFG Chip/Chunk

120-- óN115
S

!hbo
S

1
S S2N220

:
U * carbo
* N220
o N220
A z N220
A
60- I
I U

60 65 70 75 80 85 90 95 100

Lambourn Abrasion Rating N220 = 100