Addressing Rolling Resistance and Addressing Rolling Resistance and

Durability of Tires by Using Durability of Tires by Using Sulfron 3001Sulfron 3001

N. Huntink, R. Datta†, P. Paping, M. van der MadeTeijin Aramid BV, Arnhem, The Netherlands

S. Parker Teijin Aramid USA Inc., 801-F Blacklawn Road Conyers, GA 30012-5187, USA

Outline• Introduction – Tire needs

• Teijin Aramid’s offering – SULFRON

• Underlying principle of improvements

• Compounding recommendations

• Evaluation results - Truck/Bus tread compounds - Belt skim compounds

• Result tire test

• Interfering ingredients

• Conclusions

Focus of the tire industrySulfronSulfron in Tires in TiresMaking the Environment GreenMaking the Environment Green

Fuel EconomyFuel Economy

DurabilityDurabilitySafetySafety

Teijin Aramid’s offerings - SulfronSULFRON is based on a Twaron matrix, which is modified by chemicals to activate the surface of the Aramid fibers.

Reaction mechanism suggests that SULFRON does interact with filler surfaces (both carbon black and silica) thereby reducing filler-filler interaction (Payne effect)

NH NHOC COn

Fuel economy

Safety

Durability

Better 4%Better 4%

Up 20%!Up 20%!

No compromiseNo compromise

Sulfron = Twaronreacted with

special chemicals No Sulfron

+ Sulfron

Sulfron 3001Sulfron 3001 is based on a peroxide (PO), 1,1-Di(tert-butylperoxy) cyclohexane [3006-86-8]

Radicals from PO react or interact with aramid creating stable living radicals (probably on aramid surface). These living radicals react with carbon black radicals during mixing. Some pre-crosslinking of rubber is expected because of side reactions.

O

Radicals: highly reactive species

Radicals are being studied with ESR

O-O-C-CH3O

CH3

CH3

CH3-C-O-

CH3

CH3O*O*

NH

O

NH

O

NH

O

NH

O

N

O

NH

O

.

NH

O

N

O

NH

O

O

NH

O

N

O

NH

O.

O O

O

NH

O

N NH

O

C=N ; interaction with CB

O2

C=N ; interaction with CB

OH

O

NH

O

N

O

NH

O

More compatability?

+O

Some speculations on the mechanism of peroxide modification of Twaron

Effect of Silane on Payne effect : Silica compounds

Influence silane on Payne effect

Strain

Silica

Silica + TESPT

Effect of Sulfron on Payne effect : Carbon black compounds

Underlying principle of improvements by Sulfron 3001

Influence of Sulfron on Payne effect

0

50

100

150

200

250

300

0,1 1,0 10,0 100,0

log strain (%)

G' (

kP

a)

Control

S-3001

Compounding recommendations

• Mixing time and temperature

• Mixing window for optimum performance

Compound temperature (actualreal) during mixing Sulfron 3001

0

20

40

60

80

100

120

140

160

180

200

0 1 2 3 4 5 6

mixing time [min]

tem

eper

atu

re [

°C]

half black + S3001

add rest (not vulcanization package)

Sweep Dump

Adjust rpm to reach 150°C in 3 minutes

After 3 minutes maybe lower rpm to keep 150 - 165C

Note: temperature will drop after every operation, but needs to come back on target as shown

Critical point:We need 150-165°C at 3 minand keep the temperature same till 5 minutes.

Mixing procedure

Mixing window for optimum performance

DOE experiment 16 october 2008

0,08000

0,09000

0,10000

0,11000

0,12000

0,13000

0,14000

0,15000

130 140 150 160 170 180

0 phr Sulfron 3001

1 phr Sulfron 3001

2 phr Sulfron 3001

-30% improvement in hysteresis can be achieved if * mixing temperature 150-165°C * Mixing time of 2 minutes after reaching the temperature (150-165°C)- The deviation is within the error- 1 & 2 phr Sulfron: No significant differences

Mixing window

Sulfron 3001 in typical truck tread compounds

Formulation (Bias Tread)

Compounds 08194-01B 08194-02B 08194-03B 08194-04BCONTROL 1.0 S-3001 1.25 S-3001 1.5 S-3001

SIR-20 100 100 100 100HAF- N330 40 40 40 40Sulfron 3001 stnd - 1 1,25 1,5VivaTec 500 7 7 7 7Zinc oxide 5 5 5 5stearic acid 3 3 3 3Santoflex 6PPD-pst 1 1 1 1Flectol TMQ-pst 1 1 1 1MBS 0,5 0,5 0,5 0,5CBS-grs-2mm 0,5 0,5 0,5 0,5Sulphur 2 2 2 2

Total phr lab 160 161 161,25 161,5

Rheometer data at 145°C

Rheometer MDR2000E [t,ext2] ISO 6502:1999Compounds 08194-01B 08194-02B 08194-03B 08194-04B

CONTROL 1.0 S-3001 1.25 S-3001 1.50 S-3001Temp req. [°C] 145 145 145 145Time req. [min] 60 60 60 60Osc. angle [°] 0,5 0,5 0,5 0,5ts2 [min] 7,32 7,67 7,58 7,71t50 [min] 9,68 9,92 9,79 9,93t90 [min] 15,56 15,19 14,95 15,11t95 [min] 17,82 17,11 16,81 16,99ML [Nm] 0,12 0,09 0,09 0,1MH [Nm] 1,48 1,42 1,42 1,42Delta S [Nm] 1,36 1,33 1,33 1,32

Processing data

Mooney MV2000E ML(1+4) Visc. ISO 289-1:1994Compounds 08194-01B 08194-02B 08194-03B 08194-04B

CONTROL 1.0 S-3001 1.25 S-3001 1.50 S-3001Temp req. [°C] 100 100 100 100Time req. [min] 5 5 5 5Initial [MU] 54,6 45,3 50,1 48,6ML [MU] 33,2 28,0 28,0 28,1

Mooney MV2000E MS Scorch ISO 289-2:1994Temp req. [°C] 125 125 125 125Time req. [min] 60 60 60 60Initial [MU] 22,8 15,5 15,1 15,6Mmin [MU] 13,7 11,2 11 11,1tMmin [min] 9,6 10,9 10,7 6,5t5 [min] 29,4 31,8 31,2 31,4

Payne effect (RPA measurement)

0

20

40

60

80

100

120

140

160

0,1 1,0 10,0 100,0

log strain (%)

G' (k

Pa)

Control

Sulfron1.00 phr1.25 phr1.50 phr

Mechanical Properties (Cured at 145°C/t90)

Compounds 08194-01B 08194-02B 08194-03B 08194-04BCONTROL 1.0 S-3001 1.25 S-3001 1.50 S-3001

Hardness IRHD 59 58 58 59Modulus, 100% MPa 2,4 2,4 2,4 2,5Modulus, 300% MPa 12,1 12,2 12,4 13,3Tensile strength MPa 29 28,8 28,3 28,7Elongation at Break % 540 550 540 530Tear strength kN/m 195 192 196 198Abrasion loss DIN mm3 150 130 120 125Heat Build up,∆T, 100°C °C 12,2 10,1 10,1 10,0

Permanent set % 7 6,5 5,9 5,8

Viscoelastic properties (60°C, 15Hz and 2% strain)

Compounds 08194-01B 08194-02B 08194-03B 08194-04BCONTROL 1.0 S-3001 1.25 S-3001 1.50 S-3001

GABO const strain 60/10/2 CM / test piece / 1,5*t90 min. / 145°CTemperatur [°C] 60 60 60 60Frequency [Hz] 10 10 10 10Strain [%] 2 2 2 2Storage E' [MPa] 4,81 4,542 4,501 4,518Loss E'' [MPa] 0,374 0,2855 0,2627 0,2609Tan δ 0,0777 0,0629 0,0584 0,0577Complex E* [MPa] 4,825 4,551 4,509 4,526

DUPLICATE MEASUREMENTSStorage E' [MPa] 4,793 4,511 4,464 4,522Loss E'' [MPa] 0,368 0,296 0,260 0,754Tan δ 0,0768 0,0656 0,0582 0,0609Complex E* [MPa] 4,807 4,521 4,471 4,530

mean tan δ 0,07725 0,06425 0,05830 0,05930decrease of tan δ [%] - 17 25 23

Belt skim compounds

Contribution to rolling resistance: Parts of Truck tires

belt20%

tread30%bead

16%

sidewall10%

casing24%

belt20%

tread30%bead

16%

sidewall10%

casing24%

Belt FailureDue to heat and loss in adhesion

Formulations Belt skim compoundCompounds 07083-01B 07083-02B

Control S-3001SVR-10 100 100HAF- N326 45 45Zinc oxide 8 8stearic acid 0,5 0,5SP 1068 2 2Napco 105PN 0,5 0,5Sunolite 240 1 0,46PPD 1 1Flectol TMQ-pst 1 1DCBS 1 1PVI pdr-d 0,2 0,2Crystex OT20 5 5Sulfron 3001 - 1,5Total phr lab 165,2 166,1

0

20

40

60

80

100

120

140

160

0,1 1,0 10,0 100,0

log strain (%)

G' (k

Pa)

Payne effect in Belt Skim compound

Control

Sulfron 3001

Tangent delta at 60°C/10Hz (Hysteresis)

CM / test piece / 24.0 min. / 150°CGABO const strain Control S-3001Temperatur [°C] 60 60Frequency [Hz] 10 10Strain [%] 2 2Storage E' [MPa] 53,600 51,000Loss E'' [MPa] 0,475 0,393Tan δ 0,089 0,076Complex E* [MPa] 53,370 51,650

Tan δ reduced by 15%

Heat build up curves at 100°C

Time, minutes

260

212

164

116

68

200 10 20 30 4 0 50 60

Blow Out

Tem

pe

ratu

re,

°C

01 Control

02 Sulfron

Sulfron 3001 tire test results

Properties Control+Sulfron

3001Difference

Tire temperature (15 hr at 50-110 kph)  

Shoulder temperature, °C 151 132 -19°C

Crown temperature, °C 154 134 -20°C

Tire rolling resistance  

40 kph, kW 2.64 2.20 -16%

60 kph, kW 4.15 3.38 -18%

80 kph, kW 5.91 4.48 -24%

100 kph, kW 7.85 5.50 -30%

Tire endurance (110 kph till failure)  

Endurance time, hours 17.2 22.5 +31%

Endurance distance, kms 1420 1810 +28%

Truck tires: 295/R22.5 : Sulfron 1,5phr in tread only

Results of outdoor tire tests

CONTROL

+Sulfron 3001

Interfering ingredients

Effect of other compounding ingredients:

Different blacks

Different polymers

Peptizers

Different oils

Effect 2 phr Sulfron 3001 in NR compound on reduction of tan δ at RR

0,0

5,0

10,0

15,0

20,0

25,0

30,0

35,0

40,0

N110 N134 N220 N234 N326 N330 N339 N550 N660 N765

Carbon black type

Rela

tive d

ecre

ase o

f

tan

delt

a a

t R

R [

%]

ESR spectra of different types of Carbon black at RT

[G]2400 2600 2800 3000 3200 3400 3600 3800 4000 4200

-1.4

-1.2

-1.0

-0.8

-0.6

-0.4

-0.2

-0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4[*10^ 3]

[G]2400 2600 2800 3000 3200 3400 3600 3800 4000 4200

-1.4

-1.2

-1.0

-0.8

-0.6

-0.4

-0.2

-0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4[*10^ 3]

[G]2400 2600 2800 3000 3200 3400 3600 3800 4000 4200

-1.4

-1.2

-1.0

-0.8

-0.6

-0.4

-0.2

-0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4[*10^ 3]

[G]2400 2600 2800 3000 3200 3400 3600 3800 4000 4200

-1.4

-1.2

-1.0

-0.8

-0.6

-0.4

-0.2

-0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4[*10^ 3]

[G]2400 2600 2800 3000 3200 3400 3600 3800 4000 4200

-1.4

-1.2

-1.0

-0.8

-0.6

-0.4

-0.2

-0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4[*10^ 3]

[G]2400 2600 2800 3000 3200 3400 3600 3800 4000 4200

-1.4

-1.2

-1.0

-0.8

-0.6

-0.4

-0.2

-0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4[*10^ 3]

[G]2400 2600 2800 3000 3200 3400 3600 3800 4000 4200

-1.4

-1.2

-1.0

-0.8

-0.6

-0.4

-0.2

-0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4[*10^ 3]

[G]2400 2600 2800 3000 3200 3400 3600 3800 4000 4200

-1.4

-1.2

-1.0

-0.8

-0.6

-0.4

-0.2

-0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4[*10^ 3]

CB-N326

CB-N110

CB-N330 CB-N339

CB-N220 CB-N234

CB-N115 CB-N134

Good correlation between reduction in tan δ and radical

density of carbon black!!

Effect of peptizers in NR/BR formulation

Compound phr

SOG-10 80Europrene BR40 20Peptizer 0 - 0.3HAF- N326 53Sulfron 3001 0 - 2zinc oxide 5stearic acid 2Vivatec 500 86PPD 2TMQ 1Sunolite 240 2CBS 1,5Sulphur 1,5

Total phr lab 176,0

Mixing procedure

elastomers [min.] 0peptizers [min.] 0½ carbon black [min.] 1Sulfron 3001 [min.] 1ZnO + SA + rest [min.] 2,5½ carbon black [min.] 2,5sweep [min.] 4dump [min.] 5

Dump temperature between 152 - 159°C

ERT09058a

Renacit 11WG : 2,2’-dibenzamidophenyldisulfide (DBD)

Noctizer SD : 70% stearic acid + 30% di(orthobenzamidophenyl)disulfide

Tan δ at rolling conditions

Influence of peptizer on the performance of Sulfron 3001 in NR/BR compound

0,040

0,060

0,080

0,100

0,120

0,140

0,160

Control Control +S3001

Renacit 11 WG Renacit 11 WG+S3001

Noctizer SD Noctizer SD+S3001

Tan

del

ta a

t ro

llin

g r

esis

tan

ce c

on

dit

ion

s [%

]

- 31%

- 35% -32%

Interfering Ingredients

• Peptizers – Eliminate, if necessary ( Sulfron gives low viscosity)

• Silica/Silane: React silica and silane before addition of carbon black + Sulfron 3001. Unreacted silica may interfere into Sulfron 3001 reactivity.

• Performance of S-3001 depends on type of rubber:Best NR < SBR < BR Worst

• Performance of S-3001 depends on type of black:Best 300 series < 200 series < 100 series Worst    

• Aromatic oils (high levels) may interfere into Sulfron reaction. Certain oil extended polymers may give unusual effects. This is because of the nature of oil present:

Best TDAE oil < paraffinic oil < aromatic oil < high aromatic oil Worst              

Sulfron 3001 decreases filler-filler interaction thus reduces frictional energy

Reduction of Hysteresis

Reduction of Heat build up

* Improved Fuel Efficiency * Improved Durability

Improvements:(a) Payne effect(b) Heat build up, Permanent set(c) Hysteresis, tangent delta(d) Dynamic abrasion (wear)(e) Fatigue, flex, cut/chip and chunk

CONCLUSIONS