addressing rolling resistance and durability of tires by using sulfron 3001 n. huntink, r. datta...
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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
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