Battling the Effects of Reversion

in NR Compounds
Dr. Ken Bates
Struktol Company of America
SLTC/FAIT Latin-American Rubber Conference 2013
Buenos Aires, September 23-27th 2013
High Temperature Aging – NR Truck Tread
 How do Today’s Rubber Compounders
improve High-Temperature aging of NR?

• The standard practice has been to use

special cure systems that contain
reduced amounts of sulfur
• Conventional cures, CV (high sulfur)
• Semi efficient cures, semi-EV (medium sulfur)
• Efficient cures, EV (low sulfur)
Truck Tread Recipes (CV, Semi EV, EV)
Ingredient CONVENTIONAL SEMI-EV EFFICIENT
PASS #1 SIR20 100 100 100
N234 Carbon Black 50 50 50
VN3 Silica 10 10 10
ZnO 5 5 5
Napthenic Oil 3 3 3
Stearic Acid 1.5 1.5 1.5
6PPD 2 2 2
TMQ 1 1 1

FINAL Sulfur 2.5 1.4 0.25

TBBS 0.6 1.7 2.0
PVI 0.1 0.1 0.1
MBTS --- --- 2
Differences in Fatigue Resistance
2-Step Curing/Aging Procedure

150°C CURING AGING

150°C
160°C

170°C
 Materials Studied
 Struktol ZB47
• Proprietary zinc compound
• Pelletized product / 112°C softening point
 Struktol SA1341
• New product development in 2013
• Available as free-flowing powder
• 118°C softening point
 Struktol SCA98
• Triethoxy silyl propyl tetrasulfane (TESPT)
• Used as sulfur donor in carbon black compounds to promote
new crosslink formation during thermal aging
 Hexamethylene bisthiosulphate disodium salt (HTS)
• Promoted to enhance crosslink flexibility after thermal aging
processes take place
 1,3 – bis (citraconimidomethyl) benzene (CIMB)
• Capable of crosslink compensation actions as thermal aging
occurs
 CURE CORRECTIONS for EQUAL MODULUS
NO
Ingredient ADDITIVE ZB47 DURALINK SA1341 TESPT
PASS #1 SIR20 100 100 100 100 100
N234 CB 50 50 50 50 50
Ultrasil VN3 10 10 10 10 10
ZnO 5 5 5 5 5
Hyprene L2000 3 3 3 3 3
Stearic Acid 1.5 1.5 1.5 1.5 1.5
6PPD 2 2 2 2 2
TMQ 1 1 1 1 1
STRUKTOL ZB47 0 3 0 0 0
Duralink HTS 0 0 3 0 0
STRUKTOL SA1341 0 0 0 3 0
STRUKTOL SCA98 (TESPT) 0 0 0 0 3

FINAL Sulfur 1.40 1.40 1.25 1.25 1.25

TBBS 1.70 1.70 1.55 1.55 1.55
Santogard PVI 0.1 0.1 0.1 0.1 0.1

RPA Modulus (10% @100C) 1.03 1.08 1.20 1.16 1.23

Better Processing

High-Shear Viscosity
600

Pa·s @500/s
550
500
450
400
Step 1: Curing Curves at 150°C

t90
ML MH (mins)
No Additive 6.1 25.6 9.5
ZB47 5.3 25.4 11.8
SA1341 5.5 28.0 13.0
Step 2: Aging at 150°C

SA1341
ZB47

No Additive

% REVERSION
@150C
No Additive 12.1
ZB47 1.3
SA1341 0.0
 Aging at 160°C

SA1341

ZB47

No Additive

% REVERSION
@160C
No Additive 34.3
ZB47 18.0
SA1341 11.5
Aging at 170°C

SA1341

ZB47

No Additive

% REVERSION
@170C
No Additive 40.7
ZB47 32.4
SA1341 22.3
Reversion Performance of Alternative
Anti-Reversion Agents
No Additive

ZB47
HTS
SA1341
CIMB TESPT
 Modulus Change After Aging
1.4
RPA G*
Temp = 100C
1.3 Strain = 10%
Frequency = 1 Hz
1.2
Modulus (MPa)

1.1
150C
1 160C
170C
0.9

0.8

0.7

0.6
No Additive ZB47 SA1341 CIMB DBHT TESPT
 Tan Delta Increase With Aging
0.18
RPA tan delta
0.17 Temp = 100C
Strain = 10%
Frequency = 1 Hz
0.16
tan delta

0.15
150C
0.14 160C
170C
0.13

0.12

0.11

0.1
No Additive ZB47 SA1341 CIMB DBHT TESPT
 Abrasion Increase With Aging
275
150C
250 160C
DIN Abrasion (rel vol. loss)

170C
225

200

175

150

125

100
No Add ZB47 SA1341 CIMB HTS TESPT
Tear Strength Reduction After Aging
SA1341

ZB47
HTS

No
CIMB
Additive

TESPT
 Tensile Change After Aging
30
Tensile Strength (MPa)

25

150C
160C
170C
20

15
No Add ZB47 SA1341 CIMB HTS TESPT
 Conclusions
 Struktol ZB47 and SA1341 serve a dual function in
sulfur-cured NR compounds.
 Improve processing via viscosity reduction.
 Greatly reduce the detrimental effects of
anaerobic aging.
 Aging improvement is at least as effective as
competitive anti-reversion agents.

 For maximum resistance to aging SA1341 is

recommended.

 Struktol ZB47 can be added on top of an existing

conventional or semi-EV recipe to improve aging
performance.
 No cure system adjustment needed to match
unaged properties of control.