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Aramid fibers enhancing
elastomer properties
Sveriges Gummitekniska Förenings vårkonferens
10-11 april, 2013 Malmö
Ko Arts
Technical Sales Manager
Teijin Aramid BV
Teijin’s
high performance fibers
Aramid fibers
Twaron
Sulfron
Technora
Teijinconex
polyparaphenylene
terephthalamide
co-poly- (paraphenylene/3,4’-
oxydiphenylene terephthalamide)
poly- (metaphenylene
isophthalamide)
Why use aramid short fibres in rubber
compounds?
• Anisotropy
• Increase green strength
• Increase modulus
• Increase abrasion resistance
• Increase cut/tear resistance
• Lower coefficient of friction
• Lower noise generation in dynamic applications
• Lower hysteresis and therefore lower heat build up in the compound leading to a longer service life (especially for thick sections)
Teijin Aramid’s short fibers
• Twaron® :
• Chopped fibers (1, 3 & 6 mm)
• Dip-chopped fibers (1, 3 & 6 mm)
• Pulp
• Twaron ® D3500 (new!)
• Technora®
• Chopped fibers (1, 3 & 6 mm)
• Dip-chopped fibers (1, 3 & 6 mm)
• Teijinconex®
• chopped fibers (1, 3, 6 mm)
• dipped chopped fibers (1, 3, 6 mm)
• Sulfron®
Twaron
Twaron will fibrillate and break; mind this aspect Technora gets kink bands, hardly fibrillate
during processing or break
Technora
EFFECTS OF PULP, CHOPPED AND
DIP CHOPPED ARAMID FIBER
EPDM Formulation
Compounds BC1 BC2 BC3
(phr) (phr) (phr)
Ingredients Control 3 mm Technora CF 3 mm Technora DCF
Keltan 578 100 100 100
Corax N660 70 60 60
Sunpar 2280 10 10 10
ZMMBI-50 1.5 1.5 1.5
Naugard 445 1.5 1.5 1.5
Technora CF, 3 mm 10
Technora DCF, 3 mm 10
Cure recipe
Sulfur 0,31 0,31 0,31
Perkadox 14-40 Kdp 9 9 9
Total (in phr) 192.3 192.3 192.3
Influence on Tensile properties
Machine Direction Cross Machine Direction
0 50 100 150 200 250 300
0
4
8
12
16
20
24
0 50 100 150 200 250 300
0
4
8
12
16
20
24
0 50 100 150 200 250 300
0
4
8
12
16
20
24
Strain (%)
Control (BC1)
Str
ess (
MP
a)
3 mm Technora CF (BC2)Machine direction
3 mm Technora DCF (BC3)
0 50 100 150 200 250 300
0
4
8
12
16
20
24
0 50 100 150 200 250 300
0
4
8
12
16
20
24
0 50 100 150 200 250 300
0
4
8
12
16
20
24 Control (BC1)
Strain (%)
3 mm Technora CF (BC2)
Str
ess (
MP
a)
3 mm Technora DCF (BC3)
Cross-machine direction
Influence on Tear (trouser)
Compounds BC1 BC2 BC3
Properties Control 10 phr Technora 3
mm CF
10 phr Technora 3
mm DCF
MD
Average Force (F) [N] 9.3 40.8 40.8
Tear strength [kN/m] 4.5 19.7 19.5
CMD
Average Force (F) [N] 10.1 33.4 42.5
Tear strength [kN/m] 4.8 16.1 20.3
Influence on Abrasion (other compound)
• Twaron CF 3 mm : 130 mm3
• Technora CF 3 mm : 100 mm3
• Control : 170 mm3
(> 10 mm3 is significant, apart from approximately
10% spread, 80 mm3 is extreme low)
Twaron will fibrillate more than Technora
Abrasion
“on end” abrasion (iso 4649, meth A)
New! - Twaron D3500
Twaron D3500: aramid pulp masterbatch.
A reinforcement additive for rubber compounds.
Twaron D3500 is easily dispersible in rubber
compounds.
Product details:
Product form : Granules
Colour : Yellow
Specific gravity : 0.980 g/cm3
Twaron pulp type : 1095
p – aramid pulp : 40 wt %
Matrix : 60 wt %
7 (type 1095) – 14 m2/g (type 1091)
Fiber length 1 - 2 mm
0.1 – 0.3 m2/g
Fiber length 1 – 6 mm
Short fibers and pulp
Short fibers Pulp
New! - Twaron D3500
Mixing and Compounding of Twaron D3500:
Dosage 2 – 10 phr.
Twaron D3500 contains 30 % oil. Consider to compensate for this amount of oil in the
compound formulation. E.g., For 5 phr of Twaron D3500, 1.5 phr of oil could be reduced.
No specific temperature requirements for mixing.
Can be used in any type of compounds.
Mixing scheme
Time Action
0 min Rubber
1/2 min Carbon black or Silica + Twaron D3500 + Rest
2 min Oil
4 min Sweep
5 min Dump the compound
New! - Twaron D3500
Test results
Model apex formulation
Ingredients (Phr) Control Twaron D3500
SMR-10 100 100
Corax N330 35 35
Corax N550 30 30
Nytex 840 5 5
ZnO 10 10
Stearic acid 2 2
Sunolite 240 2 2
6 PPD 2 2
TMQ 1 1
Cofill 11/gr* 6 6
Twaron D3500 (Pulp MB) 0 12.6**
Insoluble Sulfur 6.5 6.5
CBS 1.0 1.0
PVI/CTPI 0.1 0.1
HMTA (Hexa-80) 1.8 1.8
Total (phr) 202.4 215.0
*Cofill 11/gr: 50% resorcinol on 50% silica carrier
** corrected for 5 phr pulp
New! - Twaron D3500
Hardness
New! - Twaron D3500
• Hot air aging, 72 hrs, 100 °C
Tensile Strength (machine direction)
New! - Twaron D3500
Tensile Strength (cross-machine direction)
• Hot air aging, 72 hrs, 100 °C
New! - Twaron D3500
Tear Strength (Crescent type)
New! - Twaron D3500
SUMMARY
• Twaron D3500 is an aramid pulp masterbatch
• A reinforcing additive in rubber compounds
• Gives strong increase in low elongation modulus
• Dispersion of Twaron D3500 is very important to achieve good properties
New! - Twaron D3500
EFFECTS OF SULFRON
Sulfron is based on Twaron, which is modified by chemicals.
polyparaphenylene terephthalamide
Sulfron reduces hysteresis in carbon black filled compounds. Sulfron can be used in
CB filled compounds. Most pronounced effects are seen in NR based compounds.
Sulfron D3001 Sulfron D3515 – new grade
Sulfron®
Main Sulfron® effect
Adding Sulfron® to a compound improves
hysteresis because tan δ reduction!
0 10 20 30 40 50 60 70 80 90 100 110 0,000
0,020
0,040
0,060
0,080
0,100
0,120
0,140
0,160
0,180
0,200
0,220
0 10 20 30 40 50 60 70 80 90 100 110 0,000
0,020
0,040
0,060
0,080
0,100
0,120
0,140
0,160
0,180
0,200
0,220
0 10 20 30 40 50 60 70 80 90 100 110 0,000
0,020
0,040
0,060
0,080
0,100
0,120
0,140
0,160
0,180
0,200
0,220 lo
ss
fac
tor
( ta
n d
)
Temperature ( o C )
Dynamic strain: 2 % Frequency: 10 Hz
Sulfron D3515 – new grade
Based on aramid pulp masterbatch
Granular shaped
Contains 40 % aramid pulp (type 1095)
Easily disperses in rubber compounds
Reduces hysteresis ( tan d at rolling
conditions)
Mixing recommendations
Sulfron has to be added together
or just after carbon black addition.
The compound temperature
has to be kept in the range of
145 – 160 °C for about
1.5 – 2 min.
The optimum dosage can vary depending on formulation. However, it is most usually
around 1.5 – 2 phr.
Natural rubber (NR) based tread formulation
Control Sulfron D3001 Sulfron D3515
Natural rubber 80 80 80
Butadiene rubber 20 20 20
Carbon black N234 50 50 50
Nytex 840 5 5 5
Zinc Oxide 4 4 4
Stearic acid 2 2 2
Sunolite 240 2 2 2
6 PPD 2 2 2
TMQ 1 1 1
Sulfron D3001 0 2 0
Sulfron D3515 0 0 2
Sulphur 1,75 1,75 1,75
TBBS 1,5 1,5 1,5
TOTAL 169,25 171,25 171,25
Phr
Ingredients
Control S3001 S3515
Temp req. [°C] 100 100 100
Time req. [min] 5 5 5
Test type "visc" "visc" "visc"
Rotor "large" "large" "large"
Initial [MU] 86 84,9 87,2
ML [MU] 53,7 51,3 51,7
Mooney Viscosity
Control S3001 S3515
Temp req. [°C] 150 150 150
Time req. [min] 30 30 30
Osc. angle [°] 0,5 0,5 0,5
ts2 [min] 5,03 5,52 5,7
t5 [min] 4,23 4,72 4,96
t50 [min] 6,21 6,58 6,77
t90 [min] 9,79 9,15 9,33
ML [Nm] 0,23 0,21 0,21
MH [Nm] 1,9 1,83 1,88
Delta S [Nm] 1,67 1,62 1,67
RH [Nm/m] 0,066 0,07 0,072
tRH [min] 0,58 0,63 0,65
Cure Characteritics
Control Sulfron D3001 Sulfron D3515
Temperature (°C) 60 60 60
Frequency (Hz) 10 10 10
Storage modulus (E') 6,7855 6,517 6,6755
Loss modulus (E'') 0,9497 0,7896 0,7865
Tan d 0,13995 0,12115 0,1178
% reduction Tan d - 13 16
DMTA
Tan d
Dynamic mechanical analysis
Control S3001 S3515
Tensile strength [Mpa] 29 27,5 26,9
Elongation at break [%] 554 515 494
Tear strength [kN/m] 114,4 121,3 100
Reduction in tan d (60°C, 10Hz and 2% DSA)
-5
0
5
10
15
20
25
120 125 130 135 140 145 150 155 160 165
Dump temperature [°C]
Reductio
n in
tan d
[%]
Effect of Sulfron with different loadings N234
0,1
0,11
0,12
0,13
0,14
0,15
0,16
0,17
0,18
47 50 53 56
Control
1 phr Sulfron D3515
2 phr Sulfron D3515
N234 content [phr]
Ta
n d
A
B
31
Effect of Sulfron with different loadings N234
- Din Abrasion -
Sulfron D3515
A
B
Improvement of:
Hysteresis (tan δ)
a slight effect on cure, processing and mechanical properties.
Conclusions
Sulfron in NR model compound shows:
Examples of applications that could benefit from Sulfron:
• Tires
• Conveyor Belts
• Vibrational dampers
Recommended