Aramid fibers enhancing elastomer properties - SGF

Aramid fibers enhancing elastomer properties - SGF

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
polyparaphenylene
terephthalamide
Sulfron
Technora
co-poly- (paraphenylene/3,4’oxydiphenylene terephthalamide)
Teijinconex
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
during processing
Technora
Technora gets kink bands, hardly fibrillate
or break
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
Perkadox 14-40 Kdp
Total (in phr)
0,31
0,31
0,31
9
9
9
192.3
192.3
192.3
Influence on Tensile properties
Machine Direction
24
Control (BC1)
3 mm Technora CF (BC2)
3 mm Technora DCF (BC3)
20
Cross Machine Direction
24
20
Cross-machine direction
16
Stress (MPa)
16
Stress (MPa)
Control (BC1)
3 mm Technora CF (BC2)
3 mm Technora DCF (BC3)
Machine direction
12
12
8
8
4
4
0
0
0
50
100
150
Strain (%)
200
250
300
0
50
100
150
Strain (%)
200
250
300
Influence on Tear (trouser)
BC1
BC2
BC3
Control
10 phr Technora 3
mm CF
10 phr Technora 3
mm DCF
[N]
9.3
40.8
40.8
[kN/m]
4.5
19.7
19.5
[N]
10.1
33.4
42.5
[kN/m]
4.8
16.1
20.3
Compounds
Properties
Average Force (F)
MD
Tear strength
Average Force (F)
CMD
Tear strength
Influence on Abrasion
(other compound)
•
•
•
Twaron
Technora
Control
CF 3 mm : 130 mm3
CF 3 mm : 100 mm3
: 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.
Product details:
Product form
Colour
Specific gravity
Twaron pulp type
p – aramid pulp
Matrix
:
:
:
:
:
:
Granules
Yellow
0.980 g/cm3
1095
40 wt %
60 wt %
Twaron D3500 is easily dispersible in rubber
compounds.
New! - Twaron D3500
Short fibers and pulp
Short fibers
0.1 – 0.3 m2/g
Fiber length 1 – 6 mm
Pulp
7 (type 1095) – 14 m2/g (type 1091)
Fiber length 1 - 2 mm
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)
SMR-10
Corax N330
Corax N550
Nytex 840
ZnO
Stearic acid
Sunolite 240
6 PPD
TMQ
Cofill 11/gr*
Twaron D3500 (Pulp MB)
Insoluble Sulfur
CBS
PVI/CTPI
HMTA (Hexa-80)
Total (phr)
*Cofill 11/gr: 50% resorcinol on 50% silica carrier
** corrected for 5 phr pulp
Control
100
35
30
5
10
2
2
2
1
6
0
6.5
1.0
0.1
1.8
202.4
Twaron D3500
100
35
30
5
10
2
2
2
1
6
12.6**
6.5
1.0
0.1
1.8
215.0
New! - Twaron D3500
Hardness
New! - Twaron D3500
Tensile Strength (machine direction)
•
Hot air aging, 72 hrs, 100 °C
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
EFFECTS OF SULFRON
Sulfron®
Sulfron is based on Twaron, which is modified by chemicals.
polyparaphenylene terephthalamide
Sulfron D3001
Sulfron D3515 – new grade
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.
Main Sulfron® effect
0,220
0,200
0,180
loss factor (tan d)
0,160
0,140
0,120
0,100
0,080
0,060
0,040
0,020 Dynamic strain: 2 %
Frequency: 10 Hz
0,000
0
10
20
30
40
50
60
70
80
90
100
110
o
Temperature ( C)
Adding Sulfron® to a compound improves
hysteresis because tan δ reduction!
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
Ingredients
Natural rubber
Butadiene rubber
Carbon black N234
Nytex 840
Zinc Oxide
Stearic acid
Sunolite 240
6 PPD
TMQ
Sulfron D3001
Sulfron D3515
Sulphur
TBBS
TOTAL
Control
80
20
50
5
4
2
2
2
1
0
0
1,75
1,5
169,25
Phr
Sulfron D3001 Sulfron D3515
80
80
20
20
50
50
5
5
4
4
2
2
2
2
2
2
1
1
2
0
0
2
1,75
1,75
1,5
1,5
171,25
171,25
Mooney Viscosity
Temp req.
Time req.
Test type
Rotor
Initial
ML
[°C]
[min]
[MU]
[MU]
Control
100
5
"visc"
"large"
86
53,7
S3001
100
5
"visc"
"large"
84,9
51,3
S3515
100
5
"visc"
"large"
87,2
51,7
Control
150
30
0,5
5,03
4,23
6,21
9,79
0,23
1,9
1,67
0,066
0,58
S3001
150
30
0,5
5,52
4,72
6,58
9,15
0,21
1,83
1,62
0,07
0,63
S3515
150
30
0,5
5,7
4,96
6,77
9,33
0,21
1,88
1,67
0,072
0,65
Cure Characteritics
Temp req.
Time req.
Osc. angle
ts2
t5
t50
t90
ML
MH
Delta S
RH
tRH
[°C]
[min]
[°]
[min]
[min]
[min]
[min]
[Nm]
[Nm]
[Nm]
[Nm/m]
[min]
Dynamic mechanical analysis
Temperature (°C)
Frequency (Hz)
Storage modulus (E')
Loss modulus (E'')
Tan d
% reduction Tan d
Tan d
DMTA
Control Sulfron D3001
60
60
10
10
6,7855
6,517
0,9497
0,7896
0,13995
0,12115
13
Sulfron D3515
60
10
6,6755
0,7865
0,1178
16
Tensile strength [Mpa]
Elongation at break [%]
Tear strength [kN/m]
Control
29
554
114,4
S3001
27,5
515
121,3
S3515
26,9
494
100
Reduction in tan d (60°C, 10Hz and 2% DSA)
25
20
Reduction in tan d [%]
15
10
5
0
120
125
130
135
140
145
150
Dump temperature [°C]
-5
155
160
165
Effect of Sulfron with different loadings N234
0,18
0,17
Control
0,16
1 phr Sulfron D3515
0,15
A
Tan d
0,14
2 phr Sulfron D3515
B
0,13
0,12
0,11
0,1
47
50
N234 content [phr]
53
56
31
Effect of Sulfron with different loadings N234
- Din Abrasion A
B
Sulfron D3515
Conclusions
Sulfron in NR model compound shows:
 Improvement of:
Hysteresis (tan δ)
a slight effect on cure, processing and mechanical properties.
Examples of applications that could benefit from Sulfron:
• Tires
• Conveyor Belts
• Vibrational dampers