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