New Approaches towards Improved Processing of … New Approaches towards Improved Processing of...

S o l u t i o n s . T a i l o r m a d e . W o r l d w i d e

New Approaches towards Improved

Processing of Special Elastomers

Dr. Volker Börger

Rubber ingredienten, 11-02-2016


Outline

- Needs in Special Elastomer Processing

- Polymers

- Requirements

- Processing (Additives)

- Peroxide Crosslinking: Struktol® HT 600

- EVM

- FKM

- Diamine Crosslinking: Struktol® HT 750

- Introduction, Processing Additives

- HNBR Zetpol 2510(White and black fillers)

- Vamac GLS (Mix of Carbon Black and Silica / Carbon Black)

Final Statements


Materials have to resist severe conditions

- Automotive Industry

• Long-term heat resistance / stability against aggressive fluids

• Physical properties

• Requirements are becoming more demanding

Polymer suppliers are responding with new grades

- Other areas

• Oil field applications

• Flame retardant articles

Special elastomers

AEM (Vamac) HNBR FKM HT-ACM EVM

Performance / Requirements Price


Special elastomers

Problems in Processing

Finally cost savings will be achieved

Bad Flow

Insufficient Dispersion

Compromise between processing and final properties

Processing Additive

Mold fouling

Bad Extrusion

Regarding processing additives traditional materials are still prominent and combinations are used

Viscosity is lowered

Faster mixing / less energy need

Higher efficiency

Extrusion: faster / better surface

Compound is sticky Injection Molding benefits


Requirements towards new materials to support Processing

Special elastomers

Multi-functional approach

HT-ACM

Release properties

Process safety

Try to maintain physical

properties

Replace expensive

Ingredients

Exclude strong blooming

As many parameters as possible should be included

Improve flow


HT-ACM

blooming effects

Good release needs . . . . . . (at least little) migration (but no blooming)

Need of special molecule structure

no blooming

Unwanted blooming effects?

Peroxide crosslinking


Struktol® HT 600 (DL)

Multi-functional material

• Reactive Processing Additive

• It is fixed to the rubber network

• No intensive blooming effects

• Good release

• Improves flow

• Contributes to crosslinking in

Peroxide cure

• Interesting influence on physical

properties

Peroxide crosslinking


EVM: Problems in Elongation at Break

recipe: 6164.8 contro

l

WS 18

0+TA

C

HT 60

0

Levapren 600 HV 100 100 100

Martinal OL-107 LEO 220 220 220

N-550 Corax 5 5 5

Stabaxol P200 2 2 2

Wing Stay 29 Pulver 2 2 2

Luvomaxx TAC 70 DL 2 2

Struktol WS 180 2

Struktol HT 600 2

Perkadox 14-40 8 8 8

sum: 339 341 339

• Struktol HT 600 replaces a combination of

Struktol WS 180 + coagent TAC

• Control compound: Elongation is too low!

• Addition of Processing Additive leads to drop

in Tensile Strength


HT-ACM

Struktol® HT 600:

• Elongation is improved at almost maintained Tensile Strength / Shore Hardness. Also Compression Set is improved

• Good release properties and lower Mooney Viscosity

EVM: Problems in Elongation at Break

recipe: 6164.8 contro

l

WS 18

0+TA

C

HT 60

0

Levapren 600 HV 100 100 100

Martinal OL-107 LEO 220 220 220

N-550 Corax 5 5 5

Stabaxol P200 2 2 2

Wing Stay 29 Pulver 2 2 2

Luvomaxx TAC 70 DL 2 2

Struktol WS 180 2

Struktol HT 600 2

Perkadox 14-40 8 8 8

sum: 339 341 339


Struktol® HT 600: • Only slight increase in Mooney Viscosity but

• Compression Set is maintained

FKM: Focus on Compression Set

#3841.7 control WS 280/HT 290 WS 280/HT 600

Viton GF-600S 100 100 100

Tremin 283-600 EST 20 20 20

Blanc Fix 35 35 35

Silox Zinc Oxide active 3 3 3

Titandioxid 1 1 1

Luvomaxx TAIC 70 DL 3,14 3,14 3,14

Trigonox 101-45D-pd 1,25 1,25 1,25

Struktol WS 280 Paste 0,5 0,5

Struktol HT 290 1,5

Struktol HT 600 1,5

sum 163,39 165,39 165,39


Processing

Flow is improved

Summary I – Peroxide cure

Crosslinking

Release is enhanced

Product is fixed to the rubber network

Influence on physical properties

Might be an alternative to co-agents Bloom is excluded

Struktol® HT 600 (DL)


Diamine crosslinking

Trouble in Processing? Release from metal parts / IM-process

Flow

Scorch Safety

Compromised properties due to too high loading of Processing Additives

AEM (Vamac) HT-ACM HNBR


Special Elastomers

Diamine crosslinking

Solutions from Schill+Seilacher „Struktol“ GmbH

Struktol® WB 222 Flow / Release

Struktol® WS 180 Flow / Release

New Development:

Struktol® HT 750 Release / Disperson

AEM (Vamac) HT-ACM HNBR


Zetpol HP: HNBR which is crosslinked with Diamines

High performance Zetpol exhibits greatly improved compression set resistance and very unique properties

when tested at a range of elevated temperatures.

These unique properties may well result in significantly improved performance in a variety of demanding

applications.

HP HNBR with Silica as filler

Zetpol 2510:

A highly saturated copolymer of butadiene and acrylonitrile with excellent low compression set

resistance, 37 wt% Acrylonitrile.

It also has excellent heat resistance, good chemical resistance to aggressive fluids and an excellent

balance of properties over a wide variation of temperatures.

Recommended filler is Silica for best long term demanding heat ageing propertes / Compression Set.



Our Targets:

- Processing / Replacement of traditional materials

- Impact of Struktol® HT 750 on Processing?

- Influence on Release?

- Is there any interaction with the Silica? Try to use the broad our knowledge in Silica compounding

- Is it possible to influence Tensile Strength and Elongation at Break? What about Compression Set?

Mixing:

- Masterbatch mixing, Struktol® additive added in this stage already.

- Curatives (Diak#1 & Rhenogran XLA-60) added on open mill

#6714 1 2 3 4 5

Zetpol® 2510 100 100 100 100 100

Ultrasil® VN2 GR 50 50 50 50 50

Alcanplast TOTM 5 5 5 5 5

Naugard 445 1,5 1,5 1,5 1,5 1,5

Stearic acid 1 1 1 1 1

Vanfre®VAM 1 1 1

Amino - Silane 1

Struktol® HT 750 2 2 2

Diak#1 2,6 2,6 2,6 2,6 2,6

Rhenogran® XLA-60 4 4 4 4 4

sum: 165,1 166,1 167,1 166,1 166,1

Vanfre® VAM: Polyoxyethylene octadecyl ether phosphate

Amino-Silane: Aminopropyltriethoxy silane

Rhenogran ® XLA-60: A DBU/Zn dialkyldiphosphate blend in acrylic polymer

Diak#1: Hexamethylenediamine carbamate


?

Are Processing Additives required?

• no Vanfre VAM

• no Amino-Silane

• no Struktol® Processing Additive

Zetpol 2510 100

Ultrasil VN 2 GR 50

Alcanplast TOTM 5

Naugard 445 1,5

Stearic acid 1

Diak#1 2,6

Rhenogran XLA-60 4

sum: 164,1



Zetpol 2510 100

Ultrasil VN 2 GR 50

Alcanplast TOTM 5

Naugard 445 1,5

Stearic acid 1

Diak#1 2,6

Rhenogran XLA-60 4

sum: 164,1

• no Vanfre VAM

• no Amino-Silane

• no Struktol® Processing Additive

Zetpol 2510 100

Ultrasil VN 2 GR 50

Alcanplast TOTM 5

Naugard 445 1,5

Stearic acid 1

Diak#1 2,6

Rhenogran XLA-60 4

sum: 164,1



Process additives are recommended :-)


compound: containing Struktol® HT 750, without Vanfre VAM: HP HNBR with Silica filler Zetpol 2510 100

Ultrasil VN 2 GR 50

Alcanplast TOTM 5

Naugard 445 1,5

Stearic acid 1

Vanfre VAM

Amino - Silane

Struktol HT 750 2

Diak#1 2,6

Rhenogran XLA-60 4

+ Struktol® HT 750

control = 100% + Amino-Silane + Struktol® HT 750 without Vanfre VAM

Mooney Viscosity [MU]: 108 110 108 113

Shore Hardness [Shore A]: 69 71 68 70

Tensile Strength [MPa]: 23,3 15 23 22,9

Elongation at Break [%]: 297 103 235 207

Compression Set

(168h@150°C) [%]: 35,2 14,8 15,8 16,9


Struktol® HT 60

Struktol® HT 750

Interaction with Silica surface

Dispersion is improved

- Additional remarks

- Balance between an interaction and insolubility in the polymer matrix leads to good release

- Compression Set after 504 h @150°C confirms the results

- A higher loading leads to more improved physical properties

- Heat ageing tests show comparable results


Struktol® HT 750: • No improvements (in Compression Set) if Silica is replaced by Carbon Black

• No big difference overall, properties are maintained

• But Release performance from metal parts is enhanced

Is it possible to reproduce the effect with Carbon Black as a filler?

Compression Set

Mooney Viscosity [MU]: 109

Shore Hardness [Shore A]: 69

Tensile Strength [MPa]: 18,3

Elongation at Break [%]: 181

Compression Set

(168h@150°C) [%]: 19,4

control = 100%

#6714.2 1 2 3

Zetpol 2510 100 100 100

N-550 Corax 40 40 40

Alcanplast TOTM 5 5 5

Alchem MBPA (CDPA) 1,5 1,5 1,5

Stearic acid 1 1 1

Vanfre VAM 1 1

Struktol® HT 750 2 2

Rhenogran XLA-60 4 4 4

Diak No 1 2,6 2,6 2,6

sum: 155,1 157,1 156,1


Injection Moulding – First trials with a Silica filled compound

Without additional additive: The Spider sticks

to the frontplate

Struktol® HT 750 shows improved release

behaviour

Pulled away from the injection

plate to the front plate

Insufficient release

Sticking is greater than the

friction of the rubber

Normally friction of the r


Vamac GLS: Silica/Carbon Black combination

Targets:

Interaction between Silica and HT 750 is expected!

- Look for Compression Set / Physical properties

• with and without silane • combination silane-additive

- Look for processing

• Does Struktol® HT 750 promote release? • Replacement of traditional Processing Additives?

- Upside down mixing

• Compounds 1+2 are partly sticking to the gate of

the mixer

Filler: N550 – VN2 combination

Filler: N550 – VN2 combination

control

#3828 1 2 3 4 5

Vamac® GLS 100 100 100 100 100

Ultrasil VN 2 25 25 25 25 25

N-550 Corax 30 30 30 30 30

Struktol® KW 759 10 10 10 10 10

Luvomaxx® CDPA 2 2 2 2 2

Armeen 18D 0,5 0,5 0,5 0,5 0,5

Stearic acid 1,5 1,5 1,5 1,5 1

Vanfre® VAM 1 1 1 1

Amino-Silane 0,5 0,5

Struktol® HT 750 1 1 2

Vulcofac ACT 55 2 2 2 2 2

Diak#1 1,5 1,5 1,5 1,5 1,5

sum 173,5 174 175 174,5 174


Vamac GLS: Silica/Carbon Black combination as filler

#3828

Vamac® GLS 100

Ultrasil® VN2 GR 25

N-550 Corax 30

Struktol KW 759 10

Luvomaxx® CDPA 2

Stearic acid 1

Vanfre® VAM

Armeen 18D 0,5

Amino-Silane

Struktol® HT 750 2

Vulcofac ACT 55 2

Diak#1 1,5

sum 174

+ 0,5 phr Amino-Silane without VAM, 1 phr Stearic Acid

control = 100% + 0,5 phr Amino-Silane + 1 phr Struktol HT 750 + 1 phr Struktol HT 750 + 2 phr Struktol HT 750

Mooney Viscosity [MU]: 37 35 35 35 38

Shore Hardness [Shore A]: 67 73 74 70 71

Tensile Strength [MPa]: 16,3 16,1 15,8 17,2 17,2

Elongation at Break [%]: 372 222 210 285 226

Compression Set

(72h@150°C) [%]: 52,4 37,5 33,8 40 34


Vamac GLS: 55 phr Carbon Black as filler

Struktol® HT 750: • No big improvements in Carbon Black filled

compounds

• Improvements in Release and Compression Set

• Vanfre VAM can be replaced by Struktol® HT 750 and the Stearic Acid content might be reduced

control

#3828

Vamac® GLS 100 100

N-550 Corax 55 55

Struktol KW 759 10 10

Luv omaxx® CDPA 2 2

Stearic acid 1,5 1

Vanfre® VAM 1

Armeen 18D 0,5 0,5

Amino-Silane

Struktol HT 750 1

Vulcofac ACT 55 2 2

Diak#1 1,5 1,5

sum 173,5 173

without VAM, 1 phr Stearic acid

control = 100% + Struktol® HT 750

Mooney Viscosity [MU]: 33 37

Shore Hardness [Shore A]: 69 70

Tensile Strength [MPa]: 18,6 18,2

Elongation at Break [%]: 245 235

Compression Set

(72h@150°C) [%]: 28,9 27,6


Silica

Summary II – Diamine crosslinking

Struktol® HT 60

Improved Silica dispersion is

achieved

Struktol® HT 750

Release is improved traditional materials might be replaced

Carbon Black

Excellent physical properties

in combination with very good

compression set

Processing package might be

adjusted

Physical properties are (at

least) maintained


Interested? Need a sample? [email protected]


Thank you for your attention!

Rubber ingredienten, 11-02-2016

New Approaches towards Improved Processing of … New Approaches towards Improved Processing of...

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