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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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)
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
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
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
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
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
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.
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
HP HNBR with Silica as filler
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
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
?
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
HP HNBR with Silica as filler
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
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
HP HNBR with Silica as filler
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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