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Crosslinking of Viton
Crosslinking of Viton
2014
Crosslinking of fluoroelastomers
and the influence on final
properties
Matthias Lückmann, Wolfgang Steinhoff
Overview
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entanglements entanglements
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crosslinking of
fluoroelastomers
radical cure:
¾ cure sites are incorporated into the polymer 'X3RQW9LWRQ® G types)
¾ peroxide controls the rate of cure, DBPH most common peroxide
¾ coagent controls the number of crosslinks, TAIC most common coagent
¾ best resistance to hot water (or other aqueous fluids like coolants)
¾ improved chemical resistance (e.g. high and low pH)
¾ metal oxides not necessary but lead to higher heat resistance and more efficient cure
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2
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Viton® A;
F-content 66%
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B and F types also cured via C=C, formed at isolated VF2 sequences
but less efficiently because curatives are less soluble in the polymer -
they cannot find the cure sites easily
Viton® B, F;
F-content 66-70%
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3
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4
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20
Torque (dNm)
15
10
0
0 0.5 1 1.5 2 2.5 3
Time (mins)
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5
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0,3
0,2
1,2 1,4 1,6 1,8 2,0 2,2
BPAF
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types of MgO
¾ usual levels are 3 phr high activity or 15 of low activity MgO (processing!!!)
Metal oxides are hygroscopic and are often the cause of scorch problems
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7
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25
20
Torque (dNm)
15
10 6 CaOH2
4 CaOH2
6 CaOH2, 0.5 VC-30
0
0 2 4 6 8 10 12 14
Time (mins)
General Trends:
reducing calcium hydroxide level from 6 to 4 phr reduces cure rate
similar reduction in cure rate by adding 0.5 phr VC-30 but increasing the modulus
adding 1.0 phr VC 30 significantly reduces cure rate but increases modulus
adding VC-30 gives a reduced cure rate because of a higher curative to accelerator ratio
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test conditions: acetic acid, 504h @ 100 C VTR 9307 vs Viton® A331C
X X X X
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8
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Viton® GAL-S,
GBL-S, GF-S
65.5-70%F
Viton® GLT-S,
GBLT-S, GFLT-S
64.5-67%F
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ts1 5.0
0.414
MH 5.0
0.390 0.366 28.01
4.5 4.5
27.38
4.0 4.0
26.75
0.342
Diak 7 phr
Diak 7 phr
3.5 3.5
26.12
Tc-50 mins vs Diak 7, Luperox 101XL45 Tc-90 mins vs Diak 7, Luperox 101XL45
tc50 5.0
0.64
tc90 5.0
0.72 1.3
1.5 1.1 0.9
4.5 0.56
4.5
Diak 7 phr
3.5 3.5
3.0 3.0
2.5 2.5
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4.0 4.0
20.5
Diak 7 phr
Diak 7 phr
3.5 3.5
21.3
312 288
3.0 3.0
2.5 2.5
18.9 19.7
2.0 2.0
304
328 320
1.5 1.5
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
Luperox 101XL45 phr Luperox 101XL45 phr
Shore A pts vs Diak 7, Luperox 101XL45 Comp Set % vs Diak 7, Luperox 101XL45 (70hrs @ 200C)
5.0 5.0
Duro 70.8 Comp 20.0 20.6
21.8
4.5 4.5
69.6
Set
70.2
4.0 4.0
21.2
Diak 7 phr
Diak 7 phr
3.5 3.5
68.4 23.0
2.5 2.5
67.2
2.0 2.0 23.6 24.2
67.8
1.5 1.5
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
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Luperox 101XL45 phr Luperox 101XL45 phr
- Coagent controls the number of cross links - the most common coagents are
- Triallylisocyanurate (TAIC) ± should be used with Viton® APA polymers
- Trimethallylisocyanurate (TMAIC) ± not recommended for Viton® APA polymers
- Triallylcyanurate (TAC) sometimes used
- TMAIC and TAC
- will give slow and inefficient curing with Viton® APA polymers
30
TAIC - 3
25
Torque (dNm)
TMAIC - 1
20
15 TMAIC - 1.5
10
TMAIC - 2
5
TAC 3
0
0 1 2 3 4
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Time (mins)
12
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Conclusions
¾ two relevant curing mechanisms ± ionic and radical
¾ radical cure
¾ requires cure site monomer that contains bromine or iodine
¾ most common peroxide and coagent are DBPH and TAIC
¾ cure rate depends mainly on peroxide level
¾ cure state depends mainly on coagent level
¾ properties influenced by ratio of peroxide and coagent
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