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DuPont™ Vamac® & DuPont™ Viton®
Performance in Automotive Fluids
Welcome to the Global & Interactive
Collaboratory
Laurent Lefebvre DPP - Global Automotive Air Duct Market Leader
Patrick Paglia DPP - Technology Associate
Plastlab
Orbassano, November 23rd, 2012
Performance of Vamac® ethylene acrylic
& Viton® fluoroelastomers in:
1. Engine & Transmission Synthetic Oils
2. Biofuels & Flex Fuels
3. Blow-By &
Exhaust Gas Acid Condensates
4. AdBlue® Urea
5. Coolant
Agenda
2
Vamac® & Viton® Performance in:
1. Engine & Transmission Synthetic Oils
2. Biofuels & Flex Fuels
3. Blow-By &
Exhaust Gas Acid Condensates
4. AdBlue® Urea
5. Coolant
Agenda
3
Auto Powertrain Engine
Seals & Gaskets based on Vamac® & Viton®
Oil Pan Gasket
Cam Cover Gasket
Torsional Vibration
Damper
Parts based on
Vamac®
Rear Engine Seal
Cranck shaft Seal
Parts based on
Viton®
Valve Stem Seal
Cylinder Head
Gasket
Oil Filter Seal
Air Intake Manifold
Gasket
Water Pump Seal
Cylinder O-rings
Parts based on
Vamac® &/or
based on Viton®
Camshaft Seal
Cylinder
(Engine Block)
Cylinder Head
Oil Pan
Cylinder Head Cover (Rocker Cover, Cam Cover)
Oil Filter
4. Rubber Gasket
3. Rubber Gasket
Main Engine Static Rubber Seals & Gaskets
2. Rubber Gasket
1. Rubber Gasket
Additional engine static seals & gaskets :
• Front cover gasket
• Oil filler cap seal
• Oil drain plug
• Grommets
NBR
AEM
ACM
LSR
NBR
HNBR
AEM
ACM
FKM
NBR
AEM
ACM
NBR
HNBR
FKM
More aggressive fluids in the engine and in the engine oil:
- New high temperature synthetic oils (fuel economy, low viscosity)
- Presence of fuel/biofuel in engine oil (GDI engines)
- Higher level of Blow-by and Exhaust Gas acid condensates
-
New opportunities in engine seals for High Performance Elastomers
(FKM, AEM, HT-ACM): Cam Cover, Front Cover, Oil Pan, …
Trends in Engine Seals & Gaskets
•Heat resistance
•Low temperature
•Oil resistance
•Sealing performance
(Compressive Stress Relaxation)
6
Automotive lubricant composition:
• base oils (75% to 85 %) : mineral or semi-
synthetic or FULLY SYNTHETIC
• package of additives content increase
(15% to 25%) : viscosifiers, antiwear,
antioxidants, detergents, corrosion
inhibitors, dispersing agents, anti-
foaming agents, alkalinity, anti-freeze
agents, extreme pressure agents
Automotive Engine Oils
If the synthetic oil can be dealt with, the
additive package can be detrimental to
several elastomers
7
New Engine Oils
Lubricants classified 0W20, 0W30 & 5W30 (fuel economy) & low SAPS* oils
to meet EURO V standards (including diesel particle filter technology)
*last generation lubricants based on Low Sulphated-Ash, Phosphorus and Sulphur technology
New engine oil with Euro V
8
Vamac® - Performance in Engine Oils
recommended by VW Group
Fuel Economy
Low SAPS oils
Fuel
Economy
Standard
VW 502.00 & VW 505.00 VW 503.00 & VW 506.00 VW 504.00 & VW 507.00
9
-5
-3
-1
1
3
5
7
9
11
13
15
Vo
lum
e s
well
(%
)
Castrol® GXL
10W40
Shell® Helix
Plus 5W40
Elf® Excellium
LDX 5W40
Castrol® SLX
Long life II
0W30
Castrol® SLX
Long life III
5W30 (low
SAPS)
Mobil® 1 ESP
Formula 5W30
(low SAPS)
Volume swell after 1 week @ 150°C
(Standard Compounds, 10 phr plasticiser, 70 sh.A)
Vamac® G
Vamac® GLS
-5
-3
-1
1
3
5
7
9
Shell® Helix Plus5W40
Elf® ExcelliumLDX 5W40
Castrol® SLX Longlife II 0W30
Castrol® SLX Longlife III 5W30 (low
SAPS)
Mobil® 1 ESPFormula 5W30 (low
SAPS)
Hard
ne
ss c
han
ge
(p
ts)
Hardness change after 1 week @ 150 °C (Standard Compounds, 10 phr plasticiser, 70 sh.A)
Vamac G Vamac GLS
Low SAPS oils
Vamac® - Performance in Engine Oils
recommended by VW Group
10
-50
-45
-40
-35
-30
-25
-20
-15
-10
-5
0
Shell® Helix Plus5W40
Elf® Excellium LDX5W40
Castrol® SLX Longlife II 0W30
Castrol® SLX Longlife III 5W30 (low
SAPS)
Mobil® 1 ESPFormula 5W30 (low
SAPS)
Elo
ng
ati
on
ch
an
ge
(%
)
Elongation change after 1 week @ 150 °C
(Standard Compounds, 10 phr plasticiser, 70 sh.A)
Vamac G Vamac GLS
Low SAPS oils
Vamac® performance in Engine Oils
recommended by VW group
11
-5
-3
-1
1
3
5
7
9
11
13
15
Fuchs® TitanSuperSyn SL
5W30
Shell® Helix UltraAB 5W30
Fuchs® TitanGT1 5W30 (low
SAPS)
Castrol® SLXLL04 0W30 (low
SAPS)
Mobil® 1 ESPFormula 5W30
(low SAPS)
Vo
lum
e s
we
ll (
%)
Volume swell after 1 week @ 150 °C
(Standard Compounds, 10 phr plasticiser, 70 sh.A)
Vamac G Vamac GLS
BMW Long life 01 BMW Long life 04
Low SAPS oils
Vamac® - Performance in Engine Oils
recommended by BMW group
12
-5
-3
-1
1
3
5
7
9
11
13
15
Elf®ExcelliumLDX 5W40
Fuchs® TitanSuperSyn SL
5W30
Shell® HelixUltra AB 5W30
Fuchs® TitanGT1 5W30(low SAPS)
Elf® SolarisLSX 5W30(low SAPS)
Mobil® 1 ESPFormula 5W30
(low SAPS)
Vo
lum
e sw
ell (
%)
Volume swell after 1 week @ 150 °C (Standard Compounds, 10 phr plasticiser, 70 sh.A)
Vamac G Vamac GLS
MB 229.3 MB 229.31 & MB 229.51
MB 229.5
Low SAPS oils
Vamac® - Performance in Engine Oils
recommended by Daimler group
13
Vamac® - Performance in Engine Oils
recommended by Fiat & Iveco
0
2
4
6
8
10
12
14
16
18
20
Urania® Turbo LD15W40 (Iveco)
Selenia® 20 K 10W40(Fiat)
Selenia® WR 5W40(Fiat)
Urania® FE 5W30(Iveco)
Vo
lum
e s
we
ll (
%)
Volume swell after 6 weeks @ 150 °C (Standard Compounds, 10 phr plasticiser, 70 sh.A)
Vamac G Vamac GLS
Turbo charged or
multivalve engines
Fuel economy for new multijet diesel engines
14
Vamac® performance in engine oils
recommended by PSA group
-5
-3
-1
1
3
5
7
9
11
13
15
Total® QuartzDiesel 7000
10W40
Total® QuartzFuture 9000
5W30
Total® G11077Lube MA3 5W30
Total® QuartzIneo ECS 5W30
(low SAPS)
Total® G03232Lube MA4 5W30
(low SAPS)
Vo
lum
e sw
ell (
%)
Volume swell after 1 week @ 150 °C (Standard Compounds, 10 phr plasticiser, 70 sh.A)
Vamac G Vamac GLS Low SAPS oils
15
Vamac® performance in aggressive
engine oil Total® Lube MA5, 0W20
-50
-40
-30
-20
-10
0
10
20
30
40
50
Volume swell (%) Hardness change (points) Elongation change (%) Absolute Elongation x10(%)
63
-40
17.3
-1
9
-51
14.4
7
1
-31
23.4
0
6
-40
19.4
0
4
-21
30.3
53
-4
36.5
Pro
pe
rtie
s
Vamac® DOTG free Compounds, 50 phr FEF / 10 phr plasticiser, 65 sh.A
Fluid ageing results after 1 week @ 150 °C in Total Lube MA5, 0W20
Vamac® G
Vamac® GLS
Vamac® Ultra IP
Vamac® VMX 3110
Vamac® VMX 3110, 30 phr FEF / 10 phr plast.
Vamac® DP peroxide
• Diamine cured Vamac®
Ultra & peroxide cured
Vamac® DP are the best
options
• Compounsd based on
Vamac® with low carbon
black level has better
retention of properties
• Compounds based on
Vamac® with metal
deactivators can be an
alternative in case of high
level of bivalent metal
ions in lubricants
X 10
16
0
2
4
6
8
10
12
14
16
18
20
Vamac® G/ DOTG Vamac® G/ ACT55 Vamac® GLS/ACT55
Vamac® Ultra IP/ACT55
MX-3110/ ACT55 Vamac® DP/Peroxide
Vo
lum
e Sw
ell,
%
Volume Change after ageing at 150°C in Mobil 1, 0W20
168 504 1008 1512 2016 2520 3024
Vamac® performance in aggressive engine oil
Mobil® 1, 0W20
17
-100%
-80%
-60%
-40%
-20%
0%
0 500 1000 1500 2000 2500 3000 3500
% C
han
ge in
Elo
nga
tio
n
Time (Hours)
Change in Elongation after ageing at 150°C in Mobil 1, 0W20
Vamac® G/ DOTG Vamac® G/ ACT55 Vamac® GLS/ ACT55Vamac® Ultra IP/ ACT55 MX-3110/ ACT55 Vamac® DP/ Peroxide
• Vamac compounds retained > 50% of original properties after 1008h @ 150°C in oil
• Vamac® DP showed the best retention of elongation after ageing in Mobil® 1, 0W20
• Vamac® G & GLS with ACT55 showed the highest elongation loss after oil ageing
Vamac® performance in aggressive engine oil
Mobil® 1, 0W20
18
0
10
20
30
40
50
60
70
80
90
100
0 500 1000 1500 2000 2500 3000 3500
Pe
rce
nt
Re
tain
ed
Se
ali
ng
(%
)
Time (Hours)
Compressive Stress Relaxation after ageing @ 150°C in Mobil 1, 0W20
Vamac G/ DOTG Vamac G/ ACT55 Vamac GLS/ ACT55Vamac Ultra IP/ ACT55 Vamac VMX-3110/ ACT55 Vamac DP/ Peroxide
• Compounds based on Vamac® Ultra IP & Vamac® DP compound showed similar good CSR
properties to Vamac® G/ DOTG compound
• Compoud based on Vamac® GLS with ACT55 showed the lowest CSR values
Vamac® performance in aggressive engine oil
Mobil® 1, 0W20
19
After one week, Vamac® Ultra IP shows more than double force
retention level vs. HT ACM at same hardness level
Vamac® sealing performance in engine oil
According to ISO 3384 -
Method B
Shawbury Wallace Test
Equipment used
Molded pips, 6 mm high &
13 mm diameter
Higher force retention
better sealing performance
0
10
20
30
40
50
60
70
80
90
100
0 50 100 150 200 250 300 350 400
Time (h)
Fo
rce
Re
ten
tio
n (
%)
Vamac® G (78 Sh.A)
Vamac® Ultra IP (79 Sh.A)
Vamac® Ultra IP (61 Sh.A)
HT-ACM (79 Sh. A)
1 WEEK
ACM
new AEM
Compressive Stress Relaxation in synthetic oil (Castrol SLX LL III, 5W30 / 150°C)
20
Vamac® in Fresh and Oxidized IRM-902
-20
-15
-10
-5
0
5
10
15
Vamac® G Vamac®
GLS
Vamac®
HVG
Vamac® DP
Tensile Change (%), 1008 hours,
fresh IRM-902
Tensile Change (%), 1008 hours,
oxidised IRM-902
Elongation Change (%), 1008 hours,
fresh IRM-902
Elongation Change (%), 1008 hours
Vamac® did not show any major negative impact caused by oxidation of IRM-902
IRM902 Fluid ageing @ 150°C
21
-80%
-70%
-60%
-50%
-40%
-30%
-20%
-10%
0%
Viton® ALtype
Viton®GAL200S
Viton®GBL200S
Viton®GF200S
Non Aerated Mobil 1 Trisynthetic 5W30
Aerated Mobil 1 Trisynthetic 5W30
Viton® in Engine Oil with/without Aeration
Elongation change (%) after 1008 h @150°C in Mobil 1 Trisynthetic
Oil Immersion Applications - Which Viton® ?
Degree of Base Resistance required
Engine Oil
GF-S, 1000 hrs
BP Cecilia 20
5W40 engine oil
Su
gg
este
d P
oly
mer
B-651C, 500 hrs
BP Cecilia 20
5W40 engine oil
B-651C, 500 hrs
Shell Helix Ultra
10W40 engine oil
x
Viton®
B-651C
un-aged
Engine is aerated – which helps neutralize the amine based additive
packages so standard Viton grades tend to work in the engine
23
Viton® resistance to lubricants
FKM Dipolymer: A-types % Fluorine
-CF2-CF- -CH2-CF2- 66%
|
CF3
FKM Terpolymer: (G)AL-, (G)B-, (G)F-types
-CF2 -CF- -CH2 -CF2 - -CF2 -CF2 - 66% to 70%
|
CF3
HFP-grades
H2
{Base}
… but is also vulnerable to attack by bases
causing further X-linking, hardening,
drop of properties & potential seal failure.
Acidic H in electron withdrawing environment of vicinal F-atoms
allowing X-linking with bisamines or bisphenols
24
More aggressive fluids in the engine and in the engine oil:
- New high temperature synthetic oils (fuel economy, low viscosity)
- Presence of fuel/biofuel in engine oil (GDI engines)
- Higher level of Blow-by and Exhaust Gas acid condensates
-
New opportunities in engine seals for High Performance Elastomers
(FKM, AEM, HT-ACM): Cam Cover, Front Cover, Oil Pan, …
Trends in Engine Seals & Gaskets
•Heat resistance
•Low temperature
•Oil resistance
•Sealing performance
(Compressive Stress Relaxation)
26
Mixture Engine Oil 15W40 / Diesel + Biodiesel
Vamac® Volume Swell
•Increase in volume with
switch from test tube to
pressure vessel
•Further increase in
volume with addition of
diesel or biodiesel RME
•No difference between
conventional diesel &
biodiesel B20
Volume IncreaseVamac® G
gasket
Vamac® GLS
gasket
VMX 3038
turbocharger
hose
15W40 -- Test Tube
0
1 14 5 23
3 15 7 24
6 13 5 22
15W40 -- Pressure Vessel
0
1 17 9 27
3 19 10 29
6 18 9 27
15W40 -- with 7% B20 (Ford)
0
1 22 12 33
3 21 11 31
6 22 12 32
15W40 -- with 7% Diesel
0
1 22 13 33
3 20 11 30
6 22 12 31
Fluid ageing tests : 1, 3 & 6 weeks @ 150°C
Engine Oil - 15W40 Valvoline "Premium Blue"
Diesel Fuel - local supply in Akron, OH (USA)
RME Biodiesel fuel - B20 from Haltermann’s in Texas (USA)
27
Mixture Engine Oil 15W40 / Diesel + Biodiesel
Vamac® : Elongation & Elongation Change
Change in control test going
from test tube to pressure
vessel appears to have
bigger effect than addition of
diesel or biodiesel
Vamac Ultra grades
(VMX3038) deliver the best
mechanical properties after
long term fluid ageing
Percent ElongationVamac® G
gasket
Vamac® GLS
gasket
VMX 3038
turbocharger
hose
V
i
t
o
n
Vamac® G
gasket
Vamac® GLS
gasket
VMX 3038
turbocharger
hose
1 2 3 1 2 3
15W40 -- Test Tube
0 269 277 431 0% 0% 0%
1 209 192 379 -22% -31% -12%
3 190 161 340 -29% -42% -21%
6 167 129 288 -38% -53% -33%
15W40 -- Pressure Vessel
0 269 277 431 0% 0% 0%
1 200 190 357 -26% -31% -17%
3 168 135 253 -38% -51% -41%
6 114 101 259 -57% -63% -40%
15W40 -- with 7% B20 (Ford)
0 269 277 431 0% 0% 0%
1 197 184 323 -27% -33% -25%
3 172 129 295 -36% -53% -32%
6 118 83 250 -56% -70% -42%
15W40 -- with 7% Diesel
0 269 277 431 0% 0% 0%
1 194 179 343 -28% -36% -20%
3 142 130 301 -47% -53% -30%
6 129 105 242 -52% -62% -44%
% change from originalAbsolute Values
Fluid ageing tests : 1, 3 & 6 weeks @ 150°C
28
New test specifications include elastomer testing in Oil / Fuel blends, very often in a
90% / 10% blending ratio. Fuels comprise biofuels like Ethanol.
AEM shows advantages over ACM in Compressive Stress Relaxation Tests
in Oil / Fuel blends.
Vamac® sealing performance in Oil / Fuel Blends
Vamac® G
Vamac® GLS
‚HT-ACM‘
29
Test Fluid
in Cup
Permeant
Collection
Cup
Compound
Sheet
Purge Gas
Vent
Collect
and
Analyze
via GC
Method used
to measure
permeation of
oil and gas
mixtures
through
elastomer
compounds
40°C temperature
Permeation Test Setup
Permeation Values for different elastomers in blend of
98% Motorcraft oil 0W30 with 2% CE10
Measured at 40°C
Units are in g / mm thickness / m2 / day
Permeation: Comparison AEM, ACM, HNBR
CE10 :
• 45% toluene
• 45% isooctane
• 10% ethanol
AEM ACM HNBR
Ethanol 7.58 13.51 6.59
Octane 0.13 0.44 0.20
Toluene 3.63 10.59 3.67
Total 11.35 24.54 10.47
w/o ethanol 3.76 11.03 3.88
31
Transmission System
New transmission systems with more gears (e.q. VW 7-speed
transmission) in order to improve driving comfort and fuel efficiency
• Increasing market -> more parts
• Transmission Seals (eg bonded
piston seals) at abt. 75-80 Shore A
• Resistance of rubbers to new ATFs
(like Dexron® VI, Pentosin FFL serie)
32
DQ250 DQ200
Example: VW DCT - DSG (Direct Shift Gearbox)
The 6-speed wet DSG is DQ250 (2003, BorgWarner) which is for torque
lower than 350 Nm.
The 7-speed dry DSG is DQ200 (2008, LUK) which is for torque lower
than 250 Nm. DQ200 is compact & light and is designed for smaller
and economical engines. Roughly use 6% less fuel than MT and 20%
than AT. (Volkswagen Automatic Transmission Dalian Plant)
34
0
5
10
15
20
25
30
Vo
lum
e S
wel
l in
%
P ento sin®
C H F 11S
T o tal®
F luide A T X
D exro n II
P etro
C anada
GM
D exro n® III
R D L 2746
Esso ®
A T F LT
71141
C astro ® l
SA F XO
75W90
Esso ®
Gear o il
B V 75W80
P etro -
C anada
D exro n® VI
R D L 3434
C astro l®
T ransmax
Z 75W90
T o tal®
T ranself
Synthese
F E75W90
M o bilube®
P T X
75W90
Volume Swell after 6 weeks @ 150°C
(Standard Vamac® compounds, 10 phr plasticiser)
Vamac® G
Vamac® GLS
Traditional fluids New fluids
Vamac® - Performance in Transmission Fluids
35
Vamac® performance vs other elastomers in ATF
• HNBR has higher property loss than Vamac after ageing in ATF Dexron ® VI
• Swell comparable between Vamac VMX3110 (or GLS) & HNBR with 34% ACN
Compounds # HNBR #1 HNBR #2 Vamac Ultra IP Vamac VMX3110
ACN % : 34% 43% - -
Curing agent Peroxide Peroxide Diamine Diamine
75 phr FEF N550 Yes Yes Yes Yes
5 phr plasticiser Yes Yes Yes Yes
Tg by DSC (°C) -25 -19 -33 -28
Comp. Set ISO 815 after 70h @ 150°C (%)
42 43 24 25
Fluid ageing Petro Canada Dexron ® VI RDL3434, 1000 h @ 150 °C Hardness (sh.A) 82 91 79 87
Delta Hd, in Shore-A + 0 + 6 -6 1
TS (MPa ) 17.0 15.6 20.8 19.6
Delta TS in % - 30 - 37 0 -4
EaB (%) 86 41 122 96
Delta EaB (%) - 59 - 83 - 40 -50
Volume Swell (% ) + 7 + 2 +15 +8
•
Ranking: Vamac® Ultra IP > Vamac® G >> HT ACM
Vamac® sealing performance in Transmission Fluid
Acc. To ISO 3384
Shawbury Wallace
Test Equipment
Cylindrical
Specimen, 6 mm
high, 13 mm
diameter
OIL AGING (Dexron® VI / 150°C)
0
10
20
30
40
50
60
70
80
90
100
0 100 200 300 400 500 600 700 800 900
Time (h)
Fo
rce
Rete
nti
on
(%
)
Vamac® G (78 Shore A)
Ultra IP (79 Shore A)
Ultra IP (61 Shore A)
HT-ACM (79 Shore A)
38
Oil Immersion Applications - Which Viton® ?
Degree of Base Resistance required
Engine Axle &
Wheel bearing
Gear box &
Transmission
ETP600-S, 1000 hrs
Mobile Axle lube GFLT-S, ETP600S
Dexron III ATF
GF-S, 1000 hrs
BP Cecilia 20
5W40 engine oil
GF-S, 1000 hrs
Dexron III ATF GF-S, 1000 hrs
Mobile Axle lube
Su
gg
este
d P
oly
mer
B-651C, 500 hrs
BP Cecilia 20
5W40 engine oil
B-651C, 500 hrs
Shell Helix Ultra
10W40 engine oil
x
Viton®
B-651C
un-aged
B-651C, 500 hrs
Dexron III ATF
B-651C, 1000 hrs
Mobile Axle lube
39
Viton® in Automatic Transmission Fluids
0
20
40
60
80
100
120
0 500 1000 1500 2000 2500 3000 3500 Hours
Pe
rce
nt
reta
ine
d E
lon
g.
(%)
GLT-S
GF-S
GBL-S
A-401C
0
20
40
60
80
100
120
0 500 1000 1500 2000 2500 3000 3500
Pe
rce
nt
reta
ine
d E
lon
g.
(%)
GLT-S
GF-S
B-651C
GBL-S
A-401C
Ageing in ATF Petro Canada Dexron VI at 150°C
Ageing in ATF Petro Canada Dexron III at 150°C
Hours
40
-70%
-60%
-50%
-40%
-30%
-20%
-10%
0%
10%
20%
30%
0 500 1000 1500 2000
% C
ha
ng
e
Time (Hours)
Elongation change after Aging in Dexron VI @ 150°C ( With and Without Aeration)
A361C A361C (Aerated)B651C B651C (Aerated)GF600S GF600S (Aerated)GFLT600S GFLT600S (Aerated)
A361
B651C
GF600S
GFLT600S
Viton® in Non Aerated & Aerated Automatic
Transmission Fluid
41
Viton® resistance to lubricants (continued)
FKM Dipolymer: A-types) % Fluorine
-CF2-CF- -CH2-CF2- 66%
|
CF3
FKM Terpolymer: (G)AL-, (G)B-, (G)F-types
-CF2 -CF- -CH2 -CF2 - -CF2 -CF2 - 66 to 70%
|
CF3
HFP-grades
acidic H in electron withdrawing environment of vicinal F-atoms
allowing X-linking with bisamines or bisphenols
H2
FKM GLT-S /GFLT-S
-CF2-CF - -CH2 -CF2- -CF2-CF2- 64.5 to 67 %
|
O
CF3
PMVE-grades
*H/H: degree of acidity
Reduction of acidity
(PO-cure mandatory)
42
Vamac® & Viton® performance to :
1. Engine & Transmission Synthetic Oils
2. Biofuels & Flex Fuels
3. Blow-By &
Exhaust Gas Acid Condensates
4. AdBlue® Urea
5. Coolant
Agenda
43
Fuel
Regulator
Fuel
Injection
Rail
Fuel
Injector
Fuel
Filter
Charcoal
Canister
Purge Valve
Ventilation Line
Feed Line
Return Line
In Tank Pump
Filler Neck
Ventilation Line
Ventilation Line
Roll Over Valve
Fuel Tank
Automotive Fuel System
44
• Fuel Filter Seal
• Fuel Injector O-ring
• Fuel Rail Seal
• Quick Connect O-ring
• Filler Neck Hose
• Fuel Vapour Line
• Fuel Return Line
• Fuel Tank Valve Seal
• Fuel Sender Seal
• Fuel Cap Seal
Viton® Fuel Applications
45
Gasket between AIM and
Electronic Throttle Valve
Control (temperature : 60C)
Gasket between AIM and
Flange (temperature : 120C)
Gasket between AIM and
Exhaust Gas Recirculation
(temperature < 250C)
3 different type of AIM Gaskets:
Air Intake Manifold Gasket
New Environmental Legislations
Reduced CO2 emissions drives the adoption of bio-fuels
Side benefit in reduced engine wear (inherent lubricity of FAME’s)
Different types of oxygen-containing fuels & biodiesel
Ethanol / Methanol / Butanol
Oxygenates : MTBE or ETBE
Biodiesel (B5 to B20)
Source: “Bilan énergétiques et gaz à effet de serre des filières de production des
biocarburants” Price Waterhouse Coopers / Institut Français du Pétrole
0
20
40
60
80
Gra
m o
f C
O2 / M
J
- 70% - 60%
47
Material Performance to Fuel/Biofuel
6500
1100
635
85
35
12
3
0.5
0.2
0.05
0.03
0.01 0.1 1 10 100 1000 10000
Silicone (VMQ)
NBR / HNBR
Fluorosilicone (FVMQ)
Nylon 12
Viton® A
Viton® B
Viton® GF
THV 500
Tefzel® ETFE
Teflon® PTFE
Teflon® FEP
g-mm/m2/d
(Log chart)
higher fluorine =
lower permeation
Permeation rate
Fuel Permeation: Material Choices for Reducing Permeation Losses
fuel system elastomer films to M15 fuel @ 23°C
48
Fuel and Permeation Resistance of Fluoroelastomers to Methanol & Ethanol Blends
Environmental factors driving current fuel system designs
Need to lower hydrocarbon emissions which includes the use of oxygenates like ethanol and methanol
Need to reduce dependence on fossil fuels and increase use of alternative renewable fuel sources like ethanol and methanol
Ethanol is used in the US, Brazil
Methanol is used in China
Drive towards global automotive platforms
Development of global specifications for fuel systems
Elastomers in fuel systems must perform in global flex fuels including ethanol and methanol fuel blends.
49
Peak permeation at ~25% Ethanol in Fuel C
Bioethanol Resistance of Viton®
Permeation Rate Permeation of Fuel C / Ethanol Blends
1008 hours at 40°C
0
20
40
60
80
100
120
GLT-S A-601C GBLT-S GFLT-S B-601C F-605C GF-S
fluorine (wt %)
Perm
rate
(g
-mm
/m²/
day)
Fuel C
CE-10
CE-25
CE-50
CE-85
E-100
low high
51
Bioethanol Resistance of Viton®
Volume Swell Volume Change in Bioethanol & fuel blends
1008 hours at 40°C (weekly fuel change)
0
5
10
15
20
25
GLT-
600S
A-601C GBLT-
600S
B-601C GFLT-
600S
VTR-
9209
F-605C GF-
600S
fluorine (wt %)
Vo
lum
e C
ha
ng
e,
%
Fuel C
CE-10
CE-25
CE-50
CE-85
E-100
low high
52
Bioethanol Resistance of Viton®
Volume Swell – Temperature Dependence
Effect of Temperature
Volume Change, CE-10
0
5
10
15
20
25
30
35
GLT-
600S
A-601C GBLT-
600S
B-601C GFLT-
600S
VTR-
9209
F-605C GF-
600S
fluorine (wt %)
Vo
lum
e C
han
ge,
%
168 hours @ 20°C
168 hours @ 40°C
168 hours @ 60°C
168 hours @ 80°C
low high 53
Biobutanol Resistance of Viton®
Volume Swell
Volume Change
1-Butanol at 40°C (weekly fuel change)
0
2
4
6
8
10
GLT-
600S
A-601C GBLT-
600S
B-601C GFLT-
600S
VTR-
9209
F-605C GF-
600S
fluorine (wt %)
Vo
lum
e C
ha
ng
e, %
168 hours
336 hours
504 hours
672 hours
1008 hours
low high
55
Volume Change
Fuel C / 1-Butanol (80/20) at 40°C (weekly fuel change)
0
5
10
15
20
25
GLT-
600S
A-601C GBLT-
600S
B-601C GFLT-
600S
VTR-
9209
F-605C GF-
600S
fluorine (wt %)
Vo
lum
e C
ha
ng
e, %
168 hours
336 hours
504 hours
672 hours
1008 hours
low high
Biobutanol Resistance of Viton®
Volume Swell
56
Performance of Viton®
with Different Bioalcohols Volume Change in Bio-alcohols & fuel blends
168 hours at 40°C
0
3
6
9
12
15
18
21
24
27
GLT-
600S
A-601C GBLT-
600S
B-601C GFLT-
600S
VTR-
9209
F-605C GF-
600S
fluorine (wt %)
Vo
lum
e C
ha
ng
e, %
ButanolEthanolFuel CFuel C/Butanol (80/20)Fuel C/Ethanol (75/25)
low high
57
What is Biodiesel ?
Don’t be confused by the name…
Unlike Bioethanol and Biobutanol which are chemically identical to their petroleum derived counterparts,
Biodiesel and Petrodiesel are chemically different and have significantly differing effects on elastomers
Biodiesel is an ester based fluid
Petroleum Diesel is a hydrocarbon fluid
59
Specifications
Similar but different specifications in U.S. and European Union Europe DIN EN 14214
US ASTM D6751
ASTM spec is broader (probably to allow for wider range of starting oils)
Both have
Water < 500ppm
Acid number < 0.5 mg KOH/g
Na + K < 5ppm
60
Volume Change
"Fresh" B100 RME at 125°C
0
20
40
60
80
100
120
GBL-S Ca(OH)2 A401C
Vo
lum
e C
han
ge, %
"Fresh" RME 336 Hrs
"Fresh" RME 1008 Hrs
"Old" RME 336 Hrs
"Old" RME 1008 Hrs
“Fresh” vs. “Old” RME
61
•Pure & Fresh Biodiesel is not aggressive to FKM compounds
•High Swell of standard FKM is caused by a seconder order effect:
- Contamination (water, residual catalyst, …)
- Degradation products (acids, aldehydes, …)
Viton® performance in “pure & fresh” Biodiesel
62
fuel change at test interval
0
20
40
60
80
100
120
"NMO" GBL-S "NMO" GF-S GBL-S
Ca(OH)2
A401C F605C
Vo
lum
e C
han
ge, %
336 hours
672 hours
1008 hours
1512 hours
2016 hours
3024 hours
Wet = addition of 0.5% distilled water to RME
"NMO"= No Metal Oxide formulation
Effect of Water Aged in “wet” B100 RME at 125°C – Volume change (%)
63
Effect of Water on Compounds
Based on Viton®
64
Volume Change
"wet" B20 RME at 125°C ( fuel change at test interval)
0
10
20
30
40
50
60
70
80
GBL-S (NMO) GF-S (NMO) GBL-S
Ca(OH)2
A401C F605C
Vo
lum
e C
han
ge,
%
336 hours
672 hours
1008 hours
1512 hours
2016 hours
3024 hours
(wet = addition of 0.5% water to RME)
64
64
Volume Change
"wet" B5 RME at 125°C ( fuel change at test interval)
0
5
10
15
20
25
GBL-S (NMO) GF-S (NMO) GBL-S
Ca(OH)2
A401C F605C
Vo
lum
e C
han
ge,
%
336 hours
672 hours
1008 hours
2016 hours
3024 hours
(wet = addition of 0.5% water to RME)
65
Effect of Water on Compounds
Based on Viton®
65
Effect of Metal Oxide Level
Volume Change
"wet" B100 RME at 125 °C ( fuel change at test interval)
0
5
10
15
20
25
30
35
GBL-S NMO GBL-S (Ca(OH)2-1.5) GBL-S (Ca(OH)2-3.0)
Vo
lum
e C
han
ge,
%
336 hours
672 hours
1008 hours
1512 hours
2016 hours
3024 hours
(wet = addition of 0.5% water to RME)
66
66
“Best-in-Class” for Aggressive BDF Volume Change
"wet" RME - 3032 hours at 125°C ("best-in-class")
0
1
2
3
4
5
6
7
8
9
10
B5 RME B20 RME B100 RME
Vo
lum
e C
han
ge,
%
GBL-S (NMO)
GF-S (NMO)
(wet = addition of 0.5% water to RME)
67
67
R M E + H 2 O R C O O H + C H 3 O H [ H + o r O H - C a t a l y z e d ]
2 R C O O H + M O [ M 2 ] [ R C O O - ] 2
M F 2 + 2 R C O O H + d e h y d r o f l u o r i n a t e d F K M
F K M
2 R C O O H + M ( O H ) 2 [ M + 2 ] [ R C O O - ] 2 + H 2 O
M F 2 + 2 R C O O H + d e h y d r o f l u o r i n a t e d F K M
F K M
1 .
2 .
3 .
Degradation pattern in wet RME
Carboxylic acid is formed by the hydrolysis of FAME. Carboxylic acid moves into FKM compound
and reacts with metal oxide/hydroxide forming metal carboxylates . Metal carboxylate causes
dehydrofluorination and double bond formation in the polymer chain.
68
Biodiesel Oxidation
Increases with the level of unsaturation (Iodine No)
Initial oxidative attack at allylic hydrogens in a chain reaction
Formation of hydroperoxides which decompose to aldehydes,
alcohols and shorter chain carboxylic acids
J. A. Waynick et. al. Characterization of Biodiesel Oxidation
and Oxidation Products, Southwest Research Institute Project
08-10721, August 2005
FAME shelf life reported as ~6 months if stored properly
Oxidation begins immediately without A/O protection
Oxidative degradation of FAME’s
69
dehydrofluorination
Peroxides from oxidation of FAME react with double bonds in the
polymer chain causing chain scission via haloform cleavage .
MF2 + 2 RCOOH CF3
(R-COO-)2M2+
2+M(-OOC-R)2
(R-COO-)2M2+ (R-COO-)2M
2+
(R-COO-)2M2+
MF2 + 2 RCOOH CF3
(R-COO-)2M2+
(R-COO-)2M2+
O
R O
MF2 + 2 RCOOH CF3
(R-COO-)2M2+
(R-COO-)2M2+
O
MF2 + 2 RCOOH CF3
(R-COO-)2M2+
(R-COO-)2M2+
O O-
H
- ROH
HO-
ROOH
Proposed mechanism
70
Different height peak was
observed at -53.5ppm、
-59ppm
Uncured GBL
NMO
Cured GBL
NMO
Uncured GBL
Ca(OH)2
Cured GBL
Ca(OH)2
After immersion in RME, Ca(OH)2 GBL-S showes higher volume swell than NMO GBL-S.
Significantly more double bonds were formed in Ca(OH)2 GBL-S after immersion in RME
compared to NMO GBL-S.
71
Long term 40°C study 40°C is warm but not unreasonably high for storage and transport
6000 hours
B100 and B20 RME Fuels with added water and acid Acid and water close to as-made spec limits (ASTM D6571(B100) and D7467 (B5 – B20 blends)
• B100 acidified to TAN 1.5 (vs. 0.5 spec)
• B20 acidified to TAN of 0.3 and 0.6 (vs. 0.3 spec)
• Water at 800 ppm (for B20 0.3 TAN) or 1000 ppm (vs. 500 ppm separate phase water spec)
• NB: acid and water levels don’t consider starting levels in RME
Fuel changed every 504 hours (3 weeks)
Compounds of A-401C, GBL-S (NMO, Ca(OH)2 and ZnO)
What About Lower Temperature
Biodiesel Resistance?
72
B20 (TAN 0.3) at 40°C Results
B20 near specification limits for acid and water is
aggressive toward metal oxide containing
compounds even at 40°C
Swell of Various Viton® Compounds in Wet, Acidified B20 at 40°C(initial TAN of 0.3 with 800 ppm water)
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
0 1000 2000 3000 4000 5000 6000 7000
Time at 40°C [hrs]
Vo
lum
e S
we
ll [
%]
A401C
GBL-S NMO
GBL-S CaOH
GBL-S ZnO
73
• Biodiesel blends such as B20 appear to be more aggressive at low
temperatures toward metal oxide containing fluoroelastomers than
B100 when water and acid are present.
• Biodiesel blends such as B20 are aggressive toward metal oxide
containing fluoroelastomers when at or near the acid and water limits in
ASTM D7467 even at relatively modest temperatures.
• Metal oxide free formulations continue to show robust behavior toward
biodiesel and biodiesel blends independent of acid and water content
• The recommendation to use specially formulated peroxide cured
compounds (NMO compounds) for critical applications and for
applications where the cost and consequence of failure are high should
not be limited to high temperature applications.
Tentative Conclusions
74
Historic Data on FKM in Flex Fuels
Historic data exists on:
FKM in various fuel-oxygenate blends at R.T.
FKM in various fuel-ethanol blends at elevated temperatures
This data indicates that fuel-methanol blends are more aggressive to FKM than the current fuel-ethanol blends which are available in the US.
75
Test Conditions
Fuels Fuel C
CM15A (15% Aggressive Methanol/ 85% Fuel C)
CM30A (30% Aggressive Methanol/ 70% Fuel C)
CM50A (50% Aggressive Methanol/ 50% Fuel C)
CM85A (85% Aggressive Methanol/ 15% Fuel C) Aggressive Methanol
Formula for Ford Aggressive Methanol
995.0 mL anhydrous methanol
5.0 mL Aggressive water
0.028 mL formic acid
Aggressive water:
1.0 liter of distilled water
0.990 g NaCl (600 ppm Cl
0.888 g Na2SO4 (600 ppm SO4)
0.828 g NaHCO3 (600 ppm HCO3)
76
Test time and temperature Immersion – 336 Hours @ 60°C
Permeation – 672 Hours @ 40°C
Long-term immersion (APA polymers only)
5000 Hours @ 60°C in CM15A
Fuel changed weekly
Samples tested at 168, 672, 2000, 3000, 4000 and 5000 Hours
Sample after 5000 Hours dried out for 4 Hours @ 100°C
Test Conditions
77
Original Physical Properties of
FKM Compounds
*
* : withdrawn grade – shown for academic purpose
FKM
A401C
FKM
B601C FKM F605C
FKM
GF600S
FKM
GLT600S
FKM
GBLT600S
FKM
GFLT600S
Physical Properties @ R.T
50% Modulus [MPa] 3.2 3.0 2.9 2.6 1.9 2.0 2.2
100% Modulus [MPa] 6.4 6.0 6.0 6.7 4.4 5.1 6.7
Tensile @ Break [MPa] 13.9 14.8 15.3 19.6 17.4 16.7 16.9
Elongation @ Break [%] 214 249 274 258 260 224 199
Hardness, Shore A [Pts] 78 75 76 75 68 69 71
Compression Set, O-Ring
168 Hours @ 150°C, % 8 12 18 11 10 11 9
Low Temperature
Tg by MDSC, °C -16.3 -14.1 -8.1 -5.3 -31.7 -27.0 -25.3
TR-10, °C -16 -13 -8 -4 -31 -27 -25
Static O-Ring Test, °C -32 -29 -23 -20 -48 -44 -41
Test Specimens Cured: 5 Minutes @ 180°C
Bisphenol-cured Grades Postcured: 16 Hours @ 232°C
Peroxide-cured Grades Postcured: 4 Hours @ 232°C
Physical Properties
78
78
Fuel Immersion – Tensile Loss
336 Hours @ 60°C
-80%
-70%
-60%
-50%
-40%
-30%
-20%
-10%
0%
FKM
A401C
FKM
B601C
FKM F605C FKM
GF600S
FKM
GLT600S
FKM
GBLT600S
FKM
GFLT600S
Perc
en
t L
oss in
Ten
sile
Fuel C
CM15A
CM30A
CM50A
CM85A
Methanol
79
79
Fuel Immersion – Elongation Loss
336 Hours @ 60°C
-60%
-50%
-40%
-30%
-20%
-10%
0%
10%
20%
30%
Viton® A401C Viton® B601C Viton® F605C Viton® GF600S Viton®
GLT600S
Viton®
GBLT600S
Viton®
GFLT600S
Perc
en
t C
han
ge in
Elo
ng
ati
on
Fuel C
CM15A
CM30A
CM15A
CM85A
Methanol
80
Fuel Immersion – Volume Change
336 Hours @ 60°C
0
10
20
30
40
50
60
70
FKM A401C FKM B601C FKM F605C FKM
GF600S
FKM
GLT600S
FKM
GBLT600S
FKM
GFLT600S
Perc
en
t V
olu
me C
han
ge
Fuel C
CM15A
CM30A
CM50A
CM85A
Methanol
81
81
Permeation Rate @ 40°C
(units, g-mm/m2/day; tested for 672 hours)
0
50
100
150
200
250
300
350
400
FKM A401C FKM B601C FKM F605C FKM
GF600S
FKM
GLT600S
FKM
GBLT600S
FKM
GFLT600S
Perm
eati
on
, g
-mm
/m2/d
ay
Fuel C
CM15A
CM30A
CM50A
CM85A
Methanol
82
82
Swell & Permeation – Normalized Values
0
2
4
6
8
10
12
14
16
Fuel C
CE 10
CE 25
CE 50
CE 85
Ethanol
A-401C GLT-600S Swell Swell Permeation Permeation
• Strong dependance of permeation on monomers types – HFP vs. PMVE
• Roughly 100 % higher permeation for PMVE (low temperature) grades
• About 10 % more swell with GLT-600S
1 1
EtOH containing fuels
+ 100
%
83
83
Swell & Permeation – Normalized Values
0
5
10
15
20
25
30
35
40
45
50
A-401C GLT-600S
Fuel C
CM 15A
CM 30A
CM 50A
CM 85A
Methanol
Swell Swell Permeation Permeation
1 1
• Strong dependance of permeation on monomers types – HFP vs. PMVE
• Roughly 50 % more swell with PMVE (low temperature) grades
• About 10 % more swell with GLT-600S
MeOH containing fuels
+ 50 %
84
84
Low Temperature Properties
Static sealing possible at about 15°C below polymer Tg
Conditioning in fuel plasticizes the seal and lowers sealing temperature
e.g. GLT-S seals to :
about –45°C (dry)
about –48°C (conditioned in unleaded fuel)
about –54°C (conditioned in Fuel C)
-60
-50
-40
-30
-20
-10
0
-35 -30 -25 -20 -15 -10 -5 0
TR-10 (°C)
Lo
w t
em
pera
ture
me
as
ure
me
nts
(°
C)
GLT-S
GFLT-S
A B
GF-S Tg (DSC,
inflection)
Sealing — soaked in fuel C Sealing — soaked in unleaded fuel
Sealing — dry O-ring
85
85
Low Temperature Properties
- 29.5
- 34.7
- 42.7
- 56.9
- 36.6 - 42.0
- 51.8
- 62.3
- 38.0 - 42.4
- 51.2
- 63.2 -70.0
-60.0
-50.0
-40.0
-30.0
-20.0
-10.0
0.0
Initial, Unaged in
fluid
Aged 22 hrs in
E100 at 23°C
Aged 22 hrs in E22
at 23°C
Aged 72 hrs in E22
at 60°C
B600 - MT
AL600 - MT
AL600 - green
°C
Renault, Fuel Injector O-ring, 19 % compression level
Tg post cured compounds
86
86
Fuel Immersion – Tensile Loss
5000 Hours @ 60 °C in CM15A
-70%
-60%
-50%
-40%
-30%
-20%
-10%
0%
0 1000 2000 3000 4000 5000 6000
Hours
Perc
en
t C
han
ge
FKM GF600S FKM GLT600S FKM GBLT600S FKM GFLT600S
Dry Out Data
87
87
Fuel Immersion – Elongation Loss
5000 Hours @ 60°C in CM15A
-50%
-40%
-30%
-20%
-10%
0%
10%
0 1000 2000 3000 4000 5000 6000
Hours
Perc
en
t C
han
ge
FKM GF600S FKM GLT600S FKM GBLT600S FKM GFLT600S
Dry Out Data
88
Fuel Immersion – Volume Swell
5000 Hours @ 60°C in CM15A
0
5
10
15
20
25
30
35
40
45
FKM GF600S FKM GLT600S FKM GBLT600S FKM GFLT600S
Vo
lum
e C
han
ge, %
168 hr 672 hr 2000 hr 3000 hr 4000 hr 5000 hr 5000 hr - Dryout
89
89
Results of Vamac® in FAM-B & in Biodiesel
*Significant swell and property loss in gasoline *After redrying, properties go back to original excellent value *Swell can be reduced only to a limited extent with Vamac® GLS & VMX 3110
*2% and 5% blends of biodiesel fuels
are compatible with Vamac® G
*For the 20% blend use of Vamac® GLS
is appropriate
Vamac® volume swell after 1 week @ 23°C
in Fuel/RME Biodiesel
0
20
40
60
80
100
120
0 10 20 30 40 50 60 70 80 90 100
% RME in the blend Fuel #2 + RME
% V
olu
me S
well
.
G standard
G/GLS (50/50) standard
GLS standard
90
Vamac® & Viton® performance to :
1. Engine & Transmission Synthetic Oils
2. Biofuels & Flex Fuels
3. Blow-By &
Exhaust Gas Acid Condensates
4. AdBlue® Urea
5. Coolant
Agenda
91
92
Blow By Gas is a leakage flow between the piston and the cyclinder wall
originated through the pressure difference between combustion chamber
and the crankcase. Blow By Gas accumulates with oil & fuel particles.
In the past, Blow By Gas was released into the
environment. Nowadays only closed crankcase
ventilation systems are allowed.
Blow By Gas composition varies and depends on :
*engine types, fuel or diesel engine (fuel more critical)
*engine performance and management
*driving style (speed, r.p.m, number of cold starts)
*design of ventilation (dead areas, air volume flow)
Blow By Gas Origin
92
Why Vamac® for Blow-By Applications ? ECO is the polymer that was often used in PCV tubes. Problems of ECO:
- Lead was used as stabilizer
- Poor heat resistance or scorch issue with ECO lead free
- Acid resistance limited
0.0%
20.0%
40.0%
60.0%
80.0%
100.0%
120.0%
1
Rete
nti
on
of
Elo
ng
ati
on
, %
Vamac® G
Vamac® GLS
ECO ( Lead-Free )
0
20
40
60
80
100
120
140
1
Vo
lum
e S
we
ll,
%
V a m a c ® G
V a m a c ® G L S
E C O ( L e a d -F re e )
Vamac® G Vamac® G LS
EC O
ECO & Vamac® after 1 week @ 90°C
Swell in Blow-By condensate from Ford
ECO & Vamac® after 1 week @ 90°C
Elongation Retention in Ford‘s Acid Condensate
Ford acid condensate chemical composition:
14.0 ml Methanoic ( Formic ) Acid 11.0 ml Nitric Acid
15.0 ml Ethanoic ( acetic ) Acid 1.0 ml Hydrochloric Acid
1.0 ml Sulphuric Acid 958.0 ml Distilled Water
93
Blow-By Resistance, BMW Condensates 1 & 2
BMW Condensate I
Component Weight-%
Naphthalene 1
FAM-A (DIN 51604-1) 44,5
Cecilia 20 44,5
Formaldehyde-10 *) 10
*) stabilized with 10 % methanol
Condensates were specified in 2001, new condensates currently in specification phase.
New condensates may have lower fuel content (C1) and might be lower in Formaldehyde.
Acid condensates in general expected to be lower in pH, and therfore much more damaging.
In Diesel engines, Blow-By acids are reinforced by additional Exhaust Gas condensate acids.
BMW Condensate II
Component Weight-%
Formaldehyde-10 *) 10
Deionized water 89,7
HNO3 (65%) 0,18
Formic Acid (98-100%) 0,06
Acetic Acid (96%) 0,06
Source: ElringKlinger, GAK Paper, 2006 94
Blow-By Resistance, BMW Condensate 1 (fuel/oil) Autoclave, 72 h @ 85 °C
Source: ElringKlinger, GAK Paper, 2006
HNBR 1 HNBR 2 HNBR 3 HNBR 4 HNBR 5
AEM 60
ShA
ACM 60
ShA
ACN content 49 43 36 25 17 GLS ?
dHd (pts) -23 -22 -25 -23 -21 -17 -24
TS original 23,3 22,6 21 20,7 16,6 11,1 9,3
TS after immersion 13,1 13,3 9,5 6,6 4,9 5,3 3,8
d TS -44 -41,2 -54,7 -68,4 -70,2 -51,7 -32,8
EaB original 461 481 472 403 314 306 240
EaB after immersion 339 350 281 164 129 135 139
d EaB -26,4 -27,3 -40,4 -59,4 -58,8 -56 -42
Volume Swell (%) 46 51 60 67 76 28 38
-Volume swell increases as ACN content decreases, ACM and AEM clearly better in terms of
volume swell
- TS and EaB change high for HNBR at low ACN content, however absolute TS and EaB after
immersion are still higher compared to ACM or AEM.
- HNBR at ACN content >40% show good retention of properties
95
95
BMW Condensate 2 (aqueous acid) Autoclave, 72 h @ 85 °C
Source: ElringKlinger, GAK Paper, 2006
-Volume swell increases as ACN content increases, ACM better than all HNBR, Vamac® outstanding
- TS and EaB change high for all HNBR grades
- Vamac clearly a class better than all other polymers, even though very likely Vamac® GLS (high
ester content) is used for this reference compound.
HNBR 1 HNBR 2 HNBR 3 HNBR 4 HNBR 5 AEM 60 ShA ACM 60 ShA
ACN content 49 43 36 25 17 GLS ?
dHd (pts) -12 -15 -12 -9 -6 -2 -12
TS original 23,3 22,6 21 20,7 16,6 11,1 9,3
TS after immersion 9,5 10,1 10,7 9,6 9 10,8 7,6
d TS -59,4 -55,3 -49,1 -53,7 -45,5 -2,8 -18,6
EaB original 461 481 472 403 314 306 240
EaB after immersion 135 139 182 151 131 291 161
d EaB -70,7 -71 -61,5 -62,6 -58,3 -5,1 -32,8
Volume Swell (%) 99 98 90 62 72 5 42
96
96
New Technologies to limit Emissions
So
urc
e:
gre
en
carc
on
gre
ss.c
om
/em
issio
ns
FOR PARTICLE REDUCTION
High pressure
diesel fuel
injection
Injection Combustion
Optimization of
the combustion
chamber
Diesel particle filter (EGR)
Additional Systems in Engines, Opening Applications for High
Performance Elastomers
97
Hose made of Vamac®
Sensor hose between pressure sensor and DPF
Temperature and Exhaust Gas exposure
Materials used : FKM, FKM/VMQ, AEM
Sensor Hoses for Diesel Particle Filter
98
There are emission control technologies currently available to
enable compliance of diesel motor vehicles to the next level of
requirements
So
urc
e:
gre
en
carc
on
gre
ss.c
om
/em
issio
ns
FOR NOx REDUCTION :
Increased recirculated gas in EGR
(Exhaust gas recirculation) High pressure
direct gasoline
injection
New technologies to limit emissions
99
High Pressure Loop (HPL) Low Pressure Loop (LPL)
Engine Engine
HPL
LPL
20% max. of EGR trapped 50% max. of EGR trapped
70% max. of Exhaust Gas Recirculating
Turbo Turbo
High Pressure
High Temperature (> 200°C)
Mainly metal pipes
Low Pressure
Low Temperature (< 150°C)
Mainly flexible rubber / plastic tubes
+ rubber seals
Exhaust Gas Recycling Loops (Diesel engine)
•EGR loops complement a Turbo-Charger for NOx reduction
•It creates a significant challenge to most materials in the Air
Management loop
100
Intercooler
or
Charged Air
Cooler
(CAC)
EGR
Actuator/
Valve
TCH / CAC Duct
(Cold Side)
TCH / CAC Duct
(Hot Side)
EGR Cooler
Turbocharger
Air Management Line - Flow and Cooling
Intake
Manifold
101
„Hot“ hose between turbo
and intercooler
Exhaust Fresh air
Inlet
manifold Turbo
charger
Exhaust manifold
Air filter
Intercooler
„Cold“ hose between IC
and AIM
Vacuum tube (molded) or
short connector between
air filter and turbo charger
Crankcase ventilation hose
for closed PCV system
AIM seals
EGR & Blow-by
contact with Euro 6
EGR contact
with Euro 6
EGR contact
with Euro 6
Blow-by gas
contact with
Euro 4
EGR contact
with Euro 4
Air management Trends : more acids
DuPont has developed an extensive data collection of our materials
performance in blow-by and EGR gases and condensates
102
-
1
E
+
pH
Acid Type
Phase
Time
Temperature
Equipment
Aeration
Sample
Mineral
Organic
Mineral /Organic
Liquid Gas
504 h
1008 h
2000 h
Yes No
Autoclave
Reflux
Finished Parts
Lab Specimens
50°C
100°C
150°C
168 h
Exhaust Gas Condensates, Test Parameters
HCl, HNO3, H2SO4 => mineral
HCOOH, CH3COOH => organic
Salts of acids
Other acids…
60°C up to 150°C with average 80-90°C
Vapour (= gas phase) or
Condensate (= liquid
phase)
168 h (short term)
up to 2008 h (long
term)
with or without
1 up to 5 with average 3
Which parameters might influence the test ?
Size and shape
Autoclave or reflux system
103
Two sets of lab specimens tested in the autoclaves (liquid phase & gas phase)
Autoclave Equipment used in DuPont Lab
Diameter: 97 mm
Length: 204 mm
Volume: around 2 litres
Thickness: 5 mm
Material: stainless steel 316L
Valves: Swagelok® serie R3A,
(ref. SS-4R3A adjusted 3.4 -24.1 bars)
104
EGR acid solutions selected
First EGR solution (pH =3.3)
defined by PSA
Concentration
mmol/l
KF 0.86
NaCl 4.23
HNO3 0.14
H2SO4 1.83
NaOH 2.81
PSA EGR chemical composition: only mineral based, pH 3.3
VW EGR chemical composition: organic based, pH 3.0
First EGR solution (pH =3.0)
defined by VW
Concentration
mmol/l
CH3CO2NH4 3.56
NH4NO3 0.44
(NH4)2SO4 0.57
HCOOH 24.66
CH3CH2COOH 10.68
Lab tests made
with fluids
close to OEM reference
N.B.: PSA & VW EGR acid solutions above have been modified recently
105
PSA EGR liquid contact, 168 h @ 90°C
17
-12
17
13
-9
12
16
-10
12
59
0 00 0
-3
0
-50
-40
-30
-20
-10
0
10
20
30
40
50
Hardness change
(points)
Tensile change (%) Elongation change (%) Volume Swell (%)
Vamac® G Vamac® GLS
Viton® A401C Viton® GF-200S
Viton® GF-200S with MO
Results of Vamac® & Viton® : Influence of acid type
VW EGR liquid contact, 168 h @ 90°C
14
71
19
38
145
-3
6
-2
-50
-40
-30
-20
-10
0
10
20
30
40
50
Hardness change
(points)
Tensile change (%) Elongation change(%) Volume Swell (%)
Vamac® GVamac® GLSViton® A401C ("destroyed")Viton® GF-200SViton® GF-200S with MO ("destroyed")
VW EGR exposure
VW EGR exposure
● Vamac® performs well in mineral &
organic acids
● Compounds of Viton® without metal
oxide have very good resistance to
all acid types
● Compounds of Viton® with metal
oxide is not recommended for use
with organic acids
Viton A401C ® ® ®
106
PSA EGR liquid contact, 168 h @ 90°C
17
3
-9
12
1
-7
-40 -39
-8
-37
-2
-9
21
-39
-26
-37
0
-3
14
-33
-19
-50
-40
-30
-20
-10
0
10
20
30
40
50
Hardness change
(points)
Tensile change (%) Elongation (%) Volume Swell (%)
Vamac® GLS Viton® GF-200S
Standard ACM 'HT-ACM'
CPE ECO
Other elastomers: Influence of acid type
VW EGR liquid contact, 168 h @ 90°C
71
19
3
-7
-31
-41
-8
-36-32
14
-3
6
-2
15
-50
-40
-30
-20
-10
0
10
20
30
40
50
Hardness change
(points)
Tensile change (%) Elongation change (%) Volume Swell (%)
Vamac® GLS Viton® GF-200S
Standard ACM 'HT-ACM'
CPE ("destroyed") ECO ("destroyed")
VW EGR exposure
127 PSA EGR exposure
CPE
ECO Viton® GF-200S
● Standard ACM, ECO & CPE: poor
resistance to EGR in this lab evaluation
● ’HT-ACM’ has poor retention of
mechanical properties vs Vamac®
75
84
107
VW EGR liquid contact, 168 h @ 90°C
-3
14
7
-2
1
19
38
145
6
-50
-40
-30
-20
-10
0
10
20
30
40
50
Hardness change
(points)
Tensile change(%) Elongation change (%) Volume Swell (%)
Vamac® GVamac® GLSViton® A401C ("destroyed")Viton® GF-200SViton® GF-200S with MO ("destroyed")
Results of Vamac® & Viton® : Gas vs liquid phase
VW EGR gas contact, 168 h @ 90°C
-6 -4
11
-16
-39
-18
36
-2 -1
13
3
11
-5-1
-7
0
-50
-40
-30
-20
-10
0
10
20
30
40
50
Hardness change
(points)
Tensile change (%) Elongation change (%) Volume Swell (%)
Vamac® G
Vamac® GLS
Viton® A401C
Viton® GF-200S
Viton® GF-200S with MO ("destroyed")
● Gas Phase is nearly as aggressive
as liquid phase, even at 90°C only
● Gas phase is less agressive than
liquid phase for Viton® A401 C
108
VW EGR liquid contact, volume swell
Results of Vamac® & Viton® : Influence of test temperature
139
16
-2
15
83
7 655
-50
-40
-30
-20
-10
0
10
20
30
40
50
Vamac® G Vamac® GLS Viton® GF-200S HT-ACM
168 h @ 90°C 168 h @ 120°C 168 h @ 150°C
-16
-32-29
27
-32
4 36 4
15
-50
-40
-30
-20
-10
0
10
20
30
40
50
Vamac® G Vamac® GLS Viton® GF-200S HT-ACM
168 h @ 90°C 168 h @ 120°C 168 h @ 150°CVo
lum
e s
well (
%)
15
-36
53
14
-3
-33
-21
-41
28 29
-50
-40
-30
-20
-10
0
10
20
30
40
50
Vamac® G Vamac® GLS Viton® GF-200S HT-ACM
168 h @ 90°C 168 h @ 120°C 168 h @ 150°C
VW EGR liquid contact, elongation change
VW EGR liquid contact, tensile change
Te
ns
ile
ch
an
ge
(%
) Elo
ng
ati
on
ch
an
ge
(%
) -56 -64
-82
276
● Vamac® clearly performs better than
HT-ACM
109
109
VW EGR acid solution - liquid contact, 94 h @ 100°C, pH =3
VW EGR liquid contact, 94 h @ 100°C, pH =1.6
1 0
-5
19
-7
-39
-8
-38
-1
6
-3
11
3 1
-2
4
-49
-40
15
-50
-40
-30
-20
-10
0
10
20
30
40
50
Hardness change
(points)
Tensile change (%) Elongation change (%) Volume Swell (%)
Vamac® G Vamac® GLS
Viton® GF-200S Standard ACM
'HT-ACM'
-2 -4
-16
105
-9
-36
-10
0
-4 -3
11 11
-8 -7
-49
22
-49-44
-50
-40
-30
-20
-10
0
10
20
30
40
50
Hardness change
(points)
Tensile change (%) Elongation change (%) Volume Swell (%)
Vamac® G Vamac® GLS
Viton® GF-200S Standard ACM
'HT-ACM'
93
79
● Volume swell increases with low pH value
● Mechanical properties worsen with lower pH
but the drop remains moderate for Viton®
GF-S without metal oxide and both
compounds of Vamac®
● Is ACM or “HT-ACM” suitable for sealing
applications in contact with acid ?
Results of Vamac® & Viton® : Influence of pH
110
Mixture of HAc / HNO3, adjusted to pH 1, 504 hours at 100°C
Lab Autoclav, liquid phase
HNBR compound (44% ACN) was tested simultaneuosly
Vamac®, Results at pH 1
Vamac G Vamac GLS Ultra IP VMX-3038
Hardness Shore A (1 sec) 73 76 65 63
Delta Hardness 1 2 -7 -8
Tensile Strength [MPa] 9,5 9,1 9,5 8,9
Delta TS [%] -45 -47 -46 -50
Elongation at break [%] 378 307 484 516
Delta Elong. [%] 59 30 58 52
Volume Change (%) -4 -4 8 12
Weight Change (%) -2 -2 8 11
More impact at such low pH values compared to pH3 results.
Still maintains most of its elastomeric properties.
Significant better results in the Gas phase.
111
HNBR slabs, after 504h at 100°C
in HNO3 / HAc mixture (pH 1)
Compound completely destroyed.
HNBR at pH 1
112
Acid Proof Viton® Bisphenol Cured
Develop a Viton® technology cured with
bisphenol cross-linker that displays excellent
resistance to concentrated acid (BbG, EGR &
aggressive biodiesel) and that is cost
competitive to peroxide curable FKM
113
114
Features: Acid resistance at lower cost than Peroxide
Product performance targeted Mechanical Properties : similar to original gum / PC
Limit hardness increase to maximum +/- 5
Limit modulus change to maximum +/-10 %
Low TºC: AL to B performance
Acid Resistance
Process (extrusion, molding): good processability – possibility to extrude veneers
Acid Proof Viton® Bisphenol Cured
Volume swell upon immersion in M15 / 7 d / room-temperature (%)
-35
-30
-25
-20
-15
-10
-5
0
0 5 10 15 20 25 30
Lo
w t
em
pera
ture
fle
xib
ilit
y
TR
-10 (°
C)
AL GAL-S
B
GFLT-S
GLT-S
GBL-S A
GF-S
F ETP-S
114
114
Product Description: VTX-9303
VTX-9303 is a bisphenol curable fluoropolymer precompound designed for
extruded hose applications with 69 % Fluorine.
VTX-9303 provides excellent resistance to
organic acid typically contained in EGR condensates and degraded FAME
(fatty acid methyl ester) based biofuels.
1.7 2.2 2.0 2.8
216
481
308
624
1.7 2.3 1.3 2.10
100
200
300
400
500
600
700
Volu
me c
hange [%
]
FKM 21201
VTX-9303, NMO
FKM 21202
VTR-9209 with MO
FKM 21203
VTX-9303. MgO 1
Post cured 16hrs @ 230°C Acid immersion 168hrs Post cured 16hrs @ 230°C Acid immersion 504hrs
Post cured 4hrs @ 175°C Acid immersion 168hrs Post cured 4hrs @ 175°C Acid immersion 504hrs
Aging in acetic acid,
1M, 168 hours, 100 °C
Acid Proof Viton® Bisphenol Cured
115
115
Fluid ageing, Acetic acid 2.5pH, 168hrs@100C
6.3
11
7.8
6.5
3.4
8.2
0
2
4
6
8
10
12
VTX-9303, NMO VTR-9209 with MO VTX-9303, MgO 1
Te
ns
ile
str
en
gth
MP
a
Tensile at 23C
Tensile after fluid ageing
Fluid ageing, Acetic acid pH 2.5, 168hrs@100C
390
330 340
450
48
370
0
100
200
300
400
500
VTX-9303, NMO VTR-9209 with MO VTX-9303, MgO 1
Elo
ng
ati
on
at
bre
ak
, %
Elongation at 23C
Elongation after ageing
• High level of
property
retention in
acid solutions
Acid Proof Viton® Bisphenol Cured
116
116
Acid Proof Viton ® : VTX 9304 for seals
Product Description: VTX-9304
VTX-9304 is a bisphenol curable fluoropolymer precompound with 66 % Fluorine
designed for injection moulding applications.
VTX-9304 provides excellent resistance to organic acid typically contained in EGR
condensates and degraded FAME (fatty acid methyl ester) based biofuels.
Volume change in EGR solution
nitric acid / acetic acid, pH = 1,
94hrs @ 100ºC : 2.5%
117
Acid Resistance - Conclusion of DuPont lab study
ECO, CPE (CM): Can be significantly affected in acid condensates (EGR, Blow-by) Increased risk of failure for the parts exposed to EGR
ACM, HT-ACM: Shows severe effects in the various tests Careful study for each application
Vamac® AEM : Standard compounds demonstrate excellent resistance to exhaust acids and gases
Vamac® can be recommended for cost-effective EGR hose and sealing solutions
Viton® FKM: Standard compounds do perform well in these acidic environments, even when highly concentrated and/or at high temperature – caution with organic acids…
Viton® recommended broadly for use in contact with EGR. Viton® peroxide cured compounds without metal oxide, are the
ultimate choice, but bisphenol technology to be become available
121
Vamac® & Viton® performance to :
1. Engine & Transmission Synthetic Oils
2. Biofuels & Flex Fuels
3. Blow-By &
Exhaust Gas Acid Condensates
4. AdBlue® Urea
5. Coolant
Agenda
122
So
urc
e:
gre
en
carc
on
gre
ss.c
om
/em
issio
ns
FOR NOx DESTRUCTION :
Exhaust gas treatment (with urea addition) NOx catalyst
Exhaust Washing Systems generate new Applications for Elastomers &
Thermoplastics
New Technologies to limit Emissions
123
SCR System
•Aggressive media detrimental to several elastomers
•DuPont developed an extensive set of data analysis of materials
performance in this environment
124
AdBlue® System
For elastomeric materials which are used in contact to
AdBlue®, additional resistance to Diesel or Engine oils is very
often required. This eliminates non-polar materials like EPDM.
125
Properties, Original
Vamac®
G
Vamac®
GLS
Vamac®
Ultra IP
Vamac®
DP
VMX-
3038
Hardness Shore A (1 second) ISO 7619-1:2004 72 74 71 61 71
Tensile properties (type 2) at 23°C ISO 37:2005 Cor 1
2008
Tensile Strength [MPa] 17,1 16,9 17,7 9,5 17,7
Elongation at break [%] 237 236 307 524 340
Modulus at 100 % [MPa] 6,9 6,8 5,7 2,1 5,5
Tear strength C - Crescent [kN/m] ISO 34-1:2004 23,9 23,5 27,7 34,3 30,4
C Set ISO 815, 70 h @ 150°C, plied disks [%] 26 29 27 30 29
C Set VW 22 hours at 150°C VW PV 3307 [%] 53 61 63 98 69
TG by DSC [°C] ISO 22768:2006
-36 -31 -37 -36 -38
Diamine cured grades were formulated at 70-75 ShA.
With the same combination of filler and plasticizer, Vamac® DP comes out at 60 ShA.
Overall properties are better for the high viscosity Vamac® Ultra grades IP and VMX-3038.
Peroxide cured Vamac® shows poorer Compression Set results.
Standard formulations at moderate plasticizer levels
126
Properties after Heat Ageing, 168 h at 175°C
Vamac®
G
Vamac®
GLS
Vamac®
Ultra IP
Vamac®
DP
VMX-
3038
Heat ageing 168 hours at 175°C ISO 188:2007
Hardness Shore A (1 second) ISO 7619-1:2004 79 82 77 71 77
Delta Hardness 7 8 6 10 6
Tensile Strength [MPa] 15,4 14,5 14,9 8,8 14,4
Delta TS [%] -10 -14 -16 -7 -19
Elongation at break [%] 252 240 348 452 389
Delta Elong. [%] 6 2 13 -14 14
Modulus at 100 % [MPa] 6,7 6,8 5,5 3,2 4,8
Delta 100% [%] -3 1 -3 52 -12
Excellent retention of properties for all diamine cured Terpolymers.
Vamac® DP shows highest level in property change.
127
Oil Ageing in Lubrizol OS 206304 for 504 h at 160°C Vamac®
G
Vamac®
GLS
Vamac®
Ultra IP
Vamac®
DP
VMX-
3038
Hardness Shore A (1 second) 68 77 67 55 64
Delta Hardness -4 3 -5 -7 -7
Tensile properties (type 2) at 23°C
Tensile Strength [MPa] 12,4 13,6 14,9 9,4 15,5
Delta TS [%] -27 -20 -16 -1 -12
Elongation at break [%] 144 153 199 411 230
Delta Elong. [%] -39 -35 -35 -22 -32
Modulus at 100 % [MPa] 7,9 8,4 6,5 2,0 6,0
Delta 100% [%] 16 25 15 -2 11
Volume Change ISO 1817:2005 14 6 16 15 18
Weight Change 9 3 11 10 12
Lubrizol OS 206304 is a reference fluid used to simulate resistance to engine oil
Excellent retention of properties
Fluid swell can be further optimized influenced by compounding
128
Ageing in AdBlue® for 168 h at 120°C
Tests were carried out in a lab autoclave using a Kalrez® FFKM seal to avoid any leakage.
Vamac® GLS with its high MA content lost all its elastic properties after 1 week at 120°C.
Vamac® G is also loosing most of its elastic properties.
The high viscosity grades Vamac® Ultra IP and VMX-3038 maintain most of their properties,
only the Modulus shows a significant increase.
The peroxide cured Vamac DP performs best in terms of Modulus retention.
Liquid Phase Vamac®
G
Vamac®
GLS
Vamac®
Ultra IP
Vamac®
DP
VMX-
3038
Hardness Shore A (1 second) 71 54 75 61 73
Delta Hardness ISO 188:2007 -1 -20 3 -1 2
Tensile Strength [MPa] 9,8 3,5 21,2 11,0 19,6
Delta TS [%] -43 -79 20 16 11
Elongation at break [%] 85 26 221 308 230
Delta Elong. [%] -64 -89 -28 -41 -32
Modulus at 100 % [MPa] 10,2 2,8 9,5
Delta 100% [%] 80 34 74
Volume Change 23 89 16 22 14
Weight Change 21 77 15 20 13
129
Ageing in AdBlue® for 168 h at 120°C - Graphical
-100
-80
-60
-40
-20
0
20
40
60
80
100
Hardness
Change (pts.)
Tensile
Change (%)
Elongation
Change (%)
Volume
Change (%)
Vamac® Ultra IP
Vamac® VMX-3038
Vamac® G
Vamac® GLS
130
Vamac® Ultra IP – Long term Ageing in AdBlue®
1008 h at 80°C
No major difference between liquid & gas phase
132
Viton® performance in AdBlue®
• Viton® is not suitable in
AdBlue® for temp. > 100ºC
• Kalrez® will be the material
of choice for temp. > 120°C
Viton® GFLT-S
133
Vamac® has long-time proven functionality in automotive hoses and seals and
meets automotive low- and high-temperature requirements (-40°C to 170°C with
peaks up to 200°C), as well as good fluid resistance (e.g. engine oil and Diesel
fuel)
Vamac® Ultra grades at medium methyl acrylate levels keep their elastomeric
properties after immersion in AdBlue® for 1 week at 120°C
Peroxide cured Vamac® DP also can be seen as a material with possible use for
AdBlue®, with higher CSet results may however be seen not as good for sealing
applications
Vamac® offers an excellent price/performance ratio compared to HNBR or FKM
grades that can be considered suitable for contact to AdBlue®
Kalrez® is the best solution recommended for temp. range 120 – 150ºC
AdBlue® Summary
134
Performance of Vamac® & Viton® in :
1. Engine & Transmission Synthetic Oils
2. Biofuels & Flex Fuels
3. Blow-By &
Exhaust Gas Acid Condensates
4. AdBlue® Urea
5. Coolant
Agenda
135
Heater Core
Transmission
Cooler
Radiator
Pumps (Mechanical + Electrical)
Cooling Hose
Fan
Thermostat / Valves
Heater
hoses
Coolant Fluid System Components
Standard for EPDM
hoses & EPDM / HNBR
seals
136
Automotive Factory Fill Coolants
• Three main categories depending on the type of anti-corrosion package used :
• The old “green coolant” uses a mixture of inorganic additives and is referred to as
IAT (inorganic additive technology).
• The IAT package if fast acting but is consumed thus OEMs recommended
flushing and replacing after 2 years.
• Green coolant is no longer used as factory fill by any major automotive
manufacturer. However, since it is not recommended to mix additive
technologies, green coolant is still in use for service applications.
• OAT (Organic Acid Technology) coolants : GM changed to OAT in the mid 1990s
and extended the service interval to 5 years/150M miles. They developed a
specification for the OAT coolants (GM6277M) and coolants meeting this spec are
allowed to use the DEX-COOL trademark. Several manufactures market their brand
of Dex-cool based on their proprietary blend of additives. Dex-cool is dyed orange.
• Chrysler and Ford have recently adopted coolants with a mix of organic and
inorganic additives denoted as HOAT (Hybrid Organic Acid Technology). The
HOAT coolants generally have “G-05” on the bottle. Ford HOAT coolant is dyed
yellow. Chrysler, just to assure maximum confusion, dye their coolant orange.
• OAT technology is used by GM, Opel, Ford Europe, VW and most Asian manufacturers.
• HOAT is used by Chrysler, Ford, BMW, Mercedes and Volvo).
137
Regulations are Driving Need for Low
Permeation AIM Gaskets
• More Stringent Environmental Regulations
Necessitate Reduction in HC Loss Through Gaskets,
etc.
• CARB LEV II, EPA Tier II, PZEV
• Silicone is highly permeable to hydrocarbons
• Regulations Also Demand Longer Vehicle Life
• CARB 15 Years / 150,000 Miles (EPA 12y / 120 k)
• While Still Meeitng Above SHED Requirements
138
Poor Resistance to OAT Coolants
Embrittlement Failure of 66 % F FKM in Coolant
Elongation (solid) & Modulus (dashed) after 135 °C
Coolant Aging
139
Advantages & Drawbacks to Traditional
Bisphenol Cured FKM for AIM Sealing
• Exceptional Permeation Resistance
• Excellent Heat Resistance
• Excellent Compression Set Resistance and CSR Performance
• Requires a Post Cure at 200 °C (or Hotter) to Achieve low
Compression Set Poperties – Detrimental to Nylon Carrier :
warpage &/or dimensional change
• Poor Resistance to Coolant
140
140
Improved Coolant Resistance Elongation
Resistance
Improved Coolant Resistance of Viton® GBL-S vs, 66 % F FKM
Elongation after 135 °C Aging in Dex-Cool® OAT Coolant
143
Improved Coolant Resistance Modulus
Retention
Improved Coolant Resistance of Viton® GBL-S vs, 66 % F FKM
Modulus after 135 °C Aging in Dex-Cool® OAT Coolant
144
Improved Coolant Resistance Compression Set
Improved Coolant Resistance of Viton® GBL-S vs, 66 % F FKM
Compression Set in Air at 150 °C Aging in Dex-Cool® OAT
Coolant
145
Vamac® in Coolant Glysantin G48
BMW and M+H spec not met. Hengst spec for low oil swell HNBR requirements
are met with Ultra LT.
Vamac G Ultra IP Ultra LT VMX-3110
Fluid ageing in Glysantin G48 / Water (50/50), 1000 h at 108°C
Coolant testing acc.to Hengst BN 10.86 (2008.02)
Hardness Shore A (1 second) ISO 7619-1:2004 66 67 66 60
Delta Hardness ISO 188:2007 -7 -6 -2 -14
Tensile properties (type 2) at 23°C ISO 37:2005 Cor 1 2008
Tensile Strength [MPa] 13,1 16,1 12,2 11,8
Delta TS [%] -24 -17 -5 -38
Elongation at break [%] 228 271 229 243
Delta Elong. [%] -11 -13 -6 -14
Modulus at 50 % [MPa] 2,3 2,5 2,4 2,1
Delta 50% [%] -3 0 21 -22
Modulus at 100 % [MPa] 5,8 6,1 5,8 5,3
Delta 100% [%] 7 7 25 -18
Volume Change [%] ISO 1817:2005 24 25 18 46
Weight Change [%] ISO 1817:2005 24 24 15 42
148
Trademark?
Specifications – Coolant G48
BMW N 602 00.0
5428
M+H 16 630 23
037 VW 2.8.1. C 70
Glysantin G48/H2O (1:1) 94h/135°C
VDA 675 303
Hardness change/ Änd. der Härte - -5 ... +5
Volume change/ Änd. d. Volumens % - 0 ... +5
Tensile strength/ Reißfestigkeit N/mm² - min 6
Elongation at break/ Reißdehnung % - min 150
Glysantin G48/H2O (1:1)
1000h/125°C
VDA 675 303
Änd. Der Härte ShA +/-10
Volumenänderung % max. +10
Masseänderung % Wert angeben
Reißfestigkeit [N/mm²] Wert angeben
Reißfestigkeitsänderung % +/-30
100 % Spannungswert [N/mm²] Wert angeben
Reißdehnung [%] Wert angeben
Änd. Der Reißdehnung % max. -50 -
149
Vamac® in Coolant Glysantin G48
Volume Change abt. 10% vs. 5% specified, all other values ok
Vamac G Ultra IP Ultra LT VMX-3110
Fluid ageing in Glysantin G48 / Water (50/50), 94 h at 135°C
Coolant testing acc. To Mann + Hummel specification 16 630 23 037 (HNBR)
Hardness Shore A (1 second) ISO 7619-1:2004 71 72 66 72
Delta Hardness ISO 188:2007 -1 0 -2 -2
Tensile properties (type 2) at 23°C ISO 37:2005 Cor 1 2008
Tensile Strength [MPa] 16,3 19,3 13,2 18,6
Delta TS [%] -5 0 3 -3
Elongation at break [%] 228 281 227 268
Delta Elong. [%] -11 -10 -6 -5
Modulus at 100 % [MPa] 6,7 6,7 5,5 7,1
Delta 100% [%] 26 19 19 9
Volume Change [%] ISO 1817:2005 14 9 9 11
Weight Change [%] ISO 1817:2005 13 10 9 11
150
Vamac in Coolant Glysantin G48
1008 h at 125°C are exceeding capabilities of the Vamac compounds used.
Ultra LT eventualy still functional.
Vamac G Ultra IP Ultra LT VMX-3110
Fluid ageing in Glysantin G48 / Water (50/50),1000 h at 125°C
Coolant testing acc.to BMW N 602 00.0 5428 (HNBR)
Hardness Shore A (1 second) ISO 7619-1:2004 47 49 67 -
Delta Hardness ISO 188:2007 -25 -24 -1 -
Tensile Strength [MPa] 3,4 4,3 8,2 2,7
Delta TS [%] -80 -78 -36 -86
Elongation at break [%] 75 81 100 71
Delta Elong. [%] -71 -74 -59 -75
Modulus at 50 % [MPa] 2,1 2,3 2,6 1,9
Delta 50% [%] -71 -74 -59 -75
Modulus at 100 % [MPa] - - 6,9 -
Delta 100% [%] - - 49 -
Volume Change [%] ISO 1817:2005 281 220 39 417
Weight Change [%] ISO 1817:2005 269 190 40 365
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The information set forth herein is furnished free of charge and is based on technical data that
DuPont believes to be reliable and falls within the normal range of properties. It is intended for use
by persons having technical skill, at their own discretion and risk. This data should not be used to
establish specification limits nor used alone as the basis of design. Handling precaution information
is given with the understanding that those using it will satisfy themselves that their particular
conditions of use present no health or safety hazards. Since conditions of product use and disposal
are outside our control, we make no warranties, express or implied, and assume no liability in
connection with any use of this information. As with any product, evaluation under end-use
conditions prior to specification is essential. Nothing herein is to be taken as a license to operate or
a recommendation to infringe on patents.
Caution: Do not use in medical applications involving permanent implantation in the human body.
For other medical applications, discuss with your DuPont customer service representative and read
Medical Caution Statement H-50103-4.
Copyright 2012. The DuPont™ Oval logo, DuPont™, Zytel®, Diak™, Viton® and Vamac® are
trademarks or registered trademarks of E.I. DuPont de Nemours or its affiliates. All rights reserved.
AdBlue® is a registered trademark of the German Association of the Automobile Industry
Castrol® is a registered trademark of Castrol
Shell® is a registered trademark of Shell Dutch Petroleum
Ell® & Total® are is a registered trademark of Total
Mobil® is a registered trademark of Exxon Mobil
Fuchs® is a registered trademark of Fuchs Lubrifiant France S.A.
Urania® & Selenia® are registered trademark of Petronas Lubricants
Pentosin® is a registered trademark of Deutsche Pentosin-Werke GmbH
152
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