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

Sealing performance of Viton® vs other elastomers

25

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

Dual Clutch Transmission Prediction in EU

33

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

Castrol® BOT 351 C3 > Castrol® BOT 428B > Pentosin® FFL-2

Vamac® - Performance in New DCT Fluids

36

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

Bioethanol Feed Stocks

Sugar cane

Corn

Switch grass

50

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

Sugar beets

Corn or

Maize

Sugar cane Switchgrass

Wheat

Biobutanol Feed Stocks

54

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

Jatropha

Rapeseed

Palm & Coconut Canola Sunflower

Algae Kelp Soybean

Biodiesel Feed Stocks

58

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

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e:

gre

en

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on

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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 Proof Viton ® : VTX 9304 for seals

118

Acid Proof Viton ® : VTX 9304 for seals

119

Acid Proof Viton ® : VTX 9304 for seals

120

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 – Short term Ageing in AdBlue®

168 h at 80°C ,100°C & 120°C

131

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

No-Postcure Polymers

Postcure not Required to Achieve Good Physical

Properties

141

Stress Relaxation at 150 °C – FKM 66 % F vs.

FKM GBL-S

142

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

Resistance of Viton® - Zytel® Adhesion to G48

146

146

147

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

151

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