nrc2014-bellander-rubber and oil in automotive applications...oil: oil basics oil = base oil +...

Rubber and Oil in Heavy DutyA t ti A li ti

N di R bb C f

Automotive Applications

Nordic Rubber ConferenceMalmö 9-10 April 2014

Martin Bellander

Agenda

Introduction Oil

Where used Where used Oil basics

Rubber for oil applications Seals gaskets hoses Seals, gaskets, hoses Temperature load

ExperimentalM t i l Materials

Oils Results Summary

OIL – where used?

Engine Lubrication & Cooling Gearbox (manual, automatic) Retarder Axles Cab tilt (hydraulic)( y ) Other hydraulic systems Steering Steering

OIL: Oil basics

Oil = Base oil + Additives

Base oil, API classification:,

Mineral oils: Group I: F ti ll di till d t l <90% t t i i d <120 Group I: Fractionally distilled petroleum, <90% saturates, visc index <120 and >80

Group II: Fractionally distilled petroleum + hydrocracked, >90% saturates, visc index <120 and >80

Group III: Fractionally distilled petroleum + hydrocracked, >90% saturates, visc index >120

Synthetic:y Group IV: Polyalphaolefins (PAO) Group V: All others, e.g. Poly alkylene glycols (PAG), Polyolesters (POE )

OIL: Oil basics, solubility

Paraffinic saturated linear Paraffinic – saturated linear Naphthenics - cyclic Aromatic

Paraffinic Naphthenics Aromatic Aniline pointIRM901 - - - 124IRM901 124IRM902 35 min 50 max 12 93IRM903 40 min 45 max 14 70

OIL: Oil basics, additives

Oil = Base oil + Additives

Additives:

Antioxidants

Antirust (corrosion inhibitors), eg Zn-dialkylditiophosphate

EP – Extreme Pressure agents (polysulphides) R RSS S

AW – Anti Wear

Detergent (hydrophilic/hydrophobic)

Dispersant (hydrophilic/hydrophobic)

Antifoam (dimethylsiloxane polymers, polyethers…)

FM – Friction modifier

Viscosity modifier

Rubber for oil applications

Oil pan gasket Oil pan gasket Cylinder head gasket Oil cooler gasket O-rings Dynamic sealings Hoses, low/high, g

pressure

Temperature load

20%

25%

Light driving conditions

Vehicle 1Depends on type of hi l / i d

Eq. h @150C518 h

10%

15%

20%Vehicle 2vehicle/engine and

type of driving (flat, hilly speed etc)

723 h

0%

5%

82 86 90 94 98 102 106 110 114 118 122 126

hilly, speed etc).Examples:

0 250,3

Heavy driving conditions

Vehicle 1Eq. h @150C1679 h

0 10,150,2

0,25Vehicle 2 2890 h

00,050,1

82 86 90 94 98 102 106 110 114 118 122 126

Rubber and oil interaction

Physical reversible volume change (+ or ) Physical – reversible, volume change (+ or -) Chemical – irreversible, reactions taking place

EXPERIMENTAL

Immersion testing (ISO 1817) 150°C (NBR 100°C)( ) 168 h and 1000 h (some 500 h) No stirring No oil exchange No oil exchange Evaluation:

Tensile properties Hardness change Volume change Compression setp Stress relaxation in 25% compression

MATERIALS NBR 30% ACN, sulfur, ~5% softener HNBR 21% ACN, peroxide, ~5% softener VMQ Peroxide FKM type 1 Copolymer, 66% F, bisphenol FKM type 3 Low temp, 67% F, peroxide AEM Vamac G, ~15% softener, diamine ACM HyTemp AR12, 65 phr N550

OILSAbbreviation Description

901 IRM901

OILS

901 IRM901 902 IRM902 903 IRM903 Ox902 Oxidized IRM903, bubbling air in oil + Cu-plate Grog EGR-grog, engine oil with H2SO4 and HNO3 Engine Scania Engine Oil, LDF-3, 10W-40 LA Scania Engine Oil – Low Ash BD 10% Scania Engine oil with 10% biodiesel (RME, rape

methyl ester) Axle Scania Axle Oil 75W-140 Gear Scania Transmission Oil 75W-90 Retard Retarder Oil, Shell Rimula R3 Multi 10W-30, ATF Automatic Transmission Fluid, Q8 Auto 14

RESULTS

20

% Volume change, NBR25

Change in IRHD, NBR

10

15

20

168 h1000 h

10

15

20

25168 h

1000 h

0

5

‐5

0

5

‐10

‐5

901 902 903 Ox902 Grog Engine LA BD 10% ATF‐15

‐10

901 902 903 Ox902 Grog Engine LA BD 10% ATF

01020

% Change in Tensile Strength, NBR

‐20‐100

% Change in strain at break, NBR

50‐40‐30‐20‐10

168 h

1000 h70‐60‐50‐40‐30

168 h

1000 h

‐80‐70‐60‐50

901 902 903 Ox902 Grog Engine LA BD 10% ATF‐100‐90‐80‐70


1000 h

IRM il ≠ l ilIRM oils ≠ real oilsIncreased hardness in real oilsSmall volume changes in real oilsTensile properties severly deteriorated in real oils

% Compression set, NBR% Volume change, NBR

60708090

100

168 h10

15

20

168 h1000 h

1020304050 500 h

‐5

0

5

010

903 Grog Engine‐10

5


01020


‐20‐100

% Change in strain at break, NBR

50‐40‐30‐20‐10

168 h

1000 h70‐60‐50‐40‐30

168 h

1000 h

‐80‐70‐60‐50



1000 h

% Compression set, NBR% Volume change, NBR

60708090

100

168 h10

15

20

168 h1000 h

1020304050 500 h

‐5

0

5

010

903 Grog Engine‐10

5

901 902 903 Ox902 Grog Engine LA BD 10% ATFFindings NBR:IRM oils ≠ real oils

01020


‐20‐100

% Change in strain at break, NBRIRM oils ≠ real oilsIncreased hardness in real oilsSmall volume changes in real oilsTensile properties severly deteriorated in real

50‐40‐30‐20‐10

168 h

1000 h70‐60‐50‐40‐30

168 h

1000 h

Tensile properties severly deteriorated in real oilsCompression set low for IRM903 due to swellingReal oils: probably extraction of softener +

‐80‐70‐60‐50



1000 hp y

increased crosslinking due to oil additives

% Volume change, HNBR Change in IRHD, HNBR

25

30

35

40 168 h

‐5

0

5

10

15

20

25

20

‐15

‐10

168 h

0

5

901 902 903 Grog Engine LA BD 10%

Axle Gear Retard ATF‐25

‐20

901 902 903 Grog Eng. LA BD 10%

Axle Gear Ret. ATF

05

10

% Change in tensile strength, HNBR

‐100

10


‐20‐100

% Change in strain at break, HNBR

‐30‐25‐20‐15‐10‐5

168 h‐70‐60‐50‐40‐30‐20

168 h80‐70‐60‐50‐40‐30

168 h

‐40‐35


Axle Gear Ret. ATF‐90‐80‐70




Axle Gear Ret. ATF

IRM il ≠ l ilIRM oils ≠ real oilsDecreased hardness in almost all oilsSmaller volume changes in real oilsTensile properties more deteriorated in real oils

% Volume change, HNBR % Compression set, HNBR

25

30

35

40 168 h

60708090

100

168 h

500 h

5

10

15

20

1020304050

0901 902 903 Grog Engine LA BD

10%Axle Gear Retard ATF

0903 Grog Engine

05

10


‐100

10


‐20‐100

% Change in strain at break, HNBR

‐30‐25‐20‐15‐10‐5

168 h‐70‐60‐50‐40‐30‐20

168 h80‐70‐60‐50‐40‐30

168 h

‐40‐35






Axle Gear Ret. ATF

% Volume change, HNBR % Compression set, HNBR

25

30

35

40 168 h

60708090

100

168 h

500 h

5

10

15

20

1020304050



0903 Grog Engine

Findings HNBR:IRM oils ≠ real oils

05

10


‐100

10


‐20‐100

% Change in strain at break, HNBRDecreased hardness in almost all oilsSmaller volume changes in real oilsTensile properties more deteriorated in real oils

‐30‐25‐20‐15‐10‐5

168 h‐70‐60‐50‐40‐30‐20

168 h80‐70‐60‐50‐40‐30

168 h

Compression set lower for IRM903 due to swelling. Decreasing with time!Decreased hardness => softening effect +

‐40‐35






Axle Gear Ret. ATF

possibly chain or crosslink scission

40% Volume change, VMQ

0

Change in IRHD, VMQ

20

25

30

35 168 h

1000 h

‐15

‐10

‐5

0

5

10

15

‐30

‐25

‐20

168 h

1000 h

‐10

‐5

901 902 903 Ox902 Grog Engine LA BD 10%‐40

‐35

901 902 903 Ox902 Grog Engine LA BD 10%

‐20‐100

% Change in tensile strength, VMQ

‐20‐100

% Change in strain at break, VMQ

‐70‐60‐50‐40‐30

168 h

1000 h

‐70‐60‐50‐40‐30

168 h

1000 h

‐100‐90‐8070

901 902 903 Ox902 Grog Engine LA BD 10%‐100‐90‐80‐70


1000 h

Volume change: IRM oils ~ real oils, except 903Decreased hardness in all oilsTensile properties ”OK”, but not for the grog


130

Compression set , VMQ

20

25

30

35 168 h

1000 h* * Measurement

interrupted after 5 days

70

90

110

130

168 h

500 h

0

5

10

15

10

30

50

‐10

‐5


‐10IRM903 EGR‐grogg Engine oil

‐20‐100


‐20‐100

% Change in strain at break, VMQ

‐70‐60‐50‐40‐30

168 h

1000 h

‐70‐60‐50‐40‐30

168 h

1000 h

‐100‐90‐8070



1000 h


130

Compression set , VMQ

20

25

30

35 168 h

1000 h* * Measurement

interrupted after 5 days

70

90

110

130

168 h

500 h

0

5

10

15

10

30

50

‐10

‐5



Findings VMQ:Volume change: IRM oils ~ real oils except 903

‐20‐100


‐20‐100

% Change in strain at break, VMQVolume change: IRM oils real oils, except 903Decreased hardness in all oilsTensile properties ”OK”, but not for the grogCompression set low for IRM903 due to

‐70‐60‐50‐40‐30

168 h

1000 h

‐70‐60‐50‐40‐30

168 h

1000 h

Compression set low for IRM903 due to swelling. Grog destroys the sampleDecreased hardness => softening effect + possibly chain or crosslink scission (especially in

‐100‐90‐8070



1000 hp y ( p ythe grog)

30

% Volume change, FKM type 1

25

Change in IRHD, FKM type 1

15

20

25

10

15

20

168 h

5

10168 h

0

5

10



‐5901 902 903 Grog Engine LA BD


‐100

10

% Change in tensile strength, FKM type 1

15

5

% Change in strain at break, FKM type 1

‐60‐50‐40‐30‐20

168 h‐55

‐35

‐15

168 h

‐90‐80‐70



‐75


Axle Gear Retard ATF

168 h

Volume change very small in all oilsSlightly increased hardness in all oilsTensile properties ”OK”, but more affected by the real oils

30


90100

% Compression set, FKM type 1

15

20

25

5060708090

168 h

500 h

5

10168 h

1020304050


10%Axle Gear Retard ATF 0

10

IRM 903 EGR‐grogg Engine oil

Findings FKM type 1:

‐100

10

% Change in tensile strength, FKM type 1

15

5

% Change in strain at break, FKM type 1Volume change very small in all oilsSlightly increased hardness in all oilsTensile properties ”OK”, but more affected by the

l il

‐60‐50‐40‐30‐20

168 h‐55

‐35

‐15

168 h

real oilsCompression set low for all oils. ”Grog resistant”Increased hardness => possibly crosslink formation

‐90‐80‐70



‐75



168 hformation

25


25

Change in IRHD, FKM type 3

10

15

20

168 h

1000 h10

15

20168 h

1000 h

0

5

10

0

5

10

‐5901 902 903 Ox902 Grog Engine LA BD




%Change in strain at break FKM t pe 3

‐30

‐20

‐10

0


‐30

‐20

‐10

0% Change in tensile strength, FKM type 3

80

‐70

‐60

‐50

‐40

168 h

1000 h80

‐70

‐60

‐50

‐40

30

168 h

1000 h

‐100

‐90

‐80



1000 h

‐100

‐90

‐80



1000 h

V l h ll i ll ilVolume change very small in all oilsSlightly increased and decreased hardnessTensile properties ”OK”, but more affected by the real oilsTensile properties better than for FKM type 1

90100

% Compression set, FKM type 325


5060708090

168 h10

15

20

168 h

1000 h

010203040 500 h

0

5

10

0IRM 903 EGR‐grogg Engine oil‐5



%Change in strain at break FKM t pe 3

Findings FKM type 3:Volume change very small in all oils

‐30

‐20

‐10

0


‐30

‐20

‐10

0% Change in tensile strength, FKM type 3

g ySlightly increased and decreased hardnessTensile properties ”OK”, but more affected by the real oils

80

‐70

‐60

‐50

‐40

168 h

1000 h80

‐70

‐60

‐50

‐40

30

168 h

1000 h

Tensile properties better than for FKM type 1Compression set low for all oils. ”Grog resistant”Increased hardness => possibly crosslink

‐100

‐90

‐80



1000 h

‐100

‐90

‐80



1000 h formation

40

% Volume change, AEM20

Change in IRHD, AEM

15

20

25

30

35 168 h

1000 h

0

5

10

15

‐5

0

5

10

15

‐25

‐20

‐15

‐10

‐5 168 h

1000 h



‐30

25



20‐100

10

% Change in tensile strength, AEM

‐10

10

% Change in strain at break, AEM

‐60‐50‐40‐30‐20

168 h

1000 h ‐50

‐30

10

168 h

‐90‐80‐70



‐70



168 h

1000 h

V l h b th + dVolume change both + and -Increased and decreased hardness, correlate ~ with volume changeTensile properties ”OK”, but more affected by the real oilsTensile properties OK for IRM oils, but terrible for most real oils

100

Compression set for AEM40

% Volume change, AEM

60

70

80

90

168 h

500 h

15

20

25

30

35 168 h

1000 h

20

30

40

50

‐5

0

5

10

15

0

10

IRM903 EGR‐grogg Engine oil



20‐100

10


‐10

10

% Change in strain at break, AEM

‐60‐50‐40‐30‐20

168 h

1000 h ‐50

‐30

10

168 h

‐90‐80‐70



‐70



168 h

1000 h

100

Compression set for AEM40

% Volume change, AEM

60

70

80

90

168 h

500 h

15

20

25

30

35 168 h

1000 h

20

30

40

50

‐5

0

5

10

15

Findings AEM:Volume change both + and -

0

10

IRM903 EGR‐grogg Engine oil



Volume change both + and Increased and decreased hardness, correlate ~ with volume changeTensile properties ”OK”, but more affected by the

20‐100

10


‐10

10

% Change in strain at break, AEMe s e p ope es O , bu o e a ec ed by e

real oilsTensile properties OK for IRM oils, but terrible for most real oils

‐60‐50‐40‐30‐20

168 h

1000 h ‐50

‐30

10

168 h

Compression set low for 903 due to swell. ”Grogsemi-resistant”, not as good as FKMHardness + and - => extraction of softener,

‐90‐80‐70



‐70



168 h

1000 hpossibly crosslink formation and scission

% Volume change, ACM10

Change in IRHD, ACM

20

25

30

35

168 h

‐5

0

5

10

5

0

5

10

15

‐25

‐20

‐15

‐10168 h


10%Axle Gear Retard ATF ‐30



%Change in tensile strength ACM

‐20

‐10

0

10

% Change in tensile strength, ACM

‐10

0

10

20

% Change in strain at break, ACM

‐60

‐50

‐40

‐30

0

168 h

‐50

‐40

‐30

‐20

10

168 h

‐90

‐80

‐70



‐70

‐60



68

V l h ti f 901 hi h f 903Volume change negative for 901, high for 903, Mostly decreased hardness, correlate ~ with volume changeTensile properties ”OK”, but more affected by the real oilsTensile properties OK for all oils

% Compression set, ACM% Volume change, ACM

70

90

168 h

500 h20

25

30

35

168 h

10

30

50

5

0

5

10

15





‐20

‐10

0

10


‐10

0

10

20

% Change in strain at break, ACM

‐60

‐50

‐40

‐30

0

168 h

‐50

‐40

‐30

‐20

10

168 h

‐90

‐80

‐70



‐70

‐60



68

% Compression set, ACM% Volume change, ACM

70

90

168 h

500 h20

25

30

35

168 h

10

30

50

5

0

5

10

15





Findings ACM:Volume change negative for 901 high for 903

‐20

‐10

0

10


‐10

0

10

20

% Change in strain at break, ACMVolume change negative for 901, high for 903, Mostly decreased hardness, correlate ~ with volume changeTensile properties ”OK”, but more affected by the

‐60

‐50

‐40

‐30

0

168 h

‐50

‐40

‐30

‐20

10

168 h

Tensile properties OK , but more affected by the real oilsTensile properties OK for all oilsCompression set low for 903 due to swell. ”Grog

‐90

‐80

‐70



‐70

‐60



68p gresistant”, almost as good as FKMHardness mostly lower => softening effect, possibly crosslink scission

Mechanisms for rubber-oil interaction

Crosslink or polymer scissionCrosslink or polymer scission

Crosslink formation

Softener extraction

Oil plasticisingp g

SUMMARY Oil = Base oil + additives Base oil - most physical effects –p y

swelling Additives = reactive speciesp Standard oils (IRM oils) mostly only

physical effectsp y Chemistry created by reactive

species, including oil additives andspecies, including oil additives and oxygen! O2

O2 O2

O2

ACKNOWLEDEGMENTS

Alice Pazat, previous diploma worker at Scania Trelleborg Ersmark, for providing samples Zeon & Erteco for providing materialp g

THANK YOU!

nrc2014-bellander-rubber and oil in automotive applications...oil: oil basics oil = base oil +...

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