Rubber and Oil in Heavy Duty Automotive ti Applications Nordic Rubber Conference Malmö 9-1 April 214 Martin Bellander
Introduction Agenda Oil Where used Oil basics Rubber for oil applications Seals, gaskets, hoses Temperature load Experimental Materials Oils Results Summary
OIL where used? Engine Lubrication & Cooling Gearbox (manual, automatic) Retarder s Cab tilt (hydraulic) Other hydraulic systems Steering
OIL: Oil basics Oil = Base oil + Additives Base oil, API classification: Mineral oils: Group I: Fractionally distilled d petroleum, <9% saturates, t visc index <12 and >8 Group II: Fractionally distilled petroleum + hydrocracked, >9% saturates, visc index <12 and >8 Group III: Fractionally distilled petroleum + hydrocracked, >9% saturates, visc index >12 Synthetic: Group IV: Polyalphaolefins (PAO) Group V: All others, e.g. Poly alkylene glycols (PAG), Polyolesters (POE )
OIL: Oil basics, solubility Paraffinic saturated linear Naphthenics - cyclic Aromatic Paraffinic Naphthenics Aromatic Aniline point IRM91 - - - 124 IRM92 3 min max 12 93 IRM93 4 min 4 max 14 7
OIL: Oil basics, additives Oil = Base oil + Additives Additives: Antioxidants Antirust (corrosion inhibitors), eg Zn-dialkylditiophosphate EP Extreme Pressure agents (polysulphides) R S R S 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 Cylinder head gasket Oil cooler gasket O-rings Dynamic sealings Hoses, low/high, g pressure
Temperature load Depends on type of vehicle/engine i and type of driving (flat, hilly, speed etc). Examples: 2% 2% 1% 1% % %,3 2,2,2,1 1,1, Light driving conditions Eq. h @1C Vehicle 1 18 h Vehicle 2 723 h 82 86 9 94 98 12 16 11 114 118 122 126 Heavy driving conditions Eq. h @1C 1679 h 289 h Vehicle 1 Vehicle 2 82 86 9 94 98 12 16 11 114 118 122 126
Rubber and oil interaction Physical reversible, volume change (+ or -) Chemical irreversible, reactions taking place
EXPERIMENTAL Immersion testing (ISO 1817) 1 C (NBR 1 C) and 1 h (some h) No stirring No oil exchange Evaluation: Tensile properties Hardness change Volume change Compression set Stress relaxation in 2% compression
MATERIALS NBR 3% ACN, sulfur, ~% softener HNBR 21% ACN, peroxide, ~% softener VMQ Peroxide FKM type 1 Copolymer, 66% F, bisphenol FKM type 3 Low temp, 67% F, peroxide AEM Vamac G, ~1% softener, diamine ACM HyTemp AR12, 6 phr N
OILS Abbreviation Description 91 IRM91 92 IRM92 93 IRM93 Ox92 Oxidized IRM93, bubbling air in oil + Cu-plate Grog EGR-grog, engine oil with H 2 SO 4 and HNO 3 Engine Scania Engine Oil, LDF-3, 1W-4 LA Scania Engine Oil Low Ash BD 1% Scania Engine oil with 1% biodiesel (RME, rape methyl ester) Scania Oil 7W-14 Gear Scania Transmission Oil 7W-9 Retard Retarder Oil, Shell Rimula R3 Multi 1W-3 ATF Automatic Transmission Fluid, Q8 Auto 14
RESULTS
2 1 1 % Volume change, NBR 1 h 2 2 1 1 1 h Change in IRHD, NBR 1 1 91 92 93 Ox92 Grog Engine LA BD 1% ATF 1 91 92 93 Ox92 Grog Engine LA BD 1% ATF 2 1 1 2 3 4 6 7 8 1 h % Change in Tensile Strength, NBR 91 92 93 Ox92 Grog Engine LA BD 1% ATF IRM oils real oils Increased hardness in real oils Small volume changes in real oils Tensile properties severly deteriorated in real oils 1 2 3 4 6 7 8 9 1 % Change in strain at break, NBR 1 h 91 92 93 Ox92 Grog Engine LA BD 1% ATF
% Volume change, NBR % Compression set, NBR 2 1 1 1 h 1 9 8 7 6 4 3 2 h 1 1 91 92 93 Ox92 Grog Engine LA BD 1% ATF 93 Grog Engine % Change in Tensile Strength, NBR % Change in strain at break, NBR 2 1 1 2 1 3 2 3 4 4 1 h 6 6 7 8 1 h 7 9 8 91 92 93 Ox92 Grog Engine LA BD 1% ATF 1 91 92 93 Ox92 Grog Engine LA BD 1% ATF
2 1 1 1 2 1 1 2 3 4 6 7 8 % Volume change, NBR 1 h 91 92 93 Ox92 Grog Engine LA BD 1% ATF 1 h 1 9 8 7 6 4 3 2 1 h % Compression set, NBR 93 Grog Engine Findings NBR: IRM oils real oils Increased hardness in real oils Small volume changes in real 1 oils Tensile properties severly deteriorated 2 in real 3 oils 4 Compression set low for IRM93 due to swelling 6 Real oils: probably extraction of softener + 7 1 h increased crosslinking due 8 to oil additives % Change in Tensile Strength, NBR 91 92 93 Ox92 Grog Engine LA BD 1% ATF 9 1 % Change in strain at break, NBR 91 92 93 Ox92 Grog Engine LA BD 1% ATF
4 3 3 2 2 1 1 % Volume change, HNBR Change in IRHD, HNBR 1 1 2 91 92 93 Grog Engine LA BD 1% 2 91 92 93 Grog Eng. LA BD 1% Gear Ret. ATF 1 1 2 1 3 1 4 2 2 6 3 7 3 8 4 9 % Change in in tensile strength, HNBR 168 h 91 92 93 Grog Engine LA BD Gear Ret. ATF 91 92 93 Grog Engine LA BD Gear Ret. ATF 1% 1% IRM oils real oils Decreased hardness in almost all oils Smaller volume changes in real oils Tensile properties more deteriorated in real oils 1 2 3 4 6 7 8 9 1 % Change in strain at break, HNBR 91 92 93 Grog Engine LA BD 1% Gear Ret. ATF
4 3 3 2 2 1 1 % Volume change, HNBR % Compression set, HNBR 91 92 93 Grog Engine LA BD 1% 1 9 8 7 6 4 3 2 1 h 93 Grog Engine 1 1 2 1 3 1 4 2 2 6 3 7 3 8 4 9 % Change in in tensile strength, HNBR 168 h 91 92 93 Grog Engine LA BD Gear Ret. ATF 91 92 93 Grog Engine LA BD Gear Ret. ATF 1% 1% 1 2 3 4 6 7 8 9 1 % Change in strain at break, HNBR 91 92 93 Grog Engine LA BD 1% Gear Ret. ATF
4 3 3 2 2 1 1 1 1 2 1 3 1 4 2 2 6 3 7 3 8 4 9 % Volume change, HNBR % Compression set, HNBR 91 92 93 Grog Engine LA BD 1% % Change in in tensile strength, HNBR 91 92 93 Grog Engine LA BD Gear Ret. ATF 91 92 93 Grog Engine LA BD Gear Ret. ATF 1% 1% 1 9 8 7 6 4 3 2 1 h 93 Grog Engine Findings HNBR: IRM oils real oils Decreased hardness in almost all oils Smaller volume changes in real oils 1 Tensile properties more 2 deteriorated in real oils 3 Compression set lower 4 for IRM93 due to swelling. Decreasing with time! 6 Decreased 168 hhardness 7 => softening effect + 8 possibly chain or crosslink scission 9 1 % Change in strain at break, HNBR 91 92 93 Grog Engine LA BD 1% Gear Ret. ATF
4 % Volume change, VMQ Change in IRHD, VMQ 3 3 1 h 2 2 1 1 1 91 92 93 Ox92 Grog Engine LA BD 1% 1 1 2 2 3 3 4 1 h 91 92 93 Ox92 Grog Engine LA BD 1% % Change in tensile strength, VMQ % Change in strain at break, VMQ 1 1 2 2 3 3 4 6 1 h 4 6 7 8 7 8 1 h 9 9 1 91 92 93 Ox92 Grog Engine LA BD 1% 1 91 92 93 Ox92 Grog Engine LA BD 1% Volume change: IRM oils ~ real oils, except 93 Decreased hardness in all oils Tensile properties OK, but not for the grog
% Volume change, VMQ 4 3 3 1 h 2 2 1 1 1 91 92 93 Ox92 Grog Engine LA BD 1% 13 11 9 7 3 1 1 h Compression set, VMQ * * Measurement interrupted after days IRM93 EGR grogg Engine oil % Change in tensile strength, VMQ % Change in strain at break, VMQ 1 1 2 2 3 3 4 6 1 h 4 6 7 8 7 8 1 h 9 9 1 91 92 93 Ox92 Grog Engine LA BD 1% 1 91 92 93 Ox92 Grog Engine LA BD 1%
4 3 2 2 % Volume change, VMQ 3 1 1 1 1 2 3 4 6 7 8 9 1 1 h 91 92 93 Ox92 Grog Engine LA BD 1% 13 11 9 7 3 1 1 h Compression set, VMQ * * Measurement interrupted after days IRM93 EGR grogg Engine oil Findings VMQ: Volume change: IRMoils ~ real oils, except 93 Decreased hardness in all oils Tensile properties OK, but 1not for the grog Compression set low for IRM93 2 due to 3 swelling. Grog destroys the 4sample Decreased hardness => softening effect + 1 h 6 possibly chain or crosslink 7 scission (especially in 1 h the grog) 8 % Change in tensile strength, VMQ 91 92 93 Ox92 Grog Engine LA BD 1% 9 1 % Change in strain at break, VMQ 91 92 93 Ox92 Grog Engine LA BD 1%
3 % Volume change, FKM type 1 2 Change in IRHD, FKM type 1 2 2 2 1 1 1 1 91 92 93 Grog Engine LA BD 1% 91 92 93 Grog Engine LA BD 1% 1 1 2 3 4 6 7 8 9 % Change in tensile strength, FKM type 1 91 92 93 Grog Engine LA BD 1% 1 3 7 9 % Change in strain at break, FKM type 1 91 92 93 Grog Engine LA BD 1% Volume change very small in all oils Slightly increased hardness in all oils Tensile properties OK, but more affected by the real oils
3 2 2 1 1 1 1 2 3 4 6 7 8 9 % Volume change, FKM type 1 91 92 93 Grog Engine LA BD 1% 1 9 8 7 6 4 3 2 1 h % Compression set, FKM type 1 IRM 93 EGR grogg Engine oil Findings FKM type 1: Volume change very small in all oils Slightly increased hardness in all oils Tensile properties OK, but more affected by the 1 real oils Compression set low for all 3 oils. Grog resistant Increased hardness => possibly crosslink formation % Change in tensile strength, FKM type 1 91 92 93 Grog Engine LA BD 1% 7 9 % Change in strain at break, FKM type 1 91 92 93 Grog Engine LA BD 1%
3 2 2 1 1 1 1 2 3 4 6 7 8 9 % Volume change, FKM type 1 91 92 93 Grog Engine LA BD 1% 1 9 8 7 6 4 3 2 1 h % Compression set, FKM type 1 IRM 93 EGR grogg Engine oil Findings FKM type 1: Volume change very small in all oils Slightly increased hardness in all oils Tensile properties OK, but more affected by the 1 real oils Compression set low for all 3 oils. Grog resistant Increased hardness => possibly crosslink formation % Change in tensile strength, FKM type 1 91 92 93 Grog Engine LA BD 1% 7 9 % Change in strain at break, FKM type 1 91 92 93 Grog Engine LA BD 1%
% Volume change, FKM type 3 Change in IRHD, FKM type 3 2 2 2 2 1 1 1 h 1 1 h 1 91 92 93 Ox92 Grog Engine LA BD 1% 91 92 93 Ox92 Grog Engine LA BD 1% 1 2 3 4 6 7 8 9 1 % Change in tensile strength, FKM type 3 1 h 91 92 93 Ox92 Grog Engine LA BD 1% Volume change very small in all oils Slightly increased and decreased hardness Tensile properties OK, but more affected by the real oils Tensile properties better than for FKM type 1 1 2 3 4 6 7 8 9 1 % Change in strain at break, FKM tpe3 type 1 h 91 92 93 Ox92 Grog Engine LA BD 1%
2 2 1 1 1 2 3 4 6 7 8 9 1 1 h % Volume change, FKM type 3 91 92 93 Ox92 Grog Engine LA BD 1% 1 9 8 7 6 3 2 1 % Compression set, FKM type 3 4 h Findings FKM type 3: Volume change very small in all oils Slightly increased and decreased hardness Tensile properties OK, but 1 more affected by the 2 real oils 3 Tensile properties better than 4 for FKM type 1 Compression set low for all oils. Grog resistant 6 7 Increased hardness => possibly crosslink 8 1 h formation % Change in tensile strength, FKM type 3 1 h 91 92 93 Ox92 Grog Engine LA BD 1% 9 1 IRM 93 EGR grogg Engine oil % Change in strain at break, FKM tpe3 type 91 92 93 Ox92 Grog Engine LA BD 1%
4 3 3 2 2 1 1 1 1 h % Volume change, AEM 91 92 93 Ox92 Grog Engine LA BD 1% 2 1 1 1 1 2 2 3 Change in IRHD, AEM 1 h 91 92 93 Ox92 Grog Engine LA BD 1% 1 1 2 3 4 6 7 8 9 % Change in tensile strength, AEM 1 1 1 h 91 92 93 Ox92 Grog Engine LA BD 1% 3 7 9 1 h V l h b th + d Volume change both + and - Increased and decreased hardness, correlate ~ with volume change Tensile properties OK, but more affected by the real oils Tensile properties OK for IRM oils, but terrible for most real oils % Change in strain at break, AEM 91 92 93 Ox92 Grog Engine LA BD 1%
4 3 3 2 2 1 1 1 1 h % Volume change, AEM 91 92 93 Ox92 Grog Engine LA BD 1% 1 9 8 7 6 4 3 2 1 Compression set for AEM h IRM93 EGR grogg Engine oil % Change in tensile strength, AEM % Change in strain at break, AEM 1 1 2 3 4 6 7 8 9 1 1 1 h 91 92 93 Ox92 Grog Engine LA BD 1% 3 7 9 1 h 91 92 93 Ox92 Grog Engine LA BD 1%
4 3 3 2 2 1 1 1 1 1 2 3 4 6 7 8 9 1 h % Volume change, AEM Findings AEM: 1 3 2 Volume change both + and - 1 91 92 93 Ox92 Grog Engine LA BD 1% % Change in tensile strength, AEM 9 8 7 6 4 h Compression set for AEM Increased and decreased hardness, correlate ~ with volume change Tensile e properties es OK, but more oeaffected ed by the real oils Tensile properties OK 1for IRM oils, but terrible for most real oils 1 Compression set low for 93 due to swell. Grog 3 semi-resistant, not as good as FKM Hardness + and - => extraction of softener, possibly crosslink formation 7 and scission 1 h 91 92 93 Ox92 Grog Engine LA BD 1% 9 1 h IRM93 EGR grogg Engine oil % Change in strain at break, AEM 91 92 93 Ox92 Grog Engine LA BD 1%
3 % Volume change, ACM 1 Change in IRHD, ACM 3 2 2 1 1 91 92 93 Ox92 Grog Engine LA BD 1% 1 1 2 2 3 91 92 93 Ox92 Grog Engine LA BD 1% 1 1 2 3 4 6 7 8 9 % Change in tensile strength, ACM 91 92 93 Ox92 Grog Engine LA BD 1% Volume change negative for 91, high for 93, Mostly decreased hardness, correlate ~ with volume change Tensile properties OK, but more affected by the real oils Tensile properties OK for all oils 2 1 1 2 3 4 6 7 8 % Change in strain at break, ACM 91 92 93 Ox92 Grog Engine LA BD 1%
3 3 2 2 1 1 % Volume change, ACM 9 7 3 h % Compression set, ACM 91 92 93 Ox92 Grog Engine LA BD 1% 1 1 IRM93 EGR grogg Engine oil 1 1 2 3 4 % Change in tensile strength, ACM 2 1 1 2 3 4 % Change in strain at break, ACM 6 7 6 8 7 9 91 92 93 Ox92 Grog Engine LA BD 1% 8 91 92 93 Ox92 Grog Engine LA BD 1%
3 3 2 2 1 1 1 1 2 3 4 6 7 8 9 % Volume change, ACM 91 92 93 Ox92 Grog Engine LA BD 1% % Change in tensile strength, ACM 91 92 93 Ox92 Grog Engine LA BD 1% 9 7 3 1 1 h % Compression set, ACM IRM93 EGR grogg Engine oil Findings ACM: Volume change negative for 91, high for 93, Mostly decreased hardness, 2 correlate ~ with 1 volume change Tensile properties OK, but 1 more affected by the 2 real oils 3 Tensile properties OK for 4 all oils Compression set low for 93 due168 to h swell. Grog 6 resistant, almost as good as FKM 7 Hardness mostly lower => 8 softening effect, possibly crosslink scission % Change in strain at break, ACM 91 92 93 Ox92 Grog Engine LA BD 1%
Mechanisms for rubber-oil interaction Crosslink or polymer scission Crosslink formation Softener extraction Oil plasticising
SUMMARY Oil = Base oil + additives Base oil - most physical effects swelling Additives = reactive species Standard oils (IRM oils) mostly only physical effects Chemistry created by reactive species, including oil additives and oxygen! O 2 O 2 O 2 O 2
ACKNOWLEDEGMENTS Alice Pazat, previous diploma worker at Scania Trelleborg Ersmark, for providing samples Zeon & Erteco for providing material
THANK YOU!