ENERGY SAVER BLACKS: CARBON BLACKS FOR IMPROVED TIRE PERFORMANCE Tire Technology Expo 2015 Cologne, Germany February 11, 2015 Wesley Wampler (presenter), Leszek Nikiel, Michael Jacobsson, Joel Neilsen, and Peter Cameron
GOAL Modify Carbon Blacks to Provide Improved Rolling Resistance in Tires ------without sacrificing other performance properties 2
ROLLING RESISTANCE Tire rolling resistance is influenced by: Tire design and dimensions Materials and compounding techniques Tire inflation Speed of the vehicle Hysteresis Heat Loss Upon Deformation 3
FILLER IMPACT ON HYSTERESIS Payne Effect G' (Pa) 7e+6 6e+6 5e+6 4e+6 3e+6 G' vs. Strain in D3192 Filled 0 phr N234 45 phr N234 2e+6 1e+6 Unfilled 0 0.1 1 10 % Strain Filler network breaks down upon straining In deformation cycles the network reforms with energy losses 4
FILLER IMPACT ON HYSTERESIS G' (Pa) 1.6e+7 1.4e+7 1.2e+7 1.0e+7 8.0e+6 6.0e+6 4.0e+6 2.0e+6 0.0 G' vs. Strain in D3192 0 phr N234 25 phr N234 35 phr N234 45 phr N234 50 phr N234 55 phr N234 0.1 1 10 % Strain The filler network strength is directly related to loading and particle size (Surface Area) 5
POLYMER-FILLER INTERACTION IMPORTANT FOR REINFORCEMENT Occluded Rubber between aggregates: Increases the effective filler fraction causing strain amplification Breaking the filler-filler network releases polymer to behave as polymer In addition, adsorption of polymer chains on surface (bound rubber) restricts their mobility 6
CB SOLUTIONS FOR LOWER HYSTERESIS Modification of the filler Decrease filler filler interactions Increase filler polymer interactions Tailored to engage in curing Energy Saver Blacks Patent Pending 7
CHEMICAL MODIFICATION OF CARBON BLACK S OH O Few Reactive Species Covalent vs. Non-covalent Adsorption Van der Waals O OH 1. Graphitic Planes 2. Amorphous Carbon 3. Crystallite Edges 4. Slit Shaped Cavities 1 2 3 4 8
SURFACE ADSORPTION O Polymer S OH O OH 1 2 3 4 Simulated CB Surface with Polymer 9
SURFACE MODIFICATION BY ADSORPTION Van der Waals interactions 10
REDUCTION OF FILLER-FILLER NETWORK G' vs. Strain in D3192 1e+7 N234 Control ES200 8e+6 G' (Pa) 6e+6 4e+6 2e+6 0.1 1 10 % Strain ES200 decreases filler-filler interaction 11
TAN Δ FOR ES200 IN RUBBER COMPOUNDS 0.30 NR 0.24 NR/BR Blend 0.40 SBR/BR Blend Tan d @ 60 o C 0.28 0.26 0.24 0.22 Tan d @ 60 o C 0.22 0.20 0.18 Tan d @ 60 o C 0.38 0.36 0.34 0.32 0.30 0.28 0.20 ES200 N110 N115 N134 N220 N234 0.16 ES200 ES200 + PVI N110 N115 N134 N220 N234 0.26 ES200 ES200 + PVI N110 N115 N134 N220 N234 Lower Tan δ indicates improved hysteresis 12
ES200 & BOUND RUBBER Bound Rubber (Normalized to N234 Control) 1.25 1.20 1.15 1.10 1.05 1.00 0.95 0.90 Bound Rubber of N234 and ES200 in Various Elastomers NR N234 ES200 Natsyn Copo 1500 Duradene 739 Duradene 741 Duradene 738 Duradene 709 Duradene 706 Bound rubber is consistently higher for treated blacks 13
POLYMER INTERACTION COEFFICIENT Concept determine increases of fillerpolymer interaction (as measured by bound rubber) in various polymers with increasing carbon black loading & available surface Slope of mg BR /m 2 CB provides a measure (coefficient) of the polymer-filler interaction 14
POLYMER INTERACTION COEFFICIENT bound rubber (g) 0.40 NR 0.35 0.30 0.25 0.20 0.15 ES200 N110 N134 N234 ES200 N326 N330 SR401 SR409 N550 N660 N762 The greater the slope (PIC) the more interac6on taking place between polymer and filler 0.10 0.05 5 10 15 20 25 30 35 40 45 50 surface area of black total (m 2 ) 15
CROSSLINK DENSITY Crosslink Density Normalized to Control 1.3 1.2 1.1 1.0 0.9 ES200 v. N234 Crosslink Density N234 ES200 0.8 SSBR:BR Natsyn Increased crosslink density for treated blacks 16
PROPOSED ENGAGEMENT IN VULCANIZATION Increased filler-polymer interaction 17
ANGLE ABRASION INDEX FOR ES200 Mass loss from rubber wheels rotating against stone 18
ANGLE ABRASION INDEX FOR ES200 102 NR 105 NR/BR Blend 105 SBR/BR Blend Angle Abrasion Index 100 98 96 94 92 Angle Abrasion Index 100 95 90 85 80 Angle Abrasion Index 100 95 90 90 ES200 N234 75 ES200 ES200 + PVI N110 N115 N134 N220 N234 85 ES200 ES200 + PVI N110 N115 N134 N220 N234 Equivalent abrasion in NR, but superior performance in the other two formulations, demonstrating improved filler-polymer interaction 19
ROLLING RESISTANCE CONTRIBUTION OF INDIVIDUAL TIRE COMPONENTS Emphasis on tread, but other components also important 20
MODIFIED CARCASS CARBON BLACKS Oil Absorption Number - Structure Structure - Surface Area Relationship 140 N650 120 ES601 100 N660 ES600 80 60 28 30 32 34 36 38 40 N2SA - Surface Area 21
COMPOUND FORMULATIONS EVALUATED A B C D E F Formula6on D3191 (SBR) D3192 (NR) An7- Vibra7on Mount Motor Mount Sidewall Compound A Sidewall Compound B A B C D E F Natural Rubber - - - 100 70 100 50 50 Synthe6c Rubber 100 - - - 30 - - - 50 50 Carbon Black 50 50 40 35 50 50 Processing oil - - - - - - 10 2.5 3 20 Zinc oxide 3 5 3 5 5 3 Stearic acid 1 3 2 2 2 1 Sulfur 1.75 2.5 0.4 1 1 1.5 Accelerator 1 0.6 11.1 2.5 0.9 1.4 Total 156.75 161.1 166.5 148.0 161.9 176.9 22
DUROMETER 1.05 N660 ES600 ES600 1.05 N650 ES601 ES601 1.00 1.00 0.95 0.95 0.90 0.90 0.85 0.85 0.80 D3191 D3192 Vibration Motor Mount Sidewall A Sidewall B 0.80 D3191 D3192 Vibration Motor Mount Sidewall A Sidewall B Equivalent or slightly elevated durometer is observed 23
TAN δ AT 60 C 1.1 N660 ES600 ES600 1.1 N650 ES601 ES601 1.0 1.0 0.9 0.9 0.8 0.8 0.7 0.7 0.6 D3191 D3192 Vibration Motor Mount Sidewall A Sidewall B 0.6 D3191 D3192 Vibration Motor Mount Sidewall A Sidewall B A lowering of Tan δ indicates better hysteresis 24
SUMMARY Energy Saver Blacks technology provides improvements in rubber compound hysteresis by Decreasing filler-filler networking Increasing polymer-filler interaction In tread compounds provides equivalent wear In sidewall & other components can provide less overall heat energy losses and overall better performance 25
Mitch Sanders Patrick Nichols Brad Abbott Dave Roberts Willy Lin Donny Hutchinson Steve Break Russell Mason Meridell Armour Ryan Crandall 26