Petroleum Oils for Rubber
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1 Petroleum Oils for Rubber Refining, Properties, Polymer Compatibility Jude Abia, PhD AEQ Technical Session Nov 8, Bromont, Quebec
2 HollyFrontier Overview Inland Merchant Refiner 5 refineries in Mid Continent USA and 1 refinery in Ontario, Canada Integrated Specialty Lubricants Producer Operate Crude and Product Pipelines, loading racks, terminals and tanks in and around refining assests ~500,000 barrels per day combined refining capacity Combined 12.1 Nelson complexity index Rubber process oils are produced at the HollyFrontier Lubes plant in Tulsa, Oklahoma and Petro- Canada Lubricants in Mississauga, Ontario 59 % interest in Holly Energy Partners, L.P. (HEP), a logistics MLP
3 HollyFrontier Lubricants & PCLI provide the broadest and purest slate of Base and Process Oils for finished products and end customers
4 Oil Refinery Process Flow Lube Oil Refinery Process Flow Light Neutral Light Neutral Base Oil Vacuum Gas Oil Atmospheric Tower Residue Vacuum Distillation Medium Neutral Heavy Neutral PDA DAO Oil Solvent extraction & Dewaxing Furfural Extraction MEK Dewaxing DWO Finishing Hydro- Finishing Catalytic dewaxing Medium Neutral Base Oil Heavy Neutral Base Oil Bright Stock Vac Tower Residue Asphalt Propane Deasphalting extraction (PDA) PDA Tar Wax Aromatic Oils Bitumen Slack Wax Furfural Extracts Bitumen blendstocks
5 Composition of Rubber Process Oil
6 Composition of Rubber Process Oil Compositional information about rubber oils can be obtained by: ASTM D2007 clay gel analysis Saturates Aromatics Polars Asphaltenes ASTM D2140 Carbon type distribution
7 Process Oil Classification Oil type ASTM D2501 VGC range Paraffinic % max. ASTM D2007* Aromatic wt% Naphthenic % Relatively Aromatic % Aromatic % min.
8 Key Properties for Rubber Process Oil Rubber Oil Properties Sundex 8000 EU Sundex SUS Naphthenic Sunpar 2280 Viscosity, 100C Density 15C Aniline Point, C Viscosity-Gravity Constant Saturates Polar Compounds Aromatics Molecular weight Polycyclic aromatic compounds (PAH) Pass Pass Pass Pass Higher density means more oil mass available to interact with polymer for the same oil volume Higher aromatic content means greater compatibility for most polymer applications such as SBR, NR, IR, BR, CR Sundex 8000 EU and Sundex 165 are Residual Aromatic Oils and meet the EU REACH restriction on PAH Sundex 165 has lower viscosity and could be easier to handle in regions where cold weather presents a challenge.
9 Oil Compatibility with Elastomer One of most important characteristics of oil is compatibility with the rubber. Due to amount and migration capabilities, oil need to have good compatibility with polymer system to mitigate blooming Oil advantages are negated if oil blooms out during rubber processing or after vulcanization Rule: Use non-polar oils with non-polar polymers; Use polar oils with polar polymers
10 Oil Compatibility with Rubber Rubber Type Aromatic Naphthenic Paraffinic NR Very good Good fair SBR Very good Good Fair EPDM Fair Good Very good BR Very good Good Fair IR Very good Good Fair IIR, CIIR, BIIR Poor Fair Good CR Very good Good Fair NBR Good Fair Poor
11 Oil Processability Ease with which an oil incorporates into rubber Greatest compatibility; Most efficient in reducing viscosity; Only small amount is required Partial compatibility; Most efficient in reducing viscosity; Higher amount is required Non-compatible; least efficient in reducing viscosity; Large amount is required
12 Oil Takeup Time, Minutes Oil Take-up Time for 100 SUS Oils in SBR Less take-up time means lesser time to process batch and higher through-put 68 Aromatic region Naphthenic region Paraffinic region Aniline Point of Oil, deg. C
13 Effect of Oil Compatibility on Rubber Physical Properties Rubber Formulation First Pass phr Solution SBR CV60 NR Proaid AC-31 Process Aid 2.00 N Ultrasil 7000 GR Silica Si69 Coupling Agent 4.80 Process Oil 10 or 20 Second Pass Zinc Oxide 1.90 Stearic Acid 1.50 Microcrystalline Wax PPD 2.00 TMQ 0.50 Final Pass TBBS 1.30 DPG 1.50 Sulfur 1.50
14 Crack Growth, DeMattia, Cycles to 1/2 inch Growth Tear Strength, psi Paraffinic region Naphthenic region Aromatic region Best performance obtained with aromatic 320 oils Aromatics, wt % Tear Strength at 10 phr Tear Strength at 20 phr Crack Growth at 10 phr Crack Growth at 20 phr
15 Tensile Strength, psi 3900 Paraffinic region Naphthenic region Aromatic region Best performance obtained with aromatic oils phr 20 phr Aromatics, wt %
16 Oil Compatibility Effect on Carbon Black Dispersion Rubber Formulation First Pass phr Solution SBR CV60 Natural Rubber Proaid AC-31 Process Aid 2.00 N330 or N220 or N Ultrasil 7000 GR Silica Si69 Coupling Agent SUS Process Oil 10 or 20 Second Pass Zinc Oxide, Activator 1.90 Stearic Acid, Activator 1.50 Microcrystalline Wax, PPD, Antiozonant 2.00 TMQ, AgeRite Resin D 0.50 Final Pass TBBS Accelerator 1.30 DPG, accelerator 1.50 Sulfur, Curative 1.50 Properties Oil Type Aromatic Naphthenic Paraffinic Density, g/ml VGC Aromatic content, wt% Aromatic Carbon % Naphthenic Carbon % Paraffinic Carbon %
17 % Dispersion Effect of Oil on Carbon Black Dispersion Aromatic oil showed 6% better dispersion than naphthenic oil Aromatic oil showed 13% better dispersion than naphthenic oil Aromatic oil showed 16% better dispersion than naphthenic oil 80 Aromatic Naphthenic Paraffinic HAF (N330) ISAF (N220) SAF (N110)
18 Summary Oil effect on rubber properties is governed by the composition of the oils Most elastomers are polar and aromatic in nature and hence most compatible with aromatic oils Types of aromatic oils are Residual Aromatic Extract (RAE), Treated Distillate Aromatic Extract (TDAE) and Distillate Aromatic Extract (DAE) RAE and TDAE satisfy the EU REACH restriction on PAH limit Sundex 8000 EU and Sundex 165 are RAE oils Uniformity of a processing oil from batch to batch is necessary once a compound has been designed and standardized HollyFrontier s rubber oils are distilled products with close control of the properties important in rubber compounding to ensure consistency in each batch
19 Technical Support Fully equipped with $2,000,000 in rubber compounding and testing equipment
20 Rubber Mixing Lab Banbury Mixer Two-roll lab mill Hydraulic Compression Press Cold Feed Extruder Mixing rubber compounds Mixing rubber compounds Curing rubber compounds Lab-scale extrusions Hydraulic clicker press Bale cutter Die cut rubber test specimens Cutting bales of rubber
21 Rubber Testing Lab Rubber Process Analyzer Dynamic Mechanical Analyzer Materials Testing Machine Rebound Resilience Tester Abrasion Tester Fatigue to Failure Tester Moving Die Rheometer Mooney Viscometer Durometer Horizon Fog Testing System Dynamic properties before, during and after curing in a single test Dynamic mechanical properties as a function of stress, temperature, time, frequency, atmosphere Tensile stress-strain properties Rebound resilience Abrasive resistance Fatigue life in tension Cure characteristics Viscosity and scotch properties Hardness Automotive interior out-gassing
22 Jude Abia, PhD Product Development Specialist Process Oils
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