Nylon 612: Viable Alternative Tubing Constructions in Fuel Systems ITB Automotive Energy Storage Systems 2013 Novi, MI March 6-7, 2013 FAST FORWARD YOUR INNOVATION TM
A. Schulman A Global Solutions Provider $2.1 BN revenue 2012 5 integrated business segments Masterbatch Solutions (35%) Custom Performance Colors (7%) Specialty Powders (16%) Engineered Plastics (26%) Distribution Services (16%) 34 manufacturing facilities 3,300 associates in 25 countries 4 technology centers - Americas and Europe Strong innovation model for growth 2
A. Schulman Engineered Plastics Polypropylene TPO Polyamide Polyester Polyoxymethylene Polypthalamide Ionomers Blends & Alloys Flame Retardant Compounds Thermoplastic Elastomers Long Glass Fiber Thermoplastics Bio-filled Compounds Specialty Masterbatches Most diverse portfolio of multi-polymer and multi-functional compounds Serving Mobility, Electrical & Electronics, Sport & Leisure markets Strong commitment to the Automotive market Wide range of OEM and regulatory material approvals Technology centers in US, Mexico, Germany 3
A. Schulman High Performance Polyamides Nylon 6 Nylon 66 Nylon Copolymers Nylon 610 Nylon 612 Unfilled Mineral Glass Fiber Glass Bead Carbon Fiber Aramid Fiber Carbon Nanotube Mineral + Fiber Plasticized Lubricated Flame Retardant Custom Colors Blends & Alloys Wide range of PA chemistries PA production in US, Mexico, Brazil, Germany and China Global technology platform for Fluid Management applications Wide range of OEM approvals Proven performance in Automotive fuel and brake systems Virtually integrated nylon producer with ability to customize at the molecular level 4
Fuel Systems Performance: Key Drivers Ref: Kuraray Fuel Evolution -ethanol-rich blends - biodiesel / biofuels -diesel Powerplant Evolution - increased hp/displacement -hybrids Legislative Evolution - CARB LEV III -EPA Tier 3 - CAFE 2025 -CO 2 emissions reduction Supply Chain Evolution - PA12 / other disruptions - Raw material price volatility - New material alternatives Raw materials and system design constructions must evolve to keep pace with the evolution of performance! 5
Schulamid and SchulaTube TM Technology Objectives Develop new materials innovative to the market Develop new tubing constructs innovative to our customers Enable development trials inhouse with our suppliers and customers Conduct seminars for training our customers SchulaTube TM Speaking the language of our customers and the market Key Deliverables Leverage our global expertise in polyamide compounds Commercialize innovation faster Develop competitive products which provide value to our customers and the market 6
A. Schulman Academy Applications Center Kerpen, Germany SOTA 3-Extruder Multilayer Tubing Line Smooth and Corrugated Capability Beta-Laser Dimensional Measurement Layer Microscopy Workstation Burst Pressure Testing Chamber 7
PA612 Performance Higher heat resistance than PA610 and PA12 (40 C higher melt temperature) Can be plasticized to be as flexible as PA12 Comparable moisture uptake to PA12, and less than PA610 Excellent salt (zinc chloride) corrosion resistance Excellent resistance to H 2 SO 4 solution Demonstrated acceptable fuel and chemical resistance Minimal oligomer extraction which can foul injectors 8
PA612 Performance Excellent Nylon 612 Nylon 12 Nylon 6 Nylon 66 Good Fair Poor Specific Gravity Tensile Strength/Modulus Flexural Strength/Modulus Elongation Notched Impact Strength Hydrolysis/Moisture Resistance General Chemical Resistance Gasoline/Diesel/Biodiesel Resistance Salt Resistance Heat Resistance (DTUL) Dimensional Stability 9
SchulaTube TM FS: Test Protocol (AIAG) I. Short-Term Validation - Straightforward, High Confidence Level (Tubing and Assemblies) 1. SAE J2044, J2045, or J2260 spec or OEM spec equivalent (must have comparison data for product being replaced). It is assumed that all assemblies prepared for the testing will be leak tested per SAE J2045 prior to test and that this leak test data will be reported. For assemblies, connections tested must include production intent technologies. A. Burst (conduct with quick-connectors, also test tubing without connectors if test result is quick-connector blow-out) B. Hi-Temp Burst (conduct with quick-connectors, also test tubing without connectors if test result is quick-connector blow-out) C. Adhesion D. Cold Impact E. Kink Resistance F. Tensile Test G. Elongation Test H. Zinc Chloride Test if the outer layer is not an alternative PA12. 10
SchulaTube TM FS: Constructions Construction: monolayer, non-conductive, smooth, 6.35mm ID SchulaTube TM FS 102 100% Mono Layer: Schulamid 612 FS 4004 Black 612 FS 4004: High molecular weight, high impact 11
SchulaTube TM FS: Gasoline Testing SAE J2260 DVP&R Results Procedure Conditions Result Pass/Fail 7.1 Room Temp Burst 23 C, 7 MPa/min 7.1 MPa Pass 7.2 High Temp Burst 115 C, 7 MPa/min 2.4 MPa Pass 7.5 Cold Temp Impact -40 C, 75% retention 7.2 MPa Pass A.4.1 Tensile Strength 50 mm/min to failure 39.4 MPa Pass A.4.1 Elongation 50 mm/min to failure 365% Pass 7.12 Zinc Chloride Test 50% ZnCL 2, 23 C, 200 hrs 5.3 MPa Pass (No cracks) 7.6 Fuel Recirculation* Expose, test to Sec 7.5 4.1 MPa Pass 7.8 Sour Gas Expose, test to Sec 7.5 4.0 MPa Pass *CM15A Fuel 12
SchulaTube TM FS: Constructions Construction: 3-layer, non-conductive, smooth, 8mm x 1mm SchulaTube TM FS 301 50% Outer Layer: Schulamid 612 FS 4104 Black 10% Middle Layer: Kuraray EVAL FP101B (EVOH) 40% Inner Layer: Schulamid 612 FS 5004W Natural SchulaTube TM FS 312 50% Outer Layer: Schulamid 612 FS 4004 Black 10% Middle Layer: Kuraray EVAL FP101B (EVOH) 40% Inner Layer: Schulamid 612 FS 4104 Natural 612 FS 4104: High molecular weight, super high impact 612 FS 4004: High molecular weight, high impact 612 FS 5004W: High molecular weight, high impact, plasticized 13
SchulaTube TM FS: Gasoline Testing Long Term Peak Inside Temperature: -40 C to +110 C max. +130 C Ambient Temperature: -40 C to +135 C max. +170 C Operating Pressure: Fuel: Inside 0.5 8.0 bar (max. 10.0 bar) Various, with and without ethanol Specifications: VW TL 52345, BMW QV 16006, DIN 73378 14
SchulaTube TM FS: Gasoline Testing Schulatube TM FS 301 Schulatube TM FS 312 Operating Performance (VW) Pass (Approved) - Operating Performance (BMW) - Pass (Approved) Processing Good Good Layer Adhesion Very good Very good Cold Impact (-40 C), Charpy 7.5J No break No break Cold Impact (-40 C), Ball 880g / 650 mm No break No break ZnCl 2 Resistance (with connector) Very good Very good Burst Pressure (+23 C) > 100 bar > 100 bar Burst Pressure (+23 C) after 10X to failure > 80 bar > 80 bar Burst Pressure (+115 C) > 40 bar > 40 bar Tensile Strength > 30 MPa > 30 MPa Elongation > 230 % > 250 % 15
SchulaTube TM FS: Gasoline Testing Oligomer Extraction: Exposure at 23 C 24 hr drying E85 fuel SchulaTube FS 312 VW and BMW Specification: < 10 mg/m 2 after 500 hrs After 200 hrs After 500 hrs < 2 mg/m² 9 mg/m² 19
SchulaTube TM FS: Constructions Construction: non-conductive, smooth, 8mm x 1mm SchulaTube TM FS 101 100% Mono Layer: Schulamid 612 FS 4004 Black SchulaTube TM FS 301 50% Outer Layer: Schulamid 612 FS 4104 Black 10% Middle Layer: Kuraray EVAL FP101B (EVOH) 40% Inner Layer: Schulamid 612 FS 5004W Natural 612 FS 4004: High molecular weight, high impact 20
SchulaTube TM FS: Diesel Testing Long Term Peak Inside Temperature: -40 C to +120 C max. +140 C Ambient Temperature: -40 C to +150 C max. +170 C Operating Pressure: Fuel: Inside 0.5 5.0 bar Various, with and without bio content Specifications: BMW QV 13032 21
SchulaTube TM FS: Diesel Testing Schulatube TM FS 101 Processing Very good Cold Impact (-40 C), Charpy 7.5J No break Cold Impact (-40 C), Ball 880g / 650 mm No break ZnCl 2 Resistance Very Good Burst Pressure (23 C) > 100 bar Burst Pressure (120 C) > 20 bar Burst Pressure (135 C) > 15 bar Burst Pressure (150 C) > 10 bar Tensile Strength (unconditioned) 29 MPa E-Modulus (unconditioned) 462 MPa Elongation (unconditioned) > 250 % Tensile Strength (after 1500h at 90 C with B20, 5 bar) 29 MPa E-Modulus (after 1500h at 90 C with B20, 5 bar) 577 MPa Elongation (after 1500h at 90 C with B20, 5 bar) > 180 % Burst pressure (23 C, after 1500h at 90 C with B20, 5 bar) 58 bar 22
SchulaTube TM FS: Diesel Testing Oligomer Extraction: 72 hrs at 60 C B20 and B30 fuels SchulaTube FS 301 24
SchulaTube TM FS: Next Steps Evaluations are proceeding with these tubing structures: PA612 / adhesive / EVOH / adhesive / PA612 PA612 / EVOH / PA612 PA612 / ETFE / PA612 PA612 / ETFE / PA6 Various barrier polymer grades Various layer thicknesses Measurables: Fuel permeation Burst strength Layer adhesion quality Conductivity Extrusion processability Connector / tubing sealing 27
SchulaTube TM FS: Conclusions PA612 is a viable polymer for use in automotive fuel systems PA612 compounds are currently approved and in use with at least 6 global OEMs The viability of PA612 in fuel systems depends on the PA612 resin and compound formulation design Innovation in tubing constructions offers potential for balancing performance with cost reduction 28
Appreciation Special thanks for their kind assistance and contributions to this presentation: Thilo Stier Peter Sebö Tom Jacques A. Schulman Germany A. Schulman Germany A. Schulman US 29
Thank you for your attention! Contact: Jeff McCoy Manager, Business Development Engineered Plastics Americas (330) 630-7135 jeff_mccoy@us.aschulman.com 30