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The World of Teijin Aramid A Crain Communications Event 1725 Merriman Road * Akron, Ohio 44313-9006 Phone: 330.836.9180 * Fax: 330.836.1005 * www.rubbernews.com ITEC 2014 Paper T-17 All papers owned and copyrighted by Crain Communications, Inc. Reprint only with permission Twaron p-aramid in Tires: Lightweight and strong solution September 9, 2014 Botond Szalma [email protected] 404.431.5014 Agenda • Quick Review – Teijin Aramid – Aromatic polyamide (aramid) - Twaron • Trends in tire developments • Industry’s impact on Twaron developments • What’s “HOT” today? – Hybrids – Cooper Tire: DOE Grant • Summary & Conclusions Teijin Aramid part of Teijin Limited • Global technology-driven group operating in six main fields Advanced fibers and composites business group • Aramids Teijin Aramid • Carbon Fiber, PET/PEN etc Healthcare business group Trading and retail business group IT business group New business development group Electronic materials and performance polymer products business group • Listed on Tokyo and Osaka stock exchanges • 150 companies and around 17,000 employees worldwide • Consolidated sales of USD 7.4 billion* * March 31, 2013 Aromatic polyamide (aramid) Twaron® : para-aramid fiber produced by Teijin Aramid Teijin Aramid product portfolio Para-aramid: • Twaron (black, tape) • Technora • Sulfron Meta-aramid: • Teijinconex Chopped Fibers, Staple Fibers: • 1-12mm fiber length • Dipped/Undipped Chopped Fibers • Pulp Chopped fibers & Pulp Masterbatch •Different length (1 – 6 mm) with or without RFL dip for improved dispersion • Twaron D3500 Masterbatch • Sulfron for lowering hysteresis Twaron type 1189 (1.5 mm) Un-dipped Technora Sulfron 3515 Teijin Aramid: A global presence… Production Delfzijl: Monomer and Polymer Emmen: Twaron Yarn, Staple Fiber, Pulp, Sulfron Arnhem: Pulp, Pelletized Monomer, Purified Polymer Iwakuni: Teijinconex Matsuyama: Technora Facts & Figures: “more than a yarn producer” • Global market leader • Serving the industry for over 30 years • Global presence - 1,500 employees worldwide (from 1,100 12 years ago) • R&D Staff: 60 120 in 12 years • More than 80 patent positions • 5% of turnover invested in R&D Technical Service: Fiber Institute • Converting – Direct cablers – Ring twisting – Assembling • Dipping – Single end dip units – Hot melt dip unit • Rubber Lab & End Use tests • Dynamic-Mechanical measurements • Textile Laboratory – Tensile testing – Moisture measurements – Krimp testing – Adhesion testing Zell dip unit Litzler dip unit Cut & Stab testing now used for Tires Aircraft Tyres: Foreign Object Damage (FOD) OTR: Sidewall protection Tire has teamed up with Ballistics (rubberized aramid fabric protection) Standard Test Methods for •Measuring Cut Resistance of Materials Used in Protective Clothing ASTM 1790 •Body Armour Standards – Cut & Spike Resistance What is Twaron and how is it different? Comparison between different reinforcing materials • High strength based on mass • 5 times stronger than Steel! 2500 • High modulus 2000 • Excellent heat, cut and Twaron chemical resistance Twaron HM 1500 • No melting point Steel PET • No Corrosion 1000 PA 66 Rayon • Hybrids with PA 6.6, PET, PEN Tenacity (mN/tex) 500 0 0 5 10 15 20 25 Elongation at break (%) High crystalline vs Thermoplastics Heat generation / strength • Hysteresis = heat (loss) generation due First scan 150 to cyclic deformation • Low hysteresis in dynamic applications is required 100 Thermoplastics PET/PA Twaron 50 Normalized Work Loss per cycle [-] cycle per Loss Work Normalized Amorphous 0 Crystalline 20 40 60 80 100 120 140 160 180 200 temperature [° C] Aramid PA 6 PA 6.6 PET HMLS Semi-crystalline Para-crystalline PET regular Rayon PEN Twaron High crystalline (no Tg) Aramid application in tires ~ 7,200 tons • High Performance PCR • Racing & Motorcycle • Aircraft • Off-the-road (OTR) • Bicycle Reinforcement - examples • PCR/Racing − Cap ply − Belt / Breaker − Carcass − Bead − Sidewall • Motorcycle − Belt • Bicycle tire − Bead • OTR − Belt/Breaker − Carcass − Sidewall • Aircraft − Belt Protective - examples • PCR (SUV’s AT’s) • Bicycle tires – Anti puncture breaker / short fibers • OTR – Cut resistant breaker – Side wall reinforcement • Aircraft tires – Aramid protective layer – FOD specification Trends in tire developments • Tire Labeling (Noise, Rolling Resistance, Wet grip, Wear) • Lower weight tires • Unsprung mass • CO2 emission passenger cars - Impact Regulation (EC) No 443/2009 • CAFE 2025 54.5mpg • “DO MORE WITH LESS RAW MATERIALS” Cost Savings!!! • CCC & Puncture Resistance, Retreadabiltiy, Larger Tires, Better Fuel Economy (RR) • Aircraft Tires • OTR, Farm, Agricultural Trends’ impact on Twaron developments Yarn developments Tires High 2 •Thinner but stronger yarns tenacity D2320 e.g. 840 dtex for • Cost effective production carcass 1 3 High modulus Twaron 2200 •Higher Modulus & Higher Tenacity e.g. for bead, • Replace steel Stress •Lower Modulus Low modulus / high • Improving fatigue performance elongation improved fatigue: e.g. 840 dtex for carcass , 1680 dtex cap ply Elongation Advantages of Twaron in Tires • Lighter weight tire – Less plies, less rubber • Lower rolling resistance – Better fuel economy • Lower Unsprung mass – More comfortable ride • No flat spotting • No corrosion • Better dynamic steering performance Arguments against aramid in Tires • Compression Fatigue • Availability • Price Lower modulus = Higher retained strength Lower Modulus = Better Dynamic Fatigue Comparison Twaron types Yarn 2-ply cord (based on 1100 - 1210 dtex data) 2500 Θ 2400 Θ 1025 2300 2100 D2200 2200 1008 2100 Breaking tenacity [mN/tex] Breaking 1000 / twist angle Θ twist angle Θ D1014 = surface angle of outer filaments in a yarn = ply angle in a cord 2000 1900 50,0 60,0 70,0 80,0 90,0 100,0 110,0 120,0 130,0 140,0 Chord modulus [Gpa] What’s “HOT” today: Hybrid solutions • In most developments Tenacity / Elongation Polyamide (PA) is used 2500 2000 Aramid PET 1500 PA 6.6 1000 ----> Tenacity (mN/tex) Tenacity ----> 500 0 0 5 10 15 20 ----> Elongation (%) Source: Y1724 Tensile 001 for Gerard.xls *) Source : Tire Technology 2012 : Presentation Conti on tire modelling Cap ply & Hybrids • After tire lift, low modulus part is consumed and high modulus of aramid keeps steel belts in shape • PA 6.6 principle is based on shrinkage forces, which however decrease quickly at high temperature Hybrid Stress-Strain Curves TW/PA 6.6 Twaron/PA6.6 in 2-ply and 3-ply hybrid constructions Greige Cord Tensile curves 700 Twaron 1680dtex 2-ply and 3-ply cords with PA 6.6 1400dtex twist level variations 600 3-ply (2x AR + 1x PA) 2-ply (1x AR + 1x PA) 500 400 300 Force [N] 200 100 0 0 2 4 6 8 10 12 14 16 18 20 Elongation [%] Source: Y5662 Hybrid Asym MvdT.xls RFL Dipped hybrid cords PA 6.6 & Polyester (PET) Tenacity / Elongation Z6.9/S6.9 1800 Tf=160 1600 1400 Tenacity / Elongation 1200 400 1000 350 300Twaron 800 Twaron 1008 3-ply 250 PET 600 Hybrid HMLS PET 200 (mN/tex) Tenacity ----> Hybrid HT PET 150 400 Hybrid SLS PET 100 Hybrid PA 6.6 PA 200 ----> Tenacity----> (mN/tex) 50 Hybrid PA 4.6 0 0 0 1 2 3 0 2 4 6 8 10 ----> Elongation (%) ----> Elongation (%) Hybrids & Fatigue – Pre-selection of cords • Fatigue test methods – GBF compression (+2,-14%) standard for carcass – GBF tension (+2, +16%) maybe indication for cap ply – Flex fatigue (AFF) belt of e.g. agricultural tires GBF compression fatigue Strength single aramid ply (1680 dtex) in several constructions with same twistfactor / T03/A11-dip GBF : 2%, -14%, 6 hrs 120% 100% 100% 100% 84% 80% 70% 63% 59% 2 ply 60% 3 ply 40% 20% 0% Not tested GBF : Full aramid GBF : hybrid 2-ply Twaron 1680*2 (315/315) 2-ply Twaron 1680*2 (315/315) Twaron 1680 + PA6,6 1400 (315/315) 3-ply Twaron 1680*3 (257/257) 3-ply Twaron 1680*3 (257/257) Twaron 1680*2 + PA6,6 1400 (257/257) • 1-ply TW + 1-ply PA 6.6 best performance • 3 ply hybrid comparable as 2-ply Twaron cord Flex fatigue Strength single aramid ply (1680 dtex) in several constructions with same twistfactor / T03/A11-dip AFF : 1mm rubber, 25 mm pulley, 2 hrs 120% 100% 100% 100% 80% 2 ply 60% 53% 3 ply 36% 40% 29% 22% 20% 0% Not tested AFF : Full aramid AFF : hybrid 2-ply Twaron 1680*2 (315/315) 2-ply Twaron 1680*2 (315/315) Twaron 1680 + PA6,6 1400 (315/315) 3-ply Twaron 1680*3 (257/257) 3-ply Twaron 1680*3 (257/257) Twaron 1680*2 + PA6,6 1400 (257/257) • Hybrids perform better during flexing Difference GBF compression and tension fatigue Strength single aramid ply (1680 dtex) in several constructions with same Strength single aramid ply (1680 dtex) in several constructions with same twistfactor / T03/A11-dip twistfactor / T03/A11-dip GBF : 2%, -14%, 6 hrs GBF : 2%, +16%, 96 hrs 120% 120% 100% 100% 100% 100% 100% 100% 84% 76% 77% 80% 70% 80% 72% 63% 59% 2 ply 2 ply 56% 60% 3 ply 60% 3 ply 40% 40% 20% 20% 0% 0% Not tested GBF : Full aramid GBF : hybrid Not tested GBF : Full aramid GBF : hybrid 2-ply Twaron 1680*2 (315/315) 2-ply Twaron 1680*2 (315/315) Twaron 1680 + PA6,6 1400 (315/315) 3-ply Twaron 1680*3 (257/257) 3-ply Twaron 1680*3 (257/257) Twaron 1680*2 + PA6,6 1400 (257/257) 2-ply Twaron 1680*2 (315/315) 2-ply Twaron 1680*2 (315/315) Twaron 1680 + PA6,6 1400 (315/315) 3-ply Twaron 1680*3 (257/257) 3-ply Twaron 1680*3 (257/257) Twaron 1680*2 + PA6,6 1400 (257/257) • Compression is more severe • Compression: 2 ply hybrid advised; not 3 ply hybrid • Tension: hybrids perform better than full aramids Dipped cord properties @ elevated temp. Dipped cord Breaking Strength @ Elevated Temperature (slack start) 1000 906 780 800 694 677 651 650 660 638 595 569 577 576 572 532
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