The World of Teijin Aramid
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ITEC 2014 Paper T-17
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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 906 780 800 694 677 651 650 660 638 595 569 577 576 572 532 499 600 475 480 467 458 473 397 322 325 321 321 400 268 281 273 272 276 BS (N) 218 243 213 206 204 184 200 0 HYBRIDS Aramid HMLS HT PET SLS PA6.6 PA 4.6 Aramid- Aramid- Aramid- Aramid- Aramid- Aramid 3-ply 3-ply 3-ply 3-ply 3-ply 3-ply HMLS HT PET SLS PA6.6 PA 4.6 2-ply
20°C 80°C 150°C
Dipped cord Breaking Strength (relative) @ Elevated Temperature (slack start)
110 100 100 100 100 100 100 100 100 100 100 100 100 100 90 86 86 88 87 87 85 85 86 84 90 83 82 74 80 72 72 71 69 69 68 67 68 70 66 64 64 BS-R (%) 60 50 HYBRIDS Aramid HMLS HT PET SLS PA6.6 PA 4.6 Aramid- Aramid- Aramid- Aramid- Aramid- Aramid 3-ply 3-ply 3-ply 3-ply 3-ply 3-ply HMLS HT PET SLS PA6.6 PA 4.6 2-ply
20°C 80°C 150°C ® Twaron - reinforced tires
Cooper Tire & Rubber Company received a grant from the DoE (US Department of Energy) to develop tire technologies to improve vehicle fuel economy by a minimum of 3% through (among other things) reducing tire weight by a minimum of 20%.
Part of the solution:
Replace heavy steel cord reinforcement with Twaron ® p-aramid in the belt and bead Contribution to Weight reduction
Cap ply • 16” PCR weights ~22.5Lbs ® Twaron belts • With Twaron belt and bead
the weight saving is ~16% Carcass
Twaron® Sidewall beads
The 16% weight reduction results in 5% reduction in rolling resistance that translates into 1% fuel savings per vehicle [source: Cooper Tire & Rubber]
Courtesy of Cooper Tire & Rubber Summary & Conclusion
• Teijin Aramid remains committed to support the Tire industry – Not only a yarn supplier – In depth understanding of yarn converting and cord property requirements • New Twaron grade developments are always focusing on industry demands
• Lower weight tires, Less heat build-up, less fuel consumption • Less reinforcing plies Cost saving on calendaring & faster tire production time • No flat spotting • No corrosion
• Hybrid Aramid/PA 6.6 is most commonly used in Cap ply • Aramid/PET application is under developement • 2-ply Hybrids better than 3-ply in GBF compression fatigue (Carcass) • Hybrids always better than full Aramid in Flex (Tension) fatigue (Cap ply)
• Aramid belted (commodity) PCR under developement at Cooper • Aramid Bead?
Twaron p-aramid in Tires: Lightweight and strong solution
Thank you for your attention!!
Sept 9, 2014 Botond Szalma [email protected] 404.431.5014