Is Super 5 Rayon possible? Dr. Axel Rußler, DI Bernhard Müller R&D Glanzstoff Industries

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1 Is Super 5 Rayon possible? Dr. Axel Rußler, DI Bernhard Müller R&D Glanzstoff Industries

2 Overview Glanzstoff Industries High Tech Cellulose The Glanzstoff Approach

3 Glanzstoff at a Glance Tire Reinforcement PPE Composites MRG Turnover: 150 Mio Employees: 800 people Fiber production Conversion

4 Glanzstoff Viscord Single-End-Cord Car Tires - Main Application Mechanical Rubber Goods Composites Fabric Precursor Material Special Uses

5 [to CO 2 -eq/to product] Rayon Sustainable in Tire Applications PET HMLS Dipped fabric RAYON dipped fabric 9,0 6,4 +2,4 29% lower GWP Sustainability contribution of Rayon +1,2 6,6 5,2 RAYON: a SUSTAINABLE reinforcement material Sources: Rayon and conversion data based on LCA study Glanzstoff (2013/2014); PET data publicly available (2014)

6 [to CO 2 -eq/to product] Rayon Sustainable in Tire Applications Comparison between Best Available Technologies PET HMLS Dipped fabric RAYON Dipped fabric 5,5 5,3 +2,4 +1,2 3,1 4,1 RAYON: a SUSTAINABLE reinforcement material Sources: Rayon and conversion data based on LCA study Glanzstoff (2013/2014); PET data publicly available (2014)

7 Glanzstoff Viscord Rayon - A Responsible Solution Benchmarking Rayon Yarn Production... Glanzstoff Industries Viscose yarn production is one of the most environmental-friendly Rayon producers worldwide Reference for world wide best available technology (BAT) in air emission treatment ISO 14001:2004 certified ISO in preparation The continuous efforts and achievements were awarded in 2012 with the prestigious Responsible Care Award And Conversion electricity gas water Source: Glanzstoff Industires Continuous investment in new machinery and technologies to reduce energy and water consumption from 2009 to 2013: - 34% Electricity - 52% Gas - 54% Water Renewable energies Photo-voltaic panels (1MW) Cogeneration Project in planning Luxembourg ISO 14001:2004 certified In Luxembourg plant CO 2 emissions were cut in half to to from

8 Rayon A Tailor Made Biopolymer Cellulose..the most abundant polymer on earth so it can create truly 21st-century materials and products Executive Director Norman Marsolan, Georgia Institute of Technology

9 Cellulose a Simple Material?

10 Cellulose a Simple Material? Strength Modulus Non-Thermoplastic Character

11 The Super Definition for Tire Cords Viscose is not Rayon Tire Cord

12 Tenacity [cn/tex] The Super Definition for Tire Cords Viscose is not Rayon Tire Cord Viscord Tire Cord Different Spin Process Different Mechanical Behaviour Different Cross-Section Different Micro-Morphology 40 Only Tire Cord is super standard textile viscose Elongation [%] Standard Textile Viscose Viscord Tire Cord Still Rayon Tire Cord Fibers are the only commercially available high tenacity fibers based on a biological feedstock!

13 The Viscord Fibers The Viscord Fiber Characteristics Tensile strength dry: ~ 850 MPa (55 cn/dtex) Tensile strength conditioned: ~ 700 MPa (45 cn/dtex) Modulus: ~ 7 GPa Elongation conditioned max.: 13 % Density: 1,5 g/cm 3

14 Tenacity [cn/tex] The Super Definition 70 Cord: 2 x 1840, oven-dry, twist: Super 1 Super 2 Super adapted from: Götze, Chemiefasern nach dem Viskoseverfahren, 1967, p.629 Slightly lost importance due to more customer oriented specifications

15 Tenacity [cn/tex] The Super Definition 70 Cord: 2 x 1840, oven-dry, twist: Super 1 Super 2 Super 3 Super 4 Super % adapted from: Götze, Chemiefasern nach dem Viskoseverfahren, 1967, p.629 Slightly lost importance due to more customer oriented specifications

16 Need for Sustainable Materials with Better Properties Force Perfect tire yarn Higher modulus Higher tenacity Sustainable High fatigue resistance Easy Dipping Low Price Elongation Aramid x2 Rayon x2 PET x2 Nylon x2 Non-thermoplastic

17 Need for Sustainable Materials with Better Properties Force Perfect tire yarn Higher modulus Higher tenacity Sustainable High fatigue resistance Easy Dipping Low Price Elongation Aramid x2 Rayon x2 PET x2 Nylon x2 Non-thermoplastic

18 Fiber Properties Literature Overview Regenerate Fibers Direct Dissolution from: Röder et al. Lenzinger Berichte 91, p. 7-12

19 Fiber properties Dependences Crystallinity Orientation DP Shape Homogeneity Length

20 Fiber properties Dependences Crystallinity Orientation DP Shape Homogeneity Length Tenacity Fibrillation Elongation Brittleness Modulus Dynamic behavior Properties wet/dry Convertability

21 Fiber properties Dependences Crystallinity Orientation DP Shape Homogeneity Length Tenacity Fibrillation Elongation Brittleness Modulus Dynamic behavior Properties wet/dry Convertability Ecology Economy Scale-up

22 Theoretical Strength of Cellulose

23 Theoretical Strength of Cellulose Material Tensile Strength Elastic Modulus Density Cellulose Nano Crystalls (CNC) 7,5 GPa 150 GPa 1,57 g/cm 3 Kevlar 49 3,5 GPa 125 GPa 1,45 g/cm 3 Carbon fiber 3,5 GPa 150 GPa 1,8 g/cm 3 Stainless steel 0,5 GPa 200 GPa 7,9 g/cm 3

24 Pure Strength? Pure Strength Is Not Enough In Tires! High dynamic forces in tires Flexibility and Strechability Toughness Adjusted Modulus

25 Pure Strength? Pure Strength Is Not Enough In Tires! High dynamic forces in tires Flexibility and Strechability Toughness Adjusted Modulus Fatigue Ressistance Right Molecular Structure Broader Field of Possibilities Desirable

26 Flexibility and Complexity of the Viscose Process The Viscose Process is very flexible. It has more Degrees of Freedom than known for Thermoplastic Fibers: Raw Materials used Constitution of the Spinning Dope and the Intermediate Polymer Additives Coagulation and Regeneration Drying and Finishing However, maybe this is not enough

27 Carbon Nano Tube (CNT) Technology Material Tensile Elastic Strength Modulus Density Cellulose Nano Crystalls (CNC) 7,5 GPa 150 GPa 1,57 g/cm 3 Kevlar 49 3,5 GPa 125 GPa 1,45 g/cm 3 Carbon fiber 3,5 GPa 150 GPa 1,8 g/cm 3 Stainless steel 0,5 GPa 200 GPa 7,9 g/cm 3 Carbon nanotubes (MWCNT) up to 150 GPa up to 950 GPa 1,8 g/cm 3 Multi Walled Carbon Nano Tube (MWCNT)

28 Carbon Nano Tube (CNT) Technology Material Tensile Elastic Strength Modulus Density Cellulose Nano Crystalls (CNC) 7,5 GPa 150 GPa 1,57 g/cm 3 Kevlar 49 3,5 GPa 125 GPa 1,45 g/cm 3 Carbon fiber 3,5 GPa 150 GPa 1,8 g/cm 3 Stainless steel 0,5 GPa 200 GPa 7,9 g/cm 3 Carbon nanotubes (MWCNT) up to 150 GPa up to 950 GPa 1,8 g/cm 3 Multi Walled Carbon Nano Tube (MWCNT)

29 Nanofilled Polymer Composite Basic Properties of Nanocomposites properties substantially different from pure matrix material affecting the nanostructure morphology exceptionally high surface to volume ratio high aspect ratio low concentrations can lead to significant changes

30 Nanofilled Polymer Composite Basic Properties of Nanocomposites properties substantially different from pure matrix material affecting the nanostructure morphology exceptionally high surface to volume ratio high aspect ratio low concentrations can lead to significant changes Basic Requirements for Nanocomposites good dispersion of the nano filler good matrix-filler interaction

31 Set Up from CNTs to Nanocomposite

32 Set Up from CNTs to Nanocomposite

33 CNT-reinforced Film Testing Standard 0,5 % CNT 1 % CNT Tensile Strength Strain at Break Modulus Work to Break

34 CNT-reinforced Fiber Spinning Good integration of the technology into the fiber spinning process Good spinability Smooth fibers Many tuning parameters This cellulosic nano-composite fiber is a complete new fiber category!

35 Results from First Fiber Spinning Trials Force Pure Rayon CNT Rayon 01 CNT Rayon 02 Elongation

36 Results from First Fiber Spinning Trials Force Scalable Properties Perfect yarn found? Up-scaling is a Challenge Elongation Aramid x2 Rayon x2 PET x2 Nylon x2

37 Results from First Fiber Spinning Trials Force Scalable Properties Perfect yarn found? Up-scaling is a Challenge Elongation Aramid x2 Rayon x2 PET x2 Nylon x2

38 CNT Concentration Easy Determination CNT technology implicates many analytical problems, one example is a quick determination of CNT concentration in fibers. Our solution: colour measurement [L*] R² = 0,9196 R² = 0, µm film 60µm film Linear (15µm film) Linear (60µm film) 0,2 0,3 0,5 0,7 0,9 1 conc. MWCNT [%]

39 Health and Environmental Issues New studies from ITV Denkendorf and Hohenstein Institutes and statements from InnoCNT (innovation alliance carbon nano tubes) show: no liberation of nanoparticles from nanoparticle containing matrixes or coatings no health issues of nanoparticles applying reasonable concentrations (no overloading tests) additionally: Toxicity of CNT material is strongly dependent on dimensions, functionalization and manner of ingestion

40 Rayon Tire Cord is Alive! Flexible Reliable Sustainable Still with new ideas

41 Thank you for your attention!