Nanomateriali nell’Industria della Gomma: l'esperienza Pirelli Dr. Luca Giannini Pirelli Tyre SpA “Nanotecnologie: nuovi sviluppi nell'ambito della filiera Automotive” ANFIA - 14 aprile 2010 – Torino

Outline Pirelli Tyre Nanotecnologia e Nanomateriali Attività di Standardizzazione e Normativa Nanomateriali come Filler Funzionali nella Gomma Mescole rinforzate con Nanomateriali Lamellari

Pirelli Tyre Global Demands on Tyre performance, environment, legislation will be challenging in next years Innovation in materials, design and manufacturing will continue to bring advances in Tyre technology Tyre is a complex product, still technologically evolving Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

NANO-TECHNOLOGY NANO-MATERIALS PRODUCT OPPORTUNITIES Nanotecnologia e Nanomateriali NANO-TECHNOLOGY NANO-MATERIALS PRODUCT OPPORTUNITIES Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

MAIN DEFINITIONS FOCUS IS ON SIZE Nanotecnologia e Nanomateriali Definitions Nanoscale: The size range typically between 1 nm and 100 nm. Nanomaterial: Material which is either a nano-object or is nanostructured. Nano-object: material confined in one, two, or three dimensions at the nanoscale. Nanostructured: having an internal or surface structure at the nanoscale. source: ISO/TS 27687:2008, ISO and OECD working definitions MAIN DEFINITIONS FOCUS IS ON SIZE Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Nanotecnologia e Nanomateriali La maggioranza dei nanomateriali non esistono come particelle singole, bensì combinati in una matrice o comunque come aggregati o agglomerati di dimensione maggiore. Nano-oggetti nanoparticelle nanotubo Assemblati (solidi nanostrutturati) Film nanostrutturato Dispersione         Alcuni prodotti consolidati ricadono nell’ambito della definizione di “Nanomateriali”: filler attivi per gomma e plastica, pigmenti, materiali assorbenti, alcuni materiali cementizi, supporti di catalizzatori, ... coating e superfici caratterizzati da spessori inferiori ai 100 nm (elettronica). La maggior parte di questi “nanomateriali” consolidati hanno minime possibilità di rilascio di nano­oggetti nel loro ciclo di vita. Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Nanotecnologia e Nanomateriali “NUOVI” Nanomateriali Quantum Dots, Nanotubi, Fullereni, ... “VECCHI” Nanomateriali Nero di Carbonio, Silice Amorfa, Catalizzatori... Nanostrutturati Nano-Oggetti ALTA AREA SUPERFICIALE MATERIALI FATTI DI PARTICELLE PICCOLE MATERIALI CON STRUTTURA FINE (es. POROSITA’)

Attività di Standardizzazione e Normativa Standardization Overview OECD – WPMN (Working Party on Manufactured Nanomaterials) project 1: development of an OECD database on EHS research project 3: safety testing of a representative set of manufactured nanomaterials (including “Carbon Black" and  “Silicon Dioxide“) project 4: manufactured nanomaterials and test guidelines ISO TC-229 “Nanotechnologies” WG 1 Terminology and Nomenclature WG 2 Measurement and characterization WG 3 Health, safety and environment Scope: The development of science-based standards in the areas of health, safety, and environmental aspects of nanotechnologies CEN/TC 352 “Nanotechnologies” ISO TC 146/SC 2 Air Quality: Workplace Atmospheres ASTM E56 Nanotechnology Details on ISO-CEN Documents Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Standard Rubber Fillers: Carbon Black Nanomateriali come Filler nella Gomma Standard Rubber Fillers: Carbon Black CAS: 1333-86-4 Production Volume: 9 x 109 Kg/yr 100-600 nm 30-400 nm Å Pellet ≈ 2 mm Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Standard Rubber Fillers: Precipitated Silica Nanomateriali come Filler nella Gomma Standard Rubber Fillers: Precipitated Silica CAS: 112926-00-8 Volume > 1,1 109 Kg/yr Amorphous precipitated silica consists of a 3D network of coagulated primary silica particles forming aggregates and agglomerates. Macroscopically Silica is compacted in particles of typically hundreds of microns Pellet Agglomerate Aggregate Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Nanomateriali come Filler nella Gomma Carbon Black and Precipitated Silica consist of primary particles typically smaller than 100 nm – surface area >60m2/g: they belong than to the family of “Nanomaterials” As primary particles of Carbon Black and Silica are strongly bound into aggregates and agglomerates, they shall be classified as “Nanostructured Materials” Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

[new] NANO MATERIALS (FILLERS)‏ Nanomateriali come Filler nella Gomma [new] NANO MATERIALS (FILLERS)‏ DIFFERENT REINFORCING MECHANISM + BARRIER LOW HYSTERESIS AT HIGH TEMP HIGH MODULUS COMPOUND HIGH IMPERMEABLE LINER HIGHER DURABILITY REDUCED WEIGHT REDUCED ROLLING RESISTANCE REDUCED ROLLING RESISTANCE BETTER DRY HANDLING Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Pirelli Developments Overview of [new] Nanomaterials Nanomateriali come Filler nella Gomma Advanced Fillers for Potential Compound Reinforcement Overview of [new] Nanomaterials Polyhedral Oligomeric Silsesquioxanes (POSS)‏ Nano Oxides (Silica, Allumina)‏ Carbon Nano Fibers (CNF)‏ Carbon Nano Tubes (SWNT & MWNT)‏ Lamellar Nanomaterials e.g. Montmorillonite Clay (MMT)‏ Graphene (delaminated Graphite)‏ Pirelli Developments Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Mescole con Nanomateriali Lamellari Organically Modified Clays used for reinforcement of Structural Compounds Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

LAMELLAR NANOMATERIAL (ORGANO)CLAY CARBON BLACK and SILICA Mescole con Nanomateriali Lamellari (Organo)Clays vs. Carbon Black and Silica LAMELLAR NANOMATERIAL (ORGANO)CLAY CARBON BLACK and SILICA FILLER SIDE: 100 – 1000 nm thickness: 1 nm SILICATE LAYER Ammonium Salt Compatibiliser diameter: 10 - 70 nm BASE UNIT SPHERE Surface Area (m2/g) > 300 on exfoliation 30 - 200 lateral dimension > 50  1 - 3 “Aspect Ratio” Thickness Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

+ + Mescole con Nanomateriali Lamellari Science Base: Organoclays Nano-Dispersion Mechanisms Organoclay + Rubber Intercalated PRIOR ART – Standard Model of Rubber-Clay Nanocomposites EXFOLIATED OUR VIEW – NEW Model of Rubber- Clay Nanocomposites EXFOLIATED Organoclay + Rubber Intercalated Ref.: Galimberti M., Lostritto A., Spatola A., Guerra G., Chemistry of Materials, 2007, 19, 2495 – 2499 Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Dynamic Behaviour of Exfoliated Organoclay in Rubber Mescole con Nanomateriali Lamellari Dynamic Behaviour of Exfoliated Organoclay in Rubber Hysteresis Thermoplasticity Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Rubber – Platelet shaped Filler COMPOSITE at the nano scale Mescole con Nanomateriali Lamellari RUBBER-CLAY NANOCOMPOSITES Aluminosilicate sheets 1 nm thick x 200-1000 nm wide Compatibilised by NR4+ Natural Rubber: cis-1,4-polyisoprene 1 nm (section view)‏ Rubber – Platelet shaped Filler COMPOSITE at the nano scale High Reinforcement Nano-Dispersion Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Mescole con Nanomateriali Lamellari P ZERO Base Compounds: Aramid Pulp and Nanobase (Nano.Co)‏ Aramid Pulp Short Fibers Nanobase Lamellar Nanomaterial Higher Stiffness Better Trade-off Handling/Comfort Thermoplastic stability Anisotropic behavior: high strength in longitudinal direction Isotropic behavior: equal performance in longitudinal and lateral directions No Decay Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Domande? Grazie a tutti per l’attenzione Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Luca Giannini - Pirelli Tyre S. p. A Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Standardization: Some Detail Attività di Standardizzazione e Normativa Standardization: Some Detail CEN ISO/TS 13830: Guide to labelling of manufactured nanoparticles and products containing manufactured nanoparticles ISO TC229 ISO/AWI TS 12901-1: Guide to safe handling and disposal of manufactured nanomaterials ISO-TC 229 ISO/NP TS 12901-2: Guidelines for occupational risk management applied to engineered nanomaterials based on a "control banding approach“ ISO-TC 229 ISO/AWI TS 80004-5: Nomenclature of nanostructured materials ISO/TS 27687:2008: Nanotechnologies - Terminology and definitions for nano-objects - Nanoparticle, nanofibre and nanoplate (PUBLISHED) Return Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Impending Regulations in Europe Attività di Standardizzazione e Normativa Impending Regulations in Europe EU commission position: REGULATORY ASPECTS OF NANOMATERIALS [SEC(2008) 2036] Current legislation applies also to nanomaterials Implementation in relation to risk assessment, need to be reviewed to effectively address risks associated with nanomaterials EU parliament position (24/04/09) 11. Calls specifically on the Commission to evaluate the need to review REACH concerning inter alia: – consideration of all nanomaterials as new substances, – a chemical safety report with exposure assessment for all registered nanomaterials, – notification requirements for all nanomaterials placed on the market on their own, in preparations or in articles; 16. Calls on the Commission to compile before June 2011 an inventory of the different types and uses of nanomaterials on the European market, ...; furthermore calls on the Commission to report on the safety of these nanomaterials at the same time; Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010

Attività di Standardizzazione e Normativa - CLP(1) : richiede la classificazione e l'etichettatura delle sostanze pericolose e delle loro forme, incluse quelle “nano”, e la trasmissione delle informazioni a ECHA entro il 3/01/2011 - REACH (2) : richiede che i produttori, gli importatori e gli utilizzatori delle sostanze messe sul mercato in Europa forniscano a ECHA una serie di dati relativi alla pericolosità delle sostanze, “registrando” le stesse, in tutte le forme rilevanti, incluse quelle “nano”, tra il 2010 e il 2018. (1) Classification, Labelling and Packaging of substances and mixtures (EC Regulation 1272/2008) (2) Registration, Evaluation, Authorisation and Restriction of Chemicals (EC Regulation 1907/2006)

Attività di Standardizzazione e Normativa Scenari e Criticità : (fonte: “Information from Industry on Applied Nanomaterials and their Safety” – deliverable 1 prepared for EC-DG Environment by Milieu-RPA - september 2009) 1) Nanomateriali “standard” GIA' STATI REGISTRATI (Carbon Black, Silice Amorfa) o lo saranno entro il 2010 2) Nanomateriali CONSIDERATI FORME DI SOSTANZE DI GRANDE VOLUME (Ag, C, ZnO, TiO2, Au) dovrebbero essere inclusi nei dossier di registrazione delle rispettive “sostanze di bulk”, attesi per il 2010 (>1000 ton/anno) 3) Nanomateriali considerati come “non phase-in”, vale a dire “nuove sostanze” devono essere registrate se introdotte sul mercato da 06/2008 in >1 ton/anno 4) Nanomateriali considerati come “phase-in”, cioè sostanze esistenti, e presenti sul mercato tra 1 e 100 ton/anno, saranno registrati solo entro il 2018 (salvo se già considerati pericolosi) 5) Nanomateriali polimerici sono al momento esenti Return

Potenziali Criticità HSE dei Nanomateriali The HSE risk of Nanomaterials as a function of their nanoscale derives from their potential to enter cells. Nanostructured materials consisting of aggregates and agglomerates much larger than 100 nm might not pose HSE risks associated to the nanoscale (SCENHIR 21-22/6/ 2007) Lamellar nanomaterials, featuring only ONE dimension at the nanoscale, are not likely to penetrate cells and might not pose HSE risks associated to the nanoscale (SCENHIR 21-22 /6/ 2007) Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010