nanomateriali nellindustria della gomma: l'esperienza pirelli dr. luca giannini pirelli tyre...

Nanomateriali nell’Industria della

Gomma: l'esperienza Pirelli

Dr. Luca GianniniPirelli 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

Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 3

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


NANO-TECHNOLOGY

NANO-MATERIALS

PRODUCT OPPORTUNITIES




DefinitionsNanoscale: 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

Film nanostrutturato

Nano-oggetti

Dispersione

Assemblati

(solidi nanostrutturati)

La maggioranza dei nanomateriali non esistono come particelle singole, bensì combinati in una matrice o comunque come aggregati o agglomerati di dimensione maggiore.

nanotubonanoparticelle

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 nano oggetti nel loro ciclo di vita.


7

ALTA AREA SUPERFICIALE

NANOMATERIALI

Nan

ostru

ttura

ti

Nan

o-O

gg

etti

“VECCHI” Nanomateriali

Nero di Carbonio, Silice

Amorfa, Catalizzatori...

“NUOVI” Nanomateriali

Quantum Dots, Nanotubi,

Fullereni, ...

MATERIALI FATTI DI PARTICELLE

PICCOLE

MATERIALI CON STRUTTURA FINE (es. POROSITA’)



Attività di Standardizzazione e

NormativaOECD – 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 AtmospheresASTM E56 Nanotechnology

Standardization Overview

Details on ISO-CEN

Documents


100-600 nm 30-400 nm

Å

Pellet

≈ 2 mm

Standard Rubber Fillers: Carbon BlackCAS: 1333-86-4 Production Volume: 9 x 109 Kg/yr

Nanomateriali come Filler nella Gomma



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

Volume > 1,1 109 Kg/yr

Standard Rubber Fillers: Precipitated Silica

CAS: 112926-00-8


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”



LOW HYSTERESIS AT HIGH TEMP

HIGH MODULUS COMPOUND

DIFFERENT REINFORCING MECHANISM + BARRIER

HIGH IMPERMEABLELINER

REDUCEDROLLING

RESISTANCE

BETTER DRYHANDLING

HIGHER DURABILITYREDUCED WEIGHT

REDUCED ROLLING RESISTANCE

[new] NANO MATERIALS (FILLERS)



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)

Advanced Fillers for Potential Compound Reinforcement

Pirelli Developme

nts

Pirelli Developme

nts



Organically Modified Clays used for reinforcement of Structural Compounds

Mescole con Nanomateriali Lamellari


FILLER

BASE UNIT

LAMELLAR NANOMATERIAL

(ORGANO)CLAY

CARBON BLACK

and SILICA

SPHERESPHERE

diameter:10 - 70 nm

Surface Area (m2/g) > 300 on exfoliation 30 - 200

1 - 3> 50“Aspect Ratio”lateral dimension

Thickness

(Organo)Clays vs. Carbon Black and Silica


SIDE: 100 – 1000 nm

thickness: 1 nm

SILICATE SILICATE LAYERLAYER

Ammonium Salt

Compatibiliser

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

Science Base: Organoclays Nano-Dispersion Mechanisms

Ref.: Galimberti M., Lostritto A., Spatola A., Guerra G., Chemistry of Materials, 2007, 19, 2495 – 2499

Organoclay

+Rubber

Intercalated

PRIOR ART – Standard Model of Rubber-Clay Nanocomposites

EXFOLIATED

Organoclay

+Rubber

IntercalatedEXFOLIATED

OUR VIEW – NEW Model of Rubber- Clay Nanocomposites



Hysteresis Thermoplasticity

Dynamic Behaviour of Exfoliated Organoclay in Rubber



Rubber – Platelet shaped Filler

COMPOSITE at the nano scale

Natural Rubber:

cis-1,4-polyisoprene

1 nm

Aluminosilicate sheets1 nm thick

x 200-1000 nm wide

Compatibilised by NR4+

(section view)

High

Reinforcement

Nano-

Dispersion

RUBBER-CLAY NANOCOMPOSITES

Mescole con Nanomateriali

Lamellari


P ZERO Base Compounds: Aramid Pulp and Nanobase (Nano.Co)

Anisotropic behavior:

high strength in longitudinal

direction

Isotropic behavior:

equal performance in longitudinal and

lateral directions

Aramid PulpShort Fibers

NanobaseLamellar Nanomaterial

Better Trade-off Handling/Comfort

Higher Stiffness

No Decay

Thermoplastic stability

Mescole con Nanomateriali

Lamellari


Domande?

Grazie a tutti

per l’attenzione


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)

Standardization: Some Detail


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Impending Regulations in EuropeEU commission position:

REGULATORY ASPECTS OF NANOMATERIALS [SEC(2008) 2036] Current legislation applies also to nanomaterialsImplementation 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;

- 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)


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


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Potenziali Criticità HSE dei Nanomateriali

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)

The HSE risk of Nanomaterials as a function of their nanoscale derives from their potential to enter cells.

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)