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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
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 4
NANO-TECHNOLOGY
NANO-MATERIALS
PRODUCT OPPORTUNITIES
Nanotecnologia e Nanomateriali
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 5
Nanotecnologia e Nanomateriali
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.
Nanotecnologia e Nanomateriali
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’)
Nanotecnologia e Nanomateriali
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 8
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
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 9
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
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 10
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
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 11
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”
Nanomateriali come Filler nella Gomma
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 12
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)
Nanomateriali come Filler nella Gomma
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 13
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
Nanomateriali come Filler nella Gomma
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 14
Organically Modified Clays used for reinforcement of Structural Compounds
Mescole con Nanomateriali Lamellari
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 15
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
Mescole con Nanomateriali Lamellari
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
Mescole con Nanomateriali Lamellari
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 17
Hysteresis Thermoplasticity
Dynamic Behaviour of Exfoliated Organoclay in Rubber
Mescole con Nanomateriali Lamellari
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 18
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
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 19
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
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 20
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 21
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 22
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
Attività di Standardizzazione e Normativa
Return
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 23
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
Attività di Standardizzazione e Normativa
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)
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
Attività di Standardizzazione e Normativa
Return
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010 26
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)
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