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
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Nanotecnologia e Nanomateriali
NANO-TECHNOLOGY
NANO-MATERIALS
PRODUCT
OPPORTUNITIES
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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
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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
Film nanostrutturato
Dispersione
(solidi nanostrutturati)








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
NANOMATERIALI
Nanostrutturati
Nano-Oggetti
MATERIALI FATTI DI
PARTICELLE
PICCOLE
ALTA AREA SUPERFICIALE
MATERIALI CON
STRUTTURA FINE
(es. POROSITA’)
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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
Details on
ISO-CEN
Documents
 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
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010
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Nanomateriali come Filler nella Gomma
Standard Rubber Fillers: Carbon Black
CAS: 1333-86-4
Production Volume: 9 x 109 Kg/yr
Pellet
≈ 2 mm
30-400 nm
100-600 nm
Å
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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
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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
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Nanomateriali come Filler nella Gomma
[new] NANO MATERIALS (FILLERS)
DIFFERENT REINFORCING MECHANISM + BARRIER
LOW HYSTERESIS HIGH MODULUS
COMPOUND
AT HIGH TEMP
REDUCED
ROLLING
RESISTANCE
BETTER DRY
HANDLING
HIGH IMPERMEABLE
LINER
HIGHER DURABILITY
REDUCED WEIGHT
REDUCED
ROLLING RESISTANCE
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010
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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)
Pirelli
Developments
 Graphene (delaminated Graphite)
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010
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Mescole con Nanomateriali Lamellari
Organically Modified Clays used for reinforcement of Structural Compounds
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Mescole con Nanomateriali Lamellari
(Organo)Clays vs. Carbon Black and Silica
FILLER
Ammonium
Salt
Compatibiliser
LAMELLAR
NANOMATERIAL
(ORGANO)CLAY
CARBON BLACK
and SILICA
SIDE: 100 – 1000 nm
diameter:
10 - 70 nm
SILICATE
LAYER
BASE UNIT
SPHERE
thickness: 1 nm
Surface Area (m2/g)
“Aspect Ratio”
> 300 on exfoliation
lateral dimension
> 50
30 - 200
 1-3
Thickness
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010
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Mescole con Nanomateriali Lamellari
Science Base: Organoclays Nano-Dispersion Mechanisms
PRIOR ART – Standard Model of Rubber-Clay Nanocomposites
Organoclay
Rubber
EXFOLIATED
Intercalated
+
OUR VIEW – NEW Model of Rubber- Clay Nanocomposites
Organoclay
Rubber
Intercalated
EXFOLIATED
+
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
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
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Mescole con Nanomateriali Lamellari
RUBBER-CLAY NANOCOMPOSITES
Natural Rubber:
Aluminosilicate sheets
1 nm thick
x 200-1000 nm wide
cis-1,4-polyisoprene
Compatibilised by NR4+
(section view)
1 nm
Rubber – Platelet shaped Filler
COMPOSITE at the nano scale
Nano-Dispersion
High Reinforcement
Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010
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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
Anisotropic
behavior:
Isotropic
behavior:
high strength in equal performance
longitudinal
in longitudinal and
direction
lateral directions
Thermoplastic stability
No Decay
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Grazie
a tutti
per l’attenzione
Domande?
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Luca Giannini - Pirelli Tyre S.p.A. – Nanomateriali e la Gomma: l'esperienza Pirelli– ANFIA Torino 14-04-2010
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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
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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
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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)
Return
5) Nanomateriali polimerici sono al momento esenti
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)
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