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Graphene Related Materials for Elastomer Nanocomposites
Silvia Guerra, Luca Giannini, Luciano Tadiello,Vincenzina Barbera, Maurizio Galimberti
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
33 collaboration projects with University20 JDAs and more than 50 NDAs with suppliers/universities
Over 100 co-operations with Premium OEMs projects on cutting edge technology
Unique motorsport know-how
Over 150 external projects on Materials, Process, Software and Electronics
~ 6,500 patents as of 2018 year end~6.5% of High Value revenues devoted to R&D
in the last three years
R&D OPEN INNOVATION PLATFORM BUILT ON A
HOLISTIC MODEL…
REPLACEMENTMARKET
O.E. CUSTOMERS
SUPPLIERS
UNIVERSITIES
LEGISLATION
Pirelli R&D
PIRELLI - R&D PLATFORM
1. Modular Integrated Robotized System
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
Tyre Insight
Tyre looks just black and round....
...but hides significant
complexity in macro-components
and in materials, down to the nano-
scale
Tyre macroscopic performance depends critically on compounds properties at lengthscales spanning 7 orders of magnitude from cm to nm
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
Polymers and Nanofillers are essential part of all Rubber Compounds
Chemicals can modify the interactions between Polymers and Fillers
The overall performance depends on the collective behaviour of all components
Tyre Compunds = Nanocomposites NanoFillers
Polymer
Curing agent
Chemicals
Tyre Insight: Nanoscale Compound’s Structure
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
Polyhedral Oligomeric Silsesquioxanes (POSS)
Nano Oxides (Silica, Allumina)
3-D at Nanoscale
Mechanical Properties(Low Hysteresis)
High Aspect Ratio Nanofillers
2-D at Nanoscale
Mechanical Properties
(High Modulus)
Modified Silicates Carbon Nano Tubes (SWNT &
MWNT) Polymeric Nanofibers
1-D at Nanoscale
Mechanical Properties
+Barrier Effect
Graphene Related Materials Clays (Montmorillonite) Zirconium Phosphates
Nanomaterials as (new)fillers in Rubber Technology: Overview
Chemical Nature Dimensionality Expected Performance
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
20.3nm(35 layers)=
D 002
Debay Scherrer equation
XRD
Nanomaterials as fillers in Rubber: Carbon-based Nanomaterials
Sample Surface area(m2/g)
Numberof layers
HSAG 330 35
GNP 750 26
CNT 200 9
CB 80 5
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
Carbon Nanomaterials from a layer of sp2-bonded carbon atoms
graphene
graphite
piled
CNT
wrapped
Gradeswith differentshape anisotropy
piled
c =0.671 nm
d002 =0.354 nm
carbon black
randomlyarranged
Nanomaterials as fillers in Rubber: Carbon-based Nanomaterials
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
CARBON BLACK
MWCNT
GRAPHENE
Mul
ti Fu
nctio
nalit
y
PRICE/DIFFICULTY IN MAKING
REINFORCEMENT
ELECTRIC CONDUCTIVITY
IMPERMEABILITY
[New] Materials for new Products: Multifunctionality
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
⇒About 40 patents per yearregarding Graphene(graphite) and
Tyres
Graphene in Tyre Patent Trend
⇒About 500 patents per year regarding Graphene(graphite) and
Elastomers
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
Graphene in Elastomers - Patent highlights
Functional targets: Mechanical reinforcement Electrical & Thermal Conductivity Impermeability
Material focus: Graphene/graphite functionalization Polymer matrix Functionalization
Applications: Sensors and «elctronic devices» Products with better mechanics Product-related improvements – e.g. for tyres:
o Impermeability of inner-liner to keep air and garantee constant performance
o Electrical conductivity for static charge dissipationo Heat management to improve curing and avoid blistering
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
From Materials to Performance Targets
GNPs
(Graphene nanoplatelets)
CB N326
(Carbon Black)
vs
Mechanical and electrical properties
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
0
0,5
1
1,5
2
2,5
3
3,5
4
4,5
0 10 20 30 40 50
G''
0.7
% (f
illed
/unf
illed
)
phr
GNPs
From Materials to Performance Targets: mechanical and electrical properties
CB N326
vs
1E-011E+001E+011E+021E+031E+041E+051E+061E+07
0 10 20 30 40 50σfil
led/σ
sigm
a un
fille
d
(at 0
.1H
z)
phr
GNPs
CB GNPs CB
Better mechanical and electrical properties of GNPs compared to CB N326 Mechanical percolation threshold and electrical percolation threshold firstly
achieved for GNPsS.Guerra, PhD Thesis. Poltecnico di Milano
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
Natural rubber/GNPs composites from NR latex
GNPs
Latex blending is acknowledged
as the best mixing procedure for obtaining the best dispersion of a filler
Introduction of polar groups on carbon allotropes
Oxidation
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
Natural rubber/GNPs composites from NR latex
GNPs
Latex blending is acknowledged
as the best mixing procedure for obtaining the best dispersion of a filler
Introduction of polar groups on carbon allotropes
Oxidation
Staudenmaier’s or Hummers’ methods
Strong acids and oxidation agents
Potentially, they might be dangerous reactions
Problematic work-up: removal of acids and metal (Mn)
oxides
Problems
Synthesis of SP
To perform functionalization reactions inspired to the principles of green chemistry,ideally by using biosourced chemicals.
Chemistry Batterica (E. Coli)
glycerol
Sugar cane
OHHO OH
NH2
HO OH
Serinol
Neat ReactionConditions: T = RT - 180°C t = 25 - 360 min
OO N- 2 H2O
OH
OH
NH2
O
O
∆N
OHHO
2-(2,5-dimethyl-1H-pyrrol-1-yl)-1,3-propanediol (serinol pyrrole, SP)
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
NOHHO
SP
+
BET = 700 m2/g
Adduct of Graphene nanoplatelets and SP
GNPs
GNPs-SP adduct
Quantitative functionalization yield Reaction does not substantially alter the bulk crystalline order of the carbon
allotrope
Thermal energy
Galimberti, M., Barbera, V., Sebastiano, R., Citterio, A., Leonardi, G. WO/2016/050887 A1 (2016)V. Barbera, A.Citterio, M. Galimberti, G. Leonardi, R. Sebastiano, S.U.Shisodia, A.M. Valerio WO 2015 189411 A1Galimberti, M., Barbera, V., Guerra, S., Conzatti, L., Castiglioni, C., Brambilla, L., & Serafini, A. (2015). Biobased Janus molecule for the facile RSC Advances
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
NOHHO
NR latex
GNP-SPwater dispersion
+ sonication 30′ H2SO4GNP-SPlatex dispersion
NR/GNPs-SPcomposite
Graphene platelets around rubber particles.Percolation at low concentration of graphitic material
Potts, J. R., Shankar, O., Du, L., & Ruoff, R. S. (2012 Macromolecules, 45(15), 6045-6055.
S.Guerra, PhD Thesis. Poltecnico di MilanoGalimberti, M., Barbera, V., Guerra, S., & Bernardi, A. (2017). Facile functionalization of sp2 carbon allotropes with a biobased Janus molecule. Rubber Chemistry and Technology, 90(2).
NR/GNPs -SP composites from NR latex
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
NR /adduct 100/10Adduct GNP-SP
NR/GNPs -SP composites from NR latex NOHHO
stacks of few layers graphene
isolated layers
Transmission Electron MicroscopyX-Ray diffraction
Poor stackingof graphene layers
S.Guerra, PhD Thesis. Poltecnico di MilanoGalimberti, M., Barbera, V., Guerra, S., & Bernardi, A. (2017). Facile functionalization of sp2 carbon allotropes with a biobased Janus molecule. Rubber Chemistry and Technology, 90(2).
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
carbon black+ Energy: mechanical, thermal
CBN326
Adduct of SP with Carbon black
10′ sonication, analysis at time 0
10′ sonication, analysis after 3 days
5′ centrifugation at 9000 rpm/min
Water suspension of CB/SP
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
NR-BR / CB-SP / silica composites
IR-BR/CB-SP (or CB)composites
melt blending
silica
+
IR-BR/CB-SP(or CB)/silicacomposites
Ingredients phr phr
IR 50 50
BR 50 50
CB N326 25 20
CB/SP 0 5
Silica1165 25 25
Silane TESPT 2 2
Stearic acid 2 2
ZnO 2,5 2,5
6PPD 2 2
TBBS 1,8 1,8
Sulphur 1,5 1,5
totale 161,80 161,80
CB-SP was used as compatibilizer of CB and silica
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
CBCB-SP
NR-BR / CB-SP / silica composites
-Composite with CB-SP shows lower modulus at lower strain and lower G’’ modulus for a given G’ modulus:
Less filler networking
-Crossover of (G’ vs strain) curves:
Stronger polymer-filler interaction with CB-SP
CBCB-SP
Galimberti, M., Barbera, V., Guerra, S., & Bernardi, A. (2017). Facile functionalization of sp2 carbon allotropes with a biobased Janus molecule. Rubber Chemistry and Technology, 90(2), 285-307.
Silvia Guerra, Polychar 27 world forum on advanced materials “ Copyright Pirelli Tyre SpA 2019
Graphene Related Materials for Elastomer Nanocomposites Graphene Related Materials for Elastomer Nanocomposites are an active field of
Research and Development both in academic and in industrial environments
Target Nanocomposite functionalities in Elastomers include Mechanical Reinforcement
Electrical and Thermal Conductivity
Impermeability
The main Technical Challenge to achieve the potential performances of Nanocomposites featuring fillers is DISPERSION and INTERFACE Control Functionalization of Graphene, Polymers and other fillers are envisaged
In the frame of an open Innovation R&D Model, Pirelli developed with its Academic Partners a functionalization approach based on a partially renewably sourced molecule, with promising initial results
Thank you!
Silvia GuerraMaterial Advanced [email protected]