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Graphene Related Materials for Elastomer Nanocomposites Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina Barbera, Maurizio Galimberti

Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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Page 1: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

Graphene Related Materials for Elastomer Nanocomposites

Silvia Guerra, Luca Giannini, Luciano Tadiello,Vincenzina Barbera, Maurizio Galimberti

Page 2: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 3: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 4: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 5: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 6: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 7: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 8: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 9: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 10: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 11: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 12: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 13: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 14: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 15: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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)

Page 16: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 17: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 18: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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).

Page 19: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 20: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 21: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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.

Page 22: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

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

Page 23: Graphene Related Materials for Elastomer Nanocomposites ... 15...Graphene Related Materials for Elastomer Nanocomposites. Silvia Guerra , Luca Giannini, Luciano Tadiello, Vincenzina

Thank you!

Silvia GuerraMaterial Advanced [email protected]