MARKET INTRODUCTION OF NANOSTRUCTURED

POLYMER MATERIALS: SOME LESSONS LEARNED.

Michel GLOTIN

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ARKEMA

2 2016 CORPORATE PRESENTATION

sales

19,000 Worldwidepresence€7.7 bn

employeesworldwide

136 3 R&D

industrial sites and innovationgeographical hubsin 50 countries

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A STORY ABOUT: MARKET INTRODUCTION OF INNOVATIVE MATERIALS

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Mc Kinsey study : new products from 118 Business units of large chemical companiesM.Miremadi, C.Musso, J.Oxgaard, Mc Kinsey on chemicals 2013

New product introduction in the chemical industry

Technology Push

Market pull

vs

4ARKEMA Internal use only - CONFIDENTIAL

to ultrafast, living and quantitative polymerization

INNOVATION 1: ANIONIC POLYMERIZATION OF (METH)ACRYLATES

S. K. Varshney; J. P. Hautekeer; R. Fayt ; R. Jérôme; P. Teyssié; Macromolecules, vol. 23(10), pp. 2618-2622, 1990

C. Navarro, X. Marcarian, B. Vuillemin; Macromolecular Symposia, vol.132 (1) ; pp. 263-272, 1998

A. Maurer, X. Marcarian, A.HE Müller, B. Vuillemin, C. Navarro; Polym Prepr (Am ChemSoc, Div Polym Chem), vol.38 (1), pp.467-469, 1997

200 nm

poly(Styrene)-b-poly(Butadiene)-b-poly[(Methyl)methacrylate)]

(V. Abetz, T. Goldacker,

Macromolecular Rapid Communication, 2000)

PS PB PMMAPS PB PMMA

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BlocBuilder™

(Tordo, Boutevin, Gnanou)

NOCH P

O

O

O

Nitroxyde

N-tert-butyl-N-(1-diethylphosphono-

2,2-dimethylpropyl) nitroxyde)

Metal free polymerization allowing good control of acrylates

Addition of functional co-monomers in hard and/or soft blocks possible

ARKEMA NANOMATERIALS – C. NAVARRO – ENSCBP – 17_01_2017

Living poly(Butyl Acrylate)Block Copolymers

PBAPMMA PMMA

Joint Arkema/CNRS Patent WO 96-124620 S. Grimaldi, F. Le Moigne, JP Finet, P. Tordo, P. Nicol - 1996

INNOVATION 2: NITROXIDE-MEDIATED CONTROLLED RADICAL POLYMERIZATION

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Apolhya : a comb copolymer

Co-continuous morphology at nanoscale

INNOVATION 3 : NANOSTRUCTURED GRAFTED COPOLYMERS (APOLHYA®)

Hélène Pernot, Ludwik Leibler , Nature Materials, 1 , 54, (2001)

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(CNT: IIJIMA 1991)P. Serp, R. Feurer, C. Vahlas, P. Kalck, WO2003/002456 A2 (2003)P.Kalk, P.Serp, M.Corrias, WO/2006/008385 A1 (2006) D. Plee, R. Philippe, B. Caussat, P. Kalck, P. Serp, WO2008/107586 A2 (2008)P. Gaillard, S. Bordere, P. Serp, B. Caussat, J. Beausoleil, WO2011/020970 A2 (2011)

Synthesis reactor of MW-CNTs

Specific equipment for the safe handling of CNTs

INNOVATION 4 : MULTI-WALL CARBON NANOTUBES (GRAPHISTRENGTH®)

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THE SCALE-UP PHASE

Development of applications

● Can it become a commercial success?

Prepare industrialization scenario.

● Process studies, costs estimates, ROI, …

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Block copolymer pilot plant (Mont –France Started 1999)

Decisions to attempt commercial scale-up of

nano materials

● Methacrylic block copolymers -anionic poly (1997)

● Nitroxyde based block copolymers (1998)

● Nanostructured grafted copolymers (2001)

● Multi-wall carbon nanotubes (2006)

Validation of technology scalability.

Identification of potential applications

Process studies, pilot plant design, construction

Genesis project

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THE « GENESIS » FRENCH COLLABORATIVE PROGRAM

6 years (1/2008 to 12/2013).

100 M€ private/public (A2I)

Scale-up and applications of

nano-structured materials.

● Automotive,

● Cable industry

● Lithium Metal Polymer batteries

● Water filtration membranes

● Fiber Reinforced Composite materials

● …

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Global Evaluation of Nanocomposites for Emerging Safe Industrial Solutions

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Best in class light transmission (>92%)

No haze even at elevated temperature

Low birefringence vs polycarbonate

Naturally resistant to UV

No craze

0

500

1000

1500

2000

2500

3000

3500

4000

Stdt Extruded Impact extruded Stdt cast Impact cast Altuglas

ShieldUp

Max s

tress b

efo

re c

raze (

psi) Acetone

Break

Acetone

Chemical Test of ECE R43 (Automotive Glazing)

Outstanding optical properties High Impact resistance High chemical resistance

ALTUGLAS SHIELDUP®: TRANSPARENT NANOSTRUCTURED ACRYLIC SHEET

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ALTUGLAS SHIELD-UP® CAST SHEETS – EXAMPLES OF APPLICATIONS

Transparent sunroof and deflectorsRenault Twizi

Bullet proof transparent sheetChemical lab equipmentMotorbikes windshields

One piece front and rear windscreens + roof – Peugeot ONYX concept car

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PERMANENTLY HYDROPHILIC WATER ULTRAFILTRATION MEMBRANES

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High mechanical strength & chemical resistance

(PVDF based).

High permeability.

Surface pores < 25 nm for bacteria & virus rejection.

Fouling resistance.

Performance retention with aging

Full fiber x-section Outer surface x-section

UF/MF water filtration plant

TEM imaging of stained membranes

In collaboration with:

13ARKEMA Internal use only - CONFIDENTIAL

Increased filtration performance durability

Lower membrane fouling

Possibility for increased production of an existing plant or lower plant footprint and costs for given water treatment volume.

NEW KYNAR® DH100 FOR WATER FILTRATION MEMBRANES

Test with Garonne river water (F)

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Microprocessor structureWafer (300 mm diameter) 1 microprocessor (few mm²)

DIRECT SELF ASSEMBLY OF BLOCK COPOLYMERS: ENABLING TECHNOLOGY FOR THE NEXT GENERATION IN MICRO-ELECTRONICS ?

STANDARD NANOLITHOGRAPHY

BakeSpin coating Etching

DIRECT SELF ASSEMBLYOF BLOCK COPOLYMERS?

0,01

0,1

1

10

1975 1980 1985 1990 1995 2000 2005 2010 2015 2020

Année

Dim

ensio

ns C

ritiq

ues

µm

103 106 109

Nbr de transistors/processeur

1012

2030

Year

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DSA DEVELOPMENT OVERVIEW

A large panel of materials and process flows available

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Graphoepitaxyfor contact

Graphoepitaxyfor L/S

Chemoepitaxyfor L/S

Graphoepitaxy for L/S

PS-b-PMMA High -

22nm < L0 < 60nm L0 < 20nm

Shrink , repair and multiply contacts

Process stabilitymonitoring

Integration

Benchmark materials Prepare metrology for

high chi

Benchmark chemo vs grapho

Prepare high chi

Next generationmaterial and processes

200 nm

Chemoepitaxyfor L/S

PLACYD

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Clean room dedicated to DSA materials

● ISO 7 Clean room

● Opened in March 2014

Dedicated production lines

● Metal decontamination

● Filtration

● Analysis: GPC, LAC, ICP

● Sampling

Production hallClean room

PRODUCTION OF NANOSTRENGTH® EO AT ARKEMA

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CROSSING THE VALLEY OF DEATH …

1997-20072013GENESIS PROJECT

SCALE-UP TO PIlOT PRODUCTION SCALE

APPLICATION DEVELOPMENT

1986-2003 2014 2015 2016

Sales for applications anticipated in the Genesis program

Sales for other applications

2008

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NEW COMPOSITE MATERIALS FOR WIND TURBINE ROTOR BLADES

Ca. 5 Million Tons of Composite Materials in windturbine rotor blades @ end 2016 expected to grow to ca. 8 MT by 2021

Wind blade life-time between 20 and 30 years

Need to anticipate and provide solutions for the end-of-life recyclability.

In 2013: Arkema decides to develop new recyclable thermoplastic for this market.

A « Market pull » / « problem solving » approachto innovation: There is (or there will be) a problem, we choose to develop a solution.

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Cumulated installed worldwide wind power (GW)

Data from 2016 and 2015 GWEC reports

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STATUS OF DEVELOPMENT ELIUM® WIND TURBINE ROTOR BLADES

Development of a new liquid resin for Thermoplasticcomposites (ELIUM®)

● Blade manufacturing by classical VARI process.

● Brings improved fatigue life resistance vs current bladecomposite materials.

Development of a new bonding adhesive with room temperature cure and faster process.

Blade demonstrators:

● 25 metre blade (Effiwind project France- sept 16)

● 9 metre blade (IACMI-USA- jan 17)

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Effiwind 25 m long demonstrator

IACMI 9 m long demonstrator

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CONCLUSIONS-1

Arkema ’s « technology push» of Nanomaterials : a 20 years, ca. 100 M€ R&D story

● Reaching TRL 4 is 50% of the time but only 5 % of the total project cost.

● TRL 4/5 to TRL 7 is the high risk phase (95% of the R&D cost)

● Highest costs:

• Pilot plant Capex and Opex

• Dedicated worldwide market/application development team.

Some difficulties:

● Prove differentiation in performance/cost vs existing solutions (being « nano » is not enough!)

● Very high initial product costs (low volumes from pilot plants) loosing money in early stage

of developments (several years).

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CONCLUSIONS-2

Some benefits : First access to an enabling technology

● A source of innovations within the existing Arkema product portfolio : ex: Altuglas® Shield-up,

Kynar® for hydrophilic membranes, conductive Rilsan® fuel lines, ...

● Development of innovative materials solutions: Elium® resins and the structural adhesive

formulations for wind blades both also make use of Arkema’s new « nano» technologies.

Market pull vs technology push?

● Technology push in materials is absolutely needed for breakthrough innovations.

● Large industry not ready to do it anymore? (aversion to risk, short term strategies).

● Can « start-ups » and SMEs afford this type of 100M€+ innovation project??

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Thank You for your attention!