innovative processes for high performance materials ...

INNOVATIVE PROCESSES FOR HIGH PERFORMANCE MATERIALS FOR LOW CARBON ENERGY

F. Schuster – F. Lomello CEA- Cross-cutting program on advanced materials

Réunion Programme - COMOS « Reporting annuel des programmes transversaux » CEA | 23 Janvier 2015

| PAGE 1

LWR

GEN IV

Fusion

Electrochemical Storage

Hydrogen

Solar

Energy Efficiency & Harvesting

Alternative Energies

Nuclear Energy

MATERIALS ARE STRATEGIC FOR THE PERFORMANCES OF THE COMPONENTS FOR LOW CARBON ENERGY

| PAGE 2

ODS

Gradient for PFC

Innovation LWR

GEN IV

Fusion

Catalysts

Nanocomposites Nanowires

Nuclear Energy

Coatings for ATF

Alternative Energies

Core Shell

10 nm

Electrochemical Storage

Hydrogen

Solar

Low friction coatings, thermal barriers, piezoelectric & thermoelectric coatings…

SOME EXAMPLES OF ADVANCED MATERIALS FOR LOW CARBON ENERGY

| PAGE 3

Ionized PVD

Spark Plasma Sintering

Mechanical alloying

Pulverization Supersonic cathodes beam

Alternative Energies

Intermediate chamber Aerodynamic lens Expansion chamber

Transverse Substrate motion Substrate Deposition chamber

Nanoparticles flow Laser Pyrolysis Pomping stages

Nano-objects synthesis

Aerosol CVD

Hybrid processes

Develop advanced manufacturing technologies if possible at industrial scale!!!

Plasma CVD, suspension plasma spraying, sol-gel

Nuclear Energy

THE KEY ROLE OF ELABORATION PROCESSES

| PAGE 4

THE APPROACH ON ELABORATION PROCESSES

Develop robust processes

Continuous upgrading of processes

Evaluate emerging processes to test new concepts Invent new processes | PAGE 5

THE APPROACH ON ELABORATION PROCESSES

Robustness - Easy upscaling - Monitoring - Simulation Drivers - Environment - Raw materials saving - Energy efficiency - Nanosafety aspects

Continuous upgrading of processes (ex: impact of new plasma power supplies on surface technology…)

Additive manufacturing

Nanomanufacturing | PAGE 6

OUTLINE

High performance metallurgy: additive manufacturing

Innovative surface engineering: Ionized PVD

Nanomaterials: synthesis & safe nanomanufacturing

| PAGE 7

ADDITIVE MANUFACTURING EVOLUTION FROM RAPID PROTOTYPING TO PRODUCTION TECHNOLOGY

   

Stereolithography (SLA) 1er patent Jean Claude André (1984). SLS Polymer. Binder Jetting (3DP). Material Extrusion (FDM).

Mégajoule Laser Mock-up 1998

Direct manufacturing ≈ 1995→2000

Rapid Tooling ≈ 1990

Rapid Prototyping ≈ 1985   

Reinforced polymers. Metal SLS. Stratoconception©.



Additive Manufacturing:  SLS, EBM, DMD, etc.  Metal Stratoconception©. Ref. Avio Arcam.

Ref. GE Aviation

Aero

&

Metallurgy understanding

Steam Generator

Heat exchanger

Basic research questions

New opportunities for open mind researchers

STILL AN EMERGING TECHNOLOGY NEW OPPORTUNITIES FOR DESIGN & BASIC QUESTIONS

Thermic field Process understanding

Architectures optimizing

Additive Layer Manufacturing a cross-cutting manufacturing innovation for advanced energy technologies? | PAGE 9

STANDARD TERMINOLOGY FOR AM (FROM ASTM F42) MANY TECHNIQUES UNDER THE VOCABLE “AM”

High energy

Low energy

Vat polymerization (SLA)

Material jetting (Objet)

Binder jetting (3DP)

Material Extrusion (FDM)

Sheet lamination (LOM)

Powder bed fusion (SLS, SLM, EBM)

Direct Energy Deposition (DMD, LENS)

High performance metallurgy

METAL ADDITIVE MANUFACTURING TECHNIQUES 3 MAIN FAMILIES OF PROCESSES

Metal Additive Manufacturing Processes

Powder bed

Laser

Powder projection

Electron Beam (EBM)

(DMLS, SLM) Selective Laser Melting (DMLS, SLM)

Realizer

PTA

EOS

Laser

S12

Wuhan Binhu

Optomec

Irepa Laser

v

A2

v

Q10/Q20

POM

Concept Efesto

Matsuura

EBFFF, IFF

Electron Beam (EBDM)

Direct Metal Deposition (LENS, DMD, LD)

SISMA A1

Renishaw

Laser (LENS, DMD, LD, LC)

Electron Beam Melting (EBM) ARCAM (Sweden)

SLM

Wired-based

3D systems

Trumpf

Wire

Sciaky (EBDM)

Honeywell (IFF)

v

Norsk Titanium

| PAGE 11

METAL HYBRID MANUFACTURING TECHNIQUES

Hybrid Additive Manufacturing Processes (subtractive processes included: machining) Selective Laser Melting (SLM)

Direct Metal Deposition (DMD)

| PAGE 12

POWDER BED FUSION TECHNIQUES THE MOST DEVELOPPED FOR THE MOMENT

Electron Beam Melting (EBM)

Selective Laser Melting (SLM) | PAGE 13

ELECTRON BEAM MELTING

Examples of parts produced by EBM: CalRAM, Inc.

CalRAM, Inc.

Chernyshev

Avio Aero S.p.A.

NASA – Marshall Space Flight Center

Lima corporate S.p.A.

| PAGE 14

SELECTIVE LASER MELTING

Examples of parts produced by SLM: SNECMA (Vernon)

Dassault Aviation

Rafale’s support

Collecting tube LSPH VINCI made of Inconel 718 (Realizer)

Airbus

Poly-Shape S.A.S.

GE Aviation LEAP 56 Fuel Nozzle made of CoCr (EOS)

NASA – Glenn Research Center

Titanium Door-Hidge

| PAGE 15

MECHANICAL PROPERTIES: COMPARAISON BETWEEN EBM & SLM & CONVENTIONAL ROUTES TA6V

M . Koike et al. Materials (2011) 4 1776

v

Ref. V. CHASTAND « Mechanical Characterization of Metallic Parts produced by Additive Manufacturing », Assises Européennes de la fabrication additive, Ecole Centrale Paris 2014.

Strong need for reliable data on metallurgical and mechanical properties of materials developed by ALM

Ref. B. VERQUIN « Tour d’horizon des procédés de fabrication additive », CETIM 2013.

SODIUM-GAZ COMPACT HEAT EXCHANGER (GEN IV) ALM, A POSSIBLE ALTERNATIVE TO HIP? Small-scale demonstrator produced by EBM

   

The heat exchanger prototypes are manufactured by HIP in two processing steps → complex. 316L (N) stainless steel is the candidate material. Heat transfer gas (Nitrogen) – smaller channels 2,5 x 2,5 mm2. Sodium: channels 3 x 6 mm2 with a reduced wall thickness equal to 2 mm.

New designs for heat exchangers Enhance compacity, reduce size Topological optimization of channels Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

| PAGE 17

MECHANICAL BEHAVIOUR OF THE 316L SS (SLM)



As-built and 650°C samples exhibit elongated grains in the building direction – strongly textured.



On the contrary, the HIP (920°C/1000 bar) sample exhibits coarse grains almost equiaxed – absence of texture. Ref. T. NIENDORF et al. « On fatigue performance of materials processed by SLS: bulk materials and lattice strectures », Conférence FATIGUE 2014.

Condition

UTS (MPa)

YS (MPa)

A [%]

As-built SLM

565 ± 5

462 ± 5

53,7 ± 5

TT @ 650°C

595 ± 5

443 ± 5

48,6 ± 3

ASTM reference

450-620

170-310

30-40

| PAGE 18

MECHANICAL BEHAVIOUR OF THE 316L SS (EBM) 

No macroscopic porosity in the built material, neither powder-induced.



The material is anisotropic. A layered structure composed remaining weld lines are seen in the Z cross sections.



Grain structure is austenitic and elongated in the Z direction → columnar grain growth.



Vertical intergranular cracks → lower strength in the X direction.

Ref. J. GOOD « Fabrication in Space: what Materials are needed? », ARCAM User’s Group Meeting 2007.

Condition

UTS (MPa)

YS (MPa)

A [%]

As-built EBM (Z direction)

539

304

34,5

As-built EBM (X direction)

384

254

14,5

450-620

170-310

30-40

ASTM reference

Still a strong need for basic metallurgical and parametric studies !!!

| PAGE 19

NUCLEAR, A QUITE ACTIVE FIELD FOR ALM (DOE STUDIES) PROTOTYPES & BASIC STUDIES

DOE Nuclear Energy Enabling Technologies (NEET) advanced manufacturing methods (AMM)

Laser Direct Manufacturing of Nuclear Power Components (Grids): SS 316 L, Inconel 600/718, Incoloy 800 and ODS steels

Environmental Cracking and Irradiation Resistant SS 316L by ALM

Laser Melting Sintered powder

(Unsintered powder)

Completed Layer

SS 316L Additive Manufactured parts: Qualification

| PAGE 20

OXIDE DISPERSION STRENGTHENED (ODS) STEELS EVALUATION OF A DIRECT ROUTE FOR ODS SYNTHESIS Materials for Advanced Fission & Fusion Reactors produced by SLM

Direct Metal Deposition (DMD) in a single step

Selective Laser Sintering of MA956 steel - R.M. Hunt et al. J. Nucl. Mat. 464 (2015) 80

Wrought MA956

As-built SLS MA956

Annealed MA956 (SLS)

We are still at the beginning of the story

| PAGE 21

MANUFACTURING OF LARGE-SIZED COMPONENTS (1) A GENERIC NEED Aeroswift Project (South Africa): Development of a SLM machine for producing large-sized aerospace components – industrial partner: AIRBUS. 

Large-sized titanium components limited by the build envelope (2 x 0,6 x 0,6 m).



8 times faster (180 cm3/h) compared with a current EOS M270.



Up to 99,9 % of final density.

| PAGE 22

MANUFACTURING OF LARGE-SIZED COMPONENTS (2) A GENERIC NEED Beihang - Northwest Polytechnical Universities (Chine): Different Airframes produced by Direct Metal Deposition (DMD) for several aircrafts including: fighter-4, J-20, J-31 stealth fighter, Y-20 Strategic Airlifter, J-15 carrier-borne fighter and C919 airliner.

Réf. www.3Ders.org

| PAGE 23

NEED FOR AN INTEGRATED APPROACH ON ALM

Before process Powders Integrated approach on ALM

(quality, reproducibility, innovative powders)

Non destructive testing Process Basic metallurgy studies Monitoring Simulation Software Design & topological optimisation

After process Post treatments Joining technologies Surface treatment

| PAGE 24

INNOVATIVE SURFACE ENGINEERING

High performance metallurgy: additive manufacturing

Innovative surface engineering: Ionized PVD

Nanomaterials: synthesis & safe nanomanufacturing

| PAGE 25

Environmental barriers Corrosion under irradiation Erosion/wear

Nanocomposites

Extreme environnements

Active surfaces Catalyst Photocatalyst Absorbant

Integration of functions into devices Photovoltaics Functionalized membranes Piezoelectrics … | PAGE 26

DC MAGNETRON SPUTTERING (dcMS) A GENERIC TECHNOLOGY WITH SOME LIMITATIONS… PVD processes are based on the vaporisation of a solid source Vaccuum chamber + inert gas

Negative voltage on the cathode: ionisation of the inert gas

Ion bombardment of the cathod

Condensation on the substrate and coating growth



 High deposition rates



   

Low energy 2→10 eV. Difficulty to cover complex shapes Columnar structure Porosity

| PAGE 27

THE SOLUTION…IONIZED PVD TECHNOLOGY Conventional Magnetron Sputtering

Ar+

Cr

I-PVD

+

Cr

Ionisation yield 50%

| PAGE 28

DC MAGNETRON SPUTTERING VS HIGH POWER IMPULSE MAGNETRON SPUTTERING

HiPIMS

dcMS

power

power

kW.cm-2

W.cm-2 time

time

o Same average power o Pulse width : 10-200µs o frequency : 50-1000 Hz | PAGE 29

STUDY OF THE PROCESS BY MASS SPECTROMETRY

Ferrec et al. Surf. Coat. Technol. 250 (2014) 52

| PAGE 30

DC MS VS HIPIMS

Ferrec et al. Surf. Coat. Technol. 250 (2014) 52

| PAGE 31

COMPARISON BETWEEN DC MS & HIPIMS

dcMS Ar+ (49%)

Cr2+ (4%)

HiPIMS Ar+ (17%)

Ar2+ (1%) Cr+ (46%)

Gaseous ions o High energies o Important number of metallic ions o Many double ionized ions (2x)

Ar2+ (3%)

Cr2+ (9%) Cr+ (71%)

Metallic ions

• substrate etching • ↗ film density • better adhesion

| PAGE 32

ADVANTAGES OF IONIZED PVD TECHNOLOGIES Ionic bombardment leads to enhancement of use properties: adhesion and mechanical properties

dcMS 6000

Cr

5000

200 sccm Ar 50 sccm N2

HiPIMS

Ar

4000 3000 2000

N2

1000 0 320

420

520

620

720

Implantation zone

820

Adhesion defect

Enhancement of residual stresses

Ehiasarian et al. J. Appl. Phys. 101 (2007) 054301 | PAGE 33

HIPIMS

dcMS

COATINGS MORPHOLOGIES: COMPARISON BETWEEN DC MS & HIPIMS

Ferrec et al. Surf. Coat. Technol. 250 (2014) 52

| PAGE 34

OXIDATION PROPERTIES OF HIPIMS COATINGS HIGH RESISTANCE IN EXTREME ENVIRONMENTS (ATF) Ferrec et al. Surf. Coat. Technol. 250 (2014) 52

Good behaviour under irradiation for: - CrN (arc evaporation) - AlCrN (arc evaporation) Tested in Halden PWR reactor at 320°C The process must be able to treat more | PAGE 35 than 1 million of cladding pins per year !!!

Solar Fusion

Anti-erosion

Wear

| PAGE 36

NANOMATERIALS & SAFE NANOMANUFACTURING

High performance metallurgy: additive manufacturing

Innovative surface engineering: Ionized PVD

Nanomaterials: synthesis & safe nanomanufacturing

| PAGE 37

High Performance Metallurgy

Surface Technologies

20nm

Architectured Materials

Nanocouches Nanolayers TiN / AlTiN

11 période period 10nm

Nuclear Energy (fission, fusion) &

Renewable Energies

Nanomaterials & Safe Nanomanufacturing

3

3 INNOVATIVE PROCESSES FOR THE SYNTHESIS AND INTEGRATION OF NANO-OBJECTS

Magnetron

Laser thermal treatment

Nanoparticles source

Aerodynamic Lens

Laser pyrolysis Lithium Ion Batteries

Aerosol CVD Supercapacitors

Substrate holder (heated & biased)

Hybrid Laser Pyrolysis/PVD Photovoltaics

| PAGE 39 Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

INNOVATIVE ELABORATION ROUTE FOR NANO-OBJECTS: LASER PYROLYSIS

Powders collection Pyrolysis " flame " Powders Ar chimney

CO2 laser

Inlet nozzle

Energy transfer laser/precursors (absorption) Collision assisted precursors dissociation Nucleation and growth of nanoparticles without any contact with reactor walls

Gaseous or liquid precursors Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

| PAGE 40

CORE-SHELL SI@C: SYNTHESIS BY INNOVATIVE DOUBLE STAGE LASER PYROLYSIS PROCESS

DOUBLE STAGE LASER PYROLYSIS PROCESS

 

Synthesis in one step Independant control of the nature and the structure of the core and the shell of the nanoparticle | PAGE 41

Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

NEW MATERIAL FOR LIB CONTROLE OF THE SHELL B

A

100 nm

C

Amorphous Si

250

200

Intensité (u.a.)

CONTROL OF THE CORE

ELECTROCHEMICAL RESULTS

150

100

50

SiH4 + He

Laser Focalisation

0

20

30

40

50

60

70

80

2 Theta (°)

1000

800

600

400

200

0 20

30

40

50

60

70

80

Lifetime X 5

Cristalline Si Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

| PAGE 42

NANOCOMPOSITES FOR SUPERCAPACITORS Different fields of applications Transport, electronic, applications for unique use, …

Supercapacitors

 Time constant : few seconds - few minutes  Performances depends on their components : - Electrodes, electroactive materials - Electrolyte

| PAGE 43 Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

STRATEGY AND OBJECTIVES DEVELOPMENT OF A ECP/VACNT NANOCOMPOSITE  Objectives ► Improvement of the electrochemical stability and of the storage capacity: specific power  Approach Nanostructured ECP / VACNT electrode

Working electrode (VACNT)

Conjugated monomers

- e-

3MT

Vertically aligned carbon nanotubes

Poly-3-methylthiophene

● High conductivity and specific surface area ● Standing on substrate (current collector) : no processing (in favor of low ESR) ● Anisotropy : ECP structuration and better ion diffusion in porous channels between CNT

●

S

Specific capacitance: 250F.g-1 ● High oxidation potential ● Association to many electrolytes (ionic liquids: large potential window) | PAGE 44

Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

SYNTHESIS OF VACNT : AEROSOL-ASSISTED CATALYTIC CHEMICAL VAPOR DEPOSITION Catalytic decomposition of a hydrocarbon precursor

Aerosol generator Liquid hydrocarbons (toluene, …) + Ferrocene

Furnace (800-850°C) Ar or Ar/H2 carrier gas

Continuous feeding of the reactor by both carbon and catalyst nebulized precursors

Quartz reactor

Traps

Black deposit = VA-CNT carpets SEM

 Multiwalled nanotubes  Base-growth mechanism  High purity  Continuous production  High growth rate (30 to 60 µm/min)  Low cost

TEM

SEM Technology patented : FR0207785, 2002 Pinault et al, Carbon 2005

Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

| PAGE 45

INNOVATIVE PROCESS TO PRODUCE P3MT/VACNT NANOCOMPOSITE ELECTRODES

Challenges  polymerisation - in confined volume, all along the CNTs - using viscous medium (ionic liquid, viscosity 20-40 cP) Sequenced galvanostatic process

- Homogeneous distribution of S along the carpet cross-section

- P3MT evenly distributed and forming a layer on each CNT Collab. Univ Cergy Pontoise

Patent FR1055526, 2010 | PAGE 46

Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

ELECTROCHEMICAL PROPERTIES OF P3MT / VACNT NANOCOMPOSITE ELECTRODES Caracterisation by cyclic voltametry

P3MT content: 85 wt%

Cm (F/g)

Cm 126 F/g

Comparison of the nanocomposite electrode with classical electrode

P3MT (%)

Collab. Univ Cergy Pontoise, France S. Lagoutte et al., Electrochimica Acta (2014)

P3MT / VACNT electrodes exhibit the highest capacitance  Benefit of P3MT structuration and CNT conductivity  Thick electrodes compared to literature, amongst the highest capacitance developed Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

| PAGE 47

SCALE-UP OF VACNT GROWTH WITH A PROTOTYPE EQUIPMENT ► Design and development of a prototype equipment (vertical configuration) ► Production on large silicon wafers : 300 mm diameter, 707 cm2 surface Synthesis conditions

1 photo du pilote annotée

● Precursors : toluene + ferrocene ● Carrier gas : Ar ● Pressure : 100 – 1000 mbar ● Temperature : 800 °C ● Immobilized substrate

Batch to batch production of large VACNT surfaces ► Concerned by : risk control ; health and environmental impact - Towards a safe by design process - Toxicity studies through in-vitro and in-vivo approaches (14C labelled CNT) Collab. CEA-DSV and DSM (INAC), INSERM.

B. Czarny et al. ACS Nano, 2014 | PAGE 48

Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

LARGE SURFACE VACNT OBTAINED WITH A PROTOTYPE EQUIPMENT

Production on large silicon wafers : 300 mm diameter 707 cm2

E=100µm V=6µm/min

P. Boulanger et al., Journal of Physics: Conference Series 429, 012050 (2013)

Optimization in progress: increase of homogeneity in thickness and of growth rate | PAGE 49 Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

VALORIZATION AND TECHNOLOGY TRANSFER

= Up-scaled High Quality VACNT Growth

Electrodes exhibiting promising properties

Conformal ECP coating

Continuous and low cost process

New concept of supercapacitors

Creation of a start-up P. Boulanger April 2013 Targeted market : next generation of supercapacitors based on VACNT-engineered electrodes License agreement between CEA and NaWa : 4 patents

50 | PAGE 50

Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

AEROSOL CVD A GENERIC TECHNOLOGY FOR NANO-OBJECTS: BIMETALLIC CATALYSTS FOR PEMFC

| PAGE 51 Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

INNOVATIVE HYBRID LASER PYROLYSIS/PVD SYSTEM FOR NANOCOMPOSITES

Supersonic Gas beam Containing Nanoparticles

Heating Setup (lamp, laser)

5. 10-3 mbar

Skimmer

Sputtered Material Beam

Magnetron Sputtering Device

< 10-2 mbar Nanoparticles Synthesis (0.2 - 1 bar)

10-5 mbar

Injection Nozzle

Turbo Pump

Turbo Pump

Magnetron Sputtering Device

Sputtered Material Beam Turbo Pump

Photovoltaics Thermal solar Self healing coatings for extreme environments? Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

| PAGE 52

UPSCALING OF THE PROCESS TO LARGE SCALE Pulverization Supersonic cathodes beam Intermediate chamber Aerodynamic lens Expansion chamber

Transverse Substrate motion Substrate

Deposition chamber

Nanoparticles flow Laser Pyrolysis Pomping stages | PAGE 53 Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

IN PARALLEL WITH PROCESSES, DEVELOPMENT OF RISK EVALUATION & MANAGEMENT TOOLS

Quantification of individual protections -

Monitoring by means of LIBS – Amodeo et al. (2009)

Flammability and explosivity risks – Boulliard et al. (2010)

Golanski et al. (2009)

Personal sampler Development of the Risk Evaluation tools

In Silico model: 99mTc- carbon nanoparticles - Péry et al. (2009)

Rapid toxicity screening tests

Releaseability of nanofillers – Golanski et al. (2012) | Page 54

Safe recovery of raw materials & liquid functionalisation.

In-situ metallic-based matrix nanocomposites

Thermal Spraying Laser clading EBM/SLM Extrusion, Forging, Spark Plasma Sintering & Machining

Functional nanocomposite thin films processed by innovative PVD (magnetron type HIPIMS / Arc)

Automotive, Aerospace, Energy and Construction

Integration and synthesis of nanopowders & aligned carbon nanotubes in organic matrix composites, membranes Technological demonstrators

NanoSafe-by-Design processes

Safe Nanomanufacturing

TWO APPROACHES FOR PROCESS INNOVATION FROM SAFE NANOMANUFACTURING TO SAFE-BY-DESIGN

| PAGE 55

SAFE NANOMANUFACTURING DEVELOPMENT & INTREGRATION OF TOOLS A complete workplace’s monitoring

Direct liquid recovery after production

Tools’ integration into the existing production lines

Granulation, liquid phase functionalization & dispersion – Faure et al. (2010)

| Page 56

SAFE NANOMANUFACTURING: PROCESSING & CONSOLIDATION ROUTES

3-D

2-D

Spark Plasma Sintering

Hot Pressing

Laser Manufacturing

Extrusion & Injection Moulding

Thermal spraying

Sol-gel & dip-coating

| Page 57

NANOPOWDERS SUSPENSION PLASMA SPRAYING FOR THERMAL BARRIERS & SOFC SPS coating

EB-PVD

1000

Colonnaire Colonnaire compacte

800 600 400 200 0 RaSubstrat,Ref

2,5 x RaSubstrat,Ref

 Porous structures  Low thermal conductivity and temperature stability  SPS coatings comparable to EBPVD reference technology

Thermal conductivity (W/mK)

Nombre de cycle avant rupture

Nb of cycles before failure

Sand blasting

2.0

Microstructure : Colonnaire Colonnaire Compacte Columnar structure

1.8 1.6 1.4 1.2 1.0 0.8

Compact columnar structure

0.6 0.4 0.2 0.0 0

200

400

600

800

1000

1200

Température (°C)

Results included in this document are CEA’s property. They cannot be disclosed without prior authorization.

| PAGE 58

NANOSAFE-BY-DESIGN PROCESSES 2-D Surface Processes Nanostructured thin films by PVD High-power impulse magnetron sputtering (HIPIMS) & Cathodic Arc

Antibacterial titania-based nanocomposites processed by DLI-MOCVD

Superlattice TiN/AlTiN with enhanced elastic properties (hardnesses > 60 GPa) Ducros et al. (2006)

Antibacterial activity against Gram-positive Staphylococcus aureus - Mungkalasiri et al. (2010)

NANOSAFE-BY-DESIGN PROCESSES 2-D Surface Processes: Hybridation of the different techniques Cathodic Arc coupled with Plasma enhanced chemical vapour deposition (PE-CVD)

Laser Pyrolysis coupled with magnetron sputtering – Leconte et al. (2012) Patent

Bendavid et al. (2005)

In-situ nitride-based nanocomposite

Properties Tailoring

Supersonic cluster beam combined with cathodic arc deposition Piazzoni et al. (2008)

| Page 60

NANOSAFE-BY-DESIGN PROCESSES

3-D Bulk Processes Oxide dispersion strengthened steels (ODS)

Thermal plasma TiC-Al(Ti) in-situ synthesis Tong et al. (2006)

CEA developed steel reinforced with Y2O3 processing by mechanical alloying and subsequently consolidated by SPS or extruded.

Processed by EB-PVD Chen et al. (2011)

NiCr-4%Y2O3 or Al2O3 reinforcements

Reactive mechanical milling TiC/Ti-Al Gu et al. (2009)

Alumina-YAG processed by solid state reaction Lomello et al. (2010) – PhD. Thesis

EXAMPLES OF TECHNOLOGICAL DEMONSTRATORS FOR LOW CARBON ENERGY & INDUSTRY

CNT-based bipolar plates for Fuel Cells

Fuel Cladding for GenIV reactors

Renewables

Nuclear

A safe nano-objects integration Automotive Polymer reinforced CNTs for automotive applications

Aeronautics High performance Al/nano-TiC MMC

| Page 62

Thank you for your attention