An overview of the Department of Advanced Physical Technologies and New Materials (FIM)

Dept. of Advanced Physical Technologies and New Materials

EERA Sherpa group meeting - Casaccia - December 20082

An overview of the

Department of Advanced PhysicalTechnologies and New Materials (FIM)

Andrea [email protected]



Department of Advanced Technologies and New Materials

“Enabling technologies" to achieve ENEA's strategic objectives: energy, environment and competitiveness of the manufacturing industry in the following areas:

• New functional materials (Composite materials, Nanomaterials)

• Materials engineering

• Materials characterization

• Non-ionising radiation technologies

• Ionising radiation technologies

• Autonomous robotics

• Information and Communication Technologies

• Modelling and simulation

• Advanced technology services

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Activities

R&D projects, generally financed by national and/or EU funding bodies;

Creation of prototypes and demonstration plants;

Technology transfer projects and dissemination of information to manufacturing industry, and in particular to SMEs;

Delivery of technical/scientific consultancy and services to private companies and public bodies;

Provision of high-level training on new and/or highly qualified skills, in collaboration with universities and manufacturing industry.

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FIM Research centres

Total number of employees: ~ 400



FIM Financial Resources

6%

67%

7%

11%

9%

UE

Res. Min.

ServicesConsortia

Other

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New materials for energy applications

Development of materials, components and processes for innovative applications in the energy sector, both for energy production and high-efficiency end uses.

• Composite materials for high temperature / high power energy cycles

• Materials for hydrogen generation, storage and fuel cells

• Cellular, metallic and polymeric components for structural lightening, mainly in vehicles

• Materials and processes for thermal and acoustic insulation in the building industry

• Nanomaterials and nanotechnologies: carbon-based nanomaterials, ceramics, nanomaterials for energy conversion processes, surface treatments

• Sensors and RFID devices and applications

• Solid-state lighting devices

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Materials and components for high-temperature, high-power energy cycles

• Carbide and nitride based materials with self-repair properties, capable of closing and repair defects during high temperature operation;

• Fiber-reinforced ceramics and study of applications to energy generation and jet propulsion;

• Development of “Near-net shaping” technologies and exploration of opportunities of technology transfer to industries;

• Development of Ceramic Matrix Composites (CMC), capable of reducing sensitivity to defects through the introduction of a second phase in the structure. In this case a development of composite production technologies through Chemical Vapor Infiltration (CVI) is sought, also through the use of innovative solutions already developed in ENEA, aimed at a reduction of process costs and therefore interesting for an industrial take-up.

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Development of CFCCs (Continuous Fiber Ceramic Composites) using CVI (Chemical Vapour Infiltration) technology - EBC development by APS and slurry coating

Fiber

Matrix

Interlayer fiber-matrix

Silicon Carbide CFCC (SiCf/SiCmatrix) properties: High temperature strength High toughness Low weight Reliability Creep resistance Resistance to shocks and fatigue

CVI process vs liquid phase process (e.g: PIP-process)Advantages: It deposits SiC with high purity and well-controlled composition and microstructure. Highly flexible process

Drawbacks: Low deposition rate

The densification rate is improved by introducing a

temperature gradient (Thermal Gradient - Chemical

Vapour Infiltration, TG-CVI ) on the fiber preform

Project for the implementation of a thermal gradient

in ENEA-Faenza CVI plant



SiCf/SiC CFCC are produced with an Isothermal/Isobaric Chemical Vapour Infiltration / Deposition (I-CVI / CVD) plant (developed in ENEA-Faenza)

Chemical Vapour Infiltration (CVI) process

The interphase (Pyrolitic Carbon Py-C) and then the SiC-matrix, are deposited on the fiber surface, within the pore network of the preform, according to the following overall equations:

CH3SiCl3(g) → SiC(s) + 3HCl(g)

CH4 → C(s) + 2H2

The starting material is a porous 2D-fiber preform maintained with a tooling

SEM images of Py-C and SiC on various substrates (SiC felts and graphite)



MATERIALS FOR POWER GENERATION MATERIALS FOR POWER GENERATION Mitgea ProjectMitgea Project

Objective: Objective: innovative processes for the industrial innovative processes for the industrial productionproduction of ceramic cores suitable for innovative DS of ceramic cores suitable for innovative DS nickel-based superalloy turbine bladesnickel-based superalloy turbine blades (increasing increasing operating temperatures and lifetime and lowering costs)operating temperatures and lifetime and lowering costs)

- Leachable Ceramic Cores for DS-investment casting;Leachable Ceramic Cores for DS-investment casting;

- Refractories, also produced using ceramic wastes;Refractories, also produced using ceramic wastes;

- Thermomechanical characterization (up to 1000 °C on Thermomechanical characterization (up to 1000 °C on metallic materials and superalloys and up to 1500° C on metallic materials and superalloys and up to 1500° C on advanced ceramic and ceramic composite materials). advanced ceramic and ceramic composite materials).

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25

0 0,0005 0,001 0,0015 0,002

strain [mm/mm]

stre

ss [

MP

a]

500 700800 10001200 22_522_6

Grain bridging mechanism

Ceramic cores Thermomechanical characterization

Microstructural characterization



MATERIALS FOR HIGH TEMPERATURES MATERIALS FOR HIGH TEMPERATURES APPLICATIONSAPPLICATIONS

Objective: substitution of traditional metallic materials with ceramics in Objective: substitution of traditional metallic materials with ceramics in thermal systems operating at high temperature (e.g. ceramic heat exchangers)thermal systems operating at high temperature (e.g. ceramic heat exchangers)

SiC-based materials with addition of Aluminum nitride and rare-earth oxides were studied and SiC-based materials with addition of Aluminum nitride and rare-earth oxides were studied and characterized with the aim of evaluating the mechanical properties and oxidation resistance at characterized with the aim of evaluating the mechanical properties and oxidation resistance at high temperature (1500°C).high temperature (1500°C).

Pressureless-sintering was patented by ENEA in 2005 (IT BO2005A000311). Results Pressureless-sintering was patented by ENEA in 2005 (IT BO2005A000311). Results demonstrated that SiC-AlN-REdemonstrated that SiC-AlN-RE22OO33 composites can successfully be used in oxidative composites can successfully be used in oxidative

environment up to 1500°C. Pre-oxidized samples showed improved fracture toughness and environment up to 1500°C. Pre-oxidized samples showed improved fracture toughness and flexural strengthflexural strength ( (CRACK-HEALING MECHANISMCRACK-HEALING MECHANISM).).

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OXIDATION TIME (h)

WE

IGH

T G

AIN

(m

g2 /cm

4 )

SiC-AlN-Y2O3

SiC-AlN-Er2O3

SiC-AlN-Yb2O3

SiC-AlN-Lu2O3

10 m

Y



THERMAL PERFORMANCE OF BUILDING MATERIALS

CE-marking of masonry clay bricks requires also the evaluation of the thermal conductivity of each element, in order to use them in structures satisfying the qualifications for thermal insulation.

The Italian legislation (ministerial decree dated April 2nd, 1998) made the statement of thermal properties compulsory, while UNI EN 771-1:2005 standard requires that the assessment of thermal properties of blocks has to be performed according to UNI EN 1745.

Complying with the needs of bricks manufacturers, in the field of both product qualification and technological innovation, ENEA, together with ISTEC-CNR and CertiMaC laboratories in Faenza, provides certification and consultancy services devoted to the assessment of thermal performances of clay bricks.



THERMAL PERFORMANCE OF BUILDING MATERIALS

Thermal values of bricks (and other building materials) are calculated by a bi- and tri-dimensional finite elements stationary model, starting from the thermal conductivity (W/m*K) of bulk, obtained using a Guarded Heat Flow Meter (see slide before) following ASTM E 1530. UNI EN 1745 requires to put in correlation this method to the reference method (ISO 8302 – Guarded Hot Plates).

The finite element brick models developed can also be applied in a non-stationary way, simulating the natural daily cycles. R&D activities is being performed, together with ISTEC-CNR, aiming at enhancing insulation properties of building materials.ANSYS 8.0

MAY 23 200716:28:57 NODAL SOLUTIONSUB =1 TIME=1 TEMP (AVG) RSYS=0PowerGraphicsEFACET=1AVRES=MatSMN =.334071 SMX =18.984

1

MN

MX

X Y

Z

.334071 2.406 4.478 6.551 8.623 10.695 12.767 14.84 16.912 18.984

ANSYS 8.0 APR 13 200716:07:28 VECTORSTEP=1 SUB =1 TIME=1 TF ELEM=2249 MIN=4.824 MAX=26.308

1

4.824 7.211 9.598 11.985 14.372 16.76 19.147 21.534 23.921 26.308

ANSYS 8.0 JUN 6 200716:17:48 NODAL SOLUTIONSTEP=1 SUB =1 TIME=1 TEMP (AVG) RSYS=0PowerGraphicsEFACET=1AVRES=MatSMN =.388217 SMX =18.653

1MN

MX X

Y

Z

.388217 2.418 4.447 6.476 8.506 10.535 12.565 14.594 16.623 18.653



Nanotechnologies

Synthesis, characterization and numerical modelling of nanoparticles and nanostructured materials.Synthesis and characterization of nanophases and nanoparticles:

Carbon nanotubes and carbon nanostructures. Colloidal synthesis of metallic and semiconducting nanoparticles for optical and magnetic applications.

Synthesis and characterization of nanocomposites and nanostructured materials. High energy ball milling for the synthesis and the processing of materials for hydrogen storage and

hydrogen generation by thermo-chemical cycles Synthesis of nano-structured surfaces by ion implantation in insulators for optical and magnetic

application. Synthesis of nano-structured polymeric materials.

Material characterization: Material characterization by electron microscopy, X-Ray diffraction, surface spectroscopy, probe

microscopy, time resolved optical spectroscopy etc. Remote operation of complex instrumentation

Development of theoretical methods and of simulation codes Classical and quantistic molecular dynamics simulation Development of multi-scale designing methods

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Sustainable hydrogen production by thermochemical cycles

Our activities are on the synthesis of materials

for the Manganese ferrite cycle

with the purpose of reducing the operation temperatures



MnO/NaOH based composites

Slurry : MnO+NaOHreazione dopo disidratazione

Temperatura (C)

300 400 500 600 700 800 900

SH

2/m

g

0

4000

8000

as prepared

dopo 4h dopo 24h

H2 f

lux

(a.u

.)

Temperature ( °C)

nanoparticles microparticles

1) MnO + NaOH = NaMnO2

2) NaMnO2 + 1/2H2O = NaOH +1/2Mn2O3

3) Mn2O3 = 2 MnO+1/202



Ferrite nanoparticles

Performances of MnFe2O4/Na2CO3 based composites

0 25 50 75 100 125 150 175 2000.0

0.2

0.4

0.6

0.8

1.0

Microstructured

Nanostructured

(d

egre

e of

con

vers

ion)

Time (min)

MnFe2O

4/Na

2CO

3 composite

Nanostructured composites speed upthe reaction kinetics allowing a temperature reduction



Nanostructured Magnesium Based Composites for Hydrogen Storage

Mg can store up to 7.6 wt% hydrogen but suffers of the following problems:

Slow kinetic of H2 desorptionHigh thermodynamic Stability of MgH2

Surface OxidationStrategy:Ball milling

Create defects Nanocrystalline materialCrack of surface MgO

Introduction of a catalyst/additive Speed up of reaction kinetics

50 μm

Catalyst

MgH2 10 nm

H2

increase H2 mobility

splitting of H2

molecules

H2

Tailoring the microstructure to the desorption process:MgH2 - MgH2Ni4, MgH2 – Fe,MgH2- LaNi5 MgH2 – (micro and nano) Nb2O5



Kinetic studies:Best results indicate an onset of the MgH2 decomposition reaction and of Hydrogen release at about 200 °C.

Metallographic studies by a specifically designed procedure allow to clarify the role of the catalyst and support the interpretation of kinetics results.

Mg

MgH2

Catalyst



Process simulation by First-principle molecular dynamics

Hydrogen desorption at Mg-MgH2 interface

Car-Parrinello Molecular Dynamics (CPMD code) technique has been used to build and optimize an Mg-MgH2 interface. Hydrogen diffusion has been studied versus temperature. At T= 700 K hydrogen starts the desorption.

Hydrogen

Magnesium

Mg surface

MgH2 surface

Interface

Starting configurations



Process simulation by First-principle molecular dynamics

Catalytic effects of Fe near the interface

Starting configuration of an interface with a Fe atom near the surface.

Insertion of one Fe atom increase the H mobility lowering the desorption temperature

Catalytic effect of Fe atom in agreement with the recent work

Fe

Fe



Stabilization of AB5 alloys against decrittation

isoterme di attivazione in H2 3%

tempo (min.)

0 20 40 60 80 100

rate

0.000

0.004

0.008

0.012 LaNiAl a 100°C mac.

SiO2 + LaNiAl a100°C mac.

LaNiAl a 150°C tal quale

time (min)

H2

flux

(a.u

.)

after high energy ball milling

composite material

as received

H2 desorption at 100 °C after the first hydriding reaction in H2/Ar 3%

LaNi5 in nanoporous Silica

Embedding in nanoporous matrix allows to combine fast reaction and structural stabilityEmbedding in nanoporous matrix allows to combine fast reaction and structural stability



Electrodes for polymeric electrolyte fuel cells based on nanomaterials

Materials optimization (Pt catalyst and carbon-based diffusive layer)

Improvement of the catalyst utilization (localization only on the substrate surface)

Increase of catalytic activity compared with traditional electrodes

The surface morphology of Carbon Nanowalls (high surface area) makes them an ideal template for electrodes allowing both an improvement of the dispersion of the catalyst and a reduction of the loading compared to traditional substrates

Purposes

PVD and ELD techniques allow the deposition of the catalyst clusters on the top of the diffusive layer



CNW as substrate for Polymer Electrolyte Fuel Cells catalyst

Pt nanostructured small particles electrodeposited onto electrodes made by carbon nanowalls

Pt is the catalyst for theHydrogen oxidation reactionat the anode in the PEFC



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E-TEK PVD GED PED

EA

S /

m2

g-1

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Pt-CNW3 Pt-CP

MS

A /

mC m

g Pt-1

Electrochemical activity of nanostructured Pt catalysts

Comparison of Electrochemical Active Surface of Pt nanoparticles deposited with different techniques with a commercial catalyst

Mass Specific Activity of Pt nanoparticleselectrodeposited on CNW and conventional substrate

Pt Loading E-TEK 0.35 mgPt cm-2 PED <0.05 mgPt cm-2

PVD <0.006 mgPt cm-2



The growing maturity of silicon technologies puts research on The growing maturity of silicon technologies puts research on other forms of PV cells in the foregroundother forms of PV cells in the foreground

PV literature survey, from: "Progress in PV: research and applications" (gen-nov 2007)

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c-Si bulk c-Si a filmsottile

a-Si, m-c-Si eEterogiunzioni

OSC DSSC CIG, CIGS

Trends in PV technologiesTrends in PV technologies

E. Shaheen et al. Mat. Res. Soc. Bull. 30-1 (2005)E. Shaheen et al. Mat. Res. Soc. Bull. 30-1 (2005)

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2002 2005 2010 2015 2020 2025 2030

MW GW30%p.a. 25%p.a.

c-Si

thin film

"New Concepts"



Trends and roadmaps for the Trends and roadmaps for the “new” technologies“new” technologies



Reduced lifetime and efficiency suggest the application of OPV Reduced lifetime and efficiency suggest the application of OPV cells to low durability and “throw away” applications cells to low durability and “throw away” applications



OLED ON PET

SOLAR CELL ON PET

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300 350 400 450 500 550

Lunghezza d'onda, (nm)

Voc=0.98 Volt; F.F. = .32

Quantum Yield

Research on these devices is currently starting in ENEA. Research on these devices is currently starting in ENEA. The general frame is to transfer esperiences and know-how on The general frame is to transfer esperiences and know-how on OLEDs to SCs. OLEDs to SCs. Preliminary experimental results were obtained on OSCs on PET.Preliminary experimental results were obtained on OSCs on PET.

Activities in ENEAActivities in ENEA



How new Solid State Lighting sources can have an How new Solid State Lighting sources can have an impact on energy efficiency in lightingimpact on energy efficiency in lighting applications applications

Source: OSRAMSource: OSRAM



Specific applications for OLED light sourcesSpecific applications for OLED light sources

Source: OSRAMSource: OSRAM



The background of ENEA in OLED The background of ENEA in OLED technologiestechnologies

Images of devices developed in ENEA (Portici) and of related characterization activitiesImages of devices developed in ENEA (Portici) and of related characterization activities



A common target for the two applications: increase A common target for the two applications: increase know-how in flexible substrate technologiesknow-how in flexible substrate technologies

Machine for roll-to-roll OLED production (ENEA specif.)Machine for roll-to-roll OLED production (ENEA specif.)



Information and Communication Technologies

Development and maintenance of a high performance computing environment, based on GRID technologies, in order to comply with the requirements of the various research groups in ENEA and to offer high-level computing services to the international scientific community and the industrial system.

Activities are mainly focused on:

High performance systems for scientific computing and modelling;

Computational GRIDs;

3D visualisation systems;

High-bandwidth low-latency connectivity;

Technologies for networking and remote operation of complex scientific instruments;

Technologies for the management of large, geographically distributed databases;

Adaptation/porting of computational codes to innovative platforms.

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GRID – Based Computing

36

NETWORKNETWORK

DATA ACQUISITIONDATA ACQUISITION DATA ANALYSISDATA ANALYSIS

Cell Centered Data Base Cell Centered Data Base ““CCDB”CCDB”

IMAGINGIMAGINGINSTRUMENTSINSTRUMENTS

COMPUTATIONALCOMPUTATIONALRESOURCESRESOURCES

MULTI-SCALEMULTI-SCALEDATABASESDATABASES

ADVANCEDADVANCEDCOMPUTERCOMPUTERGRAPHICSGRAPHICS



CASACCIACASACCIA

FRASCATIFRASCATI

S.TeresaS.Teresa

SaluggiaSaluggia

IspraIspra

BOLOGNABOLOGNA

PORTICIPORTICI

TRISAIATRISAIA

BRINDISIBRINDISI

ManfredoniaManfredonia

ENEA-GRID Computational & 3D Centers

902750

400

140

30

#CPU/Cores

45



GARR

PI2S2

GARR Other Entities

ENEA-GRID interoperability with other GRIDs

ENEA has been developing the “shared proxy” solution

•Maintain the GRID internal architecture and autonomy

•Allow multiplatform impementations

•In production on EGEE

•In production on GRISU•Required by EFDA for EGEE

EFDAEGEE



A new HPC centre in Portici

39

Infrastructures:

- New HPC centre in Naples with top level computing and storage systems ( ca. 2,700 CPUs). Currently positioned at n. 125 in TOP500;

- Development of a new class of innovative functions for GRID computing

Main applications:

- Bioinformatics

- Critical infrastructures

protection



Supercomputing: application areas

40

Engineering

Nuclear physics and engineering – nuclear fusion

Climate and environment

Materials

Bioinformatics

Critical infrastructures protection

Combustion



ENEA-GRID for Industry and Consortia

Air flow dynamics and temperature inside new train cars

Coll. with CETMA



Hydrofoil flow simulation

ENEA-GRID for Industry and Consortia

Coll. with CETMA



CRESCO for nuclear fusion

Cresco (20 Tflops peak) System for development and test

of computational codes for ITER (1 Tflops peak)

IB



ENEA GRID and experimental facilities

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DB1

CPUSENEA GRID

WEBICASSH

DNA Sequencing system (Trisaia)

DB3

DB2

Electron Microscope (Brindisi)

Controlled Nuclear Fusion:Frascati Tokamak UpgradeVideo Acquisition



Thank you for your attention!Thank you for your attention!

fim.enea.it

Documents

An overview of the Department of Advanced Physical Technologies and New Materials (FIM)