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

2. An overview of the Department of Advanced Physical Technologies and New Materials (FIM) Andrea Quintiliani andrea.quintiliani@enea.it 2

3. 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 3

4. 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. 4

5. FIM Research centres Total number of employees: ~ 400

6. FIM Financial Resources 6

7. 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 7

8. 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. 8

9. Developmentof CFCCs (Continuous Fiber Ceramic Composites) using CVI (Chemical Vapour Infiltration) technology - EBC development by APS and slurry coating • Silicon Carbide CFCC (SiCf/SiCmatrix) properties: • High temperature strength • High toughness • Low weight • Reliability • Creep resistance • Resistance to shocks and fatigue Fiber Matrix Interlayer fiber-matrix • 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 Project for the implementation of a thermal gradient in ENEA-Faenza CVI plant The densification rate is improved by introducing a temperature gradient (Thermal Gradient - Chemical Vapour Infiltration, TG-CVI ) on the fiber preform

10. Chemical Vapour Infiltration (CVI) process SiCf/SiC CFCC are produced with anIsothermal/IsobaricChemical Vapour Infiltration / Deposition (I-CVI / CVD) plant (developed in ENEA-Faenza) The starting material is a porous 2D-fiber preform maintained with a tooling 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 SEM images of Py-C and SiC on various substrates (SiC felts and graphite)

11. MATERIALS FOR POWER GENERATION Mitgea Project • Objective: innovative processes for the industrial productionof ceramic cores suitable for innovative DS nickel-based superalloy turbine blades (increasing operating temperatures and lifetime and lowering costs) • Leachable Ceramic Cores for DS-investment casting; • Refractories, also produced using ceramic wastes; • Thermomechanical characterization (up to 1000 °C on metallic materials and superalloys and up to 1500° C on advanced ceramic and ceramic composite materials). Grain bridging mechanism Thermomechanical characterization Microstructural characterization Ceramic cores

12. MATERIALS FOR HIGH TEMPERATURES APPLICATIONS Objective: substitution of traditional metallic materials with ceramics in 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 characterized with the aim of evaluating the mechanical properties and oxidation resistance at high temperature (1500°C). Pressureless-sintering was patented by ENEA in 2005 (IT BO2005A000311). Results demonstrated that SiC-AlN-RE2O3 composites can successfully be used in oxidative environment up to 1500°C. Pre-oxidized samples showed improved fracture toughness and flexural strength (CRACK-HEALING MECHANISM). Y 10 mm

13. 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.

14. 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.

15. 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   15

16. 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

17. H2 flux (a.u.) Temperature ( °C) MnO/NaOH based composites nanoparticles microparticles • MnO + NaOH = NaMnO2 • NaMnO2 + 1/2H2O = NaOH +1/2Mn2O3 • Mn2O3 = 2 MnO+1/202

18. Performances of MnFe2O4/Na2CO3 based composites Nanostructured composites speed up the reaction kinetics allowing a temperature reduction Ferrite nanoparticles

19. Nanostructured Magnesium Based Composites for Hydrogen Storage 50 μm Mg can store up to 7.6 wt% hydrogen but suffers of the following problems: Slow kinetic of H2 desorption High thermodynamic Stability of MgH2 Surface Oxidation • Strategy: • Ball milling • Create defects • Nanocrystalline material • Crack of surface MgO • Introduction of a catalyst/additive • Speed up of reaction kinetics increase H2 mobility MgH2 10 nm splittingof H2 molecules H2 Tailoring the microstructure to the desorption process: MgH2- MgH2Ni4, MgH2 – Fe, MgH2- LaNi5MgH2 – (micro and nano) Nb2O5 H2 Catalyst

20. 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

21. Hydrogen Magnesium Process simulation by First-principle molecular dynamics Hydrogen desorption at Mg-MgH2 interface Starting configurations 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. Mg surface MgH2 surface Interface

22. 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 Fe Catalytic effect of Fe atom in agreement with the recent work Fe

23. H2 desorption at 100 °C after the first hydriding reaction in H2/Ar 3% composite material H2 flux (a.u.) as received after high energy ball milling time (min) Stabilization of AB5 alloys against decrittation Embedding in nanoporous matrix allows to combine fast reaction and structural stability LaNi5 in nanoporous Silica

24. Electrodes for polymeric electrolyte fuel cells based on nanomaterials Purposes • 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 PVD and ELD techniques allow the deposition of the catalyst clusters on the top of the diffusive layer 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

25. 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 the Hydrogen oxidation reaction at the anode in the PEFC

26. Electrochemical activity of nanostructured Pt catalysts Comparison of Electrochemical Active Surface of Pt nanoparticles deposited with different techniques with a commercial catalyst Pt Loading E-TEK 0.35 mgPt cm-2 PED <0.05 mgPt cm-2 PVD <0.006 mgPt cm-2 Mass Specific Activity of Pt nanoparticles electrodeposited on CNW and conventional substrate

27. GW MW 25%p.a. 30%p.a. 3500 140 3000 120 2500 100 c-Si thin film 2000 80 "New Concepts" 1500 60 1000 40 500 20 0 0 2002 2005 2010 2015 2020 2025 2030 Trends in PV technologies The growing maturity of silicon technologies puts research on other forms of PV cells in the foreground E. Shaheen et al. Mat. Res. Soc. Bull. 30-1 (2005) PV literature survey, from: "Progress in PV: research and applications" (gen-nov 2007)

28. Trends and roadmaps for the “new” technologies

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

30. SOLAR CELL ON PET Voc=0.98 Volt; F.F. = .32 OLED ON PET Quantum Yield Activities in ENEA Research on these devices is currently starting in ENEA. The general frame is to transfer esperiences and know-how on OLEDs to SCs. Preliminary experimental results were obtained on OSCs on PET.

31. How new Solid State Lighting sources can have an impact on energy efficiency in lighting applications Source: OSRAM

32. Specific applications for OLED light sources Source: OSRAM

33. The background of ENEA in OLED technologies Images of devices developed in ENEA (Portici) and of related characterization activities

34. A common target for the two applications: increase know-how in flexible substrate technologies Machine for roll-to-roll OLED production (ENEA specif.)

35. 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. 35

36. GRID – Based Computing DATA ACQUISITION DATA ANALYSIS ADVANCEDCOMPUTER GRAPHICS NETWORK Cell Centered Data Base “CCDB” IMAGING INSTRUMENTS COMPUTATIONALRESOURCES MULTI-SCALE DATABASES 36

37. ENEA-GRID Computational & 3D Centers Ispra Saluggia BOLOGNA 30 S.Teresa #CPU/Cores CASACCIA 140 400 Manfredonia FRASCATI 2750 90 PORTICI BRINDISI 45 TRISAIA

38. PI2S2 ENEA-GRID interoperability with other GRIDs EFDA EGEE • 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 GARR GARR Other Entities

39. A new HPC centre in Portici • 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 39

40. Supercomputing: application areas Engineering Nuclear physics and engineering – nuclear fusion Climate and environment Materials Bioinformatics Critical infrastructures protection Combustion 40

41. ENEA-GRID for Industry and Consortia Air flow dynamics and temperature inside new train cars Coll. with CETMA

42. ENEA-GRID for Industry and Consortia Hydrofoil flow simulation Coll. with CETMA

43. CRESCO for nuclear fusion IB System for development and test of computational codes for ITER (1 Tflops peak) Cresco (20 Tflops peak)

44. ENEA GRID and experimental facilities DNA Sequencing system (Trisaia) DB2 ENEA GRID DB1 Controlled Nuclear Fusion: Frascati Tokamak Upgrade Video Acquisition DB3 Electron Microscope (Brindisi) WEB ICA SSH CPUS 44

45. Thank you for your attention! fim.enea.it 45