Advanced Materials

ADVANCED MATERIALS Key Enabling Technologies at CNR

Key Enabling Technologies (KETs) are defined by the European Commission as â&#x20AC;&#x153;knowledge and capital intensive and associated with research & development (R&D) intensity, rapid or integrated innovation cycles, high capital expenditure and highly-skilled employment. Their influence is pervasive, enabling process, goods and service innovation throughout the economy and they are of systemic relevance. They are multidisciplinary and trans-sectorial, cutting across many technology areas with a trend towards convergence and integration. KETs can assist technological leaders in other fields to capitalize on their research effortsâ&#x20AC;?. Six KETs have been considered and chosen as the most relevant in order to boost EU technological potential impact and its competitive position. They are: advanced materials, micro & nano electronics, photonics, nanotechnology, industrial biotechnology and advanced manufacturing systems. With regards to the KETS , the National Research Council is playing a crucial role in research & development to overcome the gap between basic knowledge and the subsequent advanced products development by implementing the complete value chain steps. Within this strategy the CNR intends to present the system approach of the research activities performed by the Institutes within Key Enabling Technologies. Among KETs, Advanced Materials offer major improvements in a wide variety of different fields, e.g. in aerospace, transport, building and health care. They facilitate recycling, lowering the carbon footprint and energy demand as well as limiting the need for raw materials that are scarce in Europe. The performance or the behavior of a given material will depend on its properties, whether mechanical, electrical, optical or thermal. However, these properties will depend on the structure of the material at different levels: chemical, crystallographic, or aggregation order. Moreover, what governs the structure, the properties and eventually the performance is the processing method used. At the nano-level, molecular organization and surface properties become more important than bulk ones. Biological materials have very specific chemistry, structure and properties. The knowledge of all the involved basic scientific and technological disciplines makes Advanced Materials highly interdisciplinary which is at the base of KETs. Based on the Horizon 2020 strategy Advanced Materials play an important role in the three pillars: Excellence Science, Industrial Leaderships and Societal Challenges. The following booklet is reporting the main activities/results, within the Advanced Materials KET, of CNRâ&#x20AC;&#x2122;s Institutes where there is a potential capability to underpin value chains in strategic areas and accelerate the development of advanced innovative products. Prof. Luigi Ambrosio, Director of Department Chemical Sciences and Materials Technology National Research Council

Advanced Materials

Index ADVANCED MATERIALS - Key Enabling Technologies at CNR Technology Readiness Levels (TRL) in Horizon 2020 ..............................................................................5 Climate Action..................................................................................................................................... 6 Geopolymers and chemically bonded ceramics........................................................................................ 7 Whole green composites from low-cost natural fibers............................................................................... 7 Multifunctional nanocomposites from oil and bio-based polymers............................................................ 8 Bio-inspired multilevel architectures in lightweight composites ................................................................ 8 A green way to polyaniline/magnetic nanoparticle composites for EMI shielding..................................... 9 Functionalization of CNT by a solvent-free mechano-chemical process................................................... 9 Stimuli responsive coatings made of functionalized polysaccharides....................................................... 10 Modification of textile wettability through functionalized diamond-like carbon (DLC) by plasma technique................................................................................................................................................... 10 Valorization of two greenhouse gases, CO2 and CH4, into syngas by dry reforming reaction................. 11 La1−xSrxCo1−yFeyO3−� perovskites for pollutants solar photocatalytic degradation.............................. 11 Recoverable magnetic stereoselective catalyst........................................................................................ 12 Nanostructured metals for catalysis.......................................................................................................... 12 Recycle, reuse, and recover of raw materials (plastic waste and scrap rubber)....................................... 13 Responsive polymer-based materials....................................................................................................... 13 Nanophase structure of biopolymers......................................................................................................... 14 Energy..................................................................................................................................................... 15 A graphene oxide based nanohybrid for label-free optical sensing . ........................................................ 16 Graphene-based composites.................................................................................................................... 16 Third generation organic photovoltaic (OPV) devices .............................................................................. 17 Nano-organized hybrid materials with higher charge generation for solar cell applications...................... 17 Ultra refractory solar absorbers for concentrated solar power systems.................................................... 18 Solid oxide fuel and electrolysis cells (SOFC/SOEC)............................................................................... 18 Enhanced IrRu-oxide electrocatalysts for water electrolysis..................................................................... 19 Design and development of new carbon-based materials for energetic................................................... 19 Magnetic shape memory alloys as multifunctional materials.................................................................... 20 Low-emissivity building materials.............................................................................................................. 20 0D- and 1D-nanomaterials for energy, M-MO nanostructures, X-ray techniques .................................... 21 Nanostructured polymeric photonic crystals (direct and inverse opals).................................................... 21 Organic molecular and polymeric materials for optoelectronics and photonics........................................ 22 Organic nanotubes and self-organized chromophoric assemblies for sensing and opto-electronics........ 22 Photocatalytic TiO2 films by screen-printing deposition............................................................................ 23 Mechanical processing for sintering and texturing thermoelectric materials............................................. 23 New molecular components for efficient and stable dye-sensitized solar cells......................................... 24 Solid oxide electrolites for application in fuel cells.................................................................................... 24 Electrolyte membranes for ZEBRA batteries............................................................................................. 25 Deposition and processing of advanced materials - CO2 laser irradiation of GeO2 planar waveguide fabricated by rf-sputtering.......................................................................................................................... 25 Transparent coloured photovoltaic cells.................................................................................................... 26 Piezoelectric ceramic materials for energy harvesting............................................................................. 26 Carbon nanotube photoactive materials.................................................................................................... 27 Novel membranes for CO2 separation and biogas purification................................................................. 27 Advanced soldering materials design for micro-electronics...................................................................... 28 Fabrication of high quality CIGS-based thin-film solar cells by pulsed electron deposition (PED) technique................................................................................................................................................... 28

Advanced Materials PE-CVD/CVS deposition of nanostructured oxides films with photocatalytic and photoelectrocatalytic functions.................................................................................................................................................... 29 Fabrication and characterization of ZnO nanostructures.......................................................................... 29 New promoted perovskites as cathodes for intermediate temperature solid oxide fuel cells.................... 30 Electrolyte membranes for ZEBRA batteries............................................................................................. 30 Metal-Organic Frameworks (MOFs): polifunctional materials for gas storage, magnetic applications and heterogeneous catalysis..................................................................................................................... 31 Innovative core-shell catalysts for methane oxidation............................................................................... 31 New solid sorbents for CO2 . .................................................................................................................... 32 Artificial photosynthesis............................................................................................................................. 32 Nanomaterials for excitonic solar cells...................................................................................................... 33 Engineered metal nano powders for advanced technologies.................................................................. 33 Nanofluids................................................................................................................................................. 34 Innovative structural metallic materials..................................................................................................... 34 Preparation of novel hybrid organic-inorganic materials for solid-state sensitized solar cells................... 35 Beyond graphene: the carbon nanoscrolls................................................................................................ 35 New approaches to the synthesis of functional inorganic-organic hybrid materials.................................. 36 Multiferroics magneto-electrics novel materials. High-Pressure (HP HT) synthesis and advanced characterization......................................................................................................................................... 36 Health...................................................................................................................................................... 37 Injectable composite materials for bone repair and regeneration............................................................. 38 Nanostructured scaffolds for tissue regeneration...................................................................................... 38 Functional gels for health.......................................................................................................................... 39 Laser-assisted repair of biological tissues . .............................................................................................. 39 Blue-emitting OLED for light therapy......................................................................................................... 40 Hybrid nano-composites for bone and osteochondral regeneration.......................................................... 40 Biomorphic transformation: hierarchically organized porous structures.................................................... 41 Biomimetic apatites and bone cements . ................................................................................................. 41 Functional materials for articular joint repair............................................................................................. 42 Crossed Hollow Fiber Membrane Bioreactor (HFMBR) for liver tissue engineering................................. 42 Biodegradable membrane system for bioengineered skin substitutes...................................................... 43 Magnetic nano-apatites for drug delivery and tissue engineering............................................................. 43 Nano-hybrid materials for biomedical applications.................................................................................... 44 Multifunctional micro/nano-composite materials for tissue repair and regeneration ................................ 44 Hydrogels for tissue engineering and drug delivery.................................................................................. 45 Neuronal regeneration in microstructured membrane systems................................................................. 45 Membrane emulsification.......................................................................................................................... 46 Functional materials on surfaces: deposition for sensing and drug delivery applications......................... 46 Drug carriers based on saccharides as tools in therapy and diagnosis ........................................................ 47 Magnetic biosensors................................................................................................................................. 47 Electrospinning for High Performance Sensing (E-HPS).......................................................................... 48 Nanostructured contrast agents for MRI................................................................................................... 48 Tailored synthesis of nitrogen tricycles as versatile tools in drug discovery and nanomedicine applications............................................................................................................................................... 49 Silk-based bio-technologies...................................................................................................................... 49 Bio catalytic nanotools . ............................................................................................................................ 50 Breakthrough honeycomb membranes..................................................................................................... 50 Electronic membranes............................................................................................................................... 50 Tailored hydrogel membranes for efficient protein crystallization.............................................................. 51 Stimuli-responsive shape memory liquid crystalline elastomers .............................................................. 51 Bracelet of micro-needles to substitute hypodermic syringe for transdermal drug delivery...................... 52 Amagnetic solid-state actuator based on SMA.......................................................................................... 52 Bed-side rehabilitation by an SMA-powered device.................................................................................. 53

Advanced Materials Pseudoelastic hinges for neuromuscular rehabilitation............................................................................. 53 Functionalized silicon nitride for bio-applications...................................................................................... 54 Space & Transport............................................................................................................................. 55 Ultra-high temperature ceramics for extreme environments..................................................................... 56 Transparent ceramics: spinel MgAl2O4 .................................................................................................... 56 Advanced joining processes for high temperature Metal-Ceramic systems.............................................. 57 ROTOsma-1: miniature actuator based on shape memory alloy antagonist elements............................. 57 Ultra-ablation resistant ceramics for propulsive application...................................................................... 58 Superhydrophobic coatings for marine application................................................................................... 58 Fiber reinforced ceramics for extreme environments................................................................................ 59 Multi scale composites enhancing damping features ............................................................................... 59 Advanced polymeric nanocomposites as active and multifunctional materials......................................... 60 ICT . ......................................................................................................................................................... 61 Tailoring of materials properties via bottom-up nanofabrication for high-performance technologies........ 62 Metal oxide nanowires for functional devices............................................................................................ 62 Magnetically enhanced memristors........................................................................................................... 63 Soft and bioresorbable electronic interfaces for bioelectric recordings..................................................... 63 CdZnTe crystals for room temperature operating X- and gamma-ray detectors....................................... 64 Time-temperature integrators.................................................................................................................... 64 Electron beam lithography for miniaturized devices.................................................................................. 65 Multifunctional ceramic materials.............................................................................................................. 65 Decontamination powders for highly-toxic chemical and biological (CBRN) warfare agents.................... 66 Metal oxide nanowire based gas sensors for security applications........................................................... 66 Alumina-based ceramic materials for electronic packaging ..................................................................... 67 Optical gas sensor based on metal oxide nanowires................................................................................ 67 Nanoporous materials for light management and chromatic sensitive systems . ..................................... 68 Quantum random number generation in a silicon transistor...................................................................... 68 Nanostructured membrane coating for wastewater treatment.................................................................. 69 Highly sensitive sensors based on nanostructured hybrid films for the analysis of beverages................. 69 Advanced membranes for efficient wastewater treatment........................................................................ 70 Impact of postharvest Îł-irradiation on food quality, traceability and safety............................................... 70 ...and More.............................................................................................................................................71 Cultural Heritage Superhydrophobic and self healing materials for cultural heritage protection........................................... 72 Advanced materials for the protection of bronze artefacts........................................................................ 72 Modelling Modeling and simulation for carbon nanostructures.................................................................................. 73 Modeling and simulation for shape-memory devices................................................................................ 73 Computational design of advanced materials........................................................................................... 74 Computational modelling of bio-metal interfaces...................................................................................... 74 Modelling hybrid and perovskite solar cells.............................................................................................. 75 Advanced Technologies Optical drawing of liquid droplets via plasmon resonance of gold nanorods............................................. 76 Study of scintillators materials with time-resolved optical spectroscopy................................................... 76 Two-photon circular dichroism for studies of chiral systems..................................................................... 77 Porous ceramics, freeze casting â&#x20AC;&#x201C; ice templating..................................................................................... 77 CNR Institutes: list of participants . ............................................................................................ 78

Advanced Materials

Technology Readiness Levels (TRL) in Horizon 2020 TRL 1 – basic principles observed TRL 2 – technology concept formulated TRL 3 – experimental proof of concept TRL 4 – technology validated in lab TRL 5 – technology validated in relevant environment (industrially relevant environment in the case of key enabling technologies) TRL 6 – technology demonstrated in relevant environment (industrially relevant environment in the case of key enabling technologies) TRL 7 – system prototype demonstration in operational environment TRL 8 – system complete and qualified TRL 9 – actual system proven in operational environment (competitive manufacturing in the case of key enabling technologies; or in space)

Advanced Materials

Climate Action The â&#x20AC;&#x153;climate action, environment, resource efficiency and raw materialsâ&#x20AC;? is focused onto interconnected and mutually reinforcing objectives aimed at creation of sustainable economy and society, resource-efficient and resilient to climate change, with the ultimate goal of keeping under control the average global warming. Sustainability, preserving the environment, being socially responsible and maintaining economic viability are mandatory purposes for all the human activities. Therefore economyâ&#x20AC;&#x2122;s ability to adapt to these requisites, while remaining competitive, depends on his own impulse to eco-innovation in the social, economic, organizational and overall technological fields. Indeed, in the contest of eco-innovation both research and technological transfer should be oriented to specific concepts: - Efficient and sustainable use of natural resources - including water; - Efficient and sustainable processes; - Renewable supply and use of raw materials; - Protection of the ecosystem. By taking into account these leanings, the research in formulation new advanced materials complying the eco-innovation directives, addresses its efforts in wider use of renewable energy/raw material sources (with specific reference to bio-based materials), fine tuning of solvent-free processes, increase of resource efficiency and reduction of sub/by-products. At the same time recycle, reuse of end-life materials, recovery of scraps and chemicals, valorization of greenhouse gases are often important challenges in providing materials with new/optimized final properties; in all the examples here reported by bringing solutions closer to the market, towards industrial and commercial implementation.

number of contributions in this section

TRL: 3 - 7

Geopolymers are inorganic polymers based on synthetic alkali-aluminosilicates or phosphates of metal oxides. Geopolymers belong to the class of the chemically bonded ceramics: they are synthesised at T<300Â°C from a variety of raw materials including recycled resources and mineral wastes, reducing the energy demands and environmental impact during their production. Geopolymers enable product designers to envisage the use of ceramic type materials with the same facility as some plastics and organic. ISTEC works on a wide range of versatile geopolymers based materials and composites finding applications in the automotive and aerospace industries, civil engineering, waste management, biomaterials, catalysis & filtration, energy etc.. Examples are fibre-based panels for thermal and acoustic insulation, heat exchangers, porous supports, refractory paints, pots, also from waste materials (fly ashes, biomass ashes, wool and fibre waste).

+ Reactive Powder

Activating Solution

Functionalizing Filler

Raw materials for geopolymer synthesis

1 cm Examples of ISTEC prototypes: a porous heat exchanger device (left); a sandwich panel for thermal insulation produced from ceramic wastes (right); a wool-geopolymer pot and its surface structure (below).

With regards to enterprises... ISTEC collaborates with several industrial partners, in particular SAB Aerospace Srl and CGS SpA, in the frame of PON Pandion. ISTEC designs the geopolymer micro- and macro-structure in Contact: term of chemistry, porosity, fillers. Valentina Medri - valentina.medri@istec.cnr.it ISTEC produces and characterizes lab scale prototypes. ISTEC - Faenza

TRL: 3

Whole green composites from low-cost natural fibers Whole green composites are the composites made from both renewable resource based polymer (biopolymer) and biofiller. They are recyclable, renewable, triggered biodegradable. The natural fiber composites show additional advantages such as low cost, light weight, recyclability and easy availability, thermal insulation, carbon dioxide neutrality and acceptable strength and stiffness. Cellulose-based reinforcements represent interesting materials in this contest. The presence of crystalline fibers is thought to increase the tortuosity in the materials leading to slower diffusion processes and, hence, to lower permeability, if their good dispersion in the matrix is achieved maintaining their high aspect ratio. Within this framework, we investigate the preparation by simple melt blending techniques of biocomposites based on natural fibers largely available from co- and by-products of industrial processes (grain legumes, textile fibers) and thermoplastic matrices. The formation of a largely extended interphase and strong polymer-fiber bonds (adhesion) is promoted through the chemical functionalization of the fiber surface or the use of compatibilizers. The significant modification of many physical properties in the interfacial regions due to the reduced mobility of the chains next to the fiber surfaces is investigated also by detailed analysis of the thermal properties of the composites.

SEM images of hemp fibers (black frame) and composite (red frame)

Nucleating effect of hemp fibers on PLA.

With regards to enterprises... This activity is supported by LEGUVAL, a 3 years research project funded by Seventh Framework Programme â&#x20AC;&#x153;Capacitiesâ&#x20AC;? (Research for the Benefit of SMEs) (Grant Agreement Number: 314251; www.leguval.eu) Contacts

S. Bronco - simona.bronco@pi.ipcf.cnr.it M. Bertoldo - monica.bertoldo@pi.ipcf.cnr.it M.C. Righetti - righetti@ipcf.cnr.it IPCF - Pisa

CLIMATE ACTION

Geopolymers and chemically bonded ceramics

CLIMATE ACTION TRL: 3

Multifunctional nanocomposites from oil and bio-based polymers Recently a new class of layered materials known as layered double hydroxides (LDHs) has attracted great interest for the preparation of polymer-based nanocomposites. Organo-LDHs can be prepared by anion exchange thus introducing moieties with specific functional properties (e.g. optical and active properties, thermal and photo-stability, antimicrobial activity, light-responsive functionalities, plasticizing effects) and at the same time increasing the compatibility with the polymer phase and enhancing the distance between the inorganic layers. The dispersion of these functional nanostructured substrates in a polymer matrix (oil or bio-based) is a convenient method to obtain polymer materials with improved propertied and broader application range. In particular PLA is a bio-based material particularly attractive due to its optical and thermal properties, and it is considered a challenging candidate for the replacement of oil-based polymers. Biodegradable polyester/ layered double hydroxide (LDH) nanocomposites have been prepared by different methods, such as the polymerization in situ of monomers into the galleries, or the intercalation of polymer chains carried out both in solution and in the melt by using specially designed organo-modified clays and different co-polyesters as interactive compatibilizers, thus improving the dispersion of the particles and the polymer-particle interactions. With regards to enterprises... –packaging Projects: DIBBIOPACK Contract Number 280676 MIUR FIRB 2003 Project NANOPACK

Melt compounding

Intercalation

Nitrate-LDH

NO3NO3-

NO3-

Organo-LDH

X+

NO3-

Anion exchange

Contact:

Elisa Passaglia, Francesca Cicogna e Serena Coiai pmc-lab@pi.iccom.cnr.it ICCOM - Fienze

TRL: 3

Bio-inspired multilevel architectures in lightweight composites Nature is able to produce a wide variety of materials or structures by combining few types of component materials. Minerals and a range of polymers (proteins or polysaccharides) are assembled in composite structures with a remarkable range of functional and structural properties. The control over shape and structure on many length scales is achieved through a hierarchical structuring. Wood, bone, diatoms are examples of multi-level lightweight composite architectures found in nature whose structures may lead to new design concepts for lightweight materials. Nano- and micro-cellular structures with porosities and reinforcements characterized by multilevel architectures were obtained by combining gas foaming and templating techniques in nano- and micro-composites and in organic-inorganic hybrid materials. Lightweight materials and structures having relevant thermal and acoustic insulation properties as well as improved mechanical and impact properties were obtained. Mimicking bone: multilevel sandwich architecture

diatoms foam

Size > 50 nm Single particle r ∼0.4 nm

Mimicking diatoms: aerogel structures within cell walls of microcellular organic-inorganic hybrid foams.

Contact:

Salvatore Iannace - salvatore.iannace@cnr.it Marino Lavorgna - marino.lavorgna@cnr.it Luigi Sorrentino - luigi.sorrentino@cnr.it Letizia Verdolotti - letizia.verdolotti@cnr.it IPCB - Napoli Fiber reinforced nano-cellular skin

Nanocomposite microcellular core

With regards to enterprises... Collaborations with technological districts, the Regional Competence Center “New Technologies”, the spin-off HYPUCEM and other industrial partners.

TRL: 4

With the advances in electronic and communication devices new technical issues have arisen in the field of shielding against electromagnetic interference (EMI). Nanocomposites comprising a conducting organic polymer and magnetic nanoparticles can find wide application in this field. Such nanocomposites are cheap, lightweight, processable, and their properties can be easily and accurately tuned by controlling both the properties of the components and their interaction during compositing. We have discovered a very effective and eco-friendly route to polyaniline (PANI)-ferrite (MFe2O4, M=Mn, Fe, Co, Ni, Cu, Zn) nanoparticle composites where the aniline dimer is polymerized in the presence of ferrite nanoparticles. The pros of this novel method are: (i) the nanoparticles are both the polymerization catalyst and the nanomagnetic load; (ii) cheap “green” oxidants (O2, H2O2) are used instead of inorganic oxidant; (iii) no heavy metal waste has to be disposed of (all ferrite is embedded in the polymer matrix).

S₁₁/S₂₂

S₂₁

K-band S-parameters for a PANI-Magnetite nanocomposite.

As can be seen in the Figure above, the PANI-Magnetite nanocomposite features low reflection and transmission coefficients of K-band microwaves, a frequency range relevant to modern devices. Contacts

Alessandro Ponti - alessandro.ponti@istm.cnr.it Anna M. Ferretti - anna.ferretti@istm.cnr.it ISTM - Milano

TEM (left) and SEM (right) images of PANI-Magnetite nanocomposites.

TRL: 4

Functionalization of CNT by a solvent-free mechano-chemical process Polymer nanofiller composites containing carbon nanotubes (CNT) have been the subject of an even growing scientific and industrial interest over the last decades. CNT exhibit outstanding mechanical, electrical and thermal properties due to their sp2-hybridized carbon. On the other hand, their most important drawback lies in the fact that they show a great tendency to establish strong van der Waals and p-p interactions which cause strong agglomeration phenomena when mixed to polymer matrices. Different approaches have been used to improve the dispersion of carbon nanofillers into a polymer phase. The most effective methods are based on non-covalent or covalent surface functionalization of the fillers. However, these methods are usually based on treatments with suitable reagents in presence of organic solvents and they need to be completed by difficult purification procedures, making the process practically unsuitable for industrial applications. In this research, maleated polypropylene (MAPP) Effects of the mechano-chemical functionalization: amount of grafted MAPP has been grafted onto the CNT surface through a on the CNT surface, dispersion stability in ethanol/xylene solution and morsolvent-free method, consisting in the solid-state phology of the surface modified CNT. mechano-chemical treatment at room temperature With regards to enterprises... IPCB cooperates with the Technological District on Engineof the nanotubes in presence of MAPP. of Polymeric and Composite Materials and Structures The proposed approach is significant because it re- ering (IMAST) for the realization of advanced functional nanopresents a simple, cheap, and eco-sustainable CNT structured composites. functionalization method easy to scale up also for Contact: industrial processes. Gennaro Gentile - gennaro.gentile@ictp.cnr.it Pierfrancesco Cerruti - pierfrancesco.cerruti@ictp.cnr.it IPCB - Napoli

CLIMATE ACTION

A green way to polyaniline/magnetic nanoparticle composites for EMI shielding

CLIMATE ACTION TRL: 3

Stimuli responsive coatings made of functionalized polysaccharides Coatings for glass or natural substrates, such as paper or leather, can be prepared from natural polymers such as polysaccharides. These lasts bring good compatibility with the substrates and are widely available from renewable resources. Additional advantage of polysaccharides is the presence of many functional groups in their backbone which provides them with a variety of properties and possibility of chemical derivatization. For instance, chitosan which is a polysaccharide bearing amine and amide functional groups providing it with pH dependent swellability, was functionalized with spiropyran groups (SP). The SP colorless isomer can transform into a colored isomer (merocyanine) upon UV illumination providing the coating with photochromic behavior. This process can be reversed by visible illumination. Similarly, amylose, a starch component, was functionalized with the same spiropyran groups and then it was coated on a paper substrated providing it with photochromic response, as well as with UV-light controlled polarity degree.

Structure of Chitosan (left) and chitosan source (left)

Structure of amylose (left) and amylose source (left)

Spiropyran (1) to Merocyanine (2)

With regards to enterprises... This activity has been supported by Fondazione Cassa di Risparmio di Pisa-Settore Ricerca Scientifica e Tecnologica. At present Contact: Monica Bertoldo - monica.bertoldo@ipcf.cnr.it we are looking for a company interested to collaborate with us IPCF - PISA for testing this materials at industrial level.

TRL: 3

Modification of textile wettability through functionalized diamond-like carbon (DLC) by plasma technique

Water wetting properties of the DLC coated cotton fabric: a water droplet, stained with red dye, remained beaded upon the superhydrophobic face of the fabric surface, while on the hydrophilic side it was completely absorbed.

New materials with superhydrophobicâ&#x20AC;&#x201C;superoleophilic properties, environmentally friendly and obtained by economically approachable methods are needed for several technological fields, such as oil/water separation process and self-cleaning applications. We developed superhydrophobicâ&#x20AC;&#x201C;superoleophilic cotton textiles, functionalised through a homogeneous layer of DLC obtained by plasma enhanced chemical vapour deposition (PECVD). In addition, we demonstrated that the hydrophobic character can be modulated, by simply underwent the cotton textile to an opportune plasma pre-treatment before the DLC deposition.

Controllable oil/water separation using the DLC coated cotton textile as a membrane for filtration. . A mixture of oil and red coloured water was poured into the upper glass tube. The oil selectively passed through the textile, whereas the red coloured water remained in the upper glass tube. Demonstration of the Self-cleaning ability of the cotton fabrics; as water drops roll off the surface they easily remove the dirt present on the fabric (a-c). Schematization of the self cleaning process under water droplet rolling off the surface (d). two drops of water as spherical balls on top of the fabric, one drop still clean while the second has removed the dirt from the surface leaving it clean (e).

Contact: daniela.caschera@ismn.cnr.it Daniela Caschera ISMN - Roma In collaboration with Barbara Cortese, Nano-Lecce

Conversion (%)

TRL: 3

Since 1993, production of hydrogen via dry reforming of methane (DRM) and other light hydrocarbons and followed water-gas shift reaction have received much attention because of the utilization of two important greenhouse gases, i.e., CH4 and CO2. Nickel is the most frequently reported metal in DRM because of its good catalytic activity and its cost-effectiveness as compared with Pt, Ru or Rh-based catalysts. Al2O3-supported Ni catalysts prepared by wetness impregnation have been widely investigated for DRM because of its high initial conversion, which however decreased with time due to carbon deposition or sintering. Addition of a small amount of Au and Pt (0.2 wt%) to Ni catalyst leads to NiAuPtAl formation of a synergistic interaction, which induces easy reduction of 100 NiPtAl NiAuAl NiO species and decrease of particle sizes. Small amount of Au and Pt adNiAl 95 dition plays an important role on catalytic performance of bi-/trimetallic 90 catalysts and carbon poisoning. The improvement of catalytic activity and 85 stability obtained for the trimetallic NiAuPt/Al2O3 catalyst is attributed to 80 the formation of high active Ni-Au-Pt nanoparticles, synergistically inte75 racting, where growth of small amount of bamboo-like carbon nanotubes 70 occurs. A direct relation between catalytic activity and typology/amount 0 5 10 15 20 25 Time (h) of carbonaceous species is found. The best catalysts (NiAuPtAl and NiAlCe) are the ones with the better combination of these two parameters Activity performance of Alumina supported Ni doped catalysts in 24 h long-run tests at 750 °C: (high amount of carbon nanotubes together with low quantity of total Filled symbols CO2 conversion, and empty symbols CH4 conversion. carbon). With regards to enterprises... We are able to prepare and characterize Ni based catalysts as powders and as well as monolithic cordierite substrates. Progetto EFOR (Energia da fonti rinnovabili) CNR-MIUR Progetto Bilaterale Italia-Marocco CNR-CNRST

Contact:

liotta@pa.ismn.cnr.it Autori: L.F. Liotta A.M. Venezia, V. La Parola, G. Pantaleo, F. Puleo. ISMN - Palermo

TRL: 3

La1−xSrxCo1−yFeyO3−� perovskites for pollutants solar photocatalytic degradation SPerovskite oxides based on lanthanum strontium cobalt ferrite (La1−xSrxCo1−yFeyO3−�) are the most studied mixed ionic and electronic conducting (MIEC) materials for cathode applications in solid oxide fuel cells. Interestingly, the physicochemical features of these materials satisfy also the requirements for their use as photocatalysts. In fact, recently, perovskite-type LaCoO3 have been proposed as photocatalysts for wastewater and air pollution treatments. Here, the solar photocatalytic experiments in gas-solid regime is described for 2 propanol abatement over La1−xSrxCo1−yFeyO3−� perovskites. The photoreactivity runs started after the system achieved the steady state conditions in the dark,i.e. when the concentration of 2-propanol remained constant with time (ca. 0.5 h). 2-propanol was partially adsorbed on the perovskite samples; indeed, after the equilibration time, the initial substrate concentration, experimentally measured, was always lower than the nominal amount. Moreover, the contemporary presence of O2, catalyst and light was needed for the occurrence of the 2-propanol degradation to obtain propanone, as the main intermediate, traces of acetaldehyde and CO2. With regards to enterprises... We are able to prepare and characterize LSCF perovskites catalysts as powders and as well as monolithic cordierite substrates.

The substituted LaCoO3 perovskites are semiconductor materials showing band gap energy values from 2.8 to 1.5 eV. These materials showed photocatalytic activity for the 2-propanol degradation in the gas-solid regime irradiating by natural solar light.

Contact:

liotta@pa.ismn.cnr.it Autori: L.F. Liotta (ISMN U.O.S. Pa), V. La Parola,, F. Puleo, A. Longo. G. Marcì, E.I. García-López, “Schiavello-Grillone” Photocatalysis Group. Dipartimento di Energia, Ingegneria dell’informazione e modelli Matematici (DEIM), Università di Palermo, Viale delle Scienze, 90128 Palermo, ISMN - Palermo

CLIMATE ACTION

Valorization of two greenhouse gases, CO2 and CH4, into syngas by dry reforming reaction

CLIMATE ACTION TRL: 4

Recoverable magnetic stereoselective catalyst Magnetic iron oxide nanoparticles are suitable as support for recovering precious catalysts. They do not interact with the catalytic center and do not interfere with the catalyzed reaction mechanism. Their permanent magnetic moment allows one to separate them from the reaction medium by externally applying a small magnet. The immobilization of an ad-hoc designed chiral imidazolidin-4-one onto mono-disperse (11 nm) iron oxide nanoparticles, using a “grafting-to” approach, provided a magnetic stereoselective catalytic system. This catalyst was tested in the Diels–Alder cycloaddition of cyclopentadiene with trans-cinnamaldehyde in pure water at room temperature, affording the product in good yield (83%) and enantiomeric excess (93%). The catalytic system can be successfully recovered by simply applying an external magnet and its recycling has been accomplished.

Easy recovery of the catalyst by a cheap NIB magnet.

The catalytic system can be stored for several months and is stable in the reaction conditions. No loss of the organic catalyst from the magnetic nanosupport during reaction has been observed. Therefore, the immobilization of chiral organocatalysts onto magnetic nanoparticles is full of promises, providing easy catalyst confinement and recovery methods, which may offer new opportunities to address separation, recycling, and waste management issues. TEM image and sketch of the recoverable catalytic system, i. e., magnetic nanoparticles bound to a stereoselective organic catalyst.

Contact:

Alessandro Ponti - alessandro.ponti@istm.cnr.it Anna M. Ferretti - anna.ferretti@istm.cnr.it; ISTM - Milano

TRL: 5

Nanostructured metals for catalysis Nanostructured metal particles (1-10 nm) are of interest in several fields ranging from material science and catalysis to biomedicine. ISTM recently developed a powerful synthetic approach to obtain size-controlled homo- and hetero-nanostructured metal particles, starting from metal vapours as reagents (metal vapour synthesis technique). The co-condensation at low temperature of metal vapours (Pd, Cu, Ag, Au, Fe, Co, Ni, Rh, Pt, …) with vapours of an organic solvent gives as products Solvated Metal Atoms (SMA) containing metal nanoparticles with tailored size (1-10 nm) weakly stabilized by the solvent. SMA can be used as a source of active metal nanoparticles to produce metal nanopowders or higly dispersed metal particles supported on a wide range of inorganic, organic and polymeric supports . Finally the versatility of metal nanoparticles obtained by this approach find wide applications in different fields such as material science (as precursors of metal-polymer nanocomposites with peculiar mechanical, thermal, electric and magnetic properties) or biomedicine (as precursors of stabilized metal nanoparticles with diagnostic and therapeutic applications).

CMVS-derived Pt/TiO2

Metal Vapour Synthesis reactor

MVS-derived Au/TiO2

With regards to enterprises... We collaborate with University of Pisa, University of Milan and Advanced Catalysts S.r.l. (Livorno) on the catalytic applications. We can offer: a) Synthesis of supported or unsupported homo- and heterometallic metal nanoparticles; b) Characterization of nanostructured materials by high resolution electron microscopy (HRTEM). Contact: Claudio Evangelisti - claudio.evangelisti@istm.cnr.it ISTM - Milano

CLIMATE ACTION

TRL: 4 - 5

Recycle, reuse, and recover of raw materials (plastic waste and scrap rubber) Tire rubber granulates and powders, often called GTR (ground tire rubber), are products commercially available on the market, which are usually produced by grinding (cryogenic, ambient and wet-ambient grinding) after metallic wires separation. The GTR may potentially replace commercial impact modifiers in both thermoplastics and thermosets thus obtaining impact modified materials. Unfortunately, the incorporation of GTR into polymer matrices significantly impairs the mechanical and viscoelastic properties of the resulting composites, even at low rubber content, because of the poor matrix filler adhesion and lack of reactive sites on the GTR surface. New methodologies for the preparation of GTR polymer composites by using “grafting through”, “grafting from” and polymerization filling approaches have been investigated in our laboratories. All these “get ready” methods resulted in thermoplastic-based composites with improved thermal, mechanical and rheological properties compared with conventional composites obtained by melt mixing.

GTR pictures and SEM analysis

Morphologies of the composites obtained with different approaches

Contact:

Elisa Passaglia, Francesca Cicogna e Serena Coiai pmc-lab@pi.iccom.cnr.it; ICCOM - Firenze

With regards to enterprises... PIRELLI PCT/EP2004/008735; WO 2006/012912 A1; European Patent Specification EP 1778753 B1. PCT/EP2004/014313; WO 2006/063606 A1; United States Patent Application Publication US 2008/0132642 A1. PCT/EP2005/009329; WO/2007/025556; United States Patent Application Publication US 2009/0156763 A1

TRL: 3 - 4

With regards to enterprises... Packaging and devices. Project: National Project ‘‘New Polymer Systems with Electric and Optical Functionalities via Nano and Micro Adhesive Dispersion to Produce Materials and Devices for Smart Applications’’ POLOPTEL 2011-2014, LaFondazione CARIPISA conv. 167/09

Polymer

Toluene λecc = 290 nm

Under UV Lamp

Instensity (a.u.)

Significant advances have recently been made in the development of functional polymers that are able to undergo light-induced responses . In particular, the introduction in a polymer matrix of luminescent aromatic molecules as chromophores, which are covalently grafted onto the polymer chain or finely dispersed, are both techniques successfully applied to obtain information about polymers’ conformation, compatibility of polymer blends, deformation and alignment of polymer chains. With the purpose to obtain light-responsive polymers, suitable for smart packaging applications, by using a nitroxide radical coupling functionalization procedure, ad-hoc synthesized nitroxides bearing chromophores have been covalently inserted onto the backbone of polyolefins and biopolyster by coupling with macroradical species. Particularly fluorescent polyethylene is obtained by functionalization of the polyolefin with a functional nitroxide bearing a fluorescent naphthalene ring, whereas, by using TEMPO derivative substituted with azobenzene, a material, which responds to UV irradiation was prepared.

P-g-(NfO-TEMPO)

Responsive polymer-based materials

Polymer NfO-TEMPO Sample 1 Sample 2

300

325

350

375

400

425

450

475

500

Wavelength (nm)

Fluorescence emission spectra of pristine polymer and samples functionalized with nitroxides bearing chromophores (sample 1, FD = 0.13 % mol and sample 2, 0.18% mol, respectively) both 5 x 10-3 M; all samples were solved in toluene; excitation at 290 nm. Inset: pictures of P and P-g-NfO-TEMPO (sample 1) under excitation.

Contact:

Elisa Passaglia, Francesca Cicogna e Serena Coiai pmc-lab@pi.iccom.cnr.it; ICCOM - Firenze

CLIMATE ACTION

With regards to enterprises... On this topic we collaborate with IPCB-CNR, University of Piemonte Orientale, Martin-Luther University Halle-Wittenberg, Germany. We can offer: thermal and mechanical characterization of polymers and biopolymers.

MAF

RAF 1.0

Weight fractions

The physical properties of semicrystalline polymeric materials have always been interpreted as a function of the crystalline degree. However, not always a direct and exact correlation between the crystallinity content and some physical properties has been observed. Recently it has been proven that many macroscopic properties of the polymeric materials are defined by both the crystalline degree and the nanophase rigid amorphous fraction (RAF). A detailed knowledge of the nanoscale phase behavior of the polymeric materials is thus decisive for the assessment of mechanical, thermal, gas permeability and other physical properties. Indeed the RAF quantification is a crucial step in the material characterization, as different processing and crystallization conditions differently affect the combined evolution of the crystalline and rigid amorphous phases. At the moment, the analysis of the nanophase structure has been applied to poly(L-lactic acid) (PLLA), a renewably derived thermoplastic polyester, characterized by good mechanical properties, compostability, biocompatibility and bioresorbability, and poly(3-hydroxybutyrate) (PHB), a biodegradable and biocompatible thermoplastic polyester produced by a wide variety of bacteria.

wMAF

0.6 0.4

0.2 0

wRAF 20

1.0

Time in min

100

PHB - crystallization at 30째C

0.8

wMAF

0.6 0.4

0.2 0.0

Contact:

PLLA - crystallization at 90째C

0.8

0.0

Weight fractions

TRL: 2

Nanophase structure of biopolymers

wRAF 40

Time in min

Maria Cristina Righetti - cristina.righetti@ipcf.cnr.it IPCF - Pisa

100

Advanced Materials

Energy “Sustainability and Energy” are an inseparable pair to overcome the present environmental challenges. Today, the perception of the need to reverse the lines that have guided the development of our civilization over the past two centuries has made urgent, and it is clear that the time has come to address these problems on a global scale, such as the exponential population growth, the reduction of available resources, the conservation of the environment and biodiversity, which threatens not only the maintenance of a well-established model of development, but the very roots of our civilization. The energy landscape towards greater energy efficiency and the use of fuels with lower environmental impact, and possibly from renewable sources are strongly pulled by the population and the economic growth at the global level. To this aim the development of new technologies is the critical key. The modern technologies allow to exploit resources more economically and make more valuable alternative energy sources to fossil fuels. The “clean”, sustainable and efficient use of the energy resources is the current challenge to efficiently address this socio economic transition. The technological challenge requires not only the development of materials and advanced and innovative technological solutions, that make the energy produced by renewables more competitive, but also a transformation in the more sustainable use of the actual resources, the fossil fuels, in full correspondence with the guidelines of Horizon 2020 with the strategic needs of our Country.

number of contributions in this section

TRL: 4

Remarkable developments can be seen in the field of optical fibre sensors in the last decade. The adsorption of gas on a solid surface can produce considerable variation in the optical properties of the solid surface and eventually lead to the identification of the gas adsorbed. Graphene, the solution-processable graphene oxide (GO) and its reduced form (rGO) have attracted scientists’ attention due to their applicability as 2D nanomaterials in many different fields. Our researches are focused on the nanofabrication of a 2D supramolecular hybrid right at the tip of a standard single mode optical fiber, as a model label-free optical sensor working in reflection mode. A fiber optics transduction solution offers many sought-after advantages, allowing to work in harsh (or difficult to be reached) environments, enabling remote sensing and multiplexing, and coupling real-time detection capability with low costs and broad applicability. Our experimental design exploits the sensitivity of the optical signal, which is reflected by the internal interface of a suitably cleaved optical fiber, to the changes in the refraction index occurring at its external interface. This setup also allows the construction of the active nanoarchitecture to be monitored in real time, building the functional layers with a great control over the various fabrication stages.

SEM images of the surface of an optical fiber tip.

With regards to enterprises... We can offer: nanofabrication, sensor design, sensors and applications development, fabrication, sensor characterization, SEM, Raman characterization. Contact: Michele Giordano - michele.giordano@cnr.it

Testing of the layered nanohybrid architecture behavior as label-free sensor, by monitoring the reflectance signal going from air to ammonia or water vapors.

Anna Borriello - borriell@unina.it IPCB - Napoli

Graphene-based composites

TRL: 4

ENERGY

A graphene oxide based nanohybrid for label-free optical sensing

Graphene is the newest and most promising of carbon-based materials. Discovered in 2004, graphene is composed of mesoscopic, robust, highly flexible sheets of carbon atoms, arranged in a honeycomb lattice. Graphene has superb mechanical, electrical, optical and thermal properties, and is intensively studied by both academia and industry for applications in different fields such as flexible electronics, transparent conductors, aeronautics and automotive composites, batteries, supercapacitors, solar cells, sensors, bio-scaffolds... Some commercial application of graphene-based composites is already available. CNR is among the institutions at the forefront of this field in Europe, being a leader of the recently launched Graphene Flagship initiative, the largest and most ambitious research program of this kind ever launched in Europe. The researchers of CNR-ISOF are able to produce on gram scale graphene solutions, graphene-polymer composites, graphene membranes and foams using both covalent and supramolecular chemistry. With regards to enterprises... CNR-ISOF is actually involved in different projects on graphene funded by the European Commission and by Regione Emilia Romagna, collaborating with large multinationals such as AIRBUS, NOKIA, BASF and local SMEs operating in Emilia Romagna. Industrial contracts directly funded by industries are also active, more focused on direct applications of graphene. In particular, CNR-ISOF is involved in a strategic collaboration between CNR and SABIC, one of the largest petrochemical companies in the world, for the development of new graphene-based materials.

Images of different graphene-based materials produced at CNR-ISOF.

Contact: Vincenzo Palermo – vincenzo.palermo@isof.cnr.it Andrea Liscio – andrea.liscio@isof.cnr.it Emanuele Treossi – emanuele.treossi@isof.cnr.it ISOF - Bologna

Organic photovoltaic devices (OPVs), that utilize organic small molecules and/or polymers to directly convert sunlight to electricity, are an attractive technology for sustainable, low cost, flexible and clean energy production. Solution-processed bulk donor/acceptor heterojunction OPVs can open up to a broad range of future applications. They can be colored or transparent and prepared on different substrates, as transparent glass or flexible light plastic foils, by simple wet depositions, as printing techniques. The advancements in OPV technology rely on several aspects, among them the development of tailored active materials plays a central role. To this purpose, understanding of materials behavior under operational device conditions is quite important. We have a long time experience and interest in solution processable OPV technologies, with a particular focus on functional characterisation of new materials and devices. We have the knowhow and the experimental facilities to fabricate and to optimize bulk heterojunction OPV devices and to assess their photovoltaic characteristics. Spectroscopical and morphological characterizations of the donor/acceptor active blends are used to probe charge photogeneration and to find the optimal conditions for deposition and processing of the active layers.

With regards to enterprises... we collaborate with ENI spa on a R&D project for the development of organic solar cells. We can offer our know-how for technological transfer on solution-processed OPV devices.

Silvia Luzzati - silvia.luzzati@ismac.cnr.it ISMAC - Milano

J [mA/cm ]

4 0

-4 -8

-12 -0,4

0 0,4 0,8 1,2 Voltage [V]

Contact:

TRL: 1

Nano-organized hybrid materials with higher charge generation for solar cell applications Photo-voltaic processes are the key ingredient for the conversion of solar energy in green electric power. Hybrid systems obtained by the integration of semiconductor nanoparticles and organic conjugated molecules are promising materials for solar cell applications. We have explored novel hybrid materials where bis(dithiocarbamate) molecules were reacted with (hexadecylamine/stearate)-capped CdSe nanocrystals (NCs) (7.5 nm diameter) to form multilayers on ITO glass via layer-by-layer alternation. Pump-Probe data reveal that the replacement of the bulky surface ligands, capping CdSe-NCs, by bis(dithiocarbamate) molecules strongly enhances the charge generation efficiency of the films. The data are in accordance with the just reported record photocurrent responses of the bis(dithiocarbamate) based multilayers. The materials combine the properties of both organic and inorganic semiconductors , but they have the advantage of being more flexible than the usually employed inorganic semiconductors and more resistant against oxidative degradation than the organic ones. With regards to to Regione Lombardia Progetto “Tecnologie e Materiali per l’uitlizzo efficiente dell’Energia Solare” decreto 3667/2013.

Contact:

Multilayers’ Scheme.

Barbara Vercelli - Vercelli Barbara vercelli@ieni.cnr.it; IENI - Milano Tersilla Virgili, IFN - Roma Arrigo Calzolari and Alice Ruini, NANO - Lecce Maria Cecilia Pasini, ISMAC - Milano Anna Berlin, ISTM - Milano

ENERGY

TRL: 4

Third generation organic photovoltaic (OPV) devices

TRL: 2 - 3

Solar thermal technology is a safe sustainable and cost-effective energy supply. Presently, the maximum operating temperature of a solar power plant is <800 K due to degradation of its components. However, efficiency of solar thermal power plants increases with increasing working temperatures. Hence, the problem to be solved is the improvement of the receiver in terms of radiative properties and chemical stability at high temperature. Ultra High Temperature Ceramics (e.g. borides and carbides of early transition metals) are considered a class of promising materials for application in the aerospace as thermal protection materials. A novel potential application is in the field of solar thermal power, as solar absorbers. UHTCs possess favorable properties (very high melting points and good thermo-mechanical properties at high temperatures and intrinsic selectivity) that can be advantageously exploited to increase the operating temperature of thermodynamic solar plants in concentrating solar power systems. ISTEC develops dense and porous UHTCs ceramics and studies the optical properties in collaboration with INO-CNR. Funded projects: National projects: FIRB project SUPERSOLAR “Assorbitori Ceramici Ultra-refrattari per generazione di energia dal solare termodinamico ad altissima temperatura». European project: STAGE-STE “Scientific and Technological Alliance for Guaranteeing the European Excellence in Concentrating Solar Thermal Energy”, Grant agreement no: 609837

Dense mirror-like polished materials.

Highly porous ceramics prepared using (a) direct foaming, (b) and (c ) replica technology, d) freeze casting.

Contact:

Diletta Sciti - diletta.sciti@istec.cnr.it Laura Silvestroni - laura.silvestroni@istec.cnr.it Valentina Medri - valentina.medri@istec.cnr.it Elena Landi - elena.landi@istec.cnr.it ISTEC - Faenza

Solid oxide fuel and electrolysis cells (SOFC/SOEC)

TRL: 5 - 6

ENERGY

Ultra refractory solar absorbers for concentrated solar power systems

Solid oxide fuel cells (SOFCs) and solid oxide electrolyzer cells (SOECs) are electrochemical devices that convert chemical energy into electric power or produce pure H2 and O2 through electricity operating at high temperatures (500800°C). SOFCs have great potentials as power supplier for stationary and mobile applications; SOEC (that work in the reverse mode of SOFC) can be applied for the conversion and storage of clean and renewable energy sources into alternative energy carriers like H2, synthetic fuels and the production of pure O2. The choice of high performing materials and compositions and the optimization of the layer microstructures are the key points for the development of SOFC/SOEC devices showing the desired properties. For this purpose ISTEC developed new materials and advanced architectures of nanomaterials to obtain high performance devices with engineered microstructure. With regards to enterprises... In this topic, we collaborated (among the others) with CNR-ITAE, CNR-IENI, Politecnico di Torino, University of Tor Vergata and German Aerospace Center (DLR, Stuttgart). We can offer: design, synthesis and optimization of micro-, nano-powders and their suspensions; development, optimization and scale up of the shaping processes for real conditions trials; chemical-physical and morphological characterizations.

Schematic diagrams of SOFC/SOEC operation.

SOFC/SOEC layers (up) and final device (on the right) produced in ISTEC.

Contact:

Alessandra Sanson - alessandra.sanson@istec.cnr.it Elisa Mercadelli - elisa.mercadelli@istec.cnr.it ISTEC -Faenza

Enhanced IrRu-oxide electrocatalysts for water electrolysis Hydrogen is a promising energy carrier that can be produced by cost-effective electrolysis of water using renewable energy sources. A challenging problem to the development of such process is the substantial energy loss associated with the oxygen evolution. High surface area nanostructured (2-10 nm) IrRu-oxide electrocatalysts can substantially reduce this loss allowing to achieve efficient hydrogen production at 4 kWh/Nm3 H2 with good perspectives for a wide scale decentralised hydrogen production. Compact water electrolyser.

ENERGY

Counts

TRL: 4

16 12 8 4 0

4 6 8 Particle size / nm

Potential / V

2 1.8 1.6 1.4 1.2

Distributed energy generation from renewables.

With regards to enterprises... R&D activities are carried out in the European FP7 FCH-JU ELECROHYPEM Project (G.A. 300081); Partners include Solvay, ITM Power Trading, Tozzi Renewable Energy, Joint Research Center European Commission, CNRS.

0.4

0.8

40 °C

50 °C

60 °C

70 °C

80 °C

90 °C

1.2 1.6 2 2.4 2.8 Current Density / A·cm-2

3.2

3.6

Nanostructured IrRuOx catalysts and related water electrolysis perfomance.

Contact:

S. Siracusano,V. Baglio, A.S. Aricò - arico@itae.cnr.it, Istituto di Tecnologie Avanzate per L’Energia ”Nicola Giordano” ITAE - Messina

TRL: 4

Design and development of new carbon-based materials for energetic Carbonaceous materials (carbon black, graphite and nanotubes) are characterized by structural features prone to be modified by chemical approaches. Wet chemical approaches recently applied to carbon black (CB), demonstrated that CB is easily transformed in a more versatile nanosized materials with tunable surface : new technological applications are hypothesized because such wet chemical transformations leave CB graphitic core untouched and preserve its conductive properties. On this basis , a wide array of new low-cost carbon-based materials and composites have been designed, produced and characterized for innovative applications in energetic (sorbents for Carbon Capture and Storages, water treatment, sensoristic, selective photooxidation). Among them: ultrathin graphene-like film (< 20 nm); high surface area microporous composites (metal-organic-framework/graphene-like); photoactive composites (TiO2/ graphene-like); surface modified carbon blacks (amino-derivated, ferromagnetites, supported ionic liquid phase) ; eumelanine/graphene-like hybrids. With regards to enterprises... On this topic, we collaborate with various academic groups and we are looking for industrial partners. We can offer: expertise in developing and characterization of low -cost carbon-based materials and inorganic/organic hybrids tailored for specific applications (sorbents for Carbon Capture and Storage strategies, water treatment, photocatalist, bioinsipred materials…), service and consulting.

Graphene-like/ferromagnetite composite.

Metal organic framework/graphene-like composite.

Contact:

M. Alfè - alfe@irc.cnr.it IRC - Napoli

Graphene-like/ferromagnetite composite.

180

P->5M 5M->7M 7M->2M 5M->P 7M->5M 2M->7M

160 140

Critical Stress (MPa)

TRL: 1

In the last 15 years the Ferromagnetic Shape Memory Alloys (FeSMA), and primarily the Ni2MnGa-based alloys, have been at the cutting edge for both materials science and engineering innovative research, as they allow to coniugate several smart functionalities. The concurrent presence of magnetically ordered states and a thermoelastic transformation enable peculiar physical effects, namely magnetic shape memory, magnetic superelasticity, giant magnetocaloric and magnetoresistive effects, suggesting a variety of applications for the design of functional devices such as sensors, actuators and energy-related appliances (energy harvesting and energy conversion devices). The principal aspects of our work fits in with the international research activity to study and obtain new alloys that improve and modulate the distinctive functional properties of Ni-Mn-Ga, (activation temperature, Shape Memory Effect, Pseudoelasticity and Magnetic and Magnetostructural response); these results rely on the control of the preparation conditions of the alloy, and in particular on the solution to the technological application issues (e.g. workability, transfer of the Magnetic Shape Memory effect from monocrystalline to polycrystalline samples). For this purpose startign from the NiMnGa many systems have been studied, Ni of Fe based (NiFeAl, NiFeGa, NiFeGaCo, NiCoAl) and our research experience drives us to actually consider new quaternary alloys as NiMnGaCo or NiMnInCo showing promising preliminary results. In collaboration with: CNR-IMEM, Parma (Italy)- Dott.ssa F. Albertini, Dott.ssa L.Righi BCMaterials & Dpto de Electricidad y Electronica- Universidad del Pais Vasco UPV/ EHU, BILBAO, (Spain) -Prof. V.A. Chernenko.

120 100 80 60 40 20 0 -200

-100

100

Temperature (°C)

Clausius-Clapeyron relationship for NiMnGa.

Contact:

Elena Villa - e.villa@ieni.cnr.it IENI - Lecco

Low-emissivity building materials

TRL: 3

ENERGY

Magnetic shape memory alloys as multifunctional materials

Under increasing pressure of environmental sensitivity and rising costs of traditional energy sources, is increasing the demand for technologies aimed at energy saving in building sector. The problem is partly addressed with the use of low-emissivity materials (low-e glasses), which are transparent to solar heat radiation, while preventing the escape of thermal radiation emitted by heating surface. The main problem of the low-e glasses is that in summer at certain latitudes and for large glass surfaces is a problem for cooling the building. A solution to this problem is represented by selective glasses that are able to retain heat in winter and reflect in summer. Within this framework, we investigate the preparation of glass plates with functional properties integrated with energy saving. Nano-structured systems obtained by coupling glasses and photoelectronic-actived nano-particle composites are developped. Three different approaches are used: 1. Synthesis of ionomeric polymers; stabilization of functional nano-particles; application on glasses. 2. Spying of functional nanoparticles suspension on conventional polymer surfaces; application on glass. 3. Spraying on glasses of composites between conventional polymer and functional nanoparticles.

With regards to enterprises... This activity is supported by: SYNERGY Regione Toscana POR CReO 2007– 2013, 1.5.a-1.6 BANDO UNICO R&S ANNO 2012 + +

+ NP

+ +

+ + + NP + + + + + + +

Stabilization of functional nanoparticles by ionomeric polymer.

G l a s s

P o l y m e r

Spraying nanoparticles

P o l y m e r

G l a s s

High T High P

Laminated glasses development with low-e properties.

Contact:

S. Bronco - simona.bronco@pi.ipcf.cnr.it; IPCF - Pisa

G l a s s

P o l y m e r

G l a s s

With regards to enterprises... We have been consultants for FERRARI GeS (Maranello, MO) in 2005 and users at ESRF, SOLEIL since 2004. We can offer: expertise in designing, fabrication and testing of taylored 0D- and 1D-nanomaterials for energy, including transportation, treatment of biomass and solar applications. Available skills for characterization are XRD, SAXS, WAXS, NEXAFS, XPS, SEM. TEM, EELS, UV-VIS spectrocopy, Light Scattering, Pycnometry. Potential interested companies: manifacturers of devices for heat transfer and energy conversion, nanofluidic lubricants for engines, car tyres and graphite based nanomaterials (protective paintings, anti-wear coatings, etc.), sub-ppm gas-sensors, biological sensors.

Top: Bismuth nanowires: left) SEM; right) diameter hystogram of counts. Bottom: Zinc nanotubes. 600

∆t = 2 ps. fmfp = 20 nm LX = LX = 20 nm

550

linear fit: Y = -0.495054 * X + 486.386 100 step; 200 ps 1000 step; 2000 ps 3000 step; 6 ns

Cell Pseudo-Temp (K)

One decade ago our lab “Nanostructures, Light Scattering and X-ray techniques” started synthesis of nanomaterials including carbon, graphite, metals (M: Cu, Zn, Sn), metal-oxides (MO: ZnO, Fe2O3, TiO2). We demonstrated that 1D Zn-ZnO nanostructures (di Stasio, CPL 2004) could be used as gas sensors for pollutants such as NO2 (Baratto, di Stasio et al. SACTB, 2004). Beyond nanomaterial synthesis, the ongoing activities include simulations of chemical reactive flows in micro-systems (FLUENT) and heat transfer models at nanoscale (Monte Carlo), synchrotron X-ray experiments (SAXS, WAXS, NEXAFS, XPS) at ESRF, SOLEIL and neutron scattering (SANS). We cooperate systematically with University of Rennes, Lund University, BIT in Peking and share cooperative projects (FP7) with CNR-INO, CNR-ISM, CNR-ISTEC, CNR-IRC.

500 450 400 350 300 250

200

Cell Array Position (nm)

400

Left) SAXS experiment at ESRF; right) phonon heat transfer in 1D nanostructures.

Contact:

Stefano di Stasio - s.distasio@im.cnr.it; IM - Napoli

TRL: 4

Nanostructured polymeric photonic crystals (direct and inverse opals) We have developed an innovative material based on the self-assembly of polymeric core-shell nanoparticles resulting in the spontaneous formation of iridescent physical color by diffraction. stabilized by crosslinking. This material can be used as : pigment or optical effect coating for surface protection (e.g. to increase cut and scratch resistance), in photonics (e.g. for the preparation of lenses., optical filters, dichroic mirrors, waveguides, optical mirrors etc.) to create functional surfaces (wetting angles control).

Schematic structure of the core-shell particles and the diffracting crystal. Inset, examples of the range of diffracted colors.

Also as a precursor to nanostructured “doped” layers to incorporate functional materials ( e.g. dyes for solar concentrators ) Organic and inorganic inverse opals with controlled porosity and order. As regards enterprises... Collaboration with Intercos SpA for cosmetic pigments application Patent request (title: “Structural iridescent colours “ , deposit number MI2012A001043)

Appearance of photonic crystal coatings; inset, AFM image

Contact:

Silvia Destri - silvia.destri@ismac.cnr.it Elisa Emilitri - elisa.emilitri@ismac.cnr.it; ISMAC - Milano

ENERGY

TRL: 4

0D- and 1D-nanomaterials for energy, M-MO nanostructures, X-ray techniques

TRL: 5

Small molecules and conjugated polymers represent the two main types of organic materials used for optoelectronic and photonic devices. They can be used in a number of applications including organic light-emitting diodes (OLEDs), photovoltaic cells, organic field effect transistors (OFETs), organic light emitting transistors (OLET), sensing, waveguides. The great interest for organic materials resides in their low cost, easy processability from solution onto large-area substrates and possibility to tailor their properties. Beside the structural design, the functionalization of the conjugated backbone represents one of the powerful tool to modulate and enhance the electro-optical properties of organic semiconductors. In this regard the fluoro-functionalization plays a key role in two directions: enhancement of electronic properties and increase of thermal and chemical stability. In the perspective of commercial applications, the stability of organic-based devices is fundamental and it is strictly connected to the stability of the active organic component. With regards to enterprises... We can offer expertise in design, synthesis and characterization of organic materials with semiconducting properties for applications in photonics and optoelectronics.

Multicolor labeling of fixed and permeabilized mammalian cells stained with a blue oligoaryleneethynylene fluorophore and red or green commercial fluorophores.

Effects of fluoro-functionalization in arylenevinylene compounds: enhancement of absorption capability and photovoltaic performance in BHJ solar cells (left); blue shifting of emission spectra (right).

Contact:

Antonio Cardone - cardone@ba.iccom.cnr.it ICCOM - Bari

Organic nanotubes and self-organized chromophoric assemblies for sensing and opto-electronics

TRL: 3

ENERGY

Organic molecular and polymeric materials for optoelectronics and photonics

Non-covalent self-assembly represents an effective tool for accessing to a large variety of structures with sizes spanning from the nano- to the mesoscopic scale and showing different architectures and functionalities. Supramolecular species containing porphyrins are interesting from a fundamental view point because they offer the possibility of mimicking photosynthetic centers and of accessing to supramolecular devices. Porphyrins, due to their photophysical behavior are an interesting class of molecules for the design and construction of optical and optoelectronic devices and for sensing applications. The ability to control in solution the spatial arrangement of porphyrins through non covalent intermolecular interactions is very important for accessing advanced functional materials with peculiar optical properties.The self-assembly allows the bottom-up fabrication of devices especially for the possibility to build up predetermined patterns on surfaces that is one of the major challenges in develoSelf assembled systems. ping new technological applications. With regards to enterprises... On this topics we collaborate with IMM-University of Nijmegen, University of Messina, University o f Padova, CNR-ITAE Messina, CNR-IPCF Messina. We can offer nano-material synthesis protocols, spectroscopic characterizations and investigation of optical response to analytes.

Aggregates for optoelectronic devices.

Porphyrin nafion membranes for sensing.

Contact:

Maria Angela Castriciano castriciano@pa.ismn.cnr.it ISMN - Palermo

Photocatalysis gains more and more attention in environmental applications such as chemical and biological depollution of water and air and solar energy production. The production of effective catalytic surfaces with scalable technologies is however a critical step towards real applications. The screen-printing process is a well-established technology that allows the manufacturing of layers up to 10 µm and more with several valuable characteristics for photocatalytic applications, including controlled porosity and easy implementation and scale-up. We have realized highly porous TiO2 photocatalytic layers using the screen-printing deposition technique. The obtained layers demonstrate a high photocatalytic activity in the degradation of toluene in air at ambient concentration (12 ppb) and a low UV-A irradiance level (200 µW cm–2). The use of screen-printing deposition technology, instead of in-situ direct synthesis of the photocatalytic layer (such as chemical vapour deposition, sol-gel synthesis or related techniques) has the big advantage of separating the realization of the catalyst from the material layering process. This can, in perspective, add great flexibility in the production line, allowing the use of different catalyst powders with the same deposition process on the final product surface.

Section of a screen-printed photocatalytic film.

Measurement system for the study of photocatalytic degradation activity in air.

Contact: With regards to enterprises... We can offer photocatalytic activity studies on special materials (ITC) and screen-printing deposition studies on ceramic and metal surfaces (ISTEC).

Alberto Strini - alberto.strini@itc.cnr.it ITC – S. Giuliano Milanese (MI) Alessandra Sanson - alessandra.sanson@istec.cnr.it ISTEC – Faenza

TRL: 4

Mechanical processing for sintering and texturing thermoelectric materials Thermoelectric technology represents a possible alternative for the improvement of efficiency of power consuming processes. In fact, it is able to produce electrical energy using the waste heat produced during the process. This capability is directly related to the material involved properties. in order to increase the conversion efficiency of the materials, the simultaneous condition of an high electrical conductivity and a low thermal one have to be satisfied. The state of art of thermoelectric materials is oriented on the development of nanostructured systems: nanostructures enable scattering mechanisms acting on thermal conductance more than on electrical carriers. With this purpose, nanopowders pure or added of nanoparticles, have commonly to be sintered in order to produce the bulks necessary to device development. Coming from metallurgy, we choose to apply mechanical processes well known, like ECAP, or expressly customized, like ODP, to thermoelectric materials. These processes allow fast sintering at relatively low temperaof compoture, preserving the nano-character of the composite material ODP site billets. treated and improving the final performance of the products. With regards to enterprises... Our solutions are oriented to large scale material production. We already verified the capability to reproduce our results on different scales and on different classes of material. Our target is to offer a cheap and easy alternative to the common procedures used in thermoelectric industry. This could allow a reduction of costs opening new fields to the technology. IENI already collaborates with TEMTE Inc., a Canadian company producing raw and semifinished materials. Contact: Carlo Fanciulli - c.fanciulli@ieni.cnr.it; IENI - Lecco

ECAP facility at CNR-IENI for composite billets processing.

Low T & Low P.

2-10 min sintering.

Open Die Pressing process for fast sintering at low T thermoelectric powders in a composite billet.

ENERGY

TRL: 3

Photocatalytic TiO2 films by screen-printing deposition

TRL:4 - 5

Dye-sensitized solar cells (DSSCs) have emerged as one of the most promising technologies for the construction of cheap, silicon-free photovoltaic devices. DSSCs are based on the use of light-harvesting dyes to sensitize the surface of a nanocrystalline semiconductor (usually TiO2). Our research focuses on the design and synthesis of new organic compounds to be used as DSSC sensitizers. We have prepared new dyes featuring new heterocyclic conjugated backbones to improve the device optical and chromatic properties. We have developed innovative compounds capable of robust anchoring to TiO2, giving DSSCs of very good stability.

Design, synthesis and characterization of new organic sensitizers.

Fabrication of lab-scale test cells and efficiency/stability measurements with class AAA solar simulator

With regards to enterprises... DSSCs have a great potential for the development of low cost PV devices with possible applications ranging from portable electronics to building integration. We collaborate with other CNR institutes, have already presented projects in collaboration with both italian and international companies working on new generation PV (Tozzi, Renewable Energy, Aurel Innovation, Solaronix, G24i), and can provide expertise in the field of dye chemistry and fundamental cell optimization.

Contact:

G. Reginato - gianna.reginato@iccom.cnr.it A. Mordini - alessandro.mordini@unifi.it M. Calamante - mcalamante@iccom.cnr.it L. Zani - lorenzo.zani@iccom.cnr.it ICCOM - Firenze

Solid oxide electrolites for application in fuel cells

TRL: 1

ENERGY

New molecular components for efficient and stable dye-sensitized solar cells

Reliable and sustainable energy conversion systems are becoming more and more urgent to face the problem of deterioration of urban air-quality, growing dependence on finite fuel stocks, and global warming. Among the various available energy conversion systems, fuel cell technology represents one of the most viable candidates to address the ambitious issues of sustainable technologies for energy conversion, storage and savings. Fuel cells deliver energy at high efficiency by consuming electroactive chemicals that are supplied on-demand to the cell as in a conventional thermal combustion system. Advanced materials and heterostructures for micro-Solid Oxide Fuel Cells are investigated at CNR-SPIN in Tor Vergata Rome. The samples are grown by Pulsed Laser Deposition and characterized by conventional laboratory instrumentation and advanced synchrotron radiation techniques. Relevant research developments on novel materials for proton/ion conduction, charge transfer processes and interfacial phenomena are attained. One of the most recent breakthrough was achieved on BaZr0.8Y0.2O3-x, a very promising electrolyte for working in the intermediate temperature range (500<T<700 째C). A value of conductivity as high as 20 S cm-1 was obtained, related to the high densities of defects, mostly dislocations, at the interface of the film with the substrate.

Sketch illustration of solid oxide fuel cell system.

With regards to enterprises... we can offer: consulting services on new materials , materials production and know-how transfer. Contact:

Carmela Aruta - carmela.aruta@spin.cnr.it SPIN - Roma

ZEBRA batteries (Zero Emission Battery Research Activities), are one of the possible solutions to electrical storage for stationary applications due to their high energy and power density. These systems are based on nickel-sodium chloride cells operating at high temperatures (about 270-350 °C), and they rely on a ceramic β”-alumina tube or planar membrane as solid electrolyte. The composition of the ceramic material as well as the ceramic process needed to produce the electrolytic compartment has a key role to enhance and adapt the batteries performances to the specific requirements for stationary regime applications. Each minimal composition or process deviation strongly influences the final properties of the device. ISTEC has studied different compositions in order to produce dense membranes either in tubular and planar configuration.

ZEBRA batteries: schemes of the two main configurations.

ENERGY

TRL: 4

Electrolyte membranes for ZEBRA batteries

With regards to enterprises... On this topic, we collaborated with some industries and CNR-ITAE. We can offer: design, synthesis and optimization of micro-, nano-powders and their suspensions; development, optimization and scale up of the shaping processes; chemical-physical and morphological characterisations.

β’’-alumina membrane produced at ISTEC and its SEM micrograph.

Contact:

Dr Elisa Mercadelli - elisa.mercadelli@istec.cnr.it ISTEC - Faenza

Deposition and processing of advanced materials - CO2 laser irradiation of GeO2 planar waveguide fabricated by rf-sputtering

Rf-sputtering apparatus for deposition of dielectric systems for deposition of amorphous glass systems.

With regards to enterprises... Optical dielectric waveguide fabrication and processing Ultra transparent glass ceramic in planar format. Contact:

Normalized Intensity [arb.units]

TRL: 4

GeO2 transparent glass ceramic planar waveguides were fabricated by a RF-sputtering technique and then irradiated by a pulsed CO2 laser. The effects of CO2 laser processing on the optical and structural properties of the waveguides were evaluated by different techniques including m-line, micro-Raman spectroscopy, atomic force microscopy, and Positron Annihilation Spectroscopy (PAS).

before irradiation after 1h irradiation after 2h irradiation

Amorphous GeO2

Film

Rutile GeO2

Substrate CO2 laser annealing for localized surface processing.

Trigonal GeO2 200

400

600

800

Raman Shift [cm-1]

1000

Micro Raman measurements carried out at room temperature for GeO2 planar waveguide. Different irradiation time allow to create different nanostructured systems.

Alessandro Chiasera - alessandro.chiasera@ifn.cnr.it; IFN - Roma Stefano Varas (IFN), Carlos Macchi (IFIMAT Argentina), Sreeramulu Valligatla (UniHyderabad India – IFN), Giorgio Speranza (FBK), Maurizio Mazzola (IFN), Nicola Bazzanella (UniTN), D.N. Rao (UniHyderabad India) , Giancarlo C. Righini (Centro Fermi), Alberto Somoza (IFIMAT Argentina), Roberto S. Brusa (UniTN), Maurizio Ferrari (IFN)

Elaboration of the PAS experimental data obtained from the measurements of the as prepared film were well-fitted considering two layers plus the silica substrate. The change in duce by Laser annealing along the thickness of the waveguide is follow without influence the structure of the sample.

TRL: 3 - 4

In recent decades, the increase in energy consumption caused an increase in the environmental contamination determining the necessity of application of renewable energy. A good solution can be provided by third generation solar cells called “Dye Sensitized solar Cells” (DSCs). These photo-electrochemical devices represent a low cost and environmental friendly solution for the direct conversion of solar radiation into electrical current. Moreover, due to their high transparency, DSCs can be applied in a wide range of applications such as the building integrated photovoltaic (BIPV). ISTEC develops new materials for highly transparent photo anodes and sealing materials and their application in final DSC devices built on different substrates. At the moment we are studying alternative photoanode materials whereas in collaboration with University of Bologna we are developing new dyes and electrolytes. The as-obtained devices are characterized in terms of cell performances (current- voltage behaviour and light-to- electricity conversion), film microstructures, electrochemical properties and interface interactions.

With regards to enterprises... ISTEC cooperated with some industries. In particular, in the frame of POR-FESR Emilia Romagna, with Daunia Solar Cells (Ravenna) and Cooperativa Impronte (Ravenna). We can offer research and characterization services on new materials for PV applications.

Photo anode engineered microstructure.

Photo anodes sensitized with different dyes.

Contact:

Alessandra Sanson - alessandra.sanson@istec.cnr.it ISTEC - Faenza

Piezoelectric ceramic materials for energy harvesting

TRL: 4

ENERGY

Transparent coloured photovoltaic cells

The process of harnessing and converting ambient energy sources (vibrations, mechanical pressure) into usable electrical energy is called energy harvesting. Piezoelectric materials are used to harvest this energy because they have the unique ability of converting mechanical strain energy source into electrical energy. In last years different system and technology to recuperate energy from vibration have been developed: piezoelectric materials installed in shoes in order to recuperate energy form walk, special flooring tiles absorb vibration and generate electricity by movement on them have been developed and installed in busy places. Fig.1 Multiayer PZT bender produced We have an excellent experience in preparation of a large vaat ISTEC “Piezo Tile” riety of piezoelectric materials, mainly PZT ceramic composites with different structures (produced by pressing, tape casting, screen printing, electrophoretic deposition etc.) an properties that enable to achieve different applications in the micro or macro scale. Piezoelectric bimorph cantilever is and highly performing structure for energy harvesting. Different types of cantilevers made of thin layers of PZT (Fig.1), “Piezo Tile” and Fig. 2 Piezoelectric foot board shown at the “Festival della a system to recuperate energy from movement (Fig. 2) have Scienza”, Genova 2009. been developed in our laboratories. Screen printing

With regards to enterprises... We developed these materials and systems in collaboration with CNR, University Departments, within contracts with Companies or national Projects . We offer: materials development, prototyping and piezoelectric characterization and integration of bulk materials and thick films.

Fig. 3 PZT film microstructure.

Contact:

Electrophoretic deposition on silicon.

Carmen Galassi - carmen.galassi@istec.cnr.it ISTEC - Faenza

Luminescent nanomaterials have an enormous technological relevance. Among others, we are interested in those containing organic and inorganic luminophores, such as complexes of lanthanide (Ln) elements. Ln trivalent ions (Eu, Tb, Yb, Nd, Er) exhibit line-like emission bands from fâ&#x20AC;&#x201C;f electronic transitions that yield a unique color purity. A lot of work has been done to harness and enhance their luminescence output, taking advantage of scaffolding materials. Among these, carbon nanotubes (CNTs) turned out to be particularly attractive, thanks to their unique physical properties. We pioneered the use of carbon nanotubes as scaffolds for luminescent lanthanide complexes, combining the distinctive emission properties of Ln complexes with the exceptional features of CNTs (e.g. thermal and electrical conductivity, physical robustness, chemical stability, cell permeability). The development of these materials is key for real life applications, such as efficient lighting and telecommunications. New strategies for CNT anchoring, based for example on the use of polymers, are being developed in our laboratories. We also test CNTs as photo- and electroactive materials for solar cells. With regards to enterprises... Our projects on CNT materials are carried out in the frame of projects funded by the European Commission, jointly with big enterprises that are leaders in the area of optoelectronics. We are open to cooperation with Italian companies working in the same field or in sensing technologies. We offer state-of-the art experimental setups for the study of luminescent materials, services, and consulting.

Sketch of the two key strategies to graft luminophores to carbon nanotubes. The emitters can be anchored outside with various types of interactions, or even hosted within the hollow interior of the tube. New concepts are now under development to extend the preparative protocols and the type of luminophores utilized, in order to attain color tuning and stronger stability.

Contact:

Nicola Armaroli - nicola.armaroli@isof.cnr.it Andrea Barbieri - andrea.barbieri@isof.cnr.it ISOF - Bologna

TRL: 4

Novel membranes for CO2 separation and biogas purification One of the core activities of the Institute of Membrane Technology, ITM, is the study of novel materials for application in gas and vapour separation membranes. The activities range from basic scientific research on the structure-property relationships of novel materials, to process design and to pilot plant development. The main fields of interest are related to important environmental challenges, such as the reduction of greenhouse gas emissions and the use of biogas produced from organic waste as a renewable energy source. On the topic of gas separation membranes, ITM collaborates with a number Membrane processes to send greof industrial enhouse gas CO2 back into the greand acade- enhouse to stimulate growth and to contrast climate change. mic partners in the frame of national and international researFrom the study of novel materials or new membranes via the ch projects. The main competences are development of experimental spiral-wound and hollow fiber membrane modules, to the design of pilot test facilities, at membrane preparation, membrane chaevery stage in close collaboration with industrial membrane racterization (thermal, mechanical and producers or end users. transport properties) as well as module construction and finally process technological evaluations. With regards to enterprises...

Two examples of industrial collaboration concern the joint development of a 50 m3/h pilot plant for biogas separation in collaboration with Tecno Project Industriale S.r.l. (Curno, BG â&#x20AC;&#x201C; Italy) in the frame of a national project on renewable energy in the agro-industry (MicroPERLA), and the development of films with controlled water vapor transport for a Swiss industry producing household appliances.

Contact:

Dr. Johannes C. Jansen - jc.jansen@itm.cnr.it Dr. Gabriele Clarizia - g.clarizia@itm.cnr.it Franco Tasselli - f.tasselli@itm.cnr.it Institute on Membrane Technology, ITM - Rende (CS)

ENERGY

TRL: 1

Carbon nanotube photoactive materials

TRL: 4 - 5

New eco solders with superior performance and with specific physical and chemical properties can be tailored acting on composition and /or particle size. A growing interest in nanomaterials came up because of their peculiar properties often quite different from those of the same bulk material. Based on a triad ”composition-structure-property”, the design and fabrication of a new series of Pb-free solders have to be approached by a method that combines multiscale modeling and experimental observation. The R&D activity is aimed to exploit the size effects on melting temperature depression and to produce nanocomposites by adding nanoparticles to solder in order to optimize the final properties of the joint. A systematic approach is adopted to fully characterize soldering materials: theoretical studies (phase diagrams and thermodynamics, surface, structural and electrical SAC alloy properties of bulk alloys, then melting depression and coalescence in nanosized systems) have to be combined with experimental work (preparation of nanoalloys, surface tension and wetting experiments, the characterization of Cu the interface (formation and growth of intermetallics as Wetting characteristics of SAC / Cu SEM-EDX Analysis of SAC / Cu in- functions of operative conditions) and finally, the testing system. terface (ε-Cu3Sn, ɳ-Cu6Sn5 inter- of mechanical properties of joints. metallic compounds)

With regards to enterprises... The activities started with European projects COST 531 and COST MP0602, both related to the development of lead-free solders and are still active in the framework of COST MP0903 (Nanoalloy). We collaborate with many academic and industrial groups in Italy as well as in different countries that have participated to the aforementioned projects.

Contact:

Rada Novakovic - r.novakovic@ge.ieni.cnr.it Donatella Giuranno - d.giuranno@ge.ieni.cnr.it Stefano Amore - s.amore@ge.ieni.cnr.it Enrica Ricci - e.ricci@ge.ieni.cnr.it IENI - Genova

Fabrication of high quality CIGS-based thin-film solar cells by pulsed electron deposition (PED) technique

TRL: 4

ENERGY

Advanced soldering materials design for micro-electronics

Photovoltaic devices, which directly convert abundant light into solar electricity, are important for the implementation of renewable energy supply systems. Today, silicon-based modules are dominating the photovoltaic market, but various emerging technologies are gaining industrial interest; thin-film photovoltaic devices can be manufactured on flexible substrates, enabling the employment of roll-to-roll deposition techniques. Amongst thin-film technologies, CuInGaSe2 (CIGS) has yielded maximum conver- PED ablation process. sion efficiencies of up to 20.8% using rigid soda lime glass (SLG) as a substrate. The commonly used deposition techniques (multi-stage thermal co-evaporation and sputtering of metal precursors followed by a post-growth selenization) are complex, expensive and problematic in term of environmental impact (highly toxic H2Se is usually used) and operation costs linked to high temperature processing. In order to overcome the limitations associated with multi-stage deposition at IMEM-CNR we recently reported the achievement of efficiencies >15% in lab-scale CIGS solar cells by using a low-temperature (<300 °C) single-stage production pro- and inner deposition chamber @ cess based on pulsed electron deposition (PED). PED is a thin film deposition tech- IMEM nique based on high-power electron-beam ablation of a bulk material (target) having the desired composition and stoichiometry (see pictures below). PED technique has been optimized and patented on CIGS at IMEM (patents n° MI2007A001531, MI2008A002091, MI2008A002090, WO2010058281 and WO2010058283); the two key process parameters whose optimisation allowed us achieve a photovoltaic efficiency > 15% are the control of the doping and the quality of the targets used for PED deposition. Thanks to this improved fabrication route based on PED, cost-effective CIGS solar cells can be deposited at low temperature onto different substrates, even low-melting-point plastics, making the fabrication of flexible solar cell a viable option. With regards to enterprises... Contact: We are currently involved in several projects with companies (Italcementi, Marazzi, Stefano Rampino - rampino@imem.cnr.it Consorzio Hypathia, Rial Vacuum, etc), aiming to the process industrialization. IMEM - Parma

At Nanotechnology labs of ISTM-CNR ( http://catalisi.istm.cnr.it/ ) is available a hybrid device able to operate under Plasma Enhanced Chemical Vapor Deposition (PE-CVD) and/or Plasma Enhanced Chemical Vapor Condensation (PE-CVS) . The apparatus can thus synthesize oxides’ thin films having peculiar nanostructured features by PE-CVD starting from a volatile metal precursor that is decomposed by plasma onto a target (max 13x13 mm). Conversely, when operating under PE-CVS, the apparatus yield nanoparticles with narrow size distribution that are collected on a standard filter. The use of a non equilibrium cold plasma allows to deposit films that are fully crystalline also on “soft” targets, such as plastics. In principle, by tuning the plasma gas composition and energy, films of metals, metal oxides, composites (oxide/carbon, etc.) can be obtained. Currently semiconductors films are under development, such as hematite for hydrogen production by water splitting using solar energy.

With regards to enterprises... Currently we collaborate with public research institutes (IIT@Polimi, IFP-CNR, ISMAC-CNR, IENI-CNR, IFN-CNR, IMEM-CNR) and universities in the framework of “Accordo Quadro CNR-Regione Lombardia” and FIRB “Futuro in Ricerca” projects . We offer preparation and characterization of nanostructured films of metal oxides (Fe2O3, TiO2, CuOx, etc.) of different composition, morphology, thickness.

SEM picture of hematite (iron oxide, Fe2O3) nanostructured film on FTO glass.

Argon/oxygen plasma during hematite PE-CVD on FTO glass

Contact:

Vladimiro Dal Santo - v.dalsanto@istm.cnr.it ISTM - Milano

TRL: 3

Fabrication and characterization of ZnO nanostructures

Zinc oxide nanostructures are attractive for application in electronics and sensors, and can be effectively used for energy harvesting (nanogenerators) by conversion of mechanical stresses induced by the environment. High efficiency ZnO devices and nanogenerators require cones or nanowires (NWs) with uniform lateral size, length and orientation. Our activity is focused on the fabrication of ZnO structures through focused ion beam milling and growth of NWs using patterned electron resist layers as template. Focus ion beam machining permits to realize single pillars and arrays of cones with top width from few hundreds to tens of nanometers. Templated chemical growth can be a viable and effective route towards large area growth of ZnO nanostructures with fine control over their position, shape and verticality. Electron beam lithography allows for fine shaping the template layer with sub100nm resolution. Apertures in the resist can be used to produce arrays of lines as well as bunches of NWs. Electrical and nano-mechanical properties of ZnO nanostructures are investigated by means of conductive AFM and nanoindentation. With regards to enterprises... We can offer: coating of surfaces with continuous and patterned layers of zinc oxide nanowires; zinc oxide selective etching; morphological, electrical and nanomechanical characterization.

Chemical growth of ZnO NWs bunch and stripes; nanocones fabricated by focused ion beam.

Characterization by conductive-AFM and compression test.

Contact:

A. Notargiacomo - andrea.notargiacomo@ifn.cnr.it M. Pea - marialilia.pea@ifn.cnr.it E. Giovine - ennio.giovine@ifn.cnr.it; IFN - Roma

ENERGY

TRL: 4

PE-CVD/CVS deposition of nanostructured oxides films with photocatalytic and photoelectrocatalytic functions

TRL: 4 - 5

Thanks to their mixed ionic/electronic conductivity and high catalytic activity for oxygen exchange reaction, La1−xSrxCo1−yFeyO3-�(LSCF) perovskites have received much attention as cathode materials for intermediate solid oxide fuel cells (IT-SOFCs) operating at relatively low-temperature, 600-800 °C. Lowering the operating temperature, however, decreases the electrode kinetics, in particular the oxygen reduction at the cathode. So, new materials composition and/or controlling the cathode properties through new syntheses are required in order to improve electronic and ionic conductivity. LSCF cathodes with metal substitution in B-site prepared by different methods, such as solid-state reaction or by impregnation of the perovskite with the metal dopant precursor, are investigated as new materials. We have recently evidenced by EXAFS analysis the promotion of La0.6Sr0.4Co0.8Fe0.2O3-δ and of La0.6Sr0.4Co0.2Fe0.8O3-δ by incorporation of palladium in the B-site of the perovskite structure through one pot synthesis by citrate method. A dual effect of Pd in promoting the electrical and ionic conductivity of La0.6Sr0.4Co0.8Fe0.2O3-δ perovskite was found. This study opens new possibilities in tailoring the electronic and ionic properties of new LSCF promoted (Pd, Ni, Pt, Ag, Rh) cathodes.

Pd promoted

New Pd-promoted cathodes for IT-SOFCS based on ceria-doped gadolinia (GDC) and Y-stabilized Zirconia (YSZ) electrolytes.

With regards to enterprises... – Collaboration with Enea and SOFCS Power

Realization of button cells. Electrolyte deposition by screen printing technique. XRD, XPS, EIS characterization tests. Collaboration with Centro Ricerche Enea Casaccia (Dr.Ing. Stephen McPhail , Dr. Francesco Padella, Dr. Elisabetta Simonetti, Dr. Claudia Paoletti). Collaboration with SOFCpower SPA (Dr. Ing. Dario Montinaro). Research Contract payed by EFESO (Industria 2015). Collaboration with Prof. Antonino Martorana (Dipartimento di Fisica e Chimica, Università di Palermo). Collaboration with Dr. A. Aricò, Dr. M. Lo Faro (ITAE-CNR, Messina).

SEM images of LSCF/GDC-YSZ

a symmetric

cathode

Contact: L.F. Liotta -liotta@pa.ismn.cnr.it A. Longo, V. La Parola, F. Puleo, G. Pantaleo; ISMN - Palermo

Electrolyte membranes for ZEBRA batteries

TRL: 2

ENERGY

New promoted perovskites as cathodes for intermediate temperature solid oxide fuel cells

Batteries are electrochemical devices which are able to storage energy and deliver it when is needed. With the advent of rechargeable batteries, the interest in metal-air batteries for portable devices has been gradually increasing, especially in the last 10 years. If compared with Li-air batteries, Zn-air batteries are much more sustainable, since Zn is a readily available and cheap mineral, it costs about a third what lithium costs and it is easily recyclable. Our research activity is aimed to satisfy the two most important challenges of metal-air rechargeable batteries, which are to find new electrode materials and to increase the power of the battery. Our strategy is to create advanced materials based on high surface area perovskite-based nanocomposites. These are prepared by the soft-hard templating approach, a novel methodology which combines the soft solution combustion synthesis (SCS) with the hard templating synthesis. The specific capacitance and the electrocatalytic activity towards the oxygen evolution and reduction reactions are strongly correlated with the structural, microstructural and surface properties of these bifunctional electrodes for Zn-air rechargeable batteries. With regards to enterprises... This activity is carried out in collaboration with the Institut National de la Recherche Scientifique – Energie, Materiaux et Telecommunications (INRS-EMT), Varennes, Quebec, Canada. We can offer: advanced synthesis and characterization of high surface area perovskite–based nanocomposites for energy storage applications.

Discharge

Zn ZnO 2OH-

Zinc Electrolyte Cathode Air ZnO Zn 2OH-

Recharge

A schematic view of a Zn-Air battery. METAL NITRATES

HARD TEMPLATE

SCS

SOFT TEMPLATE:

ADDITIVES

Contact:

NH4NO3

HEATING AT 250°C

The Soft-Hard Templating approach.

Francesca Deganello - francesca.deganello@cnr.it Valeria La Parola - valeria.laparola@cnr.it Maria Luisa Testa - marialuisa.testa@cnr.it ISMN - Palermo

Metal-Organic Frameworks (MOFs), tridimensional (3D) crystalline polymers made of organic spacers and metallic nodes, represent a promising class of materials, being porous solids that possess large surface areas and low densities. The possibility of tuning the size and shape of the organic component of the 3D scaffold makes these compounds much more versatile than zeolites or other carbon-based porous materials. ICCOM-CNR has recently gained experience in the field of MOFs synthesis and characterization. MOFs containing the simplest organic carboxylate (the formate ion, HCOO-) have been obtained, employing either Magnesium(II) (Figure 1) or lanthanide (Eu, Gd, Tb, Dy; Figure 2) salts. The Mg(II) derivatives have been tested for H2 storage with satisfactory results, while Ln-based MOFs have been exploited for luminescent and magnetic applications. At the same time, thiazole and thiazolidine-based MOFs have also been prepared and exploited for CO2 capture (Figure 3). Finally, a chiral thiazolidine-based MOF (Figure 4) has been tested as heterogeneous catalyst for selective olefins oxidation under aerobic and anaerobic conditions, giving positive results. Future development of this investigation aims at the preparation of new MOFs containing polytopic tailor-made thiazole-based spacers for assorted applications.

Figure 1 – Crystal lattice of the amine-templated Mg(II) MOF {[Mg(HCOO)3]-}∞

Figure 2 – Crystal lattice of the amine-templated Dy(III) MOF {[Dy(HCOO)4]-}∞

Figure 3 – The porous cavities of a Cu(II)-thiazole MOF for CO2 sorption

Contact:

Figure 4 – Crystal lattice of a chiral Co(II)-thiazolidine MOF

Dr. Andrea Rossin - a.rossin@iccom.cnr.it ICCOM - Firenze

TRL: 5

Innovative core-shell catalysts for methane oxidation There is a critical need for improved methane-oxidation catalysts to both reduce emissions of methane, a greenhouse gas, and improve the performance of gas turbines. However, materials that are currently available either have low activity below 400°C or are unstable at higher temperatures. We developed a supramolecular approach in which single units composed of a palladium (Pd) core and a ceria (CeO2) shell are pre-organized in solution and then homogeneously deposited onto a modified hydrophobic and stable supports. This approach allowed us to maintain the Pd cores isolated even after heating the catalyst at high temperature. Enhanced metal-support interactions led to exceptionally high methane oxidation, with complete conversion below 400°C and outstanding thermal stability under demanding conditions. This raises the potential for a catalytic solution for removing a powerful greenhouse gas from lean-burn engine exhausts. This result alone will stimulate new thinking in catalyst development and system design.

Schematic representation of the core-shell catalyst.

With regards to enterprises... We have various contacts with national and international SME on the bases of the United States Provisional Patent Application No. 61/712,681

Contact:

Maurizio Peruzzini - maurizio.peruzzini@iccom.cnr.it Paolo Fornasiero - pfornasiero@units.it ICCOM - Firenze

ENERGY

TRL: 6

Metal-Organic Frameworks (MOFs): polifunctional materials for gas storage, magnetic applications and heterogeneous catalysis

Sorbent granule.

Sorbent foam.

H2O + CO2

CO2 + N2 + O2

H2O

CO2 release

N2 + O2

CO2 uptake

TRL: 3 - 4

To mitigate the impact of fossil energy on pollution and greenhouse effect, the current technologies need to be improved for achieving limited environmental impact and high sustainability (zero emission). When CO2 sorbents are used in granular or structured forms, high superficial area and well developed open porosity are prerequisites for an effective process. A typical continuous process also requires the sorbent to be mechanically resistant, regenerable and easily available. ISTEC has tested at laboratory scale differently shaped hydroxyapatites as innovative materials able to chemically fix CO2 at 900-1200Â°C, temperatures over the activity range of conventional CaO based sorbents. This finding, along with the better performances of apatites in maintaining absorbing capacity and structural properties upon several absorbing-desorbing cycles and with the lower energy for regeneration, opens perspective for practical utilization. Furthermore, geopolymers, which can be regarded as the amorphous counterparts of zeolites, have been preliminarily tested as novel porous massive sorbents of CO2 at low temperatures (<500Â°C). With regards to enterprises... ISTEC designs, produces and characterizes at lab scale near net shape bodies with designed micro- and macro-structure, chemistry, porosity. CNR Patent MI2012A002111

Schematic of the CO2 separation.

Contact:

Francesco Miccio - francesco.miccio@istec.cnr.it Elena Landi - elena.landi@istec.cnr.it ISTEC - Faenza

Artificial photosynthesis

TRL: 2

ENERGY

New solid sorbents for CO2

Environmentally friendly fuel production is of strategic importance for medium and long-term research and technology. A solar fuel is made using solar energy as the only energy source. Artificial photosynthesis for the direct splitting of water would be an excellent way to produce clean hydrogen fuel on a large scale using an abundant feedstock. This emerging technology is based on principles learned from Nature where individual components perform distinct functions: light-harvesting (antenna system), charge-separation (reaction centre), andÂ water splitting (catalyst), in order to store solar energy in the form of chemical bonds in an usable fuel. Our group has recently participated in a EU project (EUROCORES-EuroSolarFuel) for the design and development of a bio-inspired nanostructured hybrid organic-inorganic hetero-junction modular tandem cells for solar-to-fuel conversion. The main tasks of our unit were the characterization of the energy transfer processes in the antenna system and of the charge transfer processes in the homogeneous redox catalysts using optical spectroscopy and molecular modelling techniques. With regards to enterprises... Our group has a long successful track record in the study of energy and electron transfer processes in artificial light-harvesting antenna systems and in electron transfer units for artificial photosynthesis. Our labs are well equipped with steady-state and time resolved optical spectroscopy techniques covering all time ranges from femtosecond to second. Advanced molecular modelling tools are also available.

Working principle of an artificial photosynthetic system for hydrogen production from water splitting. A light-harvesting antenna system collects and funnels the solar energy to the reaction centre where an initial charge separation takes place. The positive and negative charges produced feed an oxidation and a reduction catalyst for the production of oxygen and hydrogen, respectively.

Contact:

Andrea Barbieri - andrea.barbieri@isof.cnr.it Nicola Armaroli - nicola.armaroli@isof.cnr.it ISOF - Bologna

We are studying new nanomaterials, including metal oxide semiconductors (ZnO, SnO2, TiO2), quantum dots (PbS, CdS and their composites) and carbon nanotubes/graphene materials to be applied in high efficiency and long term stable third generation solar cells. Such innovative devices could allow significant improvement on the overall quality of solar energy conversion, with respect to traditional photovoltaic devices. In particular, the following improvement can be envisaged: Enhanced photovoltaic conversion efficiency, “Green energy” and low impact at environmental level, thanks to the use of not toxic materials, Low cost for fabrication of devices thanks to simple and cheap technologies. One of the most promising ways is application of quasi one-dimensional (1D) and hierarchical nanostructures, as explored in dye sensitized solar cells. Various types of photoelectrochemical systems are under investigation at SENSOR Lab: DSCs based on traditional polycrystalline TiO2 photoanode Nanowire-integrated photoanode Quantum dot solar cells, QDSC With regards to enterprises... We have submitted a patent for the fabrication of flexible photoanodes for dye sensitized solar cells. We have run common industrial projects with Oikos, Conchiglia, Green Vision on the development and testing of dye sensitized and quantum dot sensitized solar cells based on advanced nanomaterials.

Quantum dots sensitized solar cells: modulation of QD band gap allows for light harvesting in different regions of the solar spectrum.

ENERGY

TRL: 4

Nanomaterials for excitonic solar cells

Flexible photoanode for a dye sensitized solar cell composed of anodized TiO2 nanotubes.

Contact:

Isabella Concina - Isabella.concina@unibs.it INO - Brescia

TRL: 4 - 5

Engineered metal nano powders for advanced technologies New catalytic devices, saving significant time, energy and increasing efficiency, such as catalytic powders for hydrogenation reactions and catalytic electrodes for environmentally-friendly hydrogen fuel cell, need engineered metal nanopowder. Such a powders are produced directly from the melt via the process of gas atomisation in Metal-Spray atomizer. order to obtain rapidly-solidified particles with extremely fine microstructures (mean particle size << 20 μm). Consequently, very high active surface areas can be achieved, compared to the cast-and-crush methods and higher activity, selectivity and stability of these catalysts, as compared to conventional catalysts, are reached. The R&D acti- Ni and Ni-Alumined powders by vity is oriented to describe gas-liquid interactions phenomena occurring during metal the courtesy: IFAM (Germany), vaporization-condensation and spray-atomization technologies used to produce me- ESA-IMPRESS tal nano-particles (NPs). The primary objective is to evaluate the effect of working atmosphere (typically oxidizing mixtures) on particle growth and on the thickness of the surface oxide layer. By taking into account metal and oxygen flows and mass balances for the droplet we can evaluate the thickness of oxide layer or better the ratio between Model reference scheme of the: the thickness of layer and the final radius of droplet. The physical variables detera) under-saturated droplets and mining the particle nucleation and growth in the vapour phase are identified. The b) super-saturated droplets outcomes can be used as a design guide for implementation of the technological routes and to tailor the geometry of NPs. With regards to enterprises... This activity started in the framework of Technical outline and phases of the Intermetallic Materials Processing in Relaevaporation-condensation process tion to Earth and Space Solidification (IMContact: Enrica Ricci - e.ricci@ge.ieni.cnr.it; IENI - Genova PRESS) project supported by the European Union (6th E.C. Framework Programme). Donatella Giuranno - d.giuranno@ge.ieni.cnr.it Elisabetta Arato - Elisabetta.Arato@dicat.unige.it We still collaborate with the academic and Rada Novakovic - r.novakovic@ge.ieni.cnr.it industrial groups involved in the project.

Alkaline fuel cell by the courtesy: Johnson Matthey/ Hydrocell Oy.

TRL: 3 - 4

Nanofluids, i.e. suspensions of nanoparticles, made of oxides, metals, or various carbon allotropic forms, dispersed in common fluids, such as water, ethylene glycol or lubricating oil, can be characterized by interesting thermal and tribological properties, making them a viable alternative to common fluids, when used as heat transfer fluids, lubricants or coolants. At ITC, nanofluids are considered as potential primary or secondary fluids in heating, ventilating, air conditioning and refrigeration (HVACR) applications. In particular, characterization activities include: • stability investigation through DLS (Dynamic Light Scattering) analysis; • dynamic viscosity measurements; • thermal conductivity measurements; • compressed liquid density measurements; • heat transfer coefficient measurements in laminar and turbulent flow regime; • solubility measurements of refrigerants in nano-oils. In addition, the analysis of nanofluids performance in technological plants can be performed, where they are used as operating fluids (both primary and seHot Disk apparatus for the thermal conductivity mecondary fluids). asurements. With regards to enterprises... On this topic, we started some collaborations with industry and different research groups. We can offer an analysis of various nanofluids, basing on the forecasted applications, and of the performance of these fluids if employed in working circuits.

Rheometer for the viscosity measurements.

Solubility measurements apparatus.

Contact:

Laura Fedele - laura.fedele@itc.cnr.it ITC - San Giuliano Milanese (MI)

Innovative structural metallic materials

TRL: 5

ENERGY

Nanofluids

The increasing performance demand for components operating at high temperature requires the use of new materials with good mechanical strength and oxidation resistance. Such properties are of utmost importance in land based gas turbines, in aeroengines and in other transport application components. The materials studied at IENI UOS-Mi are mainly nickel base superalloys and TiAl base intermetallic compounds. The mechanical properties (creep, low cycle and thermomechanical fatigue, creep and fatigue crack propagation) are analysed and the parameters necessary for component design and life prediction are calculated. The scientific activity is mainly oriented in the following three directions: • Development of user friendly constitutive equations able to describe the high temperature behaviour of alloys • Support to the development of new alloys for high temperature applications • Analysis of strain and damage mechanisms at high temperatures.

With regards to enterprises... On this topic we collaborate with Ansaldo Energia, Tenaris Dalmine, Alstom (CH, UK), Siemens (UK, D), Politecnico di Milano and other important European Industries and Universities.

Thermo mechanical testing facility.

Contact:

Maurizio Maldini - maldini@ieni.cnr.it IENI - Milano

Preparation of novel hybrid organic-inorganic materials for solid-state sensitized solar cells ● Hybrid O-I perovskites for nanostructured photovoltaics: towards low-cost, efficient and colorful solar cells Hybrid perovskites (such as CH3NH3PbX3, X=Cl, Br, I) are receiving enormous attention due to their excellent photovoltaic performances in all-solid-state mesoscopic solar cells, giving efficiencies larger than those of conventional organic-sensitized DSSCs. Besides, chemical composition tuning allows colorful solar cells that may have various building applications, such as in replacing windows, roofs, and even walls.

TRL: 3

ZnO is a viable alternative to TiO2 for nanostructured photoanodes due to its good electron transport properties. ZnO porous nanobelts

ZnO porous nanosheets ZnS(en)0.5 hybrid

Perovskite-sensitized ZnO porous nanosheets

Porous ZnO diffuse reflectance (%)

100

80 60 40 20 0 350

With regards to enterprises... we offer: protocols for nano-material synthesis, production of new materials, development of related prototypes, diagnostics.

bare ZnO porous nanosheets ZnO porous NSs + CH NH PbI

450

550 650 750 850 wavelength (nm)

950

Contact:

Roberto Mosca - mosca@imem.cnr.it IMEM - Parma

TRL: 4

Beyond graphene: the carbon nanoscrolls Graphene, a one-atom thick planar sheet of carbon atoms packed in a “honeycomb” crystal lattice, is an intriguing multifunctional material. It combines optical transparency in the visible spectral region, good electrical conductivity, barrier properties, radiation shielding, etc. Many other multifunctional nanostructures can be derived from graphene, such as graphene oxide, graphane, carbon nanoscrolls, etc. Carbon nanoscrolls SEM and TEM micrographs of CCNS. can be simply obtained by sliding nanographite against the nanofibrous un-polar surface of biaxially-oriented polypropylene, causing crystal exfoliation and rolling-up of the as-produced free graphene layers. Carbon nanoscrolls combine many useful graphene properties without the disadvantages of stacking phenomena that are observed with graphene. Carbon nanoscrolls can be functionalized by embedding, during the preparation process, a number of organic and inorganic phases such as magnetic nanoparticles, fluorescent molecules, antiseptic materials, etc. These composite carbon nanoscrolls (CCNS) have applications in a variety of technological fields including biomedical (drug-delivery, image contrast agents, hyperthermie, etc.), electrical (high-porous electrodes), spectra at λ=632.8 nm for graphene (red hydrogen storage, sensors, etc. CCNS can be also used as nanoreactors Raman line) carbon nanoscrolls (blu lines) and graphite for a number of organic and inorganic chemical reactions, which allows (black line). kinetic enhancement because of confinement effects. Micro-Raman spectroscopy is used for characterizing the samples. This optical analysis is a convenient tool for evaluating different properties of CCNS, such as Contact: Gianfranco Carotenuto - giancaro@unina.it the number of layers, defects, strain, and residual charge impurity. Sergio De Nicola - sergio.denicola@spin.cnr.it

Carlo Camerlingo - carlo.camerlingo@spin.cnr.it With regards to enterprises... DFTM - Napoli Carbon nanoscrolls and other carbon nanomaterials are commercialized by Punto Quantico s.r.l. CNR Spin-Off.

ENERGY

● Mesoporous ZnO nanocrystals via hybrid O-I precursors synthesized by solvothermal routes

TRL: 1

Demanding applications such as catalysis, energy transfer, drug delivery, separation science, and sensors, drives current research in the field of hybrid inorganic-organic functional materials towards novel molecular architectures, fine control of composition, molecular weight and morphology. Covalent hybrid inorganic-organic materials offer advantages in terms of physical and chemical stability, surface coverage, and favorable electronic properties. Chemical grafting methods require specific chemical modification of the inorganic substrate. An attractive alternative is to resort to physical means of activation by making use of ionizing radiations and/or light of appropriate wavelength. This approach can be applied, for instance, to metal oxides (TiO2, ZnO or silica). Our research group aims at technologically-relevant Class II hybrid materials of controlled structure and composition through a post-synthetic activation of the inorganic support by physical rather than chemical agents. Our current focus is on (i) alkylhalosilane-silicas as starting materials for further chemistry, such as the synthesis of immobilized catalysts, and surface derivatization through click-chemistry, and (ii) polymeric materials of controlled composition and molecular weight. With regards to enterprises... Our collaborations encompass industry (Aerosekur Spa and Avantech Srl) and academia. We own two patents: PCT/IT2007/000907 and PCT/IT2010/000192. We offer g-irradiation of materials; synthetic skills for taylored polymeric materials; chemical characterization with mass spectrometry hyphenated with liquid and gaseous separation techniques, ATR FT-IR; optical microscopy, AFM, NMR.

Contact:

Ornella Ursini - ornella.ursini@cnr.it Francesca D’Acunzo - francesca.dacunzo@cnr.it IMC - Roma

Multiferroics magneto-electrics novel materials. High-Pressure (HP HT) synthesis and advanced characterization

TRL: 1 - 2

ENERGY

New approaches to the synthesis of functional inorganic-organic hybrid materials

“Multifunctional Materials” is a topic of increasing impact in the field of material science and technology. The multiferroism is a property of matter defined as the coexistence of two or more primary ferroic orders, the most important are ferromagnetism and ferroelectricity; when they cohexist, the system is defined as MagnetoElectric. This property is of great interest for a number of applications, such as sensors, advanced electronics and spintronics. Unfortunately, most of these materials can not be synthesized by standard techniques, because they require unusual thermodynamic conditions, high pressure synthesis (HP/HT)in most cases. These conditions can be achieved at the HP Lab. at the IMEM-CNR in Parma, among the best equipped in Europe, where a number of facilities (Multi-Anvil and Piston-Cylinder presses, hydrothermal system, etc.) allow the material synthesis in a wide range of PT, up to 200 kbar and up to 2200° C, simultaneously. The presence of sophisticated equipment and the tradition in the study of innovative materials, make IMEM a center of excellence in the study of magnetoelectric materials. The magnetoelectric multiferroic materials have very often a perovskite-type structure, due to the stringent constraints of symmetry, transport and dielectric properties. The perovskite is a high-density phase, thus stabilized under high pressure, and thanks to its tolerance with respect to chemical substitutions and structural distortions, in the same phase cohexist properties that are normally competitive, as in the case of magnetism and ferroelectricity. The development of complementary skills allow at IMEM to completely characterize the magnetoelectric materials, in term of structure and spatial symmetry, magnetic and electrical hysteresis (coercive field, saturation polarization and Tc) and direct measurement of the magneto-electric coupling. Contact:

Edmondo Gilioli - edmondo.gilioli@cnr.it IMEM - Parma

Advanced Materials

Health “Biomaterials” today represent an important revolution in many aspects of preventive and therapeutic healthcare practices, playing an important role in the development of new medical devices, prostheses and replacement technologies, drug delivery systems and diagnostic techniques. They have already revolutionized the areas of bioengineering, tissue repair and regenerative medicine through the promotion of novel strategies to fight and kill life threatening diseases. Specific functionalities of bio-inspired materials (i.e, bioactivity) makes them especially suitable to have an intimate contact with living tissue, in order to mimic specific biological phenomena. Meanwhile, improvements in stem cell technologies together with the discovery of new exiting but still unexplored properties (i.e., magnetic, optical, conductive, piezoelectric, etc) are concurring to increase the social impact of existing healthcare facilities for a promising application in the treatment of different diseases including cardiac failure, nerve resection, bone fractures, deep skin injuries, etc. The growing knowledge of nanotechnologies are enabling to miniaturize biomaterials at molecular and supramolecular scale for the development of a) implantable sensors able to screen more easily specific molecular levels, opening new routes towards new generation diagnostics b) innovative nano-devices in the form of particles, needles or gels with the unique opportunity to deliver drugs by targeting different locations in human body. The implementation of advanced technologies such as 3D printing are leading to the design of custom-made prostheses, scaffolds for tissue repair/regeneration and finally organs. All these progresses will concur to develop a new “healthcare” strategy, able to offer smart solutions for still unsolved clinical problems and better hospitalization.

number of contributions in this section

HEALTH

TRL: 5

Injectable composite materials for bone repair and regeneration Nowadays the treatment of bone defects after traumatic injury, pathology or congenital pathologies involves surgical techniques that are always less invasive. This is partially ascribable to the continuous development of biomaterials with tailored and appropriate morpho-functional properties able to directly influence cells recruitment and their capacity of colonize, proliferate and differentiate into the material. In this regard the optimal materials have to supply the bone function, mimic the complex structure of natural tissue, facilitate the in growth of new tissue and eventually be able to being resorbable. The solution that best fits previously requirements is represented by composite materials. Among the tissue-inspired composite materials, we proposes two different solutions based on the combination of polymers and calcium phosphates: - Calcium Phosphate gels, synthesized by sol-gel technology, have been complexed with biocompetent poly(ε-lysine) dendrons (CaP/G3-K PS), hyperbranched molecules designed to interact with the ceramic phase and to incorporate growth factors relevant to bone regeneration (i.e. bone morphogenetic proteins). - Physical hydrogels based on poly(vinyl alcohol) (PVA) have been included in self setting cements (SSC) based on calcium phosphate mixture (α -tricalcium phosphate (98% wt) and hydroxyapatite (2% wt) to improve mechanical properties and injectability of the cement with relevant outcomes in clinical surgery.

CaP/G3-K PS Injectable mate- Human mesenchymal stem celrials. ls onto CaP/G3-K PS.

Swollen PVA phases in the ce- IPVA composite cements in “n ments (ESEM). vivo“vbone cavity filled with at 12 wks (WNZ rabbit model).

With regards to enterprises... Collaboration with FINCERAMICA for patent n. TO2005A000549(03/08/2005) PCT/IB2006/052623 08/01/2006web. Contact:

Raucci Maria Grazia - mariagrazia.raucci@cnr.it Guarino Vincenzo - vincenzo.guarino@cnr.it IPCB - Napoli

TRL: 5

Nanostructured scaffolds for tissue regeneration Sub-micro and nano-structured polymers in the form of nanoparticles, nano-fibers and nano-composites are gaining relevant consensus in regenerative medicine because they often mimic the physical features of natural extracellular matrix (ECM) at the sub-micro and nano-scale level. At this stage, Electrohydrodynamic Techniques (EDT) represent the most interesting tool which allow to mold biomaterials in micro or nanostructured scaffolds with highly tunable chemical and structural features by the use of electrostatic forces acting as the driving force to assembly fibers and/or particles from an electrically charged solution. In this frame we focus on recent advances in EDTs processes used to more efficaciously control characteristic shapes and sizes at sub-micrometric scale and to incorporate biopolymers/molecules (e.g., proteins, growth factors) for time and space controlled release to use in drug delivery and passive/active targeting. This may allow to revisit old scaffold manufacturing approach based on “cell housing“, paving the way for the design of instructive platforms – analogues of the native ECM - able to sagely guide cell response towards different ways, overcoming the body’s innate power of organization and self-repair.

Design of ECM analogues by electrospinning/spraying techniques.

With regards to enterprises... Collaboration with DOMPE’ in POLIFARMA “Micro and Nanoparticle systems for the delivery of pharmacoactive molecules” 2012-2015. PON02_00029_3203241 Collaboration with Fidia Advanced Biopolymers (FAB) in Patent n. WO/2009/143947 Authors: Guarino V, Ambrosio L, Bellini D. 03.12.2009. Contact: Vincenzo Guarino - vguarino@unina.it; vincenzo.guarino@ cnr.it; IPCB - Napoli

TRL: 5

Functional gels for health Hydrogels are build up of three dimensional macromolecular network architectures exhibiting a large number of specific properties, such as ability to contain large amount of water, stability in aqueous media, and compatibility with biological systems. Recently research attention has been devoted on the design of smart hydrogel systems able to respond to specific environmental stimuli (pH, temperature, electrical field etc…). Thanks to their peculiar properties, hydrogels represent a most interesting class of ‘‘soft matter’’ with a wide range of applications as functional materials . In this frame our research is focused on the design, preparation and characterization of advanced functional gels, based on natural and/ or synthetic polymers, for health . We develop hydrogels with tunable properties to be used for a variety of applications such as three-dimensional matrices for tissue engineering, injectable fillers in minimally invasive surgery (i.e. dermal fillers for wrinkle correction in aesthetic medicine, augmentation products for vocal fold repair in otolaryngology), injectable systems for joint diseases therapy in orthopaedy, contact lens in ophthalmic field and smart thermo-sensitive platform for drug delivery .

Contact:

Assunta Borzacchiello - bassunta@unina.it assunta.borzacchiello@cnr.it IPCB - Napoli

TRL: 9

Laser-assisted repair of biological tissues We proposed new methods of laser-assisted repair of biological tissues (patented) to replace conventional suturing, based on laser induced activation of the endogenous collagen, which behaves like a thermally activated glue. Our method received the approval of the Italian Health Ministry to perform both pre-clinical and clinical experimentations in Ophthalmology and pre-clinical experimentations in brain microsurgery. A recent optimization consisted in the introduction of new light-responsive hybrid bioadhesives for tissue repair that can be precisely bonded to a biological tissue by photothermal activation. These are easily-handy and resorbable medical dressings that are embedded with laser-activatable organic chromophores or nanochromophores. Laser illumination of the chromophores triggers a strong adhesion between the bioadhesive and the tissue.

With regards to enterprises... This laser-assisted procedure has been developed in collaboration with regional enterprises and hospitals, in the framework of several regional projects (OPTOMED Innovative Technology in Ophthalmology; OPTOWELD Development of ocular tissues laser induced suturing techniques; SALTO Innovative Technology for Laser Surgery of Ocular Tissues; MILoRDS Minimally Invasive Laser Operations by Robots in Diagnosis/Surgery), and european projects (Bi-TRE, Biophotonics Plus).

Laser-induced suturing of the cornea during corneal transplant.

Repair of a coronary artery in rabbits with a laser-activated biopolymeric film.

Contact:

f.rossi@ifac.cnr.it; r.pini@ifac.cnr.it Francesca Rossi, Paolo Matteini, Fulvio Ratto, Roberto Pini - http://bnlab.ifac.cnr.it/ IFAC - Firenze

HEALTH

With regards to enterprises... On this topic we collaborate with national and international industries and we have developed some hydrogel systems that are already available on the market. We can offer design, preparation and chemical-physical characterization of hydrogels with tailored properties for the required application.

HEALTH

TRL: 4

Blue-emitting OLED for light therapy The interest in deep blue, and even ultraviolet (UV), efficient emitSmart bandage ters is growing rapidly in view of their application in biological and chemical sensing, as well as in full-color new high-definition television displays (HDTV) . Beside “conventional” applications, blue light sources are suitable for biomedical application since light in the range of 400-420 nm is effective to keep the sterility of a wound Peak 405 nm tissue without damaging the wound-healing capacity, contrary to FWHM < 50 nm Irradiance > 450μW/cm2 harmful UVB and UVC light. A further motivation is the alarmingly increasing emergence of antibiotic resistance in pathogenic bacteA first-aid rearia. In comparison to photodynamic light therapy, blue light inactidy-to-use wearable vates bacteria without the involvement of exogenous photosensitiprototype at ISMAC zer, and it is easier to accomplish. Due to their compactness, flexibility, weight and low-cost, UV-Blue organic light-emitting diodes (OLEDs) based on electroluminescent plastic materials would offer new possibilities that are not accessible to traditional UV lamps. A first-aid ready-to-use device wearable in all situations sounds to be a really appealing tool not only in the military or health risk countries, but also in ordinary life. We design, produce and test conjugated polymers as efficient and stable UV/deep blue emitters suitable for cost-effective OLED smart bandage. With regards to enterprises... We can offer our know-how for technological transfer as well as electro-optical characterization of light sources. We collaborate with local enterprises on a R&D projects about indoor lighting.

Contact:

Umberto Giovanella - u.giovanella@ismac.cnr.it ISMAC - Milano

TRL: 9

Hybrid nano-composites for bone and osteochondral regeneration 3D hybrid biomimetic and bio-resorbable scaffolds for the complete regeneration of bone and osteochondral tissues. These scaffolds are developed by a well-established bio-inspired synthesis mimicking the biologic neo-ossiﬁcation process, thus providing the new devices with very high regenerative ability. The scaffolds are based on Type I collagen fibres that assemble, organize and mineralize with biomimetic, ion-substituted hydroxyapatite nano-nuclei upon pH variation at body temperature. The extent of mineralization can be varied from zero (i.e. cartilage-like constructs) to 70 wt% (i.e. bone-like), therefore 3D scaffolds with graded composition and morphology can be developed to mimic the multifunctional tissues of osteochondral regions (sub-chondral bone, mineralized cartilage and hyaline cartilage), thus triggering relevant cell phenotypes (i.e. osteoblasts or chondrocytes). The orientation of collagen ﬁbres, pore size and interconnection is tailored by controlled freeze-drying and chemical cross-linking, to promote fast cell colonization, formation of new bone and controlled bio-degradation in vivo, in compliance with the kinetics of bone regeneration. These bio-devices are addressed to regenerate lesions of the joint surface which are a very common clinical challenge, frequently diagnosed also in young people. In most cases, an articular cartilage damage implies a simultaneous suffering of the sub-chondral bone. In this respect, the new devices can prevent the recourse to prosthetics in the case of osteochondral damages of limited entity.

With regards to enterprises... On this topic, we collaborate with several international academic groups in the framework of EU-funded Projects in FP6 and FP7 (AUTOBONE, OPHIS, SMILEY). In this respect, the close collaboration with Finceramica S.p.A., Faenza and Rizzoli Orthopaedic Institute, Bologna, provided a clear focus on relevant clinical needs for the design and development of innovative scaffolds for bone and osteochondral regeneration. On this basis several patents and commercial products have been developed and commercialized by Finceramica S.p.A. In particular, the osteochondral scaffold (WO2006092718) is now subject of multi-centric clinical study in Europe. Contact:

Monica Sandri - monica.sandri@istec.cnr.it Anna Tampieri - anna.tampieri@istec.cnr.it ISTEC - Faenza

TRL: 7

Biomorphic transformation: hierarchically organized porous structures Biomimetic, osteconductive and bioresorbable hydroxyapatite scaffolds endowed with high osteogenic ability, complete bio-resorbability and a hierarchically organized structure mimicking the complex structure of the bone tissue. The scaffolds are developed by a novel multi-step transformation process that enables the biomorphic transformation of selected wood structures into biomimetic hydroxyapatite scaffolds. In particular, Rattan wood possesses a microstructure very close to that of bone, with a channel-like oriented macro-porosity that can favour extensive angiogenesis and anisotropic mechanical properties. The careful setup of the kinetics of the different reactions involved in the biomorphic transformation process enables control of the phase composition, i.e. the degree of bioactivity and bio-resorbability, as well as the maintenance of the original wood microstructure. These new-generation bio-devices were conceived to achieve regeneration of long and load-bearing bones which is still an open challenge today, due to the lack of scaffolds endowed with bone-like composition and hierarchical structural organization that can trigger new bone formation and remodelling in an organized and functional tissue. In this respect, preliminary tests in vivo demonstrated the early colonization of the biomorphic scaffolds with the new bone and the potential of biomorphic devices to represent a new generation of hierarchically structured scaffolds for bone regeneration, particularly in the case of complex and comminuted fractures for which acceptable clinical solutions still do not exist.

Scheme of the biomorphic transformation from rattan to biomimetic hydroxyapatite.

Contact:

Andrea Ruffini - andrea.ruffini@istec.cnr.it Simone Sprio - simone.sprio@istec.cnr.it Anna Tampieri - anna.tampieri@istec.cnr.it ISTEC - Faenza

Biomimetic apatites and bone cements -Biomimetic, ion-substituted hydroxyapatite (HA) nano-phases as substitutes for bone regeneration. They closely mimic the inorganic part of bone and possess high ability of osteogenesis and bio-resorption in vivo. -New apatitic cements based on biomimetic hydroxyapatite are injectable devices for regeneration of diseased vertebral bodies able to induce new bone formation and osteointegration as well as complete bio-resorption. Biomimetic apatites are synthesized by wet methods, to exhibit biologically-competent amounts of ions replacing calcium and/or phosphate, e.g.: Mg2+, CO32-, Na+, K+, SiO44-, Sr2+, which have specific effects on the biologic processes, i.e. enhancement Morphology of biomimetic HA. of new bone formation, stabilization of the bone matrix and ability to be progressively resorbed and remodeled. Biomimetic apatites are also developed as injectable bone cements for vertebroplasty. The new cements possess high osteogenic ability, open porosity and ability to be completely resorbed and are designed for the complete regeneration of diseased vertebral bodies. They are based on metastable ionically-substituted calcium phosphates and bio-polymers that, upon spontaneous hardening in vivo, provide cell-conducive 3D constructs able to mechanically sustain the vertebral body in the early stage of the healing process. The new apatitic cements intend to replace the current use of acrylic devices that, in spite of their ability to provide early mechanical stabilization of the vertebra, are characterized by several drawbacks that severely limit Microstructure of Sr-substituted bone cement (left) and integration with bone (right). their use in young and physically-active patients.

TRL: 7

1 0 0 nm

1 Âľm

With regards to enterprises... The long-lasting collaborations with companies in the biomedical field provides a clearer focus for the development of new biomaterials and devices for solving clinical needs of relevant socio-economic impact. In particular, the collaboration with Finceramica S.p.A., as partner of many national and EU-funded research projects (e.g.: AUTOBONE, Bioprotesi, OPHIS, Ageing) led to the development of two international patents protecting the new ion-substituted biomimetic apatites and the new cements for regenerative vertebroplasty.

Contact:

Simone Sprio - simone.sprio@istec.cnr.it Andrea Ruffini - andrea.ruffini@istec.cnr.it Michele Iafisco - michele.iafisco@istec.cnr.it Monica Sandri - monica.sandri@istec.cnr.it Anna Tampieri - anna.tampieri@istec.cnr.it ISTEC - Faenza

HEALTH

With regards to enterprises... The close collaboration with Rizzoli Orthopaedic Institute, Bologna and Finceramica S.p.A., Faenza in the frame of national (Bioprotesi) and EU-funded project (TEMPLANT) provided the inspiration for this research. An international patent was developed (WO2013063201) and a new start up was established to overcome the â&#x20AC;&#x153;valley of deathâ&#x20AC;? in the translation of this new product from the research to the clinics.

Similarity between rattan wood and bone tissue.

TRL: 5

Functional materials for articular joint repair Trauma and disease of joints frequently involve structural damage to the articular cartilage surface and the underlying subchondral bone. Due to the intrinsically poor self-healing capacity of articular cartilage, joint disease and degeneration often require surgical intervention, involving the use of artificial materials. In this context, tissue engineering offers a promising approach, rooted in the fact that engineered grafts may induce a cellular response in vivo addressed to the long-term tissue regeneration while providing immediate structural and mechanical functionality. IEIIT-GE is involved in the realization, modeling and validation of engineered grafts mimicking the complex hierarchical appearance of natural articular joint tissues (meniscus, osteochondral tissues).

Cartoon showing the graft implant for articular joint repair.

Bioactive grafts based on porous polymeric scaffolds, either natural or synthetic, are properly designed and realized; their capability to support the growth of new tissue in vitro and in vivo is also investigated.

HEALTH

With regards to enterprises... We are author of some patents on functional materials for tissue engineering applications. We belong to a regional research network (Tecnobionet) and collaborate with SME involved. We can offer research service on realization, characterization and application of engineered tissues. A schematic representation of how biomaterials may influence the cellular fate, through their physical-chemical features.

Contact:

Silvia Scaglione - silvia.scaglione@ieiit.cnr.it IEIIT - Genova

TRL: 4

Crossed Hollow Fiber Membrane Bioreactor (HFMBR) for liver tissue engineering A crossed hollow fiber membrane bioreactor (HFMBR) was developed to support the long-term maintenance and differentiation of primary human hepatocytes and embryonic liver cells. The bioreactor consists of two bundles of hollow fiber (HF) membranes with different molecular weight cutoff and physicochemical properties cross-assembled in alternating manner: PEEK-WC and polyethersulfone (PES), which perform different functions. PEEK-WC HF membranes provide cells nutrients and metabolites whereas PES HF removes catabolites and cellular specific products from the cell compartment mimicking in this way the in vivo arterious and venous blood vessels. This geometry ensures an extracapillary network for cell adhesion and a high mass exchange through the optimized cross flow of the culture medium. The crossed HFMBR can be used as: â&#x20AC;˘ for the in vitro drug testing; â&#x20AC;˘ a tool for the expansion and differentiation of embryonic liver cells for cell therapies and liver tissue engineering.

Crossed HFMBR

PEEK-WC HF

PES HF

Contact:

Loredana De Bartolo - l.debartolo@itm.cnr.it Simona Salerno - s.salerno@itm.cnr.it Sabrina Morelli - s.morelli@itm.cnr.it Antonella Piscioneri - a.piscioneri@itm.cnr.it ITM - Rende (CS)

With regards to enterprises... We can offer a liver model system for drug testing.

TRL: 4

Biodegradable membrane system for bioengineered skin substitutes

With regards to enterprises... In collaboration with Prof. Augustinus Bader of Biomedical-Biotechnological Center, University Leipzig, Germany.

CHT membrane

Epidermal Substitute

CHT-PCL membrane

Dermal Substitute

Dermal/Epidermal Substitute

Contact:

Simona Salerno - s.salerno@itm.cnr.it Loredana De Bartolo - l.debartolo@itm.cnr.it Sabrina Morelli - s.morelli@itm.cnr.it ITM - Cosenza

Magnetic nano-apatites for drug delivery and tissue engineering

TRL: 4

Bioactive hydroxyapatite nano-phases endowed with intrinsic superparamagnetism, designed to act as new stimuli-responsive drug delivery systems or to enhance cell homing and colonization of bone and osteochondral scaffolds thus enhancing tissue regeneration.

a) Fe doped HA; b) Functionalized nano-beads as drug delivery systems; c) Magnetized cell for scaffold colonization in tissue regeneration.

The recent development of new intrinsically superparamagnetic hydroxyapatite nanoparticles (Fe-HA) was achieved through controlled substitution of Ca2+ ions with Fe2+/3+ ions, with specific Fe/Ca and Fe2+/Fe3+ ratios. Due to the bioactivity, bioresorbability and safety of this new biomaterial, as well as its ability to be activated by external signal, new generation bio-devices endowed with intrinsic superparamagnetic properties can be obtained. The super-paramagnetism of Fe-HA is accompanied by effective hyperthermia properties that can be exploited towards new generation anti-cancer therapies. Besides, Fe-HA nanoparticles can be linked to relevant bioactive molecules through thermo-labile ligands and released upon remotely induced hyperthermia, thus functioning as new smart, stimuli-responsive drug delivery systems. Moreover, Fe-HA nanoparticles can be functionalized and internalized by cells that can be moved, upon external signal, in targeted therapeutic sites or to provide enhanced in vivo tissue engineering thus aiding the regeneration of extended bone/ osteocartilaginous parts.

With regards to enterprises... On this topic, we collaborate with several international academic groups in the framework of EU-funded projects (MAGISTER, FP7) and National Projects (Bandiera CNR “Nanomax” – miRnano). The new devices based on Fe-HA are subject of an international patent (WO2012014172).

Contact:

Anna Tampieri - anna.tampieri@istec.cnr.it Monica Sandri - monica.sandri@istec.cnr.it Silvia Panseri - silvia.panseri@istec.cnr.it Simone Sprio - simone.sprio@istec.cnr.it Michele Iafisco - michele.iafisco@istec.cnr.it ISTEC - Faenza

HEALTH

New biodegradable polymeric membranes of chitosan (CHT) and a blend of CHT and polycaprolactone (CHT-PCL) were developed for the regeneration of human bioartificial skin equivalents. Biohybrid membrane dermal, epidermal and dermal/epidermal substitutes were realized by culturing on CHT and CHT-PCL membranes Skin derived Stem Cells (SSCs) isolated from human dermis, human keratinocytes and the organotypic co-culture of keratinocytes and SSCs respectively. The morphological and physico-chemical properties of the developed membranes play a crucial role in the guidance of the different skin layers regeneration through the modulation of cell proliferation and differentiation. The biodegradation membrane rate is consistent with the tissue formation realizing thus successful bioartificial skin equivalents. These bioengineered substitutes provide a valid tool for therapeutic and drug screening applications. In addition, the developed membrane systems elicit the differentiation of SSCs, which represent a useful cell source in regenerative medicine and in skin tissue engineering for autologous transplantation.

TRL: 4

Nano-hybrid materials for biomedical applications Nanostructured materials are promising tools for biomedical applications. The possibility to tailor their physical and chemical properties at the nanoscale is intriguing for biocompatibility achievement, imaging, drug delivery, proteomics. We developed an original approach (SuMBD) for the functionalization of inorganic materials by means of organic molecules in vacuum environment, with the possibility to create stable and reliable bonds between different species and synthesize new hybrid materials. Starting from 2D or 1D nanostructures, it is possible to model their response to specific external stimulus by using suitable organic partners. Functionalization of : 2D silicon-based technological surfaces for sensing devices (proteomics, marker detection) â&#x20AC;˘1D nanowires for photodynamic therapy, targeting â&#x20AC;˘ Inorganic surfaces to improve biocompatibility.

HEALTH

With regards to enterprises... The SuMBD process is fully compatible with silicon-based large scale production facilities, reducing needing of chemical treatments and improving material purity.

SiO2 - SiON

Contact:

Roberto Verucchi - roberto.verucchi@cnr.it IMEM - Trento

TRL: 5

Multifunctional micro/nano-composite materials for tissue repair and regeneration Tissue injuries beyond the self-repair threshold are still a challenge in reconstructive surgery, and several options are available in order to reconstruct and/or regenerate biological tissues. There exists a need for a new generation of advanced composites and multifunctional therapeutic platform that can repair and/or guide tissue regeneration. As more sophisticated fiber reinforced composites and tissue engineering approaches are developed, an increased emphasis should be placed on strategies guiding tissue repair and regeneration according to clinical needs. Fiber-reinforced composite materials have been designed to make advanced and biomimetic prostheses with tailored mechanical properties for repairing or replacing damaged tissues. The composite approach leads to a more physiologic strain distribution, also avoiding the stress-shielding phenomenon. A variety of nano-composite scaffolds for tissue engineering have been developed. While several progress have been achieved in designing and engineering biomaterials capable to provide physical, chemical, and biological cues that promote tissue growth, on the other hand enormous technological advancement have been attained to manufacture custom-made 3D scaffolds through the rapid prototyping approach. With regards to enterprises... Finceramica, ANIKA, SAMO, AvantiCell, and other industrial partners. Disc Regeneration project FP7-NMP-2007-2.3-1 MAGISTER FP7-NMP-2007-4.2.3.-1

Fiber-Reinforced Composite prostheses: a) hip; b) Intervertebral disc; c) Intervertebral disc and vertebral plates.

Multifunctional rapid prototyped scaffolds: a) Meniscus; b) Intervertebral disc; c) Mandible symphysis; d) Tibial diaphysis.

Contact:

Roberto De Santis - roberto.desantis@cnr.it Antonio Gloria - antonio.gloria@cnr.it Alfredo Ronca - alfredo.ronca@cnr.it IPCB - Napoli

TRL: 1

Hydrogels are appealing materials for biomedical applications being biocompatible and texturally similar to highly hydrated biological tissues. Different properties are required for hydrogels depending on their application either as scaffolds in tissue engineering or as vehicles for controlled delivery of drugs. In fact, whereas in the former case good mechanical properties are required, in the latter rapid responsiveness to external stimuli is advisable. Over the past few years great effort has been made in the formulation of new polymeric systems or composite materials in order to increase the mechanical strength of biodegradable hydrogels and/or to better control the drug delivery process. The design of such new materials has greatly benefited from the use of spectroscopic techniques which allow the relationship between structure and functional properties to be understood. In particular, the combination of up-to-date solution and solid state nuclear magnetic resonance (NMR) techniques has proved extremely useful.

Temperature

Hydrogels for tissue engineering and drug delivery sol

gel Concentration Temperature sensitive hydrogels for tissue engineering.

Self-assembly behavior of PEG-PLA star copolymers.

Contact:

Claudia Forte - claudia.forte@pi.iccom.cnr.it Lucia Calucci - lucia.calucci@pi.iccom.cnr.it ICCOM - Pisa

Neuronal regeneration in microstructured membrane systems

TRL: 4

Micropatterned poly(L-lactic acid) (PLLA) membranes were developed as guidance biomaterials for the polarization and orientation of hippocampal neuronal cells in order to provide permissive environments for neuronal regeneration. Dense and porous nonpatterned and micropatterned membranes were prepared from PLLA by Phase Separation Micromolding. The patterned membranes have a 3D structure consisting of channels, ridges and bricks of different widths. PLLA patterned membranes may directly improve the guidance of neurite extension enhancing their orientation with a consequently highly ordered neuronal cell matrix. Neuronal cells cultured on PLLA patterned membranes were able to regenerate in vitro a neural tissue-like structure that, mimicking the hippocampal tissue, could be used as tool for the study of neurobiological functions and/or neurodegenerative diseases. With regards to enterprises... We can offer membrane systems for neuronal regeneration and nerve repair. Contact:

Sabrina Morelli - s.morelli@itm.cnr.it Antonella Piscioneri - a.piscioneri@itm.cnr.it Simona Salerno - s.salerno@itm.cnr.it Loredana De Bartolo - l.debartolo@itm.cnr.it ITM - Rende (CS)

Hippocampal neurons in non-patterned and patterned membrane systems.

HEALTH

With regards to enterprises... We collaborate with the Institute for Biomedical Technology and Technical Biomedicine of the University of Twente. We can offer expertise in the characterization of physically and chemically cross-linked hydrogels and water/polymer interactions.

HEALTH

TRL: 4

Membrane emulsification Membrane emulsification has attracted academic and industrial interests as alternative method to produce emulsion droplets by a drop-by-drop mechanism. Fine droplets are formed in situ at the interface between membrane and continuous phase by pressing a dispersed phase through the membrane pores (Figure 1). The technology is characterized by size and size distribution control, high energy efficiency and environment-friendly production. All these properties are suitable for efficient operations in emulsions production to develop new emulsion-based products for application in chemical, biomedical, biotechnology, food and home and personal care (HPC) industries. The control of nanoscale membrane architecture and membrane surface properties together with the appropriate selection of operating process parameters and phases composition allows the production of particles whit tailored properties in terms of particle size, particle size distribution and composition. The method is suitable for the preparation of uniform simple (oil-in-water and water-in-oil emulsions (O/W, W/O)) and multiple emulsions (O/W/O, W/O/W) whose sizes can be closely controlled in the range from nano to microscale (Figure 2). Secondary reaction/processes in the emulsified droplets, such as polymerization, gelation, evaporation, freeze-drying, solidification, crystallization, etc. used individually or in combination allow the production of core-shell microcapsules, polymeric microspheres, solid microcarriers, liposomes, etc (Figure 3).

Figure 1. Membrane emulsification process.

Figure 2. Simple emulsion and Core-shell microcapsules.

Figure 3. Polymeric microspheres.

Contact:

Emma Piacentini - e.piacentini@itm.cnr.it ITM - Rende (CS)

TRL: 3

Functional materials on surfaces: deposition for sensing and drug delivery applications Metal-organic compounds and their supramolecular assemblies can be rationally synthesized and finely tuned by a suitable choice of organic ligands and metal ions, allowing to control their molecular architecture and their chemical properties. New functional nano- and micro-structures can be produced by self-assembling these organometallic compounds on different solid supports: silicon, aluminum and titanium oxide, molecular imprinted polymers (MIP), and natural fibres, to name a few. These nanostructured materials can be deposited onto a surface via simple, wet chemical methods, such as sol-gel techniques, drop casting, dip-, spray- or spin-coating, covalent grafting, etc, paving the way to potential application of these active layers as functional materials in sensing, nanoelectronics, catalysis, molecular recognition and drug delivery. drug For instance, an advanced goal would be to directly integrate sensing capabilities into “smart textiles”, that could “active layers” work as colorimetric sensors, being capable of changing surface analyte their color upon an external stimulus. Thus, smart textiles could easily measure skin temperature or sweat pH, or yield early warnings of environmental pollution, or also identify any potential hazards that may endanger the wearer, e.g., the presence of toxic gases for emergency disaster workers. With regards to enterprises... We can offer: design, development, production and characterization of sensors based on metal-mediated self-assembled materials, consulting in bioelectronics, diagnostics, etc.

Contact:

delivery

sensing

Maria Rosaria Plutino - rosaria.plutino@pa.ismn.cnr.it ISMN - Palermo

TRL: 4

Drug carriers based on saccharides as tools in therapy and diagnosis Cyclodextrins (CDs) are cyiclic saccharides widely used in drug delivery because they can host different kind of therapeutics, increasing both drug- solubility and biodisponibility. CD modified with polar and apolar groups (amphiphilic gene- A ration) in both sides generate in water core-shell nanoassemblies (Nano-CD) able to host, deliver and especially target a drug in the site of action. These carriers, have a size compatible with i.v. injection and posses high potential to optimize drug distribution in the body. Over the past B decade our reaseach group demonstrated that Nano-CDs in vitro, are capable of entrapping and delivering conventional anticancer drugs, antiviral, DNA, photosensitizers (PS), Gold Nanoparticles (AuNPs), or combined doses of photothera- C peutics for dual action.

Drug

Nanosaccharides based on Cyclodextrins (NanoCD)

Magnetic biosensors Advances in nanomagnetic solutions and technology for biomedical applications over the past decade has been spectacular. Contrast agents for Magnetic Resonance Imaging, magnetic nanoparticles for drug delivery and hyperthermia treatments are among the best known and advanced applications. In this field, we propose an innovative clinical tool based on magnetoresistive sensor technology for the early and ultra-sensitive detection of proteins in body fluids. The sensor, based on a pioneering modification of spin valve systems, will provide end users with the rapid and highly biospecific identification of pathological protein expression. The alteration of the electromagnetic signal generated by the spinning biocompetent MNP following the capture of the target pathological marker (Fig.1) will allow the detection of the proteins at levels several orders of magnitude lower than conventional bioanalytical assay (e.g. ELISA). The ambition is to translate this pioneering technology into a user-friendly diagnostic tool to be implemented in biomedical laboratories.

TRL: 2

From left to right: magnetic nanoparticles; functionalization of magnetic nanoparticles by antibodies and/or recombinant proteins; MNP/PROT bioconjugate formation; detection of the bioconjugates in dynamic and static microfluidic assisted reading by GMR/ TMR sensor array.

With regards to enterprises... On this topic we offer magnetoresistive sensor arrays, synthesis and functionalisation of magnetic nanoparticles, detection and processing protocols.

Contact:

Valentin Alek Dediu - v.dediu@bo.ismn.cnr.it ISMN - Palermo

HEALTH

With regards to enterprises... Our activities focus on developemnt of Nano-CD, tailoring with fluorescent and /or receptor targeting A) Scheme of Drug/ NanoCD assemblies; B) Morphologies of NanoCD: Empty (Left), group and or capping with metal NPs, entrapment loaded with photosensinitiser drugs (PS) (Centre) and Gold Nanoparticles (Right); of drugs, cell uptake, cell monitoring with the aim C): Uptake of PS-loaded Fluorescent-NanoCD on cancer cells (HeLa). to engineer new effective multifunctional materials for therapy and diagnosis (theranostic). On some of Contact: this topic we collaborate with ST and SIFI in the fra- Antonino Mazzaglia - antonino.mazzaglia@ismn.cnr.it mework of HIPPOCRATES (PON-Sicilia). ISMN - Palermo

TRL: 4

Electrospinning for High Performance Sensing (E-HPS) Nanostructures have been investigated as chemical sensors and potential frameworks to immobilize bio-molecules (biosensors) and cells (bio-scaffolds). Such an arrangement enhances performances of sensors by increasing the interacting surface and the density of potential binding sites. Therefore a series of transducers (gravimetric, electrochemical and conductive sensors) have been functionalized with nanofibrous coatings, creating novel and highly sensitive chemical sensors based on polymers, metaloxides and nanocomposites (projects for human diseases and for environmental monitoring in cooperation with SMEs). The generation of nanofibrous matrices with binding capacity towards biomolecules has enabled the development of improved biosensors. Several nanofibrous polymeric scaffolds, properly functionalized with oligonucleotide probes (ssDNA and dsDNA), have been electrospun to coat quartz microbalances (QCMs) and investigated as bio-inspired scaffold for biomolecules. Furthermore, a strong biocompatible material such as TiO2, through adsorbing proteins on its nanofibrous surface, was able to create novel potential bio-mimetic sensors based on gravimetric or electrochemical transducers with a wide range of potential applications for both health and environmental monitoring.

HEALTH

With regards to enterprises... We can offer: bioinspired chemical sensor or biosensors for health and environment monitoring; sensors electronic interfaces; design of electrospinning technology; clean room facilities; transducers design and manufacturing; measuring devices. The present activity is carried out within a European COST Action MP1206 (2013-2017) in cooperation with International Universities and SMEs.

Electrospinning setup layout; AFM micrographs of nanofibrous layers of pristine titanium oxide and proteins functionalized.

Contact:

Antonella Macagnano - a.macagnano@iia.cnr.it, Emiliano Zampetti, Andrea Bearzotti, Roberto Pilloton, Fabrizio De Cesare IIA - Roma

TRL: 1

Nanostructured contrast agents for MRI Boron nitride nanotubes (BNNTs) are a relatively new class of nanomaterials showing promising potential in biomedical applications, as bioimaging trackers and carriers for delivery of chemicals (e.g. drugs, radiochemicals, nucleic acids, proteins, etc.) and/or physical stimuli (e.g. mechanical, electrical, etc.). We have recently demonstrated that BNNTs purposely doped on the surface with Gd3+ ions can potentially be used as contrast agents for Magnetic Resonance Imaging (MRI). Indeed, thanks to the remarkably high longitudinal relaxivity at very low magnetic fields, Gd@BNNTs are expected to be of particular interest in microtesla MRI imaging technologies. On the other hand, transverse relaxivity of BNNTs is very high at high field (7 T), rendering these systems exploitable as contrast agents in new generation high field scanners. The application of relaxometry to these systems allows the mechanism of contrast to be investigated and structure-property relationships to be understood, thus being of aid in the design of novel contrast agents with desired properties. The possibility to endow other modalities besides MRI to BNNTs opens prospects for multimodal probes, in particular allowing simultaneous diagnostic and therapeutic applications. With regards to enterprises... We collaborate with the Center for Micro-BioRobotics@SSSA of the Italian Institute of Technology. We can offer expertise in the characterization of nanostructured materials at the solid state and in solution and in the measurement of contrast properties and mechanism in aqueous systems.

TEM image of Gd@BNNTs. 120 100 80 60 40 20 0 10000

100000.

1.ď&#x201A;´106

1.ď&#x201A;´107

Longitudinal relaxivity and contrast mechanism of Gd@BNNTs.

T2 contrast properties of Gd@BNNTs at 7 T.

Contact:

Lucia Calucci - lucia.calucci@pi.iccom.cnr.it Claudia Forte - claudia.forte@pi.iccom.cnr.it ICCOM - Pisa

TRL: 1 - 3

Tailored synthesis of nitrogen tricycles as versatile tools in drug discovery and nanomedicine applications Expertise on organic synthesis have been concerned several synthetic pathways, some of which managed in combinatorial version. A number of biologically active molecules have been reached. Among them, some compounds displayed antiproliferative activity in the sub mM range against some cancer cells allowing the individuation of promising “lead compounds”. The recent insights related to cell mechanisms of human diseases, currently described at molecular level, coupled with innovative and powerful computational methodologies opens new promising perspectives in the efforts for finding new selective bioactive molecules. Taking into account, the presence of multiple points of chemical diversity in the entire scaffold coupled with the possibility of combinatorial applications of the synthesis, libraries of new compounds can be build. By tuning the electron properties of the common tricycle scaffold, a large number of structural features could be selected for desired application.

Z N

X, Y, Z = C W = N; W, Y, Z = C; X = N W, Y, Z = N;

X=C

W, Z = C;

X,Y = N

W = C;

X,Y,Z = N

Nitrogen tricycles with different point of chemical diversity useful to introduce specific substituents and/or nitrogen replacements. The knowledge of the biological target makes the tricycle scaffold a “MULTITARGET DRUG” or “VERSATILE TOOL” depending on the mode of decoration. MSWSPSLTTQTCGAWEMKERLGTGGFGNVIRWHNQETGEQIAIKQCRQELSPRNRERWCLEIQIMRRLTHPNVVAARDVPEGMQNLAPNDLPLLAMEYCQGGDLRKYLNQFENCCGLREGAILTLLSDIASALRYLHENRIIHRDLKPENIVLQQGEQRLIHKIIDLGYAKELDQGSLCTSFVGTLQYLAPELLEQQKYTVTVDYWSFGTLAFECITGFRPFLPNWQPVQWHSKVRQKSEVDIVVSEDLNGTVKFSSSLPYPNNLNSVLAERLEKWLQLMLMWHPRQRGTDPTYGPNGCFKALDDILNLKLVHILNMVTGTIHTYPVTEDESLQSLKARIQQDTGIPEEDQELLQEAGLALIPDKPATQCISDGKLNEGHTLDMDLVFLFDNSKITYETQISPRPQPESVS

MODELLER

Amino acid Sequence

With regards to enterprises... On this topic we collaborate with National Cancer Institute NCI (USA); Department STEBICEF, University of Palermo and IBIM-CNR Palermo. We can offer research service on tailored tricycle molecules with specific structural features, including optical activity for application in optoelectronics and other new application fields.

Structure

Contact:

Francesco Mingoia - mingoia@pa.ismn.cnr.it ISMN - Palermo

TRL: 4

Silk-based bio-technologies Silk fibroin is emerging as a promising material platform for the development of innovative eco-sustainable technologies and manufacturing of the future. Silk fibroin is a natural biopolymer, that constitutes the core of the silk fibre, that was used as textile over centuries. Recently, a great deal of attention is being paid to the use of the regenerated silk fibroin solution (RSF) that can be extracted from the core fibre of the Bombyx mori cocoon by water-based-processing. Substrates obtained by RSF can be biomanufacured and used as technological materials for different applications, broadening from multifunctional biomaterials scaffold for neuroregenerative medicine, drug delivery, to diagnostic biophotonics and composites for hybrid organic neuro opto-electronics. The researchers of CNR-ISOF lead initiatives that established in loco the entire silk fibroin chain from bioproduction of raw-material to assessment for upscaled extraction/purification methodology, to fabrication of tailored biophotonic substrates and novel biomaterials targeted to neuroregenerative medicine. With regards to enterprises... The activities are developed through participation and coordination of national and international projects founded by Italian Minister of Education University and Research, EU and related collaborations. They are also carried out in the framework of collaboration with SMEs operating in Europe and in Emilia Romagna through the Laboratory of Industrial Research and Technology Transfer of the High Technology Network of Regione Emilia-Romagna.

Images of different silk based materials and device produced at CNR-ISOF.

Contact:

Valentina Benfenati– valentina.benfenati@isof.cnr.it Roberto Zamboni– Roberto.Zamboni@isof.cnr.it ISOF - Bologna

HEALTH

Validation From amino acid sequence to structure, and docking studies for validation.

TRL: 4 - 5

Bio catalytic nanotools Coupling nanoparticle sol-gel process technology with textile finishing or spinning techniques (Fig. 1) let to obtain HIGHLY VERSATILE MULTIFUNCTIONAL MEDIA, easily exploitable in environmental biotechnology, bioremediation, biodegradation, fields. The high scalability and sustainability of the process is guaranteed by the consolidated technologies involved in nanotech / sol-gel / colloidal and textile processes. The widely accepted mechanism of antibacterial action is for both TiO2 and Ag nanomaterials a direct interaction of released Ag+ ions or TiO2 photo-induced oxidative radicals with bacteria membrane, leading to an increased permeability that causes free efflux of intracellular contents, accelerating cell death (Fig .2). The immobilization of such nanoparticles into antibacterial active coatings, deposited onto textile substrates, is the best strategy for an industrial scalable exploitation of their catalytic properties (bio-catalytic nanotools), presenting the advantages of heterogeneous catalysis: higly water and gas permeability of support, catalyst recovery by easy separation, minimal costs and environmental impact.

HEALTH

With regards to enterprises... The high versatility of proposed nanotools strongly attracts the interest of companies towards two very relevant industrial sectors: pharmaceutical and biotechnology. A current project funded under La Fabbrica del Futuro SP2 (PROBIOPOL: Innovative and Sustainable Production of Biopolymers) aims to exploit such nanotools in process of recovery of biopolymers from bacteria fermentation.

TRL: 4

Fig_2 Radicals or ions leached by TiO2 and Ag nano-phases drive antibacterial action against bacteria.

Contact:

Anna Luisa Costa - anna.costa@istec.cnr.it Magda Blosi - magda.blosi@istec.cnr.it ISTEC - Faenza

Electronic membranes

Breakthrough honeycomb membranes Types Bio-inspired membranes with three-dimensionally lithographed pores tailored by a water-assisted approach.

Fig. 1_Matching between nano-particle sol-gel and textile technologies.

Types Electronic hybrid membranes working as semiconductors at low voltages. Honeycomb membrane topography AFM image collected on the top surface.

Applications Breakthrough membranes for production of pure water by using membrane contactor technologies. Breathable membranes for indoor/outdoor textiles ap- SEM micrographs collected on honeycomb membranes: a) top surfaplications. ce and b) cross section. Reservoir-like arrays for storage/controlled release. Regular platforms for (bio) Contact: sensors. Annarosa Gugliuzza, Enrico Drioli a.gugliuzza@itm.cnr.it ITM - (Rende â&#x20AC;&#x201C; CS)

Future applications Smart multi-compartment devices. Wearable electronic textiles. (Bio)Sensors. Chemicals/energy storage/ transport. Labs-on-a-chip and fluid flows on molecular length scale. Drug delivery systems. Conductive scaffolds.

SEM micrograph showing carbon nanotube networks deposited onto porous membrane surface.

SEM micrograph showing carbon nanotubes embedded in a polymeric layer.

Contact:

Annarosa Gugliuzza, Valentino Pingitore a.gugliuzza@itm.cnr.it ITM - Rende (CS)

TRL: 3

Tailored hydrogel membranes for efficient protein crystallization

With regards to enterprises... Di Profio et al. Tailored Hydrogel Membranes for Efficient Protein Crystallization, Advanced Functional Materials, 2014, DOI: 10.1002/adfm.201302240

Contact:

Gianluca Di Profio - g.diprofio@itm.cnr.it ITM - Rende (CS)

TRL: 4

Stimuli-responsive shape memory liquid crystalline elastomers Shape memory polymers (SMPs) are stimuli-responsive materials able to recover their original shape from large deformation when exposed to an external stimulus. Among SMPs, liquid crystalline elastomers (LCEs) show outstanding thermomechanical features. The combination of the entropic elasticity of polymer networks with the orientational ordering of anisotropic LC molecules gives rise to spontaneous shape change at the phase transitions, resulting in a temperature-induced strain recovery response after tensile loading strain. The most intriguing feature of these systems lies on their ability of undergoing to shape recovery using different triggering stimuli to activate heating. As an example, after the application of tensile stress, initial shape can be recovered due to an external increase of temperature. Moreover, in presence of carbon nanotubes (CNT) the increased electrical conductivity of the elastomeric nanocomposites allowed the activation of shape memory effect through resistive heating. The sample subject to an electric potential difference could recover the initial shape within 10 seconds. These systems can find application in smart biomaterials, sensors, actuators or textiles. With regards to enterprises... On this topic, we collaborate with the University of Napoli. We can offer: expertise in LCE and CNT technology and processing, sample manufacturing and characterization.

Figure 1. Optical and TEM images of a CNT doped LCE evidencing nanotube dispersion.

Figure 2. Shape recovery due to (a) external temperature increase; (b) intrinsic resistive heating.

Contact:

Pierfrancesco Cerruti - cerruti@ictp.cnr.it Gennaro Gentile - gennaro.gentile@ictp.cnr.it IPCB - Pozzuoli

HEALTH

Supported hydrogel membranes, comprising a hydrophilic thin gel layer with controlled mesh size, selected surface morphology, and tailored chemical composition, were fabricated by UV irradiation of acrylamide and poly(ethylene glycol)dimethacrylate solutions on hydrophobic polypropylene (PP) membrane supports. Hydrogel membranes were used to contact macromolecular and stripping solutions in membrane-assisted crystallization systems. The proposed approach provided a suitable tool for efficient protein crystallization, affording a crystallization platform in which protein and additives are easily delivered to the gel network, where supersaturation is generated by gradual solvent removal in vapor phase through the porous structure of both support membrane and hydrogel layer, and crystals are easily recovered. The method was found to increase the efficiency of the crystallization process so that Lysozyme and Concanavalin A crystals appeared at lower protein concentration and demonstrated enhanced diffraction features. As perspective, the method can be optimized to create an environment compatible with membrane proteins crystallization, as platform for biomineralization and polymorphs selection studies, and can provide routes to access non-classical mesocrystal structures. Shown in the figure: on the left - a bicontinuous phase morphology below a dense skin layer originated from the spinodal decomposition occurring during the photo-crosslinking reaction associated to solvent evaporation in hydrogel membrane preparation; on the right â&#x20AC;&#x201C; hen egg white lysozyme crystal obtained without precipitant agent by hydrogel membranes.

TRL: 5

Bracelet of micro-needles to substitute hypodermic syringe for transdermal drug delivery The present invention provides a unique technique for manufacturing needles with electrohydrodynamic (EHD) process based on non-contact and mold-less. The invention supports significant advantages where biodegradable micro-needles are formed by electrically attracting the bio-polymer which has to be initially in a liquid state. This method surpasses the limitations of micro-casting in that no hazardous temperatures or nasty multi-step filling processes are needed being possible to process bio-polymers at room temperature and from solutions. Moreover, drug is localized into the micro-needles and micro-needles can be directly formed onto a flexible substrate. The micro-needles should not be any more expensive than the cost of a vaccine syringe , providing a much cheaper process because it reduces the manpower and the waste disposal. The micro-needles will have important medical and biotechnology applications.

Magnified and fluorescence image of one electro-drawn microneedle.

HEALTH

Flexible multi-drug therapeutic braclet.

With regards to enterprises... We own a patent on: Metodo per la produzione di una schiera di microaghi . N° RM2013A000079 Anno:2013 CNR (INO) - IIT Italian Institute of Technology.

Contact:

Veronica Vespini - veronica.vespini@ino.it INO - Napoli

TRL: 7

Amagnetic solid-state actuator based on SMA Some important applications (e.g. in the biomedical field) require actuators with very low electromagnetic emissions. Examples of those are Magnetic Resonance Imaging (MRI) or Magnetoencephalography (MEG). The present technology tackles this question using solid-state motors based on functional materials such as Shape Memory Alloys (SMA). The amagnetic characteristics of this device are provided by special coiling of the NiTi wire: starting from a fastening point on the first disc, coiling proceeds clockwise along a series of pulleys towards a second fastening point on the second disc; from there, the wire reverses directions winding along a counter-clockwise coil, anti-parallel to the first, until it reaches the first attachment point. While a magnetic field is generated from the first coil as it is traversed by the electric current used for activating the material, that same field gets cancelled out by an equal and opposite field generated by the second coil, which is coaxial, and nearly spatially coincident with the first one. The device was made in several replicas, and tested. The prototypes were designed to generate rotations of around 40° and torques of 80-90Ncm. They underwent both mechanical and electromagnetic tests. In particular, it was verified that at a distance of 1.5m from the actuator activated with a current of 0.7A, the magnetic field intensity is in the order of 1pT. With regards to enterprises... The device used in this research is the subject of an international patent application (PCT WO/2011/141183), which is currently assigned to CNR and available for licensing.

Rotary actuator with very low emission of electromagnetic noise (1pt at 1.5m).

Contact:

Simone Pittaccio - s.pittaccio@ieni.cnr.it Stefano Viscuso Stefano Besseghini - s.besseghini@ieni.cnr.it Lorenzo Garavaglia - l.garavaglia@ieni.cnr.it IENI - Lecco

Functional MRI (fMRI) image without artefacts obtained at 3T (ITAB-Chieti) during mechanical stimulation of the ankle joint by a device powered through the SMA amagnetic actuator.

TRL: 5

Bed-side rehabilitation by an SMA-powered device Patients that are affected by the sequelae of brain damage generally experience a period of incapability to use or move some of their joints. During this paretic phase, the immobilised muscles undergo structural changes and also their innervation and control become dysfunctional. Neuromuscular rehabilitation is strongly dependent on the possibility to use and exercise the affected limbs. In order to allow at least augmented passive exercise during the paretic phase (when active work-out is impossible), a light, comfortable and portable device was designed based on compact high-energy-density actuators such as Shape Memory Alloys (SMA). The Toe-Up! ankle mobiliser can be brought to the patientâ&#x20AC;&#x2122;s bed, so, even bed-ridden and immobilised individuals can be treated. By repeated activation of a NiTi-based actuator inside the device, therapeutic cycles of dorsi-plantar-flexion are delivered to the patient in a slow and gentle manner. Current tests are demonstrating that the device is very well tolerated and flexible. By acquiring electroencephalographic (EEG) data from healthy and disabled subjects the present research is trying to evaluate to what extent passive mobilisation by this device can provide central nervous system stimulation comparable to active voluntary movement, i.e. whether it can be thought of as a surrogate of active exercise in the paretic phase. Contact:

Simone Pittaccio - s.pittaccio@ieni.cnr.it Stefano Viscuso Lorenzo Garavaglia - l.garavaglia@ieni.cnr.it Francesca Passaretti - f.passaretti@ieni.cnr.it EEG ERS/ERD maps showing regions of the brain recting to passive mobilisation by Toe-Up! IENI - Lecco

TRL: 7

Pseudoelastic hinges for neuromuscular rehabilitation Current treatment splints used for limb repositioning in spastic syndromes often impose uncomfortable constraints on the limbs and fix joint angle, thus hindering any residual use and movement of the affected segments. This may have serious side effects in the development of muscular rigidity. The present research established that the pseudoelastic behaviour of shape memory alloys (SMA) allows limbs to be treated through mild and quasi-constant corrective forces without fixing the angles of body segments, and promote the repositioning of limbs which have acquired, (or are likely to acquire), unnatural, stiffened and disabling positions due to spastic syndromes and/or muscle spasms. The pseudoelastic hinges (PH) enclose within their inner chamber NiTi or NiTiNb springs with nonlinear customisable mechanical properties and spring-back forces. The PH were built in two different embodiments, technically tested and applied to ankle and elbow braces. A pre-clinical trial on 25 patients with spasticity confirmed that PH can provide posture control, are more tolerable to patients than traditional splints, and are capable of reducing intrinsic muscular rigidity, while, by direct comparison, traditional ones worsened that problem. Functionalisation of the orthotic devices was possible because material properties could be adjusted to meet the needs of different subjects. With regards to enterprises... The device used in this research is the subject of an international patent application (PCT WO/2011/137999), which is currently assigned to CNR and available for licensing.

Contact:

Simone Pittaccio - s.pittaccio@ieni.cnr.it Stefano Viscuso Stefano Besseghini - s.besseghini@ieni.cnr.it Lorenzo Garavaglia - l.garavaglia@ieni.cnr.it IENI - Lecco

Pseudoelastic hinges applied to brace for elbow repositioning therapy.

Comparison of pre-post evolution in joint passive rigidity for pseudoelastic (P) and traditional (T) therapies, from a clinical cross-over trial on 20 ankles from paediatric patients with spasticity.

HEALTH

With regards to enterprises... The device has received approval for testing by the Ministry of Health and is currently under pre-clinical trials with a cohort of traumatic-brain-injury patients.

Toe-Up!, a bed-side device for early ankle mobilisation and rehabilitation.

HEALTH

TRL: 5

Functionalized silicon nitride for bio-applications The lifetime of a prosthetic device is 10-15 years, while 25% of the hip and knee joints are revision surgery due to premature failure. The use of advanced ceramics such as silicon nitride offers the possibility to prolong lifetime and reduce the failure of conventional joints. Si3N4 is an established biomaterial already implanted in human body. Further improvement in Si3N4 performances could be achieved by its functionalization. Compositing Si3N4 with an electro-conductive phase allows to reach outstanding mechanical behavior and the possibility of manufacturing complex parts by electro discharge machining from simple shaped components. This is cost-effective and opens the possibility to customize the large bearing surfaces with complex topographies through CAD-CAM rendering. Moreover the near net shaping through wet forming techniques, opens new opportunities for the production of complex architectures in which the porosity is a functional property to exploit for bone substitution. With regards to enterprises... Based on thirty years of experience in Advanced Ceramics, ISTEC is able to design and realize the micro- and macro-structure of Si3N4 in order to careful tailor the materialâ&#x20AC;&#x2122;s properties. In collaboration with the machinery shop AndalĂ˛ Gianni srl, ISTEC produces lab scale prototypes of real size, such as: elbow and knee prostheses, screws and plates for mini-fixation, textured surface and porous substrates for bone substitution.

Elbow prosthesis of electro-conductive silicon nitride.

1 mm

5 Âľm

Porous architectures of silicon nitride.

Contact:

Valentina Medri - valentina.medri@istec.cnr.it Mauro Mazzocchi - mauro.mazzocchi@istec.cnr.it ISTEC - Faenza

Advanced Materials

Space & Transport

The need to develop materials which can perform well in severe operating environments is increasing with advances in technology and requirements for higher efficiency in strategic areas, such as space and transport. The class of materials defined as Ultra-High Temperature Ceramics (UHTCs- borides and carbides of IV and V group transition metals like Ti, Zr, Hf, Ta) are attracting the attention for aerospace applications for their high melting points between 3000 and 4000 K, relatively to thermal protection systems and propulsion components. These compounds possess a set of characteristics: extremely high melting point, high hardness, high electrical and thermal conductivity, good resistance to oxidation, high retained strength at high temperature, which make them unique for several applications in extreme environment, such as nose cones, leading edges , control surfaces for hypersonic (reentry) vehicles, rocket nozzle inserts, air-augmented propulsion system components. The need to increase the damage tolerance of these brittle ceramics has further driven the activity towards the generation of a new class of ceramic matrix composites (UHTC-CMCs) where UHTCs matrices are reinforced by ceramic fibres made of carbon or silicon carbide, resulting in materials that couple good thermal shock resistance and good ablation resistance and are able to withstand temperatures >2000 K. Despite the advancements in the processing of the ceramic components less effort has been put on the research of reliable bonding techniques of this class of materials with metal-based counterparts. The development of sound bonds is nonetheless of utmost importance for a more extensive exploitation of UHTCs not only for a niche sector such as the aerospace one but also as highly resistant components, for example, in the steel industry and the nuclear fusion sector. Joining techniques permit to build complex and potentially multimaterial structures that cannot be obtained directly with the densification process. As for transport, major challenges are related to incorporation of nanoscale to obtain new functionalities, which also requires a fundamental understanding of how the processing, microstructure, nanostructure and properties of such material interact in order to enhance their response under severe conditions. For instance, modification of the surface reactivity of materials, through the design and deposition of inorganic or hybrid organic-inorganic coatings â&#x20AC;&#x201C; in the form of layers with different thickness from few nm to Âľm â&#x20AC;&#x201C; allows to control their wetting behavior. Depending on the required working conditions, materials can be provided of the following functionalities: i) improved affinity against water, termed as super-hydrophilicity, ii) improved repellence against water (termed as super-hydrophobicity). The latter, in the aeronautic and marine sectors, can maximize performances such as anti-icing, self-cleaning, anti-fouling, corrosion resistance and friction reduction. Transparent polycrystalline spinel (MgAl2O4) is well suited for the next-generation spacecraft protective windows that must bear harsh in-use conditions or for windows in optical spectroscopy conducted at high temperatures and in aggressive environments, as in LIBS spectroscopy on molten steel. In the current technological field of actuators, miniature shape memory actuators are promising for further optimization of smart devices for technical applications. Innovative wire shapes and new alloys could shift the virtual technological limit line of mini actuator devices for precision mechanics application nearer to the ideal one. Finally, polymer composite materials are playing a fundamental role in transport and space applications. Their lightweight feature together their high mechanical properties (fatigue, impact, etc.) and the possibility of tailoring their properties from nano to micro and macro scale makes them unique and very attractive in designing advanced structures.

number of contributions in this section

TRL: 2 - 5

Ultra-high temperature ceramics for extreme environments The ultra-high temperature ceramics (UHTC) have been drawing great interest of the materials engineers involved in designing thermal protection structures (TPS) for the sharp leading edge technology. The industrial sectors currently interested are transportation, aeronautics and aerospace: TPS for reentry vehicles or hypersonic space-crafts are two examples for which radiative equilibrium temperatures in excess of 2300K, enhanced oxidation/erosion and thermal gradients are effective projected service conditions. The sharp leading edge technology enables hypersonic flights along specific trajectories only if vehicle is designed with fuselage and control surfaces with pronounced sharp profiles. Thanks to this new concept, improved flight performances together with more safety for the crew, larger cross-range, wider launch windows, and safer landing for aborted flight plans can be achieved. Ceramic composites based on MB2 (M=Zr, Hf) combine thermal stability at high temperatures together with an outstanding ability to effectively transfer heat, making them currently among the most studied systems. The oxidation resistance of pure MB2 is poor for the intended application, so that appropriate refinements of the basic compositions must be addressed. Although some materials belonging to UHTC have demonstrated mechanical resistance (@RT) up to 1GPa, a lack of damage tolerance typical of brittle ceramics still needs to be fixed. In this sense, the development of UHTC protected ceramic matrix composites (CMC) can be a new viable approach to obtain lighter and more damage tolerant UHTC. With regards to enterprises... ISTEC collaborated in R&D research programs led by industrial stakeholders involved in the aerospace (ASI, ESA, CIRA, Thales-Alenia Space, CGS) and was selected for an international Joint Project CNR-NSF.

Sharp UHTC leading edge during a test in arc-jet plasma wind tunnel.

Contact:

Frederic Monteverde frederic.monteverdei@istec.cnr.it ISTEC - Faenza

SPACE & TRANSPORT

Transparent ceramics: spinel MgAl2O4 Cubic isotropic MgAl2O4 spinel can be regarded as an almost ideal transparent ceramic material. It is an attractive material in the aerospace sector for several applications under severe conditions such as hard front layer in transparent protection and rugged optical windows operating in harsh environment. CNR ISTEC optimized the production process of spinel components with an in-line transmittance up to 82 % close to the theoretical value. Spinel in-line transmittance.

TRL: 4

MgAl2O4 spinel sample prepared by hot pressing.

With regards to enterprises... Scientific articles L. Esposito, A. Piancastelli and S. Martelli, “Production and characterization of transparent MgAl2O4 prepared by hot pressing “, J. Eur. Ceram. Soc., 33 (2013) 737–747 S. Martelli, L. Esposito, A. Piancastelli, D. Dalle Fabbriche, «Improvements on the fabrication of transparent MgAl2O4 prepared by hot pressing”, presented at ECerS XIII, Limoges, June 2013. Contracts Contracts with industries are carried out on the development of prototypes»

Contact:

Laura Esposito - laura.esposito@istec.cnr.it ISTEC - Faenza

TRL: 4

Advanced joining processes for high temperature Metal-Ceramic systems The main strength of this topic is related to the special interest the Ultra High Temp. Ceramics (UHTC) have for many advanced applications in hostile environments. These refractory materials, based on oxides, carbides, nitrides and diborides, are being considered as components and subsystems in the field of aerospace missions and for harsh industrial applications. A critical issue is the development of joining methods, based on brazing, to assemble them into complex structures. The studies on the energetics of solid-liquid interfaces are used to support the development of new joining techniques for UHTC’s, in particular for brazing (Ti,Zr,Hf)B2, oxide ceramics, SiC-base composites to themselves or to high performance alloys (superalloys, Ti6Al4V, etc.). The approach we use to arrive at such a goal is based on: i) the use of advanced experimental techniques for reactivity-wettability studies at high temperatures; ii) thermodynamic treatments (interfacial reactivity, wettability etc.); iii) advanced phase diagram calculations through the CALPHAD method; iv) ab-initio modelling of interfacial structures; v) evaluation of the strength of the joints. With regards to enterprises... We collaborate with academic and industrial groups, in the mainframe of international projects. The last one, dealing with aerospace applications, is ADMACOM -PF7-FoF-NMP2-SL-2013-609188, with, as Partners: POLITO-DISAT(Leader); CNR-IENI; EADS (D); MT-Aerospace (D); FraunhoferIFAM (D); EMPA(CH); Nanoforce (UK). We can offer: design of ad-hoc brazing alloys, wettability tests up to 1600°C under vacuum or controlled atm., production of prototype brazed joints and microstructural characterizations.

C/SiC sleeve and electromagnetic actuator rod with brazed SiC/metal parts, components of the IXV ESA Space Reentry vehicle. ADMACOM Project Courtesy: MT Aerospace Liquid alloy

Ceramic

Typical sessile-drop test to select brazing alloys (Ni on ZrB2 at 1500°C).

200 µm

A HfB2-HfB2 joint using a Ni alloy interlayer.

Calculated NiHf-B Diagram to optimize brazing processes.

Contact:

Maria Luigia Muolo - ml.muolo@ge.ieni.cnr.it Fabrizio Valenza - valenza@ge.ieni.cnr.it Alberto Passerone - a.passerone@ge.ieni.cnr.it IENI - Genova

TRL: 4

ROTOsma-1 is a rotational actuator with a volume of 1cm3 (8x25x5mm3) and a weight of 1.13g. It is able to perform a maximum stroke of 120° in the two main directions under a torque of 0,1Nmm. It mounts two snake-like shaped NiTi wires that work in the antagonist configuration. These elements are activated by Joule effect through a current of 0,6A for 5s (reset time is 15s, maximum power consumption 1W). In the current technological field of miniature shape memory actuators, ROTOsma-1 lies on the lines representing the present technological limit and it is two orders of magnitude far from the ideal conditions. This means that both there is a great potential for further optimization and, at the same time, there is a sort of limitation in fabricating rotational SMA miniactuators which reasonably approximate the ideal one. New technical applications, innovative SMA wire shapes and new SMA alloys could shift the virtual technological limit line nearer to the ideal one.

With regards to enterprises... We can offer our know-how in the design and development of SMA mini actuator devices for precision mechanics application. A. Nespoli, E. Bassani, S. Besseghini, E. Villa, Attuatore rotazionale attivato da materiali a memoria di forma. BREVETTO: Num. domanda: MI2010A000709, CCIAA di deposito: Milano, Data di deposito: 26/04/2010.

ROTOsma-1 and snake-like shape memory alloy element.

Stroke to volume ratio in function of the torque to volume ratio of the ROTOsma-1 device, the published and commercial rotational SMA mini-actuators and the ideal rotational mini-actuator.

Contact:

Adelaide Nespoli - a.nespoli@ieni.cnr.it Elena Villa - e.villa@ieni.cnr.it IENI - Lecco

SPACE & TRANSPORT

ROTOsma-1: miniature actuator based on shape memory alloy antagonist elements

TRL: 4

Ultra-ablation resistant ceramics for propulsive application New generation thrusters demand always increasing severe combustion conditions, in terms of temperature and pressure, in order to enhance their performances. Materials based on carbides of the early transition metals, such as zirconium, hafnium and tantalum, are promising systems for these applications, combining physical properties of ceramics and electronic properties of metals: high melting points (> 3900°C), high hardness and Young’s modulus values competing with that of silicon carbide (SiC), good thermal conductivity. These features can be further enhanced through small changes in the fabrication process and in the compositional design, such as addition of sintering additive or reinforcing phases. ISTEC works on the production and characterization of ultra-refractory ceramics materials in order to enhance their intrinsic properties.

Ablation resistance Graphite

HfC

TaC

Ablation tests on simple shaped prototypes: comparison between graphite, Hafnium carbide and Tantalum carbide.

5 cm A ceramic nozzle based on Tantalum carbide.

With regards to enterprises... -2012-2014: “ Development of ultra-ablation resistant ceramics for application in the propulsion” Piano Nazionale Ricerca Militare, funded by Italian Ministry of Defence.

Contact:

Diletta Sciti - diletta.sciti@istec.cnr.it Laura Silvestroni - Laura.silvestroni@istec.cnr.it ISTEC - Faenza

TRL: 4

SPACE & TRANSPORT

Superhydrophobic coatings for marine application Highly water repellent coatings with wettability properties known as superhydrophobicity (SH) are related to surfaces with contact angle above 150° and a very small hysteresis. The small area available for these surfaces is exploited in many applications where interactions with aqueous environment are usually strongly to be avoided like for protection and friction reduction in marine environment. The development of surface coatings can be applied to the protection of metal surfaces from corrosion and fouling. With the aim to provide more resistant and long lasting coatings, the SH surfaces under investigation have been prepared by different preparation methods and studied in presence of pure water, marine waters, solutions and dispersions.

With regards to enterprises... Patent: BrevGE 2005 A 87

Water drop bouncing on a superhydrophobic surface.

After cleaning by very low water pressure, Aluminium samples protected with superhydrophobic resulted easily polished.

Contact:

Flagship Project RITMARE SP1 WP2 Friction and CO2 reduction WP5 antifouling and anticorrosion coatings

Michele Ferrari - m.ferrari@ge.ieni.cnr.it Libero Liggieri - Francesca Ravera IENI - Lecco

TRL: 2 - 3

Fiber reinforced ceramics for extreme environments In the last two decades, processing innovations at CNR-ISTEC have significantly reduced the temperatures required to fabricate dense, high-quality ultra-high temperature ceramic composites, which are constituted by IV-V group transition metal diboride/ carbide-based matrices with nominal melting temperatures up to 4200 K. Although research has successfully produced UHTCs with flexural strength up to 1 GPa, fracture toughness and thermal shock resistance still represent major concerns for the application of these ceramics in aerospace or in highly stressed environments. To address these issues, novel processing methods have been implemented to introduce elongated reinforcements (such C or SiC fibers) into UHTC-based matrices.

Examples of short fibers (left) and continuous fiber (right) reinforced refractory matrices.

Contact:

Diletta Sciti - diletta.sciti@istec.cnr.it Laura Silvestroni - Laura.silvestroni@istec.cnr.it Valentina Medri - valentina.medri@istec.cnr.it ISTEC - Faenza

TRL: 5

Advanced composite materials allow the realization of lighter structures than metallic ones due to the intrinsic high stiffness for unit weight. However, due to the mass reduction itself, structural damping is strongly depressed resulting in a more weight demanding vibro-acoustic treatment. Optimization of such contrasting weight and functional requirements is valuable. In the framework of IMAST Scarl cooperation, we developed a design approach for a multifunctional hybrid composite material that integrates high damping performances while withstanding the required structural features. Carbon nanotubes have been used as viscoelastic materials to enhance damping features. Key aspect is the definition of a viscoelastic multiscale model starting from the constituents to the lamina, and further to the hybrid laminate properties.

With regards to enterprises... We can offer: fabrication, materials design.

Contact: Michele Giordano - michele.giordano@cnr.it

Vincenza Antonucci - vincenza.antonucci@cnr.it - IPCB- Napoli IMAST

SPACE & TRANSPORT

Multi scale composites enhancing damping features

Advanced nanostructured systems have gained tremendous interest for the development of innovative multifunctional materials. On this topic, we propose graphene (GE)-based nanocomposites which exhibit enhanced electrical and gas barrier properties. This result has been obtained developing processing technologies which allow the tailoring of graphene morphology (dispersion, segregation, orientation) . Research activities have been also focused on the use of inorganic nanocarriers for the release of active compounds from hybrid nanocomposites. Chemical functionalization of nanocarriers with diverse size, architecture and surface properties has been performed with the aim to properly design active and responsive materials for automotive (i.e. anticorrosion) and active food packaging (i.e. antimicrobial film to enhance food security) application fields. With regards to enterprises... We collaborate with companies in the sector of automotive and of food packaging materials. Our competencies are related to the design, production and characterization of multifuctional nanocomposite materials for applications in packaging, cultural heritage and transport fields. Contact:

SPACE & TRANSPORT

G. G. Buonocore - giovannagiuliana.buonocore@cnr.it M. Lavorgna - marino.lavorgna@cnr.it IPCB - Napoli

A B A

Tailoring of graphene morphology to enhance the gas barrier properties and electrical properties of polymeric nanocomposites.

HNT

MMT

1,0

mt/mtot

TRL: 4

Advanced polymeric nanocomposites as active and multifunctional materials

0,5

Antimicrobial effectiveness of modified MMT. 0,0

HNT_Active aldheyde HNT_Active aldheyde with Cu 0

1000

2000 time (min)

3000

4000

Functionalized Halloysite (HNT) and montomorillonite (MMT) to control the realease of active compounds from hybrid and nanocomposites.

Advanced Materials

ICT Secure Societies Information and communications technology (ICT) is one of the pivotal driving forces in science and technology. CNR moves on the frontiers of ICT research, involving various applications, such as secure societies challenges, sustainable manufacturing, information processing and storage, sensors, Micro-(nano)-electronics and optoelectronics. Developing hybrid organic/inorganic technologies, wearable or implantable sensors, improving the performance of miniaturized organic devices, increasing the information storage density, adopting new sustainable fabrication methods and new highly performing materials are open technological challenges that, potentially, have an enormous impact in knowledge-based economy and in everyday life. Within Secure Societies challenge, advanced materials are also playing a key role in designing systems and structures for controlling food quality, traceability and safety as well as for wastewater treatment and detection/contamination of toxic chemicals/biological agents Here, the technological challenges require both the development of materials and advanced and innovative technological solutions that allow for the fabrication of new high-technological products. In order to reach these aims an extraordinary combination of competences and an interdisciplinary approach is active promoting innovative knowledge and technology well beyond the state-of-the-art possibilities, in agreement with the guidelines of Horizon 2020 program.

number of contributions in this section

TRL: 6

Tailoring of materials properties via bottom-up nanofabrication for high-performance technologies In the CNR laboratories, we have developed new low costs fabrication methods based on bottom-up technology, to exploit and improve the properties of technologically-relevant functional materials, such as organic semiconductors, magnetic materials and metal-organic frameworks. Our fabrication methods overcome the typical downsizing technology for producing micro, and nanodevices from bulk materials, but rely on a bottom-up strategy that exploits the self-organizing properties of the molecules in a spatially confined system; allowing their hierarchical structuration over multiple length scales. In particular, this is achieved by the use of external agency, such as micro, and nanostructured stamps, that control the size, density, and position of the supramolecular assemblies (Figure ). The end result is improving of the functional properties (i.e. semiconducting properties) of the processed material due to the combination of their intrinsic properties (i.e. related to his chemical Figure. Polymeric printed nanostripes with bottom-up structure) with the properties arising from his assembly and spatial fabrication. Inset: CMOS-like voltage inverter (left); Schedistribution at the micro, and nanoscale. Recently, we have shown me of fabbrication processons. that structuring a semiconducting copolymer in oriented nanometric stripes, using our easy-to-handle and low-cost techniques, his electrical properties can be enhanced and exploited to develop high-performance ambipolar organic field effect transistor and CMOSlike voltage inverter, reaching in nanostructures the performance of Contact: Massimiliano Cavallini - m.cavallini@bo.ismn.cnr.it single crystals. The techniques we have developed have been pa- ISMN - Bologna tented and well described in a protocol (Cavallini et al, Nat. Protoc. 2012, 7, 1668-1676).

TRL: 3

ICT SECURE SOCIETIES

Metal oxide nanowires for functional devices SENSOR activities are in the field of material research for functional applications. Mainly bottom-up fabrication techniques are used. Highly ordered, crystalline, quasi 1-dimensional (1-D) nanostructures of ionic metal oxides have been prepared. Nanowires, nanorods, nanotubes have an increasing scientific interest, 1-D systems and single-crystalline 1-D nanostructures are emerging as building blocks for a new generation of electronic, and optoelectronic nanometer-scaled devices with superior performances. Different oxides have been prepared at SENSOR. Mainly by physical techniques. Zn, Sn, Cu, W, Nb and In oxide nanowires (NWs) have been synthesized in form of quasi monodimensional single crystals on many substrates (glass, silicon, alumina, kapton, and MEMS. The prepared nanostructrure are fully characterized in terms of morphological, structural, electrical and optical properties in form of bundles, vertically aligned NWs or single NW. Nanowire applications at SENSOR range from Chemical Sensing, Dye and Quantum Dots based solar cells, Single Nanowire Transistors for biosensing, Electron sources for X ray emitters, Innovative electrodes for Electrochemical Biosensing, Innovative Electrodes for Li batteries, Thermolectrics, to nanowires for optoelectronics. With regards to enterprises... On this topic, we collaborate with several companies (EADS, SACMI, SIEMENS, and many others). We can offer: metal oxides nanostructures and devices fabrication, fundamental and functional characterisation.

Contact:

Fabrication of a MOX NW gas sensor.

WO3 nanowires on alumina substrates.

SnO2 nanowires on sensing transducer.

Elisabetta Comini - elisabetta.comini@ing.unibs.it INO - Brescia

TRL: 4

Magnetically enhanced memristors We have successfully combined in a two terminal hybrid organic-inorganic device memristive and spintronic magnetoresistive properties (MEM). Such devices based Alq3 organic layer confined between two spin polarized electrodes are known to show at low voltages (< 1 V) a giant magnetoresistance (GMR) effect ascribed to the injection and transport of spin polarized currents between the two electrodes. At higher voltages (1–3 V) a strong non-volatile electric resistive switching enables the device with a typical memristor behavior. Magnetic and electric field effects are interwoven: a pre-applied programming voltage can reduce or even cancel the magnetoresistance output measured at low biases. Noteworthy, a single MEM device can operate as a logic gate which was demonstrated on the basis of two selected logic operations, AND and IMP. MEMs are fully compatible with the simple cross-bar geometry, typical of 2-terminal devices, and fully exploit all of its technological advantages. At the same time, the device properties are considerably enriched by using the magnetic field as a non-contact third terminal.

Schematic layout. From the top: Co ferromagnetic electrode, followed by a thin barrier, a layer of the organic semiconductor Alq3 and the bottom ferromagnetic oxide electrode.

With regards to enterprises... We own the patent “Logic gate and a corresponding method of function” WO 2013050983 A3. On this topic we collaborate with Thales and M-Solv. We offer: expertise on resistive and magnetic memory, fabrication and characterization of hybrid devices for various applications including flexible electronics.

Contact:

Valentin Alek Dediu - v.dediu@bo.ismn.cnr.it ISMN - Bologna

Electrical signals govern in large part the functionality of our human body. Interfacing them provides important means for medical diagnosis and therapy and is at the heart of modern medical treatments based on so-called electroceuticals. New generations of implantable electroceuticals have to be developed which combine the bioelectric medical activity with minimal invasiveness during device implantation, operation and removal. Towards this goal, our research team of material scientists and electrical engeneers optimizes materials and their processing into devices which allow transduction of bioelectric signals but maintain soft and conformable mechanical properties to assure high biocompatibility. For example in a recent contribution entitled “Electrocardiographic Recording with Conformable Organic Electrochemical Transistor Fabricated on Resorbable Bioscaffold“ we present an ultrathin electrical transducer fabricated on a fully resorbable polymeric substrate. The active material of the transducer is a conducting polymer that integrates soft mechanical properties with fast and sensible potentiometric sensing in physiological conditions. The recording of small bioelectronic signals is demonstrated by measuring the electrocardiographic activity in humans. The work paves the way towards simple bioelectronic interfaces processed on implantable bioscaffolds for recording and stimulation in muscular or nervous tissue. Contact:

Mauro Murgia - m.murgia@bo.ismn.cnr.it ISMN - Bologna ECG recording with conformable organic transistor fabricated on a resorbable bioscaffold.

ICT SECURE SOCIETIES

TRL: 4

Soft and bioresorbable electronic interfaces for bioelectric recordings

TRL: 4 - 5

CdZnTe crystals for room temperature operating X- and gamma-ray detectors CdZnTe is an ideal semiconductor material for the realization of direct conversion, spectroscopic, room temperature operating X- and gamma- ray detectors. By means of standard photolitography procedures, imaging capabilities are also implemented. At IMEM , the technology for the growth of CdZnTe crystals, wafers cutting and polishing, contact deposition, and device bonding have been developed. Several detectors have been tested in lab. Projects are ongoing for testing these detectors in industrial relevant environments. With regards to enterprises... CdZnTe-based detectors are extremely important for different applications fields ranging from security, to environmental control, to medical applications. A spin-off company proposal producing CdZnTe-based detectors has been recently submitted.

Contact:

Andrea Zappettini - zapp@imem.cnr.it IMEM - Parma

TRL: 7

ICT SECURE SOCIETIES

Time-temperature integrators

Time-temperature integrator (TTI) are device capable to record the thermal history of a system. The development of TTIs is of high interest for the traceability of perishable products, whose temperature must be maintained throughout a shipping or life cycle (e.g. food, pharms, drugs, but also some electronic devices). The most reliable TTIs are based on electronic sensors such as Radio Frequency IDentification (RFID) tags, whose cost and complexity limit their large-scale penetration in the market. Further approaches to TTIs are based on other irreversible changes of some properties, these devices are very efficient for a single threshold temperature measurement; however, their complexity and fabrication hurdles dramatically increase when it is required to monitor a spectrum of temperatures. ISMN in collaboration with ISOF has been developed a new technological approach based on the use of polymorphic crystalline aggregates controlling the spatial distribution of polymorphs. CNR proved a new application of fluorescent thin films in nanostructured labels where the exposure to a specific temperature tailors the fluorescence emission advantageously exploiting two phenomena that are usually drawbacks for technological applications, such as polymorphism and recrystallization. These properties allow us to fabricate patterns with time temperature integration functionalities in an impressive range of temperatures (i.e. from room temperature to 200 째C) by using a single active material. We demonstrated the feasibility of the approach by a simple fabrication method, using model compound, however, this approach is general and can be extended to all functional materials, whose fluorescence, or color, or other photophysical properties, change irreversibly with temperature.

Temperature

Evolution of the fluorescence in patterned film recorded by a CCD versus the temperature.

Contact:

Massimiliano Cavallini m.cavallini@bo.ismn.cnr.it ISMN - Bologna

TRL: 2

Electron beam lithography for miniaturized devices The field of chemical sensors for molecule detection has benefited by the use of nanowires because of the uncommon and interesting properties that were revealed for these nanostructures. Large variation in bulk electrical or thermal conductivity, structural stability upon high temperature operation, high degree of crystalline ordering, have unveiled the potential for the sensing field and have opened up new perspectives of application and for the realization of novel device architectures. Electron beam lithography is the technique of choice for the fabrication of nanostructured devices with metal deposition methods such as thermal evaporation or sputtering. Lithography is a well-used technique in the semiconductor industry to fabricate devices using the “top-down” approach. Moreover, even in “bottom-up” approach both optical- and electronic- lithography has been largely used to fabricate electrical contacts on substrates to prepare different types of devices. Lithography was used to prepare also single nanowire device.

SEM image of a single-nanowire device fabricated by EBL and tested through nanomanipulators.

Contact:

Matteo Ferroni - matteo.ferroni@unibs.it INO - Brescia

Multifunctional materials are advanced materials which accomplish multiple performance objectives in a single material system. They exhibit a wide variety of physical properties like piezo- and ferro-electricity, colossal magnetoresistance, multiferroicity and giant capacity. These materials play a crucial role in the next-generation of intelligent devices and sensors, smart homes, autonomous devices and robotics. The activity of our group is focused on process, study and development of new ceramic materials with multifunctional properties with high quality, in the different compositions, forms or/and integrated together in complex heterostructures. Our materials covers a large scale of applications being used like sensors, actuators and transducers (Fig. 1b) in hydrophone (Fig. 1c), electric and magnetic memories or in miniaturized antenna substrate (Fig. 1d). Our recent performance was to obtain miniaturized magneto-piezoelectric structures like bar-shaped piezo-ceramic rods (Fig. 2 a.) or plates (Fig. 2b. and c.). We also perform advanced material characterizations to analyze and get insight into different physical properties of innovative materials (dielectric, piezoelectric and ferroelectric characterization).

Fig. 1 Powders, materials and prototypes obtained in our Laboratorie.

1 mm

With regards to enterprises... We developed these materials in collaboration with CNR-ISC, University Departments, within contracts with Companies or national (Project ANTENNA Fig. 2 Piezo-magnetic structures. PNR-M 2010) or Eu Projects (Cost Actiom MP 904 SIMUFER). We offer: materials development, protyping, and integration of bulk mateContact: rials and thick films. Carmen Galassi - carmen.galassi@istec.cnr.it ISTEC - Faenza

ICT SECURE SOCIETIES

TRL: 4

Multifunctional ceramic materials

TRL: 5

Decontamination powders for highly-toxic chemical and biological (CBRN) warfare agents The development of efficient tools for the detoxification of hazardous chemical and biological weapons leads to the improvement of the societal security in terms of better prevention, improved protection and minimization of negative consequences. Current conventional decontamination techniques rely on thermal decomposition or stoichiometric chemical degradation of toxic agents and need huge amounts of reactants and energy via poorly sustainable routes. CNR-ISTM has a broad expertise in the design and set-up of innovative catalysts for the safe and clean transformation of chemicals. The winning strategy is to move from stoichiometric to catalytic chemical decontamination, based on reactive sorbent materials, able to convert highly toxic species into non-toxic by-products under very mild ambient conditions. The proposed solid catalysts are based on cheap and robust nanostructured inorganic oxides in the form of powder and promote the oxidative degradation of toxic compounds by molecular oxygen or air. With regards to enterprises... This R&D activity is carried out within the NATO Science for Peace and Security Project “NanoContraChem”. Ongoing collaborations with SME: Nanodiagnostics srl and NBC System srl. Design of porous and layered inorganic oxides for the Expressions of interest by the Italian Ministry of Foreign Affairs and Ukrainian selective abatement of chem and bio hazardous agents. Ministry of Defence. We can offer: know-how for the design and development of decontaminaContact: tion/abatement catalysts; innovative formulations at multi-gram scale; tests Matteo GUIDOTTI - m.guidotti@istm.cnr.it under working conditions and specific scientific consulting. ISTM - Milano

TRL: 4

ICT SECURE SOCIETIES

Metal oxide nanowire based gas sensors for security applications Metal oxide nanowires have been widely reported in literature as suited materials for the development of efficient gas sensors, mainly exploiting the chemiresistor configuration. In this field, SENSOR Lab of CNR-INO is active in the development of chemiresistors based on different materials such as SnO2, ZnO, and their functionalization with inorganic receptors. These new materials based on nanowire technology have been integrated into a sensor array (electronic nose system) together with chemiresistors prepared by traditional thin film technology and observing an increased capability to reduce false alarms in the detection of chemical warfare agents simulants. A further transduction mechanism based on ionization of molecules adsorbed over the oxide surface (surface ionization, shortened as SI) is under development. With respect to chemiresistors, SI devices feature an increased sensitivity toward molecules containing ammine functional group such as drugs. These technologies are under test in different security fields including water pollution and border security. With regards to enterprises... In this topic we’re collaborating with AIRBUS GROUP (DE), CTECH LTD (UK), SACMI S.C. (IT), Gilardoni SpA (IT). We can offer: sensor design, sensors and applications development, fabrication, sensor characterization and calibration, development of customized electronic noses for specific applications.

SnO2 nanowire chemiresistor: calibration to DMMP (Sarin nerve agent simulant).

Surface i o n i za t i o n (SI) device layout.

Contact:

Andrea Ponzoni - andrea.ponzoni@unibs.it INO - Brescia

TRL: 3

Alumina-based ceramic materials for electronic packaging Alumina, in its α form, is widely used as ceramic substrate for microelectronic applications. When alumina is to be used in the field of microwave frequencies - as, for example, in the construction of radars for military defense - special features are required. In particular, alumina substrates with higher dielectric constant and low tangent loss in the frequency range of the X band (≈10 GHz) are highly desirable in order to reduce the size of the printed circuits. A larger thermal conductivity is also required to optimize the thermal management of the dispositive. Moreover, a thermal expansion coefficient closer to that of silicon is specifically recommended for wafer packaging technologies. Finally, flexural strength and elastic modulus should be low enough to reduce the substrate fragility. We modify the dielectric, mechanic and thermal properties of alumina through the addition of specific dopants. One-pot sol-gel methodologies and combustion-based procedures are used to warrant the homogeneous dispersion of the dopant. Moreover, the modality of introduction of the dopant has a deep influence on the final properties of the materials. We also developed a scale-up protocol which allows to produce around 100g of powder with high reproducibility. With regards to enterprises... This activity is carried out in collaboration with SELEX ES in Palermo. We can offer: synthesis of alumina powders for microelectronic applications and characterization of their structure, surface, morphology and texture.

Au circuit onto an alumina ceramic substrate.

Alumina

10 μm

Doped alumina

10 μm SEM images of sintered alumina with and without dopant addition.

Contact:

Francesca Deganello - francesca.deganello@cnr.it ISMN - Palermo Cristina Riccucci - cristina.riccucci@mlib.ismn.cnr.it ISMN - Roma

An all-optical gas sensor device has been demonstrated: it is based on ZnO [1] or SnO2 [2] single crystalline nanowires. The transducer principle makes use of adsorbate-induced changes in the photoluminescence (PL) emission intensity to indicate changes within the gas ambient. Detection of NO2 can be achieved at very low level (100 ppb attention level for NO2 pollution), while detection of ethanol and CO is much less favored. For chemical sensor with resistance transducer mechanism the detection is performed at temperatures between 200 °C and 400 °C. Direct electrical powering of gas sensors for heating and detection, however, is a potential problem as sparking and ignition might inadvertently occur. Instead in the current device, the transducers are operated at room temperature so ZnO nanowire based optical sensors can be used for NO2 detection in explosive environment. [1] C. Baratto et al. Sens. & Act. B 140 (2009) 461–466 [2] G. Faglia et al. Applied Physics Lett. 86 (2005) 011923

SEM images of ZnO nanowires. Variation of the area under PL peak due to NO2 introduction.

PL spectrum of ZnO nanowires.

With regards to enterprises... We can offer: expertise and facilities in sensor design, sensors and applications development, fabrication, sensor characterization and calibration. Requested Cooperation: joint collaboration for funded projects, development of new applications.

Contact:

Camilla Baratto - camilla.baratto@unibs.it INO - Brescia

ICT SECURE SOCIETIES

TRL: 3

Optical gas sensor based on metal oxide nanowires

TRL: 4

Nanoporous materials for light management and chromatic sensitive systems Nowadays nanoporous materials can have many kinds of geometries, structures, chemical compositions and possess unique surface, structural and optical properties. Among them colloidal structures are an excellent example of how is possible to create specific nanoporous structures that allow to control the light propagation. The engineering of the colloidal systems produces the formation of iridescent color by optical diffraction, that can be exploited in order to develop low cost, high sensitive and responsive materials that modify their optical response (color) upon external stimuli. They can be applied in several technologically important fields such as such as color displays, optically active components, and chemical, physical and biological sensors. (a)

(b)

Typical nanoporous structures, from top, clockwise: direct, disordered, inverse, and hybrid.

Contact:

Andrea Chiappini - andrea.chiappini@ifn.cnr.it Cristina Armellini (IFN-FBK), Iustyna Vasilchenko (UniTN-IFN), Anna Ĺ ukowiak (PAS Poland), Alessandro Carpentiero (IFN), Claire Duverger Arfuso (UniLeMans), Khiem Tran Ngoc (ITIMS Hanoi), Anna Piotrowska (DICAM UniTN â&#x20AC;&#x201C; IFN), Brigitte Boulard (UniLeMans), Giancarlo C. Righini (Centro Fermi), Daniele Zonta (DICAM UniTN), Maurizio Ferrari (IFN); IFN - Roma

(c)

With regards to enterprises... We offer the know-how on the synthesis and realization of colloidal systems for the development of optical sensors for different applications.

(a) Solvent chemical sensor, (b) paper ink, (c) strain sensor

TRL: 6

ICT SECURE SOCIETIES

Quantum random number generation in a silicon transistor Generation of true random numbers is not only a scientific task with major impact on genetic algorithms and Montecarlo simulations, but it consists of a key security task as classical encryption requires high quality random numbers, not obtainable with pseudo random number generated via software. Even if nominally true random number generation is nowadays embedded in computer processors, the lack of control on the commercial hardware and possible software and hardware attacks makes internal random number generators unreliable for strong security purposes. We developed a method to convert multiphonon-assisted single-electron tunneling events in a transistor producing random noise into a stream of true random bits. The direct conversion of switching times into binary number provides more than 1 Mbit/s per transistor. Novel methods have been explored to further enhance such rate. The bits prove robust against Die hard and NIST entropy tests. The extremely reduced number of electronic components required to produce the stream of data and the full CMOS compatibility of the transistor employed as true random number source makes this route viable towards compact and portable high secure encryption. With regards to enterprises... On this topic, we are pleased to collaborate with enterprises by offering our know-how as well as ultra-fast electrical characterization and CMOS circuit design.

The single electron fluctuations are generated by the tunneling from/to the channel of a transistor and a defect at the Si/SiO2 interface.

The stream of bits generated by the quantum fluctuations consists of true random numbers passing Die Hard and NIST tests at more that 1 Mbit/s/transistor.

Contact:

Enrico Prati - Enrico Prati enrico.prati@cnr.it; IFN - Roma; Davide Liperoti (Univ. Milano e IFN), Giorgio Ferrari (Polimi-DEIB)

TRL: 5

Nanostructured membrane coating for wastewater treatment The present research is directed to the production of highly hydrophilic and antimicrobial flat membranes using polymerisable bicontinuous microemulsion (PBM) for water treatment. In bicontinuous microemulsion the oil channels can be polymerized to form the matrix of liquid membranes while the aqueous phase remains unchanged. In particular, the PBM is applied as coating material of commercial membranes. PBM coated membranes have been successfully used for water purification in Membrane Bioreactor (MBR) applications. However, the possibility of tailoring the bicontinuous structure and pore size of the PBM coated membranes allow to extend their application also to other membrane pressure driving processes. The PBM coated membranes have been produced at lab scale and, then, assembled into modules and tested in MBR plants for textile waste-water treatment. With regards to enterprises... The present work is of interest to membrane companies for improving and tailoring existing commercial membrane employed in water treatment. A. Figoli et al. Bicontinuous Microemulsion Polymerised Coating for Water Treatment, Patent n째. IT GE2013A000096, filed on 27/09/2013

Figure 1: Preparation of the nanostructured PBM membrane coating.

Figure 2: Module fabrication starting from the PBM membrane coating.

Contact:

Alberto Figoli - a.figoli@itm.cnr.it ITM - Rende (CS)

Nanostructured hybrid films, consisting of gold nanoparticles functionalized with a polymer matrix or with bi-functional stabilizers, have been used for the development of sensitive and selective sensors. By varying the nature of chemical groups at the surface of gold nanoparticles, it is possible to tune the affinity toward selected target species. In particular, gold nanoparticles embedded into chitosan-based films were successfully used to develop electrochemical sensors for the determination of antioxidants in beverages, such as wine and fruit juices. Chitosan is a biocompatible and biodegradable polymer which can be obtained from crustacean shells and it is worth noting that these nanocomposite films were prepared by using green and facile preparation procedures. Chitosan films act as molecular sieves by increasing the selectivity of the sensors, whereas gold nanoparticles greatly improve the electrochemical response by improving the sensitivity. The nanostructured films were used for the functionalization of screen printed electrodes, thus allowing the production of low cost and portable devices. These sensors were tested for the analysis of complex matrices, such as wine, and the polyphenol index was determined. In contrast to classical approaches, the proposed procedure offers high sensitivity and rapid response time.

Partial deacetylation of chitin

AuNPs synthesis

CHITOSAN

AuNPs-CHITOSAN OH O

H 2N

HO Au H 2N O HO

NH2 O OH

OH O

O OH

NH O

O OH

NH2 Au OH O

NH3+

Preparation of AuNPs-chitosan films from crustacean shells.

Screen printed electrodes.

Contact:

Gabriella Di Carlo - gabriella.dicarlo@ismn.cnr.it Antonella Curulli - antonella.curulli@ismn.cnr.it ISMN - Roma

ICT SECURE SOCIETIES

TRL: 4

Highly sensitive sensors based on nanostructured hybrid films for the analysis of beverages

TRL: 3

Advanced membranes for efficient wastewater treatment Water pollution and the decreasing access to clean water have attracted increasing attention in recent years towards new efficient wastewater treatment techniques. Conventional approaches for organic pollutants removal from industrial effluents, such as adsorption, coagulation, photo-degradation and biodegradation, have relevant economic and technical limitations. Membrane separation is considered today a feasible and promising option for wastewater treatment. However, the development of advanced membranes with tailored properties is a key issue to be addressed in order to better exploit the potentialities of membrane science and technology. Important approaches toward this aim are in progress at the ITM-CNR, including: - surface functionalization by coating of functional layer or grafting of functional groups on the membrane surface or inside the pores - development of polymers membranes in the form of composite or mixed matrix membranes in which an organic and an inorganic phase coexisting in order to have synergistic effect on transport properties, mechanic and thermal stability, anti-fouling properties. - in-situ non destructive and non invasive probing of membrane and interface by electrochemical impedance spectroscopy.

Sem image of a composite membrane comprising a thin selective layer with a porous support.

Sem image of a mixed matrix membrane containing orienWith regards to enterprises... ted carbon nanotubes bundles in the selective layer. ITM-CNR collaborates with several national and international reserch groups (University of Calabria, University of Torino, King Abdulaziz City Contact: for Science and Technology (KACST, Kingdom of Saudi Arabia), etc.) Enrica Fontananova - e.fontananova@itm.cnr.it ITM - Rende (CS) We can offer: Membrane development and characterisation.

TRL: 9

ICT SECURE SOCIETIES

Impact of postharvest safety

γ-irradiation on food quality, traceability and

Treatment of food with ionizing radiations from x-ray, electron beam or γ-ray sources (60Co or 137Cs) aims at destroying pathogens and microorganisms causing spoilage, and at preventing loss from premature ripening and germination (Directive 1999/2/EC). So far, only dried aromatic herbs, spices and oily seasonings are explicitely authorized for irradiation in the EU, but the list may eventually grow to include dried fruit and cereal, and derivatives of poultry meat and offal. Furthermore, in non-EU Countries, legislation is different, and knowledge should be expanded to correctly manage and label imported food. Food irradiation is a well-established technology, and research in this field is intensifying in view of a widespread application to fresh produce and meats. Hydrocarbons and 2-alkylcyclobutanones from radiolysis of oily foods are already analyzed through standardized methods in GC and GC-MS. However, the effect of ionizing radiations on metabolites of nutraceutical interest, such as sterols, phytohormones, proteins and essential aminoacids is still to be investigated. From the point of view of traceability and safety, the impact of ionizing radiations on target metabolites, and chemical changes yielding undesired substances requires intense investigation.

With regards to enterprises... We collaborate with Contento Trade Srl and Enza Zaden Italia Srl. In our Institute a γ-ray 60Co source is available, that can be used with pure substances, mixtures, matrices of biological origin such as raw and processed food, or synthetic materials as in food packaging. The outcome of radiolysis is assessed through separation techniques (GC and LC) hyphenated with mass spectrometry; ATR FT-IR, optical microscopy, AFM.

γ-cell at IMC

Schematic of a typical food irradiation plant.

Contact:

Ornella Ursini - ornella.ursini@cnr.it; Francesca D’Acunzo - francesca.dacunzo@cnr.it IMC - Roma

Advanced Materials

...and More This sections is referred to the application of advanced materials in Cultural Heritage and other horizontal applications such as advanced technologies and modeling. The latter is very important tool to design and predict the behaviors of materials and related systems/structures.

number of contributions in this section

TRL: 4

Superhydrophobic and self healing materials for cultural heritage protection Protection of outdoor and indoor cultural heritage materials from humidity and corrosion can efficiently benefit of superhydrophobic coatings. High contact angles above 150° and a very small hysteresis are often obtained by combining roughness and chemistry of the surfaces. Mixed organic-inorganic systems providing self-healing properties have been prepared and their aging resistance has been evaluated as a function of the composition and thickness of the coating. SH surfaces under investigation can be prepared by different preparation methods with the aim to provide more resistant and long lasting coatings. No wetting of water drop in contact with a superhydrophobic surface.

Patent: BrevGE 2005 A 87

Self –cleaning properties of superhydrophobic surfaces.

Contact:

Flagship Project RITMARE SP1 WP2 Friction and CO2 reduction WP5 antifouling and anticorrosion coatings

Michele Ferrari - m.ferrari@ge.ieni.cnr.it Authors:Michele Ferrari, Libero Liggieri, Francesca Ravera IENI - Genova

AND MORE Cultural Heritage

TRL: 4

Advanced materials for the protection of bronze artefacts Bronze artifacts, after their finding, are subjected to a cyclic process of dissolution of copper, known as “bronze disease”. The corrosion phenomenon is induced by the exposure of the reactive cuprous chloride (formed during the burial at the interface between the surviving metal and the corrosion patina) to the atmospheric moisture and oxygen. Diamond-like carbon (DLC) deposited by plasma enhanced chemical vapor deposition (PECVD), have been developed as successful strategy for the protection of the ancient bronzes. With this aim in mind the properties of the amorphous DLC coatings, strictly associated with the sp2/ sp3 ratio and the hydrogen content, have been conveniently adjusted by selecting the appropriate deposition parameters. Therefore it has been possible to develop transparent thin nano-structured DLC coatings, able to modify the corrosion resistance of the artifacts. The protective effectiveness of the DLC films have been evaluated under aggressive conditions for bronzes, revealing the protective role of the coatings. DLC films can acts as barrier layer, insulating the surface of the ancient objects from the surrounding environment, ensuring the long-term protection for the archaeological bronzes.

Bronze artifact affected by “bronze disease”. Cross-section of a bronze archaeological artifacts which shows the stratified corrosion products grown during the burial.

DLC

DLC films (deposited on half of the alloy) did not affect the aesthetical appearance of the patina.

XPS results of unprotected and DLC-coated Cu-based alloys subjected to an accelerated degradation procedure show the presence of Cu(I) and Cu(II) compounds on the surface of the unprotected alloy and un-reacted CuCl2 micro-grains on the surface of the DLC-coated alloy, indicating the protective effectiveness of the DLC coating.

Contact:

F. Faraldi - federica.faraldi@ismn.cnr.it, D. Caschera - daniela.caschera@ismn.cnr.it G.M. Ingo, C. Riccucci, A. Mezzi; ISMN - Roma

Modeling and simulation for carbon nanostructures

TRL: 1

Carbon nanotubes are complex structures that can be thought of as graphene sheets wrapped up into a cylinder. Those big molecules have peculiar electro-mechanical properties which are strongly influenced by geometry. For instance, they can be either metals or semiconductors, according to the tube diameter or to the wrapping angle. In nano-electronics they have great potentiality for high-speed and low-voltage switching in Field-Effect-Transistors, or for generating ultra-high frequencies without resorting to heterostructures.

A zig-zag single-walled Carbon Nanotube.

In mechanics, CNTs are nowadays employed as reinforcing fibers in advanced composite materials. Their application as sensors and actuators are presently still in progress. Modeling and simulation of such devices, which are driven by complex physical phenomena, are fundamental tools in order to predict their electro-mechanical behavior, to access their performance limits and to design new configurations.

Electrostatic potential at thermal equilibrium for a zig-zag CNT-FET

Contact:

Paola Pietra - pietra@imati.cnr.it Ulisse Stefanelli - Ulisse.stefanelli@imati.cnr.it IMATI - Pavia

Modeling and simulation for shape-memory devices

TRL: 1

Shape-memory alloys are active materials: comparable large strains can be induced by mechanical, thermal, or magnetic stimuli. The peculiar thermo-magneto-mechanical properties of shape-memory alloys are at the basis of a variety of innovative technologies., ranging form actuators and sensors, to Aerospace and Seismic Engineering, to Biomechanics. A reference application are intravascular protheses (see Figure). The accurate description and the numerical simulation of the complex coupling dynamics in these materials is the key to device design and optimization. Actual material knowledge has to be integrated in a reliable constitutive models. Mathematics is involved in this process as a major tool in order to let the modeling more accurate, the simulations more reliable, and the design more effective.

Finite-element simulation of the deployment of a NiTi stent in situ.

Contact:

Ulisse Stefanelli - Ulisse.stefanelli@imati.cnr.it IMATI - Pavia

AND MORE Modelling

Our activity is centered in developing innovative models for shape-memory behavior. We are presently including in the picture fatigue and magnetic effects as well as grain-microstructure evolution. The corresponding models are then studied from the theoretical and computational viewpoint. In particular, they are validated agains the available material data.

TRL: 1

Computational design of advanced materials Despite the massive increase of computational resources registered in the past decade, an efficient in silico material design has still to rely on robust multi-level protocols, that allow for the simulation and understanding of large, complex and often heterogeneous systems. In this scenario, the Theoretical and Computational Chemistry lab @ICCOM groups different expertise, that range from highly accurate quantum mechanical techniques, to density functional methods, to molecular dynamics simulations of extended systems. Most of these approaches can be integrated in multi-scale procedures, allowing us to investigate large complex systems maintaining a microscopic insight often not accessible to experiment. CO2 recycling. Some of these protocol have already been coded in in-house software, and employed in the investigation of specific advanced devices, as heterogeneous catalyst based on doped metal nano-particles for CO2 recycling, smart mechanochromic polymers with tunable optical response, multi-chromophoric supramolecular aggregates for artificial photo-synthesis, Development and application of multi-level integrated approaches for advanced materials. biologically relevant systems, single-molecule magnets and electronic devices. Contact: With regards to enterprises... On this topic we can offer: development and implementation of ad hoc screening protocols, design support and simulation of prototype materials.

thc2_lab@pi.iccom.cnr.it Julien Bloino, Alessandro Ferretti, Alessandro Fortunelli Susanna Monti, Giacomo Prampolini, Fabrizio Santoro, Giovanni Villani ICCOM - Pisa

AND MORE Modelling

TRL: 1

Computational modelling of bio-metal interfaces The molecular functionalization of surfaces finds numerous applications in the field of bio-electronic; the functionalization with bio-molecules provides materials for medical implants with improved biocompatibility. Computational modeling of such interfaces may direct the development and optimization of new bio-materials and it is essential for the interpretation of experimental studies as those based on synchrotron radiation spectroscopies which have the advantage of being chemically selective and sensitive to the orientation of the adsorbed molecule. The computational procedure is applied to atomistic models that include the surface (a many layer slab), a number of bio-molecules and, possibly, a large number of molecules of water for a realistic representation of the biological environment. The dynamics of these models is simulated by molecular mechanics with reactive force-fields that are parameterized with ab-initio calculations and quantum dynamics on smaller systems. This bottom-up procedure transfers the accuracy of the quantum description to the computationally faster classical method, maintaining the capability to describe the chemical transformations occurring at the bio-inorganic interface. Quantum methods are employed for the simulation of the x-ray photoemission and absorption spectra of the main adsorbate structures, so as to correlate experimental measurements with structure and chemical composition of the interface. With regards to enterprises... We collaborate with the Dept. of Biotechnology of the Royal Institute of Technology (Sweden) and with experimentalists at synchrotrons ELETTRA (Trieste) and MAX-Lab (Sweden). We can offer expertise in the characterization and design of bio-metal interfaces for medical applications and sensors.

Binding energy of para-nitrolaniline (PNA) adsorbed on a gold surface (Au(111)).

Glycine (top) and di-glycine (bottom) adsorbed on a copper surface (Cu(110)) and the corresponding O1s, N1s ,C1s photoemission spectra (right).

Contact:

Vincenzo Carravetta - carravetta@ipcf.cnr. it IPCF - Pisa

TRL: 1 - 2

Modelling hybrid and perovskite solar cells Hybrid/organic photovoltaics has witnessed a huge research effort in the last two decades, leading to the first commercial products. Dye-sensitized Solar Cells (DSCs) have maintained a clear lead in efficiency and stability over competitive technologies, with top certified efficiency exceeding 11% and lab-cell efficiency above 13%. The field has been completely revolutionized in 2012 by the first reports of high efficiency solid-state DSCs based on organohalide metal (Sn, Pb) perovskites. These materials, used as light-absorbers in DSCs and electron conductors in new solar cell architectures, now approach 20% efficiency. First-principles computational modeling has been widely applied to the DSCs field, and more recently to perovskite solar cells. The computational design and screening of new materials, with tailored and engineered characteristics for improved device performance and stability, has played a major role in advancing the DSCs field. Suitable modeling strategies also offer an inaccessible atomistic view of the crucial heterointerSimulated maximum photocurrent generated by two or- faces ruling the device operational meganohalide metal (Sn, Pb) perovskite solar cells. chanism. With regards to enterprises... The Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO) at CNRISTM, Perugia, is a recognized leader in the advanced modeling of new materials. We have coordinated the FP7-ENERGY-2010 project â&#x20AC;?ESCORTâ&#x20AC;? devoted to DSCs together with the leading European industrial partners (Dyesol), and are currently involved in the only FP7-funded project on perovskite solar cells (Oxford PV partner). We are co-inventors of three patents on solar cells sensitizers.

Schematics of possible charge generation processes in DSCs and perovskite solar cells.

Contact:

Filippo De Angelis: filippo@thch.unipg.it Simona Fantacci: simona@thch.unipg.it Web site: www.clhyo.org ISTM - Perugia

AND MORE Modelling

TRL: 4

Optical drawing of liquid droplets via plasmon resonance of gold nanorods

Lab-on-a-chip systems are of great interest in biotechnological and chemical applications. The approach of a droplet-based system has the advantage to be compatible with wall-free structures, so that the operations can conveniently performed on the surface of a planar substrate. We have realized (in co-operation with INO, Naples) a laser-assisted electro-hydrodynamic technique for drawing microlitre droplets. The technique is based on the successful combination of a near infrared source with the plasmon resonance of gold nanorods patterned onto the surface of a pyroelectric lithium niobate crystal. The stimulation of the pyro-electrohydrodynamic effect is performed optically by a compact laser source launched in fibre. The needed thermal gradient is ensured by the efficient photothermal conversion of the gold nanorods during the plasmon resonance induced by laser illumination. This allows to generate the pyroelectric effect with high precision and selectivity and the induced electric field is able to exert a significant hydrodynamic pressure onto an underlying reservoir, thus leading to the dispensing of small droplets (ďż˝10 Îźm) from a base plate to a target plate. The method has been applied to different kinds of liquids, including oil and water with a rather fast response. With regards to enterprises... We are looking for companies in the field of biomedical and analytical diagnostics, sensors, micro-optics, etc. interested in the development/exploitation of the technology. More details on: de Angelis et al. Applied Physics Letters 103, 163112 (2013).

View of the pattern of gold nanorods film on the lithium niobate crystal plate.

Drawing of the droplets dispenser.

Contact:

Marella de Angelis - m.deangelis@ifac.cnr.it Roberto Pini - r.pini@ifac.cnr.it IFAC - Firenze

AND MORE Advanced Technologies

TRL: 1

Study of scintillators materials with time-resolved optical spectroscopy

With regards to enterprises... This kind of scintillator materials can be employed Â in homeland security, environment monitoring and medical imaging (computed tomography) fields.

emission intensity (a.u.)

Radiative recombination processes were studied in the new class of inorganic single crystal scintillators, so called multicomponent garnets (Gd,Y,Lu)3(Ga,Al)5O12:Ce, which provide the highest light yield in the group of high density fast oxide scintillators. The technique of the measurement of luminescence decay under excimer or nitrogen laser excitation and detected by photomultiplier in current regime coupled to digital oscilloscope appeared extremely useful to monitor the delayed recombination processes due to thermal ionization or tunneling processes in the excited state of Ce3+ center, Fig. 1. Luminescence decay measured over 4-5 orders of dynamical and time scales provides unique possibility to observe well both processes in a single curve and compare quantitatively their intensity ratios and temperature dependences.

GAGG: 1% Ce exc = 337 nm, em = 510 nm

-1

radiative recombination : prompt and delayed part

-2

-3

-4

120 K 150 K 170 K 205 K 230 K 293 K laser

-5

-6

-8

-7

-6

10 time (s)

-5

-4

Fig. 1- Temperature dependence of photoluminescence decay of Ce3+ center in Gd3Ga3Al2O12 single crystal host.

Contact:

Daniela Mugnai - d.mugnai@ifac.cnr.it Gian Paolo Pazzi - pazzi@ifac.cnr.it Pasquale Fabeni - p.fabeni@ifac.cnr.it Anedio Ranfagni - a.ranfagni@ifac.cnr.it IFAC - Firenze

TRL: 4

Two-photon circular dichroism for studies of chiral systems Two-photon circular dichroism (TPCD), the nonlinear counterpart of electronic circular dichroism (ECD), is the differences between the two-photon absorption (TPA) cross-sections obtained using left and right circular polarized light. TPCD takes place at twice the wavelength as ECD. This allows for studies of chiral systems in the far to near ultraviolet (UV) region, where ECD cannot be employed due to interferences from strong linear absorption of typical buffers and solvents, besides the scattering exhibited by inhomogeneous samples in this region. Other advantages are high spatial resolution, enhanced penetration depth, improved background discrimination and reduced photo damage to living specimens. TPCD is very sensitive to small structural and conformational distortions of chiral molecules, and therefore, is potentially useful for the fundamental study of optically active molecules. Finally, TPCD has the potential to penetrate into the far-UV region, where important structural/conformational information is typically obscure to ECD. This would enable the discovery of new information about molecular systems of interest such as, peptides, biological macromolecules (allowing for a deeper understanding of diseases like Alzheimer’s and Parkinson’s) and potential candidates for negative refractive index (for the developing of cloaking devices). We have developed the computational protocol and applied it to predict the response of several chiral systems, and collaborate with experimentalists in the field. With regards to enterprises... This is a result of a collaboration between theoretical (prediction of the response of molecules to circularly polarized light) and experimental (measurement of the CD spectra using the Double L-Scan spectrometer) groups, involving also the College of Optics and Photonics, CREOL, University of Central Florida, and ICCOM-Pisa.

TPCD spectrum of an allenoacetilene.

Contact:

Antonio Rizzo - antonio.rizzo@ipcf.cnr. itIPCF - Pisa

TRL: 2 - 4

With regards to enterprises... ISTEC designs, produces and characterizes lab scale prototypes. ISTEC has developed freeze-cast ceramics as bioceramics, UHTC based solar sorbents (CNR Patent MI2012A000583) and ceramics for catalysis and filtration.

ICE

Cold Substrate

1 mm

Schematic representation of unidirectional ice-growth during freezecasting and final microstructure of the ceramic sample.

1 cm

Examples of ISTEC prototypes: UHTC based solar sorbents (up); chemically bonded filters (right).

Contact:

Elena Landi - elena.landi@istec.cnr.it ISTEC - Faenza

1 cm

AND MORE Advanced Technologies

The potential field of application of porous ceramics is increasing; the porosity is a functional property, so that 3D porous ceramics with interconnected and distributed open pores are designed for the specific application. Water-based freeze casting, “ice-templating”, is a novel technique to fabricate porous ceramic 3D structures with main unidirectional oriented pores, a high open porosity and the final components resulting in a lamellar or laminate-like structure. In details, the final porosity network resembles the ice crystals grown during freezing and eliminated by sublimation, thus it can be tuned acting on several parameters, in particular the water content of the slurry and the freezing direction and kinetics. The process is environmentally friendly (compared to other templating methods that use non aqueous medium or polymeric templates, which need to be burned out) and highly versatile. This technique has seen great interest, in particular for the unique structures and properties showed by porous freeze-cast ceramics, which open new opportunities in the field of cellular ceramics.

Freezing direction

Porous ceramics, freeze casting – ice templating

CNR Institutes: list of participants DSCTM – Dipartimento di Scienze Chimiche e Tecnologie dei Materiali

IPCB

IPCB Istituto dei Polimeri, Compositi e Biomateriali - http://www.ictmp.ct.cnr.it/ ictmp/presentazioneIT.html

Main branch: Via Campi Flegrei, 34 - 80078 Pozzuoli NA

ICCOM Istituto di chimica dei composti organo metallici http://www.iccom.cnr.it/

Main branch: Via Madonna del Piano 10 - 50019 Sesto Fiorentino FI

IPCF Istituto per i Processi Chimico Fisici- http://www.ipcf.cnr.it/

Main branch: Viale Ferdinando Stagno d’Alcontres, n. 37 98158 Messina

IENI Istituto per l’energetica e le interfasi http://www.ieni.cnr.it

Main branch: Corso Stati Uniti, 4 - 35127 Padova

ISMAC Istituto per lo studio delle macromolecole http://www.ismac.cnr.it

Main branch: Via Edoardo Bassini, 15 - 20133 Milano MI

ISMN Istituto per lo studio dei materiali nano strutturati http://www.ismn.cnr.it

Main branch: c/o area della Ricerca di Roma 1 - Montelibretti Via Salaria, Km 29,5 - 00015 Monterotondo RM

ISOF Istituto per la sintesi organica e la foto reattività http://www.isof.cnr.it

Main branch: Via Piero Gobetti, 101 - 40129 Bologna BO

ISTEC Istituto di scienza e tecnologia dei materiali ceramici http://www.istec.cnr.it

Main branch: Via Granarolo, 64 - 48018 Faenza RA

ISTM Istituto di Scienze e Tecnologie Molecolari http://www.istm.cnr.it/

Main branch: Via Camillo Golgi, 19 - 20133 Milano

IMC Istituto di Metodogie Chimiche http://www.imc.cnr.it/

Main branch: c/o area della Ricerca di Roma 1 - Montelibretti Via Salaria, Km 29,5 - 00015 Monterotondo RM

ITM Istituto per la tecnologia delle membrane http://www.itm.cnr.it

Main branch: Via P. Bucci - 87036 Arcavacata di Rende CS

DSFTM – Dipartimento di Scienze Fisiche e Tecnologie della Materia

IFN Istituto di Fotonica e Nanotecnologie http://www.ifn.cnr.it

Main branch: v. Cineto Romano 42, 00156 Roma

SPIN SuPerconductors, oxides and other INnovative materials and devices http://spin.fisica.unina.it/

Main branch: Via Cinthia - 80126 Napoli

INO Istituto Nazionale di Ottica http://www.ino.it

Main branch: Largo Enrico Fermi, 6 - 50125 Firenze

NANO Istituto Nanoscienze http://www.nano.cnr.it

Main branch: Piazza San Silvestro 12 - 56127 Pisa

DIITET– Dipartimento di Ingegneria, ICT e Tecnologie per l’Energia e i Trasporti IEIIT Istituto di Elettronica e di Ingegneria dell*Informazione e delle Telecomunicazioni http://www.ieiit.cnr.it/

Main branch: Corso Duca degli Abruzzi, 24 - 10129 Torino

IFAC Istituto di fisica applicata “Nello Carrara” http://www.ifac.cnr.it

Main branch: Via Madonna del Piano, 10 - 50019 Sesto Fiorentino FI

IMEM Istituto dei materiali per l’elettronica ed il magnetismo http://www.imem.cnr.it

Main branch: Parco Area delle Scienze 37/A - 43124 Parma

ITAE Istituto di Tecnologie Avanzate per l’Energia http://www.itae.cnr.it/

Main branch: Via Salita S. Lucia sopra Contesse, 5 - 98126 Messina

IRC Istituto di Ricerche sulla Combustione http://www.irc.cnr.it/

Main branch: Piazzale Tecchio, 80 - 80125 - Napoli

ITC Istituto di Tecnologie per l costruzione http://www.itc.cnr.it/

Main branch: Viale Lombardia, 49 20098 San Giuliano Milanese MI

IMATI Istituto di Matematica Applicata e Tecnologie Informatiche http://www.imati.cnr.it/

Main branch: Via Ferrata, 1 - 27100 Pavia

IM Istituto Motori http://www.im.cnr.it

Main branch: Largo Bersanti E. e Matteucci C. Napoli

IM DSSTTA– Dipartimento Scienze del Sistema Terra e Tecnologie per l’Ambiente IIA Istituto sull’Inquinamento Atmosferico http://www.iia.cnr.it/

Main branch: Area della Ricerca di Roma 1, Montelibretti, V. Salaria Km 29,300, Monterotondo (RM)