Hybrid materials: from the laboratory to the market

Resume : Magnesium based cement represents one of the most interesting eco-sustainable alternative cementitious binder. In the last decade, research efforts on the investigation of MgO-based cements have significantly grown for two main reasons: they can be employed for radioactive waste encapsulation, and have been recognized as promising binders alternative to traditional Portland (CaO-based) cements. Research interest in MgO-based cement is growing but only a few additives have been used with this new kind of cement, while in CaO-based cement many additives are commonly used to modulate performances to specific application. It has been recently reported that Na(PO3)6 in MgO-based cements increases the fluidity of the pastes, which is essential for practical applications. In this work we tested the effect of adding tubular aluminosilicate nanoclay functionalized with phosphate groups to MgO-based cement. These compounds, perfectly compatible, should theoretically be ideal for reinforcing purpose. The effect of this additive has been studied with a multi-technique approach: the hydration reaction has been investigated by DSC, while the hydrated phases formed during the reaction have been characterized by DTG, FTIR and XRD. The morphology of the pastes has been studied by SEM. Moreover, we performed strength measurements by nanoindentation. The effect of adding functionalized nanoclay structures to magnesium silicate hydrate binder gel phase has been exploited.

Resume : We developed hybrid materials consisting of guanosine monophosphate (GMP) and layered double hydroxide (LDH) and controlled intracrystalline molecular arrangement in the hybrids. In order to prepare hybrid (GMP-LDH), four kinds of intercalation methods ? coprecipitation, exfoliation-reassembly, ion-exchange and reconstruction ? which are generally well-known to prepare LDH-based hybrids, were attempted. From X-ray diffraction (XRD) patterns of GMP-LDH hybrids prepared via exfoliation-reassembly and ion-exchange, we observed (003) peak at 2? ~7o (interlayer space ~12 Å) which corresponded to GMPs? molecular dimension (13 Å in horizontal direction) in single molecular arrangement. The scanning electron microscopic (SEM) images of the GMP-LDH hybrids showed that LDH nanoparticles were covered with organic moiety of GMPs. To modify molecular arrangement to supramolecular assembly in the interlayer space of LDH, we systematically controlled the hybridization conditions such as temperature, reaction time and GMP/LDH molar ratio. When the preparation of hybrids was progressed at room temperature, we observed that GMPs arrangement gradually shifted from single molecular to supramolecular ribbon-type assembly, showing interlayer distance expansion upto ~18 Å. As the reaction temperature of 80 oC was applied, supramolecular ribbon arrangement of GMP recovered single molecular arrangement. Similar molecular arrangement control was also observed when 1 equivalent of LDH was added during reaction.

Resume : SiO2-based nanofillers are commonly used to enhance the mechanical properties of rubber composites in automotive application. Their efficacy depends on size, shape and surface functionalities of SiO2 nanoparticles (NPs), which affect their networking in the polymer matrix, and ultimately drive the filler-rubber interaction. Nevertheless, the knowledge of the mechanism at the micro-scale by which this interaction determines the reinforcement still remains an open challenge. Aiming to face these issue, we prepared SBR nanocomposites filled with SiO2 NPs having anisotropic shape (rod-like) and controlled aspect ratio (AR=1-10). TEM, AFM tapping mode, and dynamic-mechanical analyses assessed that the reinforcement relies on the formation of a continuous network of NPs surrounded by a layer of rubber chains with restricted mobility, whose amount increases with the SiO2 AR. Particles with the highest AR provide the highest reinforcement, due to self-organization in aligned domains which immobilize large amounts of rubber. These results confirmed that the filler morphology is crucial for tuning the amount of immobilized rubber at the filler/rubber interface; moreover they suggest a way to save energy during the composite deformation in operating conditions.

Resume : Cellulose nanocrystals (CNCs) are receiving considerable interest as low-cost filler that can be used to reinforce polymers, but these nanoparticles also permit the design of advanced materials that offer new functions. For example, the possibility to moderate the interactions among CNCs and/or between CNCs and a polymer matrix has allowed the design of mechanically adaptive, healable, and shape-memory polymer nanocomposites. Responsiveness to specific stimuli can be introduced via the modification of their surfaces with specific binding motifs. Their large surface area and ease of chemical modification can also be utilized for fluorescence-based sensing schemes, the release of drug molecules, and the creation of nanoparticle-based pro-fragrances; in the case of the latter, the CNCs are decorated with fragrance molecules using short, labile linker units, which serve to covalently connect the fragrance molecules with the nanocarrier and can be cleaved and promote the release of the payload. Finally, CNCs have recently been used for the fabrication of multilayer tissue engineering scaffolds that mimic the structural design, chemical cues, and mechanical characteristics of mature articular cartilage. In part due to the surface chemistry of the CNCs, the new scaffolds are able to guide the morphology, orientation, and phenotypic state of cultured chondrocytes in a spatially controlled manner, support the growth of tissue with features that are reminiscent of the natural analogue

Resume : 3D printing (3DP) has been acknowledged as a potential manufacturing revolution, shortening the concept-to-product time for innovative new technologies. Recent generations of low-cost and office-friendly fused-deposition 3D printers provide the potential to broaden 3DP concepts from being expensive and exclusive technologies to those that are easy-to-use and affordable. In general, the 3DP technique allows the use of a wide range of feedstock polymer containing a disperse minority fraction of inorganic powders materials and thereby afford versatile possibilities to build complex 3D structures with a broad range of thermo-physical, mechanical and functional properties. In this work, we present approaches to fabricate feedstock composite filaments for fused deposition 3DP technology. Depending on the desired applications, the feedstock composite may possesses a variety of electromagnetic properties, such as high dielectric permittivity, low loss, high magnetic permeability and even superconductivity. This approach suggests increased design freedom to manipulate both permittivity and permeability spatially, along with the capability to do this in relatively complex geometries and structures direct from a digital design. We demonstrate this by examples of 3D printed structures designed for applications in the microwave frequency region. These include highly birefringent structures, dielectric resonators with tailored values of dielectric permittivity, gradient refractive index lens and a magnetic diamond-like lattice structure.

Resume : In this article, we report one-pot synthesis of Fe(III)-polydopamine (PDA) complex nanospheres, their structures, morphology evolution and the underlying mechanism. The complex nanospheres were synthesized by introducing ferric ions into the reaction mixture used for polymerization of dopamine. The structures of the nanospheres were characterized using various chemical analysis techniques, including X-ray absorption fine-structure spectroscopy. It is verified that both the oxidative polymerization of dopamine and Fe(III)-PDA complexation contribute to the “polymerization” process, in which the ferric ions form coordination bonds with both oxygen and nitrogen at a ratio of roughly 4.3 to 1. In the “polymerization” process, the complex nanostructures grow gradually, while its morphology is gradually transformed from sheet-like to spherical at the feed Fe(III)/dopamine molar ratio of 1/3. The final size of the complex spheres is significantly smaller than the corresponding neat PDA spheres. At higher feed Fe(III) concentrations, the final morphology of the “polymerization” products becomes sheet-like. The results suggest that the formation of spherical morphology is likely to be driven by covalent polymerization-induced decrease of hydrophilic functional groups, which causes re-self-assembly of the stacked oligomers to reduce specific surface area. We also demonstrate that this one-pot method allows the facile construction of carbonized PDA nanospheres embedded with Fe3O4 nanoparticles. Noble metal nanoparticles can be uniformly attached on such magnetic nanospheres, making them good recyclable support for catalytic applications.

Resume : With an emphasis on ecological sustainability, new synthetic strategies such as hydrothermal, microwave-based routes, sonochemical, and bioinspired techniques have been adopted with a focus mainly on minimizing energy consumption, waste production, and extent of hazards in the synthesis process. Bioinspired synthesis uses a biospecies as a template or a medium to synthesize different kinds of materials, especially with functionalized properties on inheriting morphological and structural features of the biospecies. In the present work, graphene modified TiO2 of small crystallites is synthesized using a green herb of chilies as a reactor as well as a catalyst. Possible mechanism of forming a hybrid nanostructure in this process is discussed. Chili is a rich source of water, proteins, carbohydrates, lipids, capsaisin, ascorbic acid, and potassium, and hence it can be used as a natural medium to control structure of such oxides. A precursor titanium tetrabutoxide was slowly injected into a batch of fresh mature green chilies (Capsicum annuum L.) and then those were fermented in open air atmosphere for a couple of days to dry them slowly. So obtained sample was powdered and burnt with camphor in open air, leaving behind a ceramic sample. The sample was washed with deionised water several times to remove potassium and other minor minerals and was annealed at 400 °C for 2h. The XRD pattern reveals that it is a phase pure antase TiO2 with an average crystallite size 14 nm. D and G bands in Raman spectrum confirm the presence of graphene oxide. The FESEM images show that the small crysrallites agglomerate forming nanoparticles and are embedded in a thick graphene oxide surface layer (nearly 8 nm) in a hybrid nanostructure. The N2 adsorption isotherm depicts the mesoporous nature of the nanostructure. The UV-vis absorption spectrum extends over visible region and the IV characteristic indicates a well conducting sample. During synthesis, a combined effect of controlled/distributed water content and phonol aromatic ring in capsaisin supporting 2D carbon skeleton, and ascorbic acid in partially reducing graphene oxide plays a major role in forming such a mesoporous hybrid nanostructure. Tuning the graphene oxide layer by selective thermal annealing can tailor the nanostructure for enhanced visible light responsive photocatalytic and optoelectronic applications. Keywords: Bioinspired synthesis, Chili, Hybrid nanostructure, Graphene oxide, Photocatalysis.

Resume : Flexible Metal Organic Frameworks (MOFs) are ordered hybrid porous solids with promising properties for gas separation. This is due to their ability to adapt their pore size to optimize the host-guest interactions. Gas separation membranes offer several advantages over other relevant technologies. This is particularly the case of pure polymer membranes which are easily processable and possess suitable properties for separation of small gases. Nevertheless, these still suffer from many drawbacks in terms of stability or selectivity. Therefore membranes combining the physico-chemical properties of polymers (mechanical, processing, permeability?) and inorganic fillers (gas adsorption, selectivity, thermal stability?) are being investigated. One suitable strategy is to load the polymer membranes with nanoparticles of porous solids such as flexible MOFs. However, during the preparation of polymer-flexible MOFs MMM, the pore opening of the flexible MOFs in the polymer solvent is often a strong limitation due to the polymer intrusion within the pores. To overcome this, we selected an organic spacer that prevents the flexible MOF to swell in the organic solvents in order to maintain the MOF into its narrow pore forms, in order to keep an optimal CO2/N2 selectivity. We report first the optimized synthesis of this Al based MOF as nanoparticles, compatible with MMMs formation (Fig 1, reference 1). To highlight the benefit of our strategy, we also describe its properties in post-combustion gas mixtures (N2/CO2) including prediction, adsorption/calorimetry measurements, in situ XRPD and finally MMMs performances and compare it with the one of a related benchmark flexible Al MOF. Reference: T Loiseau, C. Mellot-Draznieks, H. Muguerra, G. Férey, M. Haouas, F. Taulelle, C. R. Chimie, 2005, 8, 765

Resume : Organic molecules modulate the precipitation and orchestrate the assembly of inorganic building blocks, giving rise to biominerals with complex shapes. A notable case of such combination is observed when combining double hydrophilic block copolymers with different ions. In the particular case of calcium phosphate systems, unique neuron-like structures can be formed. However, such structures are more common than probably expected and they can be created using much simpler organic molecules of a wider nature. Although we are yet far away from giving an exact explanation as to how they form, it is possible to identify crucial aspects which are required to ensure their stabilization. The poor specificity existing with regard to the organic phase in these particular structures makes them particularly interesting, as all ingredients required for their formation are readily available in the body fluid. From a more technological perspective, in the field of synthetic bone grafts the interplay of organic molecules with inorganic compounds can be used also to tune the properties of biomimetic calcium phosphate materials. The combination of self-setting calcium phosphate pastes with thermoresponsive hydrogels that present a gelling transformation offers a versatile platform for bone regeneration, tissue engineering and drug delivery applications.

Resume : This study aimed to evaluate the method of intercalation of triclosan into Metal-Organic Frameworks and check the antimicrobial properties of the resulting hybrid materials. Samples based on Al-MIL-53, ZIF-8, ZIF-67, Al(OH) Fumarate and Cu-BTC with different contents of triclosan were prepared. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), differential scanning calorimetry (DSC), thermogravimetric analysis (TG), Fournier transform infrared (FIT-IR) and X-ray diffraction (XRD) was performed to verify the process of association between the antibacterial substance and MOFs. TG analysis for powders with triclosan do not show the effect of weight loss at about 300°C (the temperature decomposition of triclosan), and only a reduction in the curves at about 100-150°C associated with the loss of adsorbed water in the MOFs. It may confirm a shift in degradation process of triclosan towards higher temperatures. This phenomena is particularly noticeable for Al-MIL-53 and CuBTC. This is confirmed also by the lack of effects on the DSC curves for these two powders at a temperature of about 300°C. Furthermore antibacterial activity was tested against two bacteria: Escherichia coli (Gram negative) and Staphylococcus aureus (Gram positive). The results obtained for Al-MIL-53 implies that this framework can encapsulated large amount of triclosan. The antibacterial substance loading achievable with the MIL family are

Resume : For the past decade, hybrid organic/inorganic silica has been extensively used as dielectric matter for interconnects, in integrated circuits[1]. Indeed, due to the excellent insulating properties (i.e. low dielectric constant, k) achieved through a meticulous material design, hybrid silica is the best replacement for the historically used silica, allowing for significant improvement in microprocessor performance. As a result, advanced electronic devices (smart phones, tablets, etc.) all contain hybrid silica in their interconnects. Nevertheless, for hybrid silica, an intrinsic lower limit around k=2.4 exists. To further decrease k, the accepted path is by introducing porosity in the material[2]. Unfortunately, the presence of pores generates additional challenges during integration, the most limiting one being acute plasma damage that seriously compromises microprocessors reliability. With the aim of solving this issue, a novel integration scheme referred to as Post-Porosity Plasma Protection (P4) was developed by our group. This unique protection strategy, which relies on the design of hybrid polymeric materials to temporarily fill the porosity, enables remarkable plasma damage mitigation[3,4,]. In this presentation, we will describe the P4 process and address key parameters required to successfully refill the hybrid silica porosity. We will also show the enormous potential of P4 based on data collected on blanket films, as well as integrated structures. [1] W. Volksen et al., Chem. Rev. 2010, 110, 56. [2] W. Volksen et al., Scripta Mater. 2014, 74, 19. [3] K. Lionti et al., ECS J Solid State Technol. 2015, 4(1), N3071. [4] K. Lionti et al., J. Appl. Phys. 2015, 117, 113303

Resume : The mesoporous silica functionalized with polymers is a new and versatile class of hybrid materials offering both the functional versatility of polymers and the thermal stability of silica. They can be synthesized by i) polymerization of monomers previously impregnated in gas phase ii) initiation of monomers from initiator covalently grafted to silica surface. In mostly cases, polymer filled entire volume of the silica mesopores, resulting in quasi-nonporous materials with low activity of organic groups. In this work, we present a new and simple strategy using bifunctional copolymers for both the nanostructuration of the silica matrix and the functionalization of its interface. The functional copolymers are amphiphilic block copolymers composing of PLA (polylactide) as hydrydrophobe-degradable block and poly 2-ethyl-2-oxazoline or polypeptide as hydrophilic-biocompatible blocks. Once the nanostructuration of the silica matrix is made using these block copolymers as templates, PLA can be extracted from silica matrix leaving pores surface covered with biocompatible polymers. Several mesoporous hybrid materials were synthesized by varying the chemical nature of hydrophilic block and the composition of block copolymers. Among different obtained hybrid materials, one exhibits a pore size of 17 nm and surface area of 380 m2 g-1. The accessibility of functional polymers in silica pores was evidenced by adsorption experiments in liquid phase using I2 or benzoquinone derivatives.

Resume : Recently, in textile science and industry keynote attention is paid to development, investigations and manufacturing of functional textiles. Especially strong focus is paid to development and/or usage of ecological fibres of natural origin. One of such new fibres, developed just a few years ago, is a peat fibre. It is eco-friendly, naturally renewable fibres used for textile materials with highly good thermal properties, which are more specific to wool than for cellulose fibres. Also, these fibres have excellent sorption characteristics common to all cellulose fibres. The aim of this work – to investigate the influence of knitting structure on flammability of knits from peat fibres. It was found that flammability characteristics of the peat fibres are different from other cellulose fibres. Easy ignition and fast combustion, specific to cellulose fibres, is not characteristic to peat fibres. During combustion peat fibres behave peculiar – after removal of flame source, the flame is extinguished in less than 2 sec (according to this criterion it can be attributed to flame retardant fibres), but further fibres continuous smoulder and it is a very negative property. This negative smouldering partially can be changed by the knitting structure and fully avoided by using chemical flame retardants. During experimental investigations it also was stated that peat fibres in blended cotton/peat yarns significant increase flame retardancy and the level of flame retardancy increasing depends on the percentage amount of the peat fibre in the cotton/peat blend. It is very important for textile companies which use natural cellulose based fibres for textiles with enhanced flame retardancy (used in public areas such as hotels, hospitals, etc), such as upholsteries, curtains, carpets. Acknowledgement: The research leading to these results has received funding from Lithuanian-Swiss cooperation programme to reduce economic and social disparities within the enlarged European Union under project agreement No CH-3-ŠMM-02/01.

Resume : Environment is deteriorating at a dizzying pace and the need to slow down the use of petroleum is no longer a distant reality. Then it becomes unavoidable to evolve new ideas, allied with technological improvements that make possible the development of new environmentally friendly materials. This work was based on this assumption and its motivation was to contribute for reducing CO2 release caused by the use of oil in the manufacture of expanded polystyrene (EPS). The goal was to develop a biopolymer-based fungi and forest residues, which could guarantee full biodegradability. Three fungal species were used; Pleurotus ostreatus, Ganoderma lucidum and Lentinula edodes, to colonize substrates made of different agricultural and forestry waste such as straw, wheat bran, pine sawdust, chestnut tree, beech, oak and mixed woods. To minimize the composite growth time, some starch based additives were added, operating as natural catalysts. With proper growing conditions, favorable humidity and temperature, it was possible to create natural composites, continuously improved throughout this work. For chemical and morphological characterization the following techniques were used: Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Infrared Spectroscopy by Fourier Transformer (FTIR-ATR), and Chemical Analysis. The most interesting results were obtained for Tq1 and Tq2 composites, consisting of: chestnut sawdust, wheat bran, coffee grounds and Ganoderma lucidum.

Resume : Calcium phosphate is one of the most important biominerals. It comes in a variety of phases, e.g. hydroxyapatite, brushite, etc., and is a key component in bones, teeth, and tendons.[1-2] Biomimetic calcium phosphate mineralization, that is, the synthesis of calcium phosphate/organic composites using a synthetic template or additive, provides access to a large variety of calcium phosphate composites that could for instance be useful for bone repair. However, the details of calcium phosphate nucleation, growth, and phase selection are not fully understood yet. To rationally design tailored materials for specific applications such as healthcare, this would however be essential. Among others, interfaces are a key factor affecting the formation, structure, composition, and properties of both the calcium phosphate deposits and the resulting hybrid materials. In spite of this, there are only relatively few studies on the role of surfaces and interfaces on calcium phosphate growth. The poster will present data on calcium phosphate formation on model surfaces, both at the solid-liquid[3] and the liquid-air interface,[4-6] and discuss the effects of these interfaces on crystal formation. A special focus is put on the effects of polycations, such as poly(2-dimethylethylamino methacrylate) (PDMAEMA), because polycations have been less extensively studied than polyanions and there is hence a lack of information on their role in calcium phosphate mineralization. Our studies show that not only the type of surface (anionic vs. cationic) but also the charge of each polymer surface (charged vs. uncharged) strongly affects the outcome of the mineralization process. A preliminary hypothesis of how polycations may regulate calcium phosphate is also proposed.[7] References [1] Calcium Phosphates in Biological and Industrial Systems, Kluwer Academic Publishers, Norwell-Dordrecht, 1998. [2] Handbook of Biomineralization, Wiley-VCH, Weinheim, 2007. [3] R. Löbbicke, M. Chanana, H. Schlaad, C. Pilz-Allen, C. Günter, H. Möhwald, A. Taubert, Biomacromolecules 2011, 12, 3753. [4] O. Casse, O. Colombani, K. Kita-Tokarczyk, A. H. E. Müller, W. Meier, A. Taubert, Faraday Discuss. 2008, 139, 179. [5] M. Junginger, K. Bleek, K. Kita-Tokarczyk, J. Reiche, A. Shkilnyy, F. Schacher, A. H. E. Müller, Taubert, Nanoscale 2010, 2, 2440. [6] M. Junginger, K. Kita-Tokarczyk, T. Schuster, J. Reiche, F. A. Schacher, A. H. E. Müller, H. Cölfen, A. Taubert, Macromol. Biosci. 2010, 10, 1084. [7] A. Shkilnyy, S. Schöne, C. Rumplasch, A. Uhlmann, A. Hedderich, A. Taubert, Colloid Polym. Sci. 2011, 289, 881.

Resume : Due to their many fields of application, inorganic particles and organic/inorganic hybrids are among the most interesting materials studied today. They can be prepared using various processes including gas phase synthesis and precipitation from organic and aqueous solutions. More recently, also ionic liquids (ILs) have found some use for the preparation of inorganic materials. Among others, ILs have in the recent past been shown to be efficient solvents, templates, and also reactants that can in some cases lead to novel particles or solids. In some cases, the reaction in ILs is more effective than in a conventional process, which overall leads to a simplification (and hence a often cost reduction) of a particular particle synthesis protocol. Moreover, ILs can also be used as functional components in hybrid materials, where they impart a composite with properties such as high ionic conductivity or (if suitably doped) luminescent or magnetic properties. The poster will give an overview over our activities in IL-controlled particle synthesis. For example, it will bnanoparticle formation mechanisms in ILs and aqueous solution. Organic/inorganic hybrid materials based on ILs and silica or polymer matrix materials will be introduced and their properties such as proton transport ability will be presented as well.

Resume : Light has been recognized as an important factor in vegetable growth, since photosynthesis depends on the spectral overlap between solar irradiation and chloroplast absorption. Aim of this study is to propose different strategies based on luminescent materials and photonic structures applied on conventional polymer used in the manufacture of greenhouses in order to tune the solar spectrum into the suitable wavelengths and therefore to enhance the performance of greenhouses. Different dyes, whose emission spectra mimic with the optimum energy spectrum demanded by the vegetables. Since the wavelength emitted by the dye is fitted with the energy needed by the plant, the biological growth mechanism is enhanced. Conventional polymers films (PE), were used as host materials and were doped with luminescent dyes, were obtained on pilot scale laboratory by hot-melt extrusion processes.) Doping was done using a single molecule or a combination of different molecules in order to seek for FRET effect. Advantage of this latter concept was the ability to provide wider absorption spectra, and consequently, higher intensity of the emission. It has been proven that optical properties of dyes were not affected when they are embedded into the polymer film. Benefit of this proposal is that vegetable inside of the greenhouse receive two radiation sources: natural light from the sun, and tune radiation from the luminescent film. Moreover, photonic crystals have been designed to act as an IR filter able to prevent undesirable heating inside of the greenhouse, which also affect negatively the natural growth of the plant.

Resume : For the applications to electromagnetic interference (EMI), e.g., microwave absorbers, ferrites are attractive materials owing to their characteristic magnetic properties. Ferrite materials, however, exhibit low dielectric loss, such that it is hard to develop them as microwave absorbers. To solve this issue, dielectric loss fillers such as carbon nanotubes, graphene, and conducting polymers are usually added to ferrites for the applications to EMI materials. Here, our research aim is a development of cost effective and novel microwave absorbers. We focused on a composite material consisting of soft magnetic ferrite and carbon atoms. The ferrite/carbon composites were synthesized by a solid-state reaction method. The amount of carbon in relation to ferrite was altered to adjust a distribution of carbon atoms and the magnetic properties. The lattice parameters of the composites were decreased as carbon increased, thereby we consider that a reaction between ferrite phase and carbon atoms occurred. The magnetic properties of the composites showed typical soft magnetic characteristics with small coercivity values without any traces of magnetic impurity phases. The saturation magnetization value of the composites exhibited approximately 80 (emu/g) when the amount of carbon contents was less than 30 wt%. Moreover, coercivities were low, i.e., 10 to 25 Oe. Based on these physical properties, we believe that the present composites can be profitable for future microwave absorber.

Resume : Composites of polyamide 6 (PA 6), powdered synthetic graphite and pitch-based carbon fiber were melt processed to explore the effect of the filler contents on the anisotropic properties of the resulting composites. Optical microscopy and mechanical properties were used to determine the dispersion of graphite and carbon fiber in the PA 6 matrix. The relationship between the structure and properties showed the anisotropic filler orientation along the three principal directions. Thermal expansion in the flow direction and transverse direction decreased as filler content increased for all composites, but the decrease in the flow direction was much more significant. This anisotropic orientation also influenced the thermal conductivity of the composites resulting in an increased in-plane thermal conductivity up to 25 times that of pure PA 6. Thermography shows good agreement with the thermal conductivity results.

Resume : Due to advancement of industrial development, heavy metal ions in waste water are daily flowing into ground surface and water resources. Cases of serious side effects have been reported since they are accumulated in the human body along the food chain. Because of effectiveness of adsorption process, numerous adsorbents have been proposed for efficient removal of heavy metal ions or organic pollutants in waste water. However, previously reported adsorbents and adsorption process are not suitable for small scale enterprise and individual user. Development of a portable heavy metal ion remover which can be used even by untrained user is highly demanded. Sponge is portable, easy to use, and ubiquitous materials. Polymer brushes possess advantages of numerous reaction sites and pH-responsive behaviors for control of adsorption/desorption. Thus, highly porous sponge composites decorated with polymer brushes via “grafting-from” or “grafting-to” polymerization was developed for fast and efficient removal of heavy metal ions in waste water or drinkable water.

Resume : With the increasing industrial oily wastewater and the frequent oil spill accidents, separation of waste oils from oil/water mixture continues to be the hot issue of research. The development of low cost materials with chemically and physically stable properties has become a challenging task for oil/water separation and related applications. Various materials such as sponges, meshes, filter papers, and fabrics have been proposed for oil/water separation. Among them, metal meshes have been considered as the most suitable templates due to their characteristics of low cost, high porosity, and good liquid permeability. However, very toxic chemicals are generally used for oxidation of metal meshes. We report a facile green approach for preparing hierarchically oxidized metal meshes. Subsequently, low surface energy materials are coated on the meshes to induce superhydrophobic property. The resulting meshes exhibited a significant potential for highly efficient oil/water separation.

Resume : Since the discovery of the outstanding electronic properties of the graphene derivatives, the research in the field of functional nanomaterials has been increasingly concerned with the conception of new multifunctional nanosheet-based systems, with intensification of research in the field of layered materials. Among the possible chemical routes, the hybrid organic?inorganic approach is particularly well suited to promote multifunctionality within a single material. In this way, transition metal layered simple hydroxides (LSH), of general formula MII2(OH)3(X).mH2O (M = Co, Cu, Ni and X = nitrate, acetate?), are very well adapted to grafting reactions of various molecules.1 We have recently started to investigate the possibility to functionalize such layered simple hydroxide by molecules bearing a phosphonic acid anchoring group, which has indeed been seldom described. We will report in this poster our first results concerning the functionalization of LSH by fluorene-(di)-phosphonate molecules. We will show that the preintercalation strategy is particularly well adapted for this purpose, and allows to obtain the desired hybrid compounds with a good crystallinity. Finally, we will present the magnetic and luminescent properties of the obtained hybrid compounds, and we will propose some hints to promote synergy between the properties in these layered multifunctional systems.

Resume : Persistent organic pollutants from industry or urban regions in the aquatic ecosystems represent serious environmental issues. In this context recent studies of WHO (World Health Organization) revealed that endocrine disrupting compounds present toxic effects even at very low concentration. One such compound is ibuprofen. The use of light energy to accomplish the latest requirements concerning wastewater discharge demands performant and robust photocatalysts. Many efforts have been paid to obtain efficient photo-responsive materials. Among the promising photocatalysts, layered double hydroxides (LDHs) attracted significant consideration especially due to their composition flexibility, high surface area and tailored redox features [1]. This work presents the self-supported Fe(II) on ZnMeLDHs (Me =Al3 , Cr3 , Fe3 ) as novel efficient photocatalysts for Fenton-like catalysis. The coprecipitation method was used to prepare ZnAlLDH, ZnFeAlLDH and ZnCrLDH (molar ratio Zn2 /Me3 = 2). Fe(II) was self-supported on the LDHs matrices by using the reconstruction method, at two different values of weight concentration. X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG), Fourier transform infrared (FTIR) and transmission electron microscopy (TEM) were used to investigate the structural, textural, and micromorphology of the catalysts. The Fe(II)/ZnMeLDHs nano-hybrids were tested for the degradation of a model pharmaceutical agent, the anti-inflammatory agent ibuprofen, by photocatalysis and photo-Fenton catalysis, respectively. Results point out that the embedment Fe(II) into ZnFeAlLDH and ZnCrLDH results in a slight enhancement of ibuprofen degradation by light irradiation, whereas in case of ZnAlLDH, the degradation process is relatively low. A remarkable enhancement of ibuprofen degradation was found in the case of Fe(II)/ZnMeLDHs by photo-Fenton process.

Resume : Nanostructured materials are among the most studied materials, due to their current and potential utilization in various applications, like catalysis, electrodes for batteries and fuel cells, supercapacitors, and sensors. Particular materials are the vertical graphenes or carbon nanowalls (CNW) and the carbon nanofibers (CNF). Previously, we have developed a method suitable for growth in the same experimental setup, by chemical vapor deposition technique, of carbon nanofibers or carbon nanowalls [1, 2]. In this contribution we explore the possibility to synthesize hybrid architectures combining these two carbon nanostructures. We take advantage of the switch of growth regime by controlling the plasma characteristics or substrate temperature. Thus, in our experiments we alternated the conditions of plasma or the growth temperature reaching the growth regime of CNT or CNW. The deposited material consisted in bilayers of CNF/CNW or CNW/CNF types. The hybrid architectures were investigated by SEM, TEM and Raman spectroscopy. In TEM images at the layers interface we could observe the transition in material structure and morphology due to the switch in the growth regimes. The method is promising for fabrication of multilayered hybrid architectures. [1] S. Vizireanu, B. Mitu, G. Dinescu, L. Nistor, C. Ghica, A. Maraloiu, M. Stancu and G. Ruxandra, J OPTOELECTRON ADV M (2007) [2] T. Dinh, A. Achour, S. Vizireanu, G. Dinescu, L Nistor, K. Armstrong, D. Guay, D. Pech, Nano Energy (2014)

Resume : Hybrid coordination networks have been the subject of considerable research in recent years. This interest comes from the versatility and flexibility of their architecture as well as their potential application in many areas such as gas storage, catalysis, drug delivery, and information storage?[1-6] They are often obtained by solvothermal reaction between metal salts and neutral ligand bearing coordination functions. In our group, we have focused on the synthesis of coordination networks from imidazolium salts bearing carboxylate coordination functions to monitor the structural building process. This strategy has been successfully applied to transition metals and lanthanides giving rise to different coordination networks.[7] We will present our recent results concerning the synthesis and the characterization of new hybrid coordination networks based on achiral and chiral imidazolium dicarboxylate salts and different metal centers. Beyond the interest to explore new families of compounds, the incorporation of imidazolium salts with special functionalities into the coordination networks let glimpse the possibility to obtain new multiferroic materials. 1. G. Férey, Chem. Soc. Rev. 2008, 37, 191. 2. P. Horcajada, C. Serre, M. Vallet-Regí, M. Sebban, F. Taulelle, G. Férey, Angew. Chem. Int. Ed. 2006, 45, 5974. 3. M. Dinc?, J. R. Long, Angew. Chem. Int. Ed. 2008, 47, 6766. 4. G. Rogez, N. Viart, M. Drillon, Angew. Chem. Int. Ed. 2010, 49, 1921. 5. M. Guo, H.-L. Cai, R.-G. Xiong, Inorg. Chem. Commun. 2010, 13, 1590. 6. W.-J. Ji, Q. Zhai, S.-N. Li, Y.-C. Jiang, M.-C. Hu, Chem. Commun. 2011, 47, 3834. 7. P. Farger, R. Guillot, F. Leroux, N. Parizel, M. Gallart, P. Gilliot, G. Rogez, E. Delahaye, P. Rabu, Eur. J. Inorg. Chem., 2015, 5342.

Resume : Several chemical processes are envisaged to control at the mesoscale the growth of functional materials. As far as the porosity and shape are concerned, the main chemical strategies use supramolecular templates introducing structural features improving the properties of various functional inorganic or hybrid materials. Beyond surfactant-templated synthetic procedures used for microporous and mesoporous oxides like zeolites or silica, new approaches extend today to bio-inspired or biomorphic synthesis and biomineralization. The reactivity of potassium or sodium hexacyanoferrate(II) salt with transition metal hydroxyacetates was investigated to evaluate the possibility to insert magnetic hexacyanoferrate(II) anion into magnetic layered hydroxides (LSH) hybridized with various organic molecules. The present work[1] shows how such a reaction led, unexpectedly, to the direct formation of PBA nanoparticles, the layered hydroxide serving as a metal ion reservoir. The lamellar structure of the starting LSH collapses and copper-iron PBA nanoparticles were obtained as well defined cubic structures stacked in layers. In addition to structural and magnetic characterization, the reaction mechanism was investigated by 57Fe Mössbauer spectrometry and X-Ray photoemission spectroscopy (XPS). The layered copper hydroxide acetate turns out to be a smart precursor of well-shaped PBA nanoparticle layers, via pseudomorphic replication. [1] M. Lang, E. Delahaye, D. Foix, D. Ihiawakrim, O. Ersen, C. Leuvrey, J.-M. Grenèche, G. Rogez, P. Rabu, Eur. J. Inorg. Chem. In press.

Resume : In the last few years, the gas purification/separation methods using mixed matrix membranes have received a special attention from researchers, due to the observed advantages, such as low operating cost and environmental friendly. The aim of this study was to obtain inorganic/organic hybrid materials in order to be used as membranes for gas separation at micro scale, the whole system being available for design at industrial scale. In this respect, MCM-41 mesoporous silica was functionalized with amino groups, using APTES - (3-aminopropyl)triethoxysilane and further different mixed matrix membranes were prepared by incorporating MCM-41-NH2 in polysulfone, with loadings between 0 wt% and 20 wt%. The membranes were obtained by casting the solutions on Petri dishes resulting films with thickness around 30 µm. To better understand the interactions between the filler and the polymer matrix, a series of analysis were made: scanning electron microscopy (SEM), thermogravimetric analysis (TGA), N2 porosity (BET) and X-ray diffraction (XRD). The performances of homogenous MMMs were determined by single gas permeation measurements at room temperature. The tested gases were O2, N2 and CO2 with a 5.0 purity grade. The results shown a significant improvement over the neat polymer and the permeance coefficient decreases with the quantity of mesoporous material in polysulfone matrix. This can be explained by polymer chain stiffening at the filler-polymer interface, due to strong interaction between materials. Acknowledgement: This study has been financed by the Sectoral Operational Programme Human Resources Development 2007-2013 of the Ministry of European Funds through the Financial Agreement POSDRU/159/1.5/S/134398. Keywords: gas, MCM-41, mixed matrix membranes, permeance coefficient

Resume : ZrSiON thin films were deposited on CoCr dental alloys by means of cathodic arc evaporation method for improvement of the metal-ceramic bond strength. The corrosion resistance is crucial for materials used in dental applications subjected to the action of the aggressive oral environment. For this purpose, a defect-free microstructure is required and therefore, the coatings were obtained at two different substrate bias voltages, Vb: -50 V and -200V), in order to select the optimum parameters for the preparation of coatings with superior properties. In this study, the long term protective performance of the ZrSiON thin films was investigated during 72h immersion in artificial saliva solution by odd random phase multisine electrochemical impedance spectroscopy (ORP- multisine EIS). This method allowed, in contrast to standard single sine EIS, the possibility of quality control of the experimental data and therefore the application of optimal measurement conditions, for obtaining a linear and stationary behaviour, and also a good signal-to-noise ratio. Based on this additional information, a statistical evaluation was made to assess the fitting procedure. The results showed that ZrSiON thin film deposited at Vb= -200 V exhibited the lowest porosity and the best protective properties. Moreover, this behaviour can be associated to the enhanced formation of a stable passive layer inhibiting the corrosion of the CoCr substrate.

Resume : The need for efficient storage systems is currently a crucial issue towards a clever energy management. Supercapacitors (SCs) are electrochemical power storage devices that can replace or support the already available battery technology. The main advantages of SCs are their higher power density values, along with the much longer cycle life and fast charge/discharge rates. The fabrication of nanostructured electrodes improves the energy density without affecting the high power density. Aim of this work is the fabrication of a new composite material, combining both Electrical Double Layer Capacitance (EDLC) and Pseudocapacitance (PC) properties, to be used as electrode for SCs. A graphene aerogel is synthesized by a green hydrothermal process, starting from commercial graphene oxide (GO). The resulting 3D porous nanoarchitecture provides high surface area values (? 500 m2g-1) as required for EDLC-SCs. If Fe-doped imogolite nanotubes (IMO, (OH)3Al2-xFexO3SiOH) are mixed with GO before hydrothermal reduction, a composite with supercapacitive properties is obtained. The synthesized materials were thoroughly characterized by means of morphological, compositional and electrochemical techniques (e.g., Cyclic Voltammetry, charge/discharge galvanostatic measurements, etc.). It was shown that the presence of structural Fe3 ions within IMO nanotubes contributes to the observed electrochemical behavior by a Faradaic charge storage mechanism, due to surface or near-surface redox reactions, as typical of PCs.

Resume : Hybrid materials (HM) were synthesized by high temperature reaction of inorganic glass matrixes with various organic phosphors. As a glass matrix we used easy melting 80PbF2-20B2O3 glass, as organic phosphors – various 8-hydroxyquinoline (q) complexes of I, II and III group metals (Rb, Zn, Ba, Sr, Mg, Al, Ga, In, Sc) – Mq(x). HM’s synthesized at 600C during 30 seconds at the melt stirring. The produced HM’s were yellowish transparent glassy plates. They showed photoluminescence (PL) of varying intensity in the range of emission colors from blue to green when excited by 377 nm diode laser. HM’s based on Alq3 and Srq2 demonstrated the highest PL intensity. The luminescence bandwidth of the synthesized HM’s is considerably larger than the luminescence bandwidth of the initial crystalline Mq(x). Besides the formation of various different Mq(x) polymorphs the different exchange reactions may occur between the phosphors and the glass matrix resulting to Bq3 and Pbq2 formations. In the case of the HM based on Alq3, the PL spectrum corresponds to α-Alq3, i.e. the exchange reaction does not take place.

Resume : Oxford Photovoltaics Limited (Oxford PV) was founded in 2010 as a spin-out from the University of Oxford to develop and commercialize thin-film perovskite solar cells. The films are printed directly onto silicon solar cells, CIGS solar cells or glass. Crystalline silicon dominates the present market, having reached an efficiency record of 25%. Recent cost reductions have pushed the price to a value that is difficult to reduce further. Therefore, a breakthrough is required that can push conversion efficiencies well beyond the 25% value with only a minimal increase in cost. Oxford PV’s perovskite stack can be printed on top of conventional silicon cells, boosting the efficiency by 3-5% absolute with little additional cost. This presentation will focus on pioneering work developing perovskite thin-film solar cells to deliver a route to boosting the efficiency of current commercial cells. Oxford PV has demonstrated a 21.4% efficiency tandem silicon perovskite solar cell, with a net gain of 25% above the underlying silicon cell. Current devices meet or exceed the IEC61646 1000 hour light soaking specification under stress.

Resume : The rapid development of membrane processes in recent years is due to the drive toward greater economic and environmental efficient separation processes. The use of membranes for separation and purification has resulted from the progress made in membrane materials, membrane structure, and large-scale membrane production methods. In order to be useful for separation or purification processes, membranes must exhibit a number of characteristics such as high flux, high selectivity, mechanical stability, resistance to fouling, and low cost. The most commonly used membranes are polymeric and nonporous, the separation being based on a solution–diffusion mechanism involving molecular-scale interactions of the permeating molecule with the membrane polymer. Inorganic membranes, (molecular sieving zeolite membranes carbon membranes, alumina membranes, and silica membranes) have high thermal and chemical stabilities. Over the past years, extensive work has been reported on the synthesis, characterization, and application of inorganic membranes. Despite all the advantages, polymeric membranes cannot overcome the polymer upper-bound limit between permeability and selectivity. It is desirable to provide an alternate cost-effective membrane in a position above the trade-off curves between permeability and selectivity. Based on the need of a more efficient membrane than polymer and inorganic membranes, a new type of membranes, mixed-matrix membranes, has been developed recently. Mixed-matrix membranes are hybrid membranes containing solid, liquid, or both solid and liquid fillers embedded in a polymer matrix. This study reviews several key advances in the design, preparation, and applications of mixed-matrix membranes presented in the literature. The strategy for the development of mixed-matrix membranes is to combine the advanced features of polymer membrane and inorganic membrane into one composite membrane. Common industrial gas separations that use membrane technology include: air separation (O2/N2), hydrogen recovery (H2/CH4, H2/N2). Although technical progress has been reported, no commercial mixed-matrix membrane application is found. The lack of commercial mixed-matrix membranes could be due to current insufficient information in membrane processability, stability, and cost. Keywords: gas separation, mixed-matrix membrane

Resume : Understanding and controlling the electronic charge transport through molecular layers is one of the main goals of molecular electronics. Here, quantum interference (QI) effect in cross conjugated molecules is investigated. It results in a drastic but reversible reduction of the conductance in molecular devices at low bias voltages. We present a complete study of QI measurements in metal / Molecules /metal junctions. Based on the well-known electro-reduction of diazonium[Pinson JACS 1992], an organic thin layer iss embedded in large-area solid-state devices. Several molecules as Anthraquinone (cross conjugated molecules) are covalently bonded to the electrode and formed a dense and robust layer in which such interference effects were already reported[Rabache JACS 2013]. We found direct experimental evidences of a large quantum interference effect through measurement of the differential conductance. We demonstrated that quantum interferences are present at room temperature and are enhanced as temperature is lowered for molecular layers thicker than a monolayer. In a second step we showed that the experimental signature of the electron-phonon coupling appears at low temperature as the major source of decoherence, reducing interference effects[Bessis Scientif. Rep. 2016].

Resume : Immune homeostasis is governed by a fine balance of pathogenic effector T cells (Teff) and suppressive regulatory T cells (Treg). It was found that the T cell activation strength has an impact on T cell differentiation and immune regulation in skin autoimmunity. Low doses and chronic antigen exposure favors pTreg differentiation, whereas high doses blocks pTreg differentiation. To support these findings mice were systemically treated with the immune-suppressive drug rapamycin to reduce T cell receptor signaling, which also restored pTreg generation and rescued the mice from autoimmunity. In order to define whether the effect of rapamycin is T cell specific or acting indirectly via other cells (e.g. antigen presenting cells) the drug should be target specifically to T cells in vivo. This can be realized by means of suitable support materials such as non-toxic and biocompatible silica. In this presentation, we will present nanoparticles that allow a specific drug delivery to T cells in vivo. The nanoparticles carry at least four different functionalities: (i) the ability to enter lymph nodes (achieved by limiting the size to 15-35 nm diameter), (ii) the containment of the drug (drug is adsorbed on the surface of the particles), (iii) the option to image the distribution and cell-specificity in vivo (a fluorescent dye is incorporated) and (iv) the specific delivery of the drug to T cells (achieved by coupling a biotinylated cell-specific antibody to streptavidin-coated particl

Resume : Cellulose is a most abundant raw material on earth. As a smart material, nano-cellulose has several materials advantages. Piezoelectricity is one major actuating mechanism of cellulose-based electroactive paper (EAPap). To understand the detailed material behavior of cellulose, dielectric and polarization behaviors of EAPap were also investigated. As an actuator, electromechanical bending actuation of chitosan-blended EAPap was studied using a theoretical model. For possible sensor applications, we fabricated some cellulose based chemical sensor and tested. Also, electronic application, paper based transistor was demonstrated. For improved functionality of cellulose, hybrid cellulose composite with metal wires, semiconducting, metal oxides were also investigated for potential electronic applications. By combination of paper based actuator/sensors/energy harvesting, “papertronics” will be soon on our hands.

Resume : Nanolayered films have been often fabricated using the layer-by-layer technology, where consecutive layers of macromolecules are assembled and stabilised by different kinds of interactions. Using adequate templates, non-flat coatings can be fabricated with tuned compositions. This enables the production of very well controlled multifunctional and structural devices using mild processing conditions that could be useful in biomedicine, including in bone tissue engineering. In such applications, where there is a direct interaction between the implant with tissues and cells, the biomaterials must exhibit adequate surface characteristics, both at the chemical and topographic points of view. Examples of structures having nano-stratified multilayered organizations as building-blocks are presented, based on the use of natural macromolecules. Functional and bio-instructive multilayers may be produced by introducing special chemical groups or bioactive agents in the assembly. In particular biomimetic multilayers were produce by including bioactive glass nanoparticles obtained through sol-gel chemistry, giving to the device the capability to stimulate the deposition of apatite into the surface under physiological-like conditions. Adequate signals or cell sources may also be used to direct the osteogenic route of the developed devices, to potentiate their bone regenerative capability.

Resume : The use of microorganisms for pollution control (bioremediation) is a critical technology for water and soil depollution. While in water the process is quite well implemented, its application to soil depollution remains a challenge. Besides the intrinsic sensitivity of living organisms to their environment (pH, temperature and osmotic pressure etc?), leaching of exogenous microbial strains is a major concern. Here we propose to encapsulate the model organism Pseudomonas aeruginosa in a macroporous pectin-silica hybrid foam. Our approach takes advantage of the fine tuning possibilities conferred by the freeze-casting process over both the macrostructure of the material and the viability of the encapsulate[1]. The cell-containing biopolymer foam obtained by freeze-casting is subsequently coated with a silica layer, by vapor deposition. This hybrid material therefore combines good cytocompatibility while preventing cell leaching. Critical aspects of this work, such as synthesis challenges, its impact on cell viability and morphology as well assessment of the material?s behavior in model conditions (aqueous and soil) will be discussed. Such a material may be implemented at larger scale to tackle the pressing issue of soil pollution. [1] S. Christoph, J. Kwiatoszynski, T. Coradin, and F. M. Fernandes, ?Cellularized Cellular Solids via Freeze-Casting,? Macromol. Biosci., 2015.

Resume : We report the first example of transition metal oxoclusters-reinforced organic-inorganic hybrid materials exhibiting shape memory properties, based on the covalent incorporation of zirconium-based inorganic building blocks. The research is focused on methacrylate-functionalized zirconium oxoclusters Zr4O2(OMc)12, [Zr6O4(OH)4(OOCCH2CH3)3{OOCC(CH3)=CH2}9]2 and their covalent incorporation in a butylacrylate (BA)/polycaprolactone dimethacrylate (PCLDMA) copolymer, and on the non-covalent incorporation of [Zr6O4(OH)4(OOCCH2CH3)12]2. Shape recovery and fixity rates are studied to observe if the shape memory properties are preserved, going from simple copolymer to hybrids based on non-covalent or covalent bonds. These rates display values higher than 90%, evidencing how the oxocluster does not hinder the shape memory properties in the hybrid materials. The introduction of an inorganic phase and the progressive more stable interaction between organic and inorganic parts leads to an enhancement of the thermo-mechanical properties. The materials are characterized through FT-IR, TGA, DSC and swelling tests. Dynamical-mechanical analyses investigate whether the hybrid materials display thermally activated shape memory properties. The stability of the hybrid materials are evaluated by a combined spectroscopic approach based on FT-IR, Solid State NMR and X-ray Absorption spectroscopies.

Resume : Bioinspired silica, synthesised using biologically inspired organic “additives”, are greener alternatives to many existing silicas (Chem. Commun., 2011, 47, 7567). However, bioinspired (and other templated) silicas require high energy treatment, e.g. high-temperature calcination, leading to material and energy wastefulness. Although alternatives to calcination have been reported, e.g. solvent extraction, they are not effective (Chem. Soc. Rev., 2013, 42, 4217). It is clear that current methods are uneconomical and not scalable, creating barriers to reach market. By extensively investigating the molecular interactions between additives and silica, we discovered that pH can be used to controllably extract (partly or fully) additives from silica hybrids unlike the traditional mesoporous silicas. This has enabled us to scale-up to produce hundreds of grams per day without the need for specialist equipment, demonstrating the improved scalability of the new technique. Furthermore, process calculations indicate that extraction and additive reuse can reduce additive and water requirements by over 90%, while the room temperature reaction can reduce the energy requirement by >90% (Chem. Eng. J., 2014, 244, 483), thus significantly reducing both the cost and wastefulness. We show that this method provides an effective “lab to market” route in applications ranging from environmental remediation (Environ. Sci. Technol., 2012, 46, 13354) to drug delivery (J. Mater. Chem. B, 2014, 2, 5028).

Resume : Despite having many advantages for transport applications, Fuel Cell has not reached the broad international market. For a technical breakthrough and a wider implementation of the fuel cell technology, we need to develop new materials with a high performance at much higher temperatures, that is materials that display conductivities higher than 10-1 Scm-1 well above 120 °C. In our laboratory we are trying to develop new hybrid materials based on silica (SiO2) as the bearing matrix and as a substitute to organic polymers, and a protic ionic liquid as the charge carrier, see figure below. This research line requires designing appropriate silica pores in terms of size, geometry and surface chemistry, but also selecting the best ionic liquid with low viscosity, high mobility and possibly acid protic sites. In this contribution I will present some strategies that we follow to obtain functional hybrid materials. Focus will be on some spectroscopic methods that we employ to disentangle the nature of intermolecular interactions underlying the properties that we observe macroscopically, such as self-diffusion and conductivity. In particular, we make extensive use of 1H NMR and vibrational spectroscopy (both Raman and infrared) to probe the strength of ion-ion interactions, pulsed field gradient (PFG) NMR spectroscopy to measure the self-diffusion of all ingoing molecules, and advanced 2D solid-state NMR experiments to investigate the local coordination scheme at the IL/silica& interf

Resume : Nexar polymers by Kraton are symmetric pentablock copolymers consisting of tert-butyl styrene end blocks, hydrogenated isoprene inner blocks, and a middle block that is selectively and randomly sulfonated. The result is a polymer with controlled swelling and good mechanical properties in the hydrated state, that is designed for different applications as desalination, filtration, gas separation, reverse osmosis, fuel cell membranes. Nexar nanocomposite membranes were prepared varying the casting solvent and dispersing inside different nanomaterials (bismuth oxide, graphene oxide) being recently studied for water purification applications. The chemical, structural, morphological and optical properties of the produced materials were mainly characterized by infrared and Raman spectroscopies, scanning electron microscopy and photoluminescence. The composites have been tested as adsorbents or as photocatalysts for the removal of different water contaminants (dyes, phenols). In particular, the photocatalytic activity of such nanocomposite membranes was investigated by measuring the degradation of methylene blue (MB) and methyl orange (MO) under UV/visible or visible light illumination and compared with the powders directly dispersed in water.

Resume : The siloxane?polyether system involves transparent elastomer organic?inorganic hybrid materials of interest, which are able to entrap practically any small cation, with chemical stability and wide range of applications. In that work, new hybrid materials constituted of PEO and PPO based siloxanes were prepared by the sol-gel process. Their chemical structure was characterized by means of small-angle X-ray scattering (SAXS) measurements as well as vibrational spectroscopy and differential scanning calorimetry (DSC) analyses. Furthermore, the degradation of the hybrid materials was investigated upon UV light irradiation in order to assess their photostability. For this purpose, photooxidation of the samples was studied at the molecular scale using FTIR spectroscopy coupled with chemical treatments, and was also characterized by DSC. Eventually, Li and Eu3 doped PEO and PPO based siloxanes were achieved for respectively electrical and optical applications.

Resume : Ion-exchangeable layered perovskites exhibit especially interesting physical properties such as ferroelectricity, luminescence or non-linear optics. One key-interest of these materials is that they can be functionalized by various mono or divalent cations, including alkyl-ammonium. This feature allows to finely tune the interlayer spacing size and content, and hopefully the properties of the final hybrid compounds. We are particularly interested in the functionalization of an Aurivillius phase of formula Bi2SrTa2O9 (BST), known for its ferroelectric properties. The conversion from BST to H1.8Bi0.2Sr0.8Ta2O7 (HST) has been reported and this protonated form can be further functionalized by n-alkylamines or ?,?-diaminoalkanes. Yet, the published synthetic methods have the important drawback of being extremely long. Consequently, only a limited number of amines have been inserted into protonated Aurivillius phases. Moreover, this reaction timescale intrinsically limits the type of molecules which can be inserted to very stable and very simple ones. In order to overcome this problem, we have explored the microwave-assisted protonation of BST and its subsequent functionalization by various amines. We will show that this method enables to functionalize the starting BST in a few hours instead of more than a weak via classical method. In addition, we have been able to functionalize BST with more "interesting" amines, including chiral or aromatic amines and poly-amines.

Resume : Pressure sensing devices are used in broad applications from sound vibration detections, health-monitoring devices to tactile sensing for artificial intelligences. Of several different transduction mechanisms, piezo-resistive sensing platform has been investigated extensively due to its simple device assembly. Developing a simple and scalable device structure while maintaining high sensitivity at large operating range is a key in mass production of the pressure sensors. Here in, we report a new approach to building a piezoresistive pressure sensor with highly controllable structure over a large area. In this work, we employed micro-patterned polydimethylsiloxane (PDMS) substrates covered with hydro-dynamically assembled nanomeshes of single-walled carbon nanotubes (SWNTs) as the active material. Micro-sized pyramid arrays promote high sensitivity at low-pressure regimes (< 1 kPa) and the nanomeshes are mechanically robust with potential scalability. Moreover, by adjusting the amount of SWNTs, we can finely control the electrical conductance of the nanomesh. This allows us to adjust sensitivity and operating range of the sensor by changing contact resistance between the piezoresistive and counter electrodes. From the measurements, the pressure sensors displayed sensitivities up to 14.5 kPa-1 at pressure ranges below 50 Pa, which is relatively high compared with the existing piezoresistive sensors. The results promote a promising approach in developing highly controllable, flexible pressure sensing platform. Incorporating other chemical functionality of the assembled SWNTs, our sensor has a potential to develop into multi-functional wearable health-monitoring system in the future.

Resume : The organic-inorganic hybrids materials are promising candidates for important applications in photonics, biomedicine, etc. TiO2 hybrids attract particular interest due to a high refractive index, biocompatibility and electron transport properties. A direct-writing photonic structures was recently demonstrated using 2-photon polymerisation (2PP) of titania-based hybrids in methacrylic acid (MAA) and 3(methacryloxy)propyl-trimethoxysilane (MAPTMES) organic components. TiO2 hybrids capable accumulating trapped electrons as Ti3+ centres were used for photochemical conversion and storage of solar energy under UV illumination. It has been shown that photochromism in these hybrids is related to an efficient photoinduced electron-hole separation at the extended internal inorganic-organic interface. In our previous works, nanoparticulate photochromic materials, pHEMA/TiO2 (pHEMA=poly-2-hydroxi-methyl-methacrylate) hybrids, were proposed, which exhibit a high charge separation efficiency ~14% and high loading capacity Ti3+/Ti ~10%. However, these colloid hybrids were extremely moisture-sensitive that prohibits their use in 2PP process. In this study we describe new hybrids with the organic component composed of a mixture of HEMA and EMA (ethyl-methacrylate) monomers, which show a strong stability in humid environment totally suppressing the aggregation of inorganic nanoparticles. The size-selected nanoparticles preparation and injection in monomer solutions were performed according

Resume : Global Warming is one of main concerns in today’s world. Transportation vehicles are one of main contributors in high CO2 emissions in atmosphere and damage of ozone layer. Excessive use of fossil fuel and associated rise of CO2 level in earth atmosphere have led to development of energy saving technologies in transportation sector. Vehicle air conditioning feature put an extra burden on vehicle engine and of course more fuel consumption. Conclusively we are having inner cab comfort at cost of global warming. Thermochromic material coatings are becoming popular in smart window sector for its energy saving property. Vanadium Oxide (VO2) is a metal-insulator reversible thermochromic material at transition temperature of 68oC. VO2 coated automobile windows can block infrared (IR) solar radiations at high temperatures and can keep in cab atmosphere pleasant under hot weather conditions. Alternatively in cold weather conditions VO2 based smart windows will let IR transmissions and will keep inner weather hot. VO2 smart window is ideal choice for reducing air condition demands and fuel cost in auto mobiles. Advantages of VO2 use are a) IR radiation stop-band b) easily applicable to large substrates c) Ability to lower its phase transition temperature. Practical implementation of VO2 based automobiles smart windows is hindered by the following issues associated with optical performances of VO2 i.e., weak visible transmittance and limited solar-energy modulation efficiency, high transition temperature and loss of thermochromic properties due to dust or water particles present in environment. To satisfy the requirements for practical applications in vehicles, the transition temperature should be decreased to near room temperature. Apart from this dust and water particles in atmosphere can also influence the transmission properties of VO2 by VO2 oxidization to V205 which makes it not suitable for all weather conditions. In this work we focused on optimizing the parameters of visible transmittance, transition temperature of VO2 and air conditioning demand reduction of vehicles by using VO2 smart windows. Tungsten doping was introduced for sputtered VO2 to lower down transition temperature. Furthermore nanocone structured self-cleaning antireflection coatings (ARC) were used to enhance optical properties. Nano structured ARC with self-cleaning feature has not been explored so far for smart windows as per our knowledge. This work purposed polydimethylsiloxane (PDMS) based Nano-cone anti-reflective and self-cleaning coating on top of VO2 to enhance the visible transmission and solar modulation properties for VO2 based smart windows for all weathers. PDMS is an environment friendly, transparent, hydrophobic and low cost material. Due to its flexibility and hydrophobic nature it can be easily fitted with glass surfaces with self-cleaning feature for dust and water and also makes VO2 based windows suitable for all weather conditions.

Resume : We present a hybrid material for covering swimming pools and water reservoirs. This material exhibits both the ability to block out visible light while transmitting near infrared radiation from the sun. This translates into two different functions: algae growth inhibition together with improved solar heating. This constitutes a substantial innovation compared to currently available materials unable to combine both benefits simultaneously. As the number of pools worldwide is increasing and pools are strong consumers of water, energy and chemicals, there is a global need to reduce the carbon footprint of pool ownership. By suppressing the wavelengths present in sunlight required for the photosynthesis algae growth may be suppressed. This has been proven in laboratory and in-field testing has shown a reduction by 60% of the chemical consumption compared to an uncovered pool. Furthermore, increased heat gain has been recorded in the laboratory using a solar simulator and outdoor full scale experiments have demonstrated the cover?s ability to reach temperatures very close to the performance of fully transparent covers. Hence, even if only part of the solar energy is transmitted to the water, the temperature increase is notably high. The close comparison of the new material to transparent covers is achieved as the visible light is poorly absorbed by the water. The promising product launch this year is the fruit of a successful knowledge transfer from academia to industry.

Resume : Hybrid materials combine not only the advantages of both organic (solubility, processability, flexibility) and inorganic (robustness, transparency, mechanical strength), but also present the exciting possibility of emergent properties and multifunctionality due to synergistic interactions between the constituents. We have recently revisited a class of hybrid materials known as ureasils, which are formed from polyether-based chains grafted to a siliceous backbone through urea cross-linkages using sol-gel chemistry. While the ureasils themselves are intrinsically photoluminescent, we have demonstrated that the introduction of complementary lumophores such as conjugated polymers, organic dyes and quantum dots results in a significant enhancement in the optical properties (e.g. quantum yield1, colour tunability2, refractive index). Selected highlights from our recent work will be presented, with specific focus placed on the targeted design of this unique class of materials for application as luminescent solar concentrators to enhance the performance of solar cells.3 1. N. Willis-Fox, A.-T. Marques, J. Arlt, U. Scherf, H. D. Burrows, L. D. Carlos and R. C. Evans*, Chem. Sci., 2015, 6, 7227-7237. 2. N. Willis-Fox, M. Kraft, J. Arlt, U. Scherf, and R. C. Evans*, Adv. Funct. Mater., 2016, 26, 532–542. 3. A. Kaniyoor, B. McKenna, S. Comby, R. C. Evans*, Adv. Opt. Mater., 2016, 10.1002/adom.201500412.

Resume : The entrapment of quantum dots or metal nanoparticles within organic hydrogels have been investigated for multiple areas [1,2] including light and energy harvesting applications [3]. These hybrid materials exhibit new light-interactive properties since organogels are interesting scaffolds for embedding optically active species but also present other properties such as self-organization,[4] gel to sol low temperature transition and reversibility,[5] and high solubility in a great range of solvents. Herein we describe a new NaYF4:organogel hybrid material featuring absorption of infrared radiation (980 nm) and rendering visible emission (red, green and blue region). These materials are comprised by up-converting nanoparticles (UCNPs) of a lanthanide-doped NaYF4 stacked to self-organized fibers of naphtalimide (NAF)-based organogels. Contrary to previous examples of light harvesting materials, the fibers are not mere scaffolds, but truly acceptors of the collected energy and also fluorescence emitters. The new soft harvesters can be submitted to cycles of melting-gelification without destruction of neither the gel structure nor the excitation energy transfer (EET) ability. [1] Rivero, P. J. et al. Nanoscale Res. Lett. 2011, 6, 1. [2] Wadhavane, P. D. et al. Soft Matter 2012, 8, 4373. [3] Rao, K. V. et al. Angew. Chem. Int. Ed. 2011, 50, 1179. [4] Miravet, J. F. et al. Org. Lett. 2005, 7, 4791. [5] Abdallah, D. J. et al. Chem. Mat. 1999, 11, 2907.

Resume : We are investigating the properties and applications of hybrid materials where polyoxometalates (POMs) – discrete nanosized molecular metal oxide clusters – are covalently connected to conjugated organic systems through imido bonds. These show strong electronic coupling between organic, and inorganic components and intense visible/near-UV absorption bands due to charge transfer from the appended organic to the POM acceptor (ligand-to-polyoxometalate charge transfer, LPCT). Hyper-Rayleigh scattering (HRS) measurements indicate that these hybrid compounds are unusually efficient molecular non-linear optical (NLO) chromophores, which break through empirical performance limits (defined by intrinsic β vs absorption maximum) that apply to the vast majority of purely organic materials. Moreover, we are able to electropolymerize suitable pyrrole-containing derivatives to form redox-active thin films. We will also present preliminary results indicating that related compounds are able to significantly (near 100%) increase photovoltages when used as co-absorbents in NiO-based p-type dye-sensitized solar cells.

Resume : Metal phosphonates are widely studied due to their potential applications in several domains such as opto-electronic and non-linear optical materials. Layered lanthanide aryl and alkyl phosphonates LnH(O3PR)2 (Ln = Eu, Tb; R = CH3, C2H5, C3H7, C6H5) are of a particular interest, since they have both a good thermal stability up to 400°C-500°C and an intense luminescence comparable to commercial phosphors. In order to study the influence of crystal structure and Eu3 and Tb3 doping rate in these compounds, La1 xLnxH(O3PR)2 (0 < x ? 1) hybrids have been synthezised via hydrothermal way at 180°C. Single crystal X ray diffraction reveales that the LaH(O3PR)2 structures are composed of alternating organic and inorganic layers. Within the inorganic layers, the La ions are disposed in chains of LaO8 polyhedra linked by opposite edges. Crystal structures and microstructures of La1-xLnxH(O3PR)2 compounds are presented. La1-xEuxH(O3PR)2 phosphonates exhibit 4f-4f Eu3 related luminescence at 611 nm; La1-xTbxH(O3PR)2 phosphonates exhibit both 4f 5d and 4f-4f excitation bands, with an emission maximum at 543 nm. The maximum luminescence is obtained for La0.25Eu0.75H(O3PC2H5)2 and La0.25Tb0.75H(O3PCH3)2. Effects of host matrix, lanthanide doping rates and excitation wavelengths upon Tb3 cross relaxation and concentration quenching phenomenon in La1-xLnxH(O3PR)2 materials will be presented in details and linked with the evolution of decay times and photoluminescence intensities.

Resume : Now a days radars are available from C to Ku bands i.e., 4-18 GHz frequency range, but the absorbers which are developed earlier for stealth application does not meet the requirement of such a broad bandwidth. Therefore, it is very much required to develop a cost effective microwave absorber with acceptable coating thickness which can provide broad bandwidth in the required frequency range along with simple, less complex fabrication technique. With these constraints, some of the materials like zinc oxide, silicon oxide and iron have been selected for the development of the composite microwave absorbers because of their higher dielectric and magnetic properties. The researchers have been developed these particular materials individually as the microwave absorber but in this study, the hybrid matrix of chosen materials has been fabricated for increasing the losses due to increase in the number of interfaces. Thus, in this paper nano-sized composites of zinc oxide (nZnO) and nano zero valent iron (nZVI) has been fabricated and analysed for its microwave absorption properties. The proportion effect of silica (SiO2) has been critically analysed in nZVI and nZnO matrix for enhanced microwave absorption and bandwidth. The top down approach i.e., high energy planetary ball mill has been used to synthesize the nano-sized materials of ZnO(~15 nm) and nZVI(~20 nm). The SiO2 has been utilized in “as received” condition. For fabrication of nano-composites, nZVI and nZnO were taken in 85 wt% and 15 wt% proportion, respectively with addition of silica (0.0, 2.5, 5.0, 7.5, 10, 12.5wt%). The XRD, FESEM, EDS, VSM and VNA have been used to analyse the phases present, morphology, elemental study magnetic properties and absorption properties, respectively. The reflection loss (RL) has been calculated from measured electromagnetic parameters and it is observed that ~6 GHz absorption bandwidth (-10 dB) has been achieved for the nano-composite having 85 wt% of nZVI and 15 wt% of nZnO. The effect of silica has also been analysed and it is found that the addition of silica shifts the absorption peak towards higher frequency. This may be the simultaneous effect of increase in number of interfaces and the high dielectric constant of silica. The nano-composite with 10wt% of X, has shown RL of -30.26 dB at 3.0 mm coating thickness with -10 dB bandwidth of 7.55 GHz (5.45 to 13.0 GHz). The developed absorber can be a cost effective solution for microwave absorbers with wide absorption bandwidth.

Resume : An overwhelming economic improvement for white LED and photovoltaic (PV) markets is based on the use of lanthanide-free phosphors that are supposed to convert UV light into visible one, thanks to down-conversion (DS) process. ZnO nanoparticles (NPs) have aroused an increasing interest since they possess a variety of intrinsic defects that provide light emission in the visible range without the introduction of any additional impurity. However, high photoluminescent quantum yield (PLQY), stable green/yellow emission and easy scale?up process are expected for industrial applications. Li-doping and polymer surface modifications of ZnO nanoparticles are mainly used in order to reach high PLQY (>30%) but PLQY decay over few days, uses of sophisticated polymers or multi-step reactions are the main issues for industrial implementation. In collaboration with the company Lotus Synthesis, we developped and patented an industry-capable (in terms of legislation concerns) and cost effective chemical solution process to get unique mesospheric self-assembly hybrid ZnO system with intense (PLQY = 40-75%) and stable visible emissions. We also demonstrate that the use of mixture of commercial polyacrylic acid-based polymers can provide large scale amounts of ZnO NPs clear water suspensions that can be dried and dispersed again in water without compromising the functional performance (e.g. transparency and PLQY) of the final DS layer. We will then address the effects of the ZnO NPs surface functionalization - such as nature, molecular weight, concentration, ratio of the PAA-based polymers and self-assembly process- on the enhancement of the efficiency of DS hybrid materials for LED and PV markets (or even cosmetics one).

Resume : A Cu-based organic?inorganic perovskite framework exhibits high-temperature ferroelectricity with strong magnetoelectric effects. Both electric field control of magnetization and magnetic field control of polarization are realized. Theoretical calculations suggest that a new mechanism of hybrid improper ferroelectricity arising from the Jahn?Teller distortions of magnetic metal ions and tilting of the organic cations are responsible for the peculiar multiferroic behaviors.

Resume : It is known that commercial development of organic photovoltaics (OPV) is hindered by low conversion efficiency and poor overall stability of the devices. The second issue is a consequence of high sensitivity of organic solar cells to trace quantities of oxygen, humidity and their combined action with light. One of the key solutions is encapsulation of organic solar cells with efficient barrier. This work is dedicated to the development of new polymer-based nanocomposites with water barrier properties. The strategy is based on incorporation of inorganic particles with water scavenger properties, such as zeolites, into Ethylene vinyl alcohol copolymers polymer matrix Nanocomposite films were processed by solution mixing or by melt-mixing in two-screw extruder. The nanocomposites were characterized by UV-Visible spectroscopy, transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and water uptake experiment. The best material was chosen considering film transparency, homogeneity of particles distribution, water sorption, thermal and viscoelastic properties of the films and stability of the polymer/zeolite nanocomposite under UV-light irradiation in presence of oxygen. Acknowledgments : The research leading to these results has received funding from the European Union Seventh Framework Programme (FP7/2011) under grant agreement ESTABLIS no. 290022.

Resume : This presentation will review our recent work on the laser-assisted synthesis and functionalization of 2D nanosheets (NSs)-Nanoparticles (NPs) hybrid materials for organic electronic applications. Rapid and facile methodologies for the photochemical synthesis, functionalization and doping of NSs-NPs hybrids, based on laser irradiation in precursor liquid or gas media, will be demonstrated. Distinct examples with graphene, boron nitride and transition metal dichalcogenides (WS2, MoS2) decorated with various types of plasmonic, metal oxide, and perovskite NPs are presented and discussed. Furthermore, we present a simple photochemical method for the simultaneous functionalization and doping of the as-synthesized NSs-NPs hybrids. Using this technique Cl and N doping was rapidly carried out at room temperature in only few minutes. Potential applications of photo-synthesized hybrid materials in organic electronics, particular to bulk heterojunction organic solar cells are demonstrated and discussed.

Resume : Graphene has been proposed recently to be used as a transparent and conducting electrode in oganic devices such as organic light emitting diodes [1]. It is used also as a soft top contact for connecting molecules in molecular devices [2]. Electronic properties of interfaces between graphene and molecules [3] need thus to be investigated and understood in the near future. Here, we present a study concerning transport experiments performed in devices including a thin film composed of functional molecules (bis-thienyl benzene or BTB) with thichness ranging from few nanometers to tens of nanometers inserted between two electrodes. As demonstrated previously in metal/molecule/metal junctions, the electrical response of such organic devices shows a strong rectification with negative threshold voltages of around few volts [4]. Here we show that by inserting graphene between the top metallic electrode and the molecular thin film, a drastic change in the electrical response of the device is observed as charge injection occurs more symmetrically at both positive and negative bias voltages. A temperature dependence study is also presented in order to investigate charge transport and injection mechanisms. Interestingly, we observe that pure graphene top electrodes allow to inject charges at even lower bias voltages (below 100 mV). Graphene at the bottom electrode has been also tested and preliminary results obtained in Ni/graphene/BTB/Co spintronics devices are also presented. Graphene is grown directly on the Ni electrode to passivate it and preserve its spin injection properties [5] and is used as a support for grafting the molecules. [1] S. Pang, Y. Hernandez, X. Feng, and K. Müllen, Adv. Mater. 23, 2779 (2011). [2] T. Li, J. R. Hauptmann, Z. Wei, S. Petersen, N. Bovet, T. Vosch, J. Nygård, W. Hu, Y. Liu, T. Bjørnholm, K. Nørgaard, and B. W. Laursen, Adv. Mater. 24, 1333 (2012). [3] G. Hong, Q. H. Wu, J. Ren, C. Wang, W. Zhang, and S. T. Lee, Nano Today 8, 388 (2013). [4] P. Martin, M. L. Della Rocca, A. Anthore, P. Lafarge, and J.-C. Lacroix, J. Am. Chem. Soc. 134, 154 (2012). [5] B. Dlubak, M.-B. Martin, R. S. Weatherup, H. Yang, C. Deranlot, R. Blume, R. Schloegl, A. Fert, A. Anane, S. Hofmann, P. Seneor, and J. Robertson, ACS Nano 6, 10930 (2012).

Resume : Graphene has attracted great attention in spintronics due to their high potentiality for spin polarized transport due to their small spin-orbit coupling, vanishingly small hyperfine interaction and excellent charge carrier mobility. However, despite considerable efforts in recent years, it is still challenging to efficiently manipulate the spins of the conduction electrons in graphene-based devices. Proximity contacts with magnetic oxides are of current interest from the expectation of the induced spin polarization as well as weak interactions at the graphene/magnetic oxide interfaces for efficient spin polarized injection. Here, we provide a direct evidence for the magnetic proximity effect in the junctions of single layer graphene and half-metallic manganite La0.7Sr0.3MnO3 (LSMO). In the current study we have employed the spin-polarized metastable deexcitation spectroscopy technique with extremely high surface sensitivity and successfully demonstrated that at the graphene/manganite interface, a large spin polarization is induced in the graphene pi-band together with a high thermal robustness that is independent of the chemical environment around graphene. For this purpose (001) orientation of LSMO with the c-axis out-of-plane and (110) orientation of LSMO with the c-axis in-plane were selected. In these two orientations, the termination layer of the LSMO are different that results in different chemical environments and electronic wavefunctions for the first deposited layer of graphene. This allow us to clarify whether the observed spin polarization is due to chemical interaction or due to proximity effect of the magnetic oxide. The results clearly show evidence for the magnetic proximity effect in the single layer graphene (SLG)/LSMO interface. It is demonstrated that graphene pi band in the SLG/LSMO junction is spin-polarized along the spin polarization direction of LSMO in a broad energy range below the Fermi level. The spin polarization in the vicinity of the Fermi level is significantly high in SLG/LSMO junctions different from that at the LSMO surface.

Resume : We show theoretically that the intrinsic (phonon-limited) carrier mobility in graphene nanoribbons is considerably influenced by the presence of spin-polarized edge states. In zigzag nanoribbons, when the coupling between opposite edges switches from antiferromagnetic to ferromagnetic with increasing carrier density, the current becomes spin polarized and the mean free path rises from ten nanometers to micrometers. In the ferromagnetic state, the current flows through one majority-spin channel which is ballistic over micrometers and several minority-spin channels with mean free paths as low as 1 nm. These features predicted in technology-relevant conditions could be nicely exploited in spintronic devices. Comprehensive calculations of the carrier mobility vs nanoribbon width, carrier density and chiral angle reveal the unexpectedly rich transport properties of graphene nanoribbons.

Resume : Triarylmethyls (TAMs) are stable open-shell molecules composed of three aryl rings bonded to a central methyl carbon atom, where their unpaired electron mainly resides. TAMs have played a prominent role within the research field of molecular magnetic materials and have a range of practical applications.[1] Moreover, very recently the potential of TAMs for use in molecular spintronics has been firmly established experimentally.[2] Using accurate ab initio density functional calculations we have shown that the spin localization within any TAM derivative, regardless of the chemical funtionalization and temperature, can be controlled by the torsion angles of the three aryl rings.[3] To exploit such a powerful feature, we have designed a range of chemically viable TAM-based 2D covalent organic frameworks (2D-COFs) where, in full agreement with our previous study,[3] the spin localization can be finely controlled by applying external strain. As a consequence of the strain-induced structural and spin localisation changes, other very important properties of these 2D materials (e.g. ferromagnetism, optical bandgaps, electrical conduction) can also be finely tuned in a reversible way. [1] I. Ratera and J. Veciana, Chem. Soc. Rev., 2012, 41, 303?49. [2] R. Frisenda, R. Gaudenzi, C. Franco, M. Mas-Torrent, C. Rovira, J. Veciana, I. Alcon, S. T. Bromley, E. Burzurí and H. S. J. van der Zant, Nano Lett., 2015, 15, 3109?3114. [3] I. Alcon and S. T. Bromley, RSC Adv., 2015, 5, 98593-98599.

Resume : Mesoporous structures with controlled pore sizes are significant because of their use for adsorption, phase separation, controlled release, sensing, storage, and catalysis. These materials, therefore, offer many opportunities for practical applications in various fields including environmental, energy, optics, electronics, medical, biological among others. Gallium oxide, Ga2O3, is known as a chemically and thermally stable semiconductor material with a wide band gap and is of great interest in many applications such as catalysis, optoelectronic devices, gas sensors, luminescent materials, and photo-catalysis. In the present study, we demonstrate a novel hybrid approach to fabricate porous structures that is to use polymer chemistry (coordination polymerization) to fabricate coordination complex, which then can be converted to porous oxides though thermal degradation of organic content. Fabrication procedure involves colloidal metals in dilute acidic solution, which serve as a continuous reservoir for polymerization reaction at room temperature. This robust procedure allows us to design architecture of the intermediate products via self-assembly and tune the resultant porous network through felicitous choice of reactants, and reaction environment and offers significant opportunities for material design.

Resume : complete TITLE: Electromagnetic and microwave absorbing properties of polymer composite containing Fe-Co hollow fiber and Co powder hybrid fillers in the GHz range// The development of the microwave absorber in the GHz frequency range is great demand due to their stealth performance on combat planes, submarines and missiles decisive factor in modern warfare for the survival. To enhance the microwave absorption efficiency, cobalt spherical type powder and Fe-Co high-aspect-ratio magnetic metal hollow fiber hybrid fillers for magnetic and dielectric loss are applied to microwave absorbing composite. It is able to overcome the limitation of the Snoek’s limit and keep the permeability over the GHz high frequency range to improve the absorbing properties. SiO2 dielectric layer is coated at Fe-Co hollow fiber surface to prevent the high permittivity to meet the impedance matching for the high reflection loss at 10 GHz the intermediate frequency of the X-band. Dielectric coated Fe-Co hollow fiber and Co powder hybridized microwave absorbing polymer composite presents remarkable absorption efficiency of -35 dB at 10 GHz with the thickness of 1.420 mm. Optimization design is also carried out for the matching thickness at 10 GHz based on transmission line theory.

Resume : Up to now, ferromagnetic nanowires were mainly synthesized by electrodeposition of metals in nanoporous templates resulting in polycrystalline wires of relatively large diameters and packed at moderate densities. We have recently introduced a physical-chemistry hybrid method by adapting the seed-mediated solution phase synthesis of nanocrystals in order to directly grow them on ad-hoc crystalline thin films [1]. We have thus defined the solution growth and self-assembly of single-crystalline hcp Co nanowires of 6 nm in diameter on various 1×1 cm² thin films. Without any template, Co wires grow vertically and epitaxially on unpatterned Pt(111) films and spontaneously self-arranged in hexagonal arrays of 1e12 NWs/cm² as revealed by small angle neutron scattering [2]. At the opposite, the Co nucleation on Pt(001) films starts with epitaxial Co islands on which tilted wires grow into discrete spatial directions. The principle of this solution epitaxial growth has also been successfully extended to the growth of Fe nanostructures on Pt(111) and Pt(001) films. Supported Co wire arrays constitute interesting systems for catalysis and magnetic devices. Especially, the ultra-dense Co wire arrays on Pt(111) present an important perpendicular magnetic anisotropy (PMA) at room temperature due to their single-crystalline hcp structure and intrinsic wire shape. The combination of very high densities, PMA and low cost and scalable process confers a high interest of this system in future ultrahigh magnetic recording, especially concerning identified alternating routes as bit patterned media. Magnetometry, magnetic nuclear resonance and ferromagnetic resonance allow describing the different sources of anisotropy taking into account the strong dipolar interactions between NWs. [1] N. Liakakos, et al. ACS Nano 9 (2015) 9665 [2] N. Liakakos, T. Blon, et al. Nano Lett. 14 (2014) 3481

Resume : Introduction Photocatalysis based on semiconductor technology is highly expected to offer cost-effective solutions for effective utilization of solar energy in water purification, hydrogen generation, carbon dioxide reduction or air detoxification [1]. A key technological target to reach efficient conversion of chemical products by using solar energy is to develop a performant and robust solar-light responsive photocatalyst; however, photo-efficiency of the bare semiconductor catalysts is enough limited due to the high rate of electron-hole recombination [2]. In a semiconductor composite, designed as ensembles of specific semiconducting units, the joined heterojunction interface of the components is able to facilitate the interfacial charge transfer thus, to enhance the separation of photoinduced charges. Zinc-based layered double hydroxides (LDHs) are layered porous matrices belonging to the class of anionic clays that have recently been described as a novel class of doped semiconductors units [3]. A highly versatile chemical composition of LDHs can be obtained by tailoring either the nature of cations of the layers and/or the type of inter-layers anions. With an aim at developing novel efficient semiconducter photocatalysts we present in this work nanoparticles of gallium (GaNPs) or indium (InNPs) self-supported on the matrices of ZnAlLDHs and ZnGaLDH, respectively. Further, we present here the applications of these catalysts in degrading p-nitrophenol and p-nitrophenl-phenol mixtures, under simullated solar irradiation. Experimental ZnAlLDH and ZnGaLDH were prepared by co-precipitation method [2]. GaNPs or InNPs self-supported on ZnAlLDH and ZnGaLDH, respectively were obtained by the reconstruction of the LDHs matrices in Ga2(SO4)3 and In(C2H3O2)3, respectively. X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG), Fourier transform infrared (FTIR) transmission electron microscopy (TEM) X-ray photoelectron spectroscopy (XPS) and UV-Vis spectroscopy were used to investigate the structural, photo-responses and micromorphology features of the catalysts. Results and discussion The structure of the catalysts is examined by X-ray diffraction (not shown) revealing LDHs as the majority phase (ICDD file No. 22-700). Fig. 1A compares the UV-Vis spectra of the reconstructed samples and the mixtures of mixed oxides obtained after calcination at 750˚C. It reveals that the absorption edge gradually red-shifts from 400 to 560 nm wavelength when gallium and indium are incorporated in the catalysts. Fig.1. A) UV-Vis fetures of the tested catalysts. B) TEM micrographs of InNPs/ZnAlLDH. C) Kinetic linear fitting curves for degradation p-nitrophenol over the tested catalysts under solar irradiation. D) Variation of UV-Vis spectra of p-nitrophenolsilution on InNPs/ZnAlLDH750. The representative TEM image is displayed in Figure 1B. It reveals the presence of small NPs that can be clearly identified as dark spots that are highly dispersed on the surface of the LDHs. The plots of lnA=f(t) (A=ci/ct) are shown in Fig.1C. The kinetic results fitted well the pseudo-first order kinetic according to the good value of the correlation coefficient (R2>0.9758). The XPS results demonstrate that gallium and indium are supported on the LDHs surface as Ga2O3 and In2O3. The mineralization of 1-4 nitro-phenol, as a function of time, under the irradiation with a solar simulator Unnasol US 800 (180 W) is shown in Fig. 1D for the most efficient photocatalyst InNPs/ZnAlLDH750. Conclusions The self-supported nanoparticles of In2O3 and Ga2O3 on zinc-based LDHs and their derived mixtures of mixed oxides were tailored as novel photoresponsive nanocomposites. Results point out that the catalytic effieciency is enhanced by the presence of nanosized gallium and indium though is also influenced by the thermal treatment of the catalayst. Acknowledgements The authors gratefully acknowledge the financial support from the Romanian National Authority for Scientific Research, CNCS-UEFISCDI; project number PN-II-IDPCE 75/2013. References [1] Z. Bian, T. Tachikawa, P. Zhang, M. Fujitsuka, T Majima J. Am. Chem. Soc. 136 (2014), 458−465. [2] E.M. Seftel, M.C. Puscasu, M. Mertens, P. Cool, G. Carja, Appl. Catal. B 164 (2015) 251-260. [3] C. Gomes Silva, R. Juárez, T. Marino, R. Molinari, H. García, J. Am. Chem. Soc., 133 (2011), 595-602.

Resume : Hybrid materials with percolation network structure are strong candidate as electrodes for transparent devices and effective scaffolds for energy storage/conversion devices. Although various two-dimensional assembly techniques have been developed, challenges remain in fabricating these materials in an efficient and scalable manner in addition to making them mechanically robust without additional crosslinking steps or chemical etching. We use a biologically templated approach to assemble a large-area conductive hybrid nanomesh. Single-walled carbon nanotubes (SWNTs) were hydrodynamically assembled into a conductive hybrid nanomesh using biological glue, a genetically engineered M13 bacteriophage with strong binding affinity toward SWNTs via biomolecular recognition. Concentration polarizaion, a diffusion-based hydrodynamic phenomenon, combined with biomimetic interactions produced a conductive nanomesh with extremely well-controlled nanostructures over large area and unprecedented material properties by employing biological materials. Graphene nanosheets were additionally incorporated and assembled into a hybrid nanomesh to serve as an intercalation anode material. The specific capacity of the hybrid nanomesh was found to be 800 mAh/g without additional chemical treatment and the cycling ability is stable. By controlling the transparency and the conductivity of the hybrid nanomesh, we also demonstrate an applicability of the conductive nanomesh for the electrode of transparent battery.

Resume : The results of the recovery of electron density of states from the analysis of XPS spectra of bulk metals (Au, Pd, Pt, Ag) are presented. It is shown that logarithmic derivative of the recovered density of states at the Fermi energy level corresponds with the magnitude of the thermoelectric power of these metals. The theoretical model that allows one to restore the value of thermoelectric power from XPS spectra analysis by use of asymptotically exact stochastic method "gradient descent + Monte Carlo algorithm" is presented. The applicability of this technique for determination the thermoelectric power value of nanostructured quasi two dimensional films to create a high-performance thermoelectric materials for a new generation of betavoltaic devices is discussed.

Resume : Layered double hydroxide (LDH), also called hydrotalcite-like compound or anionic clay, is a family of lamellar ionic solids that in terms of layer charge is the counterpart of cationic clay minerals. On the basis of their specific structure and versatility in chemical composition, LDH materials have been used as catalysts and supports. Although the structure of LDH has the ability for high light absorption in the spectral range, the photocatalytic efficiency is practically low for its applications. However, the photocatalytic properties of these materials have been mostly ignored because it has a lower photocatalytic efficiency than TiO2. Therefore, we have attempted the synthesis of NiFe CO3 Layered double hydroxides using a Co-precipitation/Post microwave hydrothermal method and then alter the brucite like layers with Pd and check its activity under UV irradiation. The as-obtained Inorganic-Inorganic hybrid Pd/NiFeCO3 LDH photocatalyst have been thoroughly characterized by several techniques such as powder X-ray diffraction (PXRD), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), Brunauer?Emmett?Teller surface area analysis (BET), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). TEM analysis has shown that Pd has not been immobilized rather it has occupied the brucite-like layers. The altered inorganic material was then tested for its photocatalytic efficiency using Orange II dye as the model compound and they are anticipated as a promising candidate for other photocatalytic applications.

Resume : Delamination at various interfaces is one of the most critical reliability issues in plastic packages. Particularly delamination occurring between copper leadframe and molding compound are not fully clarified. To understand the adhesion mechanisms every adherent layer has to be fully characterized. During the molding process the copper leadframe is heated to 175°C and builds an oxide layer resulting in a multilayer system copper/copper oxide/mold. In this study we systematically investigated the copper/copper oxide layer system. The qualitative and quantitative effects of the thermal oxidation of polycrystalline copper (Cu-PHC= High Conductive Phosphor deoxidized Copper) have been analyzed. The samples have been oxidized at 175°C in air at atmospheric pressure for several minutes. To characterize the surface we used Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). The changes in grain size and roughness values have been determined. Further, the chemical composition of the oxidized copper samples have been investigated via X-ray Photoelectron Spectroscopy (XPS) and Raman spectroscopy. We used a combination of Focused Ion Beam (FIB) and SEM to determine via cross-sections directly the oxide layer thickness and investigate effects of delamination which are essential for adherence. It has been shown that the surface properties and the adherence of the oxide layer could also affect the interaction to mold compound and influence the reliability of the devices.

Resume : Zinc and Tin oxide is a promising In and Ga-free transparent semiconductors that demonstrated great potential as transparent conducting oxides in application like photovoltaic devices, flat panel displays, solar cells, due to its high electron mobility, high electrical conductivity, and low visible absorption [1 ]. Zn2SnO4 can also be applied to the field of gas sensing, if the resistance of the material is appropriate, that is not too conducting. We prepared Zn2SnO4 thin films by RF sputtering starting from sintered ceramic target with Zn:Sn ratio 2:1, investigation the influence of deposition parameters (oxygen content and substrate temperature) during deposition on the thin film properties. Amorphous films are obtained for deposition temperature up to 400°C, but they become crystalline (Zn2SnO4) after proper annealing treatment higher than 600°C. Annealing in air and in Ar resulted in porous film that are suitable for gas sensing. All films are transparent before and after annealing. We investigated optical properties of thin films by UV-VIS, Raman and photoluminescence spectroscopy and functional properties of thin films for gas sensing applications. The material demonstrated to have high potential for ethanol sensing of at 400°C and acetone at 300°C. Ternary thin films find also application in electronic nose for food analysis. References [1] Coutts TJ, Young DL, Li X, Mulligan WP, Wu X, J Vac Sci Technol 2000, A 18:2646?2660

Resume : Cu2SnSe3 nanoparticles are synthesised using oleyalmine as both a solvent and capping agent and spray coated onto conductive glass substrates to form dye-sensitised solar cell counter electrodes. The film requires annealing at only 400 °C in nitrogen, which is a lower temperature than previous reports of nanoparticle-derived films of both Cu2SnSe3 and Cu2ZnSnSe4, as well as avoiding the use of Se gas in the annealing process, shown in Fig 1. The composition and phase of the material is confirmed to be close-to-stoichiometric Cu2SnSe3 by energy-dispersive X-ray spectroscopy, X-ray diffraction and Raman analysis. Dye-sensitised solar cells using Cu2SnSe3 counter electrodes give a power conversion efficiency of 4.87 %, which is close to the efficiency of 5.35 % achieved when using a Pt counter electrode, shown in Fig 2and Table 1. Electrochemical impedance spectroscopy, Fig 3, indicates that the performance of the Cu2SnSe3 electrode is enhanced under illumination, leading to a drop in the charge transfer resistance which is attributed to the higher overpotential of photoexcited carriers in Cu2SnSe3. Coupled with a very high surface area resulting from the hierarchical structure of the film, this leads to effective catalytic operation of this earth-abundant counter electrode.

Resume : The protection of a catalytically active system by anchoring it within an organic matrix is an underlying and widely used strategy in heterogeneous catalysis. Within this scenario, the preparation of hybrid materials through the integration of the multimetallic catalytic active species into a polymeric matrix is a fertile field of research. In this communication we report the first example of hybrid materials based on polymethlymethacrylate (PMMA) matrices covalently reinforced by MyOx(OH)w(O(O)CR)z (M=Zr or Hf oxoclusters, stabilized by acrylic acids RCOOH), used as heterogeneous catalytic systems for hydrogen peroxide activation. The resulting hybrids, prepared by thermally or photochemically activated polymerization, were used to catalyze the oxidation of dibenzothiophene (DBT) to the corresponding sulfoxide (DBTO) and sulfone (DBTO2), in order to demonstrate their potential application for the oxydesulfurization of a fuel. Owing to the enhanced catalyst stability and to the higher affinity of the polymeric matrix towards polar substrates, the heterogeneous set-up displays improved performances with respect to the corresponding homogeneous systems. A DBT conversion up to 90% was thus obtained in 4 h, with a >90% selectivity for DBTO2 (T=65°C). The photopolymerized hybrids, in particular, showed a better kinetic behavior, with faster initial reaction rates, owing to a better control of cross-linking degree and, in turn, of their swelling behavior. The stability of the hybrid materials under catalytic conditions was successfully assessed by a combined spectroscopic approach, based on FT-IR, Solid State Nuclear Magnetic Resonance, X-ray Absorption and Small Angle X-ray scattering measurements.

Resume : Research on polymer electrolytes (PEs) have emerged as important ionic conducting materials due to some special features in particular good electrode?electrolyte contact, ease of processing into thin films with a large surface area to ensure high energy density, the ability of accommodating a wide range of ionic salt concentrations, good mechanical and adhesive properties and high ionic conductivity [1]. These materials present promising applications in electrochemical devies, such as secondary batteries, electrochromic devices, fuel cells, solar cells, supercapacitors and chemical sensors [2,3,4] In recent years the PE community has turned its attention on the development of light, safe and low cost devices. With this goal new PE obtained from renewable sources have been investigated to replace the traditional synthetic polymers. Natural polymers are promising substitutes of synthetic polymers, due to their richness in Nature, non-toxicity, biodegradability, good physical and chemical properties, and very low cost, and good performance. Most of these new systems have been based on hydroxyethyl cellulose [5], starch [6], chitosan [7], agar [8] and gelatin [9]. The ion transport properties of SPEs depend on many factors like degree of salt dissociation and its concentration, dielectric constant of host polymer, degree of ion aggregation, and mobility of polymer chains [9]. An effective means of increasing the ionic conductivity of SPEs consists in plasticizing the polymer electrolyte with organic molecules, such as ethylene carbonate (EC), poly(ethylene glycol) (PEG), and glycerol, which have high dielectric constant and low vapor pressure [10]. These plasticizers help improving the ionic conductivity of SPEs by (i) increasing the amorphous phase content; (ii) dissociating ionic aggregates; (iii) lowering the glass transition temperature. In the present work PEs based on k-carrageenan, a dopant (an ionic salt or an ionic liquid) and glycerol have been prepared. k-Carrageenan is a water soluble phycocolloid extracted from red algae and is used mostly as a stabilizer and structure provider in the food and ice cream industries [11]. The basic structure of carrageenan is a linear polysaccharide made up of a repeating dissacharide sequence of 1,3-linked alfa-D-galactopyranose and 1,4-linked beta-(3,6-anhydro-)D-galactopyranose. The k ?carrageenan-based conducting-PEs were prepared by the solvent casting technique. ACKNOWLEDGMENT This work was supported by FEDER, through COMPETE and Fundação para a Ciência e a Tecnologia (FCT), (FCOMP-01-0124-FEDER-037271, PTDC/CTM-BPC/112774/2009, Pest-C/CTM/LQ0011/2013, Pest-OE/QUI/UI0616/2014 and PEst-OE/SAU/UI0709/2014) and COST Action MP1202880 "Rational design of hybrid organic-inorganic interfaces" and the Portuguese National NMR Network (RNRMN) S. C. Nunes acknowledge FCT for grants (SFRH/BPD/63152/2009). The authors thank CPKelco (U.S.A.) for providing the carrageenan. REFERENCES [1] J. R. MacCallum, C. A. Vincent (Eds.), Polymer Electrolyte Reviews, vols. 1 and 2, Elsevier Applied Sciences Publisher, London, 1987 and 1989, 2. [2] E. Quartarone, P. Mustarelli, Chemical Society Reviews 40(5) (2011), 2525-2540. [3] A. Kavanagh, R. Byrne, D. Diamond, K. J. Fraser, Membranes 2(1) (2012), 16-39. [4] H. Gao, K. Lian, RSC Advances 4 (62) (2014) 33091-33113. [5] G. O. Machado, R. E. Prud'homme, A. Pawlicka, E- Polymers 115 (2007). [6] M. F. Shukur, M. F. Z. Kadir, Ionics 21(1) (2015) 111-124. [7] S. N. S. Begum, R. Pandian, V. K. Aswal, R. P. Ramasamy, R. P. (2014) J. of Nanoscience and Nanotechnology, 14 (8) 5761-5773. [8] R. D. Alves, L. C. Rodrigues, J. R. Andrade, A. Pawlicka, L. Pereira, R. Martins, E. Fortunato, M. M. Silva, Molecular Crystals and Liquid Crystals, 570 (2013) 1-11. [9] M. M. Silva, P. C. Barbosa, L. C. Rodrigues, A. Gonçalves, C. Costa, E. Fortunato, Optical Materials 32 (2010) 719?722. [10] K. Dillip, R. N. P. Pradhan, K. Choudhary, B. K. Samantaray, Int. J. Electrochem. Sci. 3 (2008) 597-608. [11] F. Van de Velde, G. A. Ruiter, "Carrageenan", in: Polysaccharides and Polyamides in the Food Industry, Vol. 1, Chapter 3, A. Steinbuchel, S. K. Rhee, Eds., Wiley-VCH, Weinheim 2005, p. 85-114.

Resume : Controlling self-assembly and disassembly of monomers by external stimuli is of great importance in the study of supramolecular polymer chemistry and has attracted more and more attention in the past few years. Supramolecular polymers, the combination of supramolecular chemistry and traditional polymer chemistry, consist of the same or different kinds of monomers held together by reversible and directional noncovalent interactions. Based on the responsive and reversible nature of the noncovalent bonds, supramolecular polymers have shown unique and interesting properties, and have become one of the most active fields in supramolecular chemistry and material science. Now, as an important part of supramolecular chemistry, host–guest interactions have become more and more popular in the fabrication of supramolecular polymers. Pillararenes, a new kind of calixarene analogues, have become one of the hottest topics in macrocyclic chemistry since they were found in 2008. Their syntheses, functionalizations, conformations, host–guest properties and applications in different areas have been actively investigated. Interestingly, Huang and coworkers prepared an alkyl chain-based dialkylammonium salt, n-octylethyl ammonium hexafluorophosphate, and found that it complexed with 1,4-dimethoxypillar[5]arene (DMpillar[5]arene) in chloroform and in the solid state to form a [2]pseudorotaxane with N-H•••π interactions and C-H•••π interactions as the main driving forces. Based on this new molecular recognition motif, herein, we synthesized a mono-functionalized pillar[5]arene with a dialkylammonium salt as an AB-type heteroditopic monomer to construct a novel anion responsive supramolecular polymer.

Resume : Functionnalized filler nanocomposites are commonly reported in polymer coating application due to their beneficial barrier effect as well as more recently regarding corrosion resistance. Aside layered double hydroxide LDH that has been largely used another 2D anisotropic material layered dingle hydroxide LSH is scarcely studied. However, possible interactions between divalent cations and alumina source (either γ-AlOOH or Al metal surface) may occur even under mild condition (neutral pH and ambient temperature). This prompts us to study the stability of the LSH filler against Al substrate. Starting from an aqueous polymer in presence of both LSH in presence of alumina source, successive X-ray diffraction analyses have been performed in time and temperature. The intralayered arrangement informed by the location of the (110) diffraction peak indicates a conversion to LDH. Such topochemical reaction is found to be temperature dependent. The mechanism of conversion proceeds through the juxtaposition of both LSH and LDH phases with no induction period of time for the observed temperature range. A full conversion is observed between both inorganic frameworks. The curve feature of the fractional evolution is satisfactorily modeled by solid state kinetic defined by Avrami-Erofe’ev and more specifically by Johnson-Mhel-Avrami-Kolmogorov (JMAK) description, adopting a first-order reaction case and associated with activation energy of about 140 kJ.mol-1.

Resume : A screening of various ?-amino (?AA) acid molecules in regard of their ability to retard corrosion on AA 2024 aluminum alloy substrate was performed for L-Arginine (L-ARG), L-Asparagine (L-ASN), L-Cysteine (L-CYS), L-Cystine, L-Histidine (L-HIS), L-Methionine (L-MET), L-Phenylalanine (L-PHE), L-Serine (L-SER), L-Tryptophan (L-TRP), L-Tyrosine (L-TYR). From their performance compared to reference additives, chromate and 2-mercapto-benzothiazolate (MBT), selected L-CYS and L-PHE and their layered double hydroxide (LDH) interleaved derivatives were further scrutinized. Different LDH phases, LiAl2, Mg2Al, Mg1Zn1Al and Zn2Al, were tested as hosts for the inhibitor ?AA substances, and characterized by XRD, FTIR, and SEM. The efficiency and durable performance as an anticorrosion agent for aluminum Alloy 2024 (AA2024) were demonstrated by using DC-polarization as well as by recording the evolution of the polarization resistance. The mechanisms of inhibition focused on the most promising hybrid materials, LDH/L-CYS, are tentatively explained with anion exchange and inorganic framework dissolution at the cathodic and anodic corrosion zones, respectively, with the particular occurrence of Cu-rich intermetallic zones. The obtained results evidence that the LDH/L-CYS assembly embedded in the polymer coating is found to retard after a prolonged time of immersion the corrosion process of AA2024 substrate.

Resume : Molecular layer deposition (MLD) has emerged from the atomic layer deposition (ALD) technique as an all-gas phase thin film growth technique capable of producing pinhole free films on large areas and complex surface geometries. The films are grown in a sequential manner using metal atoms as connection points between organic linkers. The majority of the materials deposited so far utilise bifunctional organic linkers based on alcohols, carboxylic acids or amines as functional groups, ranging from the simple molecules to more advanced amino acids. The films are typically amorphous as deposited, but lately also crystalline modifications such as the UiO-66 metalorganic framework has been produced. The current contribution will provide an overview of the field of MLD highlighting possible applications such as low-k dielectric material and bioactive surfaces.

Resume : Organic solar cells have potential advantages over conventional inorganic solar cells due to their low weight and potential low cost production in e.g. roll‐to‐roll printing. Furthermore, mechanical flexibility and the possibility to adjust the wavelength range of absorption can even open new operational areas. Within the search for highly efficient narrow band‐gap donor materials for enhancement of device performance, 2‐{[7‐(5‐N,N‐ditolylaminothiophen‐2‐yl)‐ 2,1,3‐benzothiadiazol 4‐yl]methylene}malononitrile (DTDCTB) is a promising candidate that showed good performance in organic solar cells [1] and ternary organic solar cells [2]. Morphology and grain size are strongly affecting the exciton diffusion length. The relation between morphology of the DTDCTB:C60 blend in the active layer and device performance are still to be established. In this study, we present an electron microscopy study, resolving the morphology of different DTDCTB:C60 blends. The possibility to use signals detected in scanning and transmitted electron microscopes to provide material composition will be discussed. This work was supported in part by the German Science Council Center of Advancing Electronics Dresden (cfaed). [1] H. Lin et al., Org. Electron., 13 (2012), pp. 1722–1728 [2] H. Shim et al., ACS Appl. Mater. Interfaces, 8 (2016), pp. 1214–1219

Resume : Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient PMMA continuous phase. The current study thus demonstrates that the IL-polymer miscibility and thus the morphology of the IGs is a key parameter to control the (macroscopic) properties of IGs.

Resume : We have synthesized mesoporous silica (monoliths) with defined surface chemistry via a number of addition reactions, (i) coupling of an isocyanate to a surface-immobilized thiol, (ii) addition of an epoxide to a surface-immobilized thiol, (iii) cross metathesis between two olefins, and (iv) Huisgen [2+3] cycloaddition of an alkyne-functionalized silica monolith with an azide. Functionalization of the mesopores is observed, but there are significant differences between individual approaches. Isocyanate and epoxide additions lead to high degrees of functionalization, while olefin metathesis and [2+3] cycloaddition are less effective. We further show that the efficiency of the modification is about twice as high in mesoporous silica particles compared to macroscopic silica monoliths.

Resume : We present a first-principles investigation of the electronic structures and magnetic properties of a double perovskite Sr2CrZrO6, by using the full-potential linearized augmented plane-wave (FP-LAPW) method based on Density Functional Theory (DFT) as implemented in the WIEN2K.The properties of double perovskite Sr2CrZrO6 were calculated using generalized gradient approximation (GGA) method. In order to take into account the strong on-site coulomb interaction that means we included the Hubbard correlation terms GGA+U approache.We have analyzed the structural parameters,band structure, total and partial densities of states. The results show a half-metallic ground state with the ferrimagnetic coupling of Cr and Zr spins. Keywords : Electronic structure, GGA+U, First-principales, Double perovskite, Half-metalic, Ferrimagnetic coupling.

Resume : 3d transition metal centered phthalocynanines are potential candidates for spintronics based on single molecule magnets. Weakly interacting 2D materials are attractive substrates for supporting these molecules for realizing functional devices. Here, we will present ab initio studies on the adsorption characteristics of iron and cobalt phthalocyanine molecules supported on 2D graphene and MoS2 substrates. Calculated structural, electronic and magnetic properties will be presented with a comparison between adsorbed and gas phase molecules. Influence of the substrate on the spin-dipole and magnetic anisotropy contribution of the transition metal centers will be shown along with the changes in work functions due to adsorption.

Resume : Spin dependent properties of molecules/ferromagnetic metal interfaces are known to be very sensitive to the nature of the interaction (chemisorption versus physisorption) between the two materials [1]. Here a two-step electrochemical procedure to covalently graft molecules over ferromagnetic surfaces like Co and Ni is presented. It is based on an in-solution electrochemical process [2] allowing to graft radicals (diazonium chemistry) over a conducting surface. The deposited molecular thin film is then very robust even against aggressive fabrication processes like photolithography. An other key aspect comes from the presence of undesired oxyde at the interface which might alter the electronic and magnetic properties of the magnetic material. This electrochemical process could easily remove oxyde by reducting it and passivate the Co film. The magnetic properties of functionalized thin magnetic films of Si//Pt (40 nm)/Co (8 nm)/nitro-benzene diazonium (NBD) have been investigated by Superconducting Quantum Interfermetry Device (SQUID) magnetometry. For a 8 nm thin Co film deposited over Pt, a fully in-plane magnetization is found where as for a functionalized 8 nm thin Co film an out-of-plane component emerges. Atomic force microscopy and X-ray photoelectron spectrocopy characterizations of the functionnalized surface is also presented. The roles of the different parameters of the procedure are finally discussed. [1] M. Galbiati, S. Tatay, C. Barraud, A. V. Dediu, F. Petroff, R. Mattana, and P. Seneor, MRS Bull. 39, 602 (2014). [2] T. Fluteau, C. Bessis, C. Barraud, M. L. Della Rocca, P. Martin, J.-C. Lacroix, and P. Lafarge, J. Appl. Phys. 116, 114509 (2014).

Resume : In dye-sensitized solar cells (DSSC) a crucial role for high photoconversion efficiency play electron transfer processes proceeding at the oxide semiconductor/dye/electrolyte interfaces. The exact nature of ultrafast electron injection and further charge carrier separation processes involving intermediate stage of electron-hole (e-h) pairs is so far not fully understood. In this work we propose a novel mechanism of photocurrent generation in DSSCs examined by magnetic field effect (MFE) technique. During dissociation processes singlet 1(e-h) and triplet 3(e-h) pairs are created where the electron occupies the conduction level of TiO2 and the hole is localized on an oxidized dye molecule. The external magnetic field of hundreds mT strength affects the intersystem crossing (ISC) between 1(e-h) and 3(e-h) pairs and this way change the generated photocurrent. We have observed that the magnitude of the small negative MFE on photocurrent in DSSCs is controlled by the radius and spin coherence time of e-h pairs which are modified by the photoanode morphology (TiO2 nanoparticles or nanotubes) and electronic orbital structure of various dyes (ruthenium N719, dinuclear ruthenium B1 and fully organic squarine SQ2 dyes). The observed MFE is explained by the different values of Lande factor for electron and hole entities forming e-h pairs (?g mechanism). This work was supported by the Polish Ministry of Science and Higher Education under ?Diamond Grant? 0228/DIA/2013/42.

Resume : The recent discovery of 2D materials has opened up novel exciting opportunities in terms of functionalities and performances for spintronics devices. One of them is to address the issue of the oxidation of ferromagnetic materials which considerably limit the use of air/wet processes in the fabrication of devices. The recent progress on the growth of graphene and h-BN by chemical vapour deposition on top of ferromagnetic catalysts like Ni[1] or Fe[2] has permitted to circumvent this issue. We will first show how a thin graphene passivation layer can prevent the oxidation of a ferromagnetic electrode of Ni, enabling its use in in novel humide/ambient low-cost processes for spintronics devices while adding a new interesting spin filtering property[3]. We will then highlight the passivation properties of a monolayer of h-BN on top of Fe and show the resulting successful integration of h-BN as a tunnel barrier in magnetic tunnel junctions[4]. These different experiments unveil promising uses of 2D materials for spintronics. [1] Weatherup et al. ACS Nano 6, 9996 (2012) [2] Caneva et al. Nanoletters 15, 1867 (2015) [3] Martin et al. ACS Nano 8(8) 7890 (2014), Appl. Phys. Lett. 107, 012408 (2015) [4] Piquemal et al. submitted

Resume : The study of the spin properties of ferromagnetic metal-organic (MO) interfaces has received considerable attention in the past, because of the prospect of developing new hybrid and multi-functional molecular devices. A number of studies could evidence in such systems the presence of interface states (IS) in the gap region of the organic semiconductor. If such IS were to show in addition a high spin polarization, they could be of great interest. In fact, highly spin-polarized IS close to the Fermi level are of utmost importance for the spin injection efficiency across ferromagnetic MO interfaces and thus for the performance of future organic spintronics devices. Such highly spin-polarized IS at the Fermi energy could indeed be observed in a very recent spin-resolved photoemission study of phthalocyanine (Pc) films on ferromagnetic Co(001). Having evidenced highly spin-polarized IS, the question is raised whether this property is confined to Pc molecules, or whether these results are indicative of a broader pattern. We deploy topographical and spectroscopic techniques to show that a strongly spin-polarized interface arises already between ferromagnetic Co and mere carbon atoms. Scanning tunneling microscopy and spectroscopy show how a dense amorphous semiconducting carbon film with a low band gap of about 0.4 eV is formed atop the metallic interface. Spin-resolved photoemission spectroscopy reveals a high degree of spin polarization at room temperature of carbon-induced states.

Resume : One very efficient route to tailor the spin properties of surfaces and interfaces, which was so far only applied to ferromagnetic metals, is the creation of customized hybrid interfaces between inorganic and organic materials. The interest in the spin properties of such systems was originally stimulated by the observation of magneto-resistive effects in spin-valve structures prepared with an organic-based spacer layer [1, 2]. Today, it is known that the performance of such organic spintronics devices is mostly determined by the spin-dependent properties of the hybrid interface formed between the organic molecules and the ferromagnetic electrodes: the so-called spinterface [3]. Crucially, the spin properties of a specific spinterface such as spin polarization, spin filtering, and coercive field can be in principle tuned by any external stimulus that will either modify the electronic structure of the organic molecules forming the spinterface, or change the strength of the interaction between the molecules and the ferromagnetic substrate. This concept was demonstrated, for example, for doping of the organic molecules with electron donors [4] and for chemical synthesis of tailored molecules [5, 6]. In this talk I will show that the extreme multi-functionality of organic molecules can be used to functionalize the spin properties of the more general class of spin-textured materials, opening new and exciting routes for controlling spin at the atomic scale [7]. In particular, I will present a rational design approach to customize the spin-texture of surface states of the prototypical topological insulator (TI) Bi2Se3 [8]. For the rational design we use theoretical calculations to guide the choice and chemical synthesis of appropriate molecules that customize the spin-texture of Bi2Se3. The theoretical predictions are then verified in angular-resolved photoemission experiments. We show that by tuning the strength of molecule-TI interaction, the surface of the TI can be passivated, the Dirac point can energetically be shifted at will, and Rashba-split quantum-well interface states can be created. These tailored interface properties ? passivation, spin-texture tuning, and creation of hybrid interface states - lay a solid foundation for interface-assisted molecular spintronics in spin-textured materials. [1] V. A. Dediu, L. E. Hueso, I. Bergenti, and C. Taliani, Nature Materials 8, 707 (2009); [2] M. Cinchetti et al., Nature Materials 8, 115 (2009); [3] S. Steil, et al., Nature Physics 9, 242 (2013); [4] M. Cinchetti, et al., Physical Review Letters 104, 217602 (2010); [5] A. Droghetti, et al., Physical Review B 89, 094412 (2014); [6] S. Müller, et al., New Journal of Physics 15, 113054 (2013); [7] M. Cinchetti, Nature Nanotechnology 9, 965 (2014); [8] S. Jakobs, A. Narayan, B. Stadtmüller, A. Droghetti, I. Rungger, Y. S. Hor, S. Klyatskaya, D. Jungkenn, J. Stöckl, M. Laux, O. L. A. Monti, M. Aeschlimann, R. J. Cava, M. Ruben, S. Mathias, S. Sanvito, and M. Cinchetti, Nano Letters 15, 6022 (2015).

Resume : Recently, there has been increasing interest in investigations of fundamental magnetic interactions in low-dimensional materials [1,2]. One such fundamental interaction is the Kondo effect responsible for the screening of the local moment [3], while another one, the Ruderman-Kittel-Kasuya-Yoshida (RKKY) coupling gives rise to a long-range spin ordering via the conduction electrons [4-6]. Spin-bearing smolecules such as porphyrins and phthalocyanines deposited on metallic substrates present a material to study the interplay of these two opposing interactions and can lead to even more intriguing phenomena. Here we present the first direct observation of long-range ferrimagnetic order in a 2-dimensional (2D) material created by the co-assembly of paramagnetic iron fluorinated (FeFPc) and manganese (MnPc) phthalocyanines molecules on single-crystalline Au(111) evidenced by Scanning Tunneling Microscopy/Spectroscopy (STM/STS), X-ray Magnetic Circular Dichroism (XMCD) and the Density Functional Theory (DFT+U) first-principle calculations. At the first glance 2D and 1D ferromagnets are in conflict with the classical theory of magnetism. [7] In the present system, however, the substrate is of key importance as it introduces an antiferromagnetic nearest-neighbor coupling between the Mn and Fe centers which is mediated by the surface states of Au(111) making the ordering possible. References [1] Zhao, A., Li, Q., Chen, L., Xiang, H., Wang, W., Pan, S., Wang, B., Xiao, X., Yang, J., Hou, J. G. & Zhu, Q. Controlling the Kondo effect of an adsorbed magnetic ion through its chemical bonding. Science 309, 1542–1544 (2005). [2] Franke, K. J., G. Schulze, G. & Pascual, J. I. Competition of superconducting phenomena and 2 Kondo screening at the nanoscale. Science 332, 940-944 (2011). [3] Hewson, A. C. The Kondo Problem to Heavy Fermions. (Cambridge University Press, 1993). [4] Wahl, P., Simon, P., Diekhöner, L., Stepanyuk, V. S., Bruno, P., Schneider, M. A. &. Kern, K. Exchange interaction between single magnetic adatoms. Phys. Rev. Lett. 98, 056601 (2007). [5] Tsukahara, N., Shiraki, S., Itou, S., Ohta, N., Takagi, N. & Kawai, M. Evolution of Kondo resonance from a single impurity molecule to the two-dimensional lattice. Phys. Rev. Lett. 106, 187201 (2011). [6] Prüser, H., Dargel, P. E., Bouhassoune, M., Ulbrich, R. G., Pruschke, T., Lounis S. & Wenderoth M. Interplay between the Kondo effect and the Ruderman–Kittel–Kasuya–Yosida interaction. Nat. Commun. 5, 5417 (2015). [7] Mermin, N. D. & Wagner, H. Absence of ferromagnetism or antiferromagnetism in one- or two-dimensional isotropic Heisenberg models. Phys. Rev. Lett. 17, 1133–1136 (1966).

Resume : Molecular spintronics and molecular magnetism are merging, leading to the development of hybrid molecular-inorganic devices where magnetic molecules plays a crucial role in spin and electronic transport. In this contest the use of Single-Molecule Magnets, the magnetic molecule by definition, but also of light element-based paramagnetic systems like organic radicals (e.g Nitronyl Nitroxide radicals) discloses new exciting possibilities linked to the richness the magnetic properties of these systems as well as to versatility of chemical synthesis that can allows to tune electronic and magnetic properties of these building blocks. However playing with molecules is not trivial: stability of the molecules as well as their interaction with the substrates must be taken in to account and fruitfully used. Here we will present our recent results based on wet chemistry and UHV-compatible strategies to modify the interface between a standard spin injecting electrode (La0.7Sr0.3MnO3) and an organic semiconductors (OSC). This allowed to introduce a molecular paramagnetic layer in the standard OSC-based spin-valve devices. Using a multi-technique approach we verified the intactness of molecules, the occurrence of specific interaction between the molecules and the magnetic substrate and then to test the performances of the hybrid spin valves demonstrating that the presence of this molecular paramagnetic layer does not hamper the observation of a significant magnetoresistance.

Resume : The combination of spin valve magnetoresistance and electrical memory effects (bistability) in hybrid devices including ferromagnetic electrodes and an organic spacer has opened up new possibilities for devices, in particular for the realization of multi-state memories [1]. It is well known that the interface effects between organic materials and electrodes are critical for setting the electric and magnetic behavior of these hybrid devices [2]. However, the literature concerning the relation between the bistable I-V characteristics and the magnetoresistance properties of organic devices is limited. In our study, we compare the magnetic and electrical behavior of magnetic tunnel junctions La0.7Sr0.3MnO3 (LSMO)/SrTiO3 (STO)/)/Co including epitaxial STO layer and of LSMO/STO/C60 (2 nm)/Co for which an organic C60 layer is inserted between STO and Co. Our results showed that both devices present typical tunneling magnetoresistance (TMR) in addition to a resistive switching behavior. In case of fully inorganic MTJ, the TMR is consistent with previous results [3]. In the case of C60 insertion, TMR ratio is tuned by electrical behavior of the device, in particular it is dependent on the resistive state in which is set. Data are interpreted in terms of interfacial effects, in particular taking into account hybridization between C60 and Co. [1] Prezioso, M. et al (2011) Adv. Mater., 23, 1371. [2] Barraud C. et al., Nat. Phys., 6, 615. [3] De Teresa J. M. et al., (1999) Science, 286, 507.

Resume : Molecular spintronics is an emerging research field at the frontier between organic chemistry and the spintronics. Compared to traditional inorganic materials molecules are flexible and can be easily tailored by chemical synthesis. However, due to their expected very long spin lifetime opportunity, they were first only seen as the ultimate media for spintronics devices and it was only very recently that new spintronics tailoring opportunities could arise from the chemical versatility brought by molecules and molecular engineering were unveiled. The hybridization between a ferromagnet and molecules induces a spin dependent broadening and energy shifting of the molecular orbitals leading to an induced spin polarization on the first molecular layer. We will show how tunneling anisotropic magnetoresistance measurements (TAMR) can be used to probe the spin dependent hybridization at the ferromagnetic/molecules interface. TAMR effects have been observed in Co/Alq3/Co and Co/Alq3/Cu organic spin valves. These experiments have shown that the TAMR effect comes from the bottom interface suggesting a stronger coupling at the bottom interface. This was confirmed by TMR experiments where a tunnel barrier has been inserted at the bottom or top interface in order to suppress the spin dependent hybridization. The study of the bias voltage dependence of the TAMR and TMR allows determining the spin dependent broadening and energy shifting of the molecular levels at the Co/Alq3 interfaces.

Resume : Spin-based electronics is one of the emerging branches in today?s nanotechnology and the most active area within nanomagnetism. So far spintronics has been based on conventional materials like inorganic metals and semiconductors. Still, an appealing possibility is that of using molecule-based materials, as components of new spintronic systems [1]. In particular, by taking advantage of a hybrid approach one can integrate molecular materials showing multifunctional properties into spintronic devices. In this talk we illustrate the use of this approach to fabricate multifunctional molecular devices combining light and spin-valve properties (i.e., Spin-OLEDs). So far only one report has been published which is based on the fabrication of an organic light emitting diode (OLED) with ferromagnetic electrodes [2]. Our new approach leads to a robust organic luminescent device in which light emission can be enhanced and modulated upon application of an external magnetic field. Furthermore, Hanle measurements [4] has been performed in our Spin-OLEDs probing for the first time no Hanle effect in a Spin-OLEDs organic spintronic.

Resume : Controlling the dynamics of spins on surfaces is pivotal to the design of spintronic and quantum computing devices. Proposed schemes involve the interaction of spins with graphene to enable surface-state spintronics, but several challenges remain unsolved: how can molecular spins be assembled into hybrid structures? What is the influence of the graphene environment on the spin? Can molecules be used to control coherent currents in graphene devices? Here we answer these questions,1 exploring spin-graphene interactions by using molecular magnetic materials. We detail the assembly process and showcase the relevance of dynamic scaling theory and of graphene surface defects. We then show that, while the static spin response remains unaltered, the quantum spin dynamics and associated selection rules are profoundly modulated. The couplings to graphene phonons, to other spins, and to Dirac fermions are quantified using a newly-developed model. Coupling to Dirac electrons introduces a dominant quantum-relaxation channel that, by driving the spins over Villain's threshold, gives rise to fully-coherent, resonant spin tunneling. Eventually we show how molecular spins can be used to introduce bistable behavior into coherent spin currents. These findings provide the tenets for spin-manipulation in graphene nanodevices.