NanoSD2015 Abstracts Book by Phantoms Foundation

NanoSecurity & Defense International Conference

MADRID, SPAIN

Index Foreword

Committees

Sponsors

Exhibitors

NanoSD 2015

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SPEAKERS & POSTERS (ALPHABETICAL ORDER) PAGE Rafael Abargues (INTENANOMAT S.L., Spain) Plasmonic optical sensors printed from Ag-PVA nanoinks as intelligent labels for food control Freddys Beltrán (ETSII - Universidad Politécnica de Madrid, Spain) PLA-clay nanocomposites for food packaging: Water absorption and its effects in the structure Adolfo Benedito Borrás (AIMPLAS, Spain) Electromagnetic effects of carbon based nanocomposites. Potential applications Alvaro Boluda (Universidad Politécnica de Madrid, Spain) Amperometric Xanthine Biosensor Based on Electrodeposition of Pt Nanoparticles on Polycyclotetrasiloxane Modified Electrode Alberto Boscá Mojena (Univ. Politécnica de Madrid/ ISOM, Spain) CVD-graphene growth and automated transfer for large-area, high performance applications Mariana Castrillón (Instituto Tecnológico de Aragón, Spain) Inorganic nanofillers, the new way of designing thermoplastic materials with enhanced properties Carmen Cerecedo / Victor Valcárcel (NEOKER, Spain) Ballistic ceramic with single cristal alumina fibers Santiago Cuesta-López (ICCRAM-Univ. of Burgos, Spain) Nanosafety and Critical Raw Materials Strategic Dependence For The Development Of Nanotechnology Eduardo Delgado (Bonsai Advanced Technnologies, Spain) Complete size characterization of Diatomaceous Earth Enrique Díez Barra (Universidad de Castilla La Mancha, Spain) Graphene Quantum Dots: An Eco-Friendly Preparation Maidá Domat (ITENE, Spain) Lessons learned in the exposure assessment and risk management of nanomaterials Juan José Fernandez (Industrial Química del Nalón, Spain) Nalon: an industrial partner in the Spanish security and defense field Rafael Ferrito (Nanoinnova Technologies SL, Spain) graphenit®: industrial applications Glenn A. Fox (Lawrence Livermore National Laboratory, USA) Advanced foams and nanomaterial synthesis for science and security applications Raquel Gonzalez-Arrabal (IFN-ETSII, Spain) Coatings production for civil and military markets Nuria Gordillo (IFN-ETSII, Spain) Adhesion and mechanical properties of implanted nanostructured tungsten NanoSD 2015

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Oral

Invited

Poster

Oral

Invited

19 19

Keynote

Poster Poster Invited

Invited Invited Keynote

Keynote Poster

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21 22 23 24 24 25 25 54

PAGE Pedro Heredia (GAIKER-IK4, Spain) Nanotoxicology: In vitro tests for safety assessment of nanomaterials Frank Koppens (ICFO, Spain) Graphene for security and defense Ana Ledo-Suárez (NANOGAP, Spain) Christopher Lillotte (Advanced Carbon Materials Dept. at Grupo Antolin Ingenieria, Spain) Large scale production of graphenic materials by Grupo Antolin and their applications development Jaime López de la Osa (nanoimmunotech, Spain) Improving biosensors with nanotechnology Patricia López Vicente (European Defense Agency, Belgium) Impact of Nanotechnology on European Defence Capabilities and EDA’s work Juan Pablo Martínez Pastor (University of Valencia, Spain) Efficient Photodetectors at Telecom Wavelengths based on Thin Films of Lead Sulfide Quantum Dots Bartolomé Mas (IMDEA Materials, Spain) Continuous Macroscopic Fibres of Carbon Nanotubes for Smart Textiles and Ballistic Protection Eva Mateo-Marti (Centro de Astrobiología (INTA/ CSIC), Spain) Biomolecules sensors and detection by surface science techniques Johann G. Meier (Instituto Tecnológico de Aragón, Spain) Surface silanised nanoclays – Filler modifier for rubber compounds Nieves Murillo (Tecnalia, Spain) Smart Sensors and Active Solutions for Chemical and Biological threat Detection and Protection Aleksandr Noy (Lawrence Livermore National Laboratory, USA) Bionanoelectronics with natural and artificial membrane transporters Evelyn Ospina (Universidad Politécnica de Madrid, Spain) HRP/AuNPs/Polycyclosiloxane Bioelectrochemical System as a New Peroxide Sensor George Palikaras (Metamaterial Technologies, Canada) Jorge Pedrós (ISOM/UPM, Spain) Graphene-based supercapacitors Flavio Pendolino (University of Padova, Italy) Temperature Effect on the Production of Graphene Oxide and Graphite Oxide Ovidio Peña Rodríguez (IFN-ESTSII-UPM, Spain) Designing “superabsorber” nanoparticles Adam Prats (NANOTECNOLOGÍA SPAIN S.L., Spain) Smartnanocoatings the key to advance effeciency in surface solutions, easy to clean super hidrophobic & super hidrophilic coatings NanoSD 2015

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Invited Keynote Invited Invited

Invited Keynote

26 27 28 28

Oral

31 32 34

Oral Invited

Keynote Poster

Keynote Invited Oral

Keynote Invited

Madrid (Spain)

35 36 38 38 39 40

PAGE José Manuel Ramos (AITEX, Spain) Development of fiber reinforcing thermoplastic composites based on hybrid yarns José Ramón Ramos-Barrado (Universidad de Malaga, Spain) Walking towards a transparent photo-super-capacitor Carlos Rivera (Ingeniería de Sistemas para la Defensa de España, Spain) Modulating retro-reflectors operating in the range of 0.95-1.1 µm for asymmetric communications Pedro Javier Rodríguez Cantó (INTENANOMAT S.L., Spain) UV-patternable nanocomposite containing CdSe and PbS quantum dots as miniaturized luminescent chemo-sensors Françoise D. Roure (French High Council for Economy, Industry, Energy and Technology, France) Expanding nanotechnology opportunities for Defence and Security Luis Sanz Tejedor (Spanish Patent and Trademark Office, Spain) Industrial Property and Nanotechnology Giorgio Sberveglieri (C.N.R. - National Institute of Optics, Italy) Metal oxide nanostructured gas sensors for security applications John W. Sibert (The University of Texas at Dallas, USA) New Redox-Responsive Molecular Tools and Larger Scale Systems for the Detection and Removal of Strategic Environmental Hazards Ramon Torrecillas (Nanomaterials and Nanotechnology Research Center (CINN), Spain) Hybrid SPS-Hot Press: A suitable technology for the fabrication of ceramic nanocomposite components for security and defense applications Socorro Vázquez-Campos (LEITAT, Spain) Nanosafety issues along their life cycle of nanoadditives incorporated in NM-enabled products Amaia Zurutuza (Graphenea S.A., Spain) Graphene in Security and Defence Applications

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Invited

Poster

41 43

Oral

Keynote

Invited

47 48 50

Keynote Keynote

Oral

Invited

Keynote

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Plasmonic optical sensors printed from Ag -PVA nanoinks as intelligent labels for food control 1

R. Abargues , P.J. Rodríguez-Cantó , S. Albert , I. Suárez , J. P. Martínez- Pastor 1

Intenanomat S.L., Catedrático José Beltrán 2, 46980 Paterna, Spain 2 Instituto de Ciencia de los Materiales, Universidad de Valencia, P.O. Box 22085, 46071 Valencia, Spain Rafael.Abargues@uv.es

Molecular sensing and detection based on localized surface plasmon resonance (LSPR) have attracted intense interest for detection of biomolecules with high sensitivity and low cost. LSPR of Au and Ag nanoparticles (NPs) strongly depends on its surrounding medium (substrate, solvent, and adsorbates) [1]. Recently, we proposed a novel LSPR sensing platform based on nanocomposite of Ag nanoparticles embedded in a polymer matrix such as PVA and Novolak for the detection of 2mercaptoethanol [2,3]. The advantage of these materials is that Ag NPs are in situ synthesized inside the host polymers by a one-step procedure during the bake step of the formation of a nanocomposite thin film. Additionally, these materials can be patterned by e-beam [3,4] and UV lithography [5], which may form the basis to the microfabrication of biochip sensors. In the present work we extend the sensing capability of Ag nanocomposites to and quantify trace amounts of amines in gas and water [6]. Sensing of amines is of great importance not only for environmental and industrial monitoring applications but also for the safety and quality control of food. The transduction mechanism of the sensor is based on the changes of the LSPR band of Ag NPs when analyte molecules are chemisorbed on their surface. The Ag-PVA sensors are fabricated by means of a high-precision microplotter, a direct-write technology developed for printing materials from solution. The nanoink is formulated with a metal precursor (AgNO3) and a polymer (PVA) using an adequate mixture of solvents to meet the rheological requirements for the fluid dispensing process (Figure 1 a). The LSPR intensity is the most sensitive magnitude to follow the interaction between Ag NPs embedded in PVA and amines. Ag-PVA patterns are tested as a plasmonic optical sensor for the detection of ethylenediamine (EDA) in solution showing a limit

NanoSD 2015

of detection as low as 0.3 ng or 6 ppt. We also observed a linear sensing behaviour within a concentration range between 10-10 and 10-4 M, which allows us to use Ag-PVA as quantitative sensor for EDA. Moreover Ag nanocomposite patterns are also used for sensing vapours of several biogenic (cadaverine, putrescine) and synthetic (ethylenediamine and methylenediamine) amines, where shorter amines exhibit the largest sensor response (Figure 1 b). Finally, the Ag-PVA plasmonic optical sensor was tested for real-time monitoring of chicken meat spoilage at room temperature. After 24 hours at room temperature we observed to the naked eye a noticeable colour change of the Ag-PVA label from yellow to colourless, because of the increasing amount of volatile compounds released during the chicken spoilage (Figure 1 c). We believe that Ag-PVA nanocomposite can be the basis for the development of sensor spots, barcodes and other labels for smart packaging technology, among other sensing applications.

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Figures

References [1]

[2]

[3]

[4]

[5]

[6]

Figure 1: a) Scheme of the fabrication of Ag-PVA nanocomposite sensor by microplotter printing. b) Variation of the LSPR peak intensity exposed to the vapours of a 0.1 M aqueous solution of methylenediamine, ethylenediamine, putrescine and cadaverine. c) Optical images of the Ag-PVA sensor before and after exposure to chicken meat.

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JN Anker, WP Hall, O Lyandres, NC Shah, J Zhao, RP Van Duyne, Nature Materials 7, (2008) 442. Biosensing with plasmonic nanosensors Gradess R, Abargues R, Habbou A, CanetFerrer J, Pedrueza E, Russell A, Valdés JL, Martínez-Pastor JP, J Mater Chem, 19, (2009), 9233-9240. Localized surface plasmon resonance sensor based on Ag-PVA nanocomposite thin films. Journal of Materials Chemistry Abargues, R.; Marques-Hueso, J.; CanetFerrer J.; Pedrueza E.; Valdes J.L.; Jimenez E.; Martınez-Pastor, J. P. Nanotechnology, 19, (2009), 355308. High-resolution electronbeam patternable nanocomposite containing metal nanoparticles for plasmonics Marqués-Hueso J, Abargues R, Canet-Ferrer J, Agouram S, Valdés JL, Martínez-Pastor JP, Langmuir 26, (2010), 2825-30. Au-PVA nanocomposite negative resist for one-step three-dimensional e-beam lithography Marqués-Hueso J, Abargues R, Valdés JL, Martínez-Pastor JP, J Mater Chem 20 (2010) 35, 7436. Ag and Au/DNQ-novolac nanocomposites patternable by ultraviolet lithography: a fast route to plasmonic sensor microfabrication Abargues, R., Rodriguez-Canto, P. J., Albert, S., Suarez, I., & Martínez-Pastor, J. P. Journal of Materials Chemistry C (2014), 2(5), 908915. Plasmonic optical sensors printed from Ag–PVA nanoinks.

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PLA-clay nanocomposites for food packaging: Water absorption and its effects in the structure F.R. Beltrán, E. Ortega, H. Bernabéu, S. Lorenzo, J. Moreno, A. Arenas, E. Guijarro, M. Martín, V. Lorenzo, M.U. de la Orden, J. Martínez-Urreaga Universidad Politécnica de Madrid, ETSI Industriales, Grupo “Polímeros, Caracterización y Aplicaciones”, Madrid, Spain. freddysbeltran@gmail.com

The massive use of petroleum-based plastics in the manufacture of food packaging has brought concern about the environmental impact of these materials, which has driven the development of biodegradable materials as an environmental friendly alternative. Among these materials stands out the poly(lactic acid) (PLA), an aliphatic polyester produced from the fermentation of sugars, starch and other renewable resources [1]. The PLA has seen its popularity increased due to its good optical properties, easy processability with currently available technologies and lower cost of production in comparison with other biopolymers. However, among their main drawbacks for its application in food packaging are its fragility and moderate gas barrier properties compared to those of the conventional polymers. Different alternatives have been investigated over the past years to overcome these drawbacks, being one of the more attractive the use of nanoclays as reinforcement particles, thus improving the performance of the PLA [2]. Another drawback of PLA becomes from its easy hydrolytic degradation, which leads to a significant decrease in the performance of the material, so it is important to know the behavior of the PLA when is exposed to water [3]. The objective of this work is to study the water absorption of PLA nanocomposites at different temperatures, and the effect of this absorption on the polymer structure. In this study, a commercial PLA (Ingeo 2003D, NatureWorksTM) was used. This grade is designed for packaging applications. A commercial organically modified montmorillonite (Cloisite 30BTM) was used as reinforcement of the polymer matrix. Nanocomposites with 2% wt. clay were manufactured by melt compounding. The prepared nanocomposites were then compression molded into films, which were immersed in a phosphate

NanoSD 2015

buffer (pH 7.4) at 37 ° C and 58 ° C. After definite periods of time, samples were withdrawn from the buffer solution and analysed. The water absorption was monitored measuring the weight increase after different test durations. The changes in the structure of the samples were studied by ATR-FTIR. Fig. 1 shows that the water absorption curve of the nanocomposite at 37 °C is not simple. At high immersion times the water absorption becomes faster due to the hydrolytic degradation of PLA, which generates hydrophylic terminal groups. However, absorption of water at low immersion times can be accurately described using a Fickian diffusion model. The absorption curve at 58 °C is similar but the nanocomposite absorbs more water due to the proximity of this temperature to the glass transition temperature of PLA (55-60 °C), which causes increased mobility of the molecular segments and a growth in the free volume, thus facilitating the absorption of higher amounts of water. However, the apparent diffusion coefficient at 58 °C is lower than at 37 °C. This result has been explained by considering the crystallization of PLA at 58 °C, which was observed in the analysis of the infrared spectra of the materials. Fig. 2 shows the FTIR spectra recorded at different immersion times. Changes can be seen in different regions of the spectrum. The absorption band appearing at 3400 cm-1 is mainly due to water absorption of the material. Changes seen in the bands located at 1747, 1266, 1207, 956 and 920 cm-1 are due to the increase in the crystallinity of PLA during water absorption, due to the hydrolytic degradation of the polymer [4, 5]. Finally, the appearance of the band located at 1600 cm-1 could be explained by the formation of carboxylate ions during the degradation process [6]. The results obtained in this work reveal the effect of the nanoclay on the water absorption. When

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compared to the neat polymer, the nanocomposite shows increased water absorption at long times, due to the hydrophylic nature of the clay. However, the nanoclay reduces the diffusion coefficient of the polymer, probably due to the barrier effect of the layered silicate.

References

Figures

[2]

[1]

3,0 2,5

m (%)

2,0

[3]

1,5 1,0 0,5 0,0 0

[4]

Time (days)

Figure 1: Water absorption data for the PLA nanocomposite at 37 oC.

[5]

[6]

Figure 2: FTIR Spectra of the PLA nanocomposite without inmersion (blue), after 14 days (red) and after 44 days of inmersion (green).

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M. P. Arrieta, J. López, A. Hernández and E. Rayón, "Ternary PLA–PHB–Limonene blends intended for biodegradable food packaging applications," European Polymer Journal, vol. 50, pp. 255-270, 1, 2014. S. Molinaro, M. Cruz Romero, M. Boaro, A. Sensidoni, C. Lagazio, M. Morris and J. Kerry, "Effect of nanoclay-type and PLA optical purity on the characteristics of PLAbased nanocomposite films," J. Food Eng., vol. 117, pp. 113-123, 7, 2013. P. K. Roy, M. Hakkarainen and A. Albertsson, "Nanoclay effects on the degradation process and product patterns of polylactide," Polym. Degrad. Stab., vol. 97, pp. 1254-1260, 8, 2012. E. Meaurio, N. López-Rodrí¬guez and J. R. Sarasua, "Infrared Spectrum of Poly(llactide): Application to Crystallinity Studies," Macromolecules, vol. 39, pp. 9291-9301, 12/01, 2006. J. D. Badia, L. Santonja-Blasco, A. MartínezFelipe and A. Ribes-Greus, "Hygrothermal ageing of reprocessed polylactide," Polym. Degrad. Stab., vol. 97, pp. 1881-1890, 10, 2012. X. Shi, J. Jiang, L. Sun and Z. Gan, "Hydrolysis and biomineralization of porous PLA microspheres and their influence on cell growth," Colloids and Surfaces B: Biointerfaces, vol. 85, pp. 73-80, 6/15, 2011.

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Electromagnetic effects of carbon based nanocomposites. Potential applications Adolfo Benedito Borrás Gustave Eiffel, 4 (València Parc Tecnològic) 46980 - PATERNA (Valencia), Spain abenedito@aimplas.es

Carbon based nanomaterials (CBNM) like carbon nanotubes, carbon nanofibers, nanographites and more recently graphenes have been demonstrated as the most useful nanomaterials in terms of performance once added to a matrix like thermoplastic polymers. Carbon based Nanocomposites offer a big potential for many properties, but mainly the interaction of these nanomaterials with the electric and electromagnetic fields. In this way, important effects have been reported, implying potential developments and applications in aeronautic, defense, and space technologies. Nanomaterials by themselves cannot fulfil the expectations of their good properties; they need a support, polymers, to be integrated for further transformation in useful items, plastic parts. Melt compounding or other mixing techniques allows incorporating these new materials within plastics and dispersion is the key point, if we are not able to disperse properly these nanomaterials it will be impossible to reach these properties in the final products. Plastics and its processing methods such as multilayer film die cast, co-injection or bi-injection moulding allow maximizing and economizing the effectiveness of nanomaterials.

microwave absorption [4], i.e.: avoid accumulation of ice in airplane wings. And, in general, absorption of low and high energy from electromagnetic spectra, such as, radio wave for stealth devices, outstanding x-ray shielding effects [5], for safety and protection requirements, and others. In definitive, this work will summarize the electromagnetic effects of carbon based nanocomposites and the potential applications for secutiry and defense purposes. References [1]

[2]

[3]

[4]

Therefore a holistic point of view of the challenge could give us the solution, nanomaterial plus plastic plus adequate processing method equals to desired performance. The interaction of carbon based nanocomposites with electric and electromagnetic fields give us important physical phenomena. The high levels of conductivity and absorption are responsible of sensoring, piezoelectric effects [1,2], EMI shielding [3], i.e.: shielding of drones and weigth reduction, heating processes based on Joule effect or

NanoSD 2015

[5]

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“Thermal conductivity of carbon nanotubes and their polymer nanocomposites: A review”, Zhidong Han, Progress in Polymer ScienceVolume 36, Issue 7, July 2011. “Electromechanical performance of poly(vinylidene fluoride)/carbon nanotube composites for strain sensor applications”, A. Ferrreira et al, Sensors and Actuators A: Physical, Volume 178, May 2012. “Comparative study of electromagnetic interference shielding properties of injection molded versus compression molded multi-walled carbon nanotube/polystyrene composites”, Mohammad Arjmand et al. Carbon, Volume 50, Issue 14, November 2012. “Microwave heating of polymers: influence of carbon nanotubes dispersion on the microwave susceptor effectiveness” Galindo-Galiana, B. (AIMPLAS), International conference of the Polymer Processing Society. “Enhanced X-Ray Shielding Effects of Carbon Nanotubes”. Fujimori, T. Tsuruoka, S., et all. Materials Express, Volume 1, Number 4, December 2011, pp. 273-278(6).

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Amperometric Xanthine Biosensor Based on Electrodeposition of Pt Nanoparticles on Polycyclotetrasiloxane Modified Electrode 1

Álvaro Boluda , M. P. García Armada , J. Losada , B. Alonso , C. M. Casado 1

Dpto. Ingeniería Química Industrial y M. A., UPV, Madrid, Spain. 2 Dpto. Química Inorgánica, UAM, Madrid, Spain pilar.garcia.armada@upm.es

Xanthine (3,7-dihydro-purine-2,6-dione) is present in most body tissues and fluids. It is generated from guanine by guanine deaminase and from hypoxanthine by xanthine oxidase (XOD). The determination of xanthine level in blood and tissue is essential for diagnosis and medical management of various diseases like hyperuricemia, gout, xanthinuria and renal failure. The determination of xanthine is also used in the food industries for the quality control of fish products. After the death of a fish, ATP is degraded into xanthine, which increases with storage. Thus xanthine attracts much attention as an indicator for fish freshness [1]. Xanthine oxidase is a molybdenum, iron and labile sulfur containing flavoprotein that catalyzes the oxidation of hypoxanthine to xanthine and xanthine to uric acid and plays an important role in controlling purine metabolism. In the literature, several analytical methods such as electrophoresis, high-performance liquid chromatography (HPLC), amperometric and voltammetric methods have been reported for quantitative determination of xanthine and various electrochemical xanthine biosensors based on the immobilized xanthine oxidase have been reported [2]. However these XOD based biosensors have some common drawbacks such as poor stability, reusability, slow electron transfer, and complexity of immobilization. Several metal nanoparticles have been used as electrode modified materials in the electrochemical biosensors of xanthine [3-5] and it is demonstrated that gold and platinum nanoparticles could increase the surface area and conducive to electron transfer with strong catalytic properties [6]. In accordance to these studies, Pt nanoparticles (PtNPs) show a little better catalytic behavior in the electrochemical oxidation of the enzimatically generated H2O2 than AuNPs, consequently we have used Pt nanoparticles in our biosensor.

NanoSD 2015

In this work we present a novel and selective xanthine electrochemical biosensor, based on xanthine oxidase immobilized in a nanostructured electrode surface prepared with an electrodeposited cylotetrasiloxane polymer functionalized with ferrocene units [7] (Fig. 1) used as bed for the deposition of Pt nanoparticles [8] . Figure 2 shows the SEM micrographs of both Pt wires modified with the polymer and the polymer with PtNPs in which a uniform distribution of PtNPs is showed. Once the modified electrodes were characterized, the kinetics was studied by application of Laviron model. The ∆Ep values remained invariable with the increasing scan rate indicating that there are no kinetic limitations [9]. The polymer and PtNPspolymer electrodes showed excellent electrocatalytic activity toward the oxidation and reduction of hydrogen peroxide in the phosphate buffer solution (pH 7.0). The Koutecky-Levich studies with rotary electrode let us to know the kinetics of theelectrooxidation of H2O2 and determine the rate constants, kobs = 43450 M-1s-1 and 80617 M-1s-1 for the polymer and PtNPspolymer modified electrodes respectively. These results show a good electrocatalytic behavior. Xanthine oxidase was immobilized by covalent cross-linking [10] with BSA and glutaraldehyde, and its good electrocatalytic behavior has allowed us to develop an efficient sensor capable of measuring xanthine at potentials from 0.4 V and -0.1 V (vs. SCE). The linear relationship between the current response and the concentration of XA ranging from 0 to 3,8 mM was obtained with a detection limit of 0.24 µM at pH 7.0, sensitivity of 0.146 A M-1 cm-2 at 0.4 V applied potential (Vs. SCE) and higher values for increasing applied potentials. The kinetics of biosensor was also studied and an apparent MichaelisMenten of 0.7 mM was obtained.

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The effect of the interferences caused by ascorbic acid (AA), glucose and uric acid (UA) was also studied. This new biosensor has been applied successfully to monitoring the meat freshness in fishes and to determine the xanthine derivative teophylline, present in antiasthmatic drugs. Figures

Figure 1: Cyclotetrasiloxane backbone.

Figure 2: UHSEM micrographs of Pt wires modified with the cylotetrasiloxane polymer (left) and PtNPs - cylotetrasiloxane polymer (right).

NanoSD 2015

References [1]

Rooma Devi, Manish Thakur, C.S. Pundir, Biosensors and Bioelectronics 26 (2011) 3420–3426. [2] Rooma Devi, Sandeep Yadav, C.S. Pundir, Colloids and Surfaces A: Physicochem. Eng. Aspects, 394 (2012) 38–45. [3] Dan Shan, Yan-NaWang, Huai-Guo Xue, Serge Cosnier, Shou-Nian Ding, Biosensors and Bioelectronics, 24 (2009) 3556–3561. [4] Rooma Devi, Sandeep Yadav, Renuka Nehra, Sujata Yadav, C.S. Pundir, Journal of Food Engineering, 115 (2013) 207–214. [5] Chandra Shekhar Pundir, Rooma Devi, Enzyme and Microbial Tecnology, 57 (2014) 55-62. [6] Salih Zeki Bas, Handan Gulce, Salih Yıldız, Ahmet Gulce, Talanta, 87 (2011) 189–196. [7] J. Losada, M.P. García Armada, I. Cuadrado, B. Alonso, B. González, C.M. Casado, J. Zhang,Journal of Organometallic Chemistry, 689 (2004) 2799–2807. [8] Salih Zeki Bas, Handan Gulce, Salih Yıldız, Journal of Molecular Catalysis B: Enzymatic, 72 (2011) 282-288. [9] H. D. Abruña, Electrochemical Interfaces: Modern Techniques for in-situ Interface Characterization. VCH Pub. (1991) Florida, U.S.A. [10] M. Zhou, L. Shang, B. Li, L. Huang, S. Dong, Biosensors and Bioelectronics, 24 (2008) 442–447.

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CVD-graphene growth and automated transfer for large-area, high performance applications 1,2

1,2

1,3

1,2

Alberto Boscá , J. Pedrós , J. Martínez , F. Calle

Instituto de Sistemas Optoelectrónicos y Microtecnología, UPM, Madrid, 28040, Spain Dpto. de Ingeniería Electrónica, E.T.S.I de Telecomunicación, UPM, Madrid, 28040, Spain Dpto. de Ciencia de Materiales, E.T.S.I de Caminos, Canales y Puertos, UPM, Madrid, 28040, Spain 2

alberto.bosca@upm.es

Due to its large area and excellent electrical properties, CVD graphene is a suitable nanomaterial for electromagnetic insulation (EMI) [1], for communications as FET transistors for RF [2], and for THz/IR applications [3] such as antennas or plasmonics, among others. Still, its main disadvantage is the need of transferring the graphene layer from the metal catalyst to a suitable final substrate. A manual transfer method [4] was developed to overcome this issue. It consists of protecting the graphene with a thin polymer layer, wet-etching the growth substrate, rinsing with deionized water, and finally depositing the resulting polymer/graphene membrane onto the desired target substrate. Despite this method has been strongly optimized [5, 6], it still requires strong handling skills, is time consuming, and is not suitable for an industrial process. An alternative method based on a roll-to-roll system [7] can overcome some limitations of the manual method, but it is limited to flexible substrates.

the process. A fixed platform and a substrate holder ensure a fixed position between the final substrate and the tube center. All these pieces are immersed into a liquid, starting with an etchant solution and changing gradually into deionized water for the final rinsing steps.

In this work we report on the CVD growth of largearea graphene using a cold wall reactor (Fig. 1), and a lab-scale system designed to transfer graphene automatically to arbitrary substrates, which could be easily scaled up for industrial applications. The system is composed of several modules that control the process temperature, the liquid flow and the overall system state. An Arduino UNO microcontroller is used as the real-time control system, timing and activating the rest of modules. It also allows communication with a computer for logging purposes. The passive components of the system are depicted in Fig. 2. A polytetrafluoroethylene (PTFE) tube encloses the graphene sample during the whole process. This enclosing tube has a surface treatment that centers the polymer/graphene membrane that floats inside it. The treatment avoids mechanical stress or induced ripples in the graphene during

[1]

NanoSD 2015

Finally, graphene field-effect transistors (GFETs) were processed on the same CVD material but transferred using both the standard manual method and the novel automatic method for comparison. Raman and electrical assessment of the GFETs using a theoretical model [8] demonstrate that devices on the automaticallytransferred graphene present systematically higher mobilities and less impurity contamination (Fig. 3). Acknowledgements: This work has been supported by MINECO projects RUE (CSD2009-0046) and GRAFAGEN (ENE2013-47904-C3) References

[2] [3] [4] [5] [6] [7] [8]

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Seul Ki Hong, Ki Yeong Kim et al., Nanotechnology, vol. 23, 45 (2012), p. 455704. Frank Schwierz, Nat. Mater., vol. 5, 7 (2010), p. 487. Tony Low, Phaedon Avouris, ACS Nano, vol. 8, 2 (2014), p. 1086. Alfonso Reina, Xiaoting Jia et al., Nano Lett., vol. 9, 1 (2009), p. 30. Wei-Hsiang Lin, Ting-Hui Chen et al., ACS Nano, vol. 8, 2 (2014), p. 1784. Hai Li, Jumiati Wu et al., ACS Nano, vol. 8, 7 (2014), p. 6563. Sukang Bae, Hyeongkeun Ri Kim et al., Nat. Nanotechnol., vol. 5, August (2010), p. 574. Alberto Boscá, Jorge Pedrós et al., J. Appl. Phys., vol. 117 (2015), p. 044504.

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Figures

Figure 1: CVD system chamber for 4” wafer graphene growth

Figure 2: PTFE passive components (in liquid) and the sample and final substrate positions

Figure 3: CVD graphene electrical characterization.

Inorganic nanofillers, the new way of designing thermoplastic materials with enhanced properties M. Castrillón, G. Ibarz, J.G. Meier, C. Crespo Instituto Tecnológico de Aragón, C/Maria de Luna nº8, Zaragoza 50018, Spain mcastrillon@itainnova.es

Since the emerging of nanotechnology over the last decades, this area of knowledge has rapidly grown, attracting a great interest from the scientific community as a consequence of the novel applications and improved properties of this new type of materials. In order to take advantage of the potential use of nanomaterials, it is important to provide them with

NanoSD 2015

good processability. In this context, plastics loaded with nanomaterials will present the existing qualities of the polymers, mixed with the unique properties of nanofillers. This family of materials denoted as polymer nanocomposites are prepared using a conventional polymer as host matrix which incorporates a low amount of fillers in order to obtain new materials suitable for novel applications.

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Polymer nanocomposites are the key of future advances in the defense area. Among the capabilities offered by these nanocomposites are included the production of harder/lighter platforms, materials with higher resilience and robustness, special properties such electronic/opto-electronic/magnetic for sensoring applications, improvement in properties such as UV, toxic environments and fire resistance, and novel smart materials as well as new fuel sources and storage.

observed with a magnetization saturation of ~10 emu/g and 280 Oe of coercivity field, at the same time the E-module increased up to 70%, in comparison with neat TPE matrix..

In this work, different commercial polymers such as: PVC and PC for thermal uses; PP and P6 for mechanical and wear resistance applications; and SEBS with remarkable magnetic properties, have been produced by loading them with a variety of inorganic fillers (from 1.5 to 7 wt% content) including hydrotalcites, inorganic molecular wires/ fullerenes nanotubes or cobalt nanoparticles.

[2]

The processing methods presented here can be potentially extrapolated to an industrial level and can be used in the defense fields for applications such as microwave absorbers, electromagnetic shielding, fire retardation and flammability reduction, in addition to reduce the maintenance costs (e.g., wear reduction, fatigue resistance increase). The results obtained have shown that the fire risk, measured in terms of fire performance index (FPI) of PVC nanocomposites; consisting of 5 wt% nanoparticles surface-modified with nonhalogenated fire retardant compounds, is about 70% lower with respect to pristine PVC polymer. (see Figure 1) The composites containing nanowires show a significant increase of the E-module of up to 38% at a nanowire concentration of 4 wt% in the glassy state of PA6. Likewise, for a concentration of only 2 wt% of inorganic molecular wires based in molybdenum (Mo6S2I8), a reduction of the friction coefficient by 35% compared to the neat polymer was observed. Meanwhile when the concentration was increased up to 4 wt% this reduction improved to ca. 40% together with reduction of the wear rate by ca. 57%.

References [1]

[3]

[4]

[5]

De Paiva, L.B., Morales, A.R., Valenzuela Díaz, F.R., Organoclays: Properties, preparation and applications. Appl. Clay Sci. 42, (2008), 8–24. Kiliaris, P., Papaspyrides, C.D., Polymer/layered silicate (clay) nanocomposites: An overview of flame retardancy. Prog. Polym. Sci. 35, (2010), 902–958. Meier, J. G., Mrzel, A., Canales, M., Gonzalvo, P. and Alcala, N., Tribological properties of composites of polyamide-6 and nanotubes of MoS2, and nanowires of MoO(3−x) and Mo6S2I8. Phys. Status Solidi A, (2013), 210: 2307–2313. doi: 10.1002/pssa.201329359. N. Moussaif, I. Viejo, J. M. Bielsa, C. Crespo, S. Irusta, Yagüe C. and J. G. Meier, IOP conf. series: Materials science and engineering, (2012), 40, 012026. V. Skumryev, H. J. Blythe, J. Cullen and J. M. D. Coey, J Magn Magn Mater, (1999), 196– 197, 515-517.

Figures

Figure 1: Fire performance index of different PVC nanocomposites with 5% of nanoclay content in comparison with the pristine PVC polymer.

Finally, in composites prepared with a thermoplastic elastomer matrix of SEBS and ferromagnetic cobalt nanoparticles (in 7wt% concentration), a ferromagnetic behaviour was

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Ballistic ceramic with single cristal alumina fibers Carmen Cerecedo and Victor Valcárcel NEOKER S.L., A Coruña, Spain info@neoker.org

Neoker produces single crystal alumina fibers, NKR®, a new ceramic material of high performance in composite materials. The fibers are used mainly as reinforcing phase added in composite materials: ceramic, metallic and polymeric matrix. In our constant search of new applications, Neoker pursues new products. Therefore, we research and develop new sintering technologies, as for example Spark Plasma Sintering, (SPS). The combination of SPS sintering route with the use of our NKR fibers will lead to new concepts in CMC’s. One of the main applications regarding to the improvement in mechanical properties is in the ballistic sector. In one of our latter developments, recently carried out, we have demonstrated that adding small percentages (even below 1%) of our NKR fibers in ceramic matrixes, it may be obtained

outstanding mechanical performance. Specifically, it has been shown that after a ballistic impact, the damage is limited to reduced areas, thus increasing the multiimpact resistance. In this work they are described the main results obtained so far, mainly focused in the improvement of ballistic performance in fiber reinforced ceramic armours, both after single impacts and after multiimpact essays. All these achievements enable the design of new protective components with weight/thickness reduction up to 30%. Collaborators: Carmen Cerecedo (Neoker, S.L.), Víctor Valcárcel (Neoker, S.L.), Ramón Torrecillas (CINN), Adolfo Valdés (CINN), Sergio Rivera (Nanoker), Rafael Ferrer (Fedur).

Nanosafety and Critical Raw Materials Strategic Dependence For The Development Of Nanotechnology Santiago Cuesta-López, Roberto Serrano-López, Lorena Romero-Santacreu ICCRAM, International Center for Critical Raw Materials and Advanced Industrial Technologies, University of Burgos, Plaza Misael Bañuelos s/n, 09001 Burgos, Spain scuesta@ubu.es

Without doubt one of the most difficult challenges faced in the exploitation of nanotechnology for the benefit of European society (and beyond) has been the uncertainty surrounding the potential associated risks. Moreover, as in all industrial applications, the potential exposure of humans and the environment to these materials is inevitable. As these new materials go through their life-cycle – from development, to manufacture, to consumer usage, to final disposal – different human groups (workers, bystanders, users), environmental

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compartments (air, soil, sediment, water), and species (e.g. worm, fish or human through secondary exposure) will be exposed to them. Consequently, Nano Materials (NMs) safety is of great societal concern and raises many questions for the general public, governments, industry, scientists and regulators. Identifying and controlling the hazards associated with NMs is required to ensure the safety of the general public, workers and the environment in parallel to exploiting the technological benefits.

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Our institute answers this challenge by fostering a timely key action joining industry and academy to create a collaborative excellence-based knowledge exchange network pushing forward and training scientists in new methodologies to assess long term nanosafety, test and pre-validate them, and finally discuss their relevance and suitability for standardization and inclusion in present and future EU regulations. This effort (NANOGENTOOLS [1]) is funded by the EU Commission H2020 under the MSC-RISE work programme. Given the great variety and number of NMs, it is impossible to study their toxicity using conventional toxicological and risk assays, as this would require dozens of years and would cost millions of €s. Indeed for the US Choi et al. (2009) [2] showed that costs for testing existing NMs range from $249 million for optimistic assumptions about NM hazards to $1.18 billion for a more comprehensive, precautionary approach, and would require 34-53 years to cover all existing NMs threats and much longer as new NMs are discovered. Our Center is making progress in the innovation of new genomic and biophysical methodologies capable to detect and address long-term risk of NMs in a fast and efficient way. In particular, we are fostering new microarray-based tests as a potentially rapid and cost-effective approach for identifying and assessing potential hazard, characterizing NM mode of action, and assessing human health risk [3]. On the other hand, we would also like to analyze the importance for the technology development strategy and country dependence of critical raw materials. In particular their role in nanotechnology-based value chains.

fundamental needs in the field of CRMs: On the one hand, the creation of a collaborative network of expertise to develop new materials, products and technologies based on nanotechnology, by connecting fundamental and applied research with the aim of substituting or reducing the need of CRMs in strategic EU industrial value chains. Such a research alliance focusing in Nanotechnology as a vehicle of substitution is totally new in Europe, and has the opportunity to take the lead internationally with the main actors in the context of the EIP-Raw Materials and the KIC (EIT) in Raw Materials. On the other, the establishment of a platform of knowledge and technology transfer within EUNANOFUTURES common to scientists, engineers, technologists, and European industry. The combination of different expertise can be expected to give rise to beneficial synergistic effects along the whole value chain in Nanotechnology involving CRMs, which could result in a significant scientific, technological and economic progress for EU Main activities in this context and possible synergies will be presented References [1] [2]

[3]

Difficulties in the access to Critical Raw Materials (CRMs) are expected to depress industrial sectors vital to Europe. As a response, Europe has established the Resource-Efficiency Roadmap and the European Innovation partnership (EIP) Raw Materials (RM). Moreover, the European Institute of Innovation and Technology (EIT) has warded in December 2014 a knowledge and innovation community (KIC) on raw materials. In this context, the Nanotechnology, as a strong pillar of the present and future EU industrial value chains, is expected to play a key role. Our Center is coordinating the efforts within EUNANOFUTURES [4] aiming at meeting two

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[4]

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S. Cuesta-Lopez. NONAGENETOOLS coordinator. EU-H2020-MSC-RISE-691095. Jae-Young Choi, Gurumurthy Ramachandran, and Milind Kandlikar The Impact of Toxicity Testing Costs on Nanomaterial Regulation. Environ. Sci. Technol., Article DOI: 10.1021/es802388s Publication Date (Web): 20 February 2009The Impact of Toxicity Testing Costs on Nanomaterial Regulation. MAT-TOX®. Process for quick toxicity assessment of materials: Transport, storage, pre-processing, leaching and assays of the samples under the specific procedure for samples for ecotoxicity test. Santiago Cuesta López; Lorena Romero Santacreu, Universidad de Burgos. REF: BU-147-14. 18/11/2014 - NANOSAFETOX®. Protocol Development of Toxicity Study by a battery of in vitro assays not included in REACH to assess both acute and long-term exposure to nanomaterials. Santiago Cuesta López; Lorena Romero Santacreu, Universidad de Burgos REF: BU-148-14. 18/11/2014. http://www.nanofutures.eu/groups.

Madrid (Spain)

Complete size characterization of diatomaceous Earth E. Delgado, L. Reimer, D. Sowle, R. Shimkus, P. Bouza, J. Saad Bonsai Advanced Technologies, Avda Valdelaparra 27, Alcobendas, Spain Micromeritics Instrument Corporation, 4356 Communications Drive, Norcross GA, U.S.A eduardo.delgado@bonsaiadvanced.com

Diatomaceous earth is commonly used in many manufacturing and production processes as a filtering agent. Its exceptional textural properties makes it a very interesting natural material for several defense and environmental applications such as pest control and water treatment. The quality of the diatomaceous earth greatly affects the effectiveness of the filter. One of the primary characteristics of determining diatomaceous earth quality is particle size. Traditional methods, like using sieves, can be tedious and may not offer enough information to completely characterize the material. Automated sizing techniques, such as sedimentation analysis or static light-scattering, are limited in scope since diatomaceous earth is not a uniform material, but a composite of shapes, sizes, densities, and colors. To completely characterize

the particle size of diatomaceous earth, dynamic image analysis and dynamic light scattering (DLS) analysis are used to compliment to each other to accomplish this goal. Dynamic image analysis uses shape factors to collect size data in the micron range while DLS is used to determine the size of nanoparticles that remain suspended in the medium. Testing is performed on two types of diatomaceous earth commonly used in the beer brewing industry. References [1]

Jack G. Saad. Associate Scientist. Micromeritics Instrument Corporation.

Figures

Figure 1: Images of two different grades of Diatomaceous earth: DE2 and DE3. Source: High definition camera.

Figure 2: Dynamic Image Analysis.

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Figure 3: Dynamic Light Scattering.

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Graphene Quantum Dots: An Eco -Friendly Preparation E. Díez-Barra, A. Martín-Pacheco, M. A. Herrero, E. Vázquez UCLM. Facultad de Ciencias y Tecnologías Químicas-IRICA, Campus Universitario, 13071 Ciudad Real, Spain enrique.diez@uclm.es

The application of the Principles of the Green Chemistry [1] to nanotechnology is a permanent claim. [2] Nowadays, efforts are focused on the assessment of environmental and safety risks associated with the materials themselves, rather than the risks related to their respective synthesis and/or modification. Synthetic routes are not optimized for satisfying green nanoscience objectives such as energy or waste minimization and this fact is transferred to industrial processes. Mechanochemistry provides shorter reaction times, lower energy consumption and other green aspects related to solvent-free conditions, and has become a useful tool for green and sustainable chemistry. [3]

This is indicative of a high level of homogeneity in size and/or Csp2 domains. [Figure 1] In addition large Stokes displacement, 125 nm (λex=315; λem=430), are observed.

A lot of methods for prepare GQDs have been reported, but none of them has the appropriated requirements for industrial scaleup. We report a cheap, easy and eco-friendly means to obtain graphene quantum dots (GQDs): ball-milling for the fragmentation of graphite in the presence of sodium percarbonate as solid oxidant. This approach is related to the mechanochemical methodology reported by us for the preparation of fewlayered graphene from graphite [4] and carbon fibers. [5] In contrast to the conventional techniques used for the synthesis of graphene, and now for graphene quantum dots, the ballmilling process avoids the use of strong minerals acids, high temperatures and high vacuum chambers, while the solvents, if used, can be recovered and recycled. In addition, the protocol is quite simple, making it possible to set up the experiment in a short time.

[3]

Raman spectra show a low level of defect (ID/IG <0.6) [Figure 2]. References [1]

[2]

[4]

[5]

[6]

P.T. Anastas, J. Warner, Green Chemistry: Theory and Practice; Oxford University Press: Oxford, U.K., 1998. L. M. Gilbertson, J. B. Zimmerman, D. L. Plata, J. E. Hutchison, P.T. Anastas, Chem. Soc. Rev. 2015, doi: c4cs0045k. a) L. Takacs, Chem. Soc. Rev. 2013, 42, 76497659. b) C. F. Burmeister, A. Kwade, Chem. Soc. Rev. 2013, 42, 7660-7667. c) G.–W. Wang, Chem. Soc. Rev. 2013, 42, 7668-7700. V. León; M. Quintana; M. A. Herrero; J. L. G. Fierro; A. de la Hoz; M. Prato; E. Vázquez, Chem. Commun., 2011, 47, 10936-10938. A. E. del Río-Castillo; C. Merino; E. DíezBarra; E. Vázquez, Nano Res., 2014, 7, 963972. a) L. E. Brus, Appl. Phys., 1991, 53, 465-474. b) A. L. Efros, M. Rosen, Ann. Rev. Mater. Sci., 2000, 30, 475-521.

As it is known, photoluminescence (PL) is the most valued property of quantum dots and the wavelength of emission in deeply related to the size of the QD as a consequence of the quantum confinement of the excitons. [6] The emission wavelength of the obtained GQDs is quasiindependent of the excitation wavelength.

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Figures

Figure 1: Fire PL spectra (water; [6 mg/mL].

Figure 2: Graphite and GQDs RAMAN spectra.

Lessons learned in the exposure assessment and risk management of nanomaterials Maidá Domat, Carlos Fito ITENE, Spain

The group nanosafety and emerging risks of ITENE has conducted numerous exposure assessment campaigns within different R&D projects, especially related with the nanopigments, nanocomposites and packaging industries. Regarding the exposure assessment, measurements demonstrate the potential for exposure to engineered nanostructured materials (ENMs) for key activities

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in the life cycle of the nanomaterials. The selection of adequate protection is essential to guarantee the safety of workers in processes where ENMs are manufactured and/or handled, thus, Personal Protective Equipment is also tested in an exposure chamber within ITENE facilities.

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Nalon: an industrial partner in the Spanish security and defense field Juan José Fernández Industrial Química del Nalón, S.A., Spain juanjo@nalonchem.com

Industrial Química del Nalón, S.A. (NalonChem) is an independent and private family own company founded in 1943, whose activity is focused on the carbo-chemical sector. In the past decade started to develop new activities and nowadays is producing advanced carbon materials and nanoparticles. One of the main developments in carbon materials has been obtaining precursors for the manufacture of graphene from coal liquids (European Project RFCS). The resultant graphene has been tested for energy and biomediacal aplications. Current activities are focused in the development of sustainable and scalable graphene manufacturing technologies for industrial large scale implementation. At NalónChem, an innovative, versatile and environmentally friendly technique is being developed to produce high performance nanomaterials in the form of nanosized metals, metal oxides or mixed metal oxides. Its bottom-up technology enables fast continuous production of

fully crystalline nanoparticles in the form of colloidal dispersions, with narrow size distributions and precise stoichiometries. Moreover, this technology allows an outstanding level of product control (composition, particle size, size distribution and morphology), as well as flexibility to perform in-situ surface modifications, thus providing dispersion stability and compatibility between the solvent and the formulated final product. At NalónChem we understand that since every application demands specific product characteristics and properties, a “tailor-made” material needs to be optimized and customized, so all of our customer needs are met and provided added value is maximized accordingly. We are willing to work closely with our customers to help them incorporate nanotechnology into their products with success.

graphenit®: industrial applications Rafael Ferritto Nanoinnova Technologies SL. Calle Faraday 7, 28049-Madrid info@nanoinnova.com (www.nanoinnova.com)

Graphene, few layer graphene or graphene/graphite nanoplatelets have been named for 2D low dimension carbon materials with an extraordinary potential impact in our daily life based on the extraordinary properties of graphene (single layer of graphite) at nano-scale. As every new disruptive technology the pathway to develop and market these new products it is not simple. In Nanoinnova Technologies SL, we have been

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devoted a considerable amount of resources to mature new synthetic technologies for the production of chemically modified graphite nanoplatelets with improved dispersion properties in different matrices under graphenit® brand. We will share our advances in anti-corrosion, electrical conductivity, mechanical reinforcement, etc industrial applications.

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Advanced foams and nanomaterial synthesis for science and security applications Glenn A. Fox Physical and Life Sciences; Lawrence Livermore National Laboratory, USA gafox@llnl.gov

Technology and innovation often begins with new advanced materials with tailored properties. The ability for the deterministic synthesis of materials with controlled multi-scale morphology and structure is critical in imparting novel properties into resultant bulk materials for security applications.

production. With the development of advanced manufacturing techniques, the requirements placed upon the material feedstocks—e.g., shape, size purity, doping—requires new methodology for production and eventual material scale-up. Moving from traditional, iterative and timeintensive synthesis procedures, to automated, continuous flow synthesis platforms can accelerate material synthesis and discovery and earlier adoption into technology platforms. Results from initial continuous flow system experiments will be highlighted, focusing on how such a platform allows dynamic control during materials synthesis and start to create multiple “pre-programmed building blocks” that can be assembled to manipulate materials properties.

The first part of this talk will focus on the production of advanced new and novel inorganic, organic, and organometallic foam materials from the sol-gel polymerization process. The resultant materials have interest in areas of high energy density physics, energy storage materials and as feedstock for advanced manufacturing. The remainder of the talk will focus on new methods of nanomaterial synthesis and

Coatings production for civil and military markets 1

R. Gonzalez-Arrabal , N. Gordillo , A. Rivera , M. Panizo-Laiz , J. A. Santiago , O. Peña , 1,2 3 3 3 1 G. Balabanian , I. Fernandez-Martinez , A Wennberg , F. Briones and J. M. Perlado 1

Instituto de Fusión Nuclear, ETSI de Industriales, Universidad Politécnica de Madrid, E-28006 Madrid, Spain 2 Carl Zeiss Microscopy GmbH, Carl-Zeiss-Straße 22, 73446 Oberkochen, Germany 3 Nano4Energy, C/ José Gutiérrez Abascal, 2, E-28006 Madrid, Spain raquel.gonzalez.arrabal@upm.es

Emerging civil and military markets are increasing the need for engineered coating solutions, whereas existing markets demand coatings with improved properties, decrease the coating application costs, and innovatively recycle materials… The primary reason for the interest in coatings is its wide variety of potential applications in diverse fields such as protection of materials from corrosion, abrasion, application in filters, fire-

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resistant coatings, biomedical devices….

anti-fog,

memory

and

Coating properties depend on a number of interrelated parameters and also on the manufacturing technique. Due to its properties (easy control, environmental friendly, versatility, easily scalable and low cost) sputtering methods are among the most used techniques for coating production.

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Sputtering is traditionally employed to coat planar surfaces. However, by using coaxial sputtering the inner surface of pipes can be also coated. Coating engineering is based on the concept of tuning the coating properties to the desired value. In principle this can be easily done in those sputtered coatings since their properties strongly depend on the parameters used in the sputtering process, such as working gas pressure, distance between the target and the substrate, substrate temperature, and voltage applied to the cathode. Moreover, the chemical composition of the target can be designed by using reactive sputtering. It is worthwhile to mention that such a selection also allows improving the adhesion of the coating to the surface, which is one of the most critical points.

In this talk, the capabilities of sputtering to develop corrosion, oxidation, and abrasion protective coatings as well as, lubricating and radiationresistant coatings will be shown highlighting those related to Security and Defense. The influence of the sputtering parameters on the coatings properties will be illustrated. The capabilities and ongoing work of the Institute of Nuclear Fusion related to the fabrication of coatings will be presented. Acknowledgments The work was financed by the M.I.N.E.C.O (Spain) under the projects MAT2012-38541-C02-01 and 02 and by the Comunidad de Madrid (Spain) under the project S2013/MIT-2775

Graphene for security and defense Frank Koppens The Institute of Photonic Sciences. Av. C.F. Gauss 3, Castelldefels, Barcelona, Spain frank.koppens@icfo.eu

The long list of unique properties for graphene and 2d materials have been the major driver for intense scientific research. Interestingly, this combination of unique properties has also been the justification for very exiting advances in the development of technological applications. And this led to skyrocketed expectations that flatland applications will become the next disruptive technology impacting several cornerstones of our society. Indeed, graphene can play a unique role for a wide range of applications, such as broadband sensors for night vision, security, medical imaging, ultrafast and secure data communications, wearable electronics, energy, composites etc. etc [1,2]. Despite these promises, it is a major challenge to convince large industries to adopt a new material that requires new production processes, new integration strategies and even a new way of thinking. The question arises what aspects of 2d materials can be the starting point to overcome this barrier. It is clear that the true killer applications will make a big impact on our society, but they may come from an unexpected corner

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and the crucial material properties may be completely different than the ones that drove the initial scientific interest. In this talk, recent scientific and technological progress of 2d materials in the context of applications for high impact on society, safety and security will be highlighted with a critical reflection on the question whether they will live up to their hype. References [1]

[2]

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Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems. Ferrari et al., Nanoscale 7, no. 11 (2014). Photodetectors based on graphene, other two-dimensional materials and hybrid systems. Koppens, F. H. L., Mueller, T., Avouris, P., Ferrari, A. C., Vitiello, M. S., & Polini, M. Nature nanotechnology, 9(10), 780-793 (2014).

Madrid (Spain)

Large scale production of graphenic materials by Grupo Antolin and their applications development C. Lillotte, S. Blanco, P. Merino, C. Merino Grupo Antolin Ingeniería SA, Ctra. Madrid-Irún, km. 244.8, 09007 Burgos, Spain christopher.lillotte@grupoantolin.com

Graphene oxide is mainly produced from graphite although other graphitic materials have also been employed. The major disadvantage of graphite, as starting material, is the low efficiency of the oxidation process due to the high number of stacked layers present in its structure. As an alternative route, we present an industrial process to obtain few layer sheets of graphene oxide (GRAnPH®) by using GANF® carbon nanofibers as starting material and the Hummers’ method as oxidation procedure.

in different polar solvents. Moreover, it can be deposited over a wide variety of substrates by different methods and be used for diverse applications. During the last years, competitive solutions have been developed for several industries.

GANF® presents a singular helical ribbon graphitic structure, composed by a graphitic ribbon of approximately five graphene layers rolled along the fiber axis. This structure makes them very attractive as starting material for graphene production. The low number of stacked graphene layer in GANF® allows the achievement of a highly effective oxidation. Thus, whereas GRAnPH® can be used without further purification, several centrifugation steps are absolutely necessary to remove none oxidized graphite when the oxidation was carried out from graphite as starting material. The chemical composition of GRAnPH® graphene oxide allows the preparation of stable suspensions

References [1]

Vera-Agullo J, Varela-Rizo H, Conesa JA, Almansa C, Merino C, Martin-Gullon I. Carbon. 45 (2007) 2751-8.

Figures

Figure 1: TEM micrographs of: A) HR-CNFs; B) GANF® HR-CNF, it can be observed its high graphitic structure; C) Unraveled ribbon from the HR-CNF; D) Detail of the ribbon; E) Scheme of the structure of the HR-CNFs; F) Large single graphene oxide sheets derived from GANF®.

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Improving biosensors with nanotechnology Jaime Lopez de la Osa nanoimmunotech, Spain

Biosensors is a 10 Billion USD worth Industry, and is expected to double by 2020. The incorporation of different nanomaterials into these devices is a revolution for the development of biosensors making them more sensitive, more selective, faster, cheaper and simpler. Better tools of conjugation of different nanomaterials, surfaces

and biomolecules on a proper way will enable the development of innovative biosensors that will revolutionized our capabilities on the detection of pathogens in food, contaminants In water or biomarkers involved in human, animal or vegetal diseases.

Impact of Nanotechnology on European Defence Capabilities and EDA’s work Patricia López Vicente European Defence Agency (EDA), Brussels, Belgium patricia.lopezvicente@eda.europa.eu

The European Defence Agency supports the Member States and the Council in their effort to improve European defence capabilities ,current and future ones. Therefore, EDA acts as a catalyst, promotes collaborations, launches new initiatives and introduces solutions to improve defence capabilities. It is also a key facilitator in developing the capabilities necessary to underpin the Common Security and Defence Policy of the Union. The European Defence Agency is ascribed four functions, being one of them promoting defence Research and Technology. Research and Technology in EDA supports medium and long-term European Capabilities needs through different R&T activities, from the identification of emerging technologies, to the definition of technological priorities or the establishment of research projects. These activities help to stay upto-date in a high tech environment, while maximizing the impact by researching together.

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Furthermore, designing materials will create many opportunities and challenges for defence systems development and maintenance. Due to the fast evolution of nanotechnologies, getting ready can only be achieved via cooperation with civil sector, in dual-use areas, and devoting special attention to military specific technological applications. Different R&T groups at EDA, so called CapTechs, cover areas with relation to nanotechnologies, with the objective to promote and manage research activities in this domain. CapTechs on Components, Materials or CBRN Protection are responsible for activities on nanomaterial technology applications for defence, such as nanocoatings for naval and air applications, nanostructured materials and textiles for protection or high performance applications, or nanosensors for CB detection

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Efficient Photodetectors at Telecom Wavelengths based on Thin Films of Lead Sulfide Quantum Dots 1

Alberto Maulu , Pedro J. Rodríguez-Cantó , Rafael Abargues , Juan P. Martínez-Pastor 1

Department of Applied Physics and Institute of Materials Science, University of Valencia, Spain 2 Intenanomat S.L., Calle Catedrático Beltrán 2, 46980 Paterna, España pedro.j.rodriguez@uv.es

Colloidal QDs have recently attracted significant attention as promising candidate materials for many optoelectronic applications, including photodetectors, light-emitting devices and photovoltaics among others [1]. Moreover, these QDs are chemically synthesized from organometallic precursors and retain a passivating layer of ligands that make them solution processable. This is a very attractive technology for low cost and industrial scale up fabrication of those electronic devices on practically any kind of substrate (transparent plastics, glass and Si, among others) provided the appropriate electrodes. In the most recent literature on PbS QD-solid Schotky heterostructure photodetectors we find external quantum efficiencies (EQE = Responsivity.hν/e) below 20 % at the wavelengths of the exciton absorption band (≈ 1000 nm) under negative bias [2], whereas more than 106 A/W was reported for a MOS photoconductive structure based on a PbS layer (60-80 nm thick) on graphene [3]. In the present work, we focused our research on the optimized synthesis of IR absorbing PbS QDs to develop efficient Schottky-heterostructure photodetectors in the IR region (1300 – 1700 nm) (Fig. 1). The QD-films are deposited onto glass/ITO/PEDOT substrates by using a Dr-blade coating technique. The resulting devices by using Ag as a top electrode yield responsivities in the range 0.15-0.45 A/W (Fig. 2).

[3]

G. Konstantatos, M. Badioli, L. Gaudreau, J. Osmond, M. Berneche, F. Pelayo, F. Gatti, and F. H. L. Koppens, Nature Nanotechnology 7, 363 (2012).

Figures

Figure 1: Absorbance-Photoluminescence spectra of PbS colloidal QDs of 7-8 nm in diameter (see the TEM image as an inset).

References [1]

[2]

J. P. Clifford, G. Konstantatos, K. W. Johnston, S. Hoogland, L. Levina and E. H. Sargent, Nature Nanotechnology 4, 40 (2009). B. N. Pal, I. Robel, A. Mohite, R. Laocharoensuk, D. J. Werder, and V. I. Klimov, Adv. Funct. Mater. 22, 1741 (2012).

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Figure 2: Responsivity curves in photodetectors based on 250 and 500 nm thick PbS QD-solid films (their absorption edge lies beyond 1600 nm).

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Continuous Macroscopic Fibres of Carbon Nanotubes for Smart Textiles and Ballistic Protection Bartolomé Mas, Juan J. Vilatela* IMDEA Materials, Eric Kandel 2, Getafe, Spain *juanjose.vilatela@imdea.org

We report on the synthesis of kilometers of continuous macroscopic fibers made up of carbon nanotubes (CNT) of controlled number of layers, ranging from singlewalled to multiwalled, tailored by the addition of sulfur as a catalyst promoter during chemical vapor deposition in the direct fiber spinning process. The progressive transition from single-walled through collapsed double-walled to multiwalled is clearly seen by an upshift in the 2D (G′) band and by other Raman spectra features. The increase in number of CNT layers and inner diameter results in a higher fibre macroscopic linear density and greater reaction yield (up to 9%). We present a method to spin highly oriented kilometres of continuous fibers of adjustable carbon nanotube (CNT) type, with mechanical properties in the high-performance range. The synthesis of these macroscopic fibers is carried out by directly spinning an aerogel of CNTs during growth by chemical vapour deposition. CNT number of layers, ranging from singlewalled to multiwalled, is tailored by the addition of sulfur as a catalyst promoter during CVD. By lowering the concentration of nanotubes in the gas phase, through either reduction of the precursor feed rate or increase in carrier gas flow rate, the density of entanglements is reduced and the CNT aerogel can thus be drawn (up to 18 draw ratio) and wound at fast rates (>50 m/min). This is achieved without affecting the synthesis process, as demonstrated by Raman spectroscopy, and implies that the parameters controlling composition in terms of CNT diameter and number of layers are decoupled from those fixing CNT orientation. Applying polymer fiber wet-spinning principles then, strong CNT fibers (1 GPa/SG) are produced under dilute conditions and high draw ratios, corresponding to highly aligned fibers (from wideand small-angle X-ray scattering). This is demonstrated for fibers either made up of predominantly single-wall CNTs (SWCNTs) or

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predominantly multiwall CNTs (MWCNTs), which surprisingly have very similar tensile properties. By adjusting the composition of the carbon precursor we further show evidence of fibre with superior specific tensile strength to Kevlar 49 and about twice its toughness, combined with high electrical conductivity and a very large surface area. These results demonstrate a route to control CNT assembly and reinforce their potential as a highperformance fiber for ballistic applications. Finally, we discuss the properties of CNT fibres in the context of ballistic protection, and show examples of the exploitation of their properties as sensors, supercapacitors and other devices. References [1] [2] [3]

Chem. Mater. Reguero et la, 2014, 26(11), 3550-3557 ACS Nano Qiu et al 2013, 7(10), 8412-8422 ACS Nano Belén et al 10.1021/acsnano.5b02408 2015.

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Biomolecules sensors and detectio n by surface science techniques 1

E. Mateo-Marti , Mª. Sanchez-Arenillas and C. M. Pradier

Centro de Astrobiología. INTA-CSIC. Torrejón de Ardoz, 28850 Madrid, Spain. 2 Laboratoire de Réactivité de Surface, Université Pierre et Marie Curie, Paris, France mateome@cab.inta-csic.es

Understanding of the reactivity and interaction of organic molecules on surfaces is of a great importance because its atomic arrangement determines the mechanical properties, electronic behavior and reactivity of surfaces. Therefore, the ability to control and design the surface structure at a molecular level is a crucial point, so surfaces has attracted important attention due to their promising applications in nanotechnology and biotechnology. From these molecular units arise the possibility of complex functions like molecular recognition, sensing, electronic properties, conductivity, catalysis, chirality, magnetism and chemical reactivity that are important in nanoscience. Therefore, the adsorption, bonding and interaction of biomolecules, on surfaces is a necessary step towards the broad application of the interdisciplinary emerging field of nanobiotechnology. Interaction and reactivity of different biomolecules on well-controlled surfaces provide, for instance, convenient models to understand mechanisms in the formation of higher ordered molecular structures [1-2], strategies to functionalize large molecular based nanostructures for solid state advanced biosensors [3] or organicinorganic platforms for new devices. To date, a majority of biomolecules adsorption studies have focused on adsorption on metallic surfaces such as those of copper, gold, silver, and stainless steel [4-6]; minerals can also be very promising surfaces for studying biomolecule-surface processes; among such minerals is pyrite. Although various traditional methods exist to detect biomolecules, the development of innovative detection methods is therefore one of the major challenges in modern analytical sciences. The unique properties of some biomoleculas encourage the use of powerful and complementary surface science techniques for surface characterization and molecular detection,

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specifically techniques like X-ray Photoelectron Spectroscopy (XPS), Reflection Absorption Infrared Spectroscopy (RAIRS), Atomic Force Microscopy (AFM) and Scanning Tunnelling Microscopy (STM) [3,5,7]. By the complementary use of several techniques we will obtain information of moleculesurface adsorption, to improve our understanding of molecular self-organization processes. Furthermore, those techniques provide the possibility to optimise the sensing layer as well as to detect biomolecular recognition, which open promising ways to biotechnological devices. The aim of the present research is to study the interaction of biomolecules, among them single amino acids, peptides and peptides nucleics acids (PNA) on metallic and mineral surfaces, and their chemical reactivity by means of powerful surface science techniques. We investigate surfaces chemical composition and molecular reactivity or recognition due to different nature, preparation or experimental conditions. A very important conclusion is that surface structure will dictate its molecular adsorption and reactivity properties. A delicate balance of experimental methodology helps us to control and drive molecular adsorption to the desire conditions. Additionally, surface science techniques are established as a powerful tool for molecular detection and recognition. These results present interesting consequences from a fundamental point of view, for the development of optimized biosensors and large number of bionano applications. References [1] [2]

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Raval. R., Chem. Soc. Rev., 38 (2009) 707. Kuhnle, A.; Linderoth, T.R.; Hammer, B.; Besenbacher, F. Nature, 415 (2002) 891.

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[3]

[4] [5]

Mateo-Marti, E.; Briones, C.; Pradier, C.M.; Martín-Gago, J.A., Biosensors and Bioelectronics, 22 (2007) 1926. Mateo Marti, E.; Methivier, Ch.; Pradier, C.M., Langmuir, 20 (2004) 10223. Mateo-Marti, E.; Briones, C.; Roman, E.; Briand, E.; Pradier, C.M.; Martín-Gago, J.A. Langmuir, 21 (2005) 9510.

[6]

[7]

Mateo Marti, E.; Rogero, C.; Gonzalez, C.; Sobrado, J.; De Andrés, P.; Martín-Gago, J.A., Langmuir, 26 (2010) 4113. E. Mateo-Marti and C.M. Pradier: “A novel type of nucleic acid-based biosensors: the use of PNA probes, associated with surface science and electrochemical detection techniques” (2010) 323-344. Intelligent and biosensors.

Figures

Figure 1: Schematic representation from biomoleculas on surfaces to nanodevices, through surface science techniques characterization.

Surface silanised nanoclays – Filler modifier for rubber compounds 1

Johann G. Meier , Daniel Julve , Joaquin Coronas , María Martínez , 4 2 2 Miguel Menéndez , José Ramos , Jorge Pérez 1

Aragon Institute of Technology, C/ María de Luna 7-8, 50018 Zaragoza, Spain 2 IQESIL, Calle D, nº 97 Polígono Malpica, 50057 Zaragoza, Spain Institute of Nanoscience of Aragon, University of Zaragozaa C/ Mariano Esquillor, 50018 Zaragoza, Spain 4 Aragon Institute of Engineering Research, University of Zaragoza, C/ Mariano Esquillor, 50018 Zaragoza, Spain 3

jmeier@itainnova.es

Polymers filled with organically modified montmorillonite (MMT) have been attracting intensive research interest due to the potential benefits as highly active reinforcing filler or as an additive to reduce liquid and gas permeability. The introduction of these property-enhancements into the pure polymer matrix by the filler is directly related to the highly anisotropic structure of the layers of the smectic clays and the potentially very high surface accessible in case of complete exfoliation. However, the potential benefits from the large anisotropy of the clay-layers also pose the biggest challenge – assure a good dispersion. The

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desired dispersion state of the montmorillonite clays in polymers and elastomers typically is not achieved using standard rubber processing equipment, even in the case of best possible compatibilisation with organic modifiers, impairing their application as additives. An alternative approach to overcome the dispersibility issue are synthesized layered silicates (SLS). Except Octosilicate, synthesized layered silicates are naturally occurring minerals (Magadiite, Kanemite, Kenyaite). Analogous to MMT the SLS require organic modification by ionexchange with long-tailed cations resulting in an

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extension of the layer-spacing and compatibilisation with the rubber matrix facilitating the dispersion and exfoliation of the SLS-sheets. However, synthetic layered silicates (SLS) have some important differences to layered clay minerals: the former have interlayer silanoland negatively charged sites SiO- groups, whose ordering can be defined specifically, while the charged sites of clay minerals arises from isomorphous substitution within the layers and the exact position of these sites is very difficult to define [1]. Cation-exchange should therefore yield a more regular coverage of the silicate-layers with long-tailed cations and hence a better overall compatibilisation promoting intercalation and exfoliation. Synthetic layered silicates (SLS) are assumed to have in general a lower aspect ratio, i.e. the sheet extension is smaller than the one of the familiar mined layered clays, while maintaining the typical layer thickness of the individual sheets. Because the interaction energy between the layers of the clay scales also with the surface area, intercalation and exfoliation of SLS in apolar polymers should be easier. We studied these materials for their potential as a reinforcing filler of elastomers. As a base polymer matrix we used a standard tire-tread mixture (70phr s-SBR, 30phr BR) together with the usual curing and antioxidant reagents and TESPT. Tensile tests showed an interesting synergism at high filler loadings (70-90 phr) of highly dispersable silica (HDS) and 3-5 phr SLC. Upon the addition of SLS to the base tire-tread mixture reinforced with HDS, the stress at 10% deformation was found to be lower by ca. 30% than the corresponding SLS-free mixture but higher at σ100, σ200, σ300 by 15-28%. Most interesting is that the MMT-compound does not show any additional reinforcement over the HDS-only compound, suggesting that the SLS-

compound has a much better dispersion of the layered clays than the MMT-compound. Additionally, we show the beneficial effects of SLSover MMT-additive on the dynamic mechanical properties in such a tire-tread mixture: improvement of the performance predictors for ice-wet-grip and rolling resistance by 35% without significantly impairing the wear and abrasion behavior in comparison with a reference compound. These effects were obtained using standard rubber processing equipment and industry-established silanization technology [2-4]. We reason that the performance gain is related to a much higher level of exfoliation of the synthetic layered silicates than montmorillonite. We present a detailed experimental study and develop a qualitative model of the effect of the additive on the reinforcing silica-filler network. [3] References [1] [2]

[3]

[4]

N. Takahashi and K. Kuroda, Journal of Materials Chemistry, 21 (2011) 14336. J. G. Meier, D. Julve, J. Ramos, J. Perez, J. Coronas, M. Martinez, and M. Menendez. Synthetic layered silicates as synergistic filler additive for tire tread compounds. In: N. GilNegrete and A. Alonso, editors. Constitutive Models for Rubber Viii: CRC Press, (2013). pp. 577. J. G. Meier, D. Julve, M. Martínez, J. Coronas, M. Menéndez, J. Ramos, and J. Pérez, Kautschuk Gummi Kunststoffe, 66 (2013) 46. D. Julve, J. G. Meier, M. Martinez, J. Coronas, M. Menéndez, J. Ramos, P. Bernal, and J. Pérez, Revista del Caucho, 5 (2014) 30.

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Smart Sensors and Active Solutions for Chemical and Biological threat Detection and Protection Nieves Murillo, Ana Perez and Jon Maudes TECNALIA, Pº Mikeletegi, 2. Parque Tecnológico, San Sebastian, Spain nieves.murillo@tecnalia.com

The word of sensors is very huge, including different technologies and typologies (pressure, temperature, chemical, gas, biological,....) and market sectors (petrochemical, environment, health & care, water, automotive, aerospace, defense, …). The global market for sensors was valued at $79.5 billion in 2013 and is expected to increase to $86.3 billion in 2014, $95.3 billion in 2015, and to nearly $154.4 billion by 2020, a compound annual growth rate of 10.1% over the five-year period from 2015 through 2020 [1]. Sensors, like humans, react to the environment and the stimuli (sound, light, contact, …) with or without intelligence, and are based in physical or chemical principles. A broad definition is provided by the Scottish Enterprise in “Sensing a brighter future review”: “sensors are those parts of larger systems which gather information about the world, make sense of it and then communicate that information”. The sensitive part of sensor, the smart or functional material, is combined with the electronics and the communication elements as a whole. To classify the sensor world is a difficult task, some communities classify them by the active principle (piezoelectric, resistive, capacitive, photonic chromatic, luminescent, …) and other by the final application, where 22 subsectors have been identified (noise cancelation, imaging of object, odor, physical properties, textures, presence, biological species, chemical alerts, gas detection, ...). The use of sensors for protection against chemical and biological threats is a gap on the existing technologies. The citizen protection in case of natural disasters, accidental events and manmade attacks is still a need where sensors can play an important role. Two main research areas need to be explored in this field: the development of low cost and effective sensors for the detection of chemical substances in fluids (air, water, drinkable, …) and the development of active

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solutions for the protection against biological threats and pandemics. The reason why sensors are more focused on chemical and not in biological threats is linked to the nature of attacks. It is difficult to distinguish between strains for the same bacteriological family. And sensors for identification need to be very specific to achieve the necessary success rate. In the opposite, chemical sensors are widely used for safety and security incidents and the rate success of detection with good sensibility and selectivity is achieved in most of the technologies. Most commercial available monitoring tools are based on instruments developed for two sectors: chemical and quality laboratories and military applications. Several research efforts are focused on instrument miniaturization (chromatographs, spectrometers, etc.); but the cost of such instruments is expensive for their intensive use on some security applications. The reason is the high number of detection points required, i.e. in the station hall monitoring. In this scenario, the development of low cost, small size and easy to manufacture sensors is a market opportunity and an open field for sensor research. TECNALIA is working on the development of chemical sensors technologies based on:    

Solid Oxide Resistive Sensors. Luminescent optosensors. LED induced fluorescence. Resistive sensor based on polymeric nanocomposite with CNTs or Graphene conductive fillers.

In the other hand, active solutions for the protection of citizens and personnel involved on the incident management (first responders, medical service, law enforcements, …) are the key tool for the effective minimization of the threat

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impact. In this research area, TECNALIA is focused on two main target objectives: 1. 2.

Development of Chemical materials and Biological filters and dosimeter

adsorbent

References [1] Global Markets and Technologies Sensors, BCC Research, 2014.

for

The expertise of TECNALIA in non-woven materials is the base for the developments in both applications. Figures

Figure 1: TECNALIA developments on Smart Sensors and Active Solutions for Chemical and Biological Protection.

Bionanoelectronics with natural and artificial membrane transporters 1,2

Aleksandr Noy

Biology and Biotechnology Division, Lawrence Livermore National Laboratory, 7000 East Ave. Livermore, CA USA 2 School of Natural Sciences Univ. of California Merced, Merced, CA USA noy1@llnl.gov

Bioelectronic interfaces are beginning to generate an increasing interest in the biosecurity community and beyond. Such interfaces could play an important role in a varity of fields ranging from biodetection, biosensing and countermeasure development, to medical diagnostics and humancomputer interactions. One of the promising routes to the next generation interfaces involves harnessing and mimicking biological

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functionality in electronic devices. I will present two examples of such approaches that we are currently developing at LLNL. The first example shows a general route for incorporating membrane proteins, which perform some of the key biological functions in a living cell, into nanoelectronic devices. To preserve protein functionality in the device, we use hierarchical assembly of lipid molecules and membrane proteins onto a

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nanowire transistor to create a 1-D bilayer device—a bioelectronic platform that can convert proton and ion transport events into electrical signals [2]. This presentation will present several examples of bioelectronic devices that use passive ion channels and active ATP and light-driven pumps,[1,3,4] as well as an extended version of the device that uses additional biological components to regulate the device performance [1]. The second example will show a recently developed nanoscale transport platform that replicates some of the key membrane protein transport characteristics in a structure based on a carbon nanotube. The biomimetic carbon nanotube porins (CNTPs) are capable of self-insertion into artificial lipid bilayers, as well as plasma membranes of live cells where they form well-defined nanoscale pores with interesting and useful transport characteristics [5].

[4]

[5]

Misra, N.; Martinez, J. A.; Huang, S.-C.; Wang, Y.; Stroeve, P.; Grigoropoulos, C.; Noy, A. Proc. Natl. Acad. Sci. USA, 2009, 106, 13780–13784. Geng, J.; Kim, K.; Zhang, J.; Tunuguntla, R.; Comolli, L.; Allen, F.; Cho, K.; Munoz, D.; Wang, Y.; Grigoropoulos, C. P.; Ajo-Franklin, C. M.; Noy, A. Nature, 2014, 514, 612-615.

Figures

This research was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering. References [1]

[2] [3]

Tunuguntla, R. H.; Bangar, M. A.; Kim, K.; Stroeve, P.; Grigoropoulos, C.; Ajo-Franklin, C. M.; Noy, A. Adv. Mater. 27 (2015,), 773-773. Noy, A. Bionanoelectronics. Adv. Mater., 2011, 23, 799-799. Huang, S.-C.; Artyukhin, A.; Misra, N.; Martinez, J.; Stroeve, P.; Grigoropoulos, C.; Ju, J.-W.;Noy, A. Nano Lett., 2010, 10, 1812–1816.

Figure 1: Bionanoelectronic Si nanowire transistor that incorporates bacteriorhodopsin, a photoactivated proton pump proteins. Bottom graph shows the device signal recorded over several consecutive illumination cycles.

HRP/AuNPs/Polycyclosiloxane Bioelectrochemical System as a New Peroxide Sensor 1

Evelyn Ospina , M. P. Garcia Armada , J. Losada , B. Alonso , C. M. Casado 1

Dpto. Ingeniería Química Industrial y M. A., Universidad Politécnica de Madrid, Madrid, Spain Dpto. Química Inorgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain

pilar.garcia.armada@upm.es

Ferrocenyl polymers, containing a cyclotetrasiloxane in the backbone can act as electrocatalyst in the direct oxidation of enzymes, the reduction of hydrogen peroxide generated in enzymatic reactions and in the oxygen spent in the enzyme-catalyzed reaction. Electrodes modified

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with these polymers have been used as mediators in amperometric enzyme electrodes for the detection of glucose [1]. In the other hand, it is widely know that nanostructures can improve the interface between biomolecules and an electronic transducer. The

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nanostructured surfaces have the advantages of a reduced distance between the redox center of proteins and the electrode together with the facilitation of electron transfer. Immobilizing metal nanoparticles on an electrode coated with a good electrocatalyst provide a three-dimensional structure similar to the microenvironment of redox proteins in biological systems [2], as well as facilitate the electron transfer. In addition, these surfaces allow a favorable support for immobilizing redox proteins and keep they in their native states. Gold nanoparticles (AuNPs) have good biocompatibility and can act as a tiny conduction centers to improve electron transfer rates of redox proteins. AuNPs can be self-ensambled by means of the thiol functional groups which are present in the protein structure. We present here a new peroxide biosensor with HRP covalently bonded at an AuNPs/ polycyclosiloxane electrochemical system with high reproducibility, sensitivity and good linear range. The biosensor was prepared by electrodepositing the cyclotetrasiloxane polymer on a Pt electrode surface that was further used for the electrochemical deposition of gold nanoparticles. AuNPs were obtained in a 4 g/L HAuCl4 solution by the adequate number of potential cycles into the margins from -0.4 V to 0.2 V at scan rate 0.02 V/s [2]. By means of this procedure, AuNPs aggregates between 185-200 nm with nanoparticles size about 20-44 nm were obtained. Figure 1 shows the AuNPs grown in the polymer-electrode surface. The immobilization of HRP was done by incubating the modified electrode for 2 h 30 min in a 2mg/mL HRP in 0.1 M pH 7.0 phosphate buffer solutions. Figure 2 shows the biosensor scheme.

In this work have been also investigated the electrochemical characterization, the kinetics and the electrocatalytic properties of modified electrodes in the reduction of hydrogen peroxide and the direct electrochemistry of HRP. The optimal applied potential to direct reduction of HRP was -0.2 V (vs. SCE). The obtained apparent overload heterogeneous constant was 43.1 μA/mM and the apparent Michaelis-Menten constant was 1.84 mM. Both values are indicative of the high enzymatic efficiency of the bioelectrochemical system. Also the analytical properties of the new biosensor were studied at E= -0.2 V, and a linear range from 0 to 120 μM was obtained with the detection limit of 0.32 μM and sensitivity of 526 nA/μM cm2. This biosensor was also applied to determination of other organic peroxides [3]. The obtained sensitivities for the determination of cumene and tert-butyl hydroperoxides were 457 nA/μM cm2 and 33 nA/μM cm2 respectively. Finally, this developed biosensor was successfully applied to determine hydrogen peroxide in real samples of a contact lens cleaning solution. References [1]

[2]

[3]

J. Losada, M.P. García Armada, I. Cuadrado, B. Alonso, B. González, C.M. Casado, J. Zhang, Journal of Organometallic Chemistry, 689 (2004) 2799–2807. Q. Wan, H. Song, H. Shu, Z. Wang, J. Zou, N. Yang, Colloids and surfaces B: Biointerfaces 104 (2013) 181-185. M.P. Garcia Armada, J. Losada, I. Cuadrado, B. Alonso, B. González, C. M. Casado, J. Zhang, Sensors and Actuators B 101 (2004) 143-149.

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Figure 1: UHSEM micrographs of Pt wires modified with the cylotetrasiloxane polymer and AuNPs.

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Figure 2: Scheme of the developed peroxide sensor.

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Graphene-based supercapacitors J. Pedrós, A. Boscá, S. Ruiz-Gómez, L. Pérez, J. Martínez, F. Calle Instituto de Sistemas Optoelectrónicos y Microtecnología, ETSI Telecomunicación, Universidad Politécnica de Madrid, Av. Complutense 30, Madrid, Spain j.pedros@upm.es

Security and defense sectors continuously demand better energy storage devices to power a large variety of applications. Among the key advantages of these devices are stand-alone (off-grid), back-up, or fuel-economy operation, portability, and reduced thermal and acoustic signatures.

References [1]

[2]

Graphene foams (GFs) fabricated by chemical vapor deposition (CVD) [1] provide a versatile and scalable 3-dimensional (3D) network structure retaining the outstanding properties of 2D graphene. The unique combination of high specific surface area and outstanding electrical and mechanical properties of GFs and their composites offers new possibilities in energy storage devices. In this presentation, we will focus on the CVD synthesis of graphene foams and the fabrication of supercapacitors based on GFs functionalized with conducting polymers [2,3] and metal hydroxides [4] and oxides [5].

[3]

[4]

[5]

Z. Chen, W. Ren, L. Gao, B. Liu, S. Pei, and H.-M. Cheng, Nature Materials 10 (2011) 424. J. Pedrós, A. Boscá, J. Martínez, F. Calle, S. Ruiz-Gómez, L. Pérez, V. Barranco, A. Páez, and J.García, European Patent Application EP 14382428.2 (2014). J. Pedrós A. Boscá, J. Martínez, S. RuizGómez, L. Pérez, V. Barranco, and F. Calle, submitted (2015). S. Ruiz-Gómez, A. Boscá, L. Pérez, J. Pedrós, J. Martínez, A. Páez, and F. Calle, Diamond & Related Materials 57 (2015) 63. S. Ruiz-Gómez, L. Pérez, A. Boscá, J. Pedrós, J. Martínez, A. Mascaraque, and F. Calle, submitted (2015).

Acknowledgments: MINECO projects RUE (CSD20090046) & GRAFAGEN (ENE2013-47904-C3-1-R).

Temperature Effect on the Production of Graphene Oxide and Graphite Oxide 1

Flavio Pendolino , Nerina Armata , Tiziana Masullo , Angela Cuttitta , Paolo Colombo 1

University of Padova, via Marzolo 9, Padova, Italy 2 University of Palermo, Viale delle Scienze, Palermo, Italy 3 Consiglio Nazionale delle Ricerche (IAMC-CNR), Torretta Granitola Fz. Campobello di Mazara, Italy flavio.pendolino@unipd.it

Carbon allotropes and derivates show novel behavior in a framework of promising technologies [2-4]. Lately, graphene oxide (single) and graphite oxide (multilayer), have been considered as potential materials in energy sustainable technologies, such as photovoltaic, solar heater [45]. Our work issues the effect of the temperature

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on the synthesis/oxidation of graphene-like materials and producing a different final products (see Figures). By using a few-steps method [6], two forms of carbon oxides are generated, i.e. single or multilayer, which is affected by the operating temperature. Even if apparently similar, these materials exhibit distinctive physical and chemical

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properties with a specific reactivity which impact the future applications. Archived behaviours suggest a context where the properties needed for a material can be straightforward obtained by modifying the temperature. Furthermore, the properties of the final oxidized products can be varied by using a different allotrope (e.g. single wall material) as starting materials. The prospective of modulate/engineering the oxided graphene-like materials by functionalizing oxygen domains, owing to the feasibility of a low cost and scale up production and the advantage of formulating novel materials with specific features.

References [1] [2] [3] [4] [5] [6]

Novoselov KS, Geim AK, Morozov SV, et al. Science, 306 (2004) 666. Compton OC, Nguyen ST, Small, 6 (2010) 711. Su C, Loh KP, Acc. Chem. Res., 46 (2013) 2275. Raccichini R, Varzi A, Passerini S, Scrosati B, Nat. Mater., 14 (2015) 271. Xu C, Xu B, Gu Y, et al., Energy Environ. Sci., 6 (2013) 1388. Pendolino F, Parisini E, LoRusso S, J. Phys. Chem. C, 118 (2014) 28162.

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Designing “superabsorber” nanoparticles 1,2

K. Ladutenko , P.A. Belov , O. Peña-Rodríguez , A. Mirzaei , A. Miroshnichenko and I. Shadrivov 1

ITMO University, 49 Kronverskii Ave., St. Petersburg 197101, Russian Federation Ioffe Physical-Technical Institute of the Russian Academy of Sciences, St. Petersburg 194021, Russian Federation Instituto de Fusión Nuclear, Universidad Politécnica de Madrid, José Gutiérrez Abascal 2, E-28006 Madrid, Spain 4 Nonlinear Physics Centre, Research School of Physics and Engineering, The Australian National University, ACT, 2601, Australia 2

Nanoparticles have a fundamental limit as to how much light they can absorb. This limit is based on the finite number of modes excited in the nanoparticle at a given wavelength and maximum absorption capacity per mode. The enhanced absorption can be achieved when each mode supported by the nanoparticle absorbs light up to the maximum capacity. Using stochastic optimization algorithm, we design multilayer nanoparticles, in which we can make several

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resonant modes overlap at the same frequency resulting in superabsorption (i.e., absorption larger than the theoretical limit for a single absorber). We further introduce the efficiency of the absorption for a nanoparticle, which is the absorption normalized by the physical size of the particle, and show that efficient absorbers are not always operating in the superabsorbing regime

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Smartnanocoatings the key to advance e ffeciency in surface solutions, easy to clean super hidrophobic & super hidrophilic coatings Adam Prats NANOTECNOLOGÍA SPAIN S.L., Spain adam@nanopinturas.com

Preface Coatings products based on sol-gel chemistry and nanotechnology are developed for the use on Al and Mg metals & other materials with basic principles of synthesis route and chemistry of inorganic-organic hybrid polymers. The products provide excellent protection with thin layers and without the use of heavy metals. Additional properties can be included such as eas y-to-clean properties due to hydrophilic and/or hydrophobic surfaces and protective coatings with new smart properties. Nanotecnologia Spain focus is on formulation & production of coatings for protection of surfaces, the company speciallyses in this area of study in collaboration with partner laboratories & reseach institutes. This presentation will be mainly looking at practical examples: hydrophobic solutions easy to clean surfaces on aluminium surfaces, coating for heat exchangers; coatings for refurbishment existing facades in military & civil instalations; coatings for reinforced concrete such as cooling towers at energy plants. And hydrophilic solutions, auto clean surfaces & elimination of pollutants derived form exhaust engines in civil & military instalations. Introduction Inorganic polymers as film formers are in use for many years in paint technology. Mostly used are Zinc silicates as primer coatings in heavy duty corrosion protection. They were utilised as binder – typically hydrolysed tetra ethyl ortho silicate or alkali metal silicate. In the early 80’s many investigations began to form interpenetrating organic-inorganic networks. The first work was done on epoxy polyamine network connected with polysiloxane network.

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The organic modification is critical in terms of resulting film properties and compatibility between the organic and inorganic moieties is not easy to achieve. If the level of organic modification is too low, the films are glasslike with good durability but other properties were generally poor. Too high a level of organic material show for example a too low UV stability. So, since the 90’s more progress was made in the development of new ways to synthesise novel hybrid polymers that can be used as resins for the formulation of paint materials with low coating thickness and enhanced properties. Effects and possibilities are attributable primarily to the ratio of surface to volume atoms and the quantum mechanical properties of the components. By varying the composition, shape, size or character of the surface, these nano particles can be shaped again and again like small building blocks, resulting in unprecedented scope for material design. The decisive factor is that new mechanical, optical, magnetic, electrical and chemical characteristics and properties can result from the nano-scale nature of the system components. With this technology new materials can be designed for the macroscopic world, providing new materials for the future with many possibilities. A union between substrate and coating that is produced is made possible by structures in the coating material that are very similar to those of the material surface. Substrate and coating thus enter into real, covalent chemical bonds with each other. Surface and coating grow into an inorganic polymer network at molecular level.

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Development of fiber reinforcing thermoplastic composites based on hybrid yarns José Manuel Ramos-Fernández, Javier Pascual Bernabéu AITEX, Plaza Emilio Sala Nº1 03801 Alcoy (Alicante), Spain jramos@aitex.es

Nowadays, fibre reinforced composites are in use in a variety of structures, ranging from space-craft and aircraft to buildings and bridges. This wide use of composites has been facilitated by the introduction of new materials, improvements in manufacturing processes and developments of new analytical and testing methods. Thermoplastics also offer the option to fuse or weld moulded subcomponents, which can reduce assembly weight and stress concentrations by eliminating fasteners and adhesives. Eventually, respect to others conventional materials like aluminum or steel the FRTC will have less specific density which is a significant advantage in transport applications

The speech will show a new technology to manufacture fibre-reinforced thermoplastic composites.The technology will be based on the hybridization at micro and macroscale of fibrous elements comprising the two main components of the final products (high performance filaments and thermoplastic filaments). This will result in semielaborated products (yarns and fabrics) which can be further processed into thermoplastics composites. The processing of these materials still remain a big challenge, the speech will review the different processing technologies and the works carried out at AITEX to improve processing technologies and the materials performance.

Walking Towards a transparent Photo-Super-Capacitor 1

José Ramón Ramos-Barrado , F. Martín , J. Rodríguez-Moreno , E. Navarrete-Astorga , 1 2 M.C. López-Escalante , E. A. Dalchiele 1

Nanotechnology Unit, Dep de Física Aplicada I & Ingeniería Química. Universidad de Málaga, Málaga, Spain 2 Instituto de Física & CINQUIFIMA, Facultad de Ingeniería, Montevideo, Uruguay barrado@uma.es

Store a large amount of energy in a device and can deliver it in a short time, high-power devices, low weight and size is a strong challenge for nanotechnology with important applications in defense, both in integrated wearable personal protective systems and offensive weapons; if, in addition, these devices could be transparent, flexible and solar rechargeable, because its autonomy its applications in defense will be very important. In this paper we present the latest results from our laboratory, Nanotech UNIT of UMA, in the

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development of transparent super-capacitors based in nano-structures as a previous step to an integrated photo-supercapacitor. The photocapacitor can be considered as a simple sandwich-type electrochemical cell consisting of a light-absorbing electrode (photoelectrode), a redox-free electrolyte, and a counter-electrode. The photoelectrode bears a heterojunction of dye (dye sensitized solar cells, DSSCs) or quantum dots (quantum dots sensitized solar cells, QDSSCs) and a porous layer, a counter-electrode also bears a porous layer. The first step in making a transparent

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photo-supercapacitor; really, we have prepared a pseudo-capacitor, that is, a pseudo-capacitors or redox supercapacitors using fast and reversible surface or near-surface reactions for charge storage, mainly by transition metal oxides as well as electrically conducting polymers. We have combined various nano-structures as nanorods, QDs, thin films of semiconductor materials using deposition techniques following the criterion of low-cost, easily up-scaling and friendly to ambient. For a start, we have use a mixture of PVP and LiClO4 as solid ionic conductive energy storage in transparent systems; so, the films were used in a symmetrical supercapacitor (PEDOT/PVP/PEDOT). The goal of this work was to study, by first time, the availability of the PVP/LiClO4 as solid polymer electrolyte in transparent SC [1]. In a second step, we have obtained ZnO nanorods by electrochemical methods and we have combined with QDs of CdS obtained by SpinCoating Assisted Successive-Ionic-Layer-Adsorption and Reaction Method to study the interaction of nZnO and the QDs of CdS with a mean diameter about 5 nm. The interaction between ZnO and CdS QDs/ZnO NRs was evaluated in a photoelectrochemical solar cell configuration with a polysulfide electrolyte under white illumination. The decoration of ZnO NRs with CdS QDs leads to a cell performance of JSC = 2.67 mA/cm2, VOC = 0.74 V, FF = 0.30 and η = 1.48%. The next step was to design and to do a pseudocapacitor by combining the above elements and some innovations. A hybrid nano-architecture with high electrochemical performance for supercapacitors have been obtained by growing hierarchical ZnO NRs@CuS@PEDOT@MnO2 core@shell heterostructured nanorod arrays on ITO/glass substrates, this structure is shaping as a semi- transparent supercapacitor electrode showing some novelties with respect to other similar supercapacitors that have been reported. For instance, it is the first time that it has been employed covellite by spray pyrolysis as a good electrical conductor to improve the electron transfer to the nanorod and to facilite the PEDOT electrodeposition onto the nanorod. The balance between transparency and capacitance is good comparatively to other reported results in the

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bibliography the performance transparency of the device [3].

and

the

The major impediment, which hampers many practical applications of existing supercapacitors, is their limited performance, stability, operating electrochemical windows and short lifetimes, which are strongly determined by the properties of the electrolytes being used. Now, we have introduction a new polymer electrolyte with ionic liquid. The synthesis feasibility of two different gel polymer electrolytes based each one on methyl methacrylate (MMA) and 1-Vinyl-2-pyrrolidone (VP) monomers, respectively, by using a common ion liquid i.e. 1-(2-hydroxyethyl)-3- methyl imidazolium tetrafluoroborate ([HEMIm][BF4]) as the conductive plasticizer, has been done. PVP/[HEMIm][BF4] solid-state ion gel electrolyte has then been synthesized and we can prepare supercapacitors with a more effective electrolyte. We have prepared a glass/ITO subtrate of PVP, Poly (3,4 ethylenedioxythiophene) PEDOT, HEMIm[BF4], and ZnO hybrid nano- architectures with good electrochemical performance. These hybrid nanostructured electrode exhibits excellent electrochemical performance, with high specific areal capacitance, good rate capability, cyclic stability and diffused colure transparency [4]. The next step will be to design an to prepare a complete device supercapacitor and the last step to do a photo-supercapacitor, better it is a transparent and flexible device References [1]

[2]

[3]

[4]

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J. Rodríguez, E. Navarrete, E. A. Dalchiele, L. Sánchez, J.R. Ramos-Barrado, F. Martín, Journal of Power Sources 237 (2013) 270276. G. Guerguerian, F. Elhordoy, C. Pereyra, R. Marotti, F. Mart iın, D. Leinen, J.R. RamosBarrado and E. Dalchiele, Nanotechnology 22 (2011) 505401-505410. Rodríguez-Moreno J., Navarrete-Astorga E., Dalchiele E. A., Schrebler R., Ramos-Barrado J.R., Martín F, Chemical Communication, 50 (2014) 5652. J.Rodrígue; E Navarrete-; E. Dalchiele; R. Schrebler; P. Leyton; J. R. Ramos-Barrado; F. Martín, to be published.

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Figures

Figure 1: Schematic diagram of the operation of the ZnO/CdScore/shell nanorod array PEC solar cell: electron–hole pair generation by incident photons, electron injection from the excited CdS nanocrystal shell into the ZnO nanorod core and scavenging of holes by the S2−/S2− redox couple in solution. The normal to the substrate nanorod architecture provides a direct pathway for electron transport from ZnO to the FTO substrate and then via the external circuit to the working load [2].

Figure 2: Schematic illustration of the synthesis process for the designed ZnO NRs@CuS@PEDOT@MnO2 hybrid nanostructured electrode.

Modulating retro-reflectors operating in the range of 0.95-1.1 µm for asymmetric communications 1

C. Rivera , A. F. Braña , B. J. García , J. Stupl , D. Kemp , J. Tilles , S. Wu , D. Arbitman and J. Jonsson 1

Ingeniería de Sistemas para la Defensa de España, Beatriz de Bobadilla 3, 28040 Madrid, Spain Grupo de Electrónica y Semiconductores, Universidad Autónoma de Madrid, 28049 Madrid, Spain 3 SGT, NASA Ames Research Center, Moffett Field, CA 94035, USA 4 MEI, NASA Ames Research Center, Moffett Field, CA 94035, USA 5 USRA, NASA Ames Research Center, Moffett Field, CA 94035, USA 6 NASA Ames Research Center, Moffett Field, CA 94035, USA

crivera@isdefe.es

Wireless optical communications can be implemented using a modulating retro-reflector on one end of the link, whereas the other is based on a conventional laser transmitter/receiver system. This approach is useful to relax the payload requirements for the onboard communication system, for example, in space-to-ground links or other asymmetric scenarios, thus providing relevant savings in terms of power consumption and mass, as well as reducing the pointing requirements. Modulating retro-reflectors basically consist of the combination of an optical retroreflector and an electro-optic shutter. The switching speed required for most applications makes the use of nanostructures the most promising solution. In particular, multiplequantum-well (MQW) structures have been successfully applied to develop electroabsorption modulators operating from ultraviolet to near infrared, similarly to the case of emitters and

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photodetectors where these structures are routinely used as a means to reduce threshold and control wavelength or spectral selectivity [1][2][3]. Unfortunately, MQW-technology is not well established for certain wavelength ranges, including the bands associated to 1030-nm and 1064-nm lasers, mainly due to the lack of suitable substrates for growth, even though some results were reported [4]. In this work, we address the design, simulation, fabrication and characterization of (In,Ga)As/(Al,Ga)As-MQW-based electroabsorption modulators operating in the range of 0.95-1.1 µm. The design covers aspects related to both the material growth, and the device and system engineering. As a result of this study, a segmented modulator based on a p-i-n device structure grown on a linearly graded buffer layer to accommodate the large lattice mismatch between the substrate and the quantum well materials was fabricated.

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Optical material characterization was performed by means of photoluminescence and reflectance, whereas device parameters were extracted from bias dependent electro-optic measurements and dark current. In order to explain the experimental results and assess the device performance, numerical calculations were also carried out to determine the wave functions and energy levels of the 1s exciton state for each band within the multiband envelope theory (k∙p formalism), so that absorbance and reflectance could be theoretically obtained. Figure 1 shows the expected performance as a function of applied electric field for a selected structure close to the absorption edge. The results indicate that the degree of strain under which well layers are subjected plays a critical role on the device optimization (see, for example, the surface pattern of the as-grown wafer in Figure 2). Moreover, the device speed is limited by RC considerations. Finally, we discuss the practical implementation issues related to the optical assembly and packaging, and the system

parameters, including speed, modulation efficiency, power consumption, temperature stability and insertion loss, as well as the potential applications of this non-commercial technology for security and defense, proposing future directions of development. References [1]

[2]

[3] [4]

P. G. Goetz et al., Proc. IEEE Military Communications Conference, (2010) 1601– 1606. C. Rivera et al., Proc. IEEE Int. Conf. on Space Opt. Systems and Applications, (2011) 239-244. A. E. Willner et al., Proc. IEEE, 100 (2012) 1604-1643. D. S. Katzer et al., J. Vac. Sci. Technol. B, 18 (2000) 1609-1613.

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Figure 1: (a)Absorption coefficient for the optimized structure inserting a strain relief layer to improve material quality in the well (linearly graded buffer) as a function of electric field. (b) Measured transmittance as a function of applied reverse bias (0 V black line, 5 V blue line and 10 V red line).

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Figure 2: (a) Reflectance and transmittance for one asgrown sample operating at 975 nm. (b) Scanning electron microscope micrograph of the surface of a (In,Ga)As/(Al,Ga)As-MQW-based structure, where crosshatch defects can be observed. (c) Modulator response: driver input (red) and optical modulation measured by a photodiode (blue).

(c)

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UV-patternable nanocomposite containing CdSe and PbS quantum dots as miniaturized luminescent chemo-sensors Pedro J. Rodríguez-Cantó, Rafael Abargues, Juan Martínez-Pastor Intenanomat S.L., Calle Catedrático Beltrán 2, 46980 Paterna, España pedro.j.rodriguez@uv.es

The role of nanoscience in analytical science has been greatly established for the development of (bio)chemical sensors with enhanced performance. The design of low-cost, easy-to-fabricate and portable analytical devices with a low limit of detection (LOD), good selectivity, high sensitivity and short response time are in high demand. [1,2] Part of that has been made possible by the use of nanomaterials. In particular, (bio)chemical sensors based on fluorescent quantum dots (QDs) have attracted intense interest because of their excellent optical and electronic properties compared to the routinely employed fluorescent organic dyes. [3] These properties include sizetunable light emission over a wide range of energies, high photoluminescence quantum yield (PL QY), narrow emission line width, and good solution processability. [4] In addition, the physicochemical stability of QDs, their extremely large surface area, as well as the possibility of functionalizing their surface by conjugation with appropriate molecules make them very attractive nanomaterials for ultrasensitive sensors with the possibility of multiplex (bio)chemical detection. [5] In this work, we have developed a novel multifunctional hybrid polymer-based luminescent material particularly formulated for photolithography and tested it as a miniaturized chemosensor. This nanocomposite was formulated with either luminescent CdSe (for the visible) or PbS (for the near-IR) colloidal QDs embedded in a polyisoprene-based photoresist (PIP). The resulting nanocomposite combined the extraordinary optical properties of the QDs with the lithographic characteristics of the resist matrix. Both the optical properties of QDs and the lithographic performance of the photoresist were preserved after the incorporation of QDs into the photoresist (Fig. 1). We checked the sensing capability of this QD–PIP nanocomposite using 1 cm2 square patterns

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as a disposable gas sensor by monitoring the PL intensity upon exposure to 2-mercaptoethanol (MET) and ethylenediamine (EDA) using two types of QDs: CdSe and PbS. The transduction mechanism of the sensor is based on the changes of the QD photoluminescence (PL) when molecules are adsorbed onto the QD surface. The CdSe–PIP pattern sensor showed a decay of PL when exposed to different amounts of MET and EDA in vapour and found LOD values around 10-3 ng L-1 and 125 ng L-1, respectively (Fig. 2). From the calibration curve, we determined that the binding affinity of MET to CdSe–PIP is around four orders of magnitude higher than that of EDA. We also observed a linear sensing behavior within a broad concentration range, which allows us to use CdSe–PIP as quantitative sensor for MET and EDA. Furthermore, the PbS–PIP nanocomposite showed different sensor responses depending on the target analyte, whereas the exposure of PbS–PIP sensor to EDA led to the quenching of the QD PL, and exposure to MET molecules resulted in a 6.5-fold enhancement of the PL intensity. The different responses of CdSe and PbS QDs to MET can be explained by the difference in the energy of these QDs valence band top with respect to the redox level of the thiol molecule. In conclusion, these results demonstrate that a completely disposable sensing platform technology can be developed using this novel QD– PIP luminescent nanocomposite, which may also form the basis for the development of miniaturized chemosensors, which may be of interest for several fields such as the food industry, environmental monitoring, and health

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References [1] [2]

[3]

[4] [5]

F. S. Ligler, Anal. Chem., 2009, 81, 519. R. Abargues, P. J. Rodriguez-Canto, S. Albert, I. Suarez and J. P. Martínez-Pastor, J. Mater. Chem. C, 2014, 2, 908. U. Resch-Genger, M. Grabolle, S. CavaliereJaricot, R. Nitschke and T. Nann, Nat. Methods, 2008, 5, 763. Nanocrystal Quantum Dots, ed. V. I. Klimov, CRC Press, Boca Raton, FL, 2nd edn, 2010. M. F. Frasco and N. Chaniotakis, Sensors, 2009, 9, 7266.

Figures

Figure 1: (left) Optical microscope pictures of different CdSe–PIP nanocomposite structures on glass patterned by UV lithography: (a) interdigitates,(b) solid square, and (c) framework. (right) Emission spectra of CdSe QDs in o-xylene and in the nanocomposite film upon excitation at 532 nm. Inset: Emission of the bisazide molecule contained in the photoresist film upon excitation at 404 nm.

Figure 2: PL decay response of CdSe-nanocomposite miniaturized sensor as a function of the mass concentration of EDA and MET in the vapour phase for an exposure time of 15 min. Inset: linear dependence and corresponding regression line of the sensor response.

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Expanding nanotechnology opportunities for Defence and Security Françoise D. Roure French High Council for Economy, Industry, Energy and Technology. CGEIET, France francoise.roure@finances.gouv.fr

The presentation shall focus on three main aspects: 

The contribution of nanotechnology to the Resilience loop I a globalized environment, taking into consideration the consideration dependence, interdependence and resilience along the value-chains;



The challenges for nanotechnology research commercialization in a dual-use innovations and applications based on platform technologies and advanced materials and systems; Some pre-requisites for reducing time to Nano S&D markets, including European Union policies.

Industrial Property and Nanotechnology Luis Sanz Tejedor Spanish Patent and Trademark Office Paseo de la Castellana, 75, Madrid, Spain luis.sanz@oepm.es

How would it be today’s world should IPR’s didn’t ever exist? How would cutting edge technology companies protect their inventions? Would technology be so spread as it is today? When a new technological field is born these questions are again and again on the screen. Nanotech is in a technological development scale a new born and everything is to be discovered though we count on previous experiments. It is very difficult to find any technical field where the IPR’s are not taken into account, so Nanotechnology (with its broad technical coverage) is not different. Industrial Property Rights have become a cornerstone of any R&D and Commercial strategy. In the process of internationalization every company must prepare a thorough strategy to make the best out of their investment, any conflict on IPR’s can weak the project and eventually stop it. It is no surprise how competing companies fight their way out into the markets using IPR’s either as a defensive or attacking weapon. In the Technology Transfer process, when the knowledge travels from laboratories to markets IPR’s are regarded as one of the key elements to accomplish such journey but

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more often than not they are used to put a spoke in somebody else's wheel in the name of priority. IP also brings new perspectives to R&D as patent protected cross-border technologies are public, standard, classified and structured. A better knowledge of IPR’s legal basis can help to strengthen the companies position in the market. The IPR’s strategy on the different nanotechnology areas can be seen as homogeneous despite the fact of the difference in the subject matter. The military research is not published regularly, usually kept under secret. However, some facts can arise to the surface: the Pentagon spent $300 million in nano research in 2004 and Nanotechnology is considered to have a big role in the new warfare paradigm. It is still a long way to go not only in nanotechnology to become mature, but also in the procedures to manage the knowledge produced in the nano escale. Redifining the way the patentability requirements are met in patent applications is a key factor for the technology to be well protected as much as well disclosed.

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Metal oxide nanostructured gas sensors for security applications 1

Giorgio Sberveglieri , E. Nunez Carmona , C. Cerqui , R. Ciprian , E. Comini , M. Falasconi , 2 3 2 1,2 2 A. Ponzoni , A. Pulvirenti , V. Sberveglieri , G. Zambotti , D. Zappa

1 SENSOR Lab and University of Brescia, Brescia, Italy SENSOR Lab and National Institute of Optics (INO) of CNR, Via Branze 45, Brescia, Italy 3 University of Modena and Reggio Emilia, Reggio Emilia, Italy

giorgio.sberveglieri@unibs.it

This work reports metal oxide nanostructures with thin film and nanowire morphology and their exploitation as gas sensor in the frame of selected security applications, namely, detection of chemical warfare agents and detection of hidden people. Metal oxides such as ZnO or SnO2 have been widely adopted in gas sensing, especially in a chemiresistor configuration due to the high sensitivity, low production cost, reduced weight and size of such devices. The working mechanism is based on the modulation of the metal oxide macroscopic resistivity due to red-ox reactions occurring at the metal oxide surface with adsorbing gaseous molecules [1]. Different metal oxide nanostructures will be presented in this work, based either on thin films and nanowire bundles, detailing the synthesis process [2], protocols to integrate such nanostructures into functional gas sensors devices [3] and functional performance with respect to compounds of interest in security field such as dimethyl methylphosphonate (a simulant for Sarin nerve agent), ammonia and acetone (these compounds may be produced, among other ways, by urine or breath, and may be exploited as marker of human presence). Results obtained by the work group of SENSOR laboratory and collaborators will be reviewed in terms of sensitivity, selectivity and stability in the framework of security applications. As for selectivity, sensor performance will be further shown with respect to the integration of the proposed nanostructure in an artificial olfactory system (AOS), namely an array of sensors based on different materials (each one showing its own response spectrum), with a pattern

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recognition software handling the collective response of the array [4]. Differently from analytical analyzer, AOS can be successfully used both to track the concentration of a given compound in a complex atmosphere or to identify odors, i.e. complex gas blends, without analyzing in detail their composition, but simply recognizing the presence of a particular odor (or gas) in a given atmosphere through the identification of the proper odor fingerprint (response of the sensor array to such a smell). Such a sensing system provides a large flexibility and can be tuned to identify different targets. For example, AOS based on a mixed array of metal oxide nanowires and thin films revealed suitable to distinguish chemical warfare agents from compounds typical of everyday life, such as ethanol or CO, or to identify the presence of human-related odors, [5]. Acknowledgement The research leading to these results has received funding from European Community through the FP7 project N. 313110 “Sniffer for concealed people discovery (SNOOPY)”, from Italian Ministry of Education through project FIRB FIRB RBAP115AYN “Oxides at the nanoscale: multifunctionality and applications”.

References [1] [2]

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N. Barsan, U. Weimar, J. Electroceram., 7 (2001) 143–167. A. Ponzoni, E. Comini, I. Concina, M. Ferroni, M. Falasconi, E. Gobbi, V. Sberveglieri, G.Sberveglieri; Sensors 12 (2012) 1702317045.

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[3]

[4] [5]

A. Vomiero, A. Ponzoni, E. Comini, M. Ferroni G. Faglia and G. Sberveglieri; Nanotechnology 21(2010) 145502. F. Rock, N. Barsan, U. Weimar, Chem. Rev. 108 (2008) 705−725. A. Ponzoni, C. Baratto, S. Bianchi, E. Comini, M. Ferroni, M. Pardo, M. Vezzoli, A. Vomiero, G. Faglia, G. Sberveglieri; IEEE Sens. J. 8 (2008) 735-742.

Figures

Figure 1: Metal oxide based gas sensors. SnO2 thin film prepared through RGTO technique, [2] (a); SnO2 nanowire bundle prepared through evaporation and condensation method, [2] (b); chemiresistor device (c).

Figure 2: response of SnO2 sensors prepared through nanowire and thin film technologies to repeated DMMP (dimethyl methylphosphonate – a Sarin nerve agent simulant) injections, a). Artificial Olfactory System (AOS) equipped with metal oxife chemiresistors and coupled with an autosampler for static head space generation, b).

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New Redox-Responsive Molecular Tools and Larger Scale Systems for the Detection and Removal of Strategic Environmental Hazards John W. Sibert The University of Texas at Dallas, Department of Chemistry, 800 W. Campbell Rd, Richardson, TX 75080 USA sibertj@utdallas.edu

The development of advanced materials, nanoscale structures and devices is often stimulated by the synthesis of new molecular constructs. Inspired by the famed 150-year-old compound commonly referred to as Wurster's reagent, Wurster-type receptors constitute a class of host molecules, discovered by our group, that contain the electrochemically-active phenylenediamine moiety within the receptor framework. Importantly, the phenylenediamine unit promotes strong interactions between the redox center and a variety of captured guests (cations, anions and electron deficient aromatics) using either a linking nitrogen atoms(s) or the electron-rich pi face. Modulation of the electrochemical properties via derivatization of the phenylenediamine core has created an electrochemical “tool box” which extends the range of guests that can be accommodated while maintaining the desirable electrochemical features. The possible combinations of phenylenediamine isomers, macrocyclic/ligand donor atoms and overall molecular topology endow these compounds with a rich coordination chemistry and promise in applications that include redox switches, sensors, transport agents, catalysis and molecular magnetism. In addition, receptor-modified surfaces, polymers and dendrimers extend the well-studied chemistry of the discrete molecular receptors toward the creation of devices for ultimate use in the detection, remediation and/or

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detoxification of environmental hazards. In this presentation, the synthesis, properties and coordination chemistry of representative members of the Wurster's receptors will be discussed with particular emphasis on the structure-property relationships involving receptor architecture, electrochemical properties, coordination chemistry and applications involving strategic targets.

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Hybrid SPS-Hot Press: A suitable technology for the fabrication of ceramic nanocomposite components for security and defense applications 1,2

1,3

Ramón Torrecillas San Millán , J. L. Menéndez , A. Fernández Valdés , M. Suarez , S. Rivera 1

Nanomaterials and Nanotechnology Research Center, CINN (CSIC, Universidad de Oviedo), Asturias, Spain 2 Moscow State University of Technology ‘‘STANKIN’’. Vadkovskij per. 1, Moscow, Moscow Oblast, Russia. 3 Nanoker Research, S.L., Polígono de Olloniego, Parcela 22A, nave 5, 33660, Oviedo, Asturias, Spain r.torrecillas@cinn.es

Many defense applications demand ceramic nanocomposite materials combining several structural and functional properties only attainable with a tailored design of the microstructure and an adequate processing strategy that allows the consolidation of the materials into bulk-sized components while preserving the targeted microstructure, and particularly the nanoscale grain size. Spark Plasma Sintering (SPS) is considered a promising technology for the industrial fabrication of these multifunctional materials since it allows maintaining the intrinsic properties of the initial powders and the formation of fully dense composites unachievable with other conventional methods but the cost effective industrial implementation of SPS for the manufacturing of large and/or complex-shaped ceramic products must overcome several technical limitations such as the availability of suitable technology with special features such as sufficient electrical power output, precise temperature measurement & control, optimized pressing tool systems and hybrid heating system that minimize thermal gradients occurring when using exclusively the Joule heating[1].

matrix composite materials for electromagnetic shielding and thermoelectric applications and composite materials for wireless power transmission. In this work we report the progress in the development of these materials by Spark Plasma Sintering and the challenges that must be addressed for the successful industrial fabrication by hybrid SPS-Hot Press of these materials and their use in components and devices for security and defense applications References [1]

M. Su rez, A. Fern ndez, J.L. Men ndez, R. Torrecillas, H. U. Kessel, J. Hennicke, R. Kirchner and T. Kessel (2013). Challenges and Opportunities for Spark Plasma Sintering: A Key Technology for a New Generation of Materials, Sintering Applications, Dr. Burcu Ertug (Ed.), ISBN: 978-953-51-0974-7, InTech.

Figures T. Alpha *10-6 /K-1 3 2 1

Since 2010, the Nanomaterials and Nanotechnology Research Center (CINN-CSIC) in collaboration with Nanoker Research SL is working in the development of new advanced multifunctional materials obtained by hybrid heating equipment (Hybrid SPSHot Press system) for space, aeronautics and homeland security applications. The main research areas are ultra-hard ceramic armors for personnel and vehicles, low thermal expansion satellite structures, optical payloads and windows/domes for aircraft countermeasure systems, ceramic

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Tref.: 20.0 °C Tref.: 20.0 °C

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Figure 2: Transmittance curves of some transparent ceramics obtained by Spark Plasma Sintering.

Figure 3: Example of ceramic plates with different sizes and geometries.

Nanosafety issues along their life cycle of nanoadditives incorporated in NM -enabled products A. Vilchez, E. Fernández, D. González, S. Vázquez-Campos LEITAT Technological Center. C/ Innovació 2, 08225 Terrassa, Barcelona, Spain Tel.: +34937882300; Fax: +34937891906 svazquez@leitat.org

The commercialization of nano-enabled products and their societal acceptance requires the insurability of safety at all stages of the product life cycle. Current uncertainties on the safety of such products need to be carefully addressed to avoid public fears blocking the benefits of nanotechnology. Sound scientific information must be generated to identify potential risks of nanoenabled products on human and ecosystems health and, when considered unacceptable, efficiently mitigate such risks. This has to be done in a holistic manner, taking into consideration all stages of the life cycle of these products, to protect the safety of workers, downstream users and consumers, the ecosystems, and the general population that may be exposed through the environment.

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Monitoring the release during the use phase of nano-enabled products is one of the most challenging areas, in identifying the potential risks posed by nanomaterials on human and environmental health. Several European projects are focused on evaluating the release in the use phase of nano-enabled products: Nanopolytox, GUIDEnano and NANOSOLUTIONS and Nanorelease in which LEITAT Technological Center is either participating or coordinating. In this talk, the nanosafety issues related to the use of nanoadditives in nano-enabled products will be presented. Furthermore, specific examples from the projects afore mentioned will be described.

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Madrid (Spain)

Graphene in Security and Defence Applications Amaia Zurutuza Graphenea S.A., Tolosa Hiribidea 76, E-20018 Donostia-San Sebastian, Spain a.zurutuza@graphenea.com

Graphene has emerged as an extraordinary nanomaterial for many potential applications in very different industries such as semiconductor, biotechnology, energy, transport, aerospace, security and defence. As a result of its high electrical and thermal conductivity, transparency and flexibility, graphene is quite a unique material that should impact many industries. However, at present most of these developments are at a research stage due to the many challenges that have to be overcome in order for graphene to become a success in the market place. [1,2] I would like to show the potential that graphene could have in the security and defence industry in imparting electrical, mechanical and tribological properties to materials, [3,4] in obtaining high sensitivity sensors, [5] in water purification [6] and in thermal management. [7]

References [1] [2] [3]

[4]

[5]

[6]

[7]

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H. Alcalde, J. de la Fuente, B. Kamp, and A. Zurutuza, Proc. IEEE, 101 (2013) 1799. A. Zurutuza and C. Marinelli, Nature Nanotech., 9 (2014) 730. A. Centeno, V.G. Rocha, B. Alonso, A. FernĂĄndez, C.F. Gutierrez-Gonzalez, R. Torrecillas, and A. Zurutuza, J. Eur. Ceram. Soc., 33 (2013) 3201. C.F. Gutierrez-Gonzalez, A. Smirnov, A. Centeno, A. Fernandez, B. Alonso, V.G. Rocha, R. Torrecillas, A. Zurutuza and J.F. Bartolome, Ceram. Int., 41 (2015) 7434. O. Zagorodko, J. Spadavecchia, A. Yanguas Serrano, I. Larroulet, A. Pesquera, A. Zurutuza, R. Boukherroub and S. Szunerits, Anal. Chem., 86 (2014) 11211. W.L. Wang, E.J.G. Santos, B. Jiang, E.D. Cubuk C. Ophus, A. Centeno, A. Pesquera, A. Zurutuza, J. Ciston, R. Westervelt, and E. Kaxiras, Nano Lett., 14 (2013) 450. J.D. Renteria, S. Ramirez, H. Malekpour, B. Alonso, A. Centeno, A. Zurutuza, A.I. Cocemasov, D.L. Nika and A.A. Balandin, Adv. Func. Mater. 25 (2015) 4664.

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Adhesion and mechanical properties of implanted nanostructured tungsten 1

N. Gordillo , E. Tejado , M. Panizo-Laiz , J. Y. Pastor , J. M. Perlado and R. Gonzalez-Arrabal 1

Instituto de Fusión Nuclear, ETSI de Industriales, Universidad Politécnica de Madrid, Madrid, Spain. 2 Department of Materials Science- Research Centre on Safety and Durability of Structures and Materials (CISDEM), UPM-CSIC, Madrid, Spain nuria.gordillo@upm.es

Owing to its properties: high melting point, low vapor pressure, low physical and chemical sputtering yields, low thermal expansion, electrical conductive properties and relative chemical inertness, tungsten seems to be one of the best candidates to be used as shielding material in plasma facing materials (PFM) for future nuclear fusion reactors. Nowadays, the capabilities of nanostructured materials for such applications are being attracted much attention due to their radiation-resistant and self-healing behavior. In this work, the capacity of the nanostructured W (nW) as protective role in PFM is studied and the radiation-induced changes in the structure and

NanoSD 2015

mechanical properties have been investigated. For this purpose, high density coatings made of nanometric tungsten columns (nW) were prepared by direct current (DC) magnetron sputtering and later were implanted under different conditions: (i) single implanted with H, (ii) sequentially with C and H, and (iii) simultaneously (co-implanted) with C and H at room temperature. The stress state was analyzed by X-ray diffraction, while the mechanical properties and adhesion to the substrate have been characterized using the nanoindentation and the nanoscratch techniques respectively.

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Alfonso GĂłmez 17 28037 Madrid â&#x20AC;&#x201C; Spain info@phantomsnet.net www.phantomsnet.net