NanoSD 2014 abstracts book

NanoSecurity & DefenseInternational Conference

ÁVILA, SPAIN

N a n o S e c u r i t y & D e f e n s e

I n t e r n a t i o n a l C o n f e r e n c e N a n o S D 2 0 1 4

Á v i l a , S p a i n U N E S C O a W o r l d H e r i t a g e C i t y s i n c e 1 9 8 5

N a n o S D 2 0 1 4 A v i l a ( S p a i n ) | 1

NanoSD 2014 will provide an opportunity to discuss general issues and important impacts of nanotechnology in the development of security and defense. A broad range of defense and security technologies and applications, such as nanostructures, nanosensors, nano energy sources, and nanoelectronics which are influencing these days will be discussed. It is evident that nanotechnology can bring many innovations into the defense world such as new innovate products, materials and power sources. Therefore, NanoSD 2014 will present current developments, research findings and relevant information on nanotechnology that will impact the security and defense.

Organising Committee

Antonio Correia - Phantoms Foundation (Spain) - Chairman

Ignacio Dancausa - Grupo Atenea (Spain)

Alfonso López - Grupo Atenea (Spain)

José Manuel Perlado - Instituto de Fusión Nuclear - UPM (Spain)

Honorary Committee

Excmo. y Mgfco. Sr. D. Carlos Conde Lázaro - Rector Universidad Politecnica

Madrid (Spain)

Ilmo Sr. D. José Luis Cortina - Presidente de Grupo Atenea (Spain)

Excmo. Sr. D. Alfonso de la Rosa - Teniente General - Director del Centro de

Estudios Superiores de la Defensa Nacional, CESEDEN (Spain)

Excmo Sr. D. Ignacio Cosidó Gutiérrez - Director General de la Policía (Spain)

Excmo. Sr. D. Guillermo Velarde Pinacho - General de División EA -

Presidente del Instituto de Fusión Nuclear (Spain)

2 | N a n o S D 2 0 1 4 A v i l a ( S p a i n )

Organisers

The PHANTOMS FOUNDATION based in Madrid, Spain, focuses its activities on Nanoscience and Nanotechnology (N&N) and is now a key actor in structuring and fostering European Excellence and

enhancing collaborations in these fields. The Phantoms Foundation, a non-profit organisation, gives high level management profile to National and European scientific projects (among others, the COST Bio-Inspired nanotechnologies, ICT-FET Integrated Project AtMol and ICT/FET EUPHONON Coordination Action) and provides an innovative platform for dissemination, transfer and transformation of basic nanoscience knowledge, strengthening interdisciplinary research in nanoscience and nanotechnology and catalysing collaboration among international research groups. The Foundation also works in close collaboration with Spanish and European Governmental Institutions to provide focused reports on N&N related research areas (infrastructure needs, emerging research, etc.).

The ATENEA Group is a think tank for thought, participation and debate. Our strategies and activities aim to promote awareness of security and defence in the Hispanic world and to support the strategic decisions companies and institutions need to make. The work of the Group includes Publishing, Forums and Events, Training and Consulting.

Our project’s mission is to create the ATENEA Foundation and debate Club. Our activities contribute to the assets the future Foundation needs for its projected social involvement. At the soon-to-be created ATENEA debate Club, public and private figures and organisations will converge in a creative forum of dialogue generating ideas and proposals of interest in the areas of security and defence.

The National Police Academy (Escuela Nacional de Policía) develops and delivers training courses and programs to access Basic and Executive Scales at the National Police Corps, as well as training activities for students from other police forces established in the field of police cooperation, both nationally and internationally. The Academy carries out the program and implementation of courses related to internal promotion of officials of the National Police. The headquarters of the National Police Academy lies in the city of Ávila (Spain).

The Institute of Nuclear Fusion (IFN) of the Polytechnical University of Madrid (UPM) is essentially devoted to Nuclear Research (basic and applied) related to both Nuclear Fusion and Fission are key goals in our program. Most of contributions have been (and will be) developed in Nuclear Fusion as future promising Energy Source, and in particular Inertial Confinement Fusion Energy, where the Institute is unique in Spain in size, personnel and projects (in fact no other than the Institute has a programme in this area of Energy by Laser Fusion). Science and Technology for Inertial and Magnetic development of future Engineering Facilities and Reactors have so many common areas that a general principle of the Institute from the starting of its life has been the very close collaboration with Centres in both initiatives.


Sponsors

Exhibitors


General Index

Keynote Speakers p. 5

Invited Speakers p. 6

Oral Contributions p. 6

Speakers (Alphabetical Order) p. 8

Posters List p. 11

Abstracts (Speakers) p. 12

Abstracts (Posters) p. 79


KEYNOTE SPEAKERS

PAGE Paolo Bondavalli (Thales Research and Technology, France) “Thales efforts in developing applications based on nanomaterials and nanotechnology: energy, spintronics, NVM memories and sensors”

14

Jérôme Bourderionnet (Thales Research and Technology, France) “Integrated photonics for RF filters”

15

José Mª. De Teresa (Universidad de Zaragoza, Spain) “Epitaxial graphene on SiC substrates for potential application in Security and Defense”

21

Elvira Fortunato (CENIMAT, Portugal) “Recent Advances on Nano-materials and Technologies for Thin Film Transistors”

27

Glenn A. Fox (Lawrence Livermore National Laboratory, USA) “Forensic Science at the Nanoscale”

28

Raquel González-Arrabal (IFN-ETSII, Spain) “Coatings production for military applications”

30

Antonio Hernando (IMA-UCM, Spain) “Microwires multilayers structure for two frequencies absorption”

33

Margaret E. Kosal (Georgia Tech, USA) “Nanotechnology and Diffusion of Innovation: Security Challenges for the 21st Century”

38

George Palikaras (Metamaterial Technologies Inc., Canada) “Safety & Security Applications of Optical Metamaterials”

45

Fabrice Pardo (LPN/CNRS, France) “The Optical Helmholtz Resonator: a breakthrough for extreme light confinement from IR to RF”

46

María Pilar Pina Iritia (INA, Spain) “Nanoporous chemical receptors on microcantilever-like sensors for explosives detection in vapor phase”

49

Frank Placido (UWS/Thin Film Center, UK) “Thin Film Technologies for Security and Defense Applications”

50

José Manuel Ramos (AITEX, Spain) “Textile, Nanotechnology and Defence”

53

Paul Reip (Intrinsiq Materials Ltd., UK) “Defence Applications for Plastic Electronics”

54

Steven Savage (Swedish Defence Research Agency, Sweden) “Nanotechnology – an enabling technology, a critical technology or simply a new technology with inflated ego?”

60

Brent Segal (Lockheed Martin, USA) “Nanotechnology from the Lab to the Fab”

61

Jean-Pierre Simonato (CEA-Grenoble, France) “Sensing traces of nerve agents like Sarin using nanomaterial based electrical detectors”

63

Ivano Soliani (SOLIANI EMC SRL, Italy) 64


“The tex le electrically conduc ve as security solu ons for several applica ons” Denis Spitzer (ISL-CNRS-UdS, France) “Nanostructured energetic materials: opportunities to enhance performances

66

Nava Swersky Sofer (International Commercialisation Alliance, Israel) “Best practices in commercializing nanotechnologies in defense”

67

Ian Turner (University of Derby, UK) “Applications of Nanotechnology in Forensic Science”

71

INVITED SPEAKERS

PAGE Julio Gómez Cordón (Avanzare, Spain) “Nanomaterials industrial applications in security and defense”

29

Nieves Murillo (Tecnalia, Spain) “Air Filtering Efficiency Evaluation of PC Nanofiber Filters for Capture of Biological Particles in Personal Dosimeters”

41

Ovidio Peña Rodríguez (IFN-ETSII-UPM, Spain) “Invisibility cloaking using thin all-dielectric multilayer coatings”

47

Asha Peta Thompson (Intelligent Textiles Limited, UK) “What happens when you use textiles to make electronics for soldier systems?”

48

José Mª Riola Rodríguez (SDGTECIN-DGAM, Spain) “Nanotechnologies: applications of interest for the Ministry of Defense”

57

Miguel Roncalés (ALPHASIP, Spain) “Automated Drug Detection System”

58

Pedro A. Serena (ICMM-CSIC, Spain) “Nanotechnology: the ongoing revolution”

62

Ambiörn Wennberg (Nano4Energy, Spain) “Innovative approach to thin film sensor development”

75

ORAL CONTRIBUTIONS

PAGE Soraya Artiles Burgos (Guardia Civil - SEDEX-NRBQ (CBRN Unit), Spain) “Exposure or contamina on with CBRN substances ?”

13

Carlos Campos-Cuerva (Nanoscience Institute of Aragon (INA), Spain) “Nanotechnology as a tool to end counterfeiting”

16

Juan Carlos Castellanos (Tecnobit, Spain) “Galileo PRS service, the Spanish technology approach”

18

Santiago Cuesta López (Universidad de Burgos, Spain) 19 Fernando de León Pérez (Centro Universitario de la Defensa, Spain) “Light harvesting structures optimized at infrared frequencies”

20

Manel del Valle (Universitat Autònoma de Barcelona, Spain) “Electronic tongue sensing of explosives and its mixtures”

23


PAGE Joana Fonseca (CeNTI - Centre for Nanotechnology and Smart Materials, Portugal) “From R&D to product: development of new interactive products with integrated printed electronic solutions”

26

Denis Guilhot (ICFO, Spain) “Salient Technologies @ ICFO with potential for the Aerospace, Defence & Security sector”

31

José Jiménez Jiménez (Universidad de Málaga, Spain) “Solids luminescent based in Quantum Dots for fingermark detection in different surfaces”

34

Jan Kolařík (Palacky University, Czech Republic) “Removal of arsenic compounds from water using iron-based materials”

36

Christopher Lillotte (Grupo Antolin, Spain) “Large scale production of graphenic materials by Grupo Antolin and their applications development”

39

Felipe Orgaz (Instituto de Ceramica y Vidrio, CSIC, Spain) “Transparent ballistic armour ceramics. Recent advances and issues to be overcome”

43

Julio Plaza del Olmo (Instituto Tecnológico La Marañosa, Spain) “Recent development on dual-band uncooled PbSe sensors monolithically integrated on advanced interference filters”

51

Miguel Ribeiro (CeNTI - Centre for Nanotechnology and Smart Materials, Portugal) “Keys to improve flexible organic bulk-heterojunction solar cells”

55

Luis Sanz Tejedor (Oficina Española de Patentes y Marcas (OEPM), Spain) “Industrial Property as a key factor in the Security and Defense industry”

59

Aitana Tamayo (Instituto de Cerámica y Vidrio. CSIC., Spain) “Silicon Oxycarbide Nanoparticles as New Drug Delivery Materials for Infectious Disease Treatments”

68

Luis Valles (Guardia Civil - UCO, Spain) “Technology applied to criminal investigation: What to expect from nanotechnologies?”

72

Effrosyni D. Vogli (Foundation for Research and Technology, Hellas (FORTH) Institute of Chemical Engineering Sciences (ICE-HT), Greece) “A New Concept of Carbon Nanotube based Textiles for Civil Protection Services”

73

Rogelio Zubizarreta Jiménez (Yflow, Spain) “Active substances encapsulated by Electro-Hydrodynamic techniques. Textile applications”

77


SPEAKERS (ALPHABETICAL ORDER)

PAGE Soraya Artiles Burgos (Guardia Civil - SEDEX-NRBQ (CBRN Unit), Spain) “Exposure or contamina on with CBRN substances ?”

Oral 13

Paolo Bondavalli (Thales Research and Technology, France) “Thales efforts in developing applications based on nanomaterials and nanotechnology: energy, spintronics, NVM memories and sensors”

Keynote 14

Jérôme Bourderionnet (Thales Research and Technology, France) “Integrated photonics for RF filters”

Keynote 15

Carlos Campos-Cuerva (Nanoscience Institute of Aragon (INA), Spain) “Nanotechnology as a tool to end counterfeiting”

Oral 16

Juan Carlos Castellanos (Tecnobit, Spain) “Galileo PRS service, the Spanish technology approach”

Oral 18

Santiago Cuesta López (Universidad de Burgos, Spain) Oral 19 Fernando de León Pérez (Centro Universitario de la Defensa, Spain) “Light harvesting structures optimized at infrared frequencies”

Oral 20

José Mª. De Teresa (Universidad de Zaragoza, Spain) “Epitaxial graphene on SiC substrates for potential application in Security and Defense”

Keynote 21

Manel del Valle (Universitat Autònoma de Barcelona, Spain) “Electronic tongue sensing of explosives and its mixtures”

Oral 23

Joana Fonseca (CeNTI - Centre for Nanotechnology and Smart Materials, Portugal) “From R&D to product: development of new interactive products with integrated printed electronic solutions”

Oral 26

Elvira Fortunato (CENIMAT, Portugal) “Recent Advances on Nano-materials and Technologies for Thin Film Transistors”

Keynote 27

Glenn A. Fox (Lawrence Livermore National Laboratory, USA) “Forensic Science at the Nanoscale”

Keynote 28

Julio Gómez Cordón (Avanzare, Spain) “Nanomaterials industrial applications in security and defense”

Invited 29

Raquel González-Arrabal (IFN-ETSII, Spain) “Coatings production for military applications”

Keynote 30

Denis Guilhot (ICFO, Spain) “Salient Technologies @ ICFO with potential for the Aerospace, Defence & Security sector”

Oral 31

Antonio Hernando (IMA-UCM, Spain) “Microwires multilayers structure for two frequencies absorption”

Keynote 33


PAGE José Jiménez Jiménez (Universidad de Málaga, Spain) “Solids luminescent based in Quantum Dots for fingermark detection in different surfaces”

Oral 34

Jan Kolařík (Palacky University, Czech Republic) “Removal of arsenic compounds from water using iron-based materials”

Oral 36

Margaret E. Kosal (Georgia Tech, USA) “Nanotechnology and Diffusion of Innovation: Security Challenges for the 21st Century”

Keynote 38

Christopher Lillotte (Grupo Antolin, Spain) “Large scale production of graphenic materials by Grupo Antolin and their applications development”

Oral 39

Nieves Murillo (Tecnalia, Spain) “Air Filtering Efficiency Evaluation of PC Nanofiber Filters for Capture of Biological Particles in Personal Dosimeters”

Invited 41

Felipe Orgaz (Instituto de Ceramica y Vidrio, CSIC, Spain) “Transparent ballistic armour ceramics. Recent advances and issues to be overcome”

Oral 43

George Palikaras (Metamaterial Technologies Inc., Canada) “Safety & Security Applications of Optical Metamaterials”

Keynote 45

Fabrice Pardo (LPN/CNRS, France) “The Optical Helmholtz Resonator: a breakthrough for extreme light confinement from IR to RF”

Keynote 46

Ovidio Peña Rodríguez (IFN-ETSII-UPM, Spain) “Invisibility cloaking using thin all-dielectric multilayer coatings”

Invited 47

Asha Peta Thompson (Intelligent Textiles Limited, UK) “What happens when you use textiles to make electronics for soldier systems?”

Invited 48

María Pilar Pina Iritia (INA, Spain) “Nanoporous chemical receptors on microcantilever-like sensors for explosives detection in vapor phase”

Keynote 49

Frank Placido (UWS/Thin Film Center, UK) “Thin Film Technologies for Security and Defense Applications”

Keynote 50

Julio Plaza del Olmo (Instituto Tecnológico La Marañosa, Spain) “Recent development on dual-band uncooled PbSe sensors monolithically integrated on advanced interference filters”

Oral 51

José Manuel Ramos (AITEX, Spain) “Textile, Nanotechnology and Defence”

Keynote 53

Paul Reip (Intrinsiq Materials Ltd., UK) “Defence Applications for Plastic Electronics”

Keynote 54

Miguel Ribeiro (CeNTI - Centre for Nanotechnology and Smart Materials, Portugal) “Keys to improve flexible organic bulk-heterojunction solar cells”

Oral 55


PAGE José Mª Riola Rodríguez (SDGTECIN - DGAM, Spain) “Nanotechnologies: applications of interest for the Ministry of Defense”

Invited 57

Miguel Roncalés (ALPHASIP, Spain) “Automated Drug Detection System”

Invited 58

Luis Sanz Tejedor (Oficina Española de Patentes y Marcas (OEPM), Spain) “Industrial Property as a key factor in the Security and Defense industry”

Oral 59

Steven Savage (Swedish Defence Research Agency, Sweden) “Nanotechnology - an enabling technology, a critical technology or simply a new technology with inflated ego?”

Keynote 60

Brent Segal (Lockheed Martin, USA) “Nanotechnology from the Lab to the Fab”

Keynote 61

Pedro A. Serena (ICMM-CSIC, Spain) “Nanotechnology: the ongoing revolution”

Invited 62

Jean-Pierre Simonato (CEA-Grenoble, France) “Sensing traces of nerve agents like Sarin using nanomaterial based electrical detectors”

Keynote 63

Ivano Soliani (SOLIANI EMC SRL, Italy) “The textile electrically conductive as security solutions for several applica ons”

Keynote 64

Denis Spitzer (ISL-CNRS-UdS, France) “Nanostructured energetic materials: opportunities to enhance performances”

Keynote 66

Nava Swersky Sofer (International Commercialisation Alliance, Israel) “Best practices in commercializing nanotechnologies in defense”

Keynote 67

Aitana Tamayo (Instituto de Cerámica y Vidrio. CSIC., Spain) “Silicon Oxycarbide Nanoparticles as New Drug Delivery Materials for Infectious Disease Treatments”

Oral 68

Ian Turner (University of Derby, UK) “Applications of Nanotechnology in Forensic Science”

Keynote 71

Luis Valles (Guardia Civil – CO pain “Technology applied to criminal investigation: What to expect from nanotechnologies?”

Oral 72

Effrosyni D. Vogli (Foundation for Research and Technology, Hellas (FORTH) Institute of Chemical Engineering Sciences (ICE-HT), Greece) “A New Concept of Carbon Nanotube based Textiles for Civil Protection Services”

Oral 73

Ambiörn Wennberg (Nano4Energy, Spain) “Innovative approach to thin film sensor development”

Invited 75

Rogelio Zubizarreta Jiménez (Yflow, Spain) “Active substances encapsulated by Electro-Hydrodynamic techniques. Textile applications”

Oral 77


POSTERS LIST

PAGE Mohammad Alenezi (Public Authority for Applied Education and Training/ Collage of technological studies, Kuwait) “Hierarchically Nanostructured Metal Oxide Gas Sensors”

80

Manuel Algarra (University of Malaga, Spain) “Fingerprint Detection Using Intercalated CdSe Nanoparticles on Non-Porous Surfaces”

81

Vladimir Gelever (Moscow State Technical University for Radioengineering, Electronics and Automation (MSTU MIREA), Russia) “The possibility of using hybrid nanoscope for safety of human life”

82

Martina Kilianova (Palacky University, Czech Republic) “Unusual efficiency of ultrafine superparamagnetic iron oxide nanoparticles for removing of arsenate ions from aqueous environment”

85

Francisco de Paula Martín Jiménez (Universidad de Málaga, Spain) “Semitransparent symmetric and asymmetric supercapacitors”

86

Pavel Sorokin (Technological Institute for Superhard and Novel Carbon Materials, Russia) “Theoretical investigation of semiconducting, mechanically stiff diamond films of nanometer thickness”

88


Abstracts (Speakers)


E x p o s u r e o r c o n t a m i n a t i o n w i t h C B R N s u b s t a n c e s ?

Soraya Artiles Burgos

Guardia Civil - SEDEX-NRBQ (CBRN Unit), Spain

Abstract not available


T h a l e s e f f o r t s i n d e v e l o p i n g a p p l i c a t i o n s b a s e d o n

n a n o m a t e r i a l s a n d n a n o t e c h n o l o g y : e n e r g y , s p i n t r o n i c s , N V M m e m o r i e s a n d s e n s o r s

Paolo Bondavalli

Thales Research and Technology, France

[email protected]

This contribution deals with the research efforts of Thales Research and Technology in developing nanotechnology for new potential products. The talk will deal with the recent efforts in the frame of the Graphene Flagship to develop flexible supercapacitors, the long-term research for applications dealing with spintronics, with the potential nanomaterial based flexible low cost memories and finally on sensors based on carbon nanotubes. The aim of the talk is to explain our approach and to give a sketch of the main research directions in the field of nanotechnology and nanomaterial. Bio Dr. Paolo Bondavalli, Msc, PhD, Hdr is the Head of Nanomaterial team at Thales Research and Technology (CNRS/Thales, UMR137) and he is a member of the Nanocarb Lab. (joint team Ecole Polytechnique/Thales). His research has principally dealt with carbon nanotubes gas sensors and silicon nanowires for biological detection. In the last two years, he is the first author of several scientific papers (see refs in project) dealing with CNTFET based sensors, supercapacitors and of 6 patents dealing with gas sensors, thermal management through CNTs, nanomaterials deposition, supercapacitors and memristor-like structures. Presently his work is focused on the development of new materials (e.g. graphene, cnts, nanowires) for the new generation of electronics devices and for energy storage applications and memristor. Dr Bondavalli has received his Hdr in 2011, at Paris- ud on a work on “devices based on random network of carbon nanotubes”. He is E expert and Vice-Chairman, for Marie Curie Fellowships (EIF, IIF, OIF, CIG, IRSES), NMP and ICT panel, for the French National Research Agency (ANR),

EDA, Eureka and reviewer for IOP, ACS, IEEE, ECS, Elsevier, EPJ B, Bentham, Taylor & Francis... During the last five years, he has participated, also as coordinator, in several EU projects (concerning MEMS, MOEMS, CNTs, graphene, spintronics) and ANR projects. He is involved in the Graphene Flagship initiative (Energy and High-frequency WPs). Company profile Thales Research and Technology (TRT) mission is to provide short-term and long-term competitive advantage to the THALES Group by transferring leading edge knowledge by injecting innovation. Through its internal activities and scientific links with industries and universities (such as INRIA, CEA, Ecole polytechnique), either in France or internationally, TRT is participating in the preparation of THALES industrial future in strategic R&D fields according to the Group’s strategic priorities. With 270 skilled staff, 13000 sq. m of labs of which 1700 sq. m clean rooms, TRT research teams perform pioneering work in the most advanced areas. S&T skills, ranging from materials elaboration (epitaxy/deposition of various semiconductors, metallic, magnetic thin films, ceramics, polymers), through component modeling, processing, testing, assembly and packaging, to integration in appropriate demonstrators are available on site and allow full validation of the technologies investigated before their transfer to operational divisions of the THALES Group. Specifically, the Nanomaterial team (P. Bondavalli) at the Physics Department of TRT is composed by highly skilled scientists working on the development of new kind of nanomaterials (e.g. carbonaceous nanomaterials) for the new generation of electronic devices.


I n t e g r a t e d p h o t o n i c s f o r R F f i l t e r s

J. Bourderionnet

1, S. Combrié

1, Z. Han

2, X. Chécoury

2, M. Gay

3, L. Anet-Neto

3, A. De Rossi

1

1Thales Research & Technology, Palaiseau, France

2Institut d’Électronique Fondamentale ( MR CNR 8622), Université Paris-Sud, Orsay, France 3CNRS-Foton Lab. (UMR 6082), Lannion, France

[email protected]

Photonics is now part of the heart of modern radar systems, with already hundreds of optical links implemented in latest generation of radars. Beside signal transportation, a decisive objective for radar and communication systems is to exploit photonics properties to perform more complex signal processing functions [1]. Photonics has proved for years its remarkable potential for manipulations of optically carried microwave signals, such as delaying, weighting, routing or sampling, which are enabling building blocks for signal processing implementations such as finite impulse response (FIR) filters. A classical multi-tap FIR filter implementation requires to weight time-delayed replicas of an incident signal by both positive and negative weighting coefficients [2]. The incoherent addition of the replicas reconstructs the impulse response of the filter [3,4]. Negative weighting coefficients are however extremely difficult to obtain in an integrated platform and usually requires single-sideband format and optical carrier phase tuning [5]. When the whole system is integrated on a single device, the tap-to-tap optical phase distribution within the chip can be easily stabilized. It is then possible to add the signal replicas coherently in the optical domain and to use the optical phase distribution to program the filter weighting coefficients. These coefficients result from phase interference products and can be arbitrarily positive or negative. In the frame of the ongoing Symphonie project, funded by the French research agency (ANR), we implement this concept on a Silicon On Insulator platform, using a photonic crystal directional coupler network to generate the multiple taps. Each tap then includes a fixed delay section (spiral waveguide) and a tunable delay section (photonic crystal thermally tunable

waveguide). In this structure, the tunable delay line is used for the dual purpose of delaying the optically carried RF modulation envelope (the RF signal), and to adjust the carrier optical phase. References

[1] J. Capmany, D. Novak, Nature Photonics, 1 (2007), pp. 319–330. [2] Candy, J. V., Signal processing, the modern approach, McGraw-Hill, 1988. [3] T.X.H. Huang, X. Yi, R.A. Minasian, Optics Express, 19 (2011), pp. 6231-6242. [4] J. Sancho, J. Bourderionnet, J. Lloret, S. Combrié, I. Gasulla, S. Xavier, S. Sales, P. Colman, G. Lehoucq, D. Dolfi, J. Capmany, A. De Rossi, Nature Communications, 3 (2012), pp. 1075. [5] M. Pu, L. Liu, W. Xue, Y. Ding, H. Ou, K. Yvind, J.M. Hvam, Optics Express, 18 (2010), pp. 6172-6182.


N a n o t e c h n o l o g y a s a t o o l t o e n d c o u n t e r f e i t i n g

Carlos Campos-Cuerva, Manuel Arruebo, Jesús Santamaría

Nanoscience Institute of Aragon (INA), University of Zaragoza, Edificio I+D+I, C/ Mariano Esquillor s/n, 50018, Zaragoza,Spain

[email protected]

Over the past decade, there have been a considerable number of anti-counterfeiting techniques developed to counter theft of brand and intellectual property. Nonetheless, the market for counterfeit and pirated product in 2012 was estimated in up to USD 250 billion, meaning the 2% of the worldwide market. Moreover, this matter has a significant socio-economic effect such as employment, brand value or firm reputation. Health and safe are also very important issues when counterfeit items are medicines and drugs [1]. In this work we review the input of different nanotechnologies applied in the anti-counterfeiting industry. Nanoscience involves the ability to identify and control individual atoms and molecules allowing, to engineer different structures at the nanoscale which exhibit specific optical, mechanical, magnetic or electrical properties that their macroscopic counterparts (bulk) do not. The analytical complexity to characterize many nanomaterials which may be used as labels or tags, requires highly sophisticated equipment including high-resolution electron microscopes, surface analysis focused on only a few nanometers in depth (XPS), atomic analysis and specific analytical and crystalline characterization (EDX, XRD), which are not easily reachable in common chemical laboratories hampering the process of counterfeiting. We may distinguish several different nano-based technologies in use nowadays: nanobarcodes, nanoholograms, quantum dots based markings, nanoinks, magnetic fingerprints and more. In case of magnetic firgenprinting, one of the used nanomaterials are superparamagnetic nanoparticles [2-4]. This superparamagnetic behavior exhibited by only few materials at nanoscale differs from other materials at microscale in its high magnetic susceptibility and

very low or even zero coercitivity at room temperature as shown for magnetite particles (Figure 1). Due to their lack in remanent magnetization, superparamagnetic nanoparticles allow us to distinguish them from ferromagnetic materials with the appropriate equipment. Finally, the combination of nanomaterials with different properties (optical and magnetic) or multifunctional nanoparticles displaying any or both properties in the same particle can be used as markers (many times invisible to the naked eye) on a variety of supports (paper, textiles, polymers, etc.), creating countless of unique ‘fingerprints’ each for every different item and extremely difficult to copy. References

[1] OECD (2008), The Economic Impact of Counterfeiting and Piracy, OECD Publishing. DOI: 10.1787/9789264045521-en. [2] Mendels, D. (2003). U.S. Patent Application 10/533,375. [3] Oksana V. Sakhno, Tatiana N. Smirnova, Leonid M. Goldenberg, Joachim Stumpe, Materials Science and Engineering: C, Vol. 28, 1, (2008), 28-35. [4] Bawendi, M. G., & Jensen, K. F. (2004). U.S. Patent No. 6,774,361.


Figures

Figure 1: Magnetization curves of 6 nm and 100 nm magnetite particles.


G a l i l e o P R S s e r v i c e , t h e S p a n i s h t e c h n o l o g y a p p r o a c h

Juan Carlos Castellanos

Tecnobit, Spain



T i t l e n o t a v a i l a b l e

Santiago Cuesta López Universidad de Burgos, Spain



L i g h t h a r v e s t i n g s t r u c t u r e s o p t i m i z e d a t i n f r a r e d

f r e q u e n c i e s

Fernando de León Pérez1, F. Villate Guío

2, L. Martín Moreno

2

1Centro Universitario de la Defensa, Zaragoza, Spain

2Instituto de Ciencia de Materiales de Aragón and Departamento de Física de la Materia Condensada, CSIC-Universidad de Zaragoza, Spain

[email protected]

One-dimensional light harvesting structures with a realistic geometry nano-patterned on an opaque metallic film are optimized to render high transmission efficiencies at infrared frequencies. Simple design rules are developed for the particular case of a slit-groove array with a given number of grooves that are symmetrically distributed with respect to a central slit, see Fig. 1. These rules take advantage of the hybridization of Fabry-Perot modes in the slit and surface modes of the corrugated metal surface.Same design rules apply for optical and infrared frequencies. The parameter space of the groove array is also examined with a conjugate gradient optimization algorithm that used as a

seed the geometries optimized following physical intuition. Both uniform and nonuniform groove arrays are considered. The largest transmission enhancement, with respect to a uniform array, is obtained for a chirped groove profile. Such relative enhancement is a function of the wavelength. References

[1]F. Villate-Guío, F. López-Tejeira, F. J. García-Vidal, L. Martín-Moreno, and F. de León-Pérez, Opt. Express 20, (2012) 25441-25453

Figures

Figure 1: Schematic representation of the system under study


E p i t a x i a l g r a p h e n e o n S i C s u b s t r a t e s f o r p o t e n t i a l

a p p l i c a t i o n i n S e c u r i t y a n d D e f e n s e

J. M. De Teresa1,2

, P. Godignon3

1Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC- Universidad de Zaragoza, Spain

2Laboratorio de Microscopías Avanzadas (LMA), Instituto de Nanociencia de Aragón (INA), Universidad de Zaragoza, Spain 2Centro Nacional de Microelectrónica, CNM-CSIC, Campus Bellaterra, Barcelona, Spain

[email protected]

Graphene is one of the most promising new materials. It consists of an atomic-thick layer of carbon atoms forming a hexagonal network. It presents extraordinary properties such as high heat conduction, great elasticity, good electrical conduction, transparency at visible light wavelength, etc. [1]. This is the reason why graphene is expected to be implemented in many applications where it can provide better functionality compared to other materials. Graphene is also thought to be the starting point for new disruptive applications and has been selected for a Flagship funded project by the European Union [2]. However, experiments have demonstrated that there are many “graphenes” or “graphenes” with different qualities, showing varying physical and chemical properties. Depending on the exact application, the required quality and size of graphene is different, implying a different preparation method and different properties. In terms of electronic performance, one of the highest graphene qualities is obtained for Epitaxial Graphene (EG) [3]. Such conformal growth of graphene is observed in the sublimation process of SiC wafers. Compared to other growth methods, the advantage of this method is that graphene transfer is not required due to the semi-insulating nature of SiC. Additionally, it provides a means to develop applications at wafer level. Based on its outstanding electronic quality, promising applications based on EG have been recently demonstrated. We can highlight the following ones, which could eventually have an impact in topics related to Security and Defense:

-Development of high-frequency electronic devices: Devices based on EG have shown

working frequencies beyond 100 GHz, beyond conventional Si-based and III-V based electronic devices [4-6]. This could enable faster devices in telecommunication areas.

-Development of new metrology standards based on the quantum Hall effects [7-9]. This could enable more robust and precise standards of the Ohm.

-Low-power-consumption electronic devices based on Spintronic effects [10-12]. This could facilitate the development of energy-efficient data storage, sensing and logic devices.

-High-performance sensor and biosensor platforms [13-15]. The fact that graphene is an all-surface material produces significant changes in its resistance when atoms or molecules adhere to its surface. This has been used for gas sensing using EG. Additionally, surface functionalization of EG opens the route for specific detection of targeted substances.

-Devices in the THz spectral range [16]. Devices in the THz regime such as sources, detectors, modulators, antennas and polarizers are being developed [17, 18]. In this presentation, the applications of EG will be reviewed, with special emphasis on those ones related to Security and Defense. The patterning of EG, one of the bottlenecks towards the development of devices will be discussed [19-22]. A Spanish industrial initiative towards commercialization of this technology will be presented [23]. References

[1] K. S. Novoselov et al., Nature 490 (2012) 192 [2] http://graphene-flagship.eu/


[3] S. Forti and U. Starke, J. Phys. D: Appl. Phys. 47 (2014) 094013 Iezhokin et al., Appl. Phys. Lett. 103 (2013) 053514 [4] Y-M Lin et al., Science 327 (2010) 662 [5] Y. Lin et al., Science 332 (2011) 1294 [6] S. Han et al., Nat. Comm. 5 (2011) 3086 [7] B. Jouault et al., Appl. Phys. Lett. 100 (2012) 052102 [8] F. Schopfer and W. Poirier, MRS Bulletin 37 (2012) 1255 [9] T.J.B.M. Janssen et al., New J. Phys. 13 (2011) 093026 [10] N. Tombros et al., Nature 448 (2007) 571 [11] P. Seneor et al., MRS Bulletin 37 (2012) 1245 [12] B. Dlubak et al., Nat. Phys. 8 (2012) 557 [13] Y. Shao et al., Electroanalysis 22 (2010) 1027

[14] I. Iezhokin et al., Appl. Phys. Lett. 103 (2013) 053514 [15] I.Crowe et al., Optics Express 22 (2014) 18625 [16] R. R. Hartmann et al., Nanotechnology 25 (2014) 322001 [17] V. Ryzhii et al., Infrared Physics and Technology 54 (2011) 302 [18] F. Xia et al., Nat. Nanotechn. 4 (2009) 839 [19] J. Fan et al., Solid State Communications 151 (2011) 1574 [20] M. Y. Han et al., Phys. Rev. Lett. 98 (2007) 20685 [21] J. Baringhaus et al., Nature 506 (2014) 349 [22] B. Prevel et al., Microel. Eng. 98 (2012) 206 [23] www.graphenenanotech.eu

Figures

Figure 1: Patterned Epitaxial Graphene for measurements of the Quantum Hall Effect performed at CNM by N. Camara et al., Appl. Phys. Lett. 97 (2010) 93107


E l e c t r o n i c t o n g u e s e n s i n g o f e x p l o s i v e s

a n d i t s m i x t u r e s

Xavier Cetó, Andreu Gonzàlez-Calabuig, Manel del Valle Biosensors Group, Department of Chemistry, Universitat Autònoma de Barcelona, Spain

[email protected]

With the surge of international terrorism and the increased use of explosives in terrorist attacks, law enforcement agencies throughout the world are faced with the problem of detecting hidden bombs in luggage, mail, vehicles, and aircraft, as well as on suspects. Nowadays, this has become a major analytical problem, which requires highly sensitive, specific, fast and reliable field-deployable detection strategies [1]. On that account, electrochemical sensing represents a promising solution for on-site explosive detection given the inherent redox activity of commercial explosives, which makes them ideal candidates for voltammetric monitoring. Nevertheless, despite the initial attempts made to voltammetrically detect the aforementioned compounds employing different types of electrodes and techniques [2], even achieving its detection at very low concentration levels, further work is still required to accomplish the correct identification and quantification of explosives and its mixtures. A chief challenge encountered within these analysis is the discrimination between individual compounds present, given that the voltammetric signals produced by these electrochemical methods correspond to a global overlapped, multiple peak voltammogram; i.e. there is a lack of specificity or identification of differentiated peaks for each of the compounds (Figure 1). Thus, in order to determine more accurately which type of explosive combination is used, providing the ability to discern between different explosive compounds in a mixture is necessary, especially for security issues.

In this sense, the combination of electrochemical methods with chemometric tools such as Principal Component Analysis (PCA) or Artificial Neural Networks (ANNs) can help to overcome this limitation [3], by identifying and processing the electrochemical fingerprint shown by the explosive mixture. Hence, arising as a powerful alternative to classical methods for the identification of explosive compounds [4, 5]. The followed approach, known as Electronic Tongue (ET) [6], consists in the coupling of an array of sensors with marked mix-response towards the desired species, plus a chemometric processing tool able to interpret and extract meaningful data from the complex readings, relating them with their analytical meaning. For its implementation, first it is needed an appropriate sensor array with some cross-sensitivity between them, which allows the simultaneous determination of a large number of species, while the chemometric treatment of the data allows the resolution of the interferences, drifts or non-linearity obtained with the sensors [7]. Moreover, the data processing stage may offset any matrix or interference effect from the sample itself. Thus, with this methodology, it is possible to achieve a parallel determination of a large number of different species, while any interference effect is solved using these advanced chemometric tools. Preliminary attempts to distinguish common explosive compounds such as TNT, RDX or PETN using a single bare screen-printed carbon electrode (SPCE) were performed; while in a second attempt, a miniaturized array of graphite, gold and platinum sensors was used, which allowed also the detection of peroxide-based explosive compounds such as TATP. The method


proposed herein couples field-deployable electrochemical measurements with multivariate calibration models obtained by ANNs, with the aim to examine the potential of a voltammetric device for the detection of explosive compounds and mixtures using either qualitative discrimination (Figure 2) or quantitative determination (Figures 3&4).

References

[1] J. Wang, Electroanalysis, 4 (2007) 415 [2] J. S. Caygill, F. Davis, and S. P. J. Higson, Talanta, 0 (2012) 14

[3] Y. Ni and S. Kokot, Analytica Chimica Acta, 2 (2008) 130 [4] X. Cetó A.M. O’Mahony J. Wang M. del Valle, Talanta, 107 (2013) 270 [5] A. González-Calabuig, X. Cetó, M. del Valle (Talanta, submitted) [6] M. del Valle, Electroanalysis, 14 (2010) 1539 [7] A. Riul Jr, C. A. R. Dantas, C. M. Miyazaki, and O. N. Oliveira Jr, Analyst, 10 (2010) 2481

Figures

Figure 1: Example of the different voltammograms obtained with the PCE for 50 μg mL-1 standard solutions of three common explosive pure compounds.

Figure 2: Score plot of the first three components obtained after PCA analysis.

Figure 3: Modeling ability of the optimized ANN for the single SPCE sensor. Comparison of obtained vs. expected concentrations of ternary mixtures of RDX TNT and PETN both for the training (● solid line and testing subsets (○ dotted line . Dashed line corresponds to theoretical.

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F r o m R & D t o p r o d u c t : d e v e l o p m e n t o f n e w i n t e r a c t i v e

p r o d u c t s w i t h i n t e g r a t e d p r i n t e d e l e c t r o n i c s o l u t i o n s

Miguel Ribeiro, Joana Fonseca, Jose Barbosa, Joao Gomes, Sandra Couto, Vasco Machado

CeNTI - Centre for Nanotechnology and Smart Materials, VN Famalicão, Portugal

[email protected]

Printed sensors are intrinsically flexible, lightweight, ultra-slim and cheap, being particularly suitable to be embedded in conventional products. Their widespread applicability has prompted the scientific-technologic development of printed sensors, sensible to diverse properties such as temperature, humidity, pressure, chemicals, light, etc. Target applications include environmental monitoring (e.g. radiation tags), biomedical devices (e.g. disposable biosensors), robotics (e.g. smart skin) and smart packaging (e.g. temperature tracking, safeguard product authenticity).[1-2] Printing processes like screen-printing, inkjet, flexography or rotogravure, allow direct and reproducible sensor integration on a wide variety of substrates, with reduced integration costs and high throughputs which makes them suitable for large scale production. At CeNTI we have been developing integrated printed integrated electronic solutions, using high throughputs processing technologies, such as screen printing and rotogravure. One example is fringing field capacitive sensors that have the advantage of allowing noncontact measurements, as the fringing field is projected into the object being detected, without changing the electrode configuration. Due to the nature of the collaboration between CeNTI and industrial partners, the scalability of the processes that are used is one of the major focuses of the scientific and technological approaches. In the development of the printed electronic devices an integrated and multi-

disciplinary approach has been taken comprising different steps, such as design optimization, deposition and characterization of the devices. Also the integration of the printed devices with acquisition system, treatment and transmission of data is addressed. One of the biggest challenges is the integration of printed electronics in daily objects without changing significantly their performance and functionality. These challenges involve both scientific and technological barriers that must be addressed simultaneously in a multidisciplinary approach. CeNTI is currently participating in several projects that require the integration of printed electronic for liquid level measurement, object detection and identification, interaction with objects and people. Comparison of theoretical and experimental results of these projects will be presented, based on numerical simulations and different characterization techniques such as optical microscopy, AFM, electrical and impedance analysis and profilometry. References

[1] H. Igbenehi, R. Das, Printed and Flexible Sensors 2012-2022: Forecasts, Players, Opportunities, IDTechEx, 2013. [2] J. Daniel, T. Ng, A.C. Arias, L. Lavery, S. Garner, R. Lujan, W. Wong, R. Street, B. Russo, B. Krusor, Flexible and Printed Electronics for Sensors, Displays and Photovoltaics, International Workshop on Flexible and Printed Electronics (IWFPE 10), Sept8-10, 2010, Korea.


R e c e n t A d v a n c e s o n N a n o - m a t e r i a l s a n d T e c h n o l o g i e s

f o r T h i n F i l m T r a n s i s t o r s

Elvira Fortunato, Lídia Santos, Rita Branquinho, Daniela Salgueiro, Pedro Barquinha, Luís Pereira and Rodrigo Martins

Departamento de Ciência dos Materiais, CENIMAT/I3N, Faculdade de Ciências e Tecnologia Universidade Nova de Lisboa and CEMOP/Uninova, Portugal,

[email protected]

In this work we will review some of the most promising new technologies for n- and p-type thin film transistors based on oxide semiconductors either in the form of nano-films or nanoparticles, with special emphasis to solution-processed, and we will summarize the major milestones already achieved with this emerging and very promising technology focused on the work developed in our laboratory. Transparent electronics has arrived and is contributing for generating a free real state electronics that is able to add new electronic functionalities onto surfaces, which currently are not used in this manner and where silicon cannot contribute [1,2]. The already high performance developed n- and p-type TFTs have been processed by physical vapour deposition (PVD) techniques like rf magnetron sputtering at room temperature which is already compatible with the use of low cost and flexible substrates (polymers, cellulose paper, among others). Besides that a tremendous development is coming through solution-based technologies very exciting for ink-jet printing, where the theoretical limitations are becoming practical evidences. In this presentation we will review some of the most promising new technologies for thin film transistors based on oxide semiconductors and its currently and future applications. References

[1] E. Fortunato, P. Barquinha, and R. Martins, "Oxide Semiconductor Thin-Film Transistors: A Review of Recent Advances," Advanced Materials, vol. 24, pp. 2945-2986, Jun 2012.

[2] P. Barquinha, R. Martins, L. Pereira and E. Fortunato, Transparent Oxide Electronics: From Materials to Devices. West Sussex: Wiley & Sons (March 2012). ISBN 9780470683736. Figures

Figure 1: Flexible transparent electronics developed at CENIMAT|I3N

Acknowledgments

This work was funded by the Portuguese Science Foundation (FCT-MCTES) through projects PTDC/CTM/103465/2008, PTDC/EEA-ELC/099490/2008, CMU-PT/SIA/0005/2008, PEst-C/CTM/LA0025/2011 (Strategic Project - LA 25 - 2011-2012) and E. Fortunato ERC 2008 Advanced Grant (INVISIBLE contract number 228144) and by EU-FP7 Project ORAMA CP-IP 246334-2


F o r e n s i c S c i e n c e a t t h e N a n o s c a l e

Glenn A. Fox

Lawrence Livermore National Laboratory, USA

[email protected]

Forensic science has been conventionally defined as “belonging to or used in courts of judicature ” and usually employed towards criminal, civil or environmental law. However, in the past twenty years, the term “forensics” is being applied to a much broader set of scientific activities or investigations including non-proliferation, treaty verification, and acts of domestic and international terrorism, that requires unique technical expertise and experience across the spectrum of chemical, biological, radiological, nuclear and explosive (CBRNE) threats. While the spirit of forensic investigation remains the same—reaching scientific conclusions (which are often challenged) through the examination of associated materials and the interpretation of the resulting data—the nature of CBRNE related materials can introduce expanded and often unique requirements for their analysis. The need for a broad, reliable and validated knowledge base to facilitate CBRNE forensics has driven new and innovative research in chemistry, materials science, advanced analytical techniques, computations simulation and modeling that ultimately reveal important information at the nanoscale or molecular level. This talk will focus on emerging and innovative research across the CBRNE threat spectrum, leading to understanding of physiological effects of chemical and biological agents (toxicity and dosing effects, signatures and biomarkers for exposure) to physicochemical properties of materials pertinent to forensic investigations (synthesis and agent characterization, attribution signatures, synthesis pathways determination, environmental behavior and reactivity, route attribution, isotopic information, sensing and detection). An integrated computational and experimental science-based approach towards CBRNE forensic science, can also lead to a mechanistic understanding of material and agent reactivity in operationally relevant environments

and biological systems. By developing new techniques, materials and analyticalmethodology that can be applied towards CBNRE forensic investigations, an enhanced understanding of the scope and nature of the emerging proliferant activities and possibleasymmetric threats can be obtained.


N a n o m a t e r i a l s : i n d u s t r i a l a p p l i c a t i o n s i n s e c u r i t y a n d

d e f e n s e

Julio Gómez Cordón Avanzare Innovacion Tecnologica S.L., Avda Lentiscares 4-6. 26370 Navarrete, Spain

[email protected]

Nowadays the industry is fascinated with the extraordinary properties of nanoparticles due to the impact on the performance of nanoenabled products. However there are several bottle necks in the industrial applications of nanomaterials: 1) Dispersion and re-agglomeration problems

produce micro-materials instead of nanomaterials. Most of the nanoproducts (High BET SiO2, carbon black, natural nanoclays and a great part of the nanopowders) are not real nanoproducts because of they agglomerate producing microparticles-microcomposite instead of a nanocomposite

2) Release of NP into the air when they are in solid form causing health and environmental problems

3) Processing difficulties that in most cases make the process unviable due to their low apparent density

4) Necessity of customization for each application and client: nanoparticles aren´t no ready to be directly used

5) From the economical point of view the cost of the particles and high shipping costs caused by their low apparent density of de-agglomerated materials became unaffordable.

It is necessary to solve all of these problems to obtain real industrial application of the nanoparticles. There are several applications of nanomaterials in the Security and Defense sector, due to the performance of the real nanocomposites:

•Thermal dissipation for their use in tanks

•Nanomaterials for their use in bulletproof •EMI Shielding •Energy absorbing materials •High performance composites

Other applications of nanomaterials in Security and Defense in the use on nanobiosensors.


C o a t i n g s p r o d u c t i o n f o r m i l i t a r y a p p l i c a t i o n s

R. Gonzalez-Arrabal, N. Gordillo, M. Panizo-Laiz, A. Rivera, O. Peña and J. M. Perlado

Instituto de Fusión Nuclear, ETSI de Industriales, Universidad Politécnica de Madrid, C/ José Gutierrez Abascal, 2, E-28006, Spain

[email protected]

Coatings possess a wide range of applications in both civil as well as, military sectors. This includes their use for protection of materials from corrosion, abrasion, oxidation, for optical transmission and reflection tuning in certain wavelength regions, with application in filters, fire-resistant coatings, anti-fog, and memory devices… Coating properties depend on a number of interrelated parameters and also on the manufacturing technique. Due to its properties (easy control, environmental friendly, versatility, scalable and low cost) sputtering methods are among the most used techniques for coating production. Sputtering is traditionally employed to coat planar surfaces. However, by using coaxial sputtering the inner surface of pipes can be also coated. The sputtered coatings 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. Therefore, the coating properties can be tuned to the desired value by properly selecting the sputtering parameters. 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 radiation-resistant 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.


S a l i e n t T e c h n o l o g i e s @ I C F O w i t h p o t e n t i a l f o r t h e

A e r o s p a c e , D e f e n c e & S e c u r i t y s e c t o r

Denis Guilhot ICFO – The Institute of Photonic Sciences, Spain

[email protected]

Photonics is the science and technology of harnessing light. It has been selected by the European Commission as one of the six Key Enabling Technologies (KETs) in recognition of its versatility. At ICFO, the focus is mainly on applications at the forefront of photonics, especially of laser light, and the research is oriented towards three main umbrella research programs: Light for Health, Light for Energy and Light for Information, but also towards the development of new tools for Security and Defence.

With more than 300 ICFOnians and 22 research groups, the expertise subsumes numerous areas of research from ultrafast optoelectronics and space communications to ultrasensitive devices for quantum optics, including nano and bio photonics among others. This wide range of topics leads us to develop an even wider range of devices. We present here an introduction to a variety of technologies developed at ICFO with potential for application in the Aerospace, Defence and Security sector. Sensing devices are presented, from night vision and temperature sensors to bio-chemicals and explosives detection, as well as imaging devices [1-2]. Other Light for Information program technologies will be reviewed, from devices for quantum cryptography to display-related

coatings, electrodes and projectors [3-4]. Proprietary technologies in spectroscopy, tunable laser sources and photovoltaics will also be discussed [5].

Moreover, ICFO plays a special leadership role in the Graphene Flagship, branded E ’s biggest research initiative ever with a budget of EUR one billion, through Prof. Frank Koppens appointment as co-leader of the Optoelectronics work package, in collaboration with Prof. Andrea Ferrari (Cambridge, UK), and its participation in the Intellectual Property Rights and Entrepreneurship Management group. As a result of this, a number of graphene-related technologies and devices have been developed, which will also be detailed [6-7]. Finally one of ICFO’s main goals is to maximize business opportunities arising from research being carried out at the Institute and from collaborations with industries, investors and health-care allies, through a strong Knowledge and Technology Transfer (KTT) Team that plays a key role at the interface with the industrial and corporate worlds maximizing the flow of information, knowledge, technology and talent. KTT Team is responsible for establishing strategic alliances and collaborations with industry, the private sector in general and all types of collaborators.


References

[1] Biosensing: Plasmons offer a helping hand, R. Quidant, M. Kreuzer, Nature Nanotechnol. 5, 762-763 (2010) [2] Diffuse correlation spectroscopy for non-invasive, micro-vascular cerebral blood flow measurement, T. Durduran, A. G. Yodh, NeuroImage 85, 51-63 (2014) [3] Ultra-fast quantum randomness generation by accelerated phase diffusion in a pulsed laser diode, C. Abellán, W. Amaya, M. Jofre, M. Curty, A. Acín, J. Capmany, V. Pruneri, M. W. Mitchell, Opt. Express 22, 1645-1654 (2014) [4] Superomniphobic, transparent and antireflection surfaces based on hierarchical nanostructures, P. Mazumder, Y. Jiang, D. Baker, A. Carrilero , D. Tulli, D. Infante Gómez, A. Hunt, V. Pruneri, Nano Lett. 14, 4677-4681 (2014) [5] Transparent polymer solar cells employing a layered light-trapping architecture, R. Betancur, P. Romero-Gomez, A. Martinez-Otero, X. Elias, M. Maymó, J. Martorell, Nature Photon. 7, 995-1000 (2013) [6] Hybrid graphene–quantum dot phototransistors with ultrahigh gain, G. Konstantatos, M. Badioli, L. Gaudreau, J. Osmond, M. Bernechea, F. P. Garcia de Arquer, F. Gatti, F. H. L. Koppens, Nature Nanotechnology,7, 363-368 (2012) [7] Graphene shows its colours, The Economist, May 12th 2012.


M i c r o w i r e s m u l t i l a y e r s s t r u c t u r e f o r t w o f r e q u e n c i e s

a b s o r p t i o n

Antonio Hernando Instituto de Magnetismo Aplicado. UCM Madrid and Micromag 2000 S. L. Las Rozas, Madrid, Spain

[email protected]

As is known the control of the dielectric constant by tailoring mixtures of metallic microwires with paint allow us to produce radar antireflectant coating for metallic surfaces. The characteristics of the absorption peaks obtained and the laboratory is discussed. An experiment carried on a Spanish Navy boat confirms the reliability of the method. Finally it is shown how the use of multilayers structures leads to microwave absorption at two different frequencies. The results obtained after painting a 70 m length ship clearly illustrates the accuracy that can be achieved in the absorption spectrum.


S o l i d s l u m i n e s c e n t b a s e d i n Q u a n t u m D o t s f o r

f i n g e r m a r k d e t e c t i o n i n d i f f e r e n t s u r f a c e s

José Jiménez Jiménez, Manuel Algarra González, Enrique Rodríguez Castellón Universidad de Málaga, Dpto. Química Inorgánica, Cristalografía y Mineralogía

Facultad de Ciencias. Campus de Teatinos S/N, 29071, Málaga, Spain

[email protected]

Latent fingerprints are the physical evidence in identification and generalized proof of identity in addition to the DNA test. Often, forensic investigators use special optical equipment and/or chemical substances to make latent fingerprints visible. The conventional powdering technique involves preferential adherence of powder particles to fingerprint residues to provide contrast between this and the background surface. Based on chemical constitution the powders can be classified into different types: regular, metallic and luminescent. In this last is included the Quantum Dots (QDs). The luminescent properties of QDs are due to their semiconductor properties. So, QDs formed by II-VI semiconductor compounds such as CdS, CdSe and CdTe have been investigated for latent fingermark detection [1]. Furthermore of the electronic properties, the control of particle size is decisive in the optic properties of these materials, and only when these are as nanoparticles, luminescent properties are present. In the last years we have used a mesoporous solid named PPH (Porous Phosphate Heterostructure) as template to synthesize nanoparticles of CdS and CdSe [2-4]. PPH is a porous material based in the formation of silica galleries into interlayer space of zirconium phosphate (Fig 1). The physical and chemical properties for silica surface can be modified by incorporation of organic groups such as mercaptopropyl. The thiol group can interact with group 12 cations, in this case Cd2+ and after adding S2- or Se2- or a precursor of these, the corresponding CdS or CdSe is formed into the channels of PPH. As the size of these channels is in the order of nm, we can synthesize CdS or CdSe nanoparticles: QDs. Also, these QDs are

included into a white support at difference with the most common presentation of QDs as colloidal suspensions. This supposed a challenge in the forensic application of QDs, because we can use this fluorescence powder by the firgermark detection. So, these materials have been used for fingermark detection in surfaces with different porosity as is shown in Fig 2. References

[1] M. J. Choi, A. M. McDonagh, P. Maynard, C. Roux Forensic Sci. Int 179 (2008), 87-97 [2] Manuel Algarra, José Jiménez Jiménez, Ramón Moreno Tost,, Joaquim C. G. Esteves da Silva Optical Materials 33 (2011) 893-898 [3] M. Algarra, J. Jiménez-Jiménez, M. S. Miranda, B. B. Campos, R. Moreno-Tost, E. Rodriguez-Castellón, J.C.G. Esteves da Silva Surface and Interface Analysis 45, (2013) 612-618 [4] Ksenija Radotic, Aleksandar Kalauzi, Dragosav Mutavdzic, Aleksandar Savic, Jose Jimenez-Jimenez, Enrique Rodriguez-Castellon, Joaquim C Esteves da Silva, Juan Jose Guerrero Analytica Chimica Acta 812 (2014) 228-235


Figures

Figure 1: Proposed mechanism of formation of CdSe QDs into PPH

Figure 2: PPH-CdSe QDs developed fingerprint excited with a mercury lamp in several surfaces


R e m o v a l o f a r s e n i c c o m p o u n d s f r o m w a t e r u s i n g

i r o n - b a s e d m a t e r i a l s

J. Kolařík1, R. Prucek

1, J. Tuček

1, J. Filip

1, Z. Marušál

1, V.K. Sharma

2, R. Zboril

1

1Regional Center of Advanced Technologies and Materials, Departments of Physical Chemistry and experimental Physics

Faculty of Science, Palacký University, 17. Listopadu 1192/12, 771 46 Olomouc, Czech Republic 2Chemistry Department and Center of Ferrate Excellence, Florida Institute of Technology

150 West University Boulevard, Melbourne, Florida 32901, United States

[email protected]

Arsenite (AsIIIO3

3-) and arsenate (AsVO43-)

represent a great threat to the environmental. The properties of arsenic sulfide and related compounds have been known to physicians and professional poisoners since the fifth century BC.

[1] Anthropogenic contaminations of all water types represent a danger in many countries. Arsenic compounds were using for many anthropogenic activities such as mining, agriculture, pharmacology, preservation of wood, glazier and in the last time in electronics. [2] Several recent reports highlight emergency of arsenic contaminations of the surface and drinking water in Bangladesh, [3,4] India, [5] Nepal, [6] Vietnam, [7] Taiwan [8] and Chile. [9] In these countries, the arsenic concentration are alarming when compared with the limit of 10 µg/l in drinking water, which being suggested as limiting safe-value by World Health Organization (WHO) guidelines. [10] Of the many techniques for removing arsenic compounds from water such as reversible osmosis, ion exchange and membrane filtration has found the greatest application adsorption arsenic using sorbents. [11] Many materials have been tested for arsenic removal by adsorption such as volcanic ash, clay minerals, ghoetit, surface-treated carbon black or iron oxides. [10] These materials are the environmentally friendly but the limitation of all these materials is their low sorption capacity for arsenic removal. The weight ratio of the sorbent-to-arsenic ranges from 1000:1 to 100:1 , at best 10:1 . Ferrates potassium K2FeO4 (FeVI) is environmentally friendly and has strong oxidizing properties. Its redox potential ranges from 2.2 V

in acidic environment to 0.72 in a basic environment. Fe(VI) in reaction with water rapidly reduced and transformed to iron oxides Fe(III) and is produced molecular oxygen. In this reaction, formed iron oxide serve as a good absorbent. These oxidation and adsorption effects of Fe(VI) bring very efficient purification of contaminated water.[12] We report the first example of arsenite and arsenate removal from water by incorporation of arsenic into the structure of nanocrystalline iron(III) oxide. This work investigated the process of "in-situ" arsenic removal by Fe(VI) and to compare with the effect of arsenic sorption by maghemite and KFeO2. Sorption kinetics, the removal efficiency of arsenic in dependence of the amount of sorbent and the dependence on pH value were tested. For Fe(VI) sorption As(V) and As (III) was studied and for maghemite and KFeO2 sorption As(V) was tested only. In all experiments, the amounts of arsenic were adjusted so that the concentration of arsenic was 100 mg/L. The weighted amounts of sorbent were dissolved in an aqueous solution containing arsenic species; the Erlenmeyer flasks containing reaction solutions (the final volumes of the solutions were 30 mL) were shaken on a conventional endover-end shaker for a 30 minutes and subsequently filtered through 450 nm syringe filters. Determinations of arsenic concentrations were carried out by AAS immediately after the separation of the sorbent from the solution. Samples of Fe(VI) were characterized using TEM, SQUID methods and Mössbauer spectroscopy.


References

[1] Greenwood & Earnshaw, A. Chemistry Elements. Food and Agriculture Organization of the United Nations, 1989. [2] Smith, E. at al., Adv. Agron., 64 (1998) 149–195. [3] Hossain, M. F., Agric. Ecosyst. Environ., 113 (2006) 1–16. [4] Chowdhury, U. K. et al., Arsen. Expo. Heal. Eff. Iii, (1999) 165–182. [5] Das, D. et al., Environ. Geochem. Heal., 18 (1996) 5–15. [6] Thakur, J. K. et al., Water, 3 (2010) 1–20. [7] Berg, M. et al. Environ. Sci. Technol., 35 (2001) 2621–2626. [8] Chen, S.-L. et al., Environ. Sci. Technol., 28 (1994) 877–881. [9] Ferreccio, C. et al., J. Health Popul. Nutr., 24 (2006) 164–175. [10] Mohan, D. et al., J. Hazard. Mater., 142 (2007) 1–53. [11] Bang, S. et al., J. Hazard. Mater., 121 (2005) 61–67. [12] Sharma, V. K. et al., J. Water Health, 3 (2005) 45–58. Acknowledges

The authors acknowledge the support by projects OP VaVpl CZ.1.05/2.1.00/03.0058, OPVK CZ.1.07/2.3.00/20.0056, TE01010218 and internal grant UP Olomouc PrF_2014032.


N a n o t e c h n o l o g y a n d D i f f u s i o n o f I n n o v a t i o n :

S e c u r i t y C h a l l e n g e s f o r t h e 2 1 s t C e n t u r y

Margaret E. Kosal 781 Marietta St NW

Georgia Institute of Technology Atlanta GA 30306

[email protected]

The pursuit of the minutely small – nanotechnology – is thriving in academia, in the private sector, and in global state science and technology programs. At the same time national security and intelligence communities are increasingly concerned with the emerging profile of a 21st century terrorist and insurgent who is young, educated, technically-skilled, and connected electronically. For scholars of international security, the intersection of science and technology with armed conflicts and military capabilities is a long-standing area of inquiry and are prominent factors in strategic choices, balance of power, deterrence postures, nonproliferation regimes, security doctrines, and programmatic choices. Advances in nanotechnology have and are anticipated to further marry the successful characteristics of availability, affordability, mobility, lethality, and durability that drove the proliferation of conventional weapons like the AK-47. How will the global expansion in nanotechnology affect the material instability, complexity, and burden of knowledge associated with acquisition and use of unconventional weapons, like biological and chemical agents, by state- and non-state actors? This talk will explore and probe specific characteristics and operationalizing factors – technical and non-technical – that may have decisive impact on the adoption of new technologies by non-state actors. The goal of this work is not to predict new specific technologies but to develop a robust analytical framework for assessing the impact of new technology on national security and identifying measures to prevent or slow proliferation of new technologies for malfeasant intentions. Understanding the changing paradigms and limiting the proliferation of unconventional

weapons for the 21st Century starts with an awareness of the factors driving the capabilities, analysis of the changing nature of technological progress, the nature of warfare, and the relationship between science and international security. Working at the intersection of strategy, technology, and governance, this talk explores the need to and explores understanding of the complex and interdependent relationships among science, technology, and security – politics, cultures, organizations, institutions, and individuals -- in order to explain how these phenomena intersect and potentially impact US and international security policies.


L a r g e s c a l e p r o d u c t i o n o f g r a p h e n i c m a t e r i a l s b y

G r u p o A n t o l i n a n d t h e i r a p p l i c a t i o n s d e v e l o p m e n t

C. Lillotte, S. Blanco, P. Merino, C. Merino Grupo Antolin Ingeniería SA, Ctra. Madrid-Irún, km. 244.8, 09007 Burgos, Spain

[email protected]

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. 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 attr active as starting material for graphene production, Fig 1-2[1]. 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 centrifugat ion steps are absolutely necessary to remove none oxidized graphite when the oxidation was carried out from graphite as starting material. In order to analyze the quality of GRAnPH® graphene oxide the following techniques were used X-Ray Diffraction, UV-V is, XPS and Raman spectroscopy. The most representative results are collected in table 1. For comparative purposes, results corresponding to graphite oxide (GO) also have been included. Table1. GRAnPH® and GO characterization.

Technique Results

GRAnPH® GO (Graphite)

UV-Vis max=235nm max=230 nm

XPS

O/C=0.61 60% C-C 26% C-O 14% C=O

O/C=0.62 49% C-C 45% C-O 6% C=O

XRD d(002)=0.77 nm d(002)=1.02 nm

Raman ID/IG = 1.03 ID/IG = 1.4

As it can be observed in table 1, the position of the maximum of GRAnPH® UV-Vis spectrum is five nanometers red-shifted respect to the maximum corresponding to GO. The red- shift of this band can be related to the higher amount of sp2 carbons in the graphene network. This result is consistent with the information obtaine d from the XPS measurements. Finally, t he size of the sp2 domains was evaluated by means of the ID/IG ratio obtained from the Raman spectra. The results show lower ratio for GRAnPH® than for GO. This fact means that the size of the Csp2 domains is larger f or GRAnPH® than for graphite oxide. The chemical composition of GRAnPH® graphene oxide allows the preparation of stable suspensions in different polar solvents. Moreover, it can be deposited over a wide variety of substrates by different methods and be used for diverse applications.


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®.

Figure 2: Scheme of the graphene oxide sheets derived from GANF® HR-CNFs. First step is an oxidation reaction by a modified Hummers method; second step is an exfoliation.

References

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


A i r F i l t e r i n g E f f i c i e n c y E v a l u a t i o n o f P C N a n o f i b e r

F i l t e r s f o r C a p t u r e o f B i o l o g i c a l P a r t i c l e s

i n P e r s o n a l D o s i m e t e r s

Nieves Murillo, Celina Vaquero, Fernando Seco, Jon Maudes, Ana Perez TECNALIA, Parque Tecnológico, Pº Mikeletegi, 2. Parque Tecnológico, San Sebastian, Spain

[email protected]

Efficiency is one of the big challenges during the dosimeter design phase; along with cost and autonomy (power consumption). To achieve a good equilibrium between efficiency, power consumption and autonomy; the active collection filter is the key element of the dosimeter devices. This element allows optimizing pressure drop for sub-micrometer biological particles capture. The capture of the maximum particles type and their size (virus –from 10 to 200nm-, bacteria – from 1 to 10 µm- and spores –from 0.5 to 1 µm) is vital in the case of biological threats, where the personal dosimeter is the evidence of threat exposure and the instrument to define the correct treatment to be administrate. The work reported has been focused at the electrospun nanofiber filter enhancement and characterization, without the use of other filtering elements such as metallic or textile foams or substrates. The use of electrospun nanofibers guarantees high elastic properties, efficiency improvement, constant pressure during filtering process, low pressure drop, and optimal management of power consumption. The efficiency enhancement of filters manufactured by electrospinning from PC was studied at the present work and their aerosol transport properties were characterized following the main recommendations of the UNE-EN 1822-3 standard. The electrospun nanofiber filters were exposed to mono-disperse 0.1% NaCl aerosol with mono-disperse particles range of 100-200-300-400 y 500 nm. The particles permeation across the filter and the filtration efficiency given by: P = Cout / Cin (eq. 1) and E = 1- P (eq. 2); where P is the particle

penetration across the filter, E is the filtration efficiency, Cout is the aerosol particle concentration upstream and Cin is the concentration downstream. The Quality Factor, fc is given by fc=ln(1/P /Δp = -ln(P / Δp (eq. 3 . These equations provide a useful measure for comparing the filtering performance of different materials. The PC electrospun nanofiber filters were optimized by the electrospinning parameters optimization, voltage, collector needle distance, flow viscosity … to achieve the best material-filtering properties. The electrospun nanofiber filters were compared with a commercial filter, the glass fiber PALL filter from Millipore. The main achievement of the work is the significant improvement of the particle filtering efficiency by the use of electrospun nanofiber filters and, in particular special porous geometrical topology. The comparison of results obtained from nanofiber filters manufactured from Material A - D01 E01.2 and D01 E01.3 - and Material B - D01 E05.3 shows that the efficiency enhancement goal has been largely achieved. Two main challenges have been achieve with the use of electrospun nanofiber filter, the Pressure Drop has reduced by 72% and, therefore, has improved the quality factor by nearly 400 % with efficiency of all filters near the 100%. Furthermore, compared with the reference commercial filter, the PC electrospun nanofiber filter is also able to improve the quality factor by a respectable 172%.


Figures

Figure 1: Experimental step-up used at the filtering test.

Figure 2: SEM micrograph of PC electrospun nanofibers filter

Figure 3: Quality Factor figures for the Materials A and B. Particles Penetration Speed 0,8cm/s


T r a n s p a r e n t b a l l i s t i c a r m o u r c e r a m i c s .

R e c e n t a d v a n c e s a n d i s s u e s t o b e o v e r c o m e

Felipe Orgaz Instituto de Ceramica y Vidrio, CSIC, Spain

[email protected]

Transparent armour is a system designed to be optically transparent to support dynamic fragmentation when subjected to the high strain rates produced by ballistic impacts. They are mainly used to protect vehicle occupants from terrorist actions and other hostile conflicts, as visors for non-combat use like riot control or explosive actions, etc. Light weight, small thickness, low optical distortion, compatibility with night vision equipment and multi hit capability are needed to defeat armour piercing ammunitions (AP) threats. These systems consist of a sandwich structure with a hard front layer of transparent ceramic joined to several plies of glass with polymer inter layers and polycarbonate backing. Advances in material science and technology over the last 40 years has made available sub-μm grain size polycrystalline α- Al2O3 aluminium oxynitride (AlON) , magnesium aluminate spinel (MgAl2O4)3 and single crystal sapphire (Al2O3) as alternative ceramic materials able to satisfy the requirements of transparency and hardness for armours application. In the present study the following current efforts are shortly exposed: a) the theoretical basis to get high transparency avoiding the light dispersion; b) the different processing techniques used for preparing these materials, specially for magnesium aluminate spinel (MgAl2O4)3; c) the main results and conclusions of the CERTRANS project supported by the Spanish Ministry of Defence into the framework of the COINCIDENTE programme and finally the existing current commercial products, issues to be overcome and some results on the importance of nanotechnology to get an affordable low cost versus performance transparent ceramic system are shown.

The main conclusions to be highlighted are:

-There is a general push to reduce the weight of the systems to increase transportability and flexibility and to reduce the operational costs.

-Transparent ceramics offer significant ballistic protection in relation to conventional glass/plastic systems. A few companies produce this kind of products: Surmet (ALON® technology), Armorline (Spinel), Saint Gobain Group (Sapphire), Technology Assessment and Transfer (TA&T) (Spinel). For technology transfer: Fraunhofer Institut (IKTS).

Some issues must be overcome: commercial availability, very high cost raw materials, high investments, complex processing techniques (hot pressing, hot isostatic pressing, Spark Plasma Sintering), machining and polishing costs, large formats and curved shapes, new structural designs for multi hit capability, etc

Several programs are investigating for cost reduction, new processing ways and scale up of these materials: As strategies are proposed: Conventional pressureless sintering, gel casting, nanotechnology, nanocomposite optical ceramics (NCOCs), etc.

-Pressureless sintering of translucent cubic magnesium aluminate spinel (MgAl2O4)3 with a high level of transparency has been obtained in the CERTRANS project supported by the Spanish Ministry of Defence into the framework of the COINCIDENTE programme. Partners: Universidad Rey Juan Carlos, Instituto de


Cerámica y Vidrio, INTA, Instituto Tecnológico La Marañosa.

Other alternative materials are underway (transparent glass-ceramics) to satisfy the requirements of high transparency and hardness, weight reduction, improvement in the ballistic performance for armours application. Polyurethane is also being evaluated as substitution for polycarbonate backing.

Figures

Figure 1: Optical Grade Ceramic Spinel (Armorline)

Figure 2: CERTRANS PROJEC. Pressureless sintering of magnesium aluminate spinel (MgAl2O4)3;

References

[1] R Apetz and M P. B. van Bruggen. Transparent Alumina: A Light-Scattering Model. J. Am. Ceram. Soc., 86 [3] 480–86 (2003) M. C.L.Patterson, A. DiGiovanni, D.W. Roy and G.Gilde. Spinel Armor. Clearly the way to go. Ceramic Engineering and Science Proceeding. 24,3, 441-446 (2003) [2] I. Reimanis and H.J.Kleebe. A review on the sintering and microstructure development of transparent spinel (MgAl2O4). J.Am.Ceram.Soc. 92,7, 1472-1480 (2009) [3] A. Krell, T. Hutzler and J. Klimke. Transparent ceramics for structural applications. Part 1 and 2. cfi/Ber. DKG 84(2007) No 4 and 6. [4] S.F. Wang , J. Zhang , D.W. Luo , F. Gu, D.Y. Tang c, Z.L. Dong , G.E.B. Tan , W.X. Que , T.S. Zhang S. Li , L.B. Kong , Transparent ceramics: Processing, materials and applications Progress in Solid State Chemistry 41,2013, 20-54.


S a f e t y & S e c u r i t y A p p l i c a t i o n s o f O p t i c a l

M e t a m a t e r i a l s

George Palikaras Metamaterial Technologies Inc., Canada

[email protected]



T h e O p t i c a l H e l m h o l t z R e s o n a t o r : a b r e a k t h r o u g h f o r

e x t r e m e l i g h t c o n f i n e m e n t f r o m I R t o R F

Fabrice Pardo MINAO Laboratory, Laboratoire de Photonique et Nanostructure, CNRS-LPN, 91460 Marcoussis, France

[email protected]

I will present some recent results from MINAO laboratory. MINAO (MIcro and NAno Optics) is a “Laboratoire Commun de Recherche” between CNRS (Laboratoire de Photonique et Nanostructures, Marcoussis, France) and ONERA (Departement d'Optique Théorique et Appliquée, Palaiseau, France). Mixing various backgrounds and scientific cultures, MINAO works on a wide activity spectrum from concepts (Technology Readiness Level TRL 1) to pre-industrial developments (TRL 7-8). Based on a long term collaboration (started Jan 2005), its activity is focused on nano-patterned structures for infrared applications. The evanescent wave engineering for energy redirection by magneto-electric interference [1] appears as an efficient tool to conceive perfect optical antennas from very simple

subwavelength structures. The combination of several nanoslit structures permits to do photon-sorting operation at subwavelength level [2] .This is a breakthrough for multispectral IR plane arrays, that can be developed for both bolometers [Collab. CEA-Leti] and quantum devices.

The combination of a nanoslit with a box (the Optical Helmholtz Resonator [3], Fig.1), permits to attain field intensity enhancement as high as 107 in far IR, and 105 in near IR. This open the way to several applications including SEIRA, chemical and bio sensors, highly sensitive detectors, and non-linear devices. References

[1] Light Funneling Mechanism Explained by Magnetoelectric Interference, F. Pardo et al, Phys. Rev. Lett. 107, 093902 (2011) [2] Analyt. descr. of subw. plasmonic MIM resonators and of their combination, C. Koechlin et al, Opt. Expr. 21, 7025 (2013) [3] Optical Helmholtz resonators, P. Chevalier et al, Appl. Phys. Lett. 105, 071110 (2014

Figures

Figure 1: Poynting-vector streamlines on one period of the slit-box structure at λ = 10 μm. (b treamlines of the incident wave. (c) Streamlines of the interference between the incident wave and the evanescent field.


I n v i s i b i l i t y c l o a k i n g u s i n g t h i n a l l - d i e l e c t r i c

m u l t i l a y e r c o a t i n g s

O. Peña-Rodríguez3,4

, K. Ladutenko1,2

, I.V. Melchakova1, I.V. Yagupov

1 and P.A. Belov

1

1ITMO University, St. Petersburg , Russian Federation

2Ioffe Physical-Technical Institute of the Russian Academy of Sciences, St. Petersburg, Russian Federation 3CEI Campus Moncloa, UCM-UPM, Madrid, Spain

3Instituto de Fusión Nuclear, Universidad Politécnica de Madrid, Spain

[email protected]

During the past decade there has been a strong interest in metamaterials, artificial media with exotic electromagnetic properties, mainly for applications in cloaking. Usually, the invisibility cloaks are designed using transformation optics concept and involve metamaterials with anisotropic, magnetic, and extreme material parameters. Due to the artificial nature of these media an experimental implementation of cloaking is non-trivial, especially for operation at optical frequencies. Hence, there are some recent efforts to achieve cloaking using isotropic dielectric materials readily available in nature. Cloaking devices made of a single dielectric material arranged into complicated geometry obtained through numerical optimization has been achieved. This approach is convenient for cloaking of large objects with diameter more than operating wavelength, but it is more appropriate for special cases where cloaking is required only for certain directions of incident wave. An alternative approach is based on using several dielectric materials in multilayer shell geometry. The permittivities of the layers can be optimized using a genetic algorithm. This kind of cloak is spherically symmetric and thus operates independently on incidence direction. In this talk we will discuss the state of the art in the field of cloaking, emphasizing the advantages of using all-dielectric multilayer coatings.


W h a t h a p p e n s w h e n y o u u s e t e x t i l e s t o m a k e

e l e c t r o n i c s f o r s o l d i e r s y s t e m s ?

Asha Peta Thompson Intelligent Textiles Limited, UK

[email protected]

When worn on the body of the dismounted soldier, conventional cables suffer the problems of being bulky, heavy, and stiff. Indeed they must be made deliberately stiff in order to ameliorate the risk of fatigue fracture. This hinders the ability and agility of the soldier. Electrically-conductive textiles (or e-textiles) are instead designed to be very low-profile and much more flexible, therefore requiring reduced insulation thickness and armouring, which in turn reduces their weight and reduces the burden for the soldier. E-textiles exhibit a much larger surface-area than conventional cables, but their sympathetic qualities allow them to 'disappear' into soldier garments. Indeed, their greater surface-area confers the additional benefits of improved damage-tolerance, multiple routing of network paths and superior thermal performance. Intelligent Textiles Limited has developed proprietary technologies that allow intricate circuits and networks to be manufactured as woven fabric. A single fabric component of this nature can replace an entire cable harness, with multiple end-points and connectors. The fabric components retain their textile qualities but are comparable in electrical performance to conventional cables. They exhibit competitive electrical resistance, data- throughput (USB2.0, at 480 Mbit/s) and shielding (DefStan 461E). Answer: “They finally become wearable”


N a n o p o r o u s c h e m i c a l r e c e p t o r s o n

m i c r o c a n t i l e v e r - l i k e s e n s o r s f o r e x p l o s i v e s d e t e c t i o n i n v a p o r p h a s e

M.P. Pina

1,2, F. Almazán

1, I. Pellejero

1, M.A Urbiztondo

1,3, J. Sesé

1, J. Santamaría

1, 2

1Nanoscience Institute of Aragón (INA), Zaragoza, SPAIN

2Networking Research Center on Bioengineering, Biomaterials and Nanomedicine, (CIBER-BBN), Zaragoza, SPAIN 3Centro Universitario de la Defensa (CUD), Zaragoza, SPAIN

[email protected]

In recent years, there has been a growing need for rapid detection and identification of terrorist threats including chemical and biological warfare agents, and explosives. None of the methods investigated to date solves the simultaneous problems of sensitivity, selectivity, reliability and speed required. This partly stems from the fact that explosives are composed of many chemicals, many being notoriusly difficult to detect due to their physical and chemical properties. The main problem as far as vapor phase detection is concerned is their low vapor pressure in the pure form (it ranges between 10-2 Pa to 10-7 Pa at 25ºC). In this scenario, the incorporation of pre-concentration units for trace detection in small volumes has revealed crucial for the satisfactory performance of any analytical device. Then, there is the problem of reliability: the ability of the sensor to discriminate between explosive markers and a wide variety of volatile hydrocarbon products accompanying most modern travelers (cosmetics, perfums, synthetic fabrics...) must be guaranteed to avoid false alarms. The most effective and efficient method in current use is sniffing dogs, but they also suffer from some limitations like behavioral variations and deterioration performance over time. Accordingly, extensive efforts have been devoted to the development of innovative and effective detectors, capable of monitoring explosives both in time and location, for homeland security and counter-terrorism applications. In theory, any chemical analysis scheme should be applicable for concealed explosives detection. Indeed, nearly of all known instrumental methods have already been investigated for their applicability. In particular

for rapid vapor phase detection, the most extended commercial hand-held equipments (<10 kg) for explosives detection are based on ion mobility spectrometry (IMS) with advertised sensitivity of 10 ppt (52 k$ for Ion Track Instruments ITMS Vapor Tracer); gas chromatography with electron capture detector for vapor concentration >1ppm (5 k$ for JGW International, Ltd. Graseby GVD4) and thermal redox detector with LOD <1 ppb (23 k$ for Scintrex/IDS EVD-3000). Apart from the costs, the limited portability, the operational complexity makes them inadequate for on-site monitoring. Thus, there is still need for quick, highly sensitive, robust and dependable technologies that can be readily operable by untrained first responders and homeland security operatives in the field. In view of the molecular recognition properties that nanoporous solids can offer, main strategy followed in our lab for explosives detection involves the use of nanoporous solids (micro and mesoporous; i.e zeolites, M41S, titanosilicates) as added elements on already existing platforms of sufficient sensitivity silicon microcantilevers provided with internal heating elements. Thus, different examples will be described to illustrate the progress of our work in this topic. In addition, some preliminary results on micropreconcentrator units involving zeolite policrystalline layers solids as specific coatings will be anticipated.


T h i n F i l m T e c h n o l o g i e s f o r S e c u r i t y a n d D e f e n s e

A p p l i c a t i o n s

Frank Placido Thin Film Centre

University of the West of Scotland, Paisley PA1 2BE, UK.

[email protected]

Thin film coatings, largely produced by vacuum deposition, fall naturally into the domain of nanotechnology1 by virtue of thickness and structure. The nano-structure of thin films is usually not the same as that of thin slices of the corresponding bulk materials and the density, porosity, crystallinity and chemical stoichiometry can be controlled by the deposition method and conditions to match particular applications. Thin film coatings have been of enormous industrial importance for some time but recent advances in coating technologies, materials and design techniques have led to something of a revolution in real world applications. To see why this should be, it is only necessary to realise that very many of the important properties of solids depend critically on the atomic layers at the surface, e.g. roughness, hardness, friction, corrosion, colour, reflectance, electrical conductivity, thermal conductivity, bio-compatibility, haemo-compatibility, catalytic activity and wetting ability. Obviously, we can then duplicate desirable properties in a very cost effective way if we can deposit suitable thin film coatings onto the surface of bulk materials (and make them stay there). Defense and security has driven some of the recent innovations in this field, but it is fair to say that commercial pressures and the necessity for lowering of costs and energy saving, while at the same time producing improved performance in civilian applications has also led to mutually beneficial outcomes. This has been recognised in various government ‘Crossover’ initiatives seeking military/commercial dual-use from research and development programs.

This talk will outline various thin film deposition techniques, materials and applications in a wide variety of sectors, including optics, mechanical engineering, energy saving and sensors, all of which have dual use in military and commerce. References

[1] F. Placido “Thin films: A growth area for nano applications” Nano Issue 14 (2009


R e c e n t d e v e l o p m e n t o n d u a l - b a n d u n c o o l e d P b S e

s e n s o r s m o n o l i t h i c a l l y i n t e g r a t e d o n a d v a n c e d i n t e r f e r e n c e f i l t e r s

Plaza del Olmo, Julio

1, Torquemada Vico, María del Carmen

1; Rodrigo Rodríguez, María Teresa

1;

Gómez Zazo, Luis Jorge1; Villamayor Callejo, Víctor

1; Fernández Gutiérrez, David

1; Almazán Carnero,

Rosa María1; Sierra Asensio, Cristina

2; Génova Fuster, Inés

2; Catalán Fernández, Irene

2; Gutiérrez

Martín, Clara2; Álvarez García, Mario

2; Magaz Pérez, María Teresa

3

1 Instituto Tecnológico la Marañosa (ITM), Madrid, Spain

2 Ingeniería de Sistemas para la Defensa de España (ISDEFE) 3 New Technologies Global Systems (NTGS), Madrid, Spain

[email protected]

PbSe detectors are photoconductors with optimum response in a broad band of the medium wavelength infrared region and high sensitivity at room temperature. As photonics devices, they are useful for a wide range of applications where a fast response is mandatory. These include applications such as detection and identification of chemical warfare agents or the detection of targets and threats in a cluttered environment. We report on the manufacture of a monolithic dual band uncooled infrared detector of lead selenide for smart detection. We provide selectivity to our sensors by means of multispectral discrimination, in order to produce advanced devices for detection at different wavelengths. Narrow bandpass interference filters are designed and produced. Filters are double Fabry-Perot cavities with demanding requirements that involve high transmittance for the pass band, and a broad rejection range with very low transmittance. Vapor Phase Deposition (VPD) technique allows the monolithic integration of lead selenide directly on the thin films stack of the interference filter, resulting in a sensor with spectral discrimination tailored by design [1,2]. A multicolour device was developed by hybridization of individual sensors with their spectral discrimination monolithically integrated [3]. The combination of photolithography process with the deposition method of filters

enables to achieve two different filters on a single substrate, so monolithic integration of PbSe detectors with two high pass filters resulted on the first bicolor device monolithically integrated [4]. Recently, another enhancement to the final product has been achieved by means of the dual monolithic integration of PbSe sensors on narrow band pass interference filters. The demanding requirements of some applications involve the use of filters with a high number of layers that are affected by the processing of lead selenide sensor. Mechanical instability led us to use hybrid instead of monolithic configurations [3]. Now we have successfully solved this fact and we are able to produce dual band monolithic devices. Figures

Figure 1: Transmittance spectra of the two band pass filters designed. They have maximum transmittance above 80%, bandwidth around 2% of the center wavelength, transmittance out of the pass band below 0.1%.


Figure 2: Photograph showing a PbSe detector deposited onto a configuration of two pass band interference filters. Each detector is formed by four sensors: two of them (purple) have only the common low wavelength rejection and the other two have the band pass filters of figure 1 (red and orange).

References

[1] J. Diezhandino, G. Vergara, G. Pérez, I. Génova, M. T. Rodrigo, F.J. Sánchez, M.C. Torquemada, V. Villamayor, J. Plaza, I. Catalán, R. Almazán, M. Verdú, P. Rodriguez, L.J. Gómez, .T. Montojo. “Monolithic integration of spectrally selective uncooled lead selenide detectors for low cost applications”. Applied Physics Letters. 83 (2003) 2751. [2] M. C. Torquemada, M.T. Rodrigo, L.J. Gómez; V. Villamayor, D. Fernández, R.M. Almazán, J. Plaza, C. Sierra, I. Génova, I. Catalán, C. Gutiérrez, M. Álvarez, M.T. Magaz . “Desarrollo de ensores sin Refrigerar de PbSe Dotados de Discriminación Espectral”. Congreso Nacional de I+D en Defensa y Seguridad. 5-7 Noviembre, 2013. Madrid. [3] C. Sierra, M.C. Torquemada, G. Vergara, M.T. Rodrigo, C. Gutiérrez, G. Pérez, I. Génova, I. Catalán, L.J. Gómez, V. Villamayor, M. Álvarez, D. Fernández, M.T. Magaz, R.M. Almazán. “Multicolour Pb e ensors for analytical applications” ensors and Actuators B 190 (2014 464-471. [4] M. C. Torquemada, V. Villamayor, L.J. Gómez, G. Vergara, M.T. Rodrigo, G. Pérez, I. Génova, I. Catalán, D. Fernández, R.M. Almazán, M. Álvarez, C. Sierra, C.M. Gutiérrez, M.T. Magaz, J. Plaza. “Monolithic integration of uncooled Pb e bicolor detectors”. ensors and Actuators A 199 (2013 297-303


T e x t i l e , N a n o t e c h n o l o g y a n d D e f e n c e

José Manuel Ramos Fernández and Javier Pascual

AITEX, Plaza Emilio Sala, 1 E-03801 Alcoy (Alicante), Spain

[email protected]

The textiles have a great variety of applications in defence. The traditional uses of textiles in defence have evolved from the classical applications (protect against weather inclement, camouflage etc) to a great variety of new application and functionalities (Ballistic protection, protection against chemical attacks etc, ). Nowadays, textiles are an essential part of soldier and vehicles equipment On the other hand, the nanotechnology has revolutionized the science and industry in the last 30 years. The unique properties of the materials at nano-meter size have resulted in a great variety of new improved materials and materials applications. In this talk an overview of the current application of nano-technology in the textiles will be made, moreover the applications of the new materials in defence will be explained. Eventually, the studies carried out at AITEX related with defence will be pointed out.


D e f e n c e A p p l i c a t i o n s f o r P l a s t i c E l e c t r o n i c s

Paul Reip

Director, Government and Strategic Programmes, Intrinsiq Materials Ltd. U.K.

[email protected]

Over the last 10 years there has been a growth in nanotechnology that can be applied to defence and security applications. A good example of this is in the field of energetic materials where nano scaled materials have been investigated for many years, their large surface area and enhanced reactivity offering the formulator new ways to address performance issues, whilst opening up the new applications and effects. Similarly, and in parallel with the general move to the use of commercial off the shelf equipment (COTS) where relevant in these areas, the growth of printed electronics also offers some new opportunities for the development of new and enhanced applications. Based on conventional print technologies, but with the use of nanomaterials to offer new capabilities, these structures and devices offer the potential to create new cost effective sensors and detectors and can enhance weapon and platform effectiveness, based on a cost effective and green production method. Much work still needs to be done, however this paper will examine some of the options and approaches that can be considered.


K e y s t o i m p r o v e f l e x i b l e o r g a n i c b u l k - h e t e r o j u n c t i o n

s o l a r c e l l s

M. Ribeiro1, J.Gomes

1, A. Pinto

1, L. Rino

2 and L. Pereira

2

1CeNTI - Centre for Nanotechnology and Smart Materials, VN Famalicão, Portugal

2Department of Physics and i3N - Institute of Nanostructures, University of Aveiro, Portugal

[email protected]

The soldier of the future will be carrying many electronics. From sensors, communications, weapons control, augmented reality aids, etc, they all need to be powered. In spite of the predictable impact of nanotechnologies on the efficiency and lightweight on the combat gear, weight carried by the individual soldier will be significant. Current batteries need to be frequently charged or replaced in the theater of operation with spares and chargers contributing to the total weight to be carried and, on the second case, they need a power source to plug in. Solar energy is present in most of the actual and predicted near future “war zones” and the use of solar chargers may be an attractive source of power to charge the electronics of the future soldier. However the actual solar harvesting technologies are cumbersome, with a rigid form and heavy, not ready to be easily carried by the soldier or easily deployed in the battle field. This is where organic photovoltaic’s (OPVs may have an impact since they can be flexible (bendable, foldable), thin, light weighted and very cheap to produce. OPVs emerged as a “low-cost” solar cell technology being the optimization of the sun light absorption and electrical carrier generation, in order to increase the OPV efficiency, one of the most important fields concerning such new technology. The usual polymeric bulk heterojunction solar cell (BHSC) structure employs an active layer formed by a mixture of a polymer and a carbon based nanostructure. Although some important results have been obtained, still many questions have to be overcome before a real application can be made. In this work, an active BHSC layer composed by MEH-PPV (poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) and PCBM ([6,6]-phenyl-

C61-butyric acid methyl ester) was studied by absorption spectroscopy and photoconductivity, as a function of MEH-PPV:PCBM ratio (in mass). A flexible OPV based on such active layer is then fabricated and analyzed in order to correlate the figures of merit with the morphology revealed by atomic force microscopy (AFM). Absorption data shows, besides the well-known UV organic structures absorption, a difference on the visible region of the spectrum as the MEH-PPV / PCBM ratio changes. Both MEH-PPV and PCBM absorb light in the visible spectral region, although the donor (polymer) exhibits a larger absorption in the bluish-green region due to its gap near 2 eV. The cumulative effect from both species is studied aiming the light absorption maximization. When the PCBM concentration increases, new photocurrent bands in the blue / green spectral region appears. As the spectral region of photocurrent generation becomes wider, this leads to an improvement on the solar cell electrical carrier generation. The photocurrent increases as the PCBM concentration increases only up to 80% (in mass). For both absorption and photoconductivity data, the best compromise for maximize the sun light absorption and further electrical carrier generation, points to a MEH-PPV: PCBM ratio of 1:4 (in mass). Considering both data, the maximum efficiency can be obtained by the product of the normalized absorption and photoconductivity behavior with the MEH-PPV:PCBM ratio. Figure 1 shows the overall data. Concerning the OPV (figure 1), one important point is the electrical charge collection at the electrodes, after the exciton formation and separation. Due to the complex nature of orbital hopping electrical transport, and the usual high


density of intrinsic defects in the organic layers, trapping and recombination of the electrical charge is one of the most important factors that diminishes the efficiency. Since such intrinsic defects are related with the local morphology of the films, a detailed work relating these two points must be done. It is observed that the most relevant parameter (influencing the efficiency) is the fill-factor (FF), as both the open circuit voltage and short circuit current are not significantly affected by the microscopic morphology. Different local conformation of the active films can change the FF from near 25% to more than 65%, having a strong impact in the efficiency. These results are modulated by an equivalent circuit, were the serial and parallel resistances are related with the physical behavior of the organic cells, in a direct relationship with the morphology. The best results obtained with this photovoltaic structure are shown in figure 2, where the fundamental figures of merit are presented. The efficiency is about 3.5% with a FF over 65%. Finally, it is tried to develop a model that comprises the physical nature of the observed results, considering the donor – acceptor interaction and the electrical charge formation, dissociation and transport, related with a study of different parameters for the device fabrication in order to understand the active layer conformation. Although this technology is on his beginning the expected characteristics of a near future device may be a helpful aid for the equipment of the soldier of the future, alloying to lower the individual carried weight and facilitate mass deployment on the theatre of operations without cost concerns.

Figures

Figure 1 - General solar cell scheme and organic semiconductors structures. A device picture is shown.

Figure 2 - Relative variation of absorption and photoconductivity between 1.5 – 3 eV

Figure 3 - Current Density – Voltage (J-V) data for a solar cell in dark conditions (blue) and under illumination (red). Broken lines: experimental data; full lines: theoretical modulation. The shadow area represents the fill factor FF.


N a n o t e c h n o l o g i e s : a p p l i c a t i o n s o f i n t e r e s t f o r t h e M i n i s t r y o f D e f e n s e

José Mª Riola Rodríguez

SDGTECIN.DGAM, Spain

One of the prime objectives of the Spanish MoD is to provide the Armed Forces with the best weapon systems and equipment required to complete their missions. For that reason, different Departments and Organizations of the MoD are devoted to managing and executing R&D programs and projects, together with the national technological and industrial base and in close collaboration with other national and international agencies (EDA, NATO, etc.) Nanotechnology is an important enabling technology that has potential to contribute to enhance defence systems capabilities. It offers a promising future in many and very different areas due to the ability to obtain new materials with better mechanical, chemical, electrical, etc. properties at macroscale. The integration of nanotechnologies in defence systems means better and ligher protection systems against enemy’s weapons and against CBRN threats for our soldiers, more secure and lighter aerial, ground and naval platforms with better performance from an operational point of view, a more easier and cheaper control and maintenance of the equipment, smaller and more powerful devices and sensors, new systems for the generation and storage of electrical energy, etc. All these improvements are of great interest for the Ministry as stated in the Spanish Defence Technology and Innovation Strategy (ETID).


A u t o m a t e d D r u g D e t e c t i o n S y s t e m

Miguel Roncalés ALPHASIP, Spain

The problem: it is difficult to deal with blood or urine on roadside, in the work center or at home if you are not a doctor. Medical advances are allowing a longer life expectancy and quality of life in developed countries. Traffic accidents and cardiovascular and embolic episodes are the main threats to the life along with cancer. Internet, personalized medicine and the exhaustion of the healthcare’s financial system due to great pressure (longevity, new illnesses linked to ageing and new more expensive technologies in the context of the financial global crisis) are favoring that the people demand easy, cheap and fast solutions.

Source: From DGT June 2014

If we further apply this concept to road security or in environments where privacy is important (Detoxification clinics, bus drivers, accident prevention at work or psychiatrists) it can be seen the little viability of gathering urine or blood.

Detection of 6 different Drugs in oral fluid in less than 10 minutes • COC – Cocaine 20 ng/ml • OPI - Opiates 40 ng/ml

• AMP - Amphetamines 50 ng/ml • PCP - Phencyclidine 10 ng/ml • MET – Methamphetamines 50 ng/ml • THC - Marijuana 40 ng/ml

DrugSIP & Cocachip 5x is based on microelectronics, and provides on one hand equipment to the Police forces and on the other AlphaSIP will have a interactive directory service on the internet, an online portal (to pick up saliva and perform the drug test remotely and a affiliate program) with a platform for doctors and companies to attend the private channel. The solution: a new way to measure in a fast manner with saliva. Alpha IP “Oraltrack” resolves this problem: it is a medical device manufacturer based on nanotechnology that are:

• Light •Multiparametric (from 5 to 9 drugs detected per cassette) • Fast • Portable • Hygienic • Economic •Can store and print result


I n d u s t r i a l P r o p e r t y a s a k e y f a c t o r i n t h e S e c u r i t y a n d D e f e n s e i n d u s t r y

Luis Sanz Tejedor

Head of Applied Mechanics Patent Area Spanish Patent and Trademark Office

[email protected]

It is very difficult to find any technical field where the IPR’s are not taken into account. 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 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.


N a n o t e c h n o l o g y – a n e n a b l i n g t e c h n o l o g y , a c r i t i c a l

t e c h n o l o g y o r s i m p l y a n e w t e c h n o l o g y w i t h i n f l a t e d e g o ?

Steven J. Savage

Swedish Defence Research Agency, Sweden

[email protected]

In this broad presentation I will attempt to review the background to nanotechnology, what the technology is (and what it is not) and how it may impact security and defence applications in the near-term and the more distant future. I will briefly mention the Swedish defence nanotechnology programme, which included seven projects ranging from materials for ballistic protection to self-decontaminating coatings and self-activating materials against high energy lasers. When this programme started (2003) nanotechnology was an immature field and the TRL of most materials in the projects was very low. Since this programme was completed a few years ago it is useful to see how the TRL has increased, and is some cases products have been developed. I will draw conclusions as to how nanotechnology may contribute to defence and security and how these applications will benefit from purely civilian applications. Finally I will mention some caveats which we should be aware of in applying nanotechnology.


N a n o t e c h n o l o g y f r o m t h e L a b t o t h e F a b

Brent Segal

Lockheed Martin, USA

[email protected]



N a n o t e c h n o l o g y : t h e o n g o i n g r e v o l u t i o n

Pedro A. Serena

ICMM-CSIC, Spain

[email protected]



S e n s i n g t r a c e s o f n e r v e a g e n t s l i k e S a r i n u s i n g

n a n o m a t e r i a l b a s e d e l e c t r i c a l d e t e c t o r s

Jean-Pierre Simonato Laboratory of Synthesis and Integration of Nanomaterials

CEA-Grenoble, LITEN / DTNM / SEN / LSIN 17, rue des Martyrs, 38054 Grenoble, France

[email protected]

The threat of a chemical attack on homeland and military forces continues to grow and examples such as the terrorist attack of the metro of Tokyo, or the recent use of chemical warfare agents in Syria, have clearly shown that organophosphorus agents (OPs) are powerful neurotoxic molecules that can actually be used as weapons of chemical terrorism. Some sensors are commercially available to detect toxic agents; however they suffer from some intrinsic defects that reduce significantly their interest in some specific kinds of operation. Up to now, there is still a lack of supersensitive and specific autonomous small sensors. New sensors based on one-dimensional semiconducting nanomaterials like silicon nanowires have been chemically functionalized with tailor-made molecules for detection of traces of toxic gases. In particular, a chemical receptor specific to traces of neurotoxic OPs like Sarin has been synthesized and grafted to nanomaterial based electrical devices [1]. These results show that it is possible to detect very efficiently sub-ppm traces of OPs with high selectivity by functionalized field-effect transistors. In this presentation we will show results starting at the nanoscale using functionalized nanomaterials, up to their integration in an autonomous demonstrator and tests with real Sarin.

References

[1] Angewandte Chemie Int. Ed., 2010, 49,4063; IEEE Electron Device Letters, 2011, 32(7), 976-978; Chemical Communication, 2011, 47, 6048-50; Talanta, , 2011, 85, 2542-2545 ; 3 Patents to CEA.


T h e t e x t i l e e l e c t r i c a l l y c o n d u c t i v e a s s e c u r i t y

s o l u t i o n s f o r s e v e r a l a p p l i c a t i o n s

Ivano Soliani SOLIANI EMC SRL, Italy

[email protected]

SOLIANI EMC is a SME company located in Como where we have a gain a certain quantity of fabric and textile able to be made from weaving to finishing in accordance with the final applications . The Company is involved from 40 years in the field on the electromagnetic shielding solutions with products that are made in accordance with the frequency ranfe involved and for obtain a certain dB attenuation level to shield electromagnetic signals. During these years SOLIANI EMC have made different raw materials electrically conductive and some of them are qualified in different fields as : Airplane industry, automotive , Military navy , automatisation , robot , cables shielding and medical plus new applications for composite . For each application field we have obtained a qualification as EN 9001 – EN 9100 – NATO and ISO TS 16949 Inside our company we have a laboratory where we can made inside our test electromagnetic from KHz to 18 GHz to obtain results as indication for quality suggestion to our potential customers . The scope is to support in same area involved to prevent electromagnetic solutions how our range of products could be sufficient not only to be involved for electromagnetic shielding solutions but also to be sure to cover and offer a stable conductivity surface also on the surface of the fabric or on the gaskets to close the conductivity . The range of the textile electrically conductive are obtained with several type of fibers different for the mechanicla properties and for the phisical area where these are involved. In fact we can transfer or treatment over each single filament eable to be joint with flexibility properties and strong adesion over skin fiber surface .

The metal also that we use is nickel but in alternative we can use copper nickel or zinc . The shielding performance as quality to prevent electromagnetic interferences is stronger in accordance to the metal deposition and to the connection and uniformity method that we can obtain in our line of production process. The scope to use a shielding solution able to cover differents surface as internal or external and to join with other raw materials electrically conductive offer a very wide applications and frequency for Security Solution. For these appliactions the treatment with electrochemical properties offer a solution that cannot be possible compare as quality resulst with the others systems that are made to obtain conductive fiber or fabric conductive because the quantity of metal deposition is possible only with our methood and also with all type of fiber and filaments or non woven with uniformoty quality result over the surface and inside withalso a tick important as textile compositions. The system is a method that we have made in our company with a control operation 100% to garante the quality of each single meter of fabric or textile that we made with metalisation process. The type of textile as Non woven , velkro or tridimensional fabric are new possibilities that we have made for new applications in combination for composite as pre preg or vaccum deposition or new products as thermoplastic applications for shielding results to obtain : Weight reduction Easy application to remove metal High shielding performances with absirber properties if requiered


I can now enter in details to offer a view of the applications that we have made with our range of electroless chemical process.


N a n o s t r u c t u r e d e n e r g e t i c m a t e r i a l s : o p p o r t u n i t i e s t o

e n h a n c e p e r f o r m a n c e s

Denis Spitzer ISL-CNRS-UdS, France

[email protected]

The nanostructuration of materials is currently penetrating most of the scientific and economical domains. The energetic materials are fully impacted by this revolution. Energetic materials such as explosives and thermites are currently nanostructured to enhance the performance of their classical micronsized counterparts. These higher performances may include high combustion velocities and the possibility to design smart energetic materials by adjusting precisely the structure of the materials and this on the required local scale. The high potential of these materials is timely with the current requirement to replace lead containing igniters, to be able to miniaturize detonators and also to develop bigger energetic charges as the production capacities of freshly designed techniques are currently scaled up. Different examples such as nanostructured explosives and nanothermites will be shown and the perfomance enhancement will be discussed, in terms of combustion rates, desensitization and reliability. New processes to engineer these nanosized energetic nanocomposites will also be described. As an example, the Spray Flash Evaporation (SFE) process to design high performance nanostructured explosives will be discussed (fig. below), its versatility and potential in other domains such as medicine will be shown. Finally, the possibility to use nanostructured energetic materials to synthetize ultra small particles, such as for example ultimate sized nanodiamonds or nanooxides, will also be presented. This new synthesis route is a powerfull alternative to classical synthesis chemistry when the objective becomes to reduce drastically the sizes of the desired nanoparticles, and this for various purposes.

Figures

Figure 1: Spray Flash Evaporation (SFE) pilote plan.


B e s t p r a c t i c e s i n c o m m e r c i a l i z i n g n a n o t e c h n o l o g i e s i n d e f e n s e

Nava Swersky Sofer

International Commercialisation Alliance, Israel

[email protected]



S i l i c o n O x y c a r b i d e N a n o p a r t i c l e s a s N e w D r u g D e l i v e r y M a t e r i a l s f o r I n f e c t i o u s D i s e a s e T r e a t m e n t s

A. Tamayo

1, M.D. Veiga-Ochoa

2, J. Rubio

1

1 Instituto de Cerámica y Vidrio. C/ Kelsen, 5. 28049 Madrid. Spain.

2 Facultad de Farmacia. Universidad Complutense de Madrid, Plaza de Ramón y Cajal s/n. 28040 Madrid. Spain.

[email protected]

Infectious diseases are responsible for considerable mortality globally. Human immunodeficiency virus/acquired syndrome (HIV/AIDS), Tuberculosis (TB) and malaria rank among the most deadly of infectious diseases. The World Health Organization reported over 1.7 million deaths from HIV in 2011, 1.4 million deaths from TB in 2012 and 660.000 deaths from malaria in 2010. In the absence of effective vaccines against these diseases, drug therapy remains the only treatment option. The increasing prevalence of drug resistant pathogenic strains including growing HIV has become a global concern. The development of new therapies based on nanomedicines, to reduce drug doses and dose frequencies and to shorten treatment duration, with the goal of increasing patient compliance, improving treatment outcomes and reducing occurrence of drug resistance, is a major priority for these diseases. In this aspect the new generation of nanomedicines can be designed to delivering drugs by means of selecting pharmacologically active ligands chemically of physically adsorbed on porous nanoparticles. Thus, these pharmacologically nanoparticles can deliver therapeutic drug concentrations inside the cell to prevent specific diseases. In this work we have prepared a new class of materials named as silicon oxycarbide ceramics with different kinds of porosities where acyclovir has been adsorbed in different concentrations. Acyclovir has been selected for its potent and selective antiviral activity against viruses of the herpes group. Silicon oxycarbide nanoparticles present on their surfaces a wide dispersion of active sites where acyclovir can be adsorbed with different intensities and, then when in use it can be delivery with doses according to any specific disease or in a wide range of days. Silicon

oxycarbide nanoparticles present hydroxyl and carbonyl or phenol groups on silicon oxide, carbon and oxycarbide phases and these groups have been modified with amino groups or have been increased by means of strong oxidation. In all cases the absorption and delivery of acyclovir have been characterized by means of UV-vis spectroscopy and the results have been compared with those of typical mesoporous silica materials generally studied for this subject. It has been observed that the new silicon oxycarbide nanomaterials present high absorption capacities than mesoporous silicas and that the acyclovir release is effective over a prolonged period while for mesoporous silicas occurred in few minutes. These results indicate the interesting properties of these new nanomaterials for drug delivery in infectious diseases. Figure 1 shows the nitrogen adsorption-desorption isotherms of different SiOC nanoparticles surface modified with 3-amine propil trimethoxy silane (3APS) and Figure 2 shows the corresponding pore size distributions (PSD). In this case the SiOC nanoparticles present a clear bimodal pore distribution with pores sizes close to 6 and 60 nm. Surface modification of these nanoparticles with 3APS modifies the amount of pores and mainly the pore sizes higher than 80 nm. Thus 3APM molecules tend to adsorb on the high sized pores rather than on low sized ones. Figure 3 shows the nitrogen isotherms of SiOC nanoparticles surface oxidized to create different active sites. Figure 4 shows their corresponding PSD. In this case the nanoparticles present a monomodal pore distribution with pores close to 3 nm and a minor part of 20 nm. Surface


oxidation only modify the amount of low sized pores but the distribution shape can be assigned to a typical ink-bottle distribution where small pores are located on the nanoparticle surface while wide pores are located in the bulk. All of these nanoparticles have been analyzed by means of Attenuated Transmission Infrared Spectroscopy (ATR) and the interaction of APS molecules on the surface of the SiOC nanoparticles have been described in accordance with the physical adsorption on Si-OH and C-OH grous where the APS molecules can be found in normal or parallel configurations over the SiOC nanoparticle surface. On the other hand, the surface oxidation mainly removes Si-OH groups of the silica phase and creates new C-OH groups on both carbon and silicon oxycarbide phases. These new surfaces of the SiOC nanoparticles give different interaction with acyclovir

molecules and then different release kinetics in a given medium. The absorption and release of acyclovir on these SiOC nanoparticles have been analyzed and compared with two conventional silicas normally used as controlled release materials. Table 1 shows absorbed amounts of acyclovir by the SiOC nanoparticles and two silicas and the corresponding released amounts after 30 minutes. It is clear the high capacity of acyclovir absorption of the SiOC nanoparticles compared to the mesoporous silicas and the possibility of release in different concentration depending on the surface modification of the SiOC material.

Table 1.- Properties of nanomaterials respect to controlled release of acyclovir

Nanomaterial Modification Surface Properties Acyclovir

Surface Area (m2.g-1) Pore size (nm) Absorbed (%) Released (%)

SiOC bimodal

- 440 9.6 99 5

0.25 APS 400 9.7 96 6

5 APS 310 11.0 79 16

10 APS 115 16.0 80 33

SiOC monomodal

- 200 3.5 95 4

1 hour 390 3.5 83 15

32 hours 320 3.3 46 17

Porous Silica - 524 6.3 2 98

Mesoporous Silica - 905 2.5 3 97

Figures

Figure 1 Figure 2


Figure 3 Figure 4


A p p l i c a t i o n s o f N a n o t e c h n o l o g y i n F o r e n s i c S c i e n c e

Ian Turner

Forensic Science, University of Derby, UK

[email protected]

Forensic Science is multi-disciplinary field that broadly means ‘science related to courts’ it encompasses a wide range of classical sciences, applied sciences and specialist areas. Since its origins in the 16th century, Forensic Science has embraced advances in our understanding of human anatomy and pathology, analytical chemistry and molecular biology. Forensic Scientist from Alexandre Lacassagne to Sir Alec Jeffries have applied current techniques to criminal cases and as a result revolutionized the field. Nanotechnology is now being applied and used in a range of forensic contexts and has the potential to change the way we examine evidence. Most research and development of nanotechnology in forensic science focus on the improvement of DNA microchips and arrays. However, techniques routinely used for the analysis of nanomaterials have been adapted/ modified and applied to others areas of Forensic Science including, electron microscopy (transmission electron microscopy, TEM and scanning electron microscopy, SEM), scanning probe microscope (SPM), Raman Microspectroscopy (Micro-Raman). These instruments have been used for the analysis of a range of forensic evidence types such as fingerprints, drugs, questioned documents and bloodstains and offer valuable insights potential useful in a criminal investigation. Nanotechnology is beginning to have an impact on the handling of evidence at crime scenes, its analysis in the laboratory and its presentation in the court room. This talk aims to highlight some of these applications of Nanotechnology in Forensic Science.


T e c h n o l o g y a p p l i e d t o c r i m i n a l i n v e s t i g a t i o n : W h a t t o

e x p e c t f r o m n a n o t e c h n o l o g i e s ?

Luis Valles Guardia Civil – UCO, Spain



A N e w C o n c e p t o f C a r b o n N a n o t u b e b a s e d T e x t i l e s f o r

C i v i l P r o t e c t i o n S e r v i c e s

Effrosyni D. Vogli, A. Soto Beobide and G.A. Voyiatzis Foundation for Research & Technology-Hellas– Institute of Chemical Engineering Sciences, (FORTH / ICE-HT) Greece

[email protected]

Up to now a lot of research has been done in the field of protective textile. Body armour materials have traditionally been designed to protect the wearer against any kind of weapon threats. Which are the basic concepts of body armour? First it should stop weapons’ bullets before they completely penetrate the armour and reaches the wearer’s body and second it should spread the bullet’s energy over a larger portion of the body armour, so that the final impact causes less damage. Several new fibers and construction methods for bullet-proof fabrics have been developed besides woven Kevlar® such as D M’s Dyneema® Honeywell’s Gold Flex® and pectra® Teijin Twaron’s Twaron® and Toyobo’s Zylon®. These high performance fibers are characterized by low density, high strength and high energy absorption. However, to meet the protection requirements for typical ballistic threats, several layers of fabric are required. It is also frequently to improve the body armour with stab resistant, materials including for example metal ring mesh, layers of titanium foil, rigid metal, ceramic or composite plates are utilized. The resulting bulk and stiffness of the armour limits the wearer’s mobility and agility. There is an obvious need to develop flexible and lightweight protective body armour. This gap can be filled by carbon based materials. ince Iijima’s report on carbon nanotubes (CNT) in 1991 [1], scientists have been attracted by CNT’s unique atomic structure and properties. Because of the combination of low density, nanometer scale diameters, high aspect ratio, and more importantly, unique physical properties such as extremely high mechanical strength and modulus, CNTs are ideal as

potential reinforcing filler without adding extra weight and contributing with excellent performance. In this context, a Canadian company recently announced a line of custom-fitted suits by several “sheets” of carbon nanotube fabric in its lining that will provide to the wearer a certain level of protection from bullets and knives. [2] The inclusion of CNTs in a polymeric matrix holds the potential to improve the host material’s mechanical, electrical or thermal properties by orders of magnitude well above the performance of traditional fillers. The challenges for developing high performance polymer/CNTs composites include the dispersion of CNTs in the polymeric matrix and interfacial interactions to ensure efficient load transfer from the polymeric matrix to the CNTs. Carbon nanotubes are usually present in bundles and exhibit a highly aggregated state in the polymeric matrix because of the strong inter tube Van der Walls force between the tubes, which holds the bundles together. The challenge of achieving efficient CNT dispersion and orientation within the polymer composite poses a substantial obstacle to the development of relevant beyond the state of the art fabrics. In other words, the mechanical properties of CNT composites fibers are highly dependent on CNT loading, dispersion and orientation, as well as pertinent to the polymer matrix characteristic properties. In order to obtain desirable polymer/CNTs composites, homogeneous dispersion of CNTs in polymeric matrixes is the prime task. It is in that sense that a new Raman spectroscopic methodology has been very recently proposed by our group in order to monitor the weight fraction of MWCNTs in polymeric composites. [3]


The orientation of the CNTs in the polymeric fibers, the concomitant polymer induced crystallization and the resulting mechanical strength have been evaluated. The orientation of CNTs in synthetic fibers has been investigated with polarized Raman spectra and IR dichroic ratio, while tensile tests have been performed to evaluate the mechanical properties. References

[1] Iijima S., Nature, 354 (1991) 56-58. [2] http://garrisonbespoke.com/custom-suits/bulletproof-suit/ (accessed June 16, 2014). [3] Bounos G., Andrikopoulos K.S., Karachalios T.K. and Voyiatzis G.A., Carbon, 76 (2014) 301-309. Acknowledges

The research leading to these results was cofounded by the European Regional Development Fund (FP7/2007-2013) and Western Greece Region national resources under the grant agreement n° 235527 (LEADERA - Code: 2013-006 INPROTEX).


I n n o v a t i v e a p p r o a c h t o t h i n f i l m s e n s o r d e v e l o p m e n t

Ambiörn Wennberg and Iván Fernández Martínez

Nano4Energy SL, C/o ETSII-UPM Instituto de Fusión Nuclear, C/ José Gutiérrez Abascal 2, Madrid, Spain

[email protected]

Thin film technology has become a very important area of technology during the last decades. A large variety of product have sprung up from this technology development such as, flat screens, touchscreens, precision optics, solar cells and many different types of sensors and controls. The applications are many and many more to come. Within the thin film technology there are also many different types of fabrication techniques such as laser deposition, chemical vapor deposition (CVD), physical vapor deposition (PVD) etc. Many of which are conducted in vacuum. One of the most extended and industrially used PVD methods is sputtering which is a plasma deposition method performed in vacuum. The main reason to this is its ability to deposit films in the square meter range with excellent thickness and composition uniformity combined with high deposition rates [1]. Deposition in vacuum provides high purity devices with a great deal of control of the composition, and thus the function of the device. However it does give some limitations concerning the types of materials that can be used. Metallic materials are generally fairly easy to use, pure or as metallurgically mixed deposition targets. Also mixing the metals with gas state materials are nowadays industrially implemented with a great deal of control, most often using so called reactive sputtering. Reactive sputtering is using different kinds of sensors to monitor the actual state and deposition conditions at a real time basis and reactively adjust the parameters for the desired result. The main pioneers in this field are Gencoa Ltd based in Liverpool, UK.

The rapid development in the field however increases the demand for new specialized more complex mixes of materials also including solid or liquid state non-metallic materials, such as Sulfur, Selenium, Tellurium and various types of organic materials etc. These materials have long been a challenge to introduce into the vacuum process in a controlled and cost efficient manner. Nano4Energy has applied an innovative approach to this issue using pulse technology. By evaporating the desired material at a highly controlled temperature, thus controlled vapor pressure, then introducing the vapor through a pulsed valve, using a Pulsed Valve Cracker Effusion Cell [2], where the frequency and opening time can be controlled, the composition in the substrate is highly controllable. In addition to this a reactive feedback system based on plasma emission monitoring (P.E.M) has been developed and implemented, in collaboration with Gencoa Ltd. The technology enables to maintain the balance of metal and evaporated atoms at the optimum level for obtaining high deposition rates and control of the film stoichiometry. This is crucial for obtaining high efficiency devices, previously only achieved using gas state materials. This demonstrated innovative approach not only increases controllability, thus improving process yields and reducing product cost, in the industrial scale process, it also provides a new degree of stoichiometric freedom for the development of sensors, controls and many other applications. Applications and devices that are currently under development using this technology are CIGS/CZTS solar cells, infrared sensors, Bragg mirrors and organic encapsulation of e.g. OLED technology.


Figures

Figure 1: Schematic view of the Pulsed Valve Cracker function with the reactive feedback control system [3]

Figure 2: Left: Example of Se flux measured with a Quartz Microbalance as a function of the valve aperture repetition frequency and for different aperture times (time on). The flux is linearly proportional to repetition frequency, and dependent on the valve aperture time. An active control in the valve aperture parameters allows an excellent control of the flux. Right: Schematic of the Cracker Valve controls pulses of atomic vapor. By adjusting the time on (valve aperture time) at a particular repetition frequency of pulse different average flow can be injected into the vacuum deposition system.

Figure 3: (Example of the rapid response when changing the set-point to vary the stoichiometry when using reactive feedback control and the pulsed valve cracker. The new stoichiometry is stabilized within seconds from the change in set-point.

References

[1] V. Bellido-González, B. Daniel, J. Counsell and D. Monaghan, Thin Solid Films 502, 34 (2006). [2] Nano4Energy SL, C/o ETSII-UPM, José Gutiérrez Abascal 2, E-28006 Madrid, Spain. www.nano4energy.eu [3] V. Bellido-González and I. Fernández-Martínez: GB Patent 1307097.4 (2013)


A c t i v e s u b s t a n c e s e n c a p s u l a t e d b y E l e c t r o -

H y d r o d y n a m i c t e c h n i q u e s . T e x t i l e a p p l i c a t i o n s

Rogelio Zubizarreta Jiménez1, I.G. Loscertales

1,2, A. Domínguez

1, D.Esperon

1,

P. Ballorca1, E. Dueñas

1 and J.M. Cuevas

3

1YFLOW S.L., Parque Tecnológico de Andalucía, C/Marie Curie 4, 29590 Málaga, Spain

2Departamento de Ingeniería Mecánica y Mecánica de Fluidos, Universidad de Málaga,

Dr Ortiz Ramos, s/n 29071 Málaga, Spain 3GAIKER Technology Center, Parque Tecnológico, Edificio 202, 48170 Zamudio, Spain

[email protected]

We present a novel method based on electro-hydrodynamic (EHD) techniques to produce micro or nanocapsules of active substances, suitable for applications in many industrial sectors. To from the capsules, the technique starts from dissolutions of the shell and of the active substance. The EHD processes those fluids into capsules with a variety of shapes and structures. The shapes may range from spheres to fibres, with diameters that may vary from tens of nanometres up to tens of microns, whereas the inner structures may be porous, composite, hollow, core-shell and also, in the case of fibres, bi-channel or even multi-channel. Size, shape and structure may be tuned by adjusting the fluid properties and setting the appropriate process controlling parameters. We present a broad spectrum of examples, including some for textile, smart packaging, food and material applications, among others. References

[1] Pan N, Sun G. Functional textiles for improved performance, protection and health. Cambridge (MA): Woodhead Publishing; 2012. [2] Nelson G. Application of microencapsulation in textiles. Int J Pharm. 2002; 242:55-62. [3] Zhang Y, Rochefort D. Characterisation and applications of microcapsules obtained by interfacial polycondensation. J Microencapsul. 2012;29(7):636-649.

[4] Mart M Mart ınez V Rubio L Coderch L Parra JL. Biofunctional textiles prepared with liposomes: in vivo and in vitro assessment. J Microencapsul. 2011; 28(8):79-806. [5] Ocepek B, Boh B, Sumiga B, Tavcer P. Printing of antimicrobial microcapsules on textiles. Color Technol. 2012; 128:95-102. [6] Cheng SY, Yuen CWM, Kan CW, Cheuk KKL. Development of cosmetic textiles using microencapsulation technology. Res J Text Apparel. 2008; 12:41-51. [7] Rodrigues SN, Fern andez I, Martins IM, Mata VG, Barreiro F, Rodrigues AE.Microencapsulation of limonene for textile application. Ind Eng Chem Res. 2008; 47:4142-4147. [8] Ghosh SK. Functional coatings: by polymer microencapsulation. Weinheim: Wiley-VCHVerlag GmbH; 2006. [9] Mondal S. Phase change materials for smart textiles an overview. Appl Therm Eng. 2008; 28:1536-1550. [10] Suthaphot N, Chulakup S, Chonsakorn S, Mongkholrattanasit R. Application of aromatherapy on cotton fabric by microcapsules. Paper presented at: RMUTP International Conference: Textiles & Fashion; 2012 July 3-4; Bangkok, Thailand. [11] Specos M, Garc, JJ, Tornesello J, Marino P, Della Vecchia M, Defain Tesoriero MV, Hermida LG. Microencapsulated citronella oil for mosquito repellent finishing of cotton textiles. TransRoy Soc Trop Med Hyg. 2010; 104:653-658. [12] Yoshizawa H. Trends in microencapsulation research. Kona. 2004; 22:23-31. [13] Obeidat WN. Recent patents review in microencapsulation of pharmaceuticals using the


emulsion solvent removal methods. Recent Pat Drug Deliv Formul. 2009; 3:178-192. [14] Sliwka W. Microencapsulation. Angew Chem Int Ed. 1975; 14: 539-550. [15] Benita S. Microencapsulation: methods and industrial applications. Boca Raton (FL):CRCPress; 2006. [16] Ciriminna R, Sciortino M, Alonzo G, Schrijver A, Pagliaro M. From molecules to systems: solgel microencapsulation in silica-based materials. Chem Rev. 2011; 111:765-789. [17] Bocanegra R, Gaonkar AG, Barrero A, Loscertales IG, Pechack D, Marquez M. Production of cocoa butter microcapsules using an electrospray process. J Food Sci. 2005; 70: 492-497. [18] Bock N, Woodruff MA, Hutnacher DW, Dargaville TR. Electrospraying, a reproducible method for production of polymeric microsphere for biomedical applications. Polymers. 2011; 3: 131-149. [19] Park CH, Lee J. Electrosprayed polymer particles: effect of the solvent properties. J Appl Polym Sci. 2009;114:430-437. [20] Loscertales IG, Barrero A, Guerrero I, Cortijo R, Marquez M, Gañan-Calvo AM. Micro/nanoencapsulation via electrified coaxial liquid jets. Science. 2002;295:1695 1698. [21] Lopez-Herrera JM, Barrero A, Lopez A, Loscertales IG, M arquez M. Coaxial jets generated from electrified Taylor cones. Scaling laws. J Aerosol Sci. 2003;34:535-552. [22] Loscertales IG, Barrero A, M arquez M, Spretz R, Velarde-Ortiz R, Larsen G. Electrically forced coaxial nanojets for one-step hollow nanofiber design. J Am Chem Soc. 2004; 126:5376 5377. [23] Hwang YK, Jeong U, Cho EC. Production of uniform-sized polymer core shell microcapsules by coaxial electrospraying. Langmuir. 2008; 242446-2451. [24] Chang M, Stride E, Edirisinghe M. Controlling the thickness of hollow polymeric microspheres prepared by electrohydrodynamic atomization. J R Soc Interface. 2010; 7: 451-460. [25] Kim W, Kim SS. Multishell encapsulation using a triple coaxial electrospray system. Anal Chem. 2010; 82: 4644-4647. [26] Kim W, Kim SS. Synthesis of biodegradable triple-layered capsules using a triaxial electrospray method. Polymer. 2011; 52: 3325-3336.

[27] Nguyen TTT, Ghosh C, Hwang S, Chanunpanich N, Park JS. Porous core 6 sheath composite nanofibers fabricated by coaxial electrospinning as a potential mat for drug release system. Int J Pharm. 2012; 439:296-306. [28] Smith WC. Smart textile coatings and laminates. Cambridge (MA): Woodhead Publishing; 2010. [29] Badulescu R, Vivod V, Jausovec D, Voncina B. Grafting of ethylcellulose microcapsules onto cotton fibers. Carbohydr Polym. 2008; 71: 85-91. [30] Voncina B, Majcen Le Marechal A. Grafting of cotton with b-cyclodextrin via poly (carboxylicacid). J Appl Polym Sci. 2005; 96: 1323-1328. [31] Voncina B, Kreft O, Kokol V, Chen WT. Encapsulation of rosemary oil in ethylcellulose microcapsules. Mater Res Soc Symp. 2009; 1 :13-19. [32] Yang CQ Yiping L Lickfield G. Chemical analysis of 1, 2,3,4-butanetetracarboxylic acid. Text Res J. 2002; 72: 817-824. [33] Shore J. Cellulosics dyeing. Cambridge (MA): Woodhead Publishing; 1995. [34] Taylor JA, Pasha K, Phillips DAS. The dyeing of cotton with hetero bi-functional reactive dyes containing both a monochlorotriazinyl and a chloroacetylamino reactive group. Dyes Pigments. 2001; 51:141-152. [35] Klancnik M. Kinetics of hydrolysis of halogeno-s-triazine reactive dyes as a function of temperature. Chem Biochem Eng Q. 2008; 22: 81-88. [36] Smith EA, Chen W. How to prevent the loss of surface functionality derived from aminosilanes. Langmuir. 2008; 24: 12405-12409. [37] Kanan SM, Tze WTY, Tripp CP. Method to double the surface concentration and control the orientation of adsorbed (3aminopropyl) dimethylethoxysilane on silica powders and glass slides. Langmuir. 2002; 18:6623-6627. [38] Ping W, Jian-qing Z, Zhi-jie J, Yun-chun L, Shu-mei L. Preparation of magnetic iron 6 mesoporous silica composites spheres and their use in protein immobilization. Trans Nonferrous Met Soc China. 2009; 19: 605-610. [39] Bergna HE, Roberts WO. Colloidal silica: fundamentals and applications. Boca Raton (FL): Taylor & Francis Group; 2006. [40] Grafting electrosprayed silica microspheres on cellulosic textile via cyanuric chloride reactive groups.


Abstracts (Posters)


H i e r a r c h i c a l l y N a n o s t r u c t u r e d M e t a l O x i d e G a s

S e n s o r s

Mohammad R. Alenezi College of Technological Studies, PAAET, P.O. Box 42325 Shuwaikh, (Kuwait)

[email protected]

Hierarchical nanostructures with higher dimensionality, consisting of nanostructure building blocks such as nanowires, nanotubes, or nanosheets are very attractive. They hold great properties like the high surface-to-volume ratio and well-ordered porous structures, which can be very challenging to attain forother mono-morphological nanostructures. Well-ordered hierarchical nanostructures with high surface-to-volume ratios facilitate gas diffusion into their surfaces as well as scattering of light. Therefore, hierarchical nanostructures are expected to perform highly as gas sensors.[1-3] A multistage controlled hydrothermal synthesis method to fabricate high performance single ZnO brush-like hierarchical nanostructure gas sensor from initial nanowires is reported (Fig. 1). The performance of the sensor based on brush-like hierarchical nanostructure is analyized and compared to that of a nanowire gas sensor (Fig. 2). The hierarchical gas sensor demonstrated high sensitivity toward low concentration of acetone at high speed of response. The enhancement in the hierarchical sensor performance is attributed to the increased surface to volume ratio, reduction in dimentionality of the nanowire building blocks, formation of junctions between the initial nanowire and the secondary nanowires, and enhanced gas diffusion into the surfaces of the hierarchical nanostructures.

Figures

Figure 1: (a) Low and (b) high magnification SEM imagesof the hierarchical brush-like nanostructure; (c) a singlebrush-like hierarchical nanostructure, and (d) single nanowire gas sensor.

Figure 2: Gas response of the single hierarchical brush-like nanostructure versus the single nanowire gas sensor.

References

[1] M. R. Alenezi, S. J. Henley, N. G. Emerson, S. R. P. Silva, Nanoscale, (2014), 6, 235–247. [2] M. R. Alenezi, A. S. Alshammari, K. D. G. I. Jayawardena, M. J. Beliatis, S. J. Henley, S. R. P. Silva J., Phys. Chem. C, (2013), 117, 17850–17858. [3] M. R. Alenezi, A. S. Alshammari, T. H. Alzanki, P. Jarowski, S. J. Henley, and S. R. P. Silva, Langmuir, (2014), 30, 3913–3921.


F i n g e r p r i n t D e t e c t i o n U s i n g I n t e r c a l a t e d C d S e

N a n o p a r t i c l e s o n N o n - P o r o u s S u r f a c e s

M. Algarra1 K. Radotić

2, A. Kalauzi

2 D. Mutavdžić

2 A. avić

2, J. Jiménez-Jiménez

1, E. Rodríguez-

Castellón1, J.C.G. Esteves da Silva

3, J. José Guerrero-González

4

1Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Málaga, Campus

de Teatinos s/n 29071, Málaga, Spain. 2Institute for Multidisciplinary Research, University of Belgrade, Kneza Višeslava 1 11000 Beograd, Serbia

3Centro de Investigação em Química (CIQ-UP). Faculdade de Ciências da Universidade do PortoRua do Campo Alegre 687, 4169-007 Porto, Portugal.

4Policía Científica, Cuerpo Nacional de Policía, Málaga, Spain

A fluorescent nanocomposite based on the inclusion of CdSe quantum dots in porous phosphate heterostructures, functionalized with ami no groups (PPH-NH2 @CdSe), was synthesized, characterized and used for fingerprint detection. The main scopes of this work were first to develop a friendly chemical powder for detecting latent fingerprints, especially in non-porous surfaces; their further intercalation in PPH structure enables not to spread the fluorescent nanoparticles, for that reason very good fluorescent images can be obtained. The fingerprints, obtained on different non-porous surfaces such as iron tweezers, mobile telephone screen and magnetic band of a credit card, treated with this powder emit a pale orange luminescence under ultraviolet excitation. A further image processing consists of contrast enhancement t hat allows obtaining positive matches according to the information supplied from a police database, and showed to be more effective than that obtained with the non-processed images. Experimental results illustrate the effectiveness of proposed methods.


T h e p o s s i b i l i t y o f u s i n g h y b r i d n a n o s c o p e i n

n a n o d i a g n o s t i c s f o r s e c u r i t y a n d d e f e n s e

Gelever V. D., Manushkin A. A., Usachev E.Ju Moscow State Technical University for Radioengineering, Electronics and Automation

(MSTU MIREA), 5 Sokolinaja gora st., 22, 105275 Moscow, Russia

[email protected]

Development, application and expansion of nanotechnologies generates a complex of threats and risks to national security and human life. The main causes of these threats are small geometric dimensions of nanoparticles and as a consequence their high penetrating power, reactivity and adsorption activity. Risks in connection with the development of nanotechnology relate to the production of nanomaterials and nanosystems of different structure and composition, many of which have a dual purpose. So, there is a growing role of nanodiagnostics, which should provide the means and methods of metrological support of production processes, monitoring and research of nanostruktural objects. Because of the variety of structure and composition of nanoparticles and nanocomposites, their identification and quantitative characterization is challenging. Data about the structure and composition of nanomaterials is obtained through the use of various types of microscopes. Electron and probe microscopy allow basically get two-dimensional images and it is difficult to obtain data on the internal structure as well as to do this without the distortion caused by pretreatment of samples. Examination of the internal structure of objects and acquisition of three-dimensional images may be done by using the X-ray radiation. It practically does not interact with objects and in many cases does not require special preparation of the samples. Research can be conducted in air including the liquid phase and in a vacuum. Today, nanofocusing the x- ray microscopy is rare used because of low resolution (20 nm on the synchrotron and 50nm on the demountable X-ray tubes), high cost, large dimensions and high operating costs.

Modern research needs of the surface and structure of the objects on the micro and nanoscale are beyond the scope of а single method of research. One and the same microscope can not be equally adapted for use with the variety of objects. Combining methods allows to obtain detailed information on the chemical composition and structure of the sample using two or more methods without changing the position of the sample. To better meet the needs of nanotechnology the new hybrid instrument was developed. It's economy and modular design allows to combine the basic types of microscopes, as well as spectroscopic detectors. It is possible to change device specialization by replacement, extraction or adding the individual modules with minimal cost. The base of the hybrid is a SEM microscope in tabletop configuration, and the main element is the electron probe module, which consists of a column with an electron gun and elements of the vacuum system. Column is a system of magnetic lenses with deflecting systems inside them. To maximize the density of electron beam, a system of the lenses with the optimal focusing was applied [1]. The electron gun is beneath, and objective lenses and the objects are a top. Collection of secondary and elastically scattered electrons is conducted through the OL with the aid of the detectors in front of the OL. After the OL there is a free space, where the detectors for transmitted electrons and X-ray can be installed, as well as probe and optical microscopes , x-ray spectral detectors and other devices. Such a construction enables to investigate the same area of the object with different means. HN is focused on work with objects, that have dimensions in the range of a few millimeters. This allows on one hand to reduce the size and


manufacturing cost of the device and on the other hand - to improve the resolution by using the short-focus objective lens (OL) with small aberrations. SEM is put on a transmission X-ray microscope regime, when the target (a thin layer of metal) is installed under the electron beam on a vacuum-tight substrate, that transmits X-rays on the air to the object and the X-ray detectors. For accurate and fast focusing of the electron beam on the target a secondary electron detector is used [2], since with nanoscale electron beams due to the low X-ray intensity is almost impossible to maintain focus via x-ray detection. To increase the resolution in the x-ray near focus mode is

used micron and submicron substrate, that are used for minimizing the distance between the focal spot (the electron beam on the target) and the object. X-ray microscope operates in the projection mode, when the electron beam is placed at the target point, and the x-rays transmitted through the object is registered by the coordinate-sensitive detector. Furthermore, when scanning the beam over the target and using X-ray detectors with variable aperture one can receive X-ray image of the object, whose resolution is determined by the aperture of the detector. The use of multiple detectors allows to obtain multiple images from different angles to produce three-dimensional images.

The nanoscope utilizes the tungsten thermionic cathode operating under accelerating potential 1-HN has following main modes and parameters:

№ Name of mode Conditions Max.

resolution (nm)

1. Scanning mode in secondary electrons vacuum 2-3

2. Scanning mode in transmission electrons vacuum 1-2

3. Scanning mode in elastically scattered electrons vacuum/air 10

4. Projection x–ray mode vacuum/air 20-30

5. Scanning x–ray mode vacuum/air 50

Developed device is a set of microscopes, which allows to carry out the study of nanostructured materials quickly and by different ways in vacuum and in air over a wide magnification range from a few to several million-fold respectively at micron resolution up to atomic resolution. It is simple to operate and has a small sizes with a high degree of protection against mechanical vibration and electromagnetic interference. HN can be effectively used in the identification and quantitative characterization of the products obtained with the use of nanotechnology or containing nanomaterials. Thus, depending on the type of product one can use various combinations of the modes of operation. So, for biotechnology, medicine and pharmaceuticals it is appropriate to use a low-voltage mode at the small sizes of the device.. To work in the field a version of the device can be developed with small sizes and low power consumption. To date,

for testing the design of HN several options electron- probe modules are produced (Fig.1,2) . References

[1] Gelever, V. D. / / Izvestiya , sеr. Fizichskaya, 2000 64 (8 с. 1584. [2] Gelever V. D. Patent R № 2 452 052/ Russian/ 27.12.10.3.


Figures

Figure 1

Figure 2


U n u s u a l e f f i c i e n c y o f u l t r a f i n e s u p e r p a r a m a g n e t i c

i r o n o x i d e n a n o p a r t i c l e s f o r r e m o v i n g o f a r s e n a t e i o n s f r o m a q u e o u s e n v i r o n m e n t

Martina Kilianova, Robert Prucek, Jan Filip, Jan Kolarik, Libor Kvitek, Ales Panacek,

Jiri Tucek and Radek Zboril Regional Centre of Advanced Technologies and Materials, Slechtitelu 11, 78371 Olomouc, Czech Republic

[email protected]

Arsenate, presented at aqueous source, show high risk for human life and health. For the purpose of their removing, various technologies were discovered; one of them uses a wide offer of suitable sorption materials. Iron oxide nanoparticles as sorbents are plentifully used due their high surface area and possibility of manipulation with them using of external magnetic field [1, 2]. Economy unde manding and relatively simple method to preparation of ultrafine iron oxide nanoparticles with narrow size distribution and mesoporous character was used [3]. Prepared nanoparticles were utilized for arsenate removing from aqueous environment. Completely removing of arsenate was achieved at rati o Fe/As oncoming to 20/1 and at pH in the range of 5 to 7.6. Arsenates were totally removed with above mentioned conditions during a few first minutes of experiment. This arrangement showed the highest Freundlich absorption coefficient and balanced sorption capacity at these reaction conditions. With respect to simple and low-cost preparation of this sorbent, high yield on reaction, almost monodispersed character, superparamagnetic behavior at room temperature and st rong magnetic response using small magnetic fields, these prepared nanoparticles of iron oxide could be considered like a good candidate for removing of undesirable toxic pollutants from different aqueous systems[4, 5]. This work was formed for support of project OP VaVpI CZ.1.05/2.1.00/03.005, OPVK CZ.1.07/2.3.00/20.0056 AV ČR KAN115600801

GAČR GAP304/10/1316 and internal grant UP Olomouc PřF_2013_031. References

[1] Prucek R., Hermanek M., Zboril R., Appl. Catal. A – Gen. 366, (2009) 325. [2] Prucek R., Tucek J., Kilianova M., Panacek A., Kvitek L., Filip J., Kolar M., Tomankova K., Zboril R., Biomaterials 32, (2011) 4704. [3] Cho K. H., Sthiannopkao S., Pachepsky Y. A., Kim K. W., Kim J. H.: Water Res. 46, (2011) 5535. [4] Tucek J., Zboril R., Petridis D., Nanotechnol. 6, (2006) 962. [5] Kilianova M., Prucek R., Filip J., Kolarik J., Kvitek L., Panacek A., Tucek J., Zboril R., Chemosphere 93, (2013) 2690.


S e m i t r a n s p a r e n t s y m m e t r i c a n d a s y m m e t r i c

s u p e r c a p a c i t o r s

Francisco Martín1, CJorge Rodríguez-Moreno

1, Elena Navarrete-Astorga

1, Enrique A. Dalchiele

2,

José Ramón Ramos-Barrado1 1Laboratorio de Materiales y Superficies (Unidad asociada al CSIC), Departamentos de Física Aplicada I & Ingeniería Química

Facultad de Ciencias, Campus de Teatinos, Universidad de Málaga, 29071 Málaga, Spain 2Instituto de Física & CINQUIFIMA, Facultad de Ingeniería, Herrera y Reissig 565, C.C. 30, 11000 Montevideo, Uruguay

[email protected]

We have tried to employ common and interchangeable materials to assemble electrochemical capacitors, also known as supercapacitors. Special attention was given for these devices to be transparent or at least translucent with the perspective to achieve in the future a single device having shared materials as well as integrated functions of energy generation (solar cells) and storing of the produced energy (supercapacitor). In order to accomplish those goals, ZnO and PEDOT have been selected as common compounds to be used in the supercapacitors, because they can also form diodes.The used deposition techniques have been selected following the criterion of low-cost, easily up-scaling and friendly to ambient. We present results about to supercapacitors formed on glass/ITO subtrate of PVP, Poly (3,4 ethylenedioxythiophene) PEDOT, HEMIm[BF4], and ZnO hybrid nano- architectures with good electrochemical performance These hybrid nano-structured electrode exhibits excellent electrochemical performance, with high specific areal capacitance, good rate capability, cyclic stability and diffused coloured transparency. ZnO, In2O3, and SnO2 and their doped versions are well-known and widely used in many opto- electronic applications, transparent devices based on the transparent p–n junctions are limited to the scarce existence of p-type TCOs. On the other hand, a p-type conducting polymer as the poly(3,4- ethylenedioxythipohene) (PEDOT) doped with poly (styrenesulfonic acid) (PEDOT:PSS), has attracted considerable interest in recent years because of its low-energy band gap which makes it suitable for electro-optical

applications, its excellent electrical characteristics, inherent stability and low oxidation potential. ZnO and PEDOT were selected because its availability to form n-p heterojunction [1]. Electropolymerized PEDOT and polyvinylpyrrolidone (PVP) as a solid polymer electrolyte were used in a semitransparent glass/ITO/PEDOT/PVP-LiClO4/PEDOT/ITO/glass symmetric supercapacitor [2]. It was found that the conductivity of PVP depends on the concentration of LiClO4 but also on the residual amount of ethanol from the dip process, and it was shown that that residual amount preserves a good ionic conductivity. Thus, several PVP-LiClO4 layers were exposed to air and characterized by ATR and TGA-DSC. Furthermore, to know the stability of the supercapacitor it was studied the effect of the aging time on the performance of the capacitor. PVP binds exceptionally well to polar molecules, due to its strong withdrawing group, making this polymer behave differently to other such us PEO, PVDF, PVA, PPO, etc. Besides, PVP can be easily obtained and due to its viscosity promptly adhered to the electrode surface, making very simple to control the film thickness by dip-coating. Some addition al experimental work has been done to improve the electrochemical voltage windows as well as to enhance the maximum temperature of operation. It is well known that the energy accumulated by a capacitor depend on the square of the voltage between electrodes, so our aim is not just to enhance the specific capacity but to extend the potential window of the appliance as much as possible. Ionic liquid combined with polymers provide several benefits


to previous stated ionic salt polymer electrolyte improving the mechanical and thermal properties and incorporating non-volatility. This means that a completely compatible incorporation of ionic liquid into polymer networks has been achieved. The electrochemical window was determined in conjunction with the ionic liquid conductivity. A thermogravimetric study of the ion gels was done together with measurements of the visual transmittance of the ionic gel corroborates the improved electrochemical potential window of the new assembled symmetric PEDOT/ion gel/PEDOT supercapacitor. Potential window of the supercapacitor is improved half volt in each cycle. The improvement is shows as the energy density of electrochemical capacitor is four times greater than the PEDOT/PVP/PEDOT capacitor. 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 [3], 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 facilitate the PEDOT electrodeposition onto the nanorod. The balance between transparency and capacitance is good comparatively to other reported results in the bibliography. Adding MnO2 to the PEDOT layer improves the performance and the transparency of the device. The techniques used are easy, template-free, low cost and environmentally friendly. Supercapacitors, such as the proposed in this work, that combine good transparency and specific capacitance, are of great interest due to the wide area of applications. The aim of this work was to enhance both parameters, necessary for the development of cutting-edge technologies, i.e. electronics devices, glazing systems, etc.

References

[1] Rodríguez-Moreno J., Navarrete-Astorga E., Martín F, Schrebler R., Ramos-Barrado J.R., Dalchiele E. A.Thin Solid Films 525 (2012) 88. [2] Rodríguez-Moreno J., Navarrete-Astorga E., Dalchiele E. A., Sánchez L., Ramos-Barrado J.R.,Martín F., Journal of Power Sources 237 (2013) 270. [3] Rodríguez-Moreno J., Navarrete-Astorga E., Dalchiele E. A., Schrebler R., Ramos- Barrado J.R., Martín F, Chem. Commun., 50 (2014) 5652


T h e o r e t i c a l i n v e s t i g a t i o n o f s e m i c o n d u c t i n g ,

M e c h a n i c a l l y s t i f f d i a m o n d f i l m s o f n a n o m e t e r t h i c k n e s s

Pavel B. Sorokin, Alexander G. Kvashnin, Leonid A. Chernozatonskii and Boris I. Yakobson

Technological Institute of Superhard and Novel Carbon Materials, 7a Centralnaya Street, Troitsk, Moscow, Russian Federation

Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4 Kosygin st., Moscow, Russian Federation Rice University, Houston, Texas, USA

[email protected]

Functionalization of graphene enlarges its potential application in nanoelectronics. Total hydrogenation leads to transformation of semimetallic graphene to insulating graphane. Graphene can be considered as the first member in a series of sp3 bonded diamond films with nanometer thickness consist of a number of adjusted oriented layers with unique physical properties We investigated electronic properties of the films with different crystallographic orientation of the surface and found that in distinction from graphene diamond films display semiconductor properties with effective mass close to bulk diamond. All hydrogenated films display direct band gap with nonlinear quantum confinement response upon the thickness whereas films with clean surface display both metallic and semiconducting electronic structure depending upon the surface orientation We studied the elastic properties of the structures. We found that such films are stiff but flexible and can be elastically bent out of plane. Values of the elastic constants and the acoustic velocities of hexagonal diamond (lonsdaleite) films are higher than for cubic diamond films with the same thickness. This makes hexagonal diamond films second in stiffness only to the bulk lonsdaleite and graphene (Fig. 1). Finally we studied the stability of the diamond films with a clean surface and hydrogenated structures of various thicknesses and found the critical size at which a diamond film splits into the multilayered graphene. We investigated the chemically induced phase transition when adsorption of adatoms to

graphene leads to the formation of diamond films without the energy barrier. We obtained the phase diagram (P,T,d) of the 2D carbon films of a ɗ thickness from which the conditions of diamond films formation from the multilayered graphene can be defined. Figures

Figure 1: a) the deformation sequence for hexagonal

diamond films with 0110 surface: unloaded structure,

with indentation depth = 1.6 nm, = 3.4 nm (critical strain), and after the failure. The color variation represents the bond lengths, from red (0.168 – 0.175 nm) to yellow (0.135 – 0.155 nm); The dependence of the b)

elastic constants 11C ,

12C and c) velocities of

longitudinal νLA and transverse νTA acoustic waves of the

hexagonal diamond films with 0110 (▲), 1102 (♦)

and (0001) (■) surfaces for different number of layers (different thickness) in comparison with cubic diamond films with (111) surface (● .

References

[1] A.G. Kvashnin, L.A. Chernozatonskii, B.I. Yakobson, P.B. Sorokin, Nano Letters 14 (2014) 676 [2] A.G. Kvashnin, P.B. Sorokin, J. Phys. Chem. Lett. 5 (2014) 541.

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