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2015 Fall

Materials and devices for energy and environment applications

D

12th International Symposium on Electrochemical/ Chemical Reactivity of New Materials – „Surface Science – key to understand advanced materials”

Introduction and scope:

 

This Symposium is aimed at following the tradition already established by the previous Symposia in Warsaw (1993, 1996, 2003, 2007, 2010), Szeged (1995, 2005), Dresden (1997), Sendai (1998), Mt.Tremblant (2001) and Krakow (2012).

The symposia in 2007 and 2010 were held in Warsaw as a part of the European Materials Research Society (EMRS) - Fall Meetings in order to extend the (necessary) stimulating collaboration of chemists and physicists with material scientists. Since these events were very successful, the Scientific Committee of the cyclic Symposia has decided to continue with this Symposium to be held as one of the Symposia in E-MRS Fall Meeting 2015.

The scope of our Symposium belongs to the general topic “Surface Science – key to understand advanced materials” and is aimed at promoting various opportunities for interdisciplinary collaboration of scientists from around the world in addition to presentation of new results, ideas and technologies in the field of chemical, physical properties of novel materials including nanocrystalline, amorphous materials and various kind of thin films, coatings, layers and deposits obtained by chemical/electrochemical and physical methods.

Discussion among specialists from the areas of materials science, physics, chemistry and electrochemistry should contribute to:

  • characterizing the critical factors controlling the chemical properties of novel amorphous and nanostructured materials,
  • understanding of the chemical and electrochemical process for surface modification and activation of advanced materials to applications for catalysis, electrocatalysis, photoelectrocatalysis, energy conversion and storage and biomedical applications,
  • finding efficient, interdisciplinary processes for tailoring novel functional materials,
  • getting new insight into the chemical and electrochemical processes and mechanisms in catalysis and electrocatalysis,
  • fabrication of functional amorphous and nanocrystalline oxide films by electrochemical oxidation of metals and alloys for energy conversion (fuel cells, solar cells and batteries) and also photocatalytic decomposition of pollutants.

Topics covered by the symposium:

 

  • New perspective materials for catalysis and electrocatalysis
  • Functional nanomaterials: properties, characterization and applications
  • Chemical and electrochemical methods for surface functionalization: potential applications
  • New materials in renewable energy production
  • Solid state materials characterization - physical methods
  • Vibrational spectroscopy in “Chemistry for Materials Science”
  • Electron Spectroscopy – theory and practical applications
  • New generation of biomaterials  

Symposium opening lecture:

 

  • Philippe Marcus, Institut de Recherche de Chimie Paris, France, title to be announced soon

Invited lecturers:

 

  • Andrzej Całka, Faculty of Engineering and Information Sciences, University Wollongong, Australia, Enhanced chemical reactivity of metallic and ceramic materials in plasma environment during Electric Discharge Assisted Mechanical Milling 
  • Neil Fox, School of Chemistry, University of Bristol, UK, Diamond Materials for Energy Conversion
  • Georg Held, University of Reading, Reading, UK, Photoelectron spectroscopy under Near-Ambient-Pressure Conditions - Surface Science meets the real World
  • Pavel Jelinek, Nanosurf Lab, Institute of Physics of the ASCR, Prague, Czech Republic, High resolution AFM/STM images of molecules with functionalized tips: experiment and theory
  • Torben Rene Jensen, Department of Chemistry, Aarhus University, Aarhus, Denmark, Multi-functional Energy storage materials
  • Gediminas Niaura, Center for Physical Sciences and Technology, Vilnius, Lithuania, Electrochemical SERS characterization of functional monolayers at metal surfaces
  • Markus Niederberger, Laboratory for Multifunctional Materials, ETH Zürich, Switzerland, Controlled Synthesis and Assembly of Metal Oxide Nanoparticles over Several Length Scales
  • Marek Nowicki, Institute of Experimental Physics, University of Wroclaw, Poland, Solid-Liquid Interfaces Investigated by EC-STM and CV
  • Isao Saeki, Muroran Institute of Technology, Mechanical, Aerospace, and Materials Engineering, title to be announced shortly
  • Bartosz Such, Faculty of Physics, Jagiellonian University, Krakow, Poland, SPM study of adsorption of porphyrin-based dyes on TiO2
  • Grzegorz Sulka, Faculty of Chemistry, Jagiellonian Univeristy, Krakow, Poland, Anodic valve metal oxides - synthesis and applications
  • Jolanta Światowska, Institut de Recherche de Chimie Paris, France, Contribution of surface spectroscopic techniques to characterization of materials for electrochemical energy storage and conversion systems
  • Mikito Ueda, Faculty of Engineering, Materials Science and Engineering, Ecological Materials, Hokkaido University, Japan, Electrodeposition of Al alloys in non-aqueous liquid
  • Robert A. Varin, Waterloo Institute for Nanotechnology, University of Waterloo, Canada, Mechano-chemically synthesized novel hydride nanocomposites for low temperature hydrogen generation
  • Akiko Yamamoto, National Institute for Materials Science, Tsukuba, Japan, The effects of cells and other factors on biocorrosion of Mg and its alloys.

 

Symposium Lecturers:

 

  • Jan Augustyński, Faculty of Chemistry, Warsaw University, Warsaw, Poland, Plasmonic and electrocatalytic effects of metal nanoparticles in photoelectrochemistry
  • Sebastian Fiechter, Helmholtz-Zentrum Berlin für Materialien und Energie, Berlin, Germany, Hybrid Electrolyzers for Light Driven Water splitting - Materials for Photoelectrodes and Electrocatalysts 
  • Stanisław M. Filipek, Unipress Institute of High Pressure Physics of the Polish Academy of Sciences, Interaction of selected intermetallic compounds with hydrogen under high pressure conditions
  • Koji Hashimoto, Institute for Materials Research, Tohoku University, Sendai, Japan, Renewable energy supply in the form of methane by conversion of carbon dioxide to methane via electrolytic hydrogen generation
  • Paweł Kulesza, Faculty of Chemistry, University of Warsaw, Warsaw, Poland, Importance of specific interactions between support and active centers in efficient electrocatalysis and photoelectrocatalysis
  • Arpad Molnar, Department of Chemistry, University of Szeged, Szeged, Hungary, Homeopathic Catalysis
  • Klaus Wandelt, Institute of Physical and Theoretical Chemistry University of Bonn, Bonn, Germany, Metal/Electrolyte Interfaces: Atomic scale insights and control

 

Other confirmed lecturers:

 

  • Christine Blanc, School of Chemical Sciences and Engineering, Toulouse, France, Corrosion and Stress Corrosion Cracking behaviour of metallic alloys in relation to local metallurgical state and grain boundary misorientation
  • Saschiko Hiromoto, National Institute for Materials Science, Tsukuba, Japan, In vitro and in vivo degradation behaviour of calcium phosphate-coated bioabsorbable magnesium alloy
  • Mohamed Jouini, University Paris‐Diderot Sorbonne‐Paris, France, In situ preparation and use of conducting polymers as hole transporting material in solid state dye sensitized solar cells
  • Zenta Kato, Tohoku Institute of Technology, Sendai, Japan, Influence of the coating solution and calcination condition on the durability of Ir1-xSnxO2/Ti electrodes for oxygen evolution
  • Tomasz Kobiela, Faculty of Chemistry, Warsaw University of Technology, A new procedure for efficient roughening of gold surfaces
  • Jan Krajczewski, Faculty of Chemistry, University of Warsaw, Catalytic activity for ethanol electrooxidation of differently formed platinum layers
  • Katarzyna Krupski, Department of Physics, University of Warwick, Structural Optimization Of Titanium Dioxide of (4×1) Reconstruction for Photocatalytic Applications
  • Andrzej Kudelski, Faculty of Chemistry, University of Warsaw, Synthesis and characterisation of new types of nanoresonators for Raman analysis of surfaces
  • Nazukao Kumagai, Hitachi Zosen Corporation, Kashiwa, Japan Production of Fuel from CO₂; Methanation with CO₂ and H2 Produced from Renewable Energy
  • Małgorzata Lewandowska, Faculty of Materials Science and Engineering, Warsaw University of Technology, Corrosion resistance of nanostructured aluminium alloys - effect of grains boundaries and second phase particles
  • Krzysztof Miecznikowski, Faculty of Chemistry, University of Warsaw, Electrocatalysts for Oxidating of Polyhydric and Monohydric Alcohols to Carbon Dioxide on Platinum Alloy Nanoparticles Dispersed on Noble Metal Oxides
  • Ingrid Milosev, Institut "Jožef Stefan", Ljubljana, Slovenija, Corrosion protection of aluminium alloys by hybrid coatings as alternative to chromate protection
  • Monica Santamaria, Dipartimento di Ingegneria Chimica dei Processi dei Materiali, Universita di Palermo, Italy, The Influence of Composition on Band Gap and Dielectric Constant of Anodic Al-Ta Mixed Oxides
  • Wojciech Stępniowski, Faculty of Advanced Technologies and Chemistry, Military University of Technology, Incorporation of chelate anions, organic dyes and colloids into anodic aluminum oxide
  • Hiroyuki Takano, Hitachi Zosen Corporation, Japan, Improved catalysts for carbon dioxide methanation
  • Galina Tsirlina, Lomonosov Moscow State University, Russia, Electrodeposition of non-stoichiometric oxides as a tool to tune their functional properties
  • Melvin Vopson, Department of Earth and Environmental Sciences, University of Portsmouth, Nano-multiferroic composites for magnetic data storage
  • Piotr Żabiński, Department of non-ferrous metals, AGH University of Science and Technology, Tuning of catalitical activity for hydrogen evolution of electrodeposited cobalt alloys by superimposed magnetic field

Proceedings:

 

The Selected papers will be published as a special issue of the journal Applied Surface Science. The format, letter type and lay out will be the same as for the regular issues of the Journal. There will be no page charges. On-line submission via Elsevier’s Editorial System (EES) at http://www.ees.elsevier.com/apsusc/ is required. Deadline for submission of manuscripts will be given later.

 

Co-organizers of the Symposium (institutions, companies): 

 

 

 

Symposium code: 

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Solid State Materials Characterization : Koji Hashimoto
09:15
Authors : Philippe Marcus
Affiliations : Institut de Recherche de Chimie Paris/ Physical Chemistry of Surfaces CNRS – Chimie ParisTech Ecole Nationale Supérieure de Chimie de Paris

Resume : Recent advances in the understanding of corrosion mechanisms have been achieved by investigating the chemical and electrochemical reactivity of well defined metal surfaces at the nanoscale. This lecture will focus on recent advances in the understanding of corrosion of metals and alloys at the nanoscale, using a surface science approach. The data that will be reviewed are based on the application of advanced surface analytical techniques, such as STM, STS, XPS, ToF-SIMS, combined with electrochemical measurements, and complemented by DFT modeling. The following points will be addressed: - Tools for high resolution characterization of corrosion processes - The metal-water interface: early stages of interaction studied in situ by Electrochemical Scanning Tunneling Microscopy (on Cu, Ag, Ni single crystal surfaces) - Reactivity of grain boundaries - Passive films on metals and alloys - Passivity breakdown and pit initiation - Atomistic modeling of corrosion using DFT

D.1.1
10:15
Authors : Sandra Enengl, Christina Enengl, Marek Havlicek, Helmut Neugebauer, Kurt Hingerl, Eitan Ehrenfreund, Niyazi Serdar Sariciftci
Affiliations : Linz Institute for Organic Solar Cells (LIOS), Physical Chemistry, Johannes Kepler University, 4040 Linz, Austria; Linz Institute for Organic Solar Cells (LIOS), Physical Chemistry, Johannes Kepler University, 4040 Linz, Austria; Linz Institute for Organic Solar Cells (LIOS), Physical Chemistry, Johannes Kepler University, 4040 Linz, Austria; Linz Institute for Organic Solar Cells (LIOS), Physical Chemistry, Johannes Kepler University, 4040 Linz, Austria; Center for Surface- and Nanoanalytics (ZONA), Johannes Kepler University, 4040 Linz, Austria; Department of Physics and Solid State Institute, Technion-Israel Institute of Technology, 32000 Haifa, Israel; Linz Institute for Organic Solar Cells (LIOS), Physical Chemistry, Johannes Kepler University, 4040 Linz, Austria

Resume : Doping of organic semiconductors may lead to formation of solitons, polarons, bipolarons or 2D delocalized polarons. We show the occurrence of different kinds of polarons in poly(3-hexylthiophene-2,5-diyl) (P3HT), depending on the p-doping (oxidation) level. Cyclic voltammogram studies show several peaks belonging to different charge states. We correlate the different oxidation steps in the cyclic voltammogram with in situ transmittance UV-VIS spectroelectrochemistry. A new absorption band arises in the low doping regime, shifting with the oxidation level. These results are combined with in situ attenuated total reflection (ATR) FTIR spectroelectrochemistry, where the maximum of a broad absorption band in the mid-IR range shifts as the oxidation proceeds. Characteristic new infrared active vibration (IRAV) modes do not change much with doping level. Additionally, electron paramagnetic resonance (EPR) measurements are performed, where the EPR-signal increases at the beginning of doping and broadens significantly as we increase the doping level. Analogous results are obtained and discussed by chemical doping, using iodine as an oxidation agent. We offer a model correlating the molecular levels and electronic states of P3HT with p-doping.

D.1.3
10:30 Coffee break    
 
New Materials in Renewable Energy Production : Sebastian Fiechter
11:00
Authors : Koji Hashimoto, Naokazu Kumagai*, Koichi Izumiya*, Hiroyuki Takano*, Hiroyuki Shinomiya*, Yusuke Sasaki*, Tetsuya Yoshida* and Zenta Kato
Affiliations : Tohoku Institute of Technology, Sendai, 982-8577 Japan *Hitachi Zosen Corporation, Kashiwa, 277-8515 Japan

Resume : An increase in the world energy consumption at the current rate will lead to complete exhaustion of world fossil fuels and uranium until the middle of this century. In order to avoid the crisis of no fuels and intolerable global warming, we have been proposing and studying “global carbon dioxide recycling” since more than 2 decades ago. In global carbon dioxide recycling we supply remote intermittent renewable energy to the world in the form of methane via electrolytic hydrogen generation by using carbon dioxide as a feedstock. For realization of global carbon dioxide recycling, we needed to establish the technologies of electrolytic hydrogen generation and methane synthesis by the reaction of hydrogen with carbon dioxide captured from chimney. We electrolyzed directly seawater, creating active cathodes for hydrogen production and anodes for oxygen formation without forming chlorine. However, the energy efficiency of direct seawater electrolysis is not sufficiently high, mostly because of lower activity of oxide-coated anode in addition to the limited life of the anode. For immediate industrialization we adopted alkali water electrolysis, for which we created active cathode and anode by electrodeposition. We also created remarkably active catalyst with almost 100% selectivity of methane formation by the reaction of CO2 + 4H2 = CH4 + 2H2O from amorphous Ni-Zr alloys, and found that the active catalyst is Ni supported on tetragonal Zr1-xNixO2-x type oxide stabilized by inclusion of Ni2+ and oxygen vacancies. Using the knowledge obtained from the study of catalyst formed from amorphous alloy precursors we established the mass production method of the catalysts. Based on the creation of key materials we constructed a prototype plant of global carbon dioxide recycling in 1995 and industrial scale plants in 2003, and industrial applications are in progress since 2011 with Japanese and foreign companies.

D.2.1
11:30
Authors : Pawel J. Kulesza, Iwona A. Rutkowska, Krzysztof Miecznikowski, Adam Lewera, Sylwia Zoladek, Renata Solarska, Anna Wadas, Ewelina Szaniawska
Affiliations : Faculty of Chemistry, University of Warsaw

Resume : The most commonly considered electrocatalytic systems (e.g. for oxygen reduction) utilize precious platinum and, therefore, there is a need to minimize contents of Pt. (e.g. by activating it with certain metal oxo-species including polyoxometallates of tungsten) as well as to look for alternate molecular catalysts comprising metalloporphyrins or N-chelates combined with Ru-based chalcogenides, and bifunctional materials inducing reduction of both oxygen and hydrogen peroxide intermediate. Broad utilization of hydrogen-oxygen fuel cells would require development of effective means of hydrogen production and storage. In this context, the visible-light induced photelectrocatalytic water splitting is an important concept that will be addressed in this presentation as well. The problem of oxygen reduction is even more severe in a case of alcohol-utilizing fuel cells. In this respect, heat-treated carbon-supported macrocyclic complexes and their derivatives as well as chalcogen modified transition metals are promising and selective (e.g. methanol tolerant) platinum-free catalysts. Our research interests also concern development of systems leading to the enhancement of the carbon dioxide reducytion. We can consider here supramacromolecular complexes of palladium, platinum and copper. Among important issues are specific interactions between nitrogen coordinating centers and electrogenerated metallic sites at the active interface. Some attention will also be paid to photoelectrochemical reduction at mixed semiconducting oxides (e.g. TiO2 and Cu2O) and to specific interactions between them. When it comes to electrocatalytic oxidation, the most common Pt anodes are readily poisoned by the strongly adsorbed intermediates, namely by CO-type species, requiring fairly high overpotentials for their removal. We have recently demonstrated that catalytic activity of platinum-based nanoparticles towards electrooxidation of ethanol, dimethyl ether or methanol has been significantly enhanced through interfacial modification with ultra-thin monolayer-type films of polyoxometallates, certain transition metal oxides (TiO2), and mixed-metal oxides (e.g. ZrO2 and WO3). Among important issues is the existence of large populations of hydroxyl groups, high proton mobility and electronic conductivity, as well as specific interactions with noble metal type catalytic sites (Pt, PtRu, Rh or Ir).

D.2.2
11:55
Authors : Naokazu Kumagai,Kouichi Izumiya, Hiroyuki Takano, Tetsuya Yoshida, Zenta Kato* and Koji Hashimoto*
Affiliations : Hitachi Zosen Corporation *Tohoku Insititute of Technology

Resume : Mass consumption of fossil fuels not only induces global warming but also leads to complete exhaustion of fossil fuels. Sustainable development of the world requires the use of renewable energy. We can generate electricity from renewable energy. However, the power generated from intermittent and fluctuating renewable energy does not match well with power demand, and hence surplus electric energy storage is the serious problem. For short term storage, batteries, pumping up, compressed air, flywheel, etc. can be used. However, for storage for week or month, the conversion to synthesized natural gas, methane, is most useful. We have been studying to use renewable energy in the form of methane via electrolytic hydrogen generation for more than 25 years, creating active cathodes and effective anodes to form oxygen without forming chlorine in direct seawater electrolysis and active catalysts for rapid conversion of CO2 to methane by the reaction with H2 with almost 100% methane selectivity. Based on the success of these key materials we constructed a prototype plant for global CO2 recycling in 1995 consisting of power generation by PV, H2 production by seawater electrolysis, methane production from CO2 and H2 and methane combustion using O2 with spontaneous capture of CO2 which was sent back to the methanation system. We also constructed industrial scale pilot plant consisting of seawater electrolyzer and CO2 methanation system in 2003. During this period, Hitachi Zosen developed an alkali water electrolyzer (1973-1983. Sunshine Project), Polymer Electrolyte Membrane (PEM) type water electrrolyzer (1990-1999, New Sunshine Project) and a methanation plant for CO2 from oxy-fuel combustion furnace. After Fukushima nuclear disaster, we started a joint R & D work with a foreign company for production of synthesized natural gas by methanation of CO2 from natural gas field combined with H2 production using the electricity generated by wind power. Because the energy efficiency of H2 production by direct seawater electrolysis is not sufficiently high, for the immediate industrialization we are adopting alkali water electrolysis creating active anode and cathode. Methantion of CO2 and CO in woody biomass gasification gas is also in progress by a joint work with a domestic company. We will review these efforts at this presentation.

D.2.3
12:15
Authors : Hiroyuki Takano*, Yuki Kirihata*, Koichi Izumiya*, Naokazu Kumagai*, Hiroki Habazaiki** and Koji Hashimoto***
Affiliations : *Hitachi Zosen Corporation, Kashiwa, 277-8515, Japan; **Division of Materials Chemistry & Frontier Chemistry Center, Faculty of Engineering, Hokkaido University, Sapporo, 060-8628, Japan; ***Tohoku Institute of Technology, Sendai, 277-8515, Japan

Resume : Methane synthesis from CO2 via electrolytic hydrogen generation is one of the ultimate technologies for the use of intermittent renewable energy. We have been preparing methane from CO2 for more than 2 decades. We have found that active catalysts for CO2 methanation are Ni supported on tetragonal ZrO2 type oxide, on which rapid conversion of CO2 occurs at ambient pressure with almost 100 % methane selectivity. Tetragonal ZrO2-type oxide is formed by inclusion of cations with lower valence than Zr4+ in the ZrO2 crystal. The presence of lower valent cations induces oxygen vacancies in the oxide. The oxygen vacancies strongly attract oxygen in CO2 and lead to direct formation of methane. Thus, our catalyst is characterized by no formation of intermediate CO and no carbon deposit on the catalyst. In general, the highest catalytic activity appears at the highest content of the stabilizing element in the tetragonal ZrO2 type oxide without forming the second oxide phase of the stabilizing element. Since the valence, size and saturated amount of the stabilizing element cation are different, the catalytic activity depends on the stabilizing element included. For practical applications we have been using the catalyst consisting of Ni/Zr4+1-x-yNi2+xCa2+yO2-x-y, which shows the highest activity so far obtained. The present work was conducted to examine the possibility to find further active catalyst by adding Y as the stabilizing element. The catalyst preparation was carried out as follows: ZrO2 hydrosol with Ni(NO3) 2 and Y(NO3)3, in which the Ni content was 50 atomic % of the sum of Ni, Zr and Y at various Zr/Y ratios, was calcined at 650°C for 5 h. After pulverization of the mixture of tetragonal ZrO2 type oxide and NiO, the surface NiO was reduced under H2 stream at 400°C for 5 h. Dilution of 0.01g of the catalyst powder with 4.75g -Al2O3 powder gave rise to the catalyst powder mixture of about 5 cm3. The catalyst powder mixture was filled in a Type 304 stainless steel tube of 15 mm inner diameter and 5 cm length. The catalytic performance was examined at WHSV of 1,200 Lh-1gcat-1 of the gas mixture of 1 volume CO2 and 4 volume H2 with 10 mol % N2 at the flow rate of 0.5 Lmin-1 and at 200-400°C. The catalytic activities of Ni/Zr4+1-x-yNi2+xY3+yO2-x-0.5y catalysts of various compositions were more than twice as high as those of Ni/Zr4+1-x-yNi2+xCa2+yO2-x-y.

D.2.4
12:30 Lunch break    
 
New Perspective Materials for Catalysis, Electrocatalysis and Energy Production, 1 : Paweł Kulesza
14:00
Authors : Sebastian Fiechter
Affiliations : Helmholtz-Zentrum Berlin GmbH, Institute for Solar Fuels, Hahn-Meitner-Platz 1, 14109 Berlin, Germany

Resume : The direct conversion of sunlight into chemical ener¬gy using an artificial leaf-type structure, which is able to split water into hydrogen and oxygen, is consi¬dered as a complex research target. Most challenging is the demand to only use cheap, non-toxic and abundant elements under the condition of high electrochemical stability, life time and efficiency. One possible solution is the conversion of sunlight into chemical energy via photonic excitation of a thin film photovoltaic structure immersed in water, which is combined with corrosion-stable layers at front and back contact to catalyse water splitting. Besides novel semiconduc¬ting materials, noble metal-free catalysts are needed. For this, new semiconducting materials such as oxides and oxinitrides have to be developed possessing sufficiently high charge carriers life times of light excited electron-hole pairs. Since the mobilities in this class of materials are normally very low a nanostructuring of the absorber films is mandatory. An important second question is related to the development of electrocatalysts, especially those which can be used for the oxygen evolution reaction (OER) because this process limits the efficiency of a light driven water splitting device. We investigated electrochemically deposited manganese and cobalt oxides as cheap and earth abundant catalysts towards their activity in OER and studied their surface behavior after electrochemical treatment using an in-line system to perform X-ray photoelectron spectroscopy with synchrotron radiation. For this, the oxide electrodes were subjected to different potentials in an electrochemical cell before and after the onset of OER. After a quick removal of the electrolyte, they were transferred into ultra-high vacuum without breaking the ultrapure N2 atmosphere to study their surface characteristics. While potentiostatically deposited amorphous CoOx samples are activated by a not reversible oxidation from Co2+ via Co3+ to Co4+ already at a potential below 1.35V vs. RHE, crystalline α-Mn2O3 show a reversible transition between different oxidation states at high and low anodic potentials. The results will be compared with the electrochromic behavior of the films and their activity compared to other OER electrocatalysts.

D.3.1
14:30
Authors : Jan Augustynski
Affiliations : Centre for New Technologies, University of Warsaw

Resume : There have been numerous attempts over recent years to incorporate plasmonic metal nanostructures into photoelectrochemical (PEC) systems, either semiconductor suspensions or thin film semiconductor photoelectrodes. Although significant enhancements in photon-to-current conversion efficiencies have been claimed for some water splitting photoanodes, they generally did not translate into large net photocurrents. Tungsten trioxide, WO3, is one of few semiconductor materials that combine visible light absorption (Eg = 2.5 eV) with remarkable long-term stability as photoanode during water photoelectrolyses performed in appropriate acidic solutions. Although its band energetics, with the open-circuit photopotential of ca 0.45 V vs RHE, does not allow PEC water splitting in the absence of external bias, WO3 is well suited for the application in a tandem device, combined with a photovoltaic, PV, cell capturing longer solar light wavelengths. The principal limitations to efficient operation of such a device are low visible light absorption coefficients of WO3 related to its indirect optical transition that require use of relatively thick films to form photoanodes. To address this issue we are exploring incorporation into the photoanode of various plasmonic metal nanoparticles. Recent results demonstrate the critical importance of combining the metal NPs with capping agents to limit charge carriers recombination at the semiconductor surface.

D.3.2
14:55
Authors : Annette Delices1, Adel Jarboui1, Christian Perruchot1, Mohamed Mehdi Chehimi1, Mohamed Jouini1, Jinbao Zhang2, Lei Yang2, Nick Vlachopoulos2, Anders Hagfeldt2, Vibha Saxena3, Purushottam Jha3, Dinesh K. Aswal3.
Affiliations : 1‐ University Paris‐Diderot Sorbonne‐Paris‐Cité, ITODYS, UMR 7086, 75205 Paris 13, France. 2‐ Dept. Chemistry‐Ångström‐Laboratory, Uppsala University, Lägerhyddsvägen 1, Box‐523n SE‐75120 Uppsala, Sweden. 3‐ Technical Physics Division, Bhabha Atomic Research Centre, Mumbai 400085, India.

Resume : Conducting polymers (CPs) are generally used as hole transporting material (HTM) in dye sensitized solar cells (DSSCs) to replace the unstable HTM couple iodine/iodide (I3-/I-). But till now, CPs direct deposition is done in organic solvent which is difficult because of the high oxidation potential values of the starting organic monomers. This results in DSSCs of very low light conversion efficiency. We present a method that allowed us to perform in aqueous medium on a dye modified TiO2 electrode, in‐situ Photo electro-polymerization (PEP) using 3,4-ethylenedioxithiophene (EDOT) monomer instead of the more expensive dimer Bis‐EDOT previously used. The deposited poly(EDOT) layer is highly uniform and filled perfectly the inside of the porous dye modified TiO2 electrode. This guarantees adequate contact with the dye layer for efficient dye regeneration after electron injection into the TiO2 conduction band. Moreover, the solid state dye sensitized solar cells (ssDSSCs) prepared with Poly(EDOT) obtained from EDOT in aqueous medium show higher light conversion efficiency than those based on PEDOT obtained using EDOT in organic medium. This method is environmentally friendly, easy to implement and the cost of the solid state DSSCs can be reduced drastically when using an organic dye of low‐cost synthesis. J. Zhang et al.; J. Phys. Chem. Let. 2013, 4(23), 4026‐4031; L. Yang et al.; J Phys. Chem. C 2014, 118(30), 16591‐16601.

D.3.3
15:15
Authors : M. Tresse, C. Boulanger, D. Horwat
Affiliations : Institut Jean Lamour, Université de Lorraine, Parc de Saurupt, 54011 Nancy ; Institut Jean Lamour, Université de Lorraine, 1 Boulevard Arago, 57078 Metz

Resume : Electrochromic devices based on the mobility of sodium could be “fully ceramic” and entirely synthesized by magnetron sputtering. These devices are multilayers systems allowing a regulation of the optical transmittance. The successful combination of different functional layers in an electrochromic system requires carefully studying and optimizing the electrochemical processes in action at the interfaces between the different functional layers. This can be achieved by a combination of optical, microstructural and electrochemical analyzes of partial and complete devices. Tungsten oxide, WO3, films have potential application as electrochromic film coating due to their ability to color themselves, when a voltage is applied, by cations intercalation. Usually, protons H+ or lithium ions Li+ are used. The advantages of using sodium ion Na+ are better stability regarding humidity (no presence of protons) and use of a more efficient solid electrolyte. In order to determine the electrochromic properties of the film, electrochemical analyzes were performed on films of WO3, synthesized by sputtering on a transparent and conductive indium-tin oxide (ITO). The electrochemical monitoring during chemical intercalation of sodium ions was carried out by cyclic voltammetry and chronoamperometry in an aqueous solution of Na2SO4 (0.1M) and in ionic liquid (BePipTFSI). In addition, the in-situ evolution of the film transmittance was realized. A good reproducibility of the electrochemical and optical transitions was observed in ionic liquid while a degradation of the layers occurred in aqueous solution, probably caused by the chemical reactivity of WO3 towards water.

D.3.4
15:30 Coffee break    
 
New Perspective Materials for Catalysis, Electrocatalysis and Energy Production, 2 : Gabriele Mulas, Andrzej Kudelski
16:00
Authors : Michael Bernicke[1], Denis Bernsmeier[1], Roman Schmack[1], Bjoern Eckhardt[1], Erik Ortel[2] and Ralph Kraehnert[1]*
Affiliations : [1]Technische Universit?t Berlin, Berlin, Germany, [2] BAM - Federal Institute for Materials Research and Testing, Berlin, Germany *ralph.kraehnert@tu-berlin.de

Resume : Besides fossil fuels, hydrogen is a promising alternative candidate for chemical energy storage and can be obtained via electrolysis[1]. IrO2 appears to be a stable and active catalyst for OER (oxygen evolution reaction) and the required amount of iridium can be lowered if iridium is used in the form of mixed oxides with Titania. By utilizing Evaporation Induced Self Assembling (EISA)[2] and PEO-b-PB-b-PEO as a pore template, we studied the effect of different chemical precursors in the synthesis of mesoporous Ir/TiOx. All materials were physico-chemical characterized (SEM, TEM, XRD, electrical conductivity BET, OER and active surface area[3]). The contribution will discuss the influence of used precursors, catalyst compositions and calcination temperatures on physico-chemical, electrical and electro-chemical properties. Furthermore, important parameters for the synthesis of highly active OER catalysts will be discussed and the OER performance will be compared with commercial available OER electro-catalysts. References [1] M. Carmo, D. L. Fritz, J. Mergel, D. Stolten, Int. J. Hydrogen Energy 2013, 38, 4901-4934. [2] C. J. Brinker, Y. F. Lu, A. Sellinger, H. Y. Fan, Adv. Mater. 1999, 11, 579. [3] S. Ardizzone, A. Carugati, S. Trasatti, J. Electroanal. Chem. 1981, 126, 287-292.

D.4.1
16:15
Authors : Zenta Kato, Ryo Kashima, Kohei Tatsumi, Shinnosuke Fukuyama, Naokazu Kumagai*, Koichi Izumiya*, Yusuke Sasaki and Koji Hashimoto
Affiliations : Tohoku Institute of Technology, Sendai, 982-8577 Japan *Hitachi Zosen, Co., 11 Shintoyofuta, Kashiwa, 277-8515 Japan

Resume : IrO2-coated Ti (IrO2/Ti) has been used as dimensionally stable electrode (DSE) in electrolysis industry. We have been using Ir1-xSnxO2 as intermediate layers of oxygen evolution anode for seawater electrolysis. We found that a Mn0.929Mo0.067Sn0.004O2.067 electrocatalyst deposited anodically on Ir0.84Sn0.16O2/Ti kept 100% oxygen evolution efficiency for 4300 hours at 1000 Am-2 in 0.5M NaCl at pH 1. However, this electrode resulted in a gradual increase in the cell voltage due to the oxide growth on the titanium substrate during long-term electrolysis. The oxide growth results from inward diffusion of oxygen through electrocatalyst and intermediate layers during oxygen evolution. In a previous study, the Ir1-xSnxO2/Ti electrodes prepared by coating with a 0.04 M Ir4+-0.06M Sn4+ solution and subsequent calcination for 1 hour at 450 oC showed better performance for electrolysis in 3 M H2SO4 than IrO2/Ti prepared from a 0.1 M Ir4+ solution, indicating the beneficial effect of the tin addition to IrO2 for a barrier against oxygen diffusion. Thickening of the intermediate layer will also improve the barrier performance. In the present study we examined the effects of solution composition and calcination condition on the growth rate of titanium oxide on Ir1-xSnxO2/Ti electrodes during electrolysis in 3 M H2SO4. Preparation of Ir1-xSnxO2/Ti electrodes was carried out as follows: Chloroiridic acid and tin chloride butanol solutions in which the sum of Ir4+ and Sn4+ was 0.1, 0.26 or 0.52M were coated on the titanium substrate and calcined at 250 - 650 oC for 0.5-24 hours. The optimum condition to suppress the oxide growth was estimated from the measurement of the galvanostatic polarization curve and the potential decay curve. Among the electrodes coated with solutions in which the sum of Ir4+ and Sn4+ was 0.1M and calcined for 1 hour at 450 oC, the Ir1-xSnxO2/Ti electrodes coated with a solution consisting of 0.04M Ir4+ and 0.06M Sn4+ showed the lowest oxide growth rate of titanium. However, for the electrodes calcined for 1 hour at 450 oC the beneffical effect of Sn4+ addition faded when the sum of Ir4+ and Sn4+ was higher such as 0.26 and 0.52M. In fact, among the electrodes coated with a solution of 0.26M Ir4+ and 0.26M Sn4+ and calcined for 1 hour, the best performance was found when calcined at 450 oC. On the other hand, when a solution of 0.13M Ir4+ and 0.13M Sn4+ was used, the best performance was found after calcined for 5 hours. Consequently, although 450°C is the optimum calcination temperature, the longer calcination time is required for thicker intermediate layers for the formation of a better barrier.

D.4.2
16:30
Authors : Krzysztof Miecznikowski
Affiliations : Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw, Poland

Resume : The most important tasks in the previous as well as current century are to develop fuel cells as alternative electrochemical devices for efficient generation of energy. The low-temperature acid-type systems, such as hydrogen-oxygen polymer electrolyte membrane fuel cells and direct alcohol fuel cells are, at present, the most commonly studied devices in many laboratories world-wide. While hydrogen is the best fuel in terms of energy conversion (chemical into electrical), its production, storage and distribution has several problems. Therefore, the use of different alcohols (such as ethanol, ethylene glycol) for applications in fuel cells can also be attractive considering the higher energy content of the fuel. Up to now lot of materials have been tested as electrocatalysts for small organic molecules in acidic media, such as Pt, its alloys Pt–M (M= Ru, Sn, Rh, Pb, Ir, W or Mo) in binary or ternary form and even different methods to prepare Pt thin film electrodes. Complete oxidation of alcohols into CO2 via C–C bond cleavage is mechanistically difficult at ambient (low) temperature, and the surface of catalytic platinum readily undergoes poisoning with intermediates of the alcohols oxidation. In order to increase the overall kinetic of electrooxidation of ethylene glycol or ethanol, we propose modification of bifunctional, metallic catalyst with metal oxide. Our concept involves adsorption onto the surface of commercial available Pt alloys nanoparticles ultra-thin layers of metals oxide (WO3, MoO3, ZrO2, IrO2). Presence of metals oxide on nanoparticle have led not only to the specific interactions but also increased the catalytic surface. Introduction of noble metals oxide to Pt-based alloy nanoparticles lead to the increase of the catalytic current under voltammetric and chronoamperometric conditions.

D.4.3
16:45
Authors : P. Zabinski*, K. Mech**, S. Banbur-Pawlowska*, and R. Kowalik*
Affiliations : *AGH University of Science and Technology, Faculty of Non-Ferrous Metals, Department of Physical Chemistry and Metallurgy of Non-Ferrous Metals, al. A. Mickiewicza 30, 30-059 Krakow **AGH University of Science and Technology, Academic Centre for Materials and Nanotechnology, al. A. Mickiewicza 30, 30-059 Krakow

Resume : The properties of Co-Pd alloys for the hydrogen evolution reaction are close to the properties of pure platinum. This makes it possible to use them, for example, in fuel cells. Tests performed so far have demonstrated that the Pd-Co alloys are characterized by much better electrocatalytic properties for HER than pure palladium. Application of an external magnetic field during the deposition of an alloy causes an additional convection at the electrode surface through the magnetohydrodynamic effect (MHD), paramagnetic force and magnetic field gradient force. This additional convection results in changes of the alloy composition, structure and morphology, and these, in turn, affect the further properties as magnetic as catalytical of the produced alloys. Magnetic field applied parallel to the surface of the electrode generates convection (magnetohydrodynamic effect MHD) of the electrolyte; it results in a laminar flow on the surface of the electrode which reduces the diffusion layer and increases the concentrations gradients. This results in change of the size of the grains and thus can also influence the texture and formation of various phases of the deposits. These various effects can be caused at the same time by the above mentioned convection but also by the magnetic properties, when the field is superimposed the growth in the direction of easier magnetization appears.

D.4.4
17:00
Authors : Pardis SIMON, Nicolas ZANFONI, Ludovic AVRIL, Valérie POTIN, Luc IMHOFF, Bruno DOMENICHINI, Sylvie BOURGEOIS
Affiliations : Laboratoire Interdisciplinaire Carnot de Bourgogne - Université Bourgogne Franche-Comté - 9 Avenue Alain Savary, 21078 Dijon, France

Resume : Proton exchange membrane fuel cells are considered as a promising technology for renewable energy systems as an alternative battery for portable applications. In the past years, much attention has been given to the use of micro-electronic technology for the fabrication of on-chip miniature fuel cells with catalytic layer directly deposited on silicon substrate. In parallel, there is an increasing interest in the use of ceria-based materials for fuel cells applications. In this study, Pt-doped CeO2 nanocomposite thin films were obtained on silicon substrate (Pt-CeO2/Si) in a single step synthesis by direct liquid injection chemical vapor deposition. The morphology and chemistry of the catalyst layers were locally investigated using Transmission Electron Microscopy (TEM) with associated techniques (EDX and EELS) and X-ray photoelectron spectroscopy. It was shown that the layers grown on silicon substrate are highly porous and contain a low platinum loading. It was also found that platinum is atomically dispersed and mainly in the specific oxidation state Pt2+. Moreover, high resolution TEM measurements showed that surface cerium crystals expose {100} type nanofacets which have been predicted by model studies to work as stabilizing sites for Pt2+ species, leading to higher efficiency for fuel cell performances. The authors acknowledge financial support by the EU FP7 NMP project ChipCAT No. 310191.

D.4.5
17:15
Authors : Luisa Delmondo b, Giulia Massaglia a,b,*,Valeria Agostino a,b, Nadia Garino a, Valentina Margaria a, Adriano Sacco a, Micaela Castellino a, José A. Muñoz-Tabares a, Gian Paolo Salvador a, Tonia Tommasi a, Matteo Gerosa a,b, Caterina Armato b, Angelica Chiodoni a, Marzia Quaglioa,*
Affiliations : a Center For Space Human Robotics, Istituto Italiano di Tecnologia@POLITO, C.so Trento 21, 10129 Torino, Italy b Applied Science and technology Department, Politecnico di Torino, Corso Duca Degli Abruzzi 24, 10129, Torino, Italy * Corresponding author: gianpaolo.salvador@iit.it, Tel. +39 011 090 3451; luisa.delmondo@polito.it , Tel +39 0110903431; matteo.gerosa@iit.it, Tel. +39 011 090 3416

Resume : In the field of fuel cells one of most promising electron acceptor is the oxygen molecule but, in order to facilitate its reduction (Oxygen Reduction Reaction - ORR), a proper catalyst is needed, and platinum is considered the best one due to its high overpotential. Considering the high price and relative low abundance of platinum, alternative catalytic materials are needed: manganese oxides (MnxOy) can be considered promising substitutes. They are inexpensive, environmental friendly and can be obtained into several forms, and most of them show significant electro-catalytic performance, even if strategies are needed to make it as efficient as possible. In particular by optimizing the presence of catalytic sites, that could enhance the electrode catalytic behavior, and by developing a light material, with high surface area, we should obtain a cathode with improved electrocatalytic performances. In this case aerogels and nanofibers are two of the most promising nanostructures that can be used in the field of catalysis. In this work we propose a comparison of the ORR behavior among MnxOy aerogels, nanofibers and commercial powder. Aerogel were prepared by sol-gel technique and freeze drying to remove the liquid inside gel pores, while nanofibers were obtained by electrospinning. The different MnxOy materials were characterized by FESEM, TEM, XPS, XRD, BET, and Rotating Ring Disk Electrode. These materials are studied in the framework of a NICOP project founded by the Department of the Navy, Office of Naval Research Global, USA.

D.4.6
17:30
Authors : K.J.Krupski, A. Sanchez, A.R. Krupski , C.F. McConville
Affiliations : Katarzyna J. Krupski 1; Ana Sanchez 1; Aleksander R. Krupski 1,2; Chris F. McConville 1. 1. Department of Physics, University of Warwick, Coventry CV4 7AL, United Kingdom. 2. Faculty of Science, SEES, University of Portsmouth, Portsmouth PO1 3QL, United Kingdom.

Resume : TiO2 is a non-toxic, vide band-gap semiconductor with three different crystal polymorphs (brookite, rutile and anatase). Systems based on TiO2 have large variety of possible applications including photocatalysis, heterogeneous catalysis, electrocloric devices and solar cells for hydrogen and electric energy production. We have presented the growth optimization using PLD system with variety of growth conditions. To analyze the surface was performed measurements with using LEED, RHEED, XPS, XRD and AFM techniques. Using advance Cs-corrected scanning transmission microscopy, we have observed the atomic structures of coherent TiO2/LaAlO3 heterointerfaces in anatase TiO2 deposited on single-crystal LaAlO3. Good interfaces and flat surface are very important to further experiments with adsorption of organic molecules and industry applications.

D.DI.1
 
Poster Session I : Marcin Pisarek, Aleksander Krupski, Hiroki Habazaki
17:30
Authors : K. Mech*, M. Wróbel**, P. Żabiński***, R. Kowalik***
Affiliations : * AGH University of Science and Technology, Academic Centre for Materials and Nanotechnology, al. A. Mickiewicza 30, 30-059 Krakow ** AGH, University of Science and Technology, Faculty of Metals Engineering and Industrial Computer Science, al. A. Mickiewicza 30, Krakow *** AGH University of Science and Technology, Faculty of Non-Ferrous Metals, Department of Physical Chemistry and Metallurgy of Non-Ferrous Metals, al. A. Mickiewicza 30, 30-059 Krakow

Resume : Presented results describing properties of alloys deposited at potentiostatic conditions in Ni2+ – Pd2+ – Cl– – H2O system. Electrolysis parameters were defined based on results of thermodynamic analysis as well as voltammetry coupled with electrochemical quartz crystal microbalance (EQCM). Influence of electrode potential and electrolyte composition on deposits morphology, its structure and catalytic properties towards electrochemical hydrogen generation was investigated. Alloys were deposited at different ratios of particular Ni(II) and Pd(II) complexes concentration. pH of electrolytes was defined based on E-pH diagrams. The electrolyte was prepared by dissolution of NiCl2 · 6H2O and PdCl2 (analytical grade reagent) in previously prepared diluted HCl solution. Alloys were deposited on Cu substrate. Results indicated possibilities of electrochemical synthesis of alloys of wide composition range. Electrolyte composition as well as electrode potential play an important role in further alloys properties. Deposits structure as well as crystallites size were discussed based on results of XRD measurements. Alloys composition was determined with the use of energy dispersive spectroscopy. Morphology of alloys was characterized with the use of SEM microscopy. Electrocatalytic properties of alloys towards hydrogen generation by water molecules electroreduction in 2 M NaOH were characterized based on linear voltammetry measurements. Discussion of HER mechanism was performed.

D.DI.2
17:30
Authors : A. Ben Daly,1; F. Bernardot,2;3 T. Barisien,2;3 E. Galopin,4 A. Lemaître,4 M. A. Maaref,1 and C. Testelin2;3
Affiliations : 1Laboratoire Materiaux, Molecules et Applications, IPEST, BP 51, 2092 La Marsa, Tunis, Tunisia 2Sorbonne Universite, UPMC Universite Paris 06, UMR 7588, Institut des NanoSciences, F-75005 Paris, France 3CNRS, UMR 7588, INSP, F-75005 Paris, France 4Laboratoire de Photonique et Nanostructures, CNRS, Marcoussis, France

Resume : The influence of the temperature has been studied in self-assembled InAlAs/GaAlAs quantum dots (QDs) using photoluminescence (PL) and time-resolved PL (TRPL). With increasing temperature, the exciton retrapping in QDs, after a thermal activation, is evidenced and confi rmed by a narrowing of the PL spectrum width, and an increase of the PL decay time. From the temperature dependence of the integrate PL signal, the activation energy is estimated at 110 meV, in agreement with the electronic state in QD and wetting layer (WL) determinate by PL spectroscopy measurements. The influence of the QD size on the QD confi nement energy, is also observed in the evolution of the decay time with temperature and detection energy.

D.DI.3
17:30
Authors : Suranan Anantachaisilp,a,b Siwaporn Meejoo Smith,a Cuong Ton-That,b Tanakorn Osotchan,c Anthony R. Moon,b and Matthew R. Phillips,b
Affiliations : aDepartment of Chemistry, Faculty of Science, Mahidol University, Rama VI Rd, Bangkok 10400, Thailand. b School of Physics and Advanced Materials, University of Technology, Sydney, Broadway, NSW 2007, Australia. cDepartment of Physics, Faculty of Science, Mahidol University, Rama VI Rd, Bangkok 10400, Thailand.

Resume : The effect of native surface defects on ammonia gas sensing properties of ZnO nanorods was examined using cathodoluminescence (CL) spectroscopy, X-ray absorption near edge spectroscopy (XANES) as well as electrical and gas sensing measurements. ZnO nanorods were grown via low temperature (90C) hydrothermal method and subsequently thermal annealed at 650ºC for 30 min. in pure O2 gas and Zn vapor gaseous environments. The as-grown, O2, and Zn annealed nanorods revealed CL peaks centered at 1.90 eV (YL), 1.70 eV (RL), and 2.44 eV (GL) which are attributed to LiZn deep acceptors or O interstitials, acceptor-like VZn complexes, and donor-like VO related centers, respectively. No relationship between the RL and nitrogen impurities was not found by XANES., The ammonia gas response sensitivity was found to be 22.6 for O2 anneal (RL), 1.4 for Zn vapor anneal (GL) and 4.1 for the as-grown (YL) samples. Hydrogen plasma treatment quenched the RL and inverted the ammonia electrical response due to the incorporation of shallow hydrogen donors. Changes to the gas sensing response were attributed to a shift in the ZnO Fermi level position relative to the ammonia gas chemical potential due to the formation near surface donor or acceptor centers.

D.DI.4
17:30
Authors : Su-Bin Yang1,Byeong-Chan Jang1, Cheong Kim1, , Mi-Ra Shin1, So-Hyeon Pack2, Tae-Whan Hong2, Jong-Tae Son1*
Affiliations : 1. Department of Polymer Science and Engineering, Korea National University of Transportation, Chung-ju 380-702, Republic of Korea. 2. Department of Advanced Materials Engineering, Korea National University of Transportation, Chung-ju 380-702, Republic of Korea.

Resume : Many studies of the cathode have been promoted in order to recover low cost and non toxicity materials. In this respect, LiFePO4 which has low cost non-toxicity are promising cathode material. However, LiFePO4 has low intrinsic ionic conductivity. And the key point for solving this problem is to solve the kinetic problems associated with ionic conductivity. Many studies of nano sized materials have many attentions owing to compensate ionic conductivity. Moreover, to achieve good electrochemical performance requires a fast ionic transport associated with a high Li+ solid state diffusion coefficient . To overcome these issues, Fe ions in LiFePO4 have been substituted with metal cations such as Mn2+ which as appropriate operating voltages of 3.5-4.1 V. Because Fe-ion has larger ionic radius of Mn2+ ion facilitating a wider channel for Li diffusion which enhances the mobility of the Li ion. Numerous methods have been progressed to prepare nano-size materials. Lately, anodic aluminum oxide (AAO) templates have been received considerable attention for the growth of adjustable self organized, highly ordered nano-fibers. To enhance the electrochemical performance, we synthesized LiFe0.9Mn0.1PO4 hollow nano-rod cathode material by using the AAO template. By analyzing the FE-SEM and AFM, we obtained LiFe0.9Mn0.1PO4 nano-rod cathode material which had hollow structure resulting large surface to volume ratio. We observed electrochemical test.

D.DI.5
17:30
Authors : Byeong-Chan Jang1, Cheong Kim1, Su-Bin Yang1, Mi-Ra Shin1, So-Hyeon Pack2, Tae-Whan Hong2, Do-Man Jeon3, Dal-Woo Shin4, Rae-Cheol Kang4, Ji-Yun Park4, Hyo-Ji Han4 and Jong-Tae Son1*
Affiliations : 1Department of Polymer Science and Engineering, Korea National University of Transportation, Chung-ju 380-702, Republic of Korea 2Department of Advanced Materials Engineering, Korea National University of Transportation, Chung-ju 380-702, Republic of Korea 3Research groups, EG CORP., Chungcheongnam-do 312-943, Republic of Korea 4Institute of Technology, Korea JCC CORP., Chungcheongbuk-do 1163, Republic of Korea E-mail: jt1234@ut.ac.kr

Resume : Sodium ion batteries have attentions due to the abundance and low cost of sodium resources compared to lithium ion batteries. However, sodium ion batteries have indicated two unnecessary surface reactions into charge & discharge processes. It is decreased to the electrochemical properties of the sodium ion batteries. We attempted surface coating of cathode material using poly(3,4-ehylenedioxythiophene)-co-poly(ethyleneglycol) (PEDOT-PEG) for suppress two unnecessary reactions and improved electrochemical properties. PEDOT-PEG is used as an among conductivity polymer due to high structural stability and a high electric-ion conductivity and thermal stability. Also its coating layer suppresses the unnecessary reaction. In this work, Na[Ni0.6Co0.2Mn0.2]O2 cathode materials were synthesized by using a hydroxide co-precipitation method. And then PEDOT-PEG were coated through the stirring method. Results of PEDOT-PEG coating layers were suppress two unnecessary surface reactions. Therefore PEDOT-PEG coating layers effect were improved electrochemical properties. The morphology and coating layers of the obtained PEDOT-PEG coated materials were characterized using scanning electron microscopy(SEM) and transmission electron microscope(TEM). X-ray diffraction(XRD) measurements were also carried out in order to determine the structure of PEDOT-PEG coated materials. Electrochemical properties of PEDOT-PEG coated materials were investigated with initials charge/discharge, CV, EIS, C-rate.

D.DI.6
17:30
Authors : Demianenko A.A., Takeda Y., Oyoshi K.
Affiliations : 1 Sumy State University, Sumy, Ukraine; 2 National Institute for Materials Science, Tsukuba, Japan.

Resume : Negative ion beam Au- and high-temperature annealing for structure recrystallization of amorphous AlN-TiB2-TiSi2 coating with characteristic dimension of the short-range ordering regions 0.8-1 nm was used. As a result of high-temperature annealing and subsequent ion implantation is closest to the surface layer forms 3 characteristic zones. First one with doped implanted gold Au-, in 0-40 nm depth, with interplanar spacing 0.244 nm, 0.210 nm corresponding to some increased interplanar spacing lattice of gold planes (111) and (200) respectively. Second one with amorphous-like structural state that evidence by halo figurative type of microdiffraction, in 40-100nm depth. Thirst one with crystalline structural state, in this zone detected inhomogeneous phase , in 100-130 nm depth. Direct measurements by TEM, HRTEM, XRD and SEM with microanalysis showed that annealing at 1300?C in air results to formation of nanoscale 10-15 nm AlN, AlB2, Al2O3 and TiO2 phases, and the ion implantation causes negative ions to a fragmentation (decrease) Au- ions with nanograin sizes 2-5 nm, and to subsequent nanocrystals formation from Au- ?ball? shape with a size of a few nm and to formation of an amorphous oxide film in the depth (surface layer) of the coating due to the ballistic mixing of ions and collision cascades. Amorphous-like structure is promising in the use of such coatings as diffusion barriers in the form of separate elements or as a layer in contacting layered wear-resistant coatings

D.DI.7
17:30
Authors : 1Seung Beom Kang, 2Min Hwan Kwak, 3Jong-man Joung, 4Nam Ki Son, 5Ki-Chul Kim*
Affiliations : 1POIBOS Inc., Entrepreneurship Development Center O1-406, Mokwon University, 88 Doanbuk-ro, Seo-gu, Daejeon, 302-318, Republic of KOREA; 2Department of Electrical Engineering, Changwon Moonsung University, 91 Chunghon-ro, Changwon, 641-771, Republic of KOREA; 3Distribution Laboratory, KEPCO Research Institute, 105 Munji-ro Yuseong-gu, Daejeon, 305-760, Republic of KOREA; 4DADA Korea Co., Ltd, 86 Habinno, Daegu, 711-822, Republic of KOREA; 5Department of Advanced Chemical Engineering, Mokwon University, 88 Doanbuk-ro, Seo-gu, Daejeon, 302-318, Republic of KOREA.

Resume : In this study, we propose to use terahertz time-domain spectroscopy(THz-TDS) as a novel tool to investigate the complex dielectric and optical characteristics of degraded high voltage insulating oils in the frequency range of 0.1~ 3 THz. For the assessment of degradation, several kinds of used insulating oils in the electrical high power equipment have been characterized by THz-TDS. The degraded high voltage insulating oil showed different dielectric and optical properties compared with non-aged one. The absorption coefficients, the refractive index, the complex dielectric constants and loss tanδ of oils increased as the degradation of insulating oil proceed. The results suggest that THz-TDS is a promising tool for assessing degradation of insulating oils in the electrical high power equipment. Keywords: THz time-domain spectroscopy, insulating oil, electrical high power equipment, degradation assessment

D.DI.8
17:30
Authors : 1Seung Beom Kang, 2Min Hwan Kwak, 3Nam Ki Son, 4Ki-Chul Kim*
Affiliations : 1POIBOS Inc., Entrepreneurship Development Center O1-406, Mokwon University, 88 Doanbuk-ro, Seo-gu, Daejeon, 302-318, Republic of KOREA; 2Department of Electrical Engineering, Changwon Moonsung University, 91 Chunghon-ro, Changwon, 641-771, Republic of KOREA; 3DADA Korea Co., Ltd, 86 Habinno, Daegu, 711-822, Republic of KOREA; 4Department of Advanced Chemical Engineering, Mokwon University, 88 Doanbuk-ro, Seo-gu, Daejeon, 302-318, Republic of KOREA.

Resume : Terahertz optical and dielectric properties of AlN ceramics fabricated by hot pressed sintering are investigated by THz time-domain spectroscopy in the frequency range of 0.2 to 3.5 THz. The measured properties of the pure AlN ceramics are compared with those of Y2O3-added AlN ceramics. Two prominent resonance modes, which are essentially responsible for the dielectric properties of the Y2O3-added AlN in terahertz regime, are characterized at ωTO1/(2π)=2.76 THz (92 cm-1) and ωTO2/(2π)=18.2 THz (605 cm-1) and are well described by the pseudo-harmonic oscillator model through theoretical fitting. The resonance ωTO1 at 2.76 THz is proposed to be due to the formation of a YAG (Y3Al5O12 ) secondary phase in Y2O3-added AlN ceramic. From the experimental results, good correlation is observed between the prominent peak of YAG secondary phase at 2.76 THz and thermal conductivity. Additionally, there is a high correlation between densification and refractive index of AlN ceramics fabricated by hot pressed sintering. Keywords: THz time-domain spectroscopy, AlN, thermal conductivity, densification

D.DI.9
17:30
Authors : Malcolm Govender1, Baban Dhonge1, Herbert W. Kunert2, Bonex W. Mwakikunga1
Affiliations : 1DST/CSIR National Centre for Nano-Structured Materials, P. O. Box 395, Pretoria 0001, South Africa, 2School of Physics, University of Pretoria, Pretoria 0002, South Africa

Resume : Amorphous films of WO2.67 were synthesized by physical vapour deposition by RF magnetron sputtering a tungsten trioxide target in argon atmosphere. The films were characterized using SEM, XPS and temperature-dependent Raman spectroscopy. The films were used as the active material in conductometric-type sensing. The film’s surface reaction rate and Knudsen diffusion coefficients as a function of temperature were investigated with NO2, NH3, CH4 and CO gas. It was found that NO2 was highly reactive with the surface of the film based on the change in measured electron density and resistance of the film. The other three gases were found to favour diffusion owing to their low surface reactivity as predicted by the Knudsen diffusion constants.

D.DI.10
17:30
Authors : Yueli Liu, Linlin Wang, Chao Zhang, Wei Jin, Peng Zhou, Keqiang Chen, Wen Chen
Affiliations : State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, and School of Material Science and Engineering, Wuhan University of Technology, Wuhan 430070, P. R. China

Resume : Titanium oxide is widely used to remove both organic and inorganic pollutants from various environmental media. However, the practical application of TiO2 as a photocatalyst is limited by its wide band gap of 3.2 eV, which only absorbs the UV light below 385 nm, leading to the practical difficulty in application. The photocatalytic property of the TiO2 can be improved by the modified with V2O5 semiconductor material, and the absorption edge is extended due to the narrow band gap, which makes V2O5/TiO2 system as an effective catalytic material in photocatalytic application. In the work,TiO2 hollow spheres with nanometer size were prepared by a template method, polystyrene (PS) and tetrabutyl titanate (TBOT) were employed as template and titanium source, respectively. Then TiO2@V2O5 core-shell microspheres were prepared through a sol-gel method with calcination, and it was proved that TiO2@V2O5 core-shell microspheres were successfully synthesized by XRD patterns, SEM images as well as TEM images. The as-prepared TiO2@V2O5 core-shell microspheres were used as the photocatalyst in the degradation of gaseous benzene in UV and visible light region. It was found that the photodegradation rate of TiO2@V2O5 core-shell microspheres was greatly enhanced, especially in the visible light region. As the V2O5 shell may decrease the band gap of the microspheres, which enables to enlarge the light absorption range to produce more photo-generated electrons. Moreover, the p–n heterojunctions

D.DI.11
17:30
Authors : Chun-Fu Lu, Tse-Hsuan Lee, Chian-An Chen, P. J. Prakash Yadav, Wei-Fang Su
Affiliations : Department of Materials Science and Engineering, National Taiwan University; Department of Materials Science and Engineering, National Taiwan University; Department of Materials Science and Engineering, National Taiwan University; Department of Materials Science and Engineering, National Taiwan University; Department of Materials Science and Engineering, National Taiwan University

Resume : Increasing concerns for environment protection and human health care nowadays make detecting volatile organic compounds (VOCs) more vital due to their toxicity or explosive nature. They are extensively used in R&D research, manufacturing and daily products. VOCs detection can prevent possible damage or lessen the gravity of incidents besides using other environmental friendly and innocuous chemicals as alternatives. Sensors based on nanocomposites of poly(3-hexylthiophene) and several organic/ inorganic nanoparticles have been studied. Morphology and molecular arrangements of P3HT:PCBM thin films changes dramatically upon VOCs exposure, especially chlorides and aromatic compounds, leading to prominent optical properties changes. Fluorinated or silicone compounds are known to tend to migrate to the surface of thin films due to the low surface energy. In this work, we combine the PCBMs with different amount of fluorinated compound (FPCBM) with conjugating polymer, namely P3HT, and PCBM as sensing materials. FPCBM serves as another driving force in the nanocomposites during VOCs uptake, giving higher detecting sensitivity, i.e. faster response time and larger response as compared without FPCBM. An improvement of 5 times has been achieved than those without FPCBM for a variety of VOCs in according permissible exposure limits (PEL) by US Occupational Safety and Health Administration (OSHA). The sensing setup and mechanism are suitable for real-time sensing and on-line monitoring in general. In addition to low cost and moisture insensitive nature, this work presents an advanced technique for VOCs hazards detection in the near future.

D.DI.12
17:30
Authors : Pichanan Teesetsopon
Affiliations : Department of Physics, Faculty of Science, King Mongkut’s Institute of Technology Ladkrabang, Thailand E-mail: ktpichan@kmitl.ac.th

Resume : Zinc oxide dye-sensitized solar cells (ZnO DSSCs) were prepared by thermal stimulated N719 dye adsorption process at various temperatures and times. Current-Voltage characterization, UV-VIS spectroscopy, pH determination and electrochemical impedance spectroscopy were used to investigate both physical and chemical properties of the cells. 126 % efficiency enhancement was obtained when stimulating dye adsorption process at 50 oC for 30 minutes as compared to that of the cells prepared at room temperature. Moreover, the dye loading step was 6 times shorter compared to the highest efficient cells obtained at room temperature preparation (180 minutes). The results indicated that efficiency improvement in thermal stimulated ZnO-DSSCs was not only due to the dye loading increment but also a result of charge collection efficiency enhancement at photoelectrodes. The effect of thermal stimulating process on short circuit current density, open circuit voltage and fill factor was also explained in detail. Keywords: Charge collection efficiency, Dye adsorption, Zinc oxide, Thermal stimulating process, Efficiency enhancement

D.DI.13
17:30
Authors : Konrad Trzciński1, Mariusz Szkoda1, Katarzyna Siuzdak2, Mirosław Sawczak2, Anna Lisowska-Oleksiak1
Affiliations : 1Department of Chemistry and Technology of Functional Materials, Chemical Faculty, Gdansk University of Technology, Narutowicza 11/12, 80-233 Gdansk, Poland; 2Centre for Plasma and Laser Engineering, The Szewalski Institute of Fluid-Flow Machinery, Polish Academy of Science, Fiszera 14, 80-231 Gdansk, Poland.

Resume : The bismuth vanadate is an n-type semiconducting material that attracts great attention due to its photoactivity, especially high efficiency of water photooxidation. The relatively narrow energy band gap (Eg = 2.45 eV) makes BiVO4 competitive to other wide band gap photocatalysts e.g. TiO2 and ZnO. However, the major drawback of BiVO4 is the poor efficiency of charge carrier separation. The different strategies were applied to improve BiVO4 photoactive properties e.g. formation of p-n junction. In this work we are focused on composite formation BiVO4 - PEDOT/PSS having a character of a p-n junction. The BiVO4 layers were deposited onto the FTO using pulsed laser deposition technique and composite was fabricated via a potentiostatic electropolymerization of PEDOT/PSS on the BiVO4/FTO substrate. The presence of polymer was confirmed using Raman spectroscopy. According the UV-Vis absorbance measurements, the composite material exhibits enhanced absorbance capability in visible range in comparison to its pure counterparts. The surface morphology of films before and after polymer deposition were inspected using SEM. The photocatalytic properties of the composite materials as well as bismuth vanadate layers were examined towards the degradation of methylene blue and as well as photoanodes for water splitting process carried out under VIS illumination. Financial support from the National Science Center (2012/07/D/ST5/02269) is gratefully acknowledged.

D.DI.14
17:30
Authors : Mariusz Szkoda1, Katarzyna Siuzdak2, Mirosław Sawczak2, Jacek Ryl3, Jakub Karczewski4 Anna Lisowska-Oleksiak1
Affiliations : 1Department of Chemistry and Technology of Functional Materials Chemical Faculty, Gdansk University of Technology, Narutowicza 11/12, 80-233 Gdansk, Poland; 2Centre for Plasma and Laser Engineering The Szewalski Institute of Fluid-Flow Machinery, Polish Academy of Science Fiszera 14, 80-231 Gdansk, Poland; 3Department of Electrochemistry, Corrosion and Materials Engineering, Gdańsk University of Technology, Narutowicza 11/12, 80-952 Gdańsk, Poland; 4Faculty of Applied Physics and Mathematics, Gdansk University of Technology, Narutowicza 11/12, 80-233 Gdansk, Poland

Resume : Highly ordered TiO2 nanotubes (TNT) are the one of most investigated photosensitive materials due to their unique properties such as, photo and chemical stability, low cost, non-toxicity and high specific surface area. As a result, TNT have been used in various field, such as gas sensing, solar cells, water splitting and air purification. However, due to their large band gap of 3.2 eV, different strategies were applied to modify titania structure or surface in order to shift TNT photoactivity towards visible range. Several studies have shown that doping TiO2 with nonmetals, such as nitrogen, carbon or boron could increase significantly visible-light activity. Here, the boron doping was performed as an additional electrochemical treatment of as-sensitized TNA in 0.5 M solution of H3BO3. The obtained materials were characterized by SEM, using spectroscopic techniques (UV-Vis, Raman, XPS, photoluminescence spectroscopy) and electrochemical methods. The B-doping shifts the absorption edge of TNT to the visible light region. Under the light irradiation, the B-doped TNT layer show higher photocatalytic activity towards degradation of methylene blue than pure titania. Moreover, the simple doping of TNT leads to enormous enhancement of generated photocurrent recorded at E = 0.5 V vs. Ag/AgCl/0.1KCl from 44 µA/cm2 to 310 µA/cm2 for undoped and doped electrode, respectively. Financial support from the National Science Center (2012/07/D/ST5/02269) is gratefully acknowledged.

D.DI.15
17:30
Authors : A. I. Popov (1), I. Kudryavtseva (2), A. Lushchik (2), E. Feldbach (2), J. Zimmermann (3), E. Aleksanyan (4), A. Moskina (1), J. Purans (1)
Affiliations : (1) Institute of Solid State Physics, University of Latvia, 8 Kengaraga, LV-1063 Riga, Latvia (2) Institute of Physics, University of Tartu, Ravila 14c, 50411 Tartu, Estonia (3) Fraunhofer-Institut für Silicatforschung, Brentanostr. 2, 63755 Alzenau, Germany (4) A.I. Alikhanyan National Science Laboratory, 2 Br. Alikhanyan Str., 0036 Yerevan, Armenia

Resume : ScF3 has a simple cubic ReO3 type structure down to at least 10 K and exhibits a rare property of isotropic negative thermal expansion (NTE) over a large temperature range. In order to reveal the manifestations of the NTE effect in optical spectra, we have performed the following investigations: (a) cathodoluminescence analysis of ScF3 single crystals, (b) VUV-luminescence excitation using synchrotron radiation at MAX-Laboratory in Lund, (b) Thermally stimulated luminescence (TSL) study between 80 and 350 K, excited by an electron-beam (10 keV) or VUV radiation. From the TSL data analysis and the comparison with other metal fluorites, we can conclude that in ScF3 there is the effective self-trapping of holes in the form of Vk cen-tres and their thermal destruction occurs at about 100 K. From the creation (excitation) spectra of several TSL peaks as well as the VUV-luminescence excitation spectra, we can conclude that the value of band gap energy in ScF3 exceeds 11 eV.

D.DI.16
17:30
Authors : T. Durejko, K. Krupski, M. Łazińska, P. Jóźwik, A. Krupski
Affiliations : Department of Advanced Materials and Technology, Military University of Technology, Kaliskiego 2 Street, 00-908 Warsaw, Poland, email: tomasz.durejko@wat.edu.pl and Department of Physics, University of Warwick, Coventry CV4 7AL, United Kingdom; Department of Physics, University of Warwick, Coventry CV4 7AL, United Kingdom, email: k.j.krupski@warwick.ac.uk; Department of Advanced Materials and Technology, Military University of Technology, Kaliskiego 2 Street, 00-908 Warsaw, Poland, email: mlazinska@wat.edu.pl; Department of Advanced Materials and Technology, Military University of Technology, Kaliskiego 2 Street, 00-908 Warsaw, Poland, email: pawel.jozwik@wat.edu.pl and Department of Physics, University of Warwick, Coventry CV4 7AL, United Kingdom; Faculty of Science, SEES, University of Portsmouth, Portsmouth PO1 3QL, United Kingdom, email: aleksander.krupski@port.ac.uk

Resume : Functionally Graded Materials (FGM’s) are a new class of materials characterized by a discrete/continuous variation in properties along cross section. The concept of FGM’s has been proposed to develop heterogeneous materials with structure/properties that change discrete/continuously over their volume, in order to achieve required functions of the final component. In the present work, designing, technological and material aspects of the Laser Engineering Net Shaping (LENS) manufacturing process of continuous Fe3Al-SS316L functionally graded materials is described. At the start, model and LENS manufacturing process of the selected FGM’s component was developed. Subsequently, an experimental verification of the model and the process was carried out. It has been shown that, automatically generated Data Matrix Code (DMC) allows programming variation of the continuous chemical composition gradient in Z-direction. The microstructural and phase analysis of different areas of Fe3Al-SS316L graded materials were precisely carried out with the use of SEM, AFM, XPS, XRF, XRD, and EBSD. The influence of microstructure on the hardness behavior of the Fe3Al-316L FGMs will be presented. In addition, directly fabricated FGM samples were characterized by a continuous and proportionally change of both components and are in good accordance with the designed model’s shape.

D.DI.17
17:30
Authors : F. Laatar (1), M. Hassen (1, 2), and H. Ezzaouia (1)
Affiliations : (1) Photovoltaic Laboratory, Centre for Research and Technology Energy, Tourist Route Soliman, BP 95, 2050 Hammam-Lif, Tunisia (2) Higher Institute of Applied Science and Technology of Sousse, City Taffala (Ibn Khaldun), 4003 Sousse Tunisia

Resume : In this work, cadmium selenide nanocrystals (CdSe NCs) were embedded into porous anodic alumina (PAA) layer by simple immersion in aqueous solution containing water and L-cysteine (L-Cys) functionalized CdSe NCs. The prepared samples were annealed in air at 150, 200, 250, and 300 ?C during 30 min. The influence of thermal treatment on the microstructural and optical properties of CdSe NCs/PAA has been investigated by using SEM, AFM, EDX, XRD, Raman, UV-Vis absorbance and PL techniques. X-Ray Diffraction study shows the transformation phase of deposited CdSe nanomaterial on the PAA from cubic structure to hexagonal structure at 300 ?C. The morphological change of CdSe nanoparticles onto PAA from nanocrystals to nanorods array were exhibited by SEM and AFM images. Optical properties of CdSe/PAA have been determined using optical absorption and PL spectroscopy. The optical results showed that the crystal quality of CdSe/PAA film was improved with the increase of annealing temperature upto 300?C, bringing about an enhancement in photoluminescence and a decrease in optical band-gap from 2.44 to 2.2 eV.

D.DI.18
17:30
Authors : F.Z. Satour1, A. Zegadi1,2 and A. Merabet3*
Affiliations : 1LCCNS, Département d’Electronique, Faculté de Technologie. 2URCDO-CDTA, Campus El-Bez. 3LPMMM, IOMP. Université Ferhat Abbas SETIF 1, 19000 Sétif, Algeria.

Resume : Photoacoustic spectroscopy is a powerful non-destructive technique for investigating the optoelectronic properties of semiconductors. It is virtually unique in observing non-radiative defect populations in semiconductors; these are known to be associated with energy loss mechanisms in devices. The objective of this paper is to investigate the optical properties close to subgap region of CuInSe2 following a process of annealing in different environments at various temperatures and times. The analysis is carried out by using a high resolution fully automated near-infrared photoacoustic spectrometer of the gas-microphone. The samples used in this work are obtained from ingots grown by the vertical Bridgman technique. The absorption coefficient has been derived from photoacoustic spectra in order to determine activation energies for the defect levels. These results are finally discussed in the light of recent published data.

D.DI.20
17:30
Authors : S. Bendib1, A. Zegadi1,2 and A. Merabet3*
Affiliations : 1LCCNS, Département d’Electronique, Faculté de Technologie. 2URCDO-CDTA, Campus El-Bez. 3LPMMM, IOMP. Université Ferhat Abbas SETIF 1, 19000 Sétif, Algeria.

Resume : The finite-difference time domain method (FDTD) is used in this work to analyze the wavelength spectrum as detected at the end of two dimensional photonic crystal waveguide that contains cylindrical and annular silicon rods distributed in an air wafer. A shift of 0.0758 µm in the wavelength position of the upper band edge corresponding to a sensitivity of 758 nm/RIU was observed. A local defect has been introduced, which produced a very high shift in the cutoff wavelength corresponding to a higher sensitivity of 1490nm/RIU.

D.DI.21
17:30
Authors : Ceren Yılmaz, Burcu Topaloğlu, Ugur Unal
Affiliations : Koc University Chemistry Department; Koc University Chemistry Department; Koc University Chemistry Department, Koc University Graduate School of Science and Engineering, Koc University Surface Science and Technology Center (KUYTAM)

Resume : Photocatalysis is a promising future technology for renewable and sustainable energy challenge which includes clean energy production, decrease in the CO2 emission levels and elimination of hazardous organic pollutants with solar power. Layered Aurivillius phase Bi2WO6 has been evaluated as a new kind of photocatalyst. Although, double-layered Bi2W2O9 has been reported to display photocatalytic activity over ten times higher than Bi2WO6 for water splitting under UV radiation1, there are few reports on Bi2W2O9 photocatalyst. Layered Dion−Jacobson phase KCa2Nb3O10 is shown to catalyze photochemical water splitting. However, effect of doped lanthanide ions on photocatalytic properties is not investigated. In this work, we studied photocatalytic and photoelectrochemical properties of Lanthanide-doped Bi2W2O9 and KCa2Nb3O10 powders. Visible-light harvesting photocatalysts doped with Pr(III), Nd(III), Tm(III), Ho(III) and Ce(IV) were synthesized by solid-state synthesis and were characterized by SEM, EDX, XRD, XPS and DRS technologies. The photocatalytic activities of the photocatalysts were evaluated by the decolorization of rhodamine B under 75 mW/cm2 light. Photoelectrochemical behavior of the powders in correlation with photocatalytic activity was also investigated. Effect of dopant ion identity and dopant concentration on photocatalytic activity of the powders will be discussed. Nanosheets prepared by exfoliation of the perovskites were used to construct multi-layered thin films. Photoelectrochemical properties of thin films based on the number of layers, type of perovskite and lanthanide ion will also be covered. Authors thank TUBITAK for funding (Project No.114Z452). 1Chem. Lett. 28 (1999) 1103

D.DI.22
17:30
Authors : Beata Lejbt, Agnieszka Bielecka, Ewa Biadun, Beata Krasnodebska-Ostrega, Krzysztof Miecznikowski
Affiliations : Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw, Poland

Resume : Voltammetry is a sensitive method of metal determination, only one an alternative to ICP MS. Only one limitation of the method is an influence of the organic matrix on the measurements. After the wet digestion with H2O2 accelerated with UV irradiation the evaporation of an excess of reagent is required. The photolytic oxidation in quarts tubes with anatase or tungsten oxide were investigated. The results obtained, supported by statistical tests, demonstrated the usefulness of the stable chemically and physically TiO2 or WO3 layers as a oxidation medium. The main advantages of WO3 are related to its high stability in acid media, good charge-carrier transport properties as well as the ability to absorb a reasonable (but still not impressive) fraction of the solar spectrum. The developed digestion of surfactants without of any reagent is faster method with higher sensitivity but with same LOD. Mesoporous WO3 films having thicknesses of approximately 1.0 μm were prepared by a sol-gel technique. Physicochemical properties (structure, morphology and spectroscopic identity) of the resulting hybrid (composite) WO3 films were assessed using X-ray diffraction, scanning electron microscopy, as well as UV-Vis and Raman spectroscopies. The electrochemical method (anodic stripping voltammetric - ASV) will be applied in practical study of the determination of various trace metals in natural water samples. For comparison, GFAAS and ICP-MS measurements would be performed as reference methods confirming the correctness of electrochemical measurements due to their different tolerance to the presence of the organic matrix in the samples.

D.DI.23
17:30
Authors : Jarosław Pura(1), Piotr Wieciński(1) ,Piotr Kwasniak(1), Marta Zwolińska(1), Halina Garbacz(1), Joanna Zdunek(1), Zbigniew Laskowski(2), Maciej Gierej (1,2)
Affiliations : (1) Faculty of Material Science an Engineering, Warsaw university of Technology, Wołoska 141, 02-507 Warsaw, Poland (2 )Precious Metal Mint Poland, Weteranów 95, 05-250 Radzymin, Poland

Resume : The most common catalysts for the ammonia oxidation process are 80µm diameter platinum-rhodium wires knitted or woven into a form of a gauze. In the aggressive environment and under extreme conditions (temperature 800-900°C, intensive gas flow, high pressure) precious elements are drained from the surface of the wires. Part of this separated material quickly decompose on the surface in form of characteristic “cauliflower-shape protrusions”. In our investigation we focused on effects of the degradation of gauzes from three different industrial catalytic systems. The aim of the study was to compare the degree and the mechanism of degradation under different conditions. X-ray Computer Microtomography investigation revealed, that despite of the strong differences in morphology of the wires, each catalyst has similar specific surface area. This indicate that the oxidation process and morphological changes of the wires occur in a self-regulating balance, resulting in the value of the specific surface area of the catalyst. Scanning Electron Microscope and Focused Ion Beam observations also revealed nanostructure in cauliflower-shape protrusions and large grains in wires preserved cores. High temperature in the reactor and long-term nature of the process does not favor occurrence of the nanostructure in this type of material. Further and detailed analysis of this phenomena will provide better understanding of the precious metals etching and deposition processes during oxidation

D.DI.24
17:30
Authors : M. Starowicz, J. Banaś , M. Hajos, B. Stypuła
Affiliations : AGH - University of Science and Technology Faculty of Foundry Engineering Department of Chemistry and Corrosion of Metals

Resume : Anodic dissolution of metals in electrolytes with alcohol solvents leads to several electrochemical and chemical reactions with the formation of different compounds being the product of metal and alcohol oxidation. The process can be used for the synthesis of nanoparticles of metals, oxides and salts. Our work presents the research on the application of anodic dissolution of selected metals (Ag, Zn, Mg and Cu) in anhydrous alcohol (methanol ethanol, propanol) and in mixed water-alcohol solutions for production of nano- and micro particles of metal (Ag) and oxides (Zn, Mg and Cu). Generally, the electrochemical behaviour of metals in alcohol solution of electrolytes is similar to their properties in aqueous media. The process proceeds with the participation of solvent and anions. Alcohol molecules plays a very important role in the anodic reaction. These molecules undergo competitive adsorption on the metals surface and participate in dissolution process, forming soluble alcoxides or alcoxy – chloride complexes of the general formula M[(OR)xCly]-n).]. At low potential values metal nanoparticles are formed due to disproportion reaction in the bulk solution, while at higher overvoltage, as a result of the secondary reduction process after dissolution of metal electrode proceeding parallel to alcohol oxidation. In the presence of small amount of water, soluble product (M[(OR)xCly]-n), may be a precursor of hydrolysis reaction leading to the formation of oxide nanoparticles. The formation of these nanoparticles in investigated environments was confirmed by means of spectroscopic and diffraction analysis (TEM, SEM / EDS, XPS) of anolytes.

D.DI.25
17:30
Authors : A.Mikolajczuk-Zychora1, A.Borodzinski1, P.Kedzierzawski1, B.Mierzwa1, M.Mazurkiewicz2, E.Ciecierska2, A.Zimoch1, M.Opallo1
Affiliations : 1) Institute of Physical Chemistry PAS, Warsaw, Poland 2) Faculty of Materials Science and Engineering, Warsaw University of Technology, Warsaw, Poland

Resume : We present the synthesis of highly active palladium catalysts for electro-reduction of oxygen in direct formic acid fuel cells. The catalysts were prepared by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as reducing agent. The palladium ions were reduced on the carbon black (Vulcan) or multiwall carbon nanotubes (MWCNTs) surface. The supports were either treated in nitric acid for 4 hours at 80ºC, or used as received. The structure of prepared catalysts has been characterized by TGA, XRD and HR-TEM. The catalysts were used at the cathode in direct formic acid fuel cell (DFAFC). The catalysts, which were prepared on functionalized supports show higher activity in the cathode in DFAFC than catalysts prepared on raw supports. Our results indicated that treatment of carbon support in nitric acid(V) has influenced the activity of the catalysts. The palladium catalyst supported on Vulcan, which is refluxed in nitric acid(V) for 4 hours at 80ºC, shows the best specific power in direct formic acid fuel cell. The specific power for the best Pd/Vulcan catalyst is comparable to the commercial 20% wt. Pt/Vulcan (Premetek). The increased activity of catalysts, which supports were functionalized, may be due to removal the surface impurities from supports during their treatment in nitric acid for 4 hours at 80ºC or due to the presence of crystallographic index planes of palladium, which are preferred for electro-reduction reaction of oxygen.

D.DI.26
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Solid State Materials Characterization and Electron Spectroscopy, 1 : Aleksander Krupski, Marcin Pisarek
09:00
Authors : Georg Held
Affiliations : University of Reading and Diamond Light Source

Resume : The last decade has seen a vast increase in the use of XPS under near-ambient pressure conditions due to advances in the design of differentially pumped electron analysers [1]. Both synchrotron and laboratory-based instruments can now routinely measure XP spectra in the mbar range. The first part of the talk will discuss key design features and address problems specific to heterogeneous catalysis and environmental science. In the second part I will report results of recent studies on model catalysts for hydrogenation and oxidation reactions. These experiments show remarkable differences, both between near-ambient-pressure and UHV [2,3] and between nanoparticles and single/poly crystals [4]. [1] D. E. Starr, et al. Chem. Soc. Rev., 2013, 42, 5833—5857. [2] A. Shavorskiy, et al. JACS 133 (2011) 6659 – 6667. [3] R. E. J. Nicklin, PhD thesis, Reading, 2014 [4] R. Price, et al. submitted to Topics in Catalysis

D.5.1
09:30
Authors : Jolanta Światowska
Affiliations : PSL Research University, Chimie ParisTech - CNRS, Institut de Recherche de Chimie Paris, 11 rue Pierre et Marie Curie, 75005 Paris, France

Resume : Understanding the electrode processes occurring at the electrode/electrolyte interface and in the bulk electrode material is necessary for developing the electrochemical performances of lithium-ion (LIB), sodium-ion, sulfur or metal-air batteries. The main electrode processes are insertion/extraction reactions that induce changes in the host electrode materials; they are accompanied by decomposition of electrolyte that leads to formation of a solid electrolyte interphase (SEI) layer on the electrode surface. Two principal surface-sensitive techniques, particularly suitable for analyzing these processes are: X?ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Our approach is to use model, nanometer-thick electrodes with a good surface finishing with a minimum roughness. New types of high capacity negative-electrode materials having a potential application in LIB will be presented: a conversion-type electrode consisting of iron oxide and an alloying-type electrode consisting of silicon. Apart the chemical composition of the SEI layer formed on the surfaces of these electrodes, the evidence of a dynamic increase/decrease of SEI upon lithiation/delithiation, and surface modifications upon cycling will be discussed. The irreversible chemical bulk modifications and volume changes of the electrode materials will be also evidenced by ToF-SIMS ion depth profiles. These modifications are detrimental to performance of battery cycle life.

D.5.2
10:00
Authors : C. Deeks, J. J. Pireaux, P. Louette, P. Mack, T. S. Nunney
Affiliations : Thermo Fisher Scientific; University of Namur; University of Namur; Thermo Fisher Scientific; Thermo Fisher Scientific

Resume : Sensors for biological compounds are becoming increasingly important in a wide variety of applications. These devices are typically composed of complex stacks of thin/ultrathin layers of biochemical compounds. The overall behaviour of the sensor is strongly influenced by the elemental and chemical properties of the individual layers, but the interactions at layer interfaces may also have an effect. There is an increasing requirement for compositional profiling of these devices, combining the chemical selectivity and surface specificity of XPS with some kind of ion beam sputtering. Traditional methods such as argon monomer ion profiling can result in a high degree of chemical modification during the acquisition of depth profiles for organic materials. Over the last few years, there have been numerous studies and investigations into the use of argon cluster beams for depth profiling with the goal of preserving chemical information during analysis of organic materials. Recent investigations have also found argon cluster ions to be able to profile through hard inorganic materials, while still preserving the chemical information. This talk will present data from cluster profiling studies of amino acid based biosensors. The chemical variation between amino acid layers is very subtle, but it will be demonstrated that the combination of rapid acquisition XPS and argon cluster profiling is able to characterise the changes in chemistry throughout the layer stack.

D.5.3
10:15
Authors : Pavel V. Krasovskii (1), Olga S. Malinovskaya (2), Andrey V. Samokhin (1), Yury V. Blagoveshchenskiy (1), Valery А. Kazakov (2), Artem А. Ashmarin (2).
Affiliations : (1) A.A. Baikov Institute of Metallurgy and Materials Science, Russian Academy of Sciences, Leninskii pr. 49, Moscow 119991, Russia; (2) SSC Keldysh Research Centre, Onezhskaya 8, Moscow 125438, Russia.

Resume : The analytical studies are presented on the chemical composition and bonding in the near-surface region of the nanophase tungsten carbides, particularly in connection with their promising uses in catalysis and hardmetal industry. The materials are produced through a DC thermal plasma technology that has reached a significant level of development and upscaling. The analytical information has been primarily gathered using X-ray photoelectron spectroscopy (XPS). The XPS analysis was combined with Raman spectroscopic, HRTEM, and thermal evolution studies. The analytical work resulted in a distinction between the major surface conditions for the nano-WC, including that equilibrated with the bulk. The analytical determinations concerned the nature/thickness of the surface segregations of carbon, the coverage/bonding of adsorbed oxygen, the effect of the average bulk stoichiometry on the surface composition, etc.

D.5.4
10:30 Coffee break    
 
Solid State Materials Characterization and Electron Spectroscopy, 2 : Aleksander Krupski
11:00
Authors : Pavel Jelinek
Affiliations : Nanosurf Lab, Institute of Physics of the AS CR, Prague, Czech Republic

Resume : The recent progress in Atomic Force Microscopy (AFM) and Scanning Tunneling Microscopy (STM) using functionalized tips provided unprecedented atomic resolution of single organic molecules [1,2]. Here we will provide insight into the origin of the high-resolution AFM/STM images [3]. We will show that the mechanism could also stand for atomic resolution observed in electrochemical STM [4] or high-resolution STM images taken in contact mode [5]. We will also briefly discuss what other information can be gained from the high-resolution AFM/STM images going beyond the simple imaging of chemical structure. [1] L. Gross et al., Science 325,1110 (2009). [2] C. Weiss et al., Phys.Rev.Lett. 105, 086103 (2010). [3] P. Hapala et al., Phys. Rev. B 90, 085421 (2014); P. Hapala et al., Phys. Rev. Lett. 113, 226101 (2014). [4] P. Broekmann, M. Wilims, K. Wandelt, Surf. Rev. Lett. 06, 907 (1999) [5] J.A. Stroscio, R.J. Celotta, Science 306, 242 (2004).

D.6.1
11:25
Authors : B. Madry (1), K. Wandelt (1,2), M. Nowicki (1)
Affiliations : (1) Institute of Experimental Physics, University of Wrocław, Pl. M. Borna 9, PL 50-204 Wrocław, Poland (2) Institute of Physical and Theoretical Chemistry, University of Bonn, Wegelerstrasse 12, D-53115 Bonn, Germany.

Resume : The co-adsorption of submono-, mono- and multi-layers of Cu with sulfate anions on a Au (111) electrode surface was investigated in electrochemical environment (0.1 mM CuSO4 0.1 M H2SO4) by cyclic voltammetry (CV) and in-situ scanning tunneling microscopy (STM) [1,2]. Correlated with the STM investigations the CV measurements indicate co-adsorption/desorption processes of Cu of submono-, mono- and multi-layer coverages with sulfuric acid species on Au (111). The formation of a quasi-hexagonal Moire superstructure on terraces of copper multilayers was observed in situ by STM. In detail the observed Moire-structure is similar but not identical to the one observed on the (111) surface of bulk copper [3,4]. Kinks of terrace edges correspond to single units of the Moire mesh. The mean periodicity lengths of the Moire-structure in different directions as well as angles between these directions indicate distortions within the Cu surface, which exhibits characteristic domains. High resolution STM images show the formation of a root (3) xroot (7) -like sulfate structure on all multilayer copper terraces. The interfacial Cu-Au alloy formation is suggested at negative potentials and copper coverages higher than 1ML. [1] B. Madry, K. Wandelt, M. Nowicki, Surf. Sci. 637-638 (2015) 77. [2] B. Madry, K. Wandelt, M. Nowicki, in preparation. [3] M. Wilms at al., Surf. Sci. 416 (1998) 121. [4] P. Broekmann at al., in: Topics in Applied Physics, Vol. 85, Springer, 2003, p.141

D.6.2
11:50
Authors : J. Zapała (1), T. Jaroch (1), E. Kurach (2), K. Kotwica (2), M. Góra (3), M. Salamończyk (3), E. Górecka (3), D. Djurado (4), M. Zagórska (2), A. Proń (2), R. Nowakowski (1)
Affiliations : (1) Institute of Physical Chemistry, Polish Academy of Sciences, Warsaw, Poland; (2) Faculty of Chemistry, Warsaw University of Technology, Warsaw, Poland; (3) Faculty of Chemistry, University of Warsaw, Warsaw, Poland; (4) CEA Grenoble, INAC/SPrAM, Grenoble, France

Resume : The important advantage of organic electronics is a wide possibility of precise tuning of electronic and optoelectronic properties of organic semiconductors by chemical modification of their molecular structure. This can be done by combining appropriately designed electron accepting and electron donating segments in one molecule. However, the another factor which seriously influences the final properties of electroactive organic layers (for example charge transport) is supramolecular interactions between molecules, resulting in their self-assembly in 2D and 3D. In this work we will present results of comparative STM investigations of donor-acceptor-donor type semiconductors, consisting of central acceptor group of different strength (either tetrazine, thiadiazole or diketopyrrolopyrrole) symmetrically substituted with thiophene donor groups. 2D supramolecular organization of these molecules, which consist of five parts of different nature (one acceptor group, two donor groups and alkyl substituents) is a consequence of mutual interactions between these parts in neighboring molecules as well as with the substrate (HOPG). The influence of (i) investigated electron acceptor groups, and (ii) different positions of the alkyl substituents on self-organization in monomolecular layers will be discussed. Moreover, a comparative study of 3D organization, deduced from the X-ray diffraction patterns, will be also presented clearly confirming the polymorphism for some studied adsorbates.

D.6.3
12:05
Authors : Łukasz Zając, Piotr Olszowski, Szymon Godlewski, Bartosz Such, Res Jöhr, Thilo Glatzel, Ernst Meyer and Marek Szymonski
Affiliations : Jagiellonian University, Department of Physics, Lojasiewicza 11, 30-348 Krakow, Poland; University of Basel, Department of Physics, Klingelbergstrasse 82, 4056 Basel, Switzerland

Resume : Interaction between an adsorbate and a substrate is not only dependent on their chemical identity but also on their geometric properties. In the presentation we will explore the adsorption behavior of carboxylic-substituted Zn-porphyrins on rutile (110) and (011) surfaces. The proposed surfaces are among the most stable orientations of rutile crystal and both form anisotropic reconstruction after treatment in UHV conditions. However, the position of titanium atoms in both structures are different – considerably easy access of an adsorbate to such atoms in (110) makes the surface quite reactive while for (011) orientation their position renders the surface much less reactive. Carboxylic group is the main choice when anchoring of organic molecules on titania surfaces is concerned. We will use them to anchor Zn-porphyrines – molecules relevant to applications such as construction of dye-sensitized solar cells. Moreover, in order to tune the adsorption the molecules can be equipped in various number of carboxylic groups. The forming of an ad-layer will be presented from the level of single molecule adsorption up to the coverage of two monolayers. We will show how the morphology of the resulting overlayer depends on the structure of the substrate and molecule and what the mechanisms leading to the molecular organization are.

D.6.4
12:30 Lunch break    
 
Vibrational Spectroscopy in "Chemistry for Materials Science" : Robert Nowakowski
14:00
Authors : Gediminas Niaura; Ieva Matulaitiene, Zenonas Kuodis, Olegas Eicher-Lorka
Affiliations : Department of Organic Chemistry, Center for Physical Sciences and Technology, Gostauto str. 9, LT-01108 Vilnius, Lithuania

Resume : Structure and function of adsorbed molecules at electrode/solution interface critically depends on the electrode potential. Electrochemical surface enhanced Raman spectroscopy (EC-SERS) was used to probe bonding, orientation, and interaction with solution components of adsorbed molecules at gold, silver, and copper surfaces. Formation of metal-adsorbate bond between the imidazole ring and copper was evidenced by 63Cu/65Cu isotopic frequency shift and theoretical modeling. Potential-induced modulation of chemical bonding resulted in linear dependence of C=C stretching mode of imidazole ring on potential with slope of 15 cm-1/V. Marker bands for structure and orientation of positive charge bearing self-assembled monolayer of N-(6-mercapto)hexylpyridinium (MHP) were evaluated. The metal-sulfur stretching bands were assigned by combined EC-SERS and DFT modeling. Electrostatic attraction of inorganic anions and graphene oxide by MHP was revealed. It was found that peak position of surface bound anions shifts to lower wavenumbers comparing with the solution spectrum. Linear potential-wavenumber dependence was demonstrated for both D- and G-bands of adsorbed GO at MHP with slopes of 4.7 and 5.9 cm-1/V, respectively. Interaction of methylene groups with metal surface was revealed for both adsorbed peptides and self-assembled monolayers at lower surface coverage by appearance of unusually low frequency soft CH stretching mode (2820-2835 cm-1) in potential-difference spectra.

D.7.1
14:30
Authors : Jan Krajczewski, Heman Burhnalden Abdulrahman, Karol Kołątaj, Sylwia Parzyszek, Andrzej Kudelski
Affiliations : Department of Chemistry, Warsaw University, Pasteur 1, PL-02-093 Warsaw, Poland

Resume : When electromagnetic radiation interacts with some metal nanoparticles, collective electron charge oscillations are excited. Oscillations of electrons leads to the appearance of enhanced near-field amplitude at the resonance frequency. This field is highly localized at the nanoparticle and decays rapidly away from the nanoparticle/dieletric interface. In this contribution we show examples of synthesis and applications of metal nanoparticles based on the enhanced near-field amplitude (which is due to the mentioned above surface plasmon resonance). For example, we showed that light-induced transformations of silver nanoparticles may be used for creation of nanoaggregates, which are very efficient nanoresonators for surface-enhancement Raman scattering (SERS) measurements. The first example of plasmon-driven transformation of silver nanoparticles in the oxygen-free conditions will be presented. We also realized Raman analysis of various surfaces using hollow-silver and hollow-gold nanoparticles protected by the silica layer. In contrast to solid spherical gold nanoparticles typically used for construction of nanoresonators for such surface measurements, for which a change of the diameter of the nanoparticle causes only a small change of the position of its plasmon band, the plasmon band for hollow spherical gold nanoparticles can be changed within broad range of the visible electromagnetic radiation.

D.7.2
14:45
Authors : T.Kobiela, W.Fabianowski
Affiliations : Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland

Resume : Recently an increased demand has been observed for roughened gold films. These gold structures exhibit not only the novel physical properties, but are commercially used in the electronic devices, catalysts and sensors. Biocompatibility, high conductivity and chemical resistance make these Au films also a perfect platform for building functional biosensors [1]. Vacuum deposition techniques, such as sputtering, do not have capability for selective deposition or effective roughening. In contrast, bottom-up chemical methods are simple and flexible, and therefore, they are highly attractive and widely used. We present a new method for roughening gold electrodes that uses physical methods that are well known in the semiconductor industry – operations involving vacuum and high temperatures. Au thin films are treated in vacuum with mercury vapors resulting in formation of gold amalgamate. The amalgamate is then thermally decomposed at high temperature in vacuum which results in a complete removal of mercury and all Au is recovered in the form of rough Au surface. There is no need to use any additional chemicals, in contrast to other processes for seeding and growth of Au clusters or nanorods. The entire process is controlled by technological parameters i.e. the pressure; the temperature and the time. The shape and the size of gold structures depend on the density of local defects on the surface [2]. Thus, as practical implementation, amalgam formation followed by its thermal decomposition on pre-patterned surfaces enables large-scale fabrication of organized structures consisting of separate size-selected Au structures. Other applications for roughened gold films involve photovoltaics [3], where higher and roughened surface area means more effective light trapping and therefore higher efficiency of solar cells. [1] M.Mierzwa, W.Fabianowski, L.Gorski, T.Kobiela, J.Electronal. Chem., 735, 63 (2014) [2] T. Kobiela, Z. Kaszkur, R. Duś, Thin Solid Films, 478, 152 (2005), [3] H. Yamada, H. Imahori., Y.Nishimura., I.Yamazaki. et al., J Am Chem Soc. 125, 9129 (2003)

D.7.3
15:00
Authors : Charusheela Ramanan, Sabrina Jüchter, Enrico Da Como, Elizabeth von Hauff
Affiliations : VU University Amsterdam; VU University Amsterdam; University of Bath; VU University Amsterdam

Resume : Photocurrents in organic solar cells are inherently limited by the poor electrical properties of the active layer. Strategies to increase the power conversion efficiency of polymer:fullerene solar cells include incorporating an organic dopant to fill trap states. We doped a donor-acceptor polymer with a molecular dopant and observed a subsequent increase in charge separation efficiency and photocurrents, which could be correlated to a decrease in recombination and an increase in hole mobility in the donor phase. To date, the influence of the dopant on the morphology of the polymer phase in the active layer has been largely ignored in these systems. Deconvoluting the effects of morphological variations and charge transfer induced by the dopant are crucial to understanding the potential of doping in organic electronics. We utilize both optical and electrical techniques to explore these different. With impedance spectroscopy, we probe charge-carrier dynamics at different operational points in the current-voltage characteristics. Raman spectroscopy gives further insight into morphological characteristics of the polymer. These results will be discussed in the context of correlating the optical and electrical characterizations for this and other device designs.

D.7.4
15:15
Authors : Elena Florentina Grosu1 Ken Eichi Katsumata, Kei Ikeda2, Gabriela Carja1
Affiliations : 1 Department of Chemical Engineering, Faculty of Chemical Engineering and Environemntal Protection, Tecnhical University “Gh. Asachi” of lasi, Bd. Mangeron no.71, Iasi 700554, Romania 2 Materials and Structures Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama, 226-8503, Japan

Resume : Self-assemblies of nanoparticles of gold and the anionic clay matrices of layered double hydroxides (LDHs) were fabricated using the manifestation of the structural memory effect of the LDHs in AuCl3 aqueous solutions, at room temperature [1]. We used specific compositions of ZnCeAlLDHs containing Zn2+, Ce3+ and Al3+ + as cations in the LDHs layers. Controlled thermal treatment of Au/LDHs assemblies gave rise to the complex systems of nanosized mixed oxides. Powder X-ray diffraction (PXRD), high resolution transmission electron microscopy (TEM, see Figure 1), Fourier transform infrared spectroscopy (FTIR) and UV-Visible spectroscopy (UV-Vis) were used to investigate the structural, composition and size-morphology characteristics of the Au/ZnCeLDHs. Results point out that Au/LDHs nanoarchitectonics consists of small nanoparticles of Au that are highly dispersed on much larger nanoparticles of the LDHs while the composition of the evolved mixtures of mixed oxides is a function of the composition of the LDHs precursor. UV-Vis analysis indicates specific plasmonic responses of Au nanoparticles under Vis and UV light revealing the photo-cooperativity of the components in the nanostructured gold-clay system. X-ray photoelectron spectroscopy (XPS) was used to investigate the state of gold on the surface of the specific LDH matrices. Acknowledgment: The authors are grateful for the financial supports from the Romanian National Authority for Scientific Research, CNCS-UEFISCDI (PN-II-ID-PCE-75/2013), the Kazuchika Okura Memorial Foundation, “Planting Seeds for Research” program from Tokyo Institute of Technology, “Grant-in-Aid for Young Scientists (A; 25708037)” from Japan Society for the Promotion of Science (JSPS), and by the project “Development Base of Advanced Materials Development and Integration of Novel Structured Metallic and Inorganic” of the Ministry of Education, Culture, Sports, Science, and Technology (MEXT), Japan. 1. S. Kawamura , M. C Puscasu, Y. Yoshida, Y. Izumi, G. Carja, App. Cat. A, in press DOI: 10.1016/j.apcata.2014.12.042.

D.7.5
15:30 Coffee break    
 
New Perspective Materials for Catalysis, Electrocatalysis and Energy Production,3 : Piotr Żabiński, Grzegorz Sulka
16:00
Authors : Gabriele Mulas 1, Sebastiano Garroni 1, Elisabetta Masolo 1, Stefano Enzo 1, Francesco Spanu 1, Elisa Tolu 1, Maria Dolores Barò 2, Eva Maria Pellicer 2, Jordi Sort 2
Affiliations : 1 Department of Chemistry and Pharmacy, University of Sassari and INSTM, Via Vienna 2, I-07100 Sassari, Italy 2 Departament de Física, Universitat Autònoma de Barcelona, E-08193 Bellaterra, Spain

Resume : The expected widespread diffusion of several energy related technologies relies upon the development of innovative materials, which could allow overcoming some current limitations. New chemical compositions as well as structural and thermodynamic conditions are then explored in order to develop and improve the properties different devices for energy storage and conversion including secondary batteries, supercapacitors, hydrogen production and storage systems, fuel cells, piezoelectric devices. To this regard is recent the attention to nanosized materials confined within mesoporous matrices which combine thermodynamic metastability with several advantageous morphological features as high surface area, pore diameter between 2-50 nm, good corrosion resistance etc. We focus here on the synthesis and the applicative properties of new materials related to the above cited technologies. A series of mesoporous materials were synthesized by sol-gel methods, using EISA (Evaporation Induced Self-Assembly) and Hard Templating approaches. Composite systems were also prepared by melting infiltration or wet impregnation of nanosized phases within the porous matrixes. A detailed characterization of the prepared material and the investigation of their reactivity and applicative properties is fulfilled through a number of instrumental techniques.

D.8.1
16:15
Authors : A. Gómez-Núñez, E. Máñez, C. López, A. Vilà
Affiliations : Department of Electronics, University of Barcelona, Martí i Franquès 1, E-08028-Barcelona, Spain. ; Department of Electronics, University of Barcelona, Martí i Franquès 1, E-08028-Barcelona, Spain. ; Departament of Inorganic Chemistry, University of Barcelona, Martí i Franquès 1. E-08028-Barcelona, Spain. ; Department of Electronics, University of Barcelona, Martí i Franquès 1, E-08028-Barcelona, Spain.

Resume : Inkjet printing is a noncontact deposition method. The characteristics and performance of the inks must be suitable to use with an inkjet printing technique, through which patterns are made by selective deposition of materials in a specific region, reducing both the processing time and the materials needed substantially. Consequently, the manufacturing cost is reduced. ZnO is an important n-type semiconductor due to its wide range of applications. The trend in published articles is the use of amino alcohols as additives in the sol-gel method to obtain ZnO. One of the most used stabilizers in the literature is Ethanolamine (EA). This compound stabilizes Zn(II) but increases its photoreactivity, leading to a destabilization. Furthermore, high temperatures are required to get rid of the nitrogen of inks and making the isolation of pure ZnO a challenge. We achieve pure ZnO by the sol-gel method through a sustainable novel green synthetic strategy minimizing the use of toxic materials. The aim of this work is to present new procedures and methods to prepare the inks, based on the use of nitrogen-free precursors and ecologically compatible reagents. This allows us to achieve environmentally friendly inks by using new zinc oxide precursors with a clean decomposition process.

D.8.2
16:30
Authors : Sylvain Regny, Meriem Lamouchi, Cédric Desroches, Arnaud Brioude, Mathieu Maillard
Affiliations : Laboratoire des Multimatériaux et Interfaces, UMR 5615, CNRS-Université Lyon 1 43 bd du 11 Novembre 1918, F-69622 Villeurbanne, France

Resume : This work relates to a large scale synthesis of gold-titania core shell nanoparticles and their application to photo-activated reactions. Nanoparticles have been synthesized using an innovative process involving titanyl solutions, allowing large scale synthesis of crystalline gold-titanium dioxide nanoparticles, up to 0.7 g.L-1. The absence of alkoxyde allowed us to work in aqueous media, with low cost chemicals and a controlled reactivity, which is a key parameter for industrial up-scaling. These nanoparticles have been successfully assembled into compact electrodes and probed using electrochemical methods to describe electrochemical exchange between metallic core, semi-conductor shell and various electrolytes. Reaction between gold nanoparticles and triiodide has been scrutinized to explain limitation of plasmon enhancement in standard DSSC involving iodine based electrolytes.

D.8.3
16:45
Authors : C. T. G. Smith, K. D. G. I. Jayawardena, L. J. Rozanski, C. A. Mills, V. Stolojan, S. R. P. Silva
Affiliations : Advanced Technology Institute, Department of Electronic Engineering, University of Surrey, Guildford GU2 7XH, United Kingdom.

Resume : Recent developments in carbon based materials related to carbon nanotubes and graphene show exciting potential for use in large area electronics, and in particular solution processable organic photovoltaics (OPV), which is attractive for low-cost, high throughput production. The scalability of the OPV material and module production consequently represents a significant challenge to future OPV development. In this presentation, we present the scalability of graphene oxide (GO) production and the inherent tuneable nature of the traditional hummer’s method. This allows for large quantities of GO to be produced repeatedly for use in large scale OPV production. A variety of techniques are used to give a comprehensive characterisation of the materials including thermogravimetric analysis, X-ray diffraction, Raman and UV-visible spectroscopy. GO is then used as an hole transport layer (HTL) in large area OPV devices tested over a period of one year. We present Poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)]: Phenyl C71 butyric acid methyl ester (PCDTBT:PC70BM) OPV devices with solution processable GO HTLs, exhibiting power conversion efficiencies of 5% at an area of circa 1 cm2. Increases in device shelf lifetime, when compared with PEDOT:PSS, are demonstrated and attributed to the high chemical stability of GO.

D.8.4
17:00
Authors : Elisabetta Masolo, Nina Senes, Gabriele Mulas, Sebastiano Garroni, Gavino Sanna, Nadia Spano and Maria Pilo
Affiliations : Dipartimento di Chimica e Farmacia, Università degli Studi di Sassari, Via Vienna 2, 07100 Sassari, Italy

Resume : Recently research for new materials for the energetic field is moving towards the synthesis and characterization of organic or organic-inorganic hybrid dyes, and in particular a new class of compounds with a donor-π bridge-acceptor (D-π-A) structure is gaining importance due to its interesting chemical and optical properties. Some of these compounds can be also synthesized as polymers, usually with the involvement of the donor moiety, via chemical or electrochemical methods, giving rise to an important polymer class showing promising properties like enhanced conductivity and light harvesting characteristics that can be exploited for example in solar cells. Here we present the synthesis, the optical and the electrochemical characterization of a novel D-π-A structure bearing triphenylamine, bithiophene and terpyridine fragments; the compound has also been subjected to electropolymerization on the π-bridge part (bithiophene), leading to a conducting polymer that showed promising properties for energetic applications. All the intermediate compounds involved in the synthetic path have also been fully characterized, allowing to study the effect of each subunit on the properties of each monomer and corresponding electropolymer. Aknowledgements: The authors thank Regione Autonoma Sardegna (by the project “P.O.R. SARDEGNA F.S.E. 2007-2013 - Obiettivo competitività regionale e occupazione, Asse IV Capitale umano, Linea di Attività l.3.1") and Fondazione Banco di Sardegna for the financial suport.

D.8.5
17:15
Authors : Jan Krajczewski, Sebastian Wojtysiak, Andrzej Kudelski
Affiliations : University of Warsaw, Faculty of Chemistry, ul. Pasteura 1, 02-093 Warsaw, Poland

Resume : Addition of some other metals to platinum causes significant increase of its catalytic activity towards ethanol electrochemical oxidation. In this work various M@Pt core-shell nanoparticles and hollow Pt nanoparticles were synthesized and their catalytic activity towards ethanol electro-oxidation was determined and compared with the catalytic activity of one element Pt nanoparticles. We found that higher catalytic activity towards ethanol oxidation of some core-shell nanoparticles than solid Pt nanoparticles is rather not caused by different adsorption of CO molecules on solid Pt and core-shell nanostructures. We suppose that better performance of core-shell M@Pt nanoparticles than one elements Pt nanoparticles towards ethanol electrochemical oxidation can be explained as follows: core-shell nanoparticles are probably much more defected than one-element nanoparticles, hence the M@Pt nanoparticles posses greater number of active sites (kinks, adatoms, and so on) for ethanol electrochemical oxidation.

D.8.6
 
Poster Session II : Marcin Pisarek, Aleksander Krupski, Hiroki Habazaki
17:30
Authors : Remigiusz Kowalik*, Dawid Kutyła*, Krzysztof Mech**, Piotr Żabiński*
Affiliations : *AGH University of Science and Technology, Faculty of Non-Ferrous Metals, al. A. Mickiewicza 30, 30-059 Krakow, Poland **AGH University of Science and Technology, Academic Centre for Materials and Nanotechnology, al. A. Mickiewicza 30, 30-059 Krakow

Resume : Tellurium is considered as a very important material because of its potential applications in biology, pharmacy and medicine. Nonetheless the main industrial application of tellurium is related to its semiconducting properties and its application in materials engineering. It plays significant role in optoelectronic and thermoelectric applications. It has also been used in some non-ferrous alloys and as a secondary vulcanizing agent in the natural rubber industry. This paper presents the research aimed at the description of the electrochemical deposition of tellurium thin films from citric acid solutions. Method of preparation stable bath with a high content of tellurium (0.008 - 0.064 TeO2/dm3) with the addition of citric acid (C6H8O7) has been described. The electrochemical process of tellurium deposition was analyzed by cyclic voltammetry and rotating disc electrode. Based on the results the process of electrodeposition was conducted under potentiostatic conditions. Thin films were deposited on copper substrate. The influence of deposition potential, concentrations of TeO2 and citric acid and pH on the rate of deposition, efficiency and morphology were investigated. The chemical composition of the deposits was determined by XRF and phase composition was analyzed by X-ray diffraction. Morphology of the deposits was investigated by optical microscopy and scanning electron microscopy. This work was supported by the Polish National Center of Science under grant 2011/01/D/ST5

D.D II.1
17:30
Authors : Jan Krajczewski, Karol Kołątaj, Andrzej Kudelski
Affiliations : University of Warsaw, Faculty of Chemistry, ul. Pasteura 1, 02-093 Warsaw, Poland

Resume : Silver nanoparticles have a number of interesting optical, catalytic and antibacterial properties. Many silver nanostructures may be synthesized using various photochemical reactions. In this work we describe the influence of stabilizing agent on the photochemical transformation of small, spherical silver seeds into bigger anisotropic nanostructures. In the first stage of the photochemical transformation, silver clusters (silver seeds nanoparticles) are partially dissolved. Then, Ag+ cations from the solution are photocatalyticaly reduced to Ag0. The photocatalytic reduction of Ag+, and hence deposition of metallic silver, occurs preferentially at such places of the silver nanoclusters, at which strong surface plasmons are excited (usually sharp etches or slits between nanoparticles). In this work we used sodium salts of many various poli-carboxylic acids as stabilizing agents. We found that used stabilizing agent significantly influences the photo-transformation process (finally obtained nanostructures have different shape and size). Many synthesised silver nanostructures have very interesting plasmonic properties. For example, we found that light-induced transformation of silver sols may be used to significantly increase their activity in surface-enhanced Raman scattering (SERS) measurements.

D.D II.2
17:30
Authors : Sylwia Parzyszek, Jan Krajczewski, Andrzej Kudelski
Affiliations : University of Warsaw, Faculty of Chemistry, ul. Pasteura 1, 02-093 Warsaw, Poland

Resume : The aim of this work is to analyse the function of oxygen in plasmon driven photochemical conversion of silver nanoparticles. Initially it was proven that oxygen is required for transformation of nanoparticles in aqueous silver sols stabilised by citrates. However, one can also transform deoxidized sols by irradiation with green or red light if quinone has been added. The obtained nanoparticles were studied using UV-VIS absorption spectroscopy and TEM microscope. As a result it was concluded that the only role of oxygen in plasmon driven photochemical conversion of silver nanoparticles is partial oxidation of nanoparticles. We suppose that in principle any oxidant with similar redox potential can be substituted for oxygen.

D.D II.3
17:30
Authors : K.Okulewicz, M.K.Naparty, Ł.Skowroński
Affiliations : Institute of Mathematics and Physics, UTP University of Science and Technology, S. Kaliskiego 7, 85-796 Bydgoszcz, Poland

Resume : Thin metal layers deposited on dielectric substrates exhibit tendency to form discontinuous films. The microstructure of granular layers depends strongly on the method of deposition (i.e. thermal evaporation, magnetron sputtering, ?) as well as growing conditions (a substrate, temperature, pressure,?). Indium is a material which particularly tends to create discontinuous films even for relatively thick layers. Such granular films exhibit strong surface plasmon resonance (SPR) effect, which makes it a potential sensor material. In this study, the indium layers with the mass thickness ranges from 5 nm to 50 nm were evaporated under pressure 10-5 Pa on different substrates SiO2/Si, TiO2/SiO2/Si, SnO2/SiO2/Si and Al2O3/SiO2/Si. These films were grown with a rate 0.02 nm/s controlled by a standard-quartz oscillator. The produced samples were examined by means of spectroscopic ellipsometry (SE), atomic force microscopy (AFM) and confocal optical microscopy (COM). The ellipsometric parameters Ψ and Δ were determined for three angles of incidence (65o, 70o and 75o) in the spectral range from 0.6 eV to 6.5 eV using a VASE device from J.A.Woollam Co., Inc. The topography of In films were studied using Innova (Bruker) and Lext OLS 4000 (Olympus) units. The determined complex dielectric function of In films and their microstructure strongly depend on the thickness of a metal layer as well as oxide used as a substrate.

D.D II.4
17:30
Authors : Ł.Skowroński, P.Dywel, A.Grabowski, M.K.Naparty
Affiliations : Institute of Mathematics and Physics, UTP University of Science and Technology, S. Kaliskiego 7, 85-796 Bydgoszcz, Poland

Resume : Aluminum oxide, Al2O3, is a widely used material in microelectronic, optoelectronic and high k dielectric applications due to its chemical stability, high optical transparency and insulating properties. In this study, the Al2O3 layers were produced using two methods: pulsed magnetron sputtering (PMS) [1] and - recently developed - gas injection magnetron sputtering (GIMS) [1,2,3]. Aluminum oxide films were deposited on microscope glass changing the time of deposition as well as ratio of Ar and O2 flows. Produced layers were examined by means of spectroscopic ellipsometry (VASE; J.A.Woollam Co., Inc.) and atomic force microscopy (Innova; Bruker). Additionally, transmittance and reflectance measurements were performed. Spectroscopic measurements were carried out in the spectral range from 0.6 eV to 6.5 eV. The influence of growing conditions on optical properties (the dielectric function, refractive index) and microstructure (the thickness, surface topography) of the produced Al2O3 thin films is observed and studied. [1] K.Zdunek, et al., Journal of Physics: Conference Series 11/2014. [2] K.Zdunek, et al., Surf. Coat. Tech. 228 (2013) 367-373. [3] Ł.Skowroński, et al., Appl. Surf. Sci. 322 (2014) 209–214.

D.D II.5
17:30
Authors : B.O. Postolnyi (1, 2), O.V. Bondar (1), O.V. Sobol (3), J.P. Araujo (2), A.D. Pogrebnjak (1)
Affiliations : (1) Sumy State University, 2, Rymskogo-Korsakova st., 40007 Sumy, Ukraine; (2) IFIMUP and IN-Institute of Nanoscience and Nanotechnology, Department of Physics and Astronomy, Faculty of Science, University of Porto, 687, Campo Alegre st., 4169-007 Porto, Portugal; (3) National Technical University «Kharkiv Polytechnic Institute», 21, Frunze st., 61002 Kharkiv, Ukraine

Resume : Fabrication of protective coatings with various functional purposes is one of the main task of industry, material science and solid state physics. This work is focused on study and characterization nanocomposite protective coatings based on metal nitrides MoN. Samples were obtained on high-speed steel X18H9T substrate using Arc-PVD deposition in vacuum-arc unit “Bulat-6”. Negative substrate voltage Us=-(100÷200) V and pressure of nitrogen atmosphere in chamber p=(0,2÷0,5) Pa were used. The thickness of coating was ranged from 7 µm up to 22 µm. Element composition analysis of coatings were performed using energy-dispersive spectroscopy (EDS), morphology of coatings and surface topography were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM) respectively. Structure-phase composition of coatings was investigated by X-ray diffraction analysis (XRD). The hardness and elasticity values of coatings are also shown. Relations between deposition conditions and features of the structure, composition and physical-mechanical properties of obtained coatings. The interaction at the interface between the steel substrate and MoN coatings under stress was found.

D.D II.6
17:30
Authors : 1Yeoung-Ah Noh, 2Jin-Ho Jang, 1Ki-Chul Kim*
Affiliations : 1Department of Advanced Chemical Engineering, Mokwon University, 88 Doanbuk-ro, Seo-gu, Daejeon, 302-318, Republic of KOREA; bPL Co., Ltd, S9-505, 125 Dongseo-daero, Yuseong-gu, Daejeon, 305-719, Republic of KOREA.

Resume : The anti-reflective coating using SiO2 nanoparticles (NPs) is used to improve the energy conversion efficiency of the Si solar cells [1]. In addition, TiO2 NPs are known as well decomposing the organic contaminants by photo-catalytic effect [2]. In this study, we synthesized SiO2 and TiO2 NPs with various size and surface morphology. The spherical SiO2 NPs with smooth surface are synthesized using tetraethyl orthosilicate (TEOS), ethanol, ammonia hydroxide, and water. The particle size of the silica NPs is controlled by ammonia hydroxide and stirring intensity. The wrinkled silica NPs are synthesized using TEOS, cetylpyridinium bromide, urea, iso-propanol and water. The density of wrinkles is controlled by isopropanol and n-butanol. The TiO2 NPs are synthesized using titanium (IV) butoxide, acetyl acetone, 1-butano, nitric acid and water. The anti-reflective and self-cleaning SiO2/TiO2 nano-composite films are prepared by dip or spin coating using the synthesized SiO2 and TiO2 NPs. The optical properties and surface morphology of the nano-composite films are characterized by UV-visible spectrometer, SEM, AFM, and TEM, respectively. Keywords: anti-reflective, self-cleaning, nano-composite film, surface structures [1] G. San Vicente et al., Thin Solid Films, Vol. 517, p. 3157 (2009). [2] A. L. Linsebigler et al., Chem. Rev., Vol. 95, p. 735 (1995).

D.D II.7
17:30
Authors : Sanina Y.; Tynkova A.; Sidorenko S.; Voloshko S.
Affiliations : NTUU “Kiev Polytechnic Institute”, Physical Engineering Faculty, Metal Physics Department

Resume : Ag is promissing material for modern electronic devices thus it owes the lowest resistance among metals, but easily corrodes and agglomerates at high temperatures. So, Ag thin films preparation with improved thermal stability is important point for micrielectronics. Ag(35-45 nm)/Ti(75-100 nm)/Si(001) systems were obtained by electron-beam evaporation and annealed in a vacuum 10-4 Pa and in the (Ar + 3% H2) atmosphere in the temperature range 473 – 573 K for 1-20 hours. It was observed that annealing in vacuum and in (Ar + H2) atmosphere leads to the formation of local defects on the surface of Ag/Ti samples. This phenomena is associated with Ag agglomeration on the outer layer leading to the resistance increasing up to 0,6 μOm∙cm at 573 K. Meanwhile at low temperatures (< 0.3 Tm) the kinetics of the diffusion processes during annealing in vacuum and reducing atmosphere differs significantly reflecting the effect of hierarchical film structure. The diffusion of Ag atoms in vacuum is mainly located near the original interface and the main role belongs to the C-B regime of grain boundary diffusion when mass transfer process is limited by Ti nanograin boundaries and surfaces between nanograin agglomerates. During annealing in a reducing atmosphere diffusion kinetics corresponds to C-C regime when Ag fills up only boundaries of Ti nanograins agglomerates.

D.D II.8
17:30
Authors : Michal Wrzecionek1, Maciej Bialoglowski1, Grzegorz Matyszczak1, Piotr Pietrzak1, Wojciech Gebicki2, Slawomir Podsiadlo1
Affiliations : 1 Faculty of Chemistry, Warsaw University of Technology; 2 Faculty of Physics, Warsaw University of Technology

Resume : Constantly increasing global energy demands force research communities to look for novel materials for solar energy harvesting. Cu2ZnSnS4 (CZTS) – a semiconductor, which crystallizes mostly in the kesterite structure, promise high performance, low-cost production and ecologically friendly terawatt application. This study explores the possibility to applicate CZTS nananoparticles conjugated with cheap, non-toxic and abundant metals, e.g. Ni, as photoactive materials for H2 evolution. CZTS nanopowders have been prepared in organic solvents, using metal salts and sulfur, and later subjected to electrochemical coating in aqueous solutions. The obtained materials have been characterized with X-ray powder diffraction, Raman scattering spectroscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy and cyclic voltammetry.

D.D II.9
17:30
Authors : Grzegorz Matyszczak1, Maciej Bialoglowski1, Michal Wrzecionek1, Mateusz Anuszewski1, Cezariusz Jastrzebski2, Slawomir Podsiadlo1
Affiliations : 1 Faculty of Chemistry, Warsaw University of Technology; 2 Faculty of Physics, Warsaw University of Technology

Resume : A growing interest in two-dimensional (2D) layered nanostructures has been observed due to their potential future applications in nanoelectronics and renewable energy harvesting. Tin(II) and tin(IV) sulfides show particularly appealing features, which combined with their environmental harmlessness and low-cost production makes them promising materials for use in photovoltaics. In this study, nanolayers of SnS and SnS2 ? prepared electrochemically in aqueous solutions ? have been investigated. The obtained materials have been characterized with X-ray diffraction, Raman scattering spectroscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy and cyclic voltammetry.

D.D II.10
17:30
Authors : M. Parras1, I. N. González-Jiménez1, A. Torres-Pardo1, M. Hernando1, A. Varela1, A. de Andrés Crespo2, E. Climent2 and J. M. González-Calbet1
Affiliations : 1 Dept. Química Inorgánica, Fac. Químicas, Univ. Complutense, E-28040 Madrid, Spain 2 Instituto de Ciencia de Materiales, CSIC, Cantoblanco, E-28049 Madrid, Spain

Resume : Thermochromism phenomenon can be described as a reversible change in the optical properties of a material as a result of a change in temperature. This property is known to exist in few ceramic materials, for instance in some oxides with hexagonal perovskite related structures. In particular, it has been shown that bulk 4H-SrMnO3 changes from black to violet at temperatures around 170 K. The origin of this change is not clearly established. In order to shed some light about this property, we have performed a thoroughly study of the structural evolution of this oxide with temperature. For this purpose, we have employed different diffractometric (X-Ray, Neutron and Electron diffraction) and spectroscopic (Raman spectroscopy) techniques, working in the temperature range between 40 and 450 K. Our results evidence the existence of a phase transition from a hexagonal (hchc)-4H (P63/mmc) to an orthorhombic (C2221) phase at temperature close to 340 K. This structural change would involve a slight tilting of the corner-sharing octahedra. When temperature decreases, non-trivial structural distortions take place at temperatures close to 280 and 170 K. Finally, at 120 K the maximal orthorhombic distortion seems to be achieved. These structural features are not clearly apparent when decreasing particle size down to the nanoscale. In this case, only a very small orthorhombic distortion is detected over the measured temperature range. The different structural features found in nano- and microcrystalline 4H-SrMnO3 seems to be at the origin of the different optical properties.

D.D II.11
17:30
Authors : A. Varela1, I.N. González-Jiménez1, A. Torres-Pardo1, M. Parras1, Mar García-Hernández2, and J. M. González-Calbet1
Affiliations : 1 Dept. Química Inorgánica, Facultad de Químicas, Univ. Complutense, E-28040 Madrid, Spain 2 Instituto de Ciencia de Materiales, CSIC, Cantoblanco, E-28049 Madrid, Spain

Resume : The great progress of technology during the last decade requires the continuous stabilization of new compounds at the nanometer scale for the development of advanced devices. Mn perovskite related mixed nano-oxides constitute a promising set of materials in the field of nanoscience and nanotechnology as a result in part of the high oxidation state’s number in which Mn can be stabilized providing a structural variety and a wide range of electrical and magnetic properties. In this work we report the synthesis as well as the structural and magnetic characterization of 4H-SrMnO3 particles obtained by two synthetic routes: i) from the thermal decomposition at low temperatures of the heterometallic precursor [SrMn(edta)(H2O)5]·3/2H2O ii) and an hydrothermal method from metallic salts in KOH medium. Only the former method leads to SrMn-oxide particles with nanometric size (average particle size 70 nm). Local structural information, provided by atomically-resolved electron microscopy techniques, shows that SrMnO3 nanoparticles exhibit the structural features corresponding to a 4H phase, although structural disorder due to edge-dislocations is observed. On the contrary, hydrothermal method gives rise to faceted microcrystals which morphology depends on the nature of the metallic precursor. Additionally, the mineralize concentration (KOH) directly affects their composition. K+ is introduced within the 4H-framework given rise to a slight Sr deficiency generating anionic vacancies. The magnetic characterization of nano- and microcrystalline 4H-SrMnO3 particles shows significant variations indicating that both size and morphology strongly influence the physical properties of this material.

D.D II.12
17:30
Authors : N. Korsunska1, M. Baran1, Yu. Polishchuk1, V. Kladko1, Ye. Venger, L. Khomenkova1, M. Kharchenko2, O. Gorban2, T. Konstantinova2
Affiliations : 1)V. Lashkaryov Institute of Semiconductor Physics, 45 Pr. Nauky 03028 Kyiv Ukraine; 2) O.O.Galkin Institute for Physics and Engineering, 46 Pr. Nauky 03028 Kyiv Ukraine

Resume : In recent years Cu-doped Y-stabilized ZrO2 composites are intensively investigated due to their excellent properties (such as environmental degradation, catalytic activity, tribologocal behaviour). These latter were found to be depended on Cu localisation. Therefore, the effect of calcination temperature (Tc=500-1100C) on Cu localisation in such composite was investigated byXRD, EPR and photoluminescnece (PL) methods. The samples calcinated at Tc=500-800C show the tetragonal ZrO2 phase mainly. EPR spectra demonstrate the signal caused by Cu-related surface complexes in this Tc range. At the same time, the Tc increase from 500 to 800C results in the lattice constant decrease along with the decrease of EPR signal intensity. This testifies to Cu incorporation into nanocrystals from the surface entities that is accompanied by the PL quenching due to increase of intrinsic defect density. Besides, the additional green PL band, which can be ascribed to Cu atoms at Zr sites, appears. The futher Tc increase (up to 1000C) causes the transformation of tetragonal phase to monoclinic one, the higher Cu content, the higher the temperature of this transformation. Simultaneously, the tetragonal lattice constant and total PL intensity increase. This can be explained by the outward Cu diffusion from nanocrystals that is confirmed by the decrease of green PL band intensity and the appearance of surface EPR signal for samples calcinated at Tc=1100C.

D.D II.13
17:30
Authors : A.I. Gudymenko, V. P. Kladko, A. S. Nikolenko, R. K. Savkina, A. B. Smirnov, V. V. Strelchuk
Affiliations : V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine, Kiev, Ukraine

Resume : Extreme conditions of the ultrasonic cavitation such as local temperature and the pressure are widely used in chemistry, as for example to synthesize nano-materials, to enhance the electrochemical reactions and to modify the surface properties of electrodes, as well as to generate the novel materials in a liquid medium. The ultrasonic irradiation is a powerful tool in promoting of the chemical reactivity in the liquids at solid surfaces also. In our experiments described here, an attempt to drive the chemical and structural transformations on a semiconductor surface by the ultrasonic cavitation effect was made. The properties of the silicon samples subjected to cavitation impacts have been studied. Optical, atomic force and scanning electron microscopy techniques, Raman spectroscopy as well as energy dispersive X-ray spectroscopy and X-ray diffraction measurements were used. It was found the dendrite-like micron-scale array formation as well as a change of the chemical composition up to the new phase occurrence inside the ultrasonically structured region. In particular, the sonochemical synthesis of CaSiO3 compound on the silicon surface was fixed. Calcium inosilicate have been studied as materials for hard tissue repair, artificial bones and dental roots. Biomaterials containing CaO–SiO2 appeared to excellent bioactivity and were found to bond have to living bone and soft tissue.

D.D II.14
17:30
Authors : Octavian Ciobanu, Gabriela Ciobanu
Affiliations : “Grigore T. Popa” University of Medicine and Pharmacy, Faculty of Medical Bioengineering, Universitatii Str., no. 16, Iasi, 700115, Romania; “Gheorghe Asachi” Technical University of Iasi, Faculty of Chemical Engineering and Environmental Protection, Prof. dr. docent Dimitrie Mangeron Rd., no. 63, Iasi, 700050, Romania

Resume : In recent years, a greater demand for dental and orthopedic implants can be noticed. The clinical success of these implants is related to their early osseointegration and this is related to their surface properties. Surface modification of titanium implants for bone contacting applications is a very active field of research. Presently, the approaches to the surface modification of titanium implant devices involve surface topography modification or the application of inorganic/organic coatings. In this research, the hydroxyapatite-collagen-silver coatings have been deposited onto titanium implants by a combined method involving hydroxyapatite/collagen electrochemical deposition, combined with silver ions reduction and in-situ crystallization processes on titanium surface. The electrolytic processes implies the nucleation and growth of hydroxyapatite crystals on the surface of the titanium implant in a simulated body fluid under physiological conditions of pH and temperature, applying a constant current for different periods of time. The collagen has been used to modify titanium surfaces in order to enhance their bioactivity. The silver incorporation into hydroxyapatite coatings is an alternative that can provide good antibacterial properties of these coatings. The morphology, composition and phase structure of the hydroxyapatite-collagen-silver coatings were characterized by scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX) and X-ray diffraction (XRD). The implants were tested against Staphylococcus aureus and Escherichia coli and the obtained data were indicative of good antibacterial properties of the materials.

D.D II.15
17:30
Authors : M. Pisarek1, M. Holdynski1, M. Krawczyk1, A. Malolepszy2, L. Stobinski1, A. Jablonski1
Affiliations : 1. Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka Str. 44/52, 01-224 Warsaw, Poland; 2. Faculty of Materials Science and Engineering, Warsaw University of Technology, Woloska 141, 02-507 Warsaw, Poland;

Resume : Graphene, crystalline allotrope of carbon, can be described as a one-atom thick layer of graphite. Recent investigations have shown that these graphitic layers can consist of a few graphene layers only [1,2]. An important role in the characterization of such systems based on graphene is the selection of appropriate research methods which will allow the analysis of the chemical composition with nanometric scale (AES, XPS and EPES). One of the important physical parameter determining the resolution of these method is the inelastic mean free path (IMFP). In this work, the IMFPs, characterizing electron transport in graphene based materials, was evaluated from relative EPES measurements [3] with the Au standard in the energy range 0.5–2 keV. The measured IMFPs were compared with IMFPs resulting from the TPP-2M predictive equation for the graphite reference sample. The EPES IMFPs were found to be from 4.5% to 14.5% smaller than the IMFPs obtained from the predictive formula. For the surface analysis of the graphene based materials before EPES investigation (chemical composition, chemical state of the elements) were used the XPS, AES and REELS methods. Graphene oxide and reduced graphene oxide were presently prepared by a modified Hummers method [4]. 5 mg of graphene oxide or reduced graphene oxide were dispersed in 20 ml of isopropyl alcohol using ultrasonic bath. Then 10 µl of the dispersion were dropped on the holey carbon coated TEM copper grid (300 mesh). [1] J.Wintterlin, M.-L.Bocquet, Surf.Sci. 603 (2009) 1841 [2] C.Soldano, A.Mahmood, E.Dujardin, Carbon 48 (2010) 2127 [3] A.Jablonski, J.Phys.D: Appl.Phys. 47 (2014) 055301 [4] W.S.Hummers, R.E.Offeman, J.Am.Soc., 80 (1958) 1339

D.D II.16
17:30
Authors : Katarzyna Grochowska1, Katarzyna Siuzdak1, Michał Sokołowski2, Jakub Karczewski2, Mariusz Szkoda3, Gerard Śliwiński1
Affiliations : 1Centre for Plasma and Laser Engineering, The Szewalski Institute, Polish Academy of Sciences, 14 Fiszera St., 80-231 Gdańsk, Poland; 2Faculty of Applied Physics and Mathematics, Gdańsk University of Technology, Narutowicza 11/12 St., 80-233 Gdańsk, Poland; 3Faculty of Chemistry, Gdańsk University of Technology, Narutowicza 11/12 St., 80-233 Gdańsk, Poland

Resume : Currently, roughened metal nanostructures are widely studied as highly sensitive enhanced Raman scattering (SERS) substrates that show application potential in biochemistry, food safety or medical diagnostic. In this work, we report on optical and structural properties of thin gold films deposited on highly ordered nano-patterned titanium templates for SERS applications. The templates are formed in following processes: a) formation of TiO2 nanotubes via a two-step anodization, b) etching of TiO2 nanotubes via overnight immersion in oxalic acid after the first and second anodization step. SEM images reveal the formation of honeycomb nanostructures with the cavity diameter of 80 nm. The thin (5-20 nm) quasi-continuous Au films are produced by pulsed laser deposition (PLD) using the UV (355 nm) laser operated at fluence up to 1.5 mJ/cm2 in vacuum conditions at room temperature. Due to strongly inhomogeneous distribution of the electromagnetic field in the vicinity of the Au film irregularities/discontinuities the measured average SERS signal is markedly higher than observed for bare Ti templates. It is shown that the enhancement factor can be optimized by adjusting the thickness of the deposited Au layer. Results confirm that the bimetal structures consisting of PL-deposited Au films on Ti templates can be used in surface enhanced sensing. KG and KS acknowledge the National Science Centre of Poland for financial support via grants 2012/07/N/ST5/02139 and 2012/07/D/ST5/02269.

D.D II.17
17:30
Authors : M. Krawczyk, M. Pisarek, W. Lisowski, A. Jablonski
Affiliations : Mazovia Centre for Surface Analysis, Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa, Poland

Resume : Praseodymium (Pr) is one of the light rare earth elements often applied in super-conductors and electrical transmission technology. Development of new devices using praseodymium can be realized knowing the physical and chemical properties of both the bulk and the surface region of Pr material. The surface properties can be studied by surface-sensitive electron spectroscopies, e.g. AES, XPS and elastic-peak electron spectroscopy (EPES). However, the accurate quantification of Pr-containing materials by AES and XPS requires the knowledge of the electron inelastic mean free path (IMFP) value for praseodymium. Presently, this value can only be estimated from the TPP-2M predictive formula [1]. The IMFPs can be also measured experimentally by EPES [2,3]. Recently, this method was successfully applied to evaluate the energy dependence of IMFP for cerium oxide sputtered by argon ions [4]. In the present work, the IMFP in Pr was evaluated from EPES using both Ni and Au standards in the electron energy range 500-2000 eV. Prior to EPES measurements, both the praseodymium and the standard material surfaces were in situ sputter-cleaned and amorphized by 3 keV argon ion etching. Following this procedure, oxygen and carbon contaminants were entirely removed from the surfaces, as detected by XPS-AES analysis. Relative EPES experiments were performed using the MICROLAB 350 spectrometer with a spherical sector analyzer. During the experiments, the electron gun was located at the normal to the surface, the analyzer axis was located at 60° to the surface normal, and the acceptance half-angle of the analyzer was 6°. Experimental IMFPs were uncorrected for surface excitations and compared with IMFPs resulting from the TPP-2M predictive equation [1]. Good agreement was found between the measured and predicted IMFPs in praseodymium. The experimental values were found to be only 2.5-3.8% larger than the predicted values in the energy range of 500-1000 eV. For electron energies 1500 and 2000 eV, the smallest differences between these values were observed. [1] S. Tanuma, C. J. Powell, D. R. Penn, Surf. Interface Anal. 21, 165 (1994). [2] G. Gergely, Surf. Interface Anal. 3, 201 (1981). [3] A. Jablonski, Surf. Interface Anal. 37, 1035 (2005). [4] M. Krawczyk, M. Holdynski, W. Lisowski, J. W. Sobczak, A. Jablonski, Appl. Surf. Sci. 341, 196 (2015).

D.D II.18
17:30
Authors : O. Naumenko, A. Oleshkevych, S. Voloshko, S.I. Sidorenko
Affiliations : National Technical University of Ukraine, Kyiv Polytechnic Institute, Peremogy Ave. 37, 03056 Kyiv, Ukraine

Resume : Nanoscale factor significantly affects diffusion controlled processes such as structural and phase transformations. Nowadays those factors have not been thoroughly studied, and available results are quite unusual and controversial. Interdiffusion in nanofilm systems in comparison with bulk materials is characterized by more extensive mass transfer at low temperatures. This phenomenon is caused not only by high defects concentration and small diffusion distances, but also by significant surface influence. In thin films sequence of phase formation may vary from phase formation for bulk materials, and nanoscale factor plays an important role in causing these differences. Grazing-incidence x-ray technique and secondary neutral mass spectrometry have been applied to study layer-by-layer concentration, phase composition and phase transformation in Pd(30nm)/Ho(20nm)/SiO2 thin films. According to the phase equilibrium diagram for bulk materials next phases must be formed: Ho5Pd2, Ho3Pd2, HoPd, Ho3Pd4, Ho2Pd3, HoPd2, HoPd3. However, results show that after annealing in vacuum and in hydrogen formation of HoPd3 intermetallic phase only was registered. Also reflexes from Ho2O3 and HoH2 were registered on the surface using GIXRD. An interplay of phase formation at the outer surface and in the bulk has been investigated and it was discovered that the domination of processes on the external surface inhibits phase formation in the bulk and the other way around.

D.D II.19
17:30
Authors : F. Aiouaz, M. Jeannin, J. Creus, B. Saidani, A. Merati
Affiliations : F. Aiouaz, A. Merati ] Laboratoire d?Electrochimie et Corrosion, Ecole Militaire Polytechnique, Bordj El Bahri, Alger, M. Jeannin, J. Creus ] Laboratoire des Sciences de l?Ing?nieur pour l?Environnement (LaSIE ? UMR 7356 CNRS) Universit? de La Rochelle, Avenue Michel Cr?peau, 17042 La Rochelle Cedex 1, France. B. Saidani ] Laboratoire d?Electrochimie, Corrosion et de Valorisation Energ?tique (LECVE), Facult? de Technologie, Universit? A. MIRA ? Bejaia (06000), Alg?rie.

Resume : Cerium conversion coatings were prepared on steel by cathodic electrodepostion from a low concentrated aqueous solution of Ce(NO3)3 with KNO3 addition to insure the conductivity of the electrolyte. The cerium oxide film was characterized by Scanning Electronic Microscopy (SEM). Although the deposit is uniform with current densities of 1 mA/cm2, it shows a cauliflower morphology with a crack network giving rise to bad mechanical and electrochemical behaviour. Elaboration of a calcareous deposit inside crack network of the cerium coating by cathodic polarization from artificial seawater is investigated at different applied potential, in order to increase the quality of the cerium coating formed. SEM and EDX cartography of the cross section revealed that open cracks in the cerium oxide structure are filled by calcium. Calcium was also detected inside the CeO2 film not only all around the cracks but also in all the porosity of the CeO2 film. It has precipitated as CaCO3 (aragonite form) as revealed by -Raman spectroscopy and XRD.

D.D II.20
17:30
Authors : Alexander Sherstnyov, Eugene Chubenko, Sergey Redko, Vladimir Petrovich, Vitaly Bondarenko
Affiliations : Belarusian State University of Informatics and Radioelectronics, P. Brovka str. 6, Minsk 220013, Belarus

Resume : In this paper we study the formation of functional nanocomposite materials by electrochemical deposition of zinc oxide (ZnO) nanostructures inside the porous silicon (PS) template. These nanocomposites are promising for sensor, photovoltaic and photoelectrochemical applications. PS template formation was carried out in 9 % HF solution in pulsed galvanostatic mode in darkness at 120 mA/cm2. ZnO electrochemical deposition was carried out in dimethylsulfoxide based solutions containing 0.03 M ZnCl2 and 0.1 M KCl and also polyoxyethilene (POE) and H2O2 as additives. According to SEM analysis after 60 min of ZnO deposition at different current densities nucleation of separate ZnO nanoparticles occurs all over the surface of PS layer even at the bottom parts of pores. Presence of POE in the solution helps to avoid closing of the pore openings at the high ZnO deposition current densities (>0.5 mA/cm2). Addition of 5 mM H2O2 in the solution improves stoichiometry of deposited ZnO. Catalytic activity and gas sensing ability of PS surface functionalized by electrodeposited ZnO were investigated. This research is supported by the Grant of Ministry of Education of Republic of Belarus for students, and Belarus Government Research Programs “Nanotechnology and nanomaterials”, grant 2.4.16; “Electronics 2015”, grant 1.1.14.

D.D II.21
17:30
Authors : V.I. Ivashchenko1), A.D. Pogrebnyak2), V.M. Rogoz2), Sobol O.V.3)
Affiliations : 1) Institute for Problems of Material Science, NASU, Кrzhyzhanovsky Str. 3, 03680 Kiev, Ukraine 2) Sumy State University, Rimsky-Korsakov Str. 2, 40000, Sumy, Ukraine 3)National Technical University "Kharkiv Polytechnic Institute", 21, Frunze Str,.  Kharkiv, 61002,Ukraine

Resume : The nanostructured coatings based NbN have a set of characteristics, high hardness, superconductivity at low temperatures as well as high sensitivity to the electromagnetic radiation spectrum. This provides opportunities for using this material. Introduction of Si and Al can improve the mechanical properties of the coating by creating nanocrystallites within the amorphous phase. In this paper we studied the structural-phase state and mechanical properties of coatings Nb-Si-N, and Nb-Al-N, depending on the current target, as well as the potential applied to the silicon substrate.

D.D II.22
17:30
Authors : S. Lipiński 1 , T. Durejko 1 2, J. Aniszewska 1, M. Ziętala 1, P. Jozwik 1 2, A. Krupski 3
Affiliations : 1. Department of Advanced Materials and Technology, Military University of Technology, Kaliskiego 2 Street, 00-908 Warsaw, Poland, email: tomasz.durejko@wat.edu.pl ; 2. Department of Physics, University of Warwick, Coventry CV4 7AL, United Kingdom, email: k.j.krupski@warwick.ac.uk; 3. Faculty of Science, SEES, University of Portsmouth, Portsmouth PO1 3QL, United Kingdom, email: aleksander.krupski@port.ac.uk

Resume : The Ti-6Al-4V alloy has been successfully used in orthopedics and dentistry practice. However, effective osseointegration process and cell proliferation required porous surface structures. Porous structure also helps to reduce stiffness between implant and bone tissue and allows for stable long-term fixation. Moreover, porosity and pores morphology play an very important role in bone ingrowth. It was stated that minimal size of pores should be ~100m. The conducted researches for laser textured Ti-6Al-4V showed a 200m as optimal pore size for excellent mechanical interlock between implant and bone tissue. Undoubtedly, one of the technology which enabled fabrication of mentioned above porous structure also with gradient effect is Laser Engineered Net Shaping (LENS) method. It belongs to Laser Direct Metal Deposition (LDMD) and can produce implant with greater geometrical flexibility than powder bed techniques like e.g. Selective Laser Melting (SLM). In the present work, the LENS technique have been applied using a continuous mode laser to produce multilayer porous structures also with gradient effect for biomedical applications. The microstructural analysis were carried out by a light optical microscopy and scanning electron microscopy. Surface texture and surface area of obtained samples were measured by profilometer and micro-CT methods. Chemical homogeneity after laser deposition (especially in interface region) was analyzed using an energy dispersive X-ray spectrometer coupled with SEM.

D.D II.23
17:30
Authors : Cezariusz Jastrzebski1, Dariusz Szmigiel2, Rafal Dobrowolski2, Krzysztof Świtkowski1, Monika Seniut1, Rafal Maselek1, Wojciech W. Brylinski1
Affiliations : 1 Faculty of Physics, Warsaw University of Technology; 2 The Institute of Electron Technology (ITE)

Resume : Silicon based electronics is often limited by phenomena occurring at the new structure-silicon interface. Most of the thin films used in micro-technology exhibit stress, which might affect both further processing during a fabrication cycle and final performance of fabricated micro-devices. Stress reducing is the key for improving of such opto- and/or electronic devices. Amorphization of silicon surface is one way of obtaining the goal. The silicon thin films were deposited using ASM LPCVD furnace on 100 mm oxidised silicon wafers at wide range of process conditions. The films of different structural (amorphous and polycrystalline) and mechanical (different stress level) properties were obtained. Raman studies for various wavelength excitation were performed. Confinement of phonons in a finite dimension of nano grains results in a change in the line-shape and position of the peaks in first order Raman spectrum. The average size of silicon nano grains in the thin silicon films have been obtained on the base of the spectroscopic studies. The maps of the grain size distribution to analyze the nonuniformity of the silicon film surface will be presented. Additionally appearance of specific surface and interface vibrational contribution for surface state evaluation will be discussed.

D.D II.24
17:30
Authors : Pawel Jozwik, Katarzyna Krupski, Wojciech Polkowski, Zbigniew Bojar, Tomasz Durejko, Aleksander Krupski
Affiliations : Pawel Jozwik 1,2; Katarzyna Krupski 2; Wojciech Polkowski 1; Zbigniew Bojar 1; Tomasz Durejko 1,2; Aleksander Krupski 1,2,3 1. Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2 Str., 00-908 Warszawa, Poland; 2. Department of Physics, University of Warwick, Coventry CV4 7AL, United Kingdom. 3.Faculty of Science, SEES, University of Portsmouth, Portsmouth PO1 3QL, United Kingdom.

Resume : Ni3Al intermetallic alloys are a group of perspective materials with potential outstanding physical and chemical properties (such as high catalytic activity and structural stability in corrosive environments) which make them possible candidates for many high-tech applications. In the present work, a significant influence of heat treatment after plastic working on structure and properties Ni3Al intermetallics is presented. Modification of structure and mechanical properties after annealing of samples will be shown. On the samples of fine – grained strips (after annealing at 973 K up to 0.25h) it was confirmed that the tensile strength was quite high (tensile strength over the level of 2600 MPa and yield point on the level of 2300 MPa on the level of 5% unit elongation during tensile testing at room temperature were recorded). Detailed SEM, EBSD, XRD, AFM, and XPS studies will be presented.

D.D II.25
17:30
Authors : Pawel Jozwik, Katarzyna Krupski, Wojciech Stepniowski, Zbigniew Bojar, Tomasz Durejko, Aleksander Krupski
Affiliations : Pawel Jozwik 1,2; Katarzyna Krupski 2; Wojciech Stepniowski 1; Zbigniew Bojar 1; Tomasz Durejko 1,2; Aleksander Krupski 1,2,3 1. Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2 Str., 00-908 Warszawa, Poland; 2. Department of Physics, University of Warwick, Coventry CV4 7AL, United Kingdom. 3. Faculty of Science, SEES, University of Portsmouth, Portsmouth PO1 3QL, United Kingdom;

Resume : Surface changes of Ni3Al-based foils after methanol decomposition were investigated. The material under examination - thin foils with thickness below 50mm without any additional catalytic coating, was successfully produced by SPD process. The examination has concerned on analysis of surface changes in the time of methanol decomposition at the temperature 773K. During the reaction, the growth of carbon nanofibers decorated with metal-like nanoparcticles on the catalysts surface was observed. The chemical and phase composition of the deposit was investigated with scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD).

D.D II.26
Start atSubject View AllNum.
 
New Generation of Biomaterials : Małgorzata Lewandowska
09:00
Authors : Akiko Yamamoto
Affiliations : Biomaterials Unit, International Center for Materials Nanoarchitectonics, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan

Resume : Recently, biomedical application of magnesium and its alloys as biodegradable devices are intensively studied. For the success of their biomedical application, the control of their degradation ratio in the human body is a key issue since it severely influences their mechanical integrity and biocompatibility during their implantation period. The surrounding tissue and cellular reaction depends on the amount and kind of metal ions released by their degradation. Meanwhile, the degradation of mg and its alloys can be influenced by the surrounding tissue and cells due to their metabolic activities and specific microenvironments. It is confirmed by the electrochemical measurement of an AZ31 alloy with culturing cells on its surface that living cells accelerate degradation of the alloy substrate mainly due to pH lowering. Various factors of the biological environment also influence the degradation behavior of Mg alloys. The pH of our body fluid is mainly maintained by a carbonate buffer system, in which relatively high CO2 concentration in our body fluid plays a very important role via dissociation of CO2 into the fluid and its dissociation into carbonate ion. Some of serum proteins also contribute to maintain the stable pH of our blood. Therefore, these factors have significant effects on the degradation of Mg and its alloys. It is very important to perform in vitro evaluation tests in a similar condition to in vivo for a reasonable degradation estimation.

D.9.1
09:30
Authors : Wojciech Swieszkowski
Affiliations : Faculty of Materials Science and Engineering, Warsaw University of Technology

Resume : The aim of the presentation is to show evidences how important are scaffolds and their surface properties in regenerative medicine. There are several tissues that show limited self-healing abilities. It was proven that the critical defects of peripheral nerves and bones usually do not heal themselves. One of the most promising methods in treatment of such defects is tissue engineering and using of bioactive scaffolds that could mimic the extracellular matrix (ECM) and assist in tissue regeneration. For instance, bio-composite nanofibrous scaffolds made from synthetic and natural polymeric blends provide suitable substrate for tissue engineering and it can be used as nerve guides eliminating the need of autologous nerve grafts. Nanotopography or orientation of the fibers within the scaffolds greatly influences the nerve cell morphology and outgrowth, and the alignment of the fibers ensures better contact guidance of the cells. In bone tissue engineering the composition of the scaffolds, their mechanical properties, degradation kinetics, and surface properties (wettability, surface energy, and roughness) strongly influence response of human bone marrow mesenchymal stromal cells (HBMC) and whole regeneration process. By optimising these parameters using smart materials and advance biofabrication methods we will be able to control cells reaction and enhance process of new tissue formation.

D.9.2
09:50
Authors : Sachiko Hiromoto 1, Motoki Inoue 1, Tetsushi Taguchi 1, and Naofumi Ohtsu 2
Affiliations : 1. Biomaterials Unit, International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science; 2 Instrumental Analysis Center, Kitami Institute of Technology

Resume : Mg/Mg alloys attract attention as a bioabsorbable/biodegradable metallic biomaterial for bone plates, screws and stents which degrade and disappear safely in human body. A current issue of bioabsorbable Mg/Mg alloys is to control the corrosion rate to maintain mechanical integrity until the affected part is healed sufficiently and to prevent a cavity formation around the affected part with hydrogen gas generated in magnesium corrosion reaction. Many surface modifications, especially calcium phosphate coatings, have been examined to control the corrosion and to improve biocompatibility of Mg/Mg alloys. We developed a novel simple method for hydroxyapatite (HAp) and octacalcium phosphate (OCP) coating of Mg/Mg alloys using an aqueous treatment solution. Type of calcium phosphate could be varied with pH of a treatment solution, and crystallinity of HAp and OCP is relatively high to exhibit clear X-ray diffraction peaks. In this study, corrosion behaviour of HAp- and OCP-coated AZ31 (Mg-3mass%Al-1mass%Zn) alloy was examined in vitro and in vivo. Inflammation behaviour due to the coated AZ31 was also examined in mice. HAp and OCP coatings were formed on AZ31 by a single-step chemical solution deposition method. HAp- and OCP-coated AZ31 (HAp- and OCP-AZ31) and chemically polished AZ31 (Cpol-AZ31) were immersed in a medium or implanted in transgenic mice subcutaneously. In the medium, apparent Mg ion release initiated after an incubation period of several days for HAp- and OCP-AZ31, while Cpol-AZ31 clearly released Mg ions from the very beginning. After Mg ion release was initiated, the corrosion rate was constant through the immersion period of 52 weeks for HAp- and OCP-AZ31. HAp- and OCP-AZ31 showed lower corrosion rate than Cpol-AZ31 by about 50%, and HAp-AZ31 showed lower rate than OCP-AZ31 by about 20%. The estimated hydrogen gas generation rate from HAp- and OCP-AZ31 in the medium was equivalent to a suggested tolerable rate in vivo. In mice, formation of a gas cavity due to hydrogen gas was suppressed with HAp and OCP coatings, indicating that corrosion of the substrate Mg alloy was prevented with the coatings. Also, inflammation around the implanted specimens was suppressed with the coatings, according to the thinning of a fibrous layer formed in foreign body reaction. Thickness of the fibrous layer corresponds to the degree of inflammation. Thickness around HAp-AZ31 was smaller than that around OCP-AZ31, indicating that the HAp coating exhibited higher corrosion protectiveness than the OCP coating in vivo. Interestingly, corrosion morphology of substrate Mg alloy in the medium was different from that in subcutaneous of mice. The former exhibited filiform corrosion and the latter exhibited round-shape pits. This fact suggests that the adhesion of soft tissue localized the exposure area on specimen surface to body fluid, leading to the localization of corrosion. Corrosion pits sometimes decrease fatigue strength of Mg/Mg alloys. To examine the chemical and mechanical reliability of coated Mg/ Mg alloys, the corrosion test environment should be carefully designed depending on the target part in human body. The reduction of corrosion rate and inflammation in medium and mice suggested that the HAp and OCP coatings are highly potential for corrosion controlling coatings for bioabsorbable Mg/Mg alloys.

D.9.3
10:10
Authors : 1) A.Roguska, 1) M.Pisarek, 1) M.Holdynski, 2) L.Marcon, 3) M.Andrzejczuk, 4) A.Belcarz, 1) M.Janik-Czachor
Affiliations : 1) Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland 2) Interdisciplinary Research Institute, USR CNRS 3078 Parc de la Haute Borne, 50 av. de Halley 59658 Villeneuve d’Ascq, France 3) Faculty of Materials Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw, Poland 4) Chair and Department of Biochemistry and Biotechnology, Medical University of Lublin, Chodzki 1, 20-093 Lublin, Poland

Resume : The use of TiO2 nanotubes (NT) toward biomedical applications is still the subject of numerous studies, while the bio-tolerance of TiO2 combined with a nanotubular geometry has a significant potential, and may promote the preferential growth of bone tissue. Such kind of morphology and chemistry on the micro- and nanoscale were widely found as factors which can also significantly improve the specific cell response, but the effect of different nanotube diameter on cell adhesion is still in a very early stage, and research results published until now in this area are very divergent [1-3]. TiO2 NT with diameters from 40 to 120 nm were prepared by anodic oxidation of Ti at a constant potential (10 to 28 V). Thermally stabilized TiO2 NT at temp. 450oC or 650oC were subjected also to bidirectional functionalization: by deposition of Ca-P thin layer for improvement of biocompatibility and loading with silver nanoparticles to enhance their antibacterial properties. Three factors were found to promote the proliferation of osteoblasts (U2OS) cells: larger nanotube diameter, higher annealing temperature and presence of CaP thin layer. Differentiation of these cells, according to ALP test, was stimulated by higher annealing temperature although not by Ca-P functionalization. TiO2 NT unmodified samples exhibited noticeable antibacterial properties but additional deposition of Ag nanoparticles almost completely inhibited the survivability of S. epidermidis cells just after 3 h of contact. [1] K.Lee, A.Mazare, P.Schmuki, Chem.Rev. 2014, 114, 9385 [2] I.Mutreja, D.Kumar, A.R.Boyd, B.J.Meenan, RSC Advances, 2013, 3, 11263 [3] K.S.Brammer, S.Och, Ch.J.Frandsen, S.Jin, 2011, Biomaterials and Biotechnology Schemes Utilizing TiO2 Nanotube Arrays, in Biomaterials Scince and Rngineering, ed. by R.Pignatello, InTech

D.9.4
10:25
Authors : Ludek Hromadko*1, Eva Koudelkova2, Miroslav Tejkl3, Jaroslava Moravkova3, Jan Buk3, Roman Bulanek2, Jan M. Macak1
Affiliations : 1Center of Materials and Nanotechnologies, Faculty of Chemical Technology, University of Pardubice, Nam Cs. Legii 565, Pardubice 530 02, Czech Republic *email: ludek.hromadko@upce.cz; 2Department of Physical Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentska 573, Pardubice 530 02, Czech Republic; 3Pardam Ltd., Jindrisska 2025, Pardubice 530 02, Czech Republic

Resume : An efficient separation of the air-borne moisture using silica sorbents is one of key operations in a range of industries, including electrotechnics, machinery, food preservation, chemistry to either preserve the product quality and to prevent degradation (due to aging, corrosion, decaying), or to remove quantitatively moisture from the air, whenever a low moisture air must be used (wood, paper industries). The specific surface of a sorbent material is very important parameter for high sorption capacity and should be as high as possible. This is possible using nanostructured sorbent, typically in the form of particles. However, they cannot be used repetitively as their desorption is tedious and costly. Large-scale production technologies for these materials are also often not available. Nanofiberous silicagels offer great moisture-capture capabilities and kinetics that can overcome conventional silicagels at comparable price. Moreover, they are capable of recovery at lower temperatures. Larger number of desorption cycles prolonging lifetime of these sorbent is realistic, thus making an additional positive cost figure. The presentation will show recent results in the synthesis of new efficient sorbent based on silica nanofibers using advanced production technology – force spinning – that has recently attracted large scientific as well as industrial attention. In particular, we will present results on surface and sorption characteristics of this material.

D.9.5
10:40 Coffee break    
 
New Perspective Materials for Energy : Aleksander Krupski
11:00
Authors : Robert A. Varin
Affiliations : Department of Mechanical and Mechatronics Engineering, University of Waterloo, Waterloo, Canada N2L 3G1

Resume : In the transitional stage from the fossil fuels-based economy to the clean Hydrogen Economy, that is a major challenge for this century, a wide usage of fuel cells where hydrogen gas (H2) in contact with oxygen (O2) is converted into an electrical energy, must become a wide spread reality. In this presentation, we will discuss the recent results of our research on novel nanostructured complex hydride systems for H2 generation and supply to fuel cells. Mechano-chemical activation synthesis (MCAS) during ball milling has been employed for the synthesis of those hydrides. The first group of nanostructured hydrides encompasses the hydride systems that are capable of generating, quite rapidly, 4 to 7 wt.% H2 through the mechanical dehydrogenation phenomenon at the ambient temperature. For example, the hydride/halide LiBH4-FeCl2 system rapidly generates about 4 wt.% H2 through the simultaneous synthesis of a disordered d-Fe(BH4)2 complex hydride and its rapid decomposition under a small mechanical milling energy input. This novel hydride/halide system will be compared with lithium alanate (LiAlH4)/nanometal/nano-interstitial compounds, LiAlH4/LiNH2 (hydride/hydride) and LiAlH4 /MnCl2 (hydride/halide) systems. The possible mechanisms responsible for the phenomenon of mechanical dehydrogenation will be elucidated with a special emphasis on the effect of nano- grain boundaries. The second group encompasses hydrides and their nanocomposites which generate H2 at slightly elevated temperatures (100°C), nearly compatible with the waste heat temperature of a fuel cell stack. A prominent hydride in this group is the manganese borohydride (Mn(BH4)2) recently synthesized by MCAS that co-exists with either a nanocrystalline LiCl or NaCl compound depending on the type of the precursor used, i.e. either LiBH4 or NaBH4. The most interesting observation is that (Mn(BH4)2) is synthesized as a fully nanocrystalline phase from the LiBH4 prescursor while it is formed as a disordered d-Mn(BH4)2 from the NaBH4 precursor. The (Mn(BH4)2+2LiCl) nanocomposite can desorb about 4.5 wt. % H2 at 100°C. The results of the microstructural investigations employing high resolution TEM, SEM, X-ray diffraction and infrared spectroscopy will be presented and discussed. The dehydrogenation properties of the nanostructured Mn(BH4)2-based hydride system will be compared with the dehydrogenation behavior of other nanostructured hydride nanocomposites based on LiAlH4 with catalytic additives. Practical application aspects of hydride systems for H2 generation and supply will be also briefly discussed.

D.10.1
11:25
Authors : Torben R. Jensen
Affiliations : iNANO and Department of Chemistry, Aarhus University, Denmark.

Resume : We have plenty of renewable energy available but sun and wind are unevenly distributed over time and geographically, therefore energy storage is increasingly important. Metal hydrides have extremely diverse chemistry, structures and reactivity and often high energy density [1]. We have recently developed new synthesis strategies combining mechano-chemical and solvent based methods, which are also useful for coordination chemistry. A series of 30 new complex borohydride perovskite-type materials are presented with interesting photophysical, electronic and hydrogen storage properties. Furthermore, anion-mixing provides a link to the known ABX3 halides [2]. New metal hydrides, which are fast lithium, sodium and magnesium ion-conductors are also discovered and are now tested in batteries [3]. A fascinating structural chemistry is discovered within metal borohydrides, e.g. up to 30% ‘empty’ space in the porous structures and physisorption of small molecules. Recently, we stabilized NH4BH4 with extreme hydrogen density, 24.5 wt% H2 [2]. Tailoring materials properties by nanoconfinement is also promising [4]. We conclude that the chemistry of hydrides is very divers, towards rational design of multi-functional materials, including ion-conductors for batteries, hydrogen storage etc. Ref: [1] Ley, et al, Mater. Today, 2014, 17(3), 122. [2] Schouwink, et al, Nature Comm., 2014, 5, 5706. [3] Ley, et al, Chem. Mater. 2012, 24, 1654. [4] Nielsen, et al, Nanoscale, 2011, 3, 2086.

D.10.2
11:50
Authors : H.Andrade, M.Z.Othman, S.C.Halliwell, N.A.Fox
Affiliations : University of Bristol

Resume : Diamond is a candidate electrode material for use in thermionic energy converters that harvest heat from renewable energy sources such as concentrated solar radiation. It has a number of attributes that make it attractive for use as a thermionic electron emitter, including, a low temperature emission threshold, a surface that supports a negative electron affinity (NEA), and high temperature, p-type semi conductivity. However, a key requirement for any thermionic material is that the emitting surface exhibits a NEA during repeated operation that remains constant and stable. To realise a stable NEA on diamond, the surface needs to be functionalized with a monolayer of specific atomic elements. The monolayer adatoms form surface dipoles that lower the potential barrier of the surface which induces a dramatic decrease in work function leading to a NEA surface. UHV Kelvin Probe Force Microscopy (KPFM) has been employed to study work function changes on p-type BDD diamond surfaces due to surface functionalisation. Thin film diamond samples were grown heteroepitaxially onto single crystal and Si substrates by means of hot filament chemical vapour deposition. After terminating the diamond with oxygen, lithium or magnesium sub-monolayers were deposited on the diamond films with an e-beam thermal evaporator under UHV conditions followed by in situ characterisation via KPFM. The work function of the diamond was examined under different surface coverages as well as the adatoms thermal desorption after annealing at different temperatures. Surface stability under air exposure and material performance were also tested by performing thermionic emission experiments on n-type diamond under high vacuum using a laser heated system that allows for a fine temperature control with minimum thermal inertia. Hence, thermionic emission results for Li-O terminated n-type diamond are also presented.

D.10.3
12:15
Authors : 1)S.M.Filipek, 2)V.Paul-Boncour, 3)R.S.Liu, 4)I.Jacob, 5)T.Tsutaoka, 6)A.Budziak, 1)A.Morawski, H.Sugiura, 6)P.Zachariasz, 7)K.Dybko
Affiliations : 1)Institute of High Pressure Physics PAS, ul. Sokolowska 29, 01-142 Warsaw, Poland 2)ICMPE-CMTR, CNRS-UPEC, 2-8 rue Henri Dunant, 94320 Thiais, France 3)Department of Chemistry, National Taiwan University, Taipei 106, Taiwan 4)Dept. Nuclear Eng., Ben Gurion University of the Negev, Beer-Sheva, Israel 5)Dept. of Sci. Educ., Grad. School of Educ., Hiroshima University, Hiroshima, Japan 6)Institute of Nuclear Physics PAS, 31-342 Kraków, Poland 7)Institute of Physics, PAS, 02-668 Warsaw, Poland

Resume : Hydrogen, the most simple element, can have a very complex, often unpredictable influence on certain properties of a metallic matrix while it interacts with it to form a hydride. It has been also confirmed that at high chemical potential of hydrogen (at high hydrogen pressure) it was possible to prepare a number of novel hydrides with unexpected properties. For a long time we were using the high hydrogen pressure technique to investigate metal-hydrogen systems focusing during last years on intermetallic compounds. Basing on our former reports supplemented by additional new results we present a comprehensive review on structural, magnetic and electronic properties of a number of hydrides synthesized from various intermetallic compounds, like: MeT2, Me7T3, MeNi5, Y6Mn23 and YMn12 (where Me = zirconium, yttrium or rare earth; T= transition metal). Unusual role of manganese in hydride forming processes was revealed. Hydrogen induced phase transitions, suppression of magnetism, antiferromagnetic-ferromagnetic and metal-insulator or semimetal-metal transitions are presented. Structural behavior of hydrides submitted to hydrostatic pressures up to 30 GPa is presented and discussed.

D.10.4
12:35 Lunch break    
 
Functional Materials/Nanomaterials: 1 : Stanisław M. Filipek
14:00
Authors : A.Calka
Affiliations : University of Wollongong, Faculty of Engineering and Information Sciences, Wollongong, NSW2522, Australia

Resume : Many functional materials are traditionally synthesized by slow reaction processes that are energy and time consuming. In the present world there is strong demand on development of modern materials and materials processing methods that could offer rapid reaction rates, energy efficiency and be environmentally safe. Here we report application of newly developed Electric Discharge Assisted Mechanical Milling (EDAMM) [1] technique for generation of rapid chemical reactions in plasma environment. Electro-mechano-chemical processing of solids is a new and exciting materials processing technique which combines the attributes of conventional mechanical milling with all effects generated by electric discharges. It is demonstrated that Electro-mechano-chemical method can be used to process wide range of materials and synthesize a range of functional materials in a matter of minutes, rather than days. In this study we show application of this method in reduction of oxides, generation of replacement reactions, solubility of nitrogen and hydrogen in metals and non-metals, reactions between carbon and metals, and synthesis of complex oxides from simple oxides or metals. Also the effect of AC and DC plasma on reaction rates will be presented and discussed. Obtained results will be compared and contrast with conventional processing methods such as sol-gel reactions, solid state reactions, mechanical alloying and mechano-chemical approaches that have been used to create reactions between species. [1] Nature, 419,(2002)147-151

D.11.1
14:30
Authors : Malgorzata Lewandowska, Piotr Bazarnik, Marta Lipińska, Ewa Ura-Bińczyk
Affiliations : Warsaw University of Technology Faculty of Materials Science and Engineering

Resume : Nanostructured materials are characterized by grains ranging in size from 1 – 100 nm and as a result high surface area of grain boundaries. Grain refinement down to nanometre scale offers a great increase in mechanical strength such as yield strength or hardness according to Hall-Petch relationship. However, the effect of reduced grain size on the corrosion resistance is not yet well understood. Due to high volume fraction of intercrystalline regions, they possess a great concentration of defects which increases reactivity and diffusivity. In addition, nanostructure is chemically more homogenous comparing to conventional microstructure, which can decrease the role of corrosion microcells in the electrochemical processes. In this study, the corrosion resistance of aluminium alloys with various grain size and precipitation state was investigated. The measurements were performed in 0.1M NaCl. The potentiodynamic polarization measurements showed that nanocrystalline sample has lower corrosion potential and lower corrosion current compared to microcrystalline one. The observations of surface morphology after immersion in 0.1M NaCl revealed the galvanic corrosion related to the presence of intermetallic particles. For microcrystalline sample, the intergranular corrosion attack was observed. The special attention has been paid on the role of grain boundary misorientation angle and second phase particles.

D.11.2
14:45
Authors : Ł.Skowroński 1, O.Strauss 1, A.Wachowiak 1,2, M.Naparty 1, A.Grabowski 1
Affiliations : 1 Institute of Mathematics and Physics, UTP University of Sciences and Technology, Bydgoszcz, Poland; 2 Institute of Electrical Engineering, UTP University of Sciences and Technology, Bydgoszcz, Poland

Resume : Titanium oxide is a material widely used in optoelectronic, electrochromic devices and dye-sensitized solar cells. Moreover, TiO2 (also in the doped form) can be used as protective and antireflective coatings. Generally, TiO2 is a non-absorbing material in the visible spectral range. Because of its high refractive index value (n) and strong dispersion of n for energies lower than the absorption threshold, titanium dioxide deposited on titanium creates expressive interference colors for relatively thin dielectric layers (>20 nm). An opaque TiO2/Ti interference systems are widely known and were produced using different techniques. The TiO2/Ti/TiO2/glass systems were produced using gas injection magnetron sputtering (GIMS) method. The thickness of top dielectric film directly determines the color of coating. In turn, the thickness of Ti film affects the transparency of TiO2/Ti/TiO2/glass system. Optical and microstructural properties of the metal film strongly depend on the growing conditions. In this study, we investigate the influence of Ti film thickness and its optical constants on optical properties of TiO2/Ti/TiO2/glass systems. Additionally, the role of TiO2 layers placed over and under the Ti film is discussed. The produced samples were investigated by means of spectroscopic ellipsometry (SE), atomic force microscopy (AFM) and confocal optical microscopy (COM). Additionally, the reflectance (R) and transmittance (T) measurements were performed.

D.11.3
15:00
Authors : L.L. Patera (1,2), G. Prandini (1), V. Carnevali (1,3), C. Africh (2), G. Comelli (1,2), M. Peressi (1)
Affiliations : (1) University of Trieste, Department of Physics, Trieste (Italy); (2) IOM-CNR TASC Laboratory, Trieste (Italy); (3) University of Milan, Department of Physics, Milan (Italy)

Resume : Graphene is a material with outstanding physical, chemical and electronic properties which are relevant to several technological applications, including catalysis. In fact, although perfect graphene is chemical inert, morphological defects may strongly enhance its chemical activity. In the present work we focus on structural defects in graphene epitaxially grown on Ni(111), mainly carbon vacancies partially filled by nickel adatoms. By combining high resolution scanning tunnelling microscopy images and ab-initio calculations, we identify and characterise the structural and electronic properties of the most common defects and, as a preliminary study, we investigate their interaction with small molecules of environmental interest.

D.11.4
15:15
Authors : C. D’Urso1, C. Oldani2, V. Baglio1, , L. Merlo2, A.S. Aricò1
Affiliations : 1 Istituto di Tecnologie Avanzate per l’Energia “Nicola Giordano” (CNR), via Salita S. Lucia sopra Contesse, 5 - 98126 Messina, Italy; 2Solvay Specialty Polymers Italy S.p.A., Viale Lombardia 20, Bollate (MI), Italy

Resume : A radical scavenger based on Ce-oxide supported on sulfonated silica was synthesized by a simple method and physico-chemically characterized to investigate the structure and morphology. The material was introduced in ePTFE reinforced membranes prepared starting from suitable Aquivion® PFSA dispersions. The aim is to mitigate the peroxy radicals attack to the polymeric membrane under fuel cell operating conditions. The influence of this hydrogen peroxide decomposition catalyst on the membrane durability was investigated ex-situ by using a Fenton’s test and under OCV accelerated stress test in a real fuel cell. These membranes show much longer lifetime in Accelerated Stress Tests (AST) and reduced fluoride release in Fenton’s tests than the radical scavenger-free membrane without any loss in electrochemical performance. These results confirm the stability of the modified membranes and the excellent activity of the composite scavenger in mitigating the polymer electrolyte degradation. Furthermore, the silica supported scavenger is more stable in terms of leaching behaviour than a membrane containing unanchored Ce(III) ions.

D.11.5
15:30 Coffee break    
 
Chemical and Electrochemical Methods, 1 : Philippe Marcus
16:00
Authors : Isao Saeki, Sun Shijie, Takahiro Seguchi, Yusuke Kourakata, and Yuya Hayashi
Affiliations : Department of Materials Science and Engineering, Muroran Institute of Technology,

Resume : AZ91D magnesium alloys can be used in place of steels and aluminum alloys because of their high specific strength. However, the use of the alloys is limited due to their aggressive corrosion in acidic to neutral pHs. If the corrosion resistance of the alloy is improved, the alloys are expected to use for automobile components to reduce the mass and to increase miles per a gallon. To obtain corrosion-resistant Mg alloy, a complete coverage with stable metals or materials without pinhole. Considering availability and production costs, Ni electroplating is advantageous among candidate materials. However, the common Ni electroplating baths are not applicable to Mg alloys, because Mg alloys corrodes in the acidic plating bath. Therefore, Cu electroplating from alkaline cyanide bathes are used for this purpose so far. In this study, we developed a Ni electroplating bath containing citrate ions that can operate at pH 9 – 10. In this presentation, composition of the bath, optimum condition of pretreatments for Ni deposition will be introduced. Ability of a bright Ni plating, Ni-SiC codeposition layer formation on Mg alloy will also be demonstrated.

D.12.1
16:25
Authors : Mikito Ueda
Affiliations : Faculty of Engineering, Hokkaido University

Resume : Al alloys are electrodeposited from chloroaluminate molten salt or ionic liquid containing AlCl3. In this presentation, I report electrodeposition of Al-Pt alloys, Al-Sn alloys, and Al-Ta alloys. To form Al-Pt alloys, molten salt electrolysis was carried out in an AlCl3-NaCl-KCl molten salt containing PtCl2 at 448 K. The voltammogram showed cathodic reduction of Pt ions to start at a potential of 1.4 V vs. Al/Al(III) in the molten salt. Deposition of pure Pt was possible at 1.2 V and there was co-deposition of Al and Pt at potentials more negative than 1.0 V. The co-deposit was a mixture of intermetallic compounds of AlPt2 or AlPt3. Electrodeposition of Al-Sn alloys was performed in the AlCl3-NaCl-KCl molten salt containing SnCl2 at 423 K or 1-ethyl-3-methyl imidazolium chloride (EMIC)- AlCl3 ionic liquid containing SnCl2 at 303 K. Co-deposition of Al and Sn occurred at potentials more negative than 0.1 V. In comparison of morphology of electrodeposits, Al-Sn electrodeposit formed in ionic liquid became more fine particles than that formed in molten salt. In the structural observations of Al-Sn alloys, an alternate stacked structure of Al and Sn is obtained in the molten salt. Al-Ta alloys was electrodeposited in the AlCl3-NaCl-KCl molten salt containing TaCl5 at 423 K. In the voltammogram, 2 step cathodic reduction of Ta ions occurred at potential of 0.7 and 0.45 V in the molten salt. When Ta concentration in the electrodeposit increased, size of Al-Ta electrodeposit d

D.12.2
16:50
Authors : Jacek Banaś
Affiliations : AGH University of Science and Engineering

Resume : Thermal waters are one of the most environmentally friendly energy sources. The use of geothermal energy eliminates environmental pollution from combustion processes, particularly from carbon dioxide. Because of continues circulation of water in cycle producing - injection well (doublet operating system), we can talk about "renewable" energy sources. In this system, hot geothermal water after exchange of the heat is injected into the geothermal aquifer and can be re-used as a heat carrier. One of the serious problems determining the costs of geothermal systems exploitation is the corrosion of installation and tubing as well as colmatage of injection well. Both phenomena are stimulated by microbial corrosion in anaerobic environment H2O-NaCl-Na2SO4-CO2 . The lecture presents the review of our investigations of the mechanism and kinetics of corrosion and passivation of iron, carbon steels and chromium steels in the H2O – NaCl – CO2 – H2S system, in elevated temperature and at high pressure. The work is very important for the selection of corrosion resistant steels for geothermal plants. Corrosion mechanism of carbon steel is discussed and the influence of chromium content in the steel and the effect of thermal treatment of the alloys on the mechanism of anodic layer formation and corrosion resistance of the alloys are explained. The paper presents also the passive behavior of stainless chromium steels in thermal water with high salinity (brine). The investigations were performed in laboratory (autoclave) and in field conditions, in Polish geothermal power plants (electrochemical measurements at high pressure and high water flow rate, up to 2m/s). Special attention was paid to impact of microbial corrosion in geothermal installations. The lecture presents a comprehensive study of the corrosion deposits structure and biofilm formation in two geothermal plants exploiting low mineralized (Geotermia Mazowiecka SA) and high mineralized water (Geotermia Pyrzyce). The studies revealed the presence of sulphate reducing bacteria (SRB) in sediments of the installation. Their presence is the main cause of formation of biofilm layer (EPS), and corrosion products containing iron sulfide. Voltammetric and electrochemical impedance measurements carried out both in the laboratory and under field condition allowed to demonstrate the impact of the SRB on the corrosion mechanism of carbon steel in low and high mineralized geothermal waters. The work was financially supported by The National Centre for Research and Development , NCBiR, Project: INNOTECH-K1/IN1/38/151093/NCBR/12, Development and implementation of methods for continuous monitoring of corrosion and microbial biofilm formation in the Polish geothermal installations

D.12.3
17:10
Authors : Christian Caspers, Pedro Freire da Silva, Jean-Philippe Ansermet
Affiliations : École Polytechnique Fédérale de Lausanne EPFL/LPMN, 1015 Lausanne, Switzerland; Instituto Superior Técnico, UT Lisboa, 49-001 Lisboa, Portugal

Resume : Electron Spin Resonance can be used as an analytical tool to characterize the surfaces of oxides, for example. However, the number of spins at surfaces is critically low and the spectral resolution may often be insufficient to distinguish among various sites. Both these issues can be improved by going to high fields. Quasi-optical Martin-Puplett (MP) interferometry is perfectly suitable to conduct cw ESR. Our newly developed MP spectrometer runs at about 260 GHz in a field of 9.4 Tesla. We present first promising results for DPPH recorded with only 0.1 mW microwave power. This quasi-optical Martin-Puplett ESR is design to operate in-line with the high-power sub-THz radiation (260 GHz) generated by a tunable gyrotron. Our aim is to control dynamic nuclear polarization (DNP) experiments by parallel monitoring of the electronic spin resonance.

D.15.6
17:30
Authors : Christina Enengl, Sandra Enengl, Marek Havlicek, Eric Daniel Glowacki, Helmut Neugebauer, Eitan Ehrenfreund, Kurt Hingerl, Niyazi Serdar Sariciftci
Affiliations : Linz Institute for Organic Solar Cells (LIOS), Physical Chemistry, Johannes Kepler University, 4040 Linz, Austria; Linz Institute for Organic Solar Cells (LIOS), Physical Chemistry, Johannes Kepler University, 4040 Linz, Austria; Linz Institute for Organic Solar Cells (LIOS), Physical Chemistry, Johannes Kepler University, 4040 Linz, Austria; Linz Institute for Organic Solar Cells (LIOS), Physical Chemistry, Johannes Kepler University, 4040 Linz, Austria; Linz Institute for Organic Solar Cells (LIOS), Physical Chemistry, Johannes Kepler University, 4040 Linz, Austria; Department of Physics and Solid State Institute, Technion-Israel Institute of Technology, 32000 Haifa, Israel; Center for Surface- and Nanoanalytics (ZONA), Johannes Kepler University, 4040 Linz, Austria; Linz Institute for Organic Solar Cells (LIOS), Physical Chemistry, Johannes Kepler University, 4040 Linz, Austria

Resume : We report on in-situ spectroscopic studies during chemical as well as electrochemical oxidation of quinacridone and compare these results to its well-known analog pentacene. While pentacene shows one oxidation peak in the cyclic voltammogram, quinacridone has two well-defined oxidation peaks. At the beginning of the electrochemical oxidation of quinacridone a broad absorption band arises in the mid-IR while no spectral changes are observed in the UV-VIS. During the second oxidation the electronic transition in the mid-IR decreases and several absorption bands appear in the UV-VIS. Interestingly, by chemical oxidation just the first oxidation peak is reached showing analogous spectral behavior as obtained by electrochemical oxidation. The creation of different kinds of radical cations during distinct oxidation states is confirmed by electron paramagnetic resonance (EPR) measurements. Pentacene behaves differently upon oxidation. It shows several absorption bands in the UV-VIS range and a transition in the mid-IR, at which the maximum is shifting as the oxidation proceeds. In addition, the initially increasing EPR signal decreases upon oxidation. From these measurements we conclude that reactions, like dimerizations, occur, which are blocked in quinacridone by introducing heteroatoms on a pentacene like frame. Similar behavior is obtained for the electrochemical reduction for both organic semiconductors.

D.12.5
18:00 Best Student Presentation Awards Ceremony and Reception - Main Hall    
Start atSubject View AllNum.
09:00 Plenary Session - Main Hall    
 
Short Communications : Marcin Pisarek
12:05
Authors : M. Gioti1, C. I. Chaidou1, D. Kokkinos1, C. Pitsalidis1, C. Polyzoidis1, A.K. Andreopoulou2,3, E. Mparmpoutsis2, J.K. Kallitsis2,3, S. Logothetidis1
Affiliations : 1 Laboratory for Thin Films-Nanosystems and Nanometrology (LTFN), Physics Department, Aristotle University of Thessaloniki, GR-54124 Thessaloniki, Greece; 2 Department of Chemistry, University of Patras, University Campus, Rio-Patras GR26504, Greece; 3 Foundation for Research and Technology Hellas, Institute of Chemical Engineering Sciences (FORTH/ICE-HT), Platani Str., Patras GR26504, Greece

Resume : New synthesized anthracene-based and carbazole-based polymers as well as commercially available polymers such as polyfluorenes and polyphenylene vinylenes were applied as emitting materials in organic light-emitting diode (OLED) devices. Initially, spin coating and subsequently printing processes were used for the fabrication of the polymer thin films and the final devices either in rigid or flexible form. The photoluminescence (PL) of the polymeric films were evaluated by Fluorescence Spectroscopy revealing the characteristic emission of each material. The optical properties of the polymers were investigated by NIR-Vis-far UV Spectroscopic Ellipsometry. The accurate determination of the thickness and the optical constants (refractive index, dielectric function and absorption coefficient as a function of wavelength) were derived. Furthermore, quantum yield measurements, brightness, chromaticity and current density–voltage characteristics of the devices were obtained. A strong correlation between the optical properties, the thickness and the devices’ performance was established since external quantum efficiency of electroluminescence also depends on the optical interference of the beams of emitted light multiply reflected from the layer interfaces. This provides substantial insights into the final design of the optimum final multi-layer structure of the OLEDs whereas the potentiality for the development of flexible OLEDs with bigger active area devices is demonstrated.

D.13.1
12:15
Authors : Xue Yang, Yanyuan Qi, Yueli Liu, Yang Yu, Wen Chen
Affiliations : State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, P. R. China

Resume : Although WO3 nanorods [1] and nanowires [2] have better electrochemical properties compared with the bulk WO3, they also have suffered from poor capacity retention, rate capacity, and bad conductivity. Recently, several metal oxides (e.g. NiO [3], Cu2O [4]) directly grown on metallic substrates have been reported for the electrochemical application of LIBs and exhibited superior performance. Therefore, it is still needed to enrich the understanding of the directly grown nanostructures on metallic substrate for the high-performance electrochemical energy storage application. In the present work, WO3 nanoflower arrays prepared by anodization process consist of the ordered nanoplates with a thickness of 10 nm. Subsequently, the Ag nanoparticles are loaded on the as-prepared WO3 nanoflower arrays by screen-printing. They have been studied by CV, EIS, and the charge-discharge test at various current densities. The results indicate that Ag loaded WO3 nanoflower arrays electrodes present outstanding electrochemical properties, especially the rate capability, which can be mainly ascribed to the Ag loaded 3D composite structures and a direct growth on a conductive substrate. The 3D structure accommodates the stress by the volume change during the electrochemical reaction, and the loaded Ag leads to a perfect conductivity. Moreover, direct growth on metallic substrate can form good adhesion and a better electrical contact between WO3 nanoflower arrays and the metallic substrates.

D.13.3
12:25
Authors : Amir Pakdel, Takao Mori, Yoshio Bando, Dmitri Golberg
Affiliations : National Institute for Materials Science (NIMS), Tsukuba 305-0044, Japan

Resume : Today many aspects of science and technology are progressing into the nanoscale realm where surfaces and interfaces are intrinsically important in determining properties and performances of materials and devices. This is because the physical and chemical processes taking place at surfaces and interfaces tend to be different from the ones in bulk phases. Therefore, nanoscale manipulation of interfacial features can lead us to obtain materials with modified or totally new properties. Here we report the results of a systematic research work on the development of a CVD method to synthesize hierarchical boron nitride (BN) nanostructures (such as nanotubes, nanosheets, etc), followed by the application of a plasma method to achieve covalent chemical functionalization on their surfaces. Then, the influence of morphology manipulation and surface functionalization on the static and dynamic wetting properties of the BN nanostructures is discussed. In short, an unusual rise to intrinsic water-repellency of BN was observed due to nanoscale topography, and by controlling the surface roughness, a wide range of water contact angles (CAs) between ~50? to ~160? was achieved. Moreover, by controlled grafting of functional groups, superhydrophilic, hydrophilic, hydrophobic, and superhydrophobic patterns could be created on the hierarchical BN nanoarchitectures. Finally, by introducing a gradient of the functional groups, directional liquid spreading was achieved on the surfaces.

D.13.4
12:40 Lunch break    
 
Functional Materials/Nanomaterials: 2 : Hiroki Habazaki
14:00
Authors : Markus Niederberger
Affiliations : Laboratory for Multifunctional Materials, Department of Materials, ETH Zurich, Vladimir-Prelog-Weg 5, 8093 Zurich, Switzerland

Resume : Nanostructures including nanoparticles, nanowires and nanosheets are the ideal building blocks for the bottom-up fabrication of functional materials. They offer an immense variety of interesting properties, which not only depend on the composition, but also on the crystal structure, the particle size and shape and on the surface chemistry. Accordingly, potential synthesis routes have to provide full control over all these parameters. In addition, for most applications the nanoparticles have to be assembled and processed into useful geometries, architectures and bodies, and for this purpose, the surface properties of the nanoparticles have to be tailored carefully. The talk will cover the synthesis of metal oxide nanoparticles with different morphologies by nonaqueous sol-gel chemistry and their use as building blocks for the fabrication of 2- and 3-dimensional architectures. Fine-tuning of the surface chemistry of the nanoparticles makes it possible to self-assemble them over several length scales from the nanometer to the centimeter range [1]. For specific applications the nanoparticles can also be processed into thin films. Finally, we will show how such a bottom-up approach using preformed building blocks can be extended to the fabrication of macroscopic metal sponge monoliths [2]. [1] Metal Oxide Particles in Materials Science: Addressing All Length Scales, D. Koziej, A. Lauria, M. Niederberger, Adv. Mater. 2014, 26, 235-257. [2] Wet-Chemical Preparation of Copper Foam

D.14.1
14:30
Authors : G.D. Sulka*, L. Zaraska, J. Kapusta-Kołodziej, A. Brzózka, M. Jarosz, E. Kurowska-Tabor, E. Wierzbicka, A. Brudzisz, K. Syrek, A. Pawlik
Affiliations : Department of Physical Chemistry and Electrochemistry, Jagiellonian University in Krakow, Ingardena 3, 30060 Krakow, Poland *e-mail: sulka@chemia.uj.edu.pl

Resume : Anodic valve metal oxides have recently received significant attention due to a successful combination of functional chemical/physical properties with a well controllable nano-architecture. By controlling parameters of the electrochemical oxidation, especially the applied anodizing potential, temperature, electrolyte composition and the process duration, a great variety of unique oxide structures with different morphologies and characteristic parameters can be easily obtained. Here, we present some data on the fabrication of various nanoporous/nanotubular metal oxides including Al2O3, TiO2, SnO2, ZrO2, WO3, and Fe3O4. Nanoporous anodic aluminum oxide (AAO) membranes formed by two-step anodization have become the most popular templates used for fabrication of diverse metal, polymer, composites nanowire arrays. Anodic titanium oxide (ATO) and zirconium oxide, fabricated by electrochemical anodization under well-controlled conditions, exhibits high-ordered, close-packed and hexagonally arranged pores. As-prepared anodic films on stainless steel have amorphous structures and comprise of iron oxyhydroxides. On the other hand, anodization of tin and tungsten results rather in porous oxide layers with a random pore distribution. There are several potential technological applications of these nanomaterials in energy storage systems, photovoltaics, electrocatalysis and as novel thermoelectric materials, chemical and biochemical sensors as well as biocompatible materials for bone implants.

D.14.2
14:55
Authors : Galina A. Tsirlina
Affiliations : Dept of Electrochemistry, Moscow State University

Resume : The processes of cathodic and anodic electrocrystallization of conducting and semiconducting oxides are addressed in the context of medium and deposition potential effects on stoichiometry and phase composition of newly formed oxides. Various functional properties of oxide films formed by means of electrodeposition are discussed, with the focus on electrochromic and electrocatalytic applications. To avoid misunderstandings, the principle difference of oxides electrocrystallisation and oxides electrochemically induced deposition is explained. The advantages of the former approach consist in much higher controllability (as provided by potential-dependent oversaturation) and possibility of direct monitoring (based on coulometry). In addition, the deposit morphology can be also controlled and monitored when electrocrystallisation takes place, because nucleation and growth modes responsible for morphology can be understood from the details of deposition current transients. Illustrations from original research are presented for deposition of oxides of IV and VI transition metal groups. The problems of fabrication of metal/oxide and polymer/oxide compositions on the basis of electrodeposition are listed, and possible solutions are proposed.

D.14.3
15:15
Authors : Dickon H.L. Ng (1), Jia Li (2)
Affiliations : (1) Department of Physics, The Chinese University of Hong Kong, Shatin, Hong Kong, China; (2) School of Material Science and Engineering, University of Jinan, Jinan, China

Resume : Magnetic hollow fibers containing ZnFe2O4 nano-crystallites were fabricated by bio-templating. In sample preparation, kapok fibers were submerged in a mixture of Zn(NO3)2 and Fe(NO3)2. The infiltrated kapok fibers were dried and heat-treated at high temperature in ambient. Characterization showed that the appearance of the as-prepared sample resembled to those of the original kapok fibers. However, they were fully covered with ZnFe2O4 nano-crystallites (size of 30 to 50 nm), and with pores ranging from 2 to 10 nm. The adsorption kinetics and thermodynamics of the organic dye (acid fuchsin) molecules attached onto the ZnFe2O4 fibers were investigated. The adsorption was spontaneous and exothermic and the process could be well-described by the Langmuir model, and the pseudo second order kinetics model as well. The maximum adsorption capacity of these hollow fibers for acid fuchsin was determined to be 150.4 mg/g. Electrostatics and specific interactions between the dye molecules and the organic groups on the fiber surface were considered to be the drive of adsorption. The hollow fibers also exhibited strong ferrimagnetic behavior. This favored their high-efficient magnetic separation from waste water under applied magnetic field after dye adsorption. The fabrication route of the magnetic ZnFe2O4 hollow fibers by using kapok as bio-template is facile. In adsorbing organic dyes during water treatment, they appear effective and user-friendly.

D.14.4
15:30 Coffee break    
 
Chemical and Electrochemical Methods, 2 : Jacek Banaś
16:00
Authors : Christine Blanc, Mathilde Guérin, Joël Alexis, Eric Andrieu, Lydia Laffont, Williams Lefebvre, Grégory Odemer
Affiliations : Christine Blanc, Mathilde Guérin, Eric Andrieu, Lydia Laffont, Grégory Odemer: Université de Toulouse, CIRIMAT, UPS/INPT/CNRS, ENSIACET, 4 allée Emile Monso BP44362, 31 030 Toulouse Cedex 4, France Williams Lefebvre:Université de Rouen, GPM - UFR Sciences et Techniques, Avenue de l’Université - BP12 76801 Saint Etienne du Rouvray, France Joël Alexis: Université de Toulouse, LGP, ENIT/INPT, 47 avenue d’Azereix, BP1629, 65016 Tarbes cedex, France

Resume : The corrosion behaviour of aluminium alloys is often explained by the nature and the distribution of intermetallic precipitates but experimental results suggested that metallurgical parameters at the polycristal scale have to be considered The nature of the interfaces, the grain size and their internal misorientation represent factors of main interest. The material studied was a AA 2050 alloy in both a non-aged metallurgical state (NHT) and an aged metallurgical state (HT). During continuous immersion in a NaCl solution, NHT samples are susceptible to intergranular corrosion and intragranular corrosion is observed for HT samples. The corroded interfaces and/or grains were detected by combining scanning electron microscopy observations and energy dispersive spectroscopy to generate corrosion maps. These maps were superimposed to electron backscattered diffraction cartographies, obtained for healthy samples and for the same zone, allowing to identify accurately the corroded interfaces and/or corroded grains. The corrosion susceptibility of the interfaces was correlated to their misorientation level but galvanic coupling between grains of different internal misorientations contributed to explain intergranular corrosion susceptibility. Concerning the intragranular corrosion, links were clearly established between the internal misorientation of grains and their corrosion susceptibility.

D.15.1
16:20
Authors : Peter Rodič, Barbara Volarič, Ingrid Milošev
Affiliations : Jožef Stefan Institute, Ljubljan, Slovenia

Resume : Improvement of corrosion resistance of aluminium and its alloys, especially under operating conditions in aeronautic, nautic and automobile industries, is a necessity. Chromate conversion coatings were used with great success for decades but due to their cancerogenic and toxic activity their use is restricted by the RoHS Directive 2002/95/EC which took effect in 2006 in the EU. Due to this restriction, considerable efforts have been directed in the last decade towards the investigation of technologies alternative to chromate conversion coatings. Various approaches have been studied; however, a full alternative has not yet been put into market. In the last decade the European automobile industry has more than doubled the average amount of aluminium used in passenger cars and the trend in increasing. This implies an increased need for aluminium protection. Among conversion coatings lanthanide salts, especially cerium has been identified. Cerium is the most active and the only lanthanide, which can be oxidized in a stable salt with a higher oxidization state. The mechanism of surface protection includes the formation of a protective layer of hydroxide and/or oxide. This reaction is carried out on metal inclusions (Zn, Cu, Mg), which are electrochemically more negative compared to remaining surface of aluminium alloy, and act as a cathode site. Instead using individual inhibitors, a mixture of inhibitors may achieve an enhanced effect. Two methodologies were taken – non-accelerated immersion and accelerated conversion coatings. Another approach includes barrier hybrid coatings based on sol-gel methodology. The sol-gel process allows the introduction of organic molecules into an inorganic network, forming hybrid organic-inorganic coatings, the so-called ormosils also known as silanes. Prepared conversion and hybrid coatings were studied by electrochemical corrosion measurements in combination with various surface analytical methods.

D.15.2
16:40
Authors : H. Habazaki, K. Kure, T. Hiraga, E. Tsuji, Y. Aoki
Affiliations : Faculty of Engineering, Hokkaido University

Resume : Superhydrophobic and superoleophobic surfaces have attracted much attention because of their potential applications such as self-cleaning, anti-freezing and anti-biofouling. Compared with superhydrophobic surfaces, the fabrication of superoleophobic surfaces for liquids with low surface tensions is difficult, because the most of the solid surface is practically oleophilic. To achieve the superoleophobicity, the geometrical control of the solid surface, which can introduce an effective pinning effect, is of crucial importance. Micro- and nano-scale hierarchically rough surfaces are one of the suitable surface geometry for superoleophobicity. The present study demonstrated the formation of superoleophobic Type 430 stainless steel surface by combining the electrochemical etching, anodizing and organic monolayer coating. Type 430 stainless steel specimen was electrochemically etched in 37 wt% HNO3 for 50 - 1500 s. Then, the etched specimens were anodized at 80 V in ethylene glycol electrolyte containing 0.05 - 0.2 mol dm-3 NH4F and 0.1 - 0.5 mol dm-3 H2O at 293 K for 300 - 1800 s. After the anodized specimens were annealed at 628 K in the air for 30 min, the specimens were coated with a layer of mono-[2-(perfluorooctyl)ethyl]phosphate (FAP) by immersing in a 2 wt% solution of FAP in ethanol for 3 days at room temperature. By combining the electrochemical etching and anodizing, hierarchical surfaces with microscale roughness produced by etching and nanopores developed by anodizing were obtained. The hierarchical surfaces with optimized geometry showed superhydrophobicity and also superoleophobicity for rapeseed oil.

D.15.3
16:55
Authors : Micael Alonso Frank1,2, Christian Meltzer3, Björn Braunschweig3, Wolfgang Peukert3, Aldo. R. Boccaccini2 and Sannakaisa Virtanen1
Affiliations : 1-Institute of Surface Science and Corrosion, University of Erlangen-Nuremberg, Germany 2-Institute of Biomaterials, University of Erlangen-Nuremberg, Germany 3-Institute of Particle Technology, University of Erlangen-Nuremberg, Germany

Resume : The interactions between organic molecules and surfaces of steels were studied. Various organic acids were used with different chain lengths and different chemical bonding. Two materials were used as substrates, stainless steel 316L and carbon steel N80. These two materials were chosen regarding their opposite corrosion resistance: stainless steel 316L has a high resistance and a wide range of applications, whereas carbon steel N80, which is used for instance in petroleum industries, shows a low corrosion resistance. Surface binding was created and the surface energy was decreased, which induced a decrease in the wettability. In order to analyze the homogeneity of the coatings as a function of the immersion time, concentration, chain length and the chemical bond between the molecules and the surface, sum frequency generation spectroscopy was used. In a previous study for this kind of organic coating, the interaction between surface roughness and surface energy according to the Cassie-Baxter model led to superhydrophobic surfaces with a contact angle above 150°. We also examined the correlation between the immersion time, concentration, chain length and chemical binding of the molecules and the corrosion resistance and wettability. Electrochemical investigations revealed a shift of the corrosion potential values into the positive direction, a decrease of the corrosion current density, this correlating with an improvement in the hydrophobicity of the samples.

D.15.4
17:10
Authors : Andrei Ionut Mardare, Jan Philipp Kollender, Martina Hafner, Achim Walter Hassel
Affiliations : Christian Doppler Laboratory for Combinatorial oxide chemistry at the Institute for Chemical Technology of Inorganic Materials Johannes Kepler University Linz, 4040, Linz, Austria; CEST Competence Centre for Electrochemical Surface Technology Viktor Kaplan Strasse 2, 2700, Wiener Neustadt, Austria

Resume : Scanning droplet cell microscopy (SDCM) recently found applications in fields with implications beyond pure electrochemistry. Due to a new special tip design allowing for stationary or flowing electrolyte conditions, a high reproducibility of the wetted area is achieved which makes the SDCM a preferred tool for local corrosion testing on metallic surfaces as well as for performing electrochemical screening of thin film combinatorial libraries. The electrochemical behavior of Hf-Ta thin film alloys deposited by co-sputtering in a wide compositional range (21 to 91 at.% Ta) was investigated. The transition from hexagonal Hf to tetragonal Ta along the compositional spread occurs through an amorphisation region where Hf-Ta metallic glasses were evidenced. The properties of anodic oxides grown on Hf-Ta alloys were mapped along the compositional gradient. Remarkable dielectric properties of the mixed Hf-Ta oxides were identified with direct applications in electronics as high-k materials. The use of highly sensitive downstream analytics (inductively-coupled plasma mass spectrometer) coupled to a flow-type SDCM allowed a careful quantitative study of the corrosion behavior of the Hf-Ta alloys. The corrosion rates dependence on the Hf-Ta composition are presented for the entire compositional spread analyzed. This is highly relevant for challenging applications such as nuclear fuel element cladding, liquid alkali metal containment or bio-medical applications (e.g. orthopedic implants).

D.15.5
18:15 Symposium dinner and concert    

Symposium organizers
Marcin PISAREKInstitute of Physical Chemistry / Polish Academy of Sciences

Kasprzaka 44/52 PL-01-224 Warsaw Poland

+48 22 343 32 91
mpisarek@ichf.edu.pl
Maria JANIK-CZACHOR (Honorary Chairperson)Institute of Physical Chemistry - Polish Academy of Sciences

Kasprzaka 44/52 PL-01-224 Warsaw Poland

+48 22 343 33 33
mczachor@ichf.edu.pl
Hiroki HABAZAKIDivision of Materials Chemistry, Faculty of Engineering, Hokkaido University

North 13, West 8, Kita-ku Sapporo 060-8628 Japan

+81-11-706-6575
habazaki@eng.hokudai.ac.jp
Aleksander KRUPSKI [UK]Department of Earth & Environmental Sciences, Faculty of Science, University of Portsmouth

Burnaby Road PO1 3QL Portsmouth United Kingdom

+44 23 92 84 2294
Aleksander.Krupski@port.ac.uk
Aleksander KRUPSKI [PL]Department of Advanced Materials and Technologies, Faculty of Advanced Technology and Chemistry, Military University of Technology

2 Gen. Sylwestra Kaliskiego Str. 00-908 Warsaw Poland

+48 261 839 992
+48 261 839 445
Aleksander.Krupski@wat.edu.pl