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Abstracts selected for Oral and Poster Presentations in Advanced Nanomaterials (ANM) session

No. Name Title ID


Development of an antimicrobial therapeutic system encompassing aqueous-core
lipid nanoballoons housing strictly lytic bacteriophage particles for Pseudomonas
1 Victor Balco aeruginosa, targeted to the treatment of bacterial pneumonia 1
Carbon nanostructures for water remediation technologies
2 Tito Trindade 4
Carolina Alves Silver nanoparticles stabilized by bioactive polymers pluronic F68, PVP and PVA
3 dos Santos 5
Developments of Organic Light Emitting Diodes towards Solid State Lighting: state
4 Luiz F.R. Pereira of the art and challenges in nanotechnology 8
5 Liubov Antipina Enhanced electron coherence in atomically thin Nb3SiTe6 11
6 Jie Jin Stress transfer in polymer/CNT nanocomposites 14
Abdelmounaim Effects of molarity on physical properties of nanostructured copper oxide films
7 Chetoui deposited by spray pyrolysis for gas sensing applications 19
Fabrication of Ni-GDC Nanocomposite Material Prepared by Aqueous Based Tape
8 Wilson Acchar Casting Process 21
Fabrication and characterization of nano-zirconia films produced by aqueous based
9 Wilson Acchar tape casting process 22
Eduardo G. Synthesis and characterization of a novel catalyst based on dendrimer of core-POSS
10 Vieira and its applications in epoxidation of olefins 26
11 Aiping Zeng Plasma Treated Active Carbon for Capacitive Deionization of Saline Water 28
El Montassir Physical, antioxidant and antimicrobial properties of -chitin whiskers-reinforced
12 Dahmane chitosan nanocomposite films incorporated with Artemisia herba alba essential oil 35
13 Jan Krajczewski Plasmon-Driven Transformation of Silver Nanoparticles in O2-Free Conditions 42
Catalytic Activity of Hollow Platinum Nanoparticles Towards Reduction of 4-
14 Jan Krajczewski Nitrophenol 45
Scaling properties and related issues in the charge transport through molecular
15 Ioan Bldea junctions 48
16 Patrycja Bober Conducting Colloids Based on Extended Polypyrrole Nanostructures 51
Gloria Jimnez
17 Snchez Multifunctional gold nanoparticles for imaged guided radiotherapy 52
bouchemat-
Study of Photonic Crystal Biosensor using DNA Filled Microcavity in the
Boumaza
Sandwiched Waveguide Structure
18 Touraya 57
Interface Induced Growth and Transformation of Polymer-Conjugated
ProtoCrystalline Phases in Aluminosilicate Hybrids: A Multiple-Quantum 23Na-
19 Jiri Brus 23Na 60
Martina Structural characterization of pharmaceutical liquisolid systems by solid-state NMR
20 Urbanova spectroscopy 62
Porphyrin-Based Conjugated Microporous Polymers as Solid-State Photosensitizers
21 Jan Hynek of Singlet Oxygen 69
22 Monica Cerquido Fabrication of biocompatible gold mushroom-shaped microelectrode arrays 72
Surface acoustic waves for photoluminescence modulation of quasi-two-
23 Sumeet Walia dimensional MoS2 nanoflakes 73
Stability analysis of resistive switching in Nb-doped amorphous SrTiO3-x at high
24 Sumeet Walia temperatures 74
Nanostructured materials for the photocatalytic abatement of N-containing
25 Ilenia Rossetti pollutants from waste water 75
Highly Conductive Polymer Transparent Electrodes for Efficient ITO-Free Organic
26 Yoon Kyung Seo Optoelectronic Devices 77
Highly conductive poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) films
optimized with a novel solvent and post-treatment as transparent electrodes for
27 Yoon Kyung Seo ITO-free organic light-emitting diodes 78
Structured charge transport layers as a light outcoupling system for organic light-
28 Yoon Kyung Seo emitting diodes 79
Solvent doping and post-treatment process for poly(3,4-
ethylenedioxythiophene):poly(styrene sulfonate) as alternative transparent
29 Yoon Kyung Seo electrodes for ITO-free organic light-emitting diodes 80
Heman MnO2-Protected Silver Nanoparticles: Efficient Electromagnetic Nanoresonators for
30 Abdulrahman Raman Analysis of Surfaces in Basis Environment 82
Hanna
31 Maltanava Synthesis and characterization of efficient TiO2 mesoporous photocatalysts 84
Decahedral silver nanoparticles with silica layer as the new type of SHINERS
32 Karol Kotaj nanoresonators 87
A Three Dimensional Approach for Structural and Electrical Characterization of
33 Zsolt Zolnai Planar Sets of Gold Nanoparticles 89
34 Imen Ben Amara Exciton and trion features in MoS2/WS2 heterobilayers: Theoretical study 90
Bouchemat Theoretical study on silicon photonic crystal microcavity biosensor with improved
35 Mohamed sensitivity 91
Investigation of Growth Parameters on Hydrogen Defect Formation in
Nanocrystalline Diamond Films Grown by Microwave Plasma Chemical Vapour
36 Chunjiu Tang Deposition 93
Simulations of biophysically detailed neurons connected with nanoscale
37 Paulo Aguiar memristors 94
38 Nikita Kazennov Fullerene-Clad Ultra-Long Carbon Nanotube 95
Thermally conductive graphene-polymer composites: size, percolation and synergy
39 Oren Regev effects 102
Dzmitry Intermediate phase in Bi1-xPrxFeO3 ceramics at the rhombohedral-orthorhombic
40 Karpinski phase boundary 105
Anielle Christine Controlling Densities of Oxygen Vacancies in TiO2 Nanocrystals: Thermal annealing
41 Almeida Silva and Acidity of the Medium 106
Noelio Oliveira Synthesis of Simonkolleite Nanocrystals and Control of Transformation to Zinc
42 Dantas Oxide by Thermal Annealing 109
Roberto
Fernndez de Composite -AgVO3@V5+ 1.6V 4+ 0.4O4.8 hydrogels and xerogels. Protonic
43 Luis conduction and pollutant sequestration 111
44 Fa-Nian Shi Design Porous Co3O4 Ribbon for Electromagnetic Wave Absorption 116
Ekaterina Hexamethyldisiloxane Based Plasma Polymeric Nanomaterials for Gas Sensors
45 Radeva Application 118
Parnia Physical Vapour Deposition of Transparent Conducting Oxides and Barrier Layers
46 Navabpour for Large Area Optoelectronic Devices 120
47 Maria Messing Generation of Stainless Steel Nanoparticles with Tuned Composition 121
Preparation and characterization of non-toxic Er3+/Yb3+ doped strontium
48 M Pedro Graa lanthanum aluminate phosphors 122
TSDC and dielectric characterization of Hydroxyapatite/-Tricalcium Phosphate
49 P.R.S. Prezas bioceramics 123
Mariana Amorim Plasma-assisted atomic layer deposition of TiO2 thin films: effect of direct plasma
50 Fraga exposure during deposition on film structure and morphology 127
Tommaso Del Synthesis of colloidal dispersions of gold-oxocarbons nanocomposites by
51 Rosso atmospheric CO2 recycle during pulsed laser ablation in water 128
Micro and Nanoscale Mapping of Electrical Characterization of Graphene and
52 Ghazi Alsharif Semiconductor Heterostructures 129
Elaine Yoshiko Lithium intercalation in Carbon Nanotube/Bone Charcoal Composite coating with
53 Matsubara Metals Nanoparticles 130
54 Daniel Bek Nanoparticles of MOF-545/PCN-222: Synthesis and Phototoxicity 131
55 Catarina Dias Resistive Switching of Si/Ag interfaces with different layer thicknesses 133
Mariana Amorim
56 Fraga High Adhesion of Ultrananocrystalline Diamond Coatings to WC-Co Substrate 134
Koichi Zero-Dimensional Hybrid OrganicInorganic Halide Perovskite Modeling: Insights
57 Yamashita from First Principles 143
Development of e-nose biosensors based on organic semiconductors towards low-
58 Luiz F.R. Pereira cost health care diagnosis in gynecological diseases 147
59 Luiz F.R. Pereira Bulk-Heterojunction Organic Solar Cells area-dependent parameters fluctuation 148
60 David Kolousek A novel nanostructured complex adsorbent from aluminosilicate binders 159
Ammonolytical conversion of bulk wafers of gallium arsenide GaAs to polytype
61 Jerzy F. Janik specific nanopowders of the gallium nitride GaN semiconductor 160
62 Leonel Marques New carbon phases obtained from C70 at high-pressure and high-temperature 165
Space Charge Induced Electrostatic Doping of Two-Dimensional Materials:
63 Andrea Paradisi Graphene as a Case Study 169
Filipe
64 Matusalem Formation of stanene on SiC surfaces: An ab inito study 172
Arkadii
65 Arinstein Estimation of Polymer Stretching Degree Arising During Electrospinning 173
Anderson Effect Of Annealing Process In TiO2 Thin Films: Structural, Morphological, And
66 Dussan Cuenca Optical Properties 178
67 Heiddy Quiroz Natural Photonic Nanostructure of Greta Otto Butterfly 180
Evidence of Iridescence in TiO2 Nanostructures: an Approximation in Plane Wave
68 Heiddy Quiroz Expansion method 181
A Hierarchical Structure of Tb3+ functionalized MOF Coatings on ZnO Micronano
69 Yangyi Yang Arrays for Highly Selective Sensing Acetone 184
70 Norbert Nagy Introducing Nanoscaled Surface Morphology into Mesoporous Silica Films 185
Agnieszka Corrosion and Biological properties of Oxide and Nanooxide Layers on the
71 Ossowska Ti13Nb13Zr Alloy 187
Daniel Gonzalez Intracellular sulfidization of silver nanoparticles by microglia inhibits nanoparticle
72 Carter toxicity and reduces inflammation and neurodegeneration 191
73 Jeong Ho Chang Sol-gel preparation of size-controlled spherical silicified-liposomes particles 195
Controlled astaxanthin release with silicified phospholipids assembled boron
74 Jeong Ho Chang nitride complex for cosmetic application 196
Thermoresponsive Elimination of Hexavalent Chromium with PNIPAm grafted
75 Jeong Ho Chang Amino-functionalized Mesoporous Silica 197
Photoluminescent and electrical properties of ZnO thin films subjected to the
76 Lesya Gritsenko thermal annealing and a hydrogen plasma treatment 199
Kymbat
77 Amirkhanova Synthesis of fullerenes by arc discharge 204
78 Leonard Francis On the filling of Nanotubes New 1D HeteroNanostructures 207
Synthesis of high purity Ca(OH)2 nanoparticles with improved properties for
79 Marcos Lanzn consolidation of cultural heritage materials 208
Testing the efficiency of diluted nanolime suspensions in consolidating heritage
80 Marcos Lanzn materials: a case study for stone, plasters and adobe samples 209
Optimization of synthesis conditions for high electrical conductivity of polypyrrole
81 Martin Varga nanotubes 210
High-purity alumina production technology: hydrothermal oxidation of aluminum
82 Andrey Zhuk and following thermal treatment 214
Influence of operating parameters and ion doping on the photocatalytic activity of
83 Sandra S. Lucas mortars containing titanium dioxide nanoparticles 218
Mariana Amorim Correlation Between Metal Doping (Ti, Al and Ag) and Basic Properties of DLC Films
84 Fraga Produced by DC and HiPIMS Magnetron Sputtering 220
Anna D.
Dobrzaska-
85 Danikiewicz The CNTs-Re nanocomposites observed under electron microscopes 221
86 Kamila Mizera Flame retardant polyurethane composites with addition of carbon nanotubes 222
Serap SENTURK Size Effect and Geometric Thermal Stability of Hollow Pt3Ni Nanospheres: A
87 DALGIC Molecular Dynamics study 223
88 Gulsen TEZGOR Molecular Dynamics Simulations of AgPd Nanorings 224
89 Xiao-Yu Yang Self-assembly of Hierarchical Nanomaterals with High Activity and High Stability 229
Razika TALA- Aging Time Effect On ZnO Thin Films Photocatalytic Activity Synthesized By Sol- Gel
90 IGHIL Dip Coating Method 231
Maryam A Nano Zeolite Modified Carbon Paste Electrode for Electrocatalytic Oxidation of
91 Abrishamkar Hydrogen Peroxide in Alkaline Media 241
Sena Gler
92 zkap First principles study on the electronic properties of BN nanowires 244
93 Filipe Amaral SIS-CCTO polymer matrix composites for embedded capacitors 245
Amirbekova
94 Gulzhanat Ferroelectricity of CsRbPb2I6 superlattice 246
Eduardo F. Competitive binding between polymer and protein onto carbon nanotubes as
95 Marques probed by diffusion NMR 248
Eduardo F. Molecular trends in the non-covalent functionalization of carbon nanotubes with
96 Marques surfactants 249
Study on Nanosize and Temperature Effect on a Bioglass-ceramic Grossular
97 Vildan GUDER Ca3Al2Si3O12 Cubic Nanoparticle by Molecular Dynamics Simulations 251
Jorge Romero
98 Garca Electrospun nanofibers of Poly(vinyl alcohol) Thiolated Loaded with Cisplatin 253
Suddhasatwa
99 Basu Application of carbon nitride nanofibers as cathode catalyst in microfluidic fuel cell 269
Suddhasatwa In-situ Solid State Synthesis of Silver and Nickel Doped g-C3N4 for Efficient
100 Basu Photoelectrocatalytic Water Splitting 270
Mohamed Nanostructured transition metal oxides as co-catalyst anodes for direct ethanol fuel
101 Mohamedi cells 273
Carbon nanotubes synthesis through laser ablation in ionic liquids and their surface
102 Catalin Croitoru properties tuning ability in a HDPE matrix 277
Optomagnetism and ultrafast spintronics in Carbon-based materials via optical
103 Jamal Berakdar vortices 280
104 Derya Kaya Sputtering of Cu2ZnTiS4 thin films for solar cells 281
Yusuf Selim Conversion from p- to n-type conductivity in copper (II) oxide thin films by cobalt
105 Ocak doping 283
Yusuf Selim Characterization of Ultrasonically Sprayed Cu2CdSnS4 Thin Films For Solar Cell
106 Ocak Applications 286
Ricardo
Henrquez Effect of electron-surface scattering and thiols adsorption on the electrical
107 Correa resistivity of metallic ultra thin films 290
Roberto
108 Vazquez-Muoz Silver nanoparticles surpass antibiotic-resistance and enhance antibiotics activity 292
109 Flavio Carsughi Enhancing European competitiveness in nanoscience research and innovation 298
Amir Bagheri
110 Garmarudi Optimized fabrication of ZSM-5 zeolite nano sheets for catalytic applications 299
Fohlerova A comparative Study of TiO2 Surfaces with Different Topographies on Osteoblast
111 Zdenka Behavior 300
Studies on Synthesis and Optical-Electrical Features of Zn0.5Cd0.5S Quantum Dot
112 Pukazh Selvan Dispersed Magnesium Niobate Nanocrystals 302
113 Ajay Kaushal Y doped CeO2 nanopowder: Synthesis, structural and optical properties 303
Enhanced local piezoelectric response in the Erbium-doped ZnO nanostructures
114 Ajay Kaushal prepared by wet chemical synthesis 304
115 Atul Kumar Anti-Bacterial Biofilm Activity of Magnesium Ferrite Thin Film 307
116 Zeke Insepov Atomic Layer Deposition for TiO2 and TiN Nanometer Films 309
117 Zeke Insepov Multiscale modelling of fluid flow in nanopump 310
Milena Effect of multiwall carbon nanotubes electrochemical modification on the electrical
118 Kurkowska properties of the epoxy carbon nanotube composites 313
Azadeh Nanofillers Reinforced Polymer Composites Fabricated by Melt Compounding for
119 Moteallah Biomedical Application 316
120 Gianvito Caputo Laser light-triggered formation of SnO2/PMMA nanocomposites 317
121 Bar zkap Electronic band structures of Te-doped GaN nanowires 319
Henrque Leonel
122 Gomes Materials for implantable bioelectronic devices 325
Manipulation of Electrical Conductivity of Graphene Oxide Films by Addition of
123 Olena Okhay Carbon Nanotubes and Thermal Treatment 327
124 S. Simonetti SiO2(111) surface optimization by DFT calculations 329
Facile synthesis of well dispersed Pd nanoparticles on reduced graphene oxide for
125 Rahul Krishna electrocatalytic oxidation of ethanol 330
Devaraj Investigation on the effect of Weld Defect on the Fatigue Behavior of Welded
126 Ramasamy Structures 332
Devaraj Effect of homogenization on Mechanical Property of newly developed self-healing
127 Ramasamy alloy 333
1

Development of an antimicrobial therapeutic system encompassing aqueous-core lipid nanoballoons housing strictly
lytic bacteriophage particles for Pseudomonas aeruginosa, targeted to the treatment of bacterial pneumonia

Alessandra Rios1, Marta Vila1,3, Marco Chaud1, Matthieu Tubino3, Marcelo Farias4, Rodrigo Portugal4 and Victor Balco1,2,*
1
LaBNUS - Biomaterials and Nanotechnology Laboratory, i(bs)2 intelligent biosensing and biomolecule stabilization research group,
University of Sorocaba, Sorocaba/SP, Brazil, victor.balcao@prof.uniso.br, presenting author
2
CEB - Centre of Biological Engineering, University of Minho, Braga, Portugal
3
Institute of Chemistry, University of Campinas, Campinas/SP, Brazil
4
LNNano/CNPEM - Brazilian National Nanotechnology Laboratory, Campinas/SP, Brazil

SUBJECT
ANM - Advanced Nanomaterials - Poster

INTRODUCTION Figure 1. Figure 2. Cryo-TEM images of Figure 3. NS-TEM images of


Due to the increasing awareness of the worlwide Propagation the concentrated phage the W/O/W multiple emulsion
of phage suspension (PS) (a), showing produced, at different
appearance of multiple bacterial resistance to conventional JG004. the phage tail fibers adhered to magnifications.
chemical antibiotics, phage particles (natural predators of cell debris (b, zoomed portion
of a cryo-TEM image of PS).
bacteria) are high-potential candidates for
biopharmaceutical applications, due to the fact that these Two homogenization cycles of 10 min at 12500 rpm were
inert particles replicate directly at the site of infection, found to be critical for producing stable LN dispersions
becoming profusely available where they are most needed1. with a pH of 6.40, average HS of (188.542.20) nm, PI of
However, phage particles are fragile, and therefore their (0.2080.010) and ZP of (-30.181.60) mV. Figure 3
full structural and functional stabilization is required2. The displays NS-TEM images of the LNs integrating the
aim of this study was to optimize a water-in-oil-in-water optimized W/O/W ME housing phage entities, allowing to
multiple emulsion (W/O/W ME) integrating aqueous-core observe the close-to-spherical shape of the particles and the
lipid nanoballoons (LN) encasing strictly lytic phage absence of aggregation. NTA analyses showed a
particles with broad lytic spectrum against P. aeruginosa, concentration of ca. 2.39 x 1012 particles/mL. The positive
aiming at their structural and functional stabilization, and antimicrobial activity of the W/O/W ME integrating phage
entail its thorough physicochemical characterization. particles, assessed in vitro against a pathogenic strain of P.
aeruginosa, further suggests functional stabilization of the
EXPERIMENTAL/THEORETICAL STUDY phage particles. The diffusion coefficient (D) of the LNs
Phage particles with broad lytic spectrum able to infect P. (calculated as 2.6070x10-12 m2.s-1, using the Stokes-
aeruginosa, viz. phage DSM JG004, propagated in their Einstein equation) was of the same order of magnitude as
host (Figure 1) and duly purified, were imprisoned within that of nanoparticles, viz. 10-12 m2.s-1. The lower D, the
W/O/W MEs. Two emulsions were prepared sequentially, more stable the ME is, and this was indeed observed. XRD,
a primary emulsion (W/O), followed by emulsification of DSC and FTIR analyses of ME without and with
this emulsion in another (external) aqueous phase (W), thus imprisoned phage, showed no chemical interaction
forming a ME (W/O/W). The inner aqueous phase (1000 between the entrapped entity and chemical components.
L) was constituted by HCl 1000 mM (20 L), Tween 80
(10 mg) and strictly lytic phage particles (2.983x109 CONCLUSION
virions); the intermediate oily phase encompassed glycerol Cytotoxicity and genotoxicity assays confirmed that the
(5 mL), Softisan 100 (500 mg) and soybean nanosystem produced with imprisoned phage JG004
phosphatidylcholine (375 mg); the outer aqueous phase particles was virtually nontoxic, indicating its potential of
encompassed poloxamer 188 (250 mg), methylparaben (50 use in aerossols targeted to control bacterial infections
mg) and UP water (40 mL). The W/O/W ME was without impacts to the human body.
characterized via DLS for particle hydrodynamic size (HS),
size distribution (PI) and particle charge via Zeta potential REFERENCES
(ZP); surface morphology and diffusion coefficient via 1. V.M. Balco et al., Colloids and Surfaces B: Biointerfaces 123,
NTA; thermal analyses via TGA and DSC, infrared 478-485 (2014).
spectrophotometry with Fourier transform (FTIR), X-ray 2. V.M. Balco and M.M.D.C. Vila, Advanced Drug Delivery
diffraction (XRD), and transmission electron microscopy Reviews 93, 25-41 (2015).
(TEM) following negative staining with uranyl acetate
(NS-TEM) or cryo-freezing in liquid ethane (cryo-TEM). ACKNOWLEDGEMENTS
Project funding by FAPESP (So Paulo, Brazil) (Ref. No.
RESULTS AND DISCUSSION 2013/03181-6, Project PneumoPhageKill), is hereby
After propagation (see Figure 1) and purification, a phage gratefully acknowledged. This work also received support
suspension was obtained with ca. 2.983x109 virions/mL from CNPq in the form of a Productivity in Research (PQ)
(see Figure 2). fellowship granted to Victor M. Balco.
2

Carbon nanostructures for water remediation technologies

Tito Trindade
Departamento de Qumica-CICECO
Universidade de Aveiro
Portugal
tito@ua.pt

There have been renewed efforts to find technological solutions to ensure


sustainable water supply. Nanotechnology plays here an important role by
providing processes that might result into more efficient management of water
resources. Two illustrative approaches in water remediation technologies will
be addressed in this lecture. These include the use of nanoadsorbents for the
uptake of water pollutants by using magnetic separation technologies and the
photodegradation of water contaminants by using nanomaterials. In particular,
the application of carbon nanostructures in both applications will be discussed
envisaging their application in water treatment plants of industrial and
laboratory units.

Acknowledgements

Thanks due to FCT UTAP-ICDT/CTM-NAN/0025/2014 and project CICECO-Aveiro Institute of


Materials, POCI-01-0145-FEDER- 007679 (FCT Ref. UID /CTM /50011/2013), financed trough
national funds (FCT/MEC) and FEDER when applicable (PT2020).
3

Silver nanoparticles stabilized by bioactive polymers pluronic F68, PVP and PVA
Carolina Alves dos Santos1*, Marco Chaud1, Victor Balco1,2 Marta Vila1,3 and Mahendra Rai 4
1 LaBNUS - Biomaterials and Nanotechnology Laboratory, i(bs)2 intelligent biosensing and biomolecule stabilization research group,
University of Sorocaba, Sorocaba/SP, Brazil, carolinasantos@usp.br* presenting author
2 CEB - Centre of Biological Engineering, University of Minho, Braga, Portugal
3 Institute of Chemistry, University of Campinas, Campinas/SP, Brazil
4 Biotechnology Department, SGB Amravati University, Amravati-444 602 Maharashtra, India

SUBJECT RESULTS AND DISCUSSION


ANM - Advanced Nanomaterials - Poster In each experiment, the UV-Vis spectrum (not shown) had
a maximum absorbance at 420nm, which provides evidence
INTRODUCTION for the conversion of silver salt into silver nanoparticles, as
The increasing and alarming panorama of infections and this wavelength characterizes the plasmon absorption band
associated morbidities that occur during medical and of the silver nanoparticles. Regardless of the addition of
hospital procedures, the development of technologies that pluronic and other adjuvant polymers, the final pH in the
aid in controlling these infections becomes essential and reacting medium is the same. Besides, regardless of the
urgent. See recent studies showing that formulations metal polymeric covering, the particle sizes determined by DLS
nanoparticles have good antibacterial properties against a were bimodal. The particle sizes and morphologies found by
broad spectrum of microorganisms. Moreover, it was DLS are consistent with the observations by SEM. In all but
demonstrated that some biologically active polymeric one combinations of capping agents, the dominant
materials, when applied in combination with antimicrobial population was within the sizer range of 70 to 80 nm and the
agents potentiate the therapeutic action of the latter. This other one within the range of 5 to 15 nm. When PVP alone
study aimed at the characterization of silver nanoparticles was the polymeric covering, the particles were smaller, with
obtained by chemical reduction and stabilized by the sizes of 39.8 and 2.4 nm. The images obtained by SEM also
polymers PVA, PVP and co- stabilized by Pluronic F68. show that most particles are spherical, though hexagonal,
and rods and triangular particles are also present. A high
EXPERIMENTAL/THEORETICAL STUDY proportion of silver atoms have been found in all
A 500mL jacketed reactor was filled with deionized water compositions, confirming that the particles are truly silver.
and heated to 89C. Under controlled stirring and
temperature, 90mg of silver nitrate (AgNO3) and 135mg of
either PVA or PVP were added. Thereafter, 10 mL of a 1
wt% sodium citrate aqueous solution was added using a
peristaltic pump under constant heating and stirring. The
resulting sodium citratetosilver molar ratio was 0.68.
After 20 minutes of reaction, 10 mL samples of the Figure 1: Image of the silver nanoparticles obtained by
dispersion were collected and immediately cooled to SEM and TEM
ambient temperature in order to quench the reaction.In
experiments with co-stabilization of pluronic the particles CONCLUSION
pre-formed was cooled to 52C and 6g of pluronic (m.m AgNps in the proper size (medium 70nm) to be used as
8400) was added to the reactor under constant stirring and antimicrobial agent were obtained and the addition of
temperature. The reaction was allowed to proceed for pluronic F68 did not promote increase in the sizes and
additional 20 minutes. UV-Vis Spectrophotometric shapes of the obtained particles, nor did it promote
measurements of the reacting media were made at room variations in the process pH measures. The presence of PVA
temperature on a Hewlett-Packard UV-Vis 8453 and PVP seems to facilitate the linkage of pluronic and high
spectrophotometer, using a quartz cuvette at a 300 to 700nm the percentage of silver in the samples studied. It is believed
scan range. Particle sizes were determined by dynamic light that the pluronic F68 can be used as AgNps co-stabilizer, as
scattering (DLS) at 25C with a N4 plus Submicron Particle suggested herein, resulting in AgNps with superior
Size Analyzer (Beckman Coulter) operating at a 90C antimicrobial activity.
angulation. Particle morphology was assessed by scanning
electron microscopy (SEM) with with field emission gun REFERENCES
(Nano SEM 400 model, FEI Company). Detector Timeline 1. Santos, C.A et al. Journal of Nanobiotecnhology, 2012
Explorer (DTE), (SE) mode, 5.0E+04 to 20.0E+04 was used 2. Rai, M.K et al. Critical Review in Microbiology, 2015
for the measurement of size and topology of the synthesized
silver nanoparticles. Transmission Electron Microscopy ACKNOWLEDGEMENTS
(TEM) was carried out on a JEOL 2010 microscope with The authors thank the financial support from FAPESP,
electric field working at a 200kV voltage. CNPQ and CAPES.
4

Developments of Organic Light Emitting Diodes towards Solid State Lighting: state
of the art and challenges in nanotechnology

L. Pereira

Department of Physics and i3N Institute of Nanostructures, Nanomodelling and Nanofabrication, University of Aveiro,
Portugal, luiz@ua.pt
CeNTI - Centre for Nanotechnologies and Smart Materials, Portugal

In this work a review of some recent and practical such source of lighting, both general and decorative, will
developments of Organic Light Emitting Diodes be perhaps the future of this so competitive marketplace.
(OLEDs) for Solid State Lighting (SSL) is presented.
RESULTS
The present work is mainly focused on the device
The large area OLEDs, specifically based on active layers
concept and design, figures of merit needs and typical
following the concept of host: guest materials are the key
problems to overcome in order to fulfill the
answer to efficient, energy saving, human comfort and
application requirements. A special emphasis to the
environment and architectural friendly lighting. But the
2D low dimensional structure devices and
main challenge is controlling the physical dynamics
correspondent nanotechnological developments will be
associated with the energy transfer among the materials
summarized, showing the major milestones already
inside such active layer. The development of our work
achieved in this emerging and very promising
started with an extensive research on the dynamics of
technological application of OLEDs, based on the
organic materials used in order to get a controllable
work developed in our laboratory.
active layer matrix. Once obtained, a simple device
structure composed by only three organic layers has been
INTRODUCTION
established. The process was simulated using genetic
The OLEDs appear as the most effective technology for
algorithms in order to achieve an optimized layer
the future of SSL. Their unique capabilities, in particular
thickness. Finally, the experimental data together with the
light color modulation, very thin emitters including
physical simulation, allowed an improvement of the
flexible ones, relatively low cost fabrication technologies
electroluminescence output (dc measurements) and a
and diffuse emission (not point source), allowing the
correct balanced injection of carrier (ac measurements).
coverage of large areas for an environmental comfortable
The results are very promising and its the first time that
lighting, are the best keys for a huge worldwide research
an impressive color tuning ability, allied with high
in this field. In the case of an OLED light emitting
stability is reported, in a low level of complexity and
surface that can operate at lower light intensities by
large area emission. Thermal effects, that can be a real
increasing the active area without changing the luminous
problem, are currently studied using finite elements
flux the device can operation at low voltages with the
thermal models, towards an efficient thermal distribution.
decreased in heat generation. The mass production of
OLED devices is planned for the next years, with the use
of large substrates and optimization of production
processes. However, an OLED is a 2D nanometric device
with a global organic layers thickness in order of
hundreds of nanometers. When increasing the device
emitting area up to a macroscopic scale of several square
centimeters, several constraints appear, namely the layers
homogeneity and the effects associated with the electrical
field and thermal distribution. Such questions give rise to
a non-uniform light emission from the surface and a local
thermal and electrical fluctuations, that in ultimately can
affecting the practical applications. And the organic Figure 1. A large area (4 cm2) sunlight White-OLED and
materials degradation still a problem without an efficient a thermal map of a similar device with 16 cm2 of area, at
device encapsulation. Nevertheless, the benefits are 90% of full bright and approximately 10 minutes after
prodigious. From the scientific point of view up to emission starts.
practical lighting applications properties, we present here
a set of ideas and experimental dada concerning the above ACKNOWLEDGMENTS
mentioned OLEDs particularities including fabrication The author would like to acknowledge the i3N support
aspects and general applications. Several concepts and the from UID/CTM/50025/2013.
actual state of the art are focused in order to explain why
5

Enhanced electron coherence in atomically thin Nb3SiTe6

J. Hu1, X. Liu1, C.L. Yue1, J.Y. Liu1, H.W. Zhu1, J. B. He2, J. Wei1, Z.Q. Mao1, L.Yu. Antipina3,4, P.B. Sorokin3,4, T.J. Liu5,
P.W. Adams5, S. Radmanesh6, L. Spinu6, H. Ji7 and D. Natelson7
1
Department of physics and Engineering Physics, Tulane University, New Orleans, USA
2
Coordinated Instrument Facility, Tulane University, New Orleans, USA
3
Emanuel Institute of Biochemical Physics, Moscow, Russian Federation,
4
National University of Science and Technology MISiS, Russian Federation
5
Department of Physics and Astronomy, Louisiana State University, Baton Rouge, USA
6
Advanced Materials Research Institute and Department of Physics, University of New Orleans, New Orleans, USA
7
Department of Physics and Astronomy, Rice University, Houston, USA
antipinalyu@gmail.com

INTRODUCTION sharing NbTe6 prisms and Si ions insert into the


We report [1] the experimental observation of long- interstitial sites among these prisms.
predicted suppression of electron-phonon interaction
When the thickness of the Nb3SiTe6 crystals is reduced
caused by 2D confinement in a new ternary 2D system -
below a few unit-cells, we observe an unexpected
Nb3SiTe6 few-layer crystals. It is now well established
enhancement of the weak-antilocalization (WAL)
that many of the technologically important properties of
signature in magnetotransport. We supposed basing in
two dimensional (2D) materials, such as the extremely
DFT calculations that the suppression of e-ph scattering in
high carrier mobility in graphene and the large direct band
our samples cannot be attributed to 2D confinement on
gaps in MoS2 monolayers, arise from quantum
electronic band structure. Instead, confinement should
confinement. However, the influence of reduced
play a much more important role in its modification of the
dimensions on electron-phonon (e-ph) coupling and its
phonon spectrum. We show that the phonon wavelength
attendant dephasing effects in such systems has remained
estimated from both the experiments and ab initio
unclear. Although phonon confinement is expected to
calculations is much larger than the thickness of those
produce a suppression of e-ph interaction in 2D systems
devices displaying an enhanced WAL. This implies that
with rigid boundary conditions, experimental verification
the phonon spectrum develops a 2D character in our thin
of this has remained elusive. Here we show that the e-ph
crystals.
interaction is, indeed, modified by a phonon
dimensionality crossover in layered Nb3SiTe6 atomic
crystals.
EXPERIMENTAL/THEORETICAL METHODS
The Nb3SiTe6 bulk single crystals were synthesized with a
stoichiometric mixture of starting elements using the
chemical vapor transport. The crystal was investigated by
Energy-dispersive X-ray spectroscopy, X-ray diffraction
measurements, TEM measurements. The Nb3SiTe6 Fig. 1 Crystal structure of Nb3SiTe6. The isosurface
nanodevices were fabricated using standard electron- (0.04e/3) of the spatial electron distribution of the Nb/Si
beam lithography followed by a deposition of Ti(5nm)/Au plane. The unit cell is represented by solid rectangle.
(50nm). The transport measurement for both bulk and CONCLUSION
nano devices are performed in a physical properties We have investigated quantum confinement on e-ph
measurement system (PPMS). interaction through magnetotransport measurements on
atomically thin Nb3SiTe6. We found the enhancement of
The electronic band structure calculation was performed WAL signature with reducing dimensionality, which can
using density functional theory in the framework of only be attributed to the weakening of e-ph interaction
generalized gradient approximation (GGA) in Perdew- that results from the quantum confinement of phonon
Burke-Ernzerhof parameterization with periodic boundary spectrum. Our results provide clear evidence for the long-
conditions using Vienna Ab-initio Simulation Package. predicted theory, and more importantly, highlight the
RESULTS AND DISCUSSION advantage of using crystallized 2D materials to study the
The structure of Nb3SiTe6 is similar to that of MX2 (e.g. electron transport in reduced dimensions.
MoS2); both are formed from the stacks of sandwich ACKNOWLEDGMENTS
layers, with comparable van der Waals (vdW) gaps. In LYA and PBS acknowledge the support of the Russian
MX2, each X-M-X sandwich layer is composed of edge- Science Foundation (project #14-12-01217).
sharing trigonal MX6 prisms, whereas the Te-(Nb,Si)-Te
sandwich layer of Nb3SiTe6 consists of face- and edge- REFERENCES
J. Hu et al. Nature Physics 11, 6, 471-476 (2015)
6

Stress transfer in polymer/CNT nanocomposites

Jie Jin, Yao Tong and Mo Song


Department of Materials, Loughborough University, Loughborough, LE11 3TU, United Kingdom
j.jin@lboro.ac.uk

INTRODUCATION RESULTS AND DISCUSSION


Carbon nanotubes (CNTs) have generated a great deal of Semicrystalline polymers/CNT nanocomposites were
interest since their discovery, due to their unique physical treated at their crystallization temperature with different
properties. CNTs are known to have an extremely high times to make sure that the crystal layer was formed on
Youngs modulus of up to 1TPa and tensile strength the surface of CNTs. It was found with a certain thickness
approaching 60GPa. Much research has focused on of the crystal layer, the Youngs modulus of the
nanotubes as fillers in polymers with enhanced nanocomposites reached their maximum value. In this
mechanical [1], thermal [2] and electrical properties [3]. case, the optimization of tress transfer was achieved. An
Most significantly, CNTs are considered to be ideal Empirical formula was found as follows.
candidates for mechanical reinforcement of polymers. Yc =(1 - Vf)YPo + VfYCNT, = 0.399YPo (GPa-1)
Although a templating transition model has been used to Yc, YPo and YCNT are the Youngs modulus of
explain ideal combination of polymers and nanotube nanocomposite, polymer and CNTs, respectively. Vf is
diameters to maximally enhance the mechanical the volume fraction of CNTs, and f is the coefficient of
properties of composite structures, the disagreement tress transfer.
between experimental data and theoretical values is Figure 1(a) and (b) gives a comparison of experimental
obvious [4]. Significant mismatch of CNTs with polymer data with the model prediction for CNT-PU and CNT-
matrix exists. In order to utilize the super mechanical PVA composites, respectively. It can be found that the
properties of CNTs and develop high strength polymer model can predict the enhancement of Youngs modulus
composites, it is necessary to understand and reduce the for the PU and PVA and polyester PU composites well.
mismatch of CNTs with polymer matrix. A modified
model has been suggested for prediction of the Youngs
moduli of CNT-polymer composites. In this model, a 0.04
Model prediction PU
10
Model prediction PVA

coefficient of stress transfer between the stiffer nanotubes Experimental Experimental


Young's modulus (GPa)

Young's modulus (GPa)


and the softer polymer matrix was introduced. Empirical
0.03

relationships among the Youngs modulus, of the CNT-


0.02

polymer composite, Youngs modulus, of the polymer and 0.01


2

volume fraction of the CNTs have been found. In this 0.00


0

communication, we will introduce the concept and discuss


0.000 0.002 0.004 0.006
0.000 0.002 0.004 0.006 0.008
Volume fraction of CNTs
Volume fraction of CNTs

experimental results.
EXPERIMENTAL
Materials Figure 1: Comparison of experimental data with the model prediction for
Multi-walled and single-walled carbon nanotubes were CNT-polyester PU and CNT-PVA nanocomposites. Solid lines are for
purchased from Chengdu Organic Chemistry Co., Ltd eyes guidance.
(China). Poly(vinyl alcohol) (PVA) was purchased from CONCLUSION
Aldrich Co, (UK). Polycaprolactone (PCL) diol with a A model was suggested for prediction of the Youngs
molecular weight of ~ 2000 was a Solvay product, kindly moduli of CNT-polymer nanocomposites. In this model, a
provided by Brian Jones & Associates Ltd, UK. Tolylene coefficient of stress transfer between the stiffer nanotubes
2,4-diisocyanate terminated poly(propylene glycol) and the softer polymer matrix was introduced. Empirical
(polyTDI) was purchased from Aldrich with a molecular relationship between the Youngs modulus of the CNT-
weight of ~ 2000. The 4,4-Methylenebis(phenyl polymer composite, Youngs modulus of the semi-
isocyanate) flake was provided by Hyperlast Ltd. N,N- crystalline polymer and volume fraction of the CNTs was
dimethylformamide(Aldrich) was redistilled before use. found. The coefficient of stress transfer is correlation with
The antifoam agent BYK-535 was provided by Blagden Youngs moduli of polymers. The conclusion is that
Specialty Chemicals Ltd, UK. higher Youngs modulus of the polymer is, higher the
Sample preparation coefficient of stress transfer and lower mismatch between
Polyurethane/NT nanocomposites were prepared by in- NTs and polymer matrix.
situ polymerisation. PVA/NT nanocomposites were REFERENCES
prepared by blending method. Ultrasonic irradiation was 1. A. Wall, J.N. Coleman and M.S. Ferreira, Physical
used for dispersion of NTs. The details for the preparation Review B 71, 125421 (2005)
of PVA and PU/NT nanocomposites can be found in 2. H.S. Xia, and M. Song, J Mater. Chem. 16, 1843
references 1 and 5. (2006)
7

Effects of molarity on physical properties of nanostructured copper oxide films


deposited by spray pyrolysis for gas sensing applications

Abdelmounam Chetoui1, Amara zouaoui1


Physics department, university of science and technology, Algiers, Algeria.
Authors email: chetoui_mounaim@yahoo.fr
INTRODUCTION

Copper oxide is a material of interest in many


Technological fields such as photocatalysis1,
photodetectors2, biosensors3, and gas sensors4. A gas
sensor is evaluated through its main characteristics viz.
sensitivity and selectivity. This work shows the formation
of highly porous film using 0.05M concentration and the
gas sensing tests show a good response to different CO2
concentrations even at room temperature.

EXPERIMENTAL STUDY

In this work, we present the effect of four different


solution concentrations on the physical properties of
copper oxide films for gas sensing applications. The Fig. 2 Gas sensing measurements as a function of CO2
copper oxide films were deposited at a fixed substrate Concentrations.
temperature of 350C using pneumatic spray pyrolysis
method. Copper nitrate was used as a source material CONCLUSION
(precursor). The films were obtained by scanning the
substrate surfaces with an optimal speed of [5(x),1(y)].
This short section is to summarise the work based on the
RESULTS AND DISCUSSION facts in evidence and point out the main areas covered in
the writing. It may also contain the future directions of
Fig.1 depicts the AFM micrographs of the most porous the work.
film. This film was obtained with 0.05M precursor REFERENCES
concentration. This porous character should increase the References must be numbered. Keep the same style.
accessible surface area and thus increasing sensors
sensitivity. 1. L. Wang, et. al, J. Colloid Interface Sci., 384, 1-
9(2012).
2. C. Hung et. Al, Sens. Actuators A: phys., 171,
207-211(2011).
3. M. M. Rahman et. Al, sensors, 10, 4855
4886(2010).

4. F. A. Akgul et. Al, materials chemistry and


physics. 147, 987-995 (2014).

ACKNOWLEDGMENTS
Fig. 1 AFM micrographs of the most porous film. Authors are very grateful to LTM laboratory of Grenoble
(FRANCE).
As shown in Fig.2, the gas sensing measurements confirm
that the most porous film presents the highest sensitivity
of 3% at room temperature.
8

Fabrication of Ni-GDC Nanocomposite Material Prepared


by Aqueous Based Tape Casting Process
Wilson Acchar1, Antonio Carlos Silva da Costa1 and Herval Ramos Paes Junior2
1
Pos-graduation Program of Science and Materials Engineering, Federal University of Rio Grande do Norte, Natal, RN
59072-970, Brazil, wacchar@gmail.com
2
Northern Rio de Janeiro State University, Av. Alberto Lamego 2000, 28013602, RJ, Brazil

INTRODUCTION the suspension with 55.5 wt.% solids, 4.5 wt.% binder,
Solid oxide fuels cells (SOFCs) have been intensively 1.5 wt.% dispersant, 0.1 wt.% anti-foam and 0.1 wt.%
developed in the last years due to their high-energy surfactant.
efficiency and good electrical properties1-2.
Tape casting is a well-known and low cost processing RESULTS AND DISCUSSION
technique to produce thin and flat ceramic tapes. This Figure 1 shows the viscosity versus shear rate curves of
process basically started with a especially slurry which the slurries containing 4,5 wt.% of binder.
can be cast and dried into a flexible solid tape which can
be sintered into a hard ceramic substrate layer. Usually, 2,5

tape casting slurries are prepared by dispersion of a


powder in an organic solvent with a dispersant, followed 2,0

by the addition of binders, plasticizers, antifoam and other


additives. These slurries are cast through a so-called

Viscosity [Pa.s]
1,5

doctor blade over a flat carrier. However the use of


organic solvent are not good for the human health. 1,0

Recently aqueous-based tape casting technique has been


studied in order to produce thin tapes of ceramic materials 0,5

with no health hazardous. Ni-GDC composite materials


has a high ionic conductivity and a thermal coefficient
0,0
0 200 400 600 800 1000

close to that of the others SOFC components and are


-1
Shear rate [s ]

considered to be one of the most promising materials for Figure 1 Viscosity versus shear rate of slurries with 4.5
SOFC operating below 650 C3. In this work, aqueous wt.% binder.
tape casting was used to produce Ni-GDC composite
materials for solid oxide fuel cell (SOFC). It can be observed that there is a decrease of the viscosity
of the slurries by increasing the shear rate. The viscosity
EXPERIMENTAL is maximal at repose state or zero shear rate. The viscosity
Tape casting slurries were prepared with 55 wt.% solid of the slurries decreases under the shear forces generated
content. The starting powder for the fabrication of green when flowing through the blade. After passing the blade,
tapes was a powder mixture consisting of NiO (25wt.%, the shear rate returns to zero and the viscosity increases
average particle size = 50 nm) and GDC (20 wt.%). The and returns to maximal level. The Ni-GDC suspension
powder was deagglomerated in distilled water with an shows a shear-thinning behavior that is adequate to
addition of 1.5 wt.% dispersant (Poly-Acrylic Acid, produce films with a homogeneous surface and free od
Sigma Aldrich) using ball milling for 24 hours. After this defects (pores, cracks).
step, an polyacrylic binder (Polyvinyl Alcohol partially
hydrolyzed, Sigma Aldrich), antifoamer (Octanol, Sigma- CONCLUSIONS
Aldrich), plasticizer (Poly-ethylene glycol (PEG400), Aqueous tape casting is an alternative method to produce
Sigma Aldrich) and a surfactant (2,4,7,9 tetramethyl 5 flat Ni-GDC composite materials to be used in the SOFC.
decyne - 4,7 - diol ethoxylate, Sigma-Aldrich) were Slurries with 4.5 wt.% binder were successfully prepared,
added and the slurry was mixed by ball milling for the showing a shear-thinning behavior and a homogeneous
next 1 hour. Tape casting was performed at 25 C using a tape surface.
laboratory tape casting machine (Richard E. Mistler, Inc,
TTC-1200) with moving polyethylene carrier film coated REFERENCES
with a silicon layer and using a cast speed of 202 1.V. Moreno et. al, Mat..Sci.Forum. 727, 752-757 (2012).
mm/min. Stable slurry with good rheological behavior is 2.A. Tok et al, J.Mater.Proc.Tech. 89-90, 508-512 (1999).
a fundamental pre-requisite to produce a good tape layer 3. C. Fu et al, Int.J.Hydro.Energy, 35,301-307 (2010).
without defects. Viscosity measurements were carried out
in a rheometer (Haake Mars, Thermo Fischer Scientific) ACKNOWLEDGMENTS
with parallel plate and at room temperature. The shear The authors thank the Brazilian agencies CNPq and
dependence behavior of the suspensions was measured for CAPES for the financial supports.
9

Fabrication and characterization of nano-zirconia films


produced by aqueous-based tape casting process

Wilson Acchar and Micheline dos Reis Arajo


1
Pos-graduation Program of Scince and Materials Engineering,
Federal University of Rio Grande do Norte, Natal, RN, Brazil, wacchar@gmail.com

10
20 wt% binder
INTRODUCTION 9
25 wt% binder
8

The tape casting process is one of the main techniques to 7

produce thin ceramic sheets that are widely used in

Viscosity (Pa.s)
6

electronic devices1 and tailored structural parts, such as 5

multilayered composites, with enhanced mechanical or 4

chemical properties. ZrO2 based ceramic has been 3


intensively investigated as a potential material to be used 2
in the Solid Oxide Fuel Cells2. Typical tape cast slurries 1
are prepared by dispersion of a nano-zirconia powder in 0
an organic or nonorganic solvent with a dispersant, 0 200 400 600 800 1000

followed by the addition of binders, plasticizers, and other -1


Shear Rate (s )

additives.
Fig. 1 - Viscosity versus shear rate of slurries with 20wt%
and 25 wt% binder.
EXPERIMENTAL

In this work, aqueous tape casting was used to produce


nano-zirconia films. A commercial acrylic emulsion was
used as binder, and two different slurry compositions
were tested. Rheological behavior of the slurries was
examined and the microstructure, density and mechanical
behavior of the laminates were also evaluated. Viscosity
were carried out at room temperature in a rheometer
(Haake Mars, Thermo Fischer Scientific) with parallel
plate. Tapes with different slurry compositions were
Fig. 2 - Green tapes after 24 h drying.
laminated in 3 layers and arranged as follows: one in the
cast direction and the other perpendicular to the cast
CONCLUSION
direction. Tape casting was performed at 25 C using a
laboratory tape casting machine (Richard E.Mistler, Inc, Thin, smooth, homogeneous and flexible green tapes were
TTC-1200). manufactured, validating the alternative use of aqueous-
based tape casting process for the production of zirconia
films.
RESULTS AND DISCUSSION

The viscosity versus shear rate curves of the slurries REFERENCES


containing 20 wt% and 25 wt% binder is shown in Figure
1. It can be observed that there is a decrease of the 1. R.E. Mistler, Cer. Bull 6, 10221026 (1990).
200 m 200 m
viscosity of the slurries by increasing the shear rate. Both 2. V. Moreno et al, Mat.Sci.Forum 727, 752-757 (2012).
slurries showed similar shear-thinning behavior, but the
one with 25wt% presented a higher viscosity. Tape
casting slurries are expected to present a shear-thinning
ACKONWLEDGMENTS
behavior to produce films with a homogeneous and
smooth surface. At higher shear rates both compositions The authors thank the Brazilian agency CAPES for
presented similar viscosities. It was possible to obtain financial supports.
tapes with good flexibility and without cracks or fissures
apparent.
10

Synthesis and characterization of a novel catalyst based on dendrimer of core-POSS and its applications in
epoxidation of olefins

Eduardo G. Vieira1*, Newton L. Dias Filho1


1
UNESP - Univ Estadual Paulista, So Paulo, Brazil, eduardo_vieira5007@yahoo.com.br

INTRODUCTION
In this research we report the preparation and
characterization of a new dendrimer of second-generation
with a core of silsesquioxane (POSS-DG2.0)1. Polyhedral
oligomeric silsesquioxanes (POSS), are nanoplatforms
with one to eight reactive or nonreactive organofunctional
groups (R) anchored to the eight possible vertices of the
cubic silsesquioxane2. In this nanomaterial was anchored
six tungsten organometallic complexes
([W(CO)3Br2(NCMe)2]) for application in catalytic
epoxidation of olefins, as illustrated in Figure 1. To the
best of our knowledge, this study is the first that has
reported the preparation of POSS-DG2.0-[W(CO)3Br2]
for catalytic epoxidation of cyclooctene and styrene.

EXPERIMENTAL/THEORETICAL STUDY
The material was characterized using infrared
spectroscopy, elemental analysis, solid-state 29Si and 13C Fig. 1 Second-generation dendrimer from a core-POSS as
nuclear magnetic resonance and scanning electronic a new catalyst in the epoxidation of olefins
microscope (SEM) coupled to an energy dispersive
spectroscopy (EDS). CONCLUSION
The synthesis of the material was successfully performed
RESULTS AND DISCUSSION and the organometallic complexe showed good catalytic
The new organometallic nanomaterial POSS-DG2.0- activity in epoxidation of cyclooctene and styrene in the
[W(CO)3Br2] was tested as a catalyst in the epoxidation of presence of TBHP.
cyclooctene and styrene.
The catalyst behaved as an excellent catalytic precursor REFERENCES
for the epoxidation of cyclooctene and styrene using 1. E.G. Vieira et al, New J. Chem., 37, 1933-1943 (2013)
TBHP (tert-butyl hydroperoxide). 2. I.V. Soares et al, Chem. Eng. J., 218, 405-414 (2013)
The material selectively catalyzed the epoxidation for the
corresponding epoxides, with and without formation of ACKNOWLEDGMENTS
diols depending on the substrate, with high conversions E.G.Vieira is grateful for the financial support by the
and TOFs. No reaction took place without a metal FAPESP - Fundao de Amparo a Pesquisa do Estado de
containing catalyst. So Paulo (Grant No 2014/05566-5)
11

Plasma Treated Active Carbon for Capacitive Deionization of Saline Water

Aiping Zenga,b*, Maheshwar Shresthaa, Victor F. Netob, Brbara Gabrielb, Qi Hua Fana
a
Department of Electrical Engineering and Computer Science, South Dakota State University, Brookings, SD 57007, USA
b
Centre for Mechanical Technology and Automation, Department of Mechanical Engineering, Aveiro Institute of
Nanotechnology, University of Aveiro, Aveiro 3810-193, Portugal
*
Corresponding author. E-mail address: aiping@gmail.com (A. Zeng).

Abstract
Capacitive deionization (CDI) is an electrochemical water
treatment that purifies saline water by removing ionic
species while storing energy. This treatment has low
environmental impact. Cost considerations are of key
importance to making CDI an affordable mass-production
technology. Activated carbon (AC) from natural sources
is currently considered the most promising material for
the CDI electrodes. However, the activation process is
energy intensive (~960C for a couple of hours) with
serious environmental concerns due to the use of KOH.
Therefore, activating biocarbon has become a critical
barrier to commercializing AC for CDI. This work
demonstrates that capacitively coupled RF plasma is a
potentially efficient approach to activating biochar.

The plasma treatment was carried out in a capacitively


coupled plasma system using Ar+10%O2 at pressure of
4.0 Torr. The RF plasma power ranged from 50 W to 100
W and the processing time was 10 min. Commercial AC
YP50 was used. The carbon electrode film was fabricated
by electrophoretic deposition. Micro-Raman
Spectroscopy revealed the highly increased disorder of
sp2 C for the AC treated at 75 W. Capacitance values as
large as 599.89 F/g and as small as 76.03 F/g in 0.5 M
NaCl were recorded by cyclic voltammetry for the AC
treated at powers of 75 W and 50 W, respectively. For
comparison, the untreated and 100 W plasma treated AC
led to specific capacitance of 120.32 F/g and 151.70 F/g.
The largest capacitance obtained from the AC treated at
the power of 75 W was confirmed by deionization
experiments. An electro-sorption capacity of 6.15 mg/g is
recorded for the carbon treated at 75 W in a 0.1 mM NaCl Fig. 1. a) The potential applied between a pair of
solution when 1.5 V was applied during the charge electrodes and b) the corresponding adsorption capacities
period, while a capacity of the untreated AC was 1.01 for the electrodes using untreated and treated YP-50. The
mg/g. The plasma treatment led to 5.09 times increase in saturated capacities were 1.01mg/g, 0.11mg/g, 6.15mg/g
the absorption capacity. and 2.10mg/g for untreated, 50 W, 75 W and 100 W
treated YP-50, respectively.
12

Physical, antioxidant and antimicrobial properties of -chitin whiskers-reinforced


chitosan nanocomposite lms incorporated with Artemisia herba alba essential oil.

El Montassir Dahmane 1*, Moha Taourirte 1, Nadia Eladlani 1 and Mohammed Rhazi 2.
1*
Laboratoire de chimie Bio organique et Macromolculaire (LCBM) ; Dpartement des Sciences Chimiques, Facult des
Sciences et Techniques Guliz (FSTG), B.P. 549, Marrakech, 40000, Morocco.
*
Corresponding author : E-mail : el_montassirfstg@yahoo.fr, elmontassirfstg@gmail.com , Tl. 00 212 5 24 43 46 88, Fax:
00 212 5 24 43 31 70
2
Equipe des Macromolcules Naturelles (LMN), Ecole Normale suprieure, BP S41, Marrakech, 40000, Morocco.

INTRODUCTION

Combining antimicrobial and antioxidant agents such as


plant essential oils directly into a food packaging is a
form of active packaging 1. In this work -chitin whiskers
and Artemisia herba alba essential oil were incorporated
into chitosan films to evaluate their properties.

Fig. 1 Scanning electronic microscopic images of (A)


EXPERIMENTAL/THEORETICAL STUDY chitosan film without -chitin whiskers, (B) chitosan film
with -chitin whiskers
Active films based on chitosan incorporated Artemisia
herba alba essential oil with and without -chitin
whiskers were developed. The physico-mechanical, CONCLUSION
wettability, swelling index, total phenol, antimicrobial
and antioxidant characteristics of the films were The results showed that chitosan films incorporated with
investigated. The agar diffusion method was used to Artemisia herba alba essential oil could be used as active
determine the antimicrobial activities of chitosan films. films due to its antibacterial and antioxidant activities.
For the antioxidant activity, tow different analytical
assays were used (2,2-diphenyl-1-picrylhydrazyl and
Ferrous ion-chelating ability assay). REFERENCES

1. T. Phakawat et. al, Food Hydrocolloids. 56, 93-


107. (2016)
RESULTS AND DISCUSSION

The tensile strength of -chitin whiskers reinforced


chitosan films with A. herba alba essential oil increased
from that of the pure chitosan film (with A. herba alba
essential oil and without -chitin whiskers), while the
percentage of elongation at break decreased from that of
the pure chitosan. The films also exhibited antioxidant
and antibacterial activity against: Staphylococcus aureus,
Enterococcus hirae, Pseudomonas aeruginosa and
Escherichia coli.
13

Plasmon-Driven Transformation of Silver Nanoparticles in O2-Free Conditions


Jan Krajczewski, Karol Kotaj, and Andrzej Kudelski
Faculty of Chemistry, University of Warsaw, Poland, jkrajczewski@chem.uw.edu.pl

INTRODUCTION nm) than those obtained in the deaerated conditions (in


this case all nanostructures have the size below 60 nm).
Light is a valuable tool for formation of various metallic We also found that small amount of L-arginine solution
nanostructures. In 2001 Jin et al.1 reported a plasmon- (0.01ml of 0.1M) added to 9 mL of Ag sol could
driven transformation (PDTr) of silver nanoparticles significantly increase the yield of reaction.
during light illumination; initially spherical Ag
nanoparticles turned into nanoprisms. It is possible to
control the final geometry of obtained silver nanoparticles
by changing the wavelength of the excitation radiation. In
2011 Zhang et al.2 demonstrated that using different
starting silver seeds it is possible to obtain different final
nanoparticles, like nanoprisms or nanorods.
The standard photo-transformation is a result of two
consecutive processes: 1) slow dissolution of silver
nanoparticles under the influence of an oxidant present in
the solution, 2) photochemical reduction of silver ions at
the specific sites of the nanoparticles. As far as we know Fig. 1 TEM image of Ag nanoprisms obtained by PDTr in
in all previous PDTr reactions oxygen was used as an the presence of O2.
oxidizing agent. In this work we present the first example
of PDTr process of silver nanoparticles in oxygen-free We investigated the SERS activity of obtained silver
conditions. As an oxidizing agent 1,4-benzoquinone has nanoparticles using 3 model Raman scatterers: crystal
been used. The presence of 1,4-benzoquinone allows to violet, rhodamine 6G, and p-mercaptobenzoic acid. The
maintain a constant potential during the whole process. SERS activity of nanoparticles photochemically
transformed in the presence of oxygen is about one order
EXPERIMENTAL of magnitude higher than the activity of Ag nanoparticles
In a typical light-induced transformation about 9 mL of a before transformation. The phototransformation using
chemically prepared silver sol (obtained by a standard 1,4-benzoquinone in the O2 - free solution gives Ag
chemical reduction of Ag+ ions by sodium borohydride, nanoparticles about 2.5 times more SERS-active than the
with the average diameter of nanoparticles equal to Ag nanoparticles transformed under air.
3.50.7 nm) was put into the cylindrical glass reactor
(with diameter of 2 cm) and then illuminated for 24 h CONCLUSION
using 2 light-emitting diode (LED) clusters generating
light beams with relative narrow spectral half-width ( < In this work we present the first example of the plasmon-
20 nm). Irradiation has been carried out using LED driven transformation of Ag nanoparticles in the oxygen-
clusters emitting radiation of various wavelengths: =660 free solution. We found that when different than oxygen
nm (red), =520 nm (green), =470 nm (blue), =440 oxidising agent has been added to the reaction mixture,
nm (blue-violet) and =410 nm (violet). Average PDTr of silver nanoparticles can be carried out even in the
luminous flux was 270 lumens. In the case of experiments deoxidised solution. In case of using 1,4-benzoquinone
in the O2 - free environment, the reactor was filled with instead of oxygen allows to formation of significantly
chemically prepared silver sol, the reaction mixture was smaller anisotropic Ag nanostructures which can be
deaerated by bubbling with argon for 1 h, and then the significantly better nanoresonators for SERS
reactor was hermetically sealed under the argon measurements than Ag nanostructures obtained under air.
atmosphere.
For optical analysis we use Thermo Scientific Evolution REFERENCES
201 spectrophotometer. For analysis of geometry of 1. R. Jin et. al, Nature, 294, 1901-1903 (2001).
obtained silver nanoparticles we used a LIBRA 120 2. J. Zhang et. al, Nano Lett., 11, 2495-2498 (2011).
(Zeiss, Germany) transmission electron microscope
(TEM) working at an accelerating voltage of 120 kV. ACKNOWLEDGMENTS

RESULTS AND DISCUSSION This work was financed from the funds of the National
TEM analysis of silver nanoparticles synthesized by PDTr Science Centre (Poland) allocated on the basis of the
proved that nanoprisms obtained in the presence of decision number DEC-2012/07/B/ST5/02462.
oxygen (see Figure 1) are significant bigger (above 80
14

Catalytic Activity of Hollow Platinum Nanoparticles


Towards Reduction of 4-Nitrophenol
Jan Krajczewski, Karol Kotaj, and Andrzej Kudelski
Faculty of Chemistry, University of Warsaw, Poland, jkrajczewski@chem.uw.edu.pl

INTRODUCTION RESULTS AND DISCUSSION

Nanoparticles of noble metals are widely used as catalysts The absorption spectrum of 4-nitrophenol is dominated by
in many important fields1. High price and rare reserve of the broad band centred at 316 nm. When solution of
noble metals significantly limit, however, their practical sodium borohydride is added to the solution of 4-
applications. To decrease the consumption in practical nitrophenol, the formed mixture immediately changes
commercial catalysts of expensive noble metals the colour to bright yellow. This change of the colour is due
formation from noble metals of hollow nanostructures to the formation of the phenolic salt with maximum
have been applied. In this work we show that hollow absorption at 399 nm. After addition of some
platinum nanoparticles are equally good catalyst like full, nanoparticles bright yellow solution quickly fades which
standard platinum nanoparticles. is the result of the reduction of 4-nitrophenolate ions to 4-
aminophenol with the strong absorption band at 303 nm.
EXPERIMENTAL/THEORETICAL STUDY

Platinum hollow nanoparticles were synthesize using


procedure similar to those reported by Liang et al2.
Briefly, 100 ml of water was placed in a three-neck bottle.
CoCl2 and Na3Cit solutions were added. Subsequently, the
flask was sealed and solution was deoxygenated by
nitrogen influx. After this time freshly prepared sodium
borohydride solution was rapidly injected. The reaction
mixture adopted dark brown color which indicated
formation of cobalt nanoparticles. An anaerobic
Fig. 1 Typical temporal evolution of the absorption at 399
environment is vital for this reaction because cobalt
nm for 5 samples containing the same amount of 4-
nanoparticles are unstable in the presence of oxygen. In
nitrophenol and sodium borohydride.
this time solutions containing 10 ml of water and various
amounts (15-35 l) of 0.1 M K2PtCl4 were prepared (for
CONCLUSION
example, when using 15 l of 0.1 M K2PtCl4 solution the
ratio of numbers of moles of Pt and Co in the final
The first example of high catalytic activity of hollow
reaction mixture was equal to 0.13:1). Finally, samples of
platinum nanoparticles towards non-electrochemical
30 ml of prepared cobalt nanoparticles were added to the
reaction is reported. Contrary to studied so far catalytic
prepared K2PtCl4 solutions. Obtained in this reaction sol
processes involving hollow platinum nanoparticles to
of hollow platinum nanoparticles was colorless. Pt and
carry out this reaction it is not need to couple analysed
Au@Pt nanoparticles were synthesized in standard
platinum nanoparticles to the surface of an electrode.
ethylene glycol reaction.
Simplification of the experimental procedure should
The catalytic properties of metal nanoparticles were
significantly decreases the error of measured parameters.
examined by the analysis of the kinetic of the reduction of
It was found that hollow platinum nanoparticles are
4-nitrophenol by sodium borohydride. Typically, 2 ml of
equally good catalysts like standard, full platinum
water, 20 l of 0.01 M aqueous solution of 4-nitrophenol
nanospheres, however their synthesis require smaller
and ca. 40 l of suspension of metal nanoparticles (the
amount of platinum.
actually added volume was corrected in such a way that
the same mass of platinum was introduced) were placed
REFERENCES
into quartz cuvette. To investigate the decomposition of
1. P. Waszczuk et. al, J. Catal. 203, 16, (2001).
nitro-aromatic compounds UV-Vis absorption spectra
2. H.P. Liang et. al, Angew. Chem. Int. Ed. 43, 1540
were recorded in the spectral range between 250 and 500
1543, (2004).
nm every 30 s.
UV-vis absorption spectra were collected using a Thermo
Scientific Evolution 201 spectrophotometer. The
transmission electron microscopy (TEM) analysis were
carried out using LIBRA 120 (Zeiss, Germany) electron
microscope working at an accelerating voltage of 120 kV
and equipped with the In-column OMEGA filter.
15

Scaling properties and related issues in the charge transport through molecular
junctions

Ioan Bldea1,2*
1
Theoretische Chemie, Universitt Heidelberg, INF 229, D-69120 Heidelberg, Germany
2*
Institute for Space Sciences, National Institute for Lasers, Plasma and Radiation Physics, Bucharest-Magurele, Romania
*ioan.baldea@pci.uni-heidelberg.de

INTRODUCTION
Peak voltage (Vp) spectroscopy (PVS) 1,2,3 is an alias for
the increasingly popular transition voltage (Vt)
spectroscopy (TVS) 4 introduced to eliminate confusions
in the community of molecular electronics, emphasizing
that, rather than marking a mechanistic transition between
direct and Fowler-Nordheim tunneling (as initially
claimed4), VpVt is a reproducible property of molecular
junctions that quantifies the current nonlinearity. Vp is
simply related to the molecular orbital energy offset
relative to the Fermi energy (e.g. Ref. 5). The profound
role played by Vp in the charge transport via tunneling
was exemplary demonstrated in a recent joint theoretical
and experimental study1 demonstrating that, after
appropriate voltage (V) and current (I) rescaling, an
appealingly simple law of corresponding states iI/Ip vs.
vV/Vp holds for benchmark junctions with symmetric I-V
curves. Unprecedentedly, this law of corresponding states Fig. 1 Experimental (red points) and theoretical (solid
is free of any empirical parameter. green line) expressing the universal property of current-
voltage characteristics after the rescaling discussed in the
RESULTS AND DISCUSSION main text. Measured data correspond to a representative
The main new result reported in this work represents a asymmetric CP-AFM molecular junction of anthracene
generalization of the important result of Ref. 1 to the case linked to platinum and gold electrodes.
of molecular junctions possessing asymmetric I-V curves.
Namely, I demonstrate that, after appropriately using the
peak voltages Vp at positive and negative biases and the REFERENCES
corresponding currents Ip, universal curves exist, whose 1. I. Bldea, Z. Xie, and C. D. Frisbie, Nanoscale 7,
asymmetry can be characterized by a unique 10465 (2015)
dimensionless quantity: the ratio Vp+/Vp-. Representative
for the good agreement between the theoretical result 2. I. Bldea, Phys. Chem. Chem. Phys. 17, 20217 (2015)
deduced in this work and experiments is the the example 3. I. Bldea, Phys. Chem. Chem. Phys. 17, 31260 (2015)
of Fig. 1, wherein the experimental data were measured
for asymmetric CP-AFM (conducting probe atomic force 4. J. M. Beebe et al, Phys. Rev. Lett. 97, 026801 (2006)
microscopy) molecular junctions based on oligoancenes 5. Z. Xie, I. Bldea, C. Smith, Y. Wu, and C. D. Frisbie,
and dissimilar metallic (Au, Ag, Pt) electrodes6. ACS Nano 9, 8022 (2015)
Another important part of the present talk will cover 6. K. BongSoo, S. H. Choi, X. Y. Zhu, and C. D. Frisbie,
several counterintuitive aspects related to the J. Am. Chem. Soc. 133, 19864 (2011)
nanotransport through molecular junctions.
7. I. Bldea, J. Am. Chem. Soc. 134, 7958 (2012)
CONCLUSION
In view of the fact that nanotransport data for molecular
devices are often plagued by strong stochastic ACKNOWLEDGMENTS
fluctuations7, unraveling universal scaling properties like Financial support for this work provided by the DFG
that reported in this work is particularly promising for (grant BA 1799/3-1) and partial support by the bwHPC
gaining significant conceptual insight in the transport at initiative and bwHPC-C5 project funded by the Ministry
the nanoscale and indispensable for fabricating smart of Science, Research and Arts (MwK) Baden-
functionalized nanodevices. Wrttemberg and the DFG are gratefully acknowledged.
16

Conducting Colloids Based on Extended Polypyrrole Nanostructures

Patrycja Bober,1 Yu Li,1,2 Jaroslav Stejskal1


1
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6, Czech Republic
2
Department of Applied Chemistry, School of Science, Xian Jiaotong University, Xian 710049, Peoples Republic of China
e-mail: bober@imc.cas.cz

INTRODUCTION
During past years we can observe growing interests in
conducting inks, which can be potentially processed by
printing techniques. Polypyrrole (PPy)1 is one of the most
known conducting polymers possessing interesting
properties, such as biocompatibility and tunable electrical
conductivity, which can be controlled by reversible
doping. When the polymerization of pyrrole is carried out
in the presence of water-soluble polymer, colloidal
nanoparticles are obtained.2 The preparation of extended
PPy nanostructured colloids, rather then globular one, is
expected to produce the conducting objects with high
aspect ratio, which would produce a conducting network
after drying and increase the conductivity of printed films.

EXPERIMENTAL
Polypyrrole colloids with extended nanostructures have
been obtained by oxidation of pyrrole with iron(III)
chloride in the presence of methyl orange and steric
stabilizer, poly(N-vinylpyrrolidone). Globular PPy
colloids have been synthesised in absence of methyl Fig. 1. Transmission electron micrographs of PPy colloids
orange. The resulting colloids were characterized by prepared with 0.2 wt% (a,b) and 1 wt% PVP (c,d), in the
transmission electron microscopy, dynamic light absence of MO (a,c) and with 0.0025 M MO (b,d).
scattering, UV-vis spectroscopy, cyclic voltammetry and
conductivity measurement.
CONCLUSION
RESULTS AND DISCUSSION New polypyrrole colloids based on extended polypyrrole
The extended PPy nanostructures formed a stable aqueous nanostructures composed of nanotubes and nanorods with
colloid. Dynamic light scattering measurement shows that increased conductivity have been synthesized in the
the PPy nanostructures with extended morphology have presence of methyl orange and at low concentration of
average particles size of 600700 nm and the dispersity supporting water-soluble polymer.
index is mainly around 0.3, which is higher to that of the
nanoglobules. The conductivity of the films deposited
REFERENCES
from extended PPy nanostructured colloids was high, 1.54 1. M. Omastov, et. al, Synth. Met. 138, 447 (2003)
S cm1, two orders of magnitude higher compared with
2. M. Omastov, et. al, Electrochim. Acta 10, 296 (2014)
the globular analogue. Moreover, the nanotubular colloid
exhibited improved electrochemical activity. The results
ACKNOWLEDGMENTS
of thorough characterization of the particles will be The financial support of the Czech Science Foundation
presented on the conference.
(14-05568P) is gratefully acknowledged.
17

Multifunctional gold nanoparticles for imaged guided radiotherapy


Gloria Jimnez Snchez1, Gautier Laurent1, Claire Bernhard2, Sandrine Dufort3, Rana Bazzi1, Irene Tsiapa4, Penelope
Bouziotis4, Frdric Boschetti5, Franck Denat2, Graldine Le Duc6, Olivier Tillement7, Stphane Roux1
1
Institut UTINAM, UMR 6213 CNRS-Universit de Franche-Comte, France
2
ICMUB, UMR 5260 CNRS- Universit de Bourogne, France
3
nano-H SAS, France; 4National Center for Scientific Research, Greece
5
CheMatech SAS France; 6ID17 Biomedical Beamline, European Synchotron Radiation Facility, France
7
Institut Lumiere Matiere, UMR 5306 CNRS Universit de Lyon, France; gloria.jimenez_sanchez@univ-fcomte.fr

INTRODUCTION RESULTS AND DISCUSSION


Owing to their large range of properties, multifunctional After intravenous injection to healthy and to tumor
nanoparticles are promising candidates for image-guided bearing mice and rats, the biodistribution study shows that
therapy. In this context, we developed the synthesis of the gold nanoparticles freely circulate in bloodstream
gold nanoparticles which combine multimodal imaging without undesirable accumulation in healthy tissue and
(magnetic resonance imaging (MRI), nuclear imaging, are efficiently cleared by renal elimination5. However a
ultrasound imaging and X-ray imaging) and passive accumulation in tumor zone can be observed in
radiotherapy1-3 in the same object. the case of rats bearing 9L gliosarcoma.
Au@DTDTPA ultrasmall nanoparticles (hydrodynamic
NP
diameter between 6 and 8 nanometers) are composed of a NP
t1
gold core (2.5 nm) providing a strong X-ray absorption
(x-ray imaging and radiosensitization)4 encapsulated NP-RGD NP-RGD
within an organic shell of DTDTPA (dithiolated t2
polyaminocarboxylate linear ligand). The organic ligand
Time of retention in tumor
ensures a great colloidal stability in large pH range and Intravenous injection
of NP or NP-RGD
Rat bearing
a gliosarcoma t2 > t1
the immobilization of paramagnetic gadolinium (III) ions
and radioisotopes (68Ga3+ and 111In3+). As a result, the The post-functionalization of Au@DTDTPA
biodistribution of the labeled gold nanoparticles nanoparticles (NP) by RGD peptide (NP-RGD) induces a
(Au@DTDTPA(M)) can be monitored by MRI more long-lasting accumulation of the nanoparticles in
(M=Gd3+), by SPECT (M=111In3+) or by PET (M=68Ga3+). comparison with the Au@DTDTPA(Gd) nanoparticles.
To increase the time of residence of the nanoparticles in Such an accumulation should explain the increase of the
the tumor, RGD peptide (arginine, glycine and aspartic lifespan which was observed in preliminary tests of
acid) is conjugated to the Au@DTDTPA nanoparticles. radiotherapy after intravenous injection of nanoparticles
RGD normally interacts preferentially with the V3 functionalized with the RGD peptide in comparison with
integrins which are over-expressed in the new blood the Au@DTDTPA(Gd) nanoparticles.
vessels which irrigate the tumor. CONCLUSION
The conjugation of RGD to Au@DTDTPA(M)
EXPERIMENTAL STUDY nanoparticles improves the promising potential of these
Au@DTDTPA nanoparticles were synthesized by gold nanoparticles for imaged-guided radiotherapy owing
reducing gold salt in presence of highly hydrophilic to a better controlled accumulation in angiogenesis zone
DTDTPA. The size of their gold core was measured by of the tumor environment.
transmission electron microscopy and their hydrodynamic
diameter by Dynamic Light Scattering. Based on NHS- REFERENCES
1. P.-J. Debouttire et al., Adv. Funct. Mater. 16, 2330
ester chemistry, a pentapeptide containing RGD moiety
was successfully grafted onto the gold nanoparticles. The 2339 (2006)
follow-up after intravenously injection was performed by 2. C. Alric et al., J. Am. Chem. Soc. 130, 59085915
MRI (Gd3+) and SPECT (68Ga3+). The biodistribution of (2008)
RGD conjugated Au@DTDTPA(M) nanoparticles was 3. D. R. Arifin et al., Radiology. 260, 790798 (2011)
monitored after intravenous injection to 9L gliosarcoma 4. I. Miladi et al., Small. 10, 1116-1124 (2014)
beraing rats by MRI (M=Gd3+), SPECT (M=111In) and
5. C. Alric et al., Nanoscale. 5, 5930-5939 (2013)
PET (M=68Ga3+) and compared to the one of
Au@DTDTPA(M) (intravenous injection without post ACKNOWLEDGMENTS
fonctionalisation). We wish to thank the Agence Nationale de la
The treatment by radiotherapy was performed by Recherche for the financial support (ANR 2011
Microbeam Radiation Therapy (MRT) at the Biomedical NANO17 and ANR 2012 RPIB10), the region Franche-
Beamline of the European Synchrotron Radiation Facility Comt for the doctoral grant (GJS) and the ESRF
(ESRF, Grenoble, France). Biomedical Beamline.
18

Study of Photonic Crystal Biosensor using DNA Filled Microcavity in the Sandwiched Waveguide Structure

Dallel Benelarbi, Touraya Bouchemat, Mohamed Bouchemat


Electronics Department, Mentouri University of Constantine, Constantine 25000, Algeria
E-mail address: tboumaza2001@yahoo.fr

(a) (b)

INTRODUCTION
Photonic crystal (PC) biosensors have concentrated
varying researches because of locally confined optical
state into extremely small volume [1]. They can be
utilized for sensing biomaterials, chemicals and refractive
indices [2].
In this work, we design the characteristics of photonic
crystals (PhCs) waveguides coupled to linear cavity as
biochemical sensor. The structure of PhC is based on 2D
hexagonal lattices. The properties of the sensor are
simulated using the finite-difference time-domain method
algorithm (fullwave simulator). The sensing principle is
based on the shift of resonance wavelength 0, which
occurs due to the change in refractive index (RI) of the
sensor when the PhCs air holes are full of homogenous Fig. 1 Two-dimensional photonic crystal biosensor (a)
deionized water or polymer (DNA). The simulation shows structure,(b)Resonance wavelength shift for seven
that the most important parameters in Biosensing different samples.
applications, which are the sensitivity and the quality Fig. 1(b) represents the transmission spectra of designed
factor are improved. This range allows this biosensor to sensor structure using the 2D finite-difference time
be used efficiently in the applications such as domain (FDTD) method. The results from the testing
spectroscopy, microscopy and endoscopy. samples (from 1.33(water) to 1.45(DNA)) show that the
EXPERIMENTAL/THEORETICAL STUDY sensitivity and quality factor increased dramatically and
The electromagnetic fields evolution and the transmission reached the highest amount of s = 655 nm/RIU,Q=30371.
spectra are calculated using the FDTD method, this These show an efficient improvement in comparison to
method is directly based on Maxwells curl equations and previous reports[4].
accounts all optical phenomena of reflection, refraction, CONCLUSION
and diffraction. It provides a solution to Maxwells In this work, a new design of integrated sensor based on
equations, a system in which the electric and magnetic PhC two waveguides coupled with microcavity has been
field components are solved based on the corresponding proposed with a change of the air holes size localized at
previous spatial field components [3]. The grid size each side of the two lines defect.
should be quite smaller than one-tenth the lattice constant REFERENCES
of the crystal. [1] X.F.I.M. White, S.I. Shopova, H. Zhu, J.D. Suter, Y.
RESULTS AND DISCUSSION Sun, "Sensitive optical biosensors for unlabeled targets":
The structure of PhC is based on 2D hexagonal lattices, a review, Anal. Chim. Acta (2008).
consisting of air holes with a lattice constant 'a' of 410 nm [2] S. Olyaee, S. Najafgholinezhad, H. Alipour Banaei,
and air hole radius 'r' is 120nm. The whole structure has a "Four-channel label-free pho-tonic crystal biosensor using
InP wafer substrate with 230 nm thick layer thickness, nanocavity resonators", Photon. Sens. 3 (3) (2013).
and the size of photonic crystal is 19 13. The RI of the [3] S.K Patra,., S.Adhikari, , S. Pal,: "Design and analysis
dielectric and holes were considered as 3.32 (InP) and 1 of Chess board like photonic crystal for improved light
extraction in GaN/InGaN LEDs". IEEE J. Disp. Technol.
(air), respectively. Fig. 1(a) show two waveguides which
9(5), 339345 (2013).
are created by removing a row of air holes and are used to
4] F. Bougriou, T. Bouchemat, M. Bouchemat, N. Paraire:
couple light in and out of the PhC microcavity. The
"High sensitivity of sensors based on two-dimensional
microcavity is obtained by substituting the radius of three
photonic crystal". In: Electronics, Communications and
air holes.
Photonics Conference (SIECPC). Saudi International
(2011).
19

Interface Induced Growth and Transformation of Polymer-Conjugated Proto-


Crystalline Phases in Aluminosilicate Hybrids: A Multiple-Quantum 23Na-23Na
MAS NMR Correlation Spectroscopy Study

Jiri Brus1*, Libor Kobera1, Martina Urbanova1, and Jiri Czernek1


1
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic University, Czech Republic,
brus@imc.cas.cz

INTRODUCTION aluminosilicate matrix. This epoxide phase not only


Geopolymers, non-crystalline analogs of zeolites which enhances the mechanical integrity of the resulting hybrids
are characterized by the amorphous nature of their three- but also introduces additional binding sites accessible for
dimensional Al-O-Si framework, have received compensating negative charge on the aluminosilicate
considerable attention due to their low production cost, framework. This way, the polymer network initiates
excellent mechanical and physical properties, low energy growth and subsequent transformation of protocrystalline
consumption during manufacturing and reduced short-range ordered zeolite domains that are located at the
greenhouse emissions. However, geopolymers, offer organic-inorganic interface. By applying 2D 23Na-23Na
even greater application potential when the double-quantum (DQ) MAS NMR spectroscopy we
aluminosilicate network is modified, and the desired high discovered multiple sodium binding sites in these
compressive strength and mechanical integrity are protocrystalline domains, in which immobilized Na+ ions
complemented by enhanced sorption or catalytic and/or form pairs or small clusters. It is further demonstrated that
photocatalytic activity. In particular, selective sorption these sites, the local geometry of which allows for the
toward metal contaminants, such as Pb, Co, Ni, and Cs pairing of sodium ions, are preferentially occupied by
ions, is currently being extensively explored. Following Pb2+ ions during the ion exchange.
the potential application of hybrid inorganic-organic
geopolymers as inorganic systems for removing metal
cations from waste water, our work is aimed at tailoring
preparation of these systems with controllable amounts of
in situ synthesized nano-sized zeolitic domains and
subsequent characterizing their structures in detail.
EXPERIMENTAL/THEORETICAL STUDY
For detail study of local arrangement of geopolymer
composites on atomic level we applied two-dimensional
(2D) 23Na and 27Al triple-quantum (3Q) magic-angle- Fig. 1 Schematic representation of the distribution of
spinning (MAS) NMR experiments combined with sodium sites in the epoxy-modified nanocrystalline hybrid
23
Na{1H} cross-polarization techniques and 23Na-23Na (Nano-Hybrid, left), and the corresponding 2D 23Na-23Na
double-quantum (DQ) correlation MAS NMR based on DQ/MAS NMR correlation spectrum (right).
the BR212 recoupling sequence. This way we were able to
probe the local framework structures as well as the CONCLUSION
arrangement of extra-framework cations in short-range The proposed synthesis protocol thus allows for the
ordered domains at the interfacial area. The growth and preparation of a novel type of geopolymer hybrids with
transformation of these protocrystalline domains was ex- polymer-conjugated zeolite phases suitable for capturing
situ monitored during the long-term hydrothermal and storage of metal cations. The demonstrated 23Na-23Na
synthesis. Local interfacial structures were further probed DQ MAS NMR combined with DFT calculations
using the standard density functional theory (DFT)-based represents a suitable approach for understanding the role
B3LYP/6-311G** quantum chemical method. of Na+ ions in aluminositicate solids and related
inorganic-organic hybrids, particularly their specific
RESULTS AND DISCUSSION arrangement and clustering at interfacial areas.
The aluminosilicate hybrids with polymer-conjugated
nano-sized zeolites specifically grown at the organic- ACKNOWLEDGMENTS
inorganic interface were prepared by a combined The authors thank the Czech Science Foundation (GA13-
multistep synthesis. The inorganic amorphous Al-O-Si 24155S) and the COST Action MP1202 HINT (Ministry
framework is formed by alkali activated low-temperature of Education, Youth and Sports LD14010) for financial
transformation of metakaoline, whereas simultaneous support. The work was supported by the Ministry of
copolymerization of organic co-monomers creates a Education, Youth and Sports of CR within the National
secondary epoxide network covalently bound to the Sustainability Program I (NPU I), Project POLYMAT
LO1507.
20

Structural characterization of pharmaceutical liquisolid systems


by solid-state NMR spectroscopy
Martina Urbanova1*, Jiri Brus1
1
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Czech Republic,
urbanova@imc.cas.cz

INTRODUCTION RESULTS AND DISCUSSION


The approximately 70% of (Active Pharmaceutics We have developed relatively simply and robust
Ingredients) APIs are in solid dosage forms that are experimental technique based on solid-state NMR
administered orally. Also, an increasing number of experimentation that allows for reliable characterization
compounds with desirable activity may never reveal their of a wide range of liquisolid systems. The proposed
true potential because the properties of the bulk material procedure is able not only to distinguish different physical
display unfavorable bioavailability. Particularly, for states of the loaded active compounds (crystalline,
poorly water-soluble drugs which comprise 40% of the amorphous, viscous liquids and gels, and solutions) but
new chemical entities currently being discovered, oral also allows probing the extent of interfacial interactions
administration is problematic because it may pose a risk (API-polymer-silica) as well as segmental dynamics.
of compromised bioavailability. Thus, pharmaceutical
research focuses on increasing the absorbency of these
substances. Generally, improving the solubility is a
crucial step for a successful development.

The novel and promising approach to overcome the


adverse consequences is a liquisolid technique which is
based upon the admixture of drug loaded solutions and/or
liquid drug with appropriate carrier and coating materials.
This technique can be improved by the choice of
additives. Non-toxicity and hydrophilic properties of the
solvent, the carrier and the coating excipients as well as
their ratios are typically dependent on the individual API.

The successful development of these structurally


complicated drug-mesoporous inorganic carriers requires Fig. 1 Schematic representation of different types of
precise structural and physicochemical characterization. liquisolid pharmaceutical drug delivery systems
In this contribution we have focused on structural characterized by 1H MAS NMR spectra.
methodology for distinguishing different types of
liquisolid systems. The following analysis has been done CONCLUSION
to illustrate the typical features of NMR spectra of The combination of 1H MAS NMR with T1-filtered 13C
organic compounds at different physical states MAS NMR and 13C CP/MAS NMR spectroscopy under
(crystalline, amorphous, viscous liquids and gels, and the optimized experimental conditions can be used to
solutions). evaluate physical state of active substances on the surface
of drug couriers.
EXPERIMENTAL/THEORETICAL STUDY
All NMR spectra were measured using Bruker AVANCE
ACKNOWLEDGMENTS
III HD solid state NMR spectrometer (Karlsruhe,
Germany, 2013). The prepared liquisolid systems were The authors thank Czech Science Foundation (Grant No.
subsequently characterized by a range of solid-state NMR GA14-03636S, GA16-04109S) for financial support.
techniques. In detail we discussed of basic 1H, T1-filtered
13
C MAS and 13C CP/MAS NMR experiments.
The model system used in this study was crystalline
simvastatin with Tm=137C, amorphous simvastatin
prepared by quench cooling with Tg=33C and 10% w/w
solution of simvastatin in deuterated ethanol.
The experimental parameters were optimized to highlight
differences between the samples and to allow
identification (recognition) of different physical states.
21

Porphyrin-Based Conjugated Microporous Polymers as Solid-State Photosensitizers


of Singlet Oxygen

Jan Hynek1, Ji Rathousk2, Jan Demel1, Kamil Lang1


1
Institute of Inorganic Chemistry of the Czech Academy of Sciences, e, Czech Republic
2
J. Heyrovsk Institute of Physical Chemistry of the Czech Academy of Sciences, Praha, Czech Republic

INTRODUCTION
Conjugated microporous polymers (CMPs) are polymeric
materials with large surface areas and microporous
nature.1 CMPs, built of porphyrin units, can be used as
solid sensitizers of reactive singlet oxygen, O2(1g), under
visible light irradiation for the preparation of bactericidal
materials for medical applications. Presented CMPs were
rationally designed and synthesized in order to maximize
their photosensitizing properties by tuning the porphyrins
environment.
EXPERIMENTAL/THEORETICAL STUDY
CMPs were prepared using the Suzuki coupling
polycondensation reactions. Combination of
tetrasubstituted porphyrin and para-disubstituted benzene
as a linker led to CMPs with the two-dimensional (2D) Fig. 1 Reaction of photosensitized O2(1g) produced by
network, whereas the utilization of trans-disubstituted CMPs and MOFs dispersions in acetonitrile with 9,10-
porphyrins and substituted tetraphenyl methane led to the diphenyl anthracene.
corresponding three-dimensional (3D) materials. The
prepared materials were characterized by MAS-NMR, CONCLUSION
FTIR, thermal and elemental analyses. The surface areas We prepared a series of new porphyrin-containing 3D
and pore characteristics were investigated by nitrogen CMPs with a diamond-like topology and compared their
sorption measurement at 77K. To elucidate the structure photophysical properties with those of corresponding 2D
properties relationship, we investigated the photophysical CMPs and water-stable MOFs. 3D CMPs were the most
and photochemical properties of CMPs and compared effective producers of O2(1g). We found that the
them with the properties of two known porphyrin-based
efficiency of the O2(1g) production is not dependent on
2D CMPs and metal-organic frameworks (MOFs). The
the BET surface area or the corresponding pore volume,
efficiency of the O2(1g) generation was determined using but strongly correlates with a porphyrin environment.
an in-situ reaction with 9,10-diphenylanthracene. Compared with the MOFs, CMPs offer the control over
RESULTS AND DISCUSSION the porphyrin environment and superior stability by
3D CMPs displayed a markedly higher productivity of replacing the susceptible coordination bonds with the
O2(1g) in comparison with 2D CMPs and MOFs (Fig.1). robust covalent bonds; therefore, CMPs are more suitable
CMPs were stable in organic solvents and underwent no and efficient photosensitizers.
measurable photobleaching. The most efficient material is
composed of Pd (II) tetraphenyl porphyrin (TPP). The use REFERENCES
of TPP enlarges the distance between neighboring 1. J.-X. Jiang et. al, Angew. Chem. Int. Ed. 46, 8574
porphyrin cores resulting in larger yields of O2(1g) than (2007)
in the case of diphenyl porphyrin (DPP) building units.
The activity of CMPs to produce O2(1g) is correlated ACKNOWLEDGMENTS
neither with the surface area nor the pore volume as these This work was supported by the Czech Science
parameters do not directly characterize an accessibility of Foundation (No. 16-15020S).
oxygen to the porphyrin units and a degree of porphyrin-
porphyrin interactions within the structure.
22

Fabrication of biocompatible gold mushroom-shaped microelectrode arrays


M. Cerquido*1, D. Leito2, M. Proena1,3, C. Dias1, S. Cardoso2, P. P. Freitas2, L. Leito4,5, M. Lamghari4,5, P. Aguiar4,5 and J.
Ventura1
1) IFIMUP and IN-Institute of Nanoscience and Nanotechnology, and Department of Physics and Astronomy, Faculty of Sciences, University of Porto, Portugal.
2) INESC-MN and IN-Institute of Nanoscience and Nanotechnology, Lisbon, Portugal.
3) ISOM - Instituto de Sistemas Optoelectrnicos y Microtecnologa, Universidad Politcnica de Madrid, Spain
4) i3S Instituto de Investigao e Inovao em sade, Universidade do Porto, Portugal.
5) INEB Instituto de Engenharia Biomdica, Universidade do Porto.
*monicacccerquido@gmail.com

INTRODUCTION
We are at the tipping point of connecting electronic
elements and biological neurons [1, 2]. Several methods
are presently available to record neuronal activity,
including optical imaging, magnetic resonance,
electroencephalography, electrocorticography and
magnetoencephalography [3]. However, these methods
record the activity of a set of neurons, and thus do not Fig. 1 SEM images of the gold - mushroom
have the resolution to record single neuron activity [3]. microelectrode.
For higher resolution studies, we have intracellular and For the cell culture, the microelectrodes were carefully
extracellular methods. Intracellular methods have a good sterilized for 24h and coated with 0.1 mg.mL-1 PDL for
coupling, a high signal-to-noise ratio and provide the 24h. ND7/23 cells (DMEM GlutaMAXTM, 1% P/S; 10%
measurement of voltages in the cell without distortion FBS) were plated at a density of 6.0 x 104 cells/cm2 on,
through time. However, they require bulky manipulators and left undisturbed at 37 C, in a humidified atmosphere
and the recording time is restricted due to cell instability with 5% CO2. After three days of culture, cells were fixed
[3]. On the other hand, extracellular methods are and actin filaments were labelled with Alexa Fluor-
noninvasive, allow recording neural activity for long Phalloidin 488 (Invitrogen). Imaging was performed on
periods without damaging the plasma membrane and can an inverted confocal microscope Leica TCS SP5 II.
stimulate and record simultaneously. Nevertheless, these CONCLUSION
methods still show low signal-to-noise ratio and record Recent studies showed that a good coupling between cell
action potentials only, restricting the analysis of neuronal and electrode, as well as longer periods of recordings, can
networks in culture or in vivo [3]. be achieved using gold mushrooms-shaped
Recently, Microelectrode arrays (MEA) were created, microelectrode arrays. To fabricate them, we deposited a
allowing the measurement and recording of neural signals thin seed layer of chromium and a thin film of gold and
through the connection between neural cells and electric grew the gold microelectrodes using an electrodeposition
circuits. In particular, gold mushroom-shaped process in a lithographed patterned. Neuronal culture
microelectrodes show the best tradeoff between coupling experiments and confocal imaging showed proper cell
coefficient and stable recording time, in comparison with adhesion to the microelectrode array.
others techniques, allowing stable measurement of REFERENCES
neuronal signals up to two days. 1. Zoltan Fekete, Sensors and Actuators B: Chemical 215
EXPERIMENTAL STUDY AND RESULTS (2015), pp. 300315.
To produce gold mushrooms arrays it is necessary to use 2. Gregory Panaitov et al., Microelectronic engineering 88
lithography and deposition techniques. To produce these (2011), pp. 18401844.
microelectrodes, we first deposited a Cr (3 nm)/Au (40 3. Micha E Spira and Aviad Hai, Nature Nanotechnology
nm) structure on a silicon wafer using magnetron 8 (2013), pp. 8394.
sputtering. Then, we exposed a lithography mask
constituted by 1.5 m dots disposed in a square array with ACKNOWLEDGMENTS
a lattice spacing of 10 m. Gold mushrooms were then This work was supported in part by PTDC/CTM-
fabricated using electroplating in a gold solution (Orosene NAN/122868/2010 and PTDC/CTM-NAN/3146/2014
E +4gr/lt, for Italgalvano s.p.a.) under -1 V for 70 from Fundao para a Cincia e Tecnologia (FCT). The
minutes. authors acknowledge funding from FEDER and ON2
The produced gold mushroom microelectrodes were then through project Norte-070124-FEDER-000070 and from
characterized using Scanning Electron Microscopy FCT through the Associated Laboratory - IN. J. V.
(SEM), displaying stalks of 1.4 m, caps with heights of acknowledges financial support through FSE/POPH.
1.0 m and diameters of 3.8 m. The stalk of the MPP, DL and CD are thankful to FCT for grants
fabricated gold mushrooms is also seen to vary with the SFRH/BPD/84948/2012, SFRH/BPD/72359/2010 and
height, increasing from 0.6 m at the base to 3 m at the SFRH/BD/101661/2014.
top. This difference can be explained by the profile
induced on the photoresist during exposure.
23

Surface acoustic waves for photoluminescence modulation of quasi-two-dimensional


MoS2 nanoflakes
Sumeet Walia1*, Amgad Rezk2, Rajesh Ramanathan3, Hussein Nili4, Jian Zhen Ou5, Vipul Bansal3, James R. Friend6, Madhu
Bhaskaran1, Leslie Y. Yeo2 and Sharath Sriram1
1*
Functional Materials and Microsystems Research Group, RMIT University, Australia, presenting author
sumeet.walia@rmit.edu.au
2
Micro/Nano Physics Research Laboratory, RMIT University, Australia
3
NanoBiotechnology Research Laboratory, RMIT University, Australia
4
Department of Electrical and Computer Engineering, University of California Santa Barbara, USA
5
School of Engineering, RMIT University, Australia
6
Department of Mechanical and Aerospace Engineering, University of California San Diego, USA

INTRODUCTION
In this work, a novel integration of a surface acoustic
wave (SAW) platform with two-dimensional (2D) MoS2
is presented (Fig. 1a-c). Here, we report a new technique
for manipulating photoluminescence (PL) response of
MoS2 using a SAW. We couple the energy of a travelling
SAW with 2D MoS2 to demonstrate that the spatial
manipulation of the electro-acoustic field associated with (d)
the SAW leads to alterations in the excitonic PL. In
particular, we show that a SAW is capable of reversibly
modulating the PL of a quasi-2D (Q2D) thin film that is
composed of re-stacked MoS2 nanoflakes, by interfering
with the excitonic lifetimes. It is shown that this technique
does not require any compositional changes, or complex
tailoring of the lattice.
EXPERIMENTAL
Synthesis of quasi 2D MoS2 nanoflakes: The two-
dimensional (2D) MoS2 nanoflakes were synthesized
using a liquid exfoliation technique.1 Fig. 1 (a) Schematic of the interdigitated electrodes with
gap g and width w of 30 m each, used for creating
RESULTS AND DISCUSSION travelling SAW with a wavelength of ~120 m.
The confinement of the photogenerated electron-hole (e (b) Artists impression of the experimental configuration
h) pairs to two dimensions, together with the SAW, to assess coupling of travelling surface acoustic waves to
allows for a reversible charge separation. Altogether, the a 2D MoS2 flake. (c) An artists illustration of travelling
dislocated free carriers from the semiconducting part of SAW under MoS2 nanoflakes. It shows the interdigitated
the nanoflakes decrease the eh overlap integral, which in electrodes, blue light excitation and the MoS2 molecules
turn reduces the fluorescence quantum yield (and as a on the surface of a SAW compatible LiNbO3 substrate.
result the recombination efficiency) of the system. Such (d) PL intensities measured in situ under blue light
an electro-acoustic field induced carrier separation at excitation and varying SAW powers, showing
opposite sides of the 2D confined space leads to a reduced reversibility and dependence the power.
overlap of electron and hole wavefunctions, and
subsequently an increased recombination lifetime. This CONCLUSION
drastically reduces the recombination probability of the An externally applied travelling SAW was successfully
electrons and holes (increase the photogenerated exciton used to reversibly modulate PL characteristics. As such,
lifetime). This phenomenon is observed as quenching in this finding offers a new pathway for realising tunable
the PL intensity (Fig. 1d), where the PL is an indicator of electronic and optoelectronic devices based on 2D MoS2
the radiative recombination of excitons. and other analogous 2D materials.
REFERENCES
1. S. Walia et. al, Adv. Opt. Mater. 3, 888 (2015)
24

Stability analysis of resistive switching in Nb-doped amorphous SrTiO3-x at high


temperatures
Taimur Ahmed*,1, Hussein Nili2, Sumeet Walia1, Madhu Bhaskaran1 and Sharath Sriram1
1
Functional Materials and Microsystems Research Group, RMIT University, Australia presenting author,
sumeet.walia@rmit.edu.au
2
Electrical and Computer Engineering Department, University of California Santa Barbara, Santa Barbara , CA 93106, USA

Here we correlate the resistive switching performace with regime has a field dependence, shifting to the lower
the material properties in donor (Nb) doped amorphous temperatures and exhibiting lower thermal activation
SrTiO3-x memristive devices in a wide temperature range energies for higher biases. These results highlight the
(148-548 K) and evaluate the stability of resistive states. origin of stable intermediate resistive states during the
RESET transition of the device [2].
INTRODUCTION
Finally, stability is evaluated by measuring the ON state
Recently, amorphous strontium titanate (a-STOx) has
conductance by a READ bias (100 mV) at higher
been identified as an alternative for multifunctional
temperatures (398-548 K) for 10 hours (Fig. 1c). These
memristive devices due to its self-doping tendency by
results indicate progressive stages of localized dissolution
modulation in oxygen [1]. Moreover, low-concentration
of the filamentary network which is confirmed by a single
doping of donor species into a-STOx can improve the
SET voltage sweep after the retention measurements (Fig.
operational energy requirements and induce electrical and
1d). Above 498 K, drastic current drop to OFF state level
mechanical field tenability [2]. In this context, evaluation
underlines the critical temperature for the onset of
of state stability, role of oxygen deficiency induced defect
retention failure.
structure and metal-oxide interface in switching
mechanism of donor doped a-STOx devices will unveil
the criteria for energy optimization and switching stability
through oxide engineering. We identify the role of donor
species and oxygen vacancies in the switching
performance of Nb doped a-STOx (Nb:a-STOx) devices.
Specifically two characteristics are examined, namely
device performance in a wide temperature range (148-548
K) and time-dependent evolution of conduction under
sustained biases.
EXPERIMENTAL
A 100 nm thin film of Nb:a-STOx is co-sputtered at room
temperature, from comercial ceramic (SrTiO3) and
metallic (Nb) sources, onto a Pt(50 nm)/Ti(10 nm) bottom
electrode patterned on SiO2/Si substrate. Top
Pt(50 nm)/Ti(10 nm) electrode is deposited by electon
beam depositon to complete the metal-insulator-metal
structure of the devices. Top and bottom electrodes are
patterned by photolithography/lift-off processes. Detailed
description of device fabrication can be found in [2]. Fig. 1 Conduction characteristics of Nb:a-STOx devices at
high temperatures (148-548 K).
RESULTS AND DISCUSSION
The bipolar resistive switching of Nb:a-STOx devices in CONCLUSION
the temperature range of 300-398 K is depicted in Fig. 1a. We have experimentally confirmed that the resisitive
This stable and reproducible switching behaviour switching in Nb:a-STOx devices is predominantly
indicates that current transport in either steady switching dependent on the current transport across a filamentary
state is independent of Pt/Nb:a-STOx interfacial conduction network and their stability is evaluated at
inhomogeneities [3]. From state retention measurements it highg temperature.
is found that there is only 3.1% loss in ON state retention REFERENCES
over 105 s at 398 K and OFF state retention remains 1. H. Nili et al., Adv. Funct. Mater., vol. 24, 2014.
unchanged. In order to investigate the electronic
2. H. Nili et al., Adv. Funct. Mater., vol. 25, 2015.
conductivity and its correlation with OFF transition,
temperature-dependent OFF state conductivity 3. H. Kim et al., J. Phys. D: Appl. Phys.,vol. 42, 2009.
measurements are performed under different biases (Fig.
1b). The non-linear deviation in the higher temperature
25

Nanostructured materials for the photocatalytic abatement of N-containing


pollutants from waste water

Matteo Compagnoni1, Ilenia Rossetti1*, Gianguido Ramis2, Francesca Freyria3, Marco Armandi3, Barbara Bonelli3
1
Dip. Chimica, Universit degli Studi di Milano and INSTM Unit Milano-Universit, Milan, Italy, presenting author email
ilenia.rossetti@unimi.it
2
Dip. Ing. Chimica, Civile ed Ambientale, Universit degli Studi di Genova and INSTM Unit Genova, Genoa, Italy,
3
Department of Applied Science and Technology and INSTM Unit of Torino-Politecnico, Politecnico di Torino, Turin, Italy

INTRODUCTION The characterization of the synthesized nanomaterials was


The development of effective methods for the abatement carried our by N2 adsorption/desorption, FT-IR, XPS,
of some harmful pollutants from waste waters and from SEM, TEM, XRD, DR-UV-Vis.
hydric resources is a challenging task. Nitrogen
The photocatalytic performance of the samples, to be
containing compounds, such as inorganic ammonia,
correlated with nanomaterials properties, has been
nitrites and nitrates, and some organic N-containing
checked for the photoreduction of nitrate ions by means
compounds (dyes, pesticides, drugs, etc.), are harmful
of two batch photoreactors. A first design is based on
contaminants for drinking water, inducing acute and/or
external irradiation through a quartz window, a second
chronic diseases, especially affecting infants and children.
prototype is based on an immersed UV lamp.
Furthermore, when released in waste waters they
contribute to eutrophication, or possibly contaminate
ground water. This is particularly relevant in
agriculturally intensive zones and in the case of some RESULTS AND DISCUSSION
The FP procedure proved an interesting method for the
relevant industrial processes involving e.g. nitration
reactions. preparation of nanostructured Ti-based photocatalysts.
Particle size ranged between 5 and 60 nm, depending on
In the present work, we developed nanostructured synthesis conditions and the resulting phase was a mixture
photocatalysts for the abatement of N-containing of anatase and rutile, their proportion depending mainly
compounds, focusing on selectivity towards innocuous on flame temperature and residence time in the hottest
N2, to be applied for the treatment of waste waters to meet zone of the flame. Doping of the sample with Au (0.1-0.5
legislative specifications. wt%) induced the appearance of a plasmonic band with
increased absorption in the visible portion of the
EXPERIMENTAL/THEORETICAL STUDY
spectrum. No significant Au leaching or variation of
The photocatalysts have been prepared in nanosized form
absorption spectrum was assessed after used.
by using an innovative flame pyrolysis (FP) approach,
Doping with Ag also resulted important to improve the
able to synthesise in one step single or mixed oxide
harvesting of visible light, the sample becoming light
nanoparticles, characterized by homogeneous particle size
purple. In this case the FP technique provided a very rapid
and good phase purity. In the present investigation TiO 2
and effective mean for the incorporation of this dopant in
and SrTiO3 have been prepared by means of a home made
the nanomaterial.
apparatus, starting from Titanium isopropoxide, dissolved
in o-xylene and added 1:1 with propionic acid (in case
CONCLUSION
containing Sr nitrate for the preparation of SrTiO3).
Photocatalysts have been synthesized by means of flame
Different pyrolysis conditions have been set in order to
spray pyrolysis and compared with commercial
optimize materials properties.
nanostructured TiO2 supports. The FP synthesis proved
Noble metals have been added to the samples by post flexible and versatile also for catalyst doping and to
synthesis deposition-precipitation (Au), photodeposition widely tune materials properties.
(Pt) and/or directly during the FP synthesis (Ag). The role
of the metal nanoparticles was the enhancement of the
ACKNOWLEDGMENTS
lifetime of the photoproduced charges by electron
trapping and/or the enhancement of the materials
The financial support of Fondazione Cariplo through the
absorption in the visible region, which is one of the most
measure Ricerca sullinquinamento dellacqua e per una
practically relevant goals of this research.
corretta gestione della risorsa idrica, grant no. 2015-
The same materials formulations have been prepared 0186, is gratefully acknowledged.
starting from commercial nanostructured TiO2 supports
for comparison purposes.
26

Highly Conductive Polymer Transparent Electrodes for Efficient ITO-Free Organic


Optoelectronic Devices

Yong Hyun Kim1* , Jin Hee Kim1, Ji Yoon Oh1 and Yoon Kyung Seo1
1*
Department of Display Engineering, Pukyong National University, Busan 608-737, Republic of Korea,
yhkim113@pknu.ac.kr

INTRODUCTION Furthermore, we report efficient transparent OLEDs with


The development of transparent electrodes is of great improved stability based on conductive, transparent
importance for realizing the full advantages of organic PEDOT:PSS electrodes. Based on optical simulations, the
photovoltaic cells (OPV cells) and organic light-emitting device structures are carefully optimized by tuning the
diodes (OLEDs) such as being cheap and flexible. The thickness of doped transport layers and electrodes. As a
commonly used indium tin oxide (ITO) as a bottom result, the performance of PEDOT:PSS-based OLEDs
electrode remarkably increases device costs due to limited reaches that of ITO-based reference devices. In addition,
indium supply and the inherent brittleness of the material not only the efficiency but also the long-term stability of
which hinders the applications in flexible devices. PEDOT:PSS-based OLEDs is significantly improved.
Therefore alternative electrodes are extensively Next, a highly efficient OLEDs based on internal light
investigated to replace ITO. Among various alternative extraction system and PEDOT:PSS electrodes are
electrodes, poly(3, 4- developed by using a simple and easy manufacturing
ethylenedioxythiophene):poly(styrenesurfonate) process. The metal oxide embedded nanostructures
(PEDOT:PSS) is regarded as an especially promising combined with PEDOT:PSS electrodes exhibit an good
alternative electrode due to its high conductivity and refractive index matching from the organic layers to the
transmittance, excellent flexibility, and low-cost substrate and provide excellent light scattering effects.
processing1. Here, we present high performance ITO-free This novel architecture results in a 2.9-fold enhanced
OPV cells and OLEDs with PEDOT:PSS electrodes EQE for white OLEDs and leads to excellent color
which show comparable performance to the ITO-based stability over a broad range of viewing angles.
devices. Furthermore, the ITO-free white OLEDs based
on PEDOT:PSS electrodes on internal light extraction CONCLUSION
systems show a greatly improved efficiency as well2. In summary, we demonstrate low-cost, efficient ITO-free
OPV cells and OLEDs with highly conductive
PEDOT:PSS electrodes. The PEDOT:PSS-based organic
EXPERIMENTAL/THEORETICAL STUDY devices achieve comparable performance to the ITO-
PEDOT:PSS (PH1000, Heraeus) is mixed with various based devices. The chemical and structure engineering for
solvents for enhancing the conductivity of films and is both the PEDOT:PSS electrodes and the devices greatly
spin-coated on substrates. Solvent post-treatments such as improves the efficiency and stability of devices, which is
ethylene glycol- or methanol-based dip or drop treatment beneficial for realizing low-cost, flexible, and long living
are performed to further improve the conductivity of OPV cells and OLEDs applications. Furthermore, we
PEDOT:PSS electrodes. The optimized highly conductive show a novel concept to strongly improve the
PEDOT:PSS electrodes are adopted as anodes to OPV performance of white OLEDs based on a combination of
cells and OLEDs. readily fabricated internal light extraction system
composed of a metal oxide nanostructure and a highly
conductive low refractive index PEDOT:PSS electrode.
RESULTS AND DISCUSSION
We have prepared highly conductive, transparent REFERENCES
PEDOT:PSS films for use as an electrode in organic solar 1. Y. H. Kim et. al, Adv. Funct. Mater. 21, 1076 (2011)
cells. By the addition of solvent, the conductivity of the 2. Y. H. Kim et. al, Adv. Funct. Mater. 23, 3763 (2013)
thin-films increases, and by the additional solvent post-
treatment method, the conductivity increases further ACKNOWLEDGMENTS
attributed to the removal of PSS from the PEDOT:PSS
layer. The highest conductivity of 1418 S/cm has been This work was funded by the European Union (EFRE),
obtained for a single layer PEDOT:PSS film. Multi- the Fraunhofer Gesellschaft, and the Free State of Saxony
layered PEDOT:PSS films show low sheet resistances (< as part of the Dresdner Innovationszentrum
65 ohm/sq) with high transparencies (> 80 %). Based on Energieeffizienz, and by the Technology Innovation
the post-treated PEDOT:PSS electrodes, we could Program (No. 10052923) funded by the Ministry of
produce OPV cells with a comparable efficiency to that of Trade, Industry & Energy.
an ITO-based cell.
27

Highly conductive poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) films


optimized with a novel solvent and post-treatment as transparent electrodes for
ITO-free organic light-emitting diodes

Yoon Kyung Seo1, Chul Woong Joo2, Jin Hee Kim1, Ji Yoon Oh1, Jeong-Ik Lee2, Jonghee Lee2, and Yong Hyun Kim1*
1*
Department of Display Engineering, Pukyong National University, Busan 608-737, Republic of Korea,
yhkim113@pknu.ac.kr
2
Research Center, Electronics and Telecommunications Research Institute (ETRI), Daejeon 305-700, Republic of Korea

INTRODUCTION
The development of high performance electrodes is of
great importance for efficient, low-cost organic
optoelectronic devices such as organic solar cells and
organic light-emitting diodes (OLEDs). The commonly
used indium tin oxide (ITO) as a bottom electrode
remarkably increases device costs due to limited indium
supply and the inherent brittleness of the material, which
hinders the applications in flexible devices. Poly(3,4-
ethylenedioxythiophene):poly(styrenesulfonate)
(PEDOT:PSS), a conductive polymer, is in particular
regarded as a promising electrode material due to its high
transmittance and conductivity, and mechanical
flexibility. It is investigated that an addition of polar
organic compounds with a high boiling point or various
solvent post-treatment methods greatly increases the Fig. 1. Conductivity, transmittance and sheet resistance of
conductivity of PEDOT:PSS films1. a) PEDOT:PSS with AS with respect solvent
EXPERIMENTAL/THEORETICAL STUDY concentration.
PEDOT:PSS (Clevios PH1000, Heraeus, Germany)
solutions were mixed with ethylene glycol or AS. The CONCLUSION
formulations were filtered through a 0.45 m and spin In summary, we report on the new solvent which
coated at 1500 rpm for 30 s on glass substrates, pre- significantly improves the conductivity of PEDOT:PSS
treated with UV/ozone for 10 min. The films were films. To further improve electrical properties of
subsequently annealed on a hot plate at 120 oC for 15 min PEDOT:PSS with AS films, methanol-based drop
in ambient atmosphere. Post treatment for several treatment are performed. The post-treatment significantly
PEDOT:PSS films was performed by dropping methanol reduces sheet resistance of PEDOT:PSS films. The results
on the films (drop treatment). The white OLEDs were indicate that the optimized PEDOT:PSS films with AS
fabricated on the various transparent electrodes can be a promising transparent electrode for low-cost,
investigated here. flexible ITO-free OLEDs.

RESULTS AND DISCUSSION REFERENCES


In this work, we demonstrate high conductivity 1. Y. H. Kim et. al, Adv. Funct. Mater. 21, 1076 (2011)
PEDOT:PSS films with a new alcohol solvent (AS) which
greatly improves the conductivity of PEDOT:PSS films ACKNOWLEDGMENTS
up to 761.7 S/cm. Additionally, a solvent post-treatment
performed for the PEDOT:PSS films further enhances the This work was supported by the Technology Innovation
conductivity of AS doped PEDOT:PSS films up to 940.9 Program (No. 10052923) funded by the Ministry of
S/cm. The sheet resistance of the post-treated Trade, Industry & Energy. C. W. Joo, J. -I. Lee, and J.
PEDOT:PSS film greatly decreases from 162.3 ohm/sq to Lee acknowledge the support of the Industrial Strategic
116.2 ohm/sq. The optimized PEDOT:PSS shows a low Technology Development Program. (No. 10045269).
transmittance of 82.3 % with a low sheet resistance of
116.2 ohm/sq, which values are sufficient for the
transparent electrode in OLEDs. The optimized
PEDOT:PSS films with AS are adopted as a bottom
electrode for OLEDs and show good device performance.
28

Structured charge transport layers as a light outcoupling system for organic light-
emitting diodes

Ji Yoon Oh1, Dong Woo Kim1, Uk Hyeon Ban1, Jin Hee Kim1, Yoon Kyung Seo1, Kwon Taek Lim1, and Yong Hyun Kim1*
1*
Department of Display Engineering, Pukyong National University, Busan 608-737, Republic of Korea,
yhkim113@pknu.ac.kr

INTRODUCTION improves a light outcoupling efficiency of devices by


Conventional organic light-emitting diodes (OLEDs) reducing the waveguide mode of devices.
suffer from poor light extraction efficiency because of the
total internal reflection at the waveguided interfaces.
Although the use of phosphorescent emitter materials
enables for a nearly 100 % of internal quantum efficiency
of OLEDs, a large number of photons are still trapped Fig. 1. Fabrication process of structured PEDOT:PSS
inside the device. Therefore, the development of efficient layers by colloidal lithography.
light outcoupling structures is of great necessity to
achieve high efficiency OLEDs1. Here, we report on a
high performance light extraction system for OLEDs
consisting of randomly structured polymers combined
with low-index PEDOT:PSS layers fabricated by a simple
colloidal lithography process. The preparation of the
outcoupling structures is very simple and easily scaled-up
process.

EXPERIMENTAL/THEORETICAL STUDY
Polystyrene (PS) nanoparticles mixed with PEDOT:PSS Fig. 2. SEM images of structured PEDOT:PSS layers by
(Clevios AI4083) solutions are successfully prepared on colloidal lithography.
glass substrates. By a removal of the PS nanoparticles
from the PS embedded PEDOT:PSS films, the structured CONCLUSION
PEDOT:PSS films are obtained. The green OLEDs are The structured PEDOT:PSS films are successfully
fabricated on the structured PEDOT:PSS films. The fabricated by a simple colloidal lithography process. The
device structure was as follows (bottom to top): ITO / efficiency of OLEDs with the structured PEDOT:PSS
structured PEDOT:PSS (hole transport layer) / layer are improved due to the reduced waveguide mode.
PVK:CBP:Ir(mppy)3 (emission layer) / TPBi (electron The results indicate that the structured PEDOT:PSS
transport layer) / Al (electrode) internal outcoupling system proposed here is a promising
technology to achieve highly efficient OLEDs.
RESULTS AND DISCUSSION REFERENCES
The structured hole transport layers are fabricated by a 1. Y. H. Kim et. al, Adv. Funct. Mater. 24, 2553 (2014)
simple colloidal lithography process as shown in Fig. 1.
Figure 2 shows the morphology of the structured
PEDOT:PSS layers. Structures are well formed on the ACKNOWLEDGMENTS
surface of PEDOT:PSS films. It is expected that the
structures embedded in the hole transport layers of This work was supported by the Technology Innovation
OLEDs can efficiently extract light which is trapped Program (No. 10052923) funded by the Ministry of
inside the device due to the total internal reflection at the Trade, Industry & Energy.
interfaces of transparent electrodes/organic layers and
glass substrate. OLEDs with the structured PEDOT:PSS
layers are prepared to investigate the light outcoupling
effect. The OLEDs based on the structured PEDOT:PSS
layer show an improved current efficiency and power
efficiency compared to the reference OLED with a
conventional PEDOT:PSS hole transport layer. The
results indicate that the structured PEDOT:PSS film
29

Solvent doping and post-treatment process for poly(3,4-


ethylenedioxythiophene):poly(styrene sulfonate) as alternative transparent
electrodes for ITO-free organic light-emitting diodes

Jin Hee Kim1, Chul Woong Joo2, Yoon Kyung Seo1, Ji Yoon Oh1, Jeong-Ik Lee2, Jonghee Lee2, and Yong Hyun Kim1*
1*
Department of Display Engineering, Pukyong National University, Busan 608-737, Republic of Korea,
yhkim113@pknu.ac.kr
2
Research Center, Electronics and Telecommunications Research Institute (ETRI), Daejeon 305-700, Republic of Korea

INTRODUCTION PEDOT:PSS films is 16.2 %, which is higher than that of


The high cost, inherent brittleness, and high temperature reference OLEDs based on PEDOT:PSS doped with
processing of indium tin oxide (ITO), commonly used ethylene glycol (13.5 %).
transparent electrodes in optoelectronic applications,
significantly limit its application in low-cost and flexible
devices such as organic light-emitting diodes (OLEDs),
which boosts a search for alternative electrode
technologies. Poly(3,4-
ethylenedioxythiophene):poly(styrenesulfonate)
(PEDOT:PSS), a conductive polymer, is in particular
regarded as a promising electrode material due to its high
transmittance and conductivity, and mechanical
flexibility. It is reported that OLEDs based on
PEDOT:PSS electrodes have shown promising features.
In particular, thin films of PEDOT:PSS optimized by a
solvent post-treatment resulted in drastically improved
electrical and stability properties, and allowed successful
application in OLEDs as an alternative electrode1. In this
work, we report 1,3-dimethyl-2-imidazolidinone (DMI) as
a novel solvent for PEDOT:PSS films for improving the
conductivity of films. The electrical and optical Fig. 1. External quantum efficiency of white OLEDs with
performance of PEDOT:PSS films with DMI is compared ITO, PEDOT:PSS with EG, Zonyl, and drop-treated
with those of films doped with a conventional solvent. PEDOT:PSS with DMI, Zonyl electrodes.

CONCLUSION
EXPERIMENTAL/THEORETICAL STUDY In summary, we demonstrate on a highly conductive
PEDOT:PSS (Clevios PH1000, Heraeus, Germany) PEDOT:PSS thin films doped with DMI. The obtained
solutions were mixed with ethylene glycol or DMI. The highest conductivity of post-treated PEDOT:PSS with
formulations were spin coated at 1500 rpm for 30 s on DMI films is 986.2 S/cm. Furthermore, the solvent post-
glass substrates. The films were subsequently annealed on treated PEDOT:PSS films are successfully adopted as
a hot plate at 120 oC for 15 min in air. Post treatment for transparent electrodes for white OLEDs and shows an
several PEDOT:PSS films was performed by immersing high device efficiency. The results indicate that the
films in methanol bath (dip treatment) or by dropping optimized PEDOT:PSS films with the new solvent of
methanol on the films (drop treatment). The white OLEDs DMI can be a promising transparent electrode for low-
consist of red, green, blue emitting layers are fabricated cost, flexible ITO-free white OLEDs.
on various electrode investigated here.
REFERENCES
1. Y. H. Kim et. al, Adv. Funct. Mater. 21, 1076 (2011)
RESULTS AND DISCUSSION
DMI significantly increases the conductivity of ACKNOWLEDGMENTS
PEDOT:PSS films up to 812.1 S/cm. Moreover, the post-
treated PEDOT:PSS films show significantly reduced This work was supported by the Technology Innovation
sheet resistances compared to untreated films. In addition, Program (No. 10052923) funded by the Ministry of
the PEDOT:PSS films are adopted as a bottom electrode Trade, Industry & Energy. C. W. Joo, J. -I. Lee, and J.
for white OLEDs. The maximum external quantum Lee acknowledge the support of the Industrial Strategic
efficiency of OLEDs with solvent post-treated Technology Development Program. (No. 10045269).
30

MnO2-Protected Silver Nanoparticles: Efficient Electromagnetic Nanoresonators


for Raman Analysis of Surfaces in Basis Environment
Heman Abdulrahman, Karol Kotaj, Pawe Lenczewski, Jan Krajczewski, and Andrzej Kudelski
Faculty of Chemistry, University of Warsaw, Poland, hemin.80@mail.ru

INTRODUCTION deposition of the MnO2 layer was realized according to


Very promising method of analysis of surfaces of various the same procedure, so formed MnO2 layers should have
materials is developed by Li et al. so-called shell-isolated roughly the same thickness). As can be seen in Figure 2,
nanoparticle-enhanced Raman spectroscopy (SHINERS).1 the SHINERS spectrum obtained using MnO2-covered
In this method the investigated surface is covered by the silver nanoresonators are about 30 times stronger than the
layer of the plasmonic metal nanoparticles (Au, Ag) respective SHINERS spectrum recorded using gold
protected by very thin (typically 2-5 nm) layer of nanoresonators despite that in both cases we deposited
chemically inert dielectric. Nanoparticles of plasmonic Au@MnO2 and Ag@MnO2 nanoresonators produced
metals act as electromagnetic resonators, significantly from the same number of moles of gold and silver on the
locally enhancing the electric field of the incident same area of the MBA-modified gold substrate.
radiation, and hence leading to a large increase of the
efficiency of Raman scattering from the molecules being
in the close proximity to such plasmonic nanoparticles.
Protecting dielectric layer separates metal nanoparticles
from direct contact with the surface of the analyzed
sample and keeps metal nanoparticles from
agglomerating. Since SiO2 and Al2O3 (typically used for
the first SERS measurements) could not be used as
protecting layer in the alkaline media, for SHINERS
measurements in the alkaline conditions Lin et al.
suggested using gold nanoresonators protected by the
MnO2 layer (Au@MnO2). In 2012 it was shown that
using silver nanoparticles as SHINERS nanoresonators
instead of gold nanostructures allows for larger (even by Fig. 1. TEM micrograph of an obtained Ag@MnO2
two orders of magnitude) increase of the sensitivity of nanoparticle.
SHINERS analysis.3,4 Therefore, in this work, we decided Fig. 2 (a) Raman spectrum of the MBA monolayer on
to synthesize MnO2-protected silver nanoresonators. gold before deposition of nanoresonators and covered
with (b) Au@MnO2, and (c) Ag@MnO2 nanoparticles.
EXPERIMENTAL
Coating of Ag and Au nanoparticles with MnO2 layer was CONCLUSION
realized according to the modified procedure proposed by The first example of the synthesis of Ag@MnO2
Lin et al.2 Briefly, MnO2 was deposited during the nanoparticles has been reported. The obtained Ag@MnO2
reduction of KMnO4 by K2C2O4 in the presence of metal nanoparticles are almost two orders of magnitude more
nanoparticles. Lin et al. alkalized metal sol to pH=9.5, efficient in enhancing Raman signal than the previously
however, this original procedure is unsuccessful for the used for SHINERS measurements in the alkali
formation of Ag@MnO2 nanostructures - we found that environment Au@MnO2 nanostructures.
the reaction must be carried out in the pH range 11.5-13.
Raman measurements were carried out using a Horiba REFERENCES
Jobin-Yvon Labram HR800 spectrometer equipped with 1. J.F. Li, et. al, Nature 464, 392395 (2010).
He-Ne (632.8 nm) and Nd:YAG (532 nm) lasers. For 2. X.D. Lin, et. al, J. Raman Spectrosc. 43, 4045 (2012).
analysis of geometry of obtained nanoparticles we used a 3. V. Uzayisenga, et. al, Langmuir 28, 91409146 (2012).
LIBRA 120 (Zeiss, Germany) transmission electron 4. A. Kudelski, et. al, J. Phys. Chem. C 116,
microscope (TEM) working at an accelerating voltage of 1616716174 (2012).
120 kV.
ACKNOWLEDGMENTS
RESULTS AND DISCUSSION This work was financed from the funds of the National
An example TEM image of the obtained Ag@MnO2 Science Centre (Poland) allocated on the basis of the
nanoparticle is presented in Figure 1. Figure 2 shows decision number DEC-2013/11/B/ST5/02224.
SHINERS spectra of the gold substrate with deposited
4mercaptobenzoic acid (MBA) monolayer covered with
Au@MnO2 and Ag@MnO2 nanoresonators (in both cases
31

Synthesis and characterization of efficient TiO 2 mesoporous photocatalysts

Sergey Poznyak1* , Evgeni Ovodok1, Hanna Maltanava1, Maria Ivanovskaya1,


Alexander Kudlash2, Nico Scharnagl3 and Joao Tedim4
1*
Research Institute for Physical Chemical Problems, Belarusian State University, Belarus, poznyak@bsu.by
2
Chemical Department, Belarusian State University, Belarus
3
Helmholtz-Zentrum Geesthacht Zentrum fur Material und Kustenforschung GMBH, Germany
4
DEMaC, CICECO-Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal

INTRODUCTION strongly upon annealing, and after treatment at 400 C the


Among various oxide semiconductors, titania is vibrations related to these groups are not observed. Based
considered as the most important photocatalyst due to its on the obtained results, multistep mechanism for TiC
biological and chemical inertness, strong oxidizing power, conversion to TiO 2 is proposed.
nontoxicity, and long-term stability against photo and
Table 1. Results of XRD analysis and N 2 adsorption
chemical corrosion. Recently, mesoporous TiO 2 powders
desorption measurements for the TiO 2 samples annealed
have been proven to be very promising materials for
at different temperatures
photocatalytic applications owing to their high surface
area and narrow pore size distribution, while retaining a T, Phase CS, S, d aver , V por ,
crystalline framework. Mesoporous TiO 2 powders are nm m2/g nm cm3/g
usually synthesized through conventional approaches 70 An, XA 4.0 290 3.1 0.224
using various surfactants as templates. 200 An, XA 3.9 353 3.4 0.300
We describe in this study a simple template-free synthesis 400 (air) An 7.4 135 5.5 0.185
of the mesoporous titania with an anatase framework via 400 (Ar) An 7.5 125 6.2 0.193
chemical treatment of TiC using nitric acid as an An anatase phase, XA X-ray amorphous phase, CS
oxidizing agent. The focus of the present research is on crystallite size calculated from XRD patterns.
characterization of the structure, surface properties and
photocatalytic activity of this material. Measurement of zeta potential vs pH dependences
provided additional information about surface state and
EXPERIMENTAL METHODS adsorption ability of the TiO 2 samples. The presence of
To prepare titania, titanium carbide powder was oxidized nitrate groups on the TiO 2 surface shifts the point of zero
by HNO 3 according to the previously described procedure charge from common pH values (5.5-6.5) to lower ones
[1], with some modifications in the acid concentration and (2.5-3.5), providing an efficient adsorption of positively
initial ratio of the components. The as-prepared TiO 2 charged dyes on the powder. All the mesoporous TiO 2
powder was annealed at different temperatures under inert powders prepared in this study show superior
and air atmosphere. The resulting materials were photocatalytic efficiency as compared with the
characterized by XRD, N 2 adsorption, SEM, TEM, commercial Degussa P-25. Solution of Rhodamine B dye
TG/DSC, EPR, Raman and FTIR spectroscopies. was effectively bleached in the presence of the TiO 2
powder annealed at 200 C under both UV and visible
RESULTS AND DISCUSSION light irradiation. The photocatalytic activity is reduced
Only broadened peaks characteristic of anatase phase are slightly for the samples annealed at 400 C.
observed in XRD patterns of the as-prepared powder and
the powders annealed at 200 and 400 C, indicating that CONCLUSION
TiC is completely oxidized by nitric acid, resulting in the Mesoporous TiO 2 powders were synthesized by oxidative
formation of fine-grained TiO 2 . The average size of the decomposition of TiC with nitric acid. The enhanced
anatase crystallites was estimated by the half-width of the photocatalytic activity of the samples heated at 200 C
(101) peak and is about 4 nm and 7 nm for the samples can be attributed to the associated effects of high surface
annealed at 200 and 400 C, respectively (Table 1). area, small crystalline size, mesoporous structure, anatase
Raman spectra confirm the presence of only anatase phase crystallite framework and the presence of negatively
and the fine-grained structure of the samples. Results charged nitrate, nitrite and carboxyl surface groups.
obtained from N 2 adsorptiondesorption isotherms (type REFERENCES
IV) of the synthesized TiO 2 powders demonstrate their 1. D.-L. Shieh et. al, Micropor. Mesopor. Mater. 98 339
pronounced mesoporous structure, with the highest (2007)
specific surface area of 353 m2 g-1 and an average pore
size of 3.4 nm for the sample annealed at 200 C (Table ACKNOWLEDGMENTS
1). FTIR spectra show the presence of hydroxyl, nitrate, We gratefully acknowledge the financial support of the
nitrite and carboxyl surface groups. Intensity of the bands European Commission (Project 645662 SMARCOAT -
belonging to the nitrate and nitrite groups is reduced H2020-MSCA-RISE-2014) for this research.
32

Decahedral silver nanoparticles with silica layer as the new type of SHINERS
nanoresonators

Karol Kotaj1, Jan Krajczewski1 and Andrzej Kudelski1


1
Department of Chemistry, University of Warsaw, Poland, kkolataj@chem.uw.edu.pl

INTRODUCTION plasmonic properties (the plasmonic peak at 517 nm) than


In 2010 Tian reported a new analytical method of the spherical ones. The plasmonic peak for nanoparticles
chemical analysis of surfaces named SHINERS (shell- coved with silica layer is red shifted (see Fig. 1).
isolated nanoparticle-enhanced Raman spectroscopy)1. In
this approach the analyzed surface was covered with the
layer of gold nanoparticles protected by a thin layer of
silica or alumina, and then the Raman spectrum of the
investigated sample was recorded. Gold nanoparticles act
as electromagnetic resonators, significantly enhancing the
electric field of the incident electromagnetic radiation,
and hence leading to very large increase of the Raman Fig. 1. On the right are spectra of obtained spherical
signal from the surface on which nanoparticles have been Ag@SiO2 (blue), decahedral Ag (orange) and decahedral
spread. The protecting coating separates metal cores from Ag@SiO2 (gray) nanoparticles. On the right is TEM
direct contact with the probed material and keeps them micrograph of decahedral Ag@SiO2 nanoparticles.
from agglomerating. Therefore, metal nanoparticles
covered with protecting layer might be used for broader Obtained nanoparticles have mainly decahedral shape and
range of systems, also for living cells. average size of 50 nm. The averaged thickness of the
silica layer is ca. 3 nm (see Fig. 1).
In this contribution we report the synthesis of new type of
SHINERS nanoparticles with the decahedral silver core Synthesized nanoparticles have been used as the
and show their application for Raman studies of some nanoresonators in Raman measurements of yeast cells
molecules and yeast cells. (Saccharomyces boulardii) (see Fig. 2).
EXPERIMENTAL
To obtain decahedral silver nanoparticles we prepared
15.5 ml of aqueous solution of sodium citrate (3.5 mM),
polyvinylpyrrolidone (0.2 mM), L-arginine (0.03 mM)
and AgNO3 (0.14 mM). This solution containing silver
salt was reduced by the addition of 0.16 ml of 100 mM
NaBH4 and after this it was then irradiated for 5h by the Fig. 2. Raman spectrum of yeast cells without (left) and
blue radiation (470 nm) and centrifuged2. To create a thin with Ag@SiO2 nanoparticles (right).
silica layer on nanoparticles we used method developed
As we see in Figure 2 spectra obtained with Ag@SiO2
by Mirkin3. Briefly speaking an ethanolic solution of 16-
nanoparticles are much stronger and we were able to
mercaptohexadecanoic acid (20M) was added to
record some well visible Raman peaks from compounds
nanoparticles solution and then the solution was
from the cell wall of yeasts.
centrifuged. Afterwards nanoparticles were redispersed in
ethanolic solution of tetraethyl orthosilicate (0.16 mM) CONCLUSION
and aqueous solution of dimethylamine (20 %) was added In our work we produced a new type of SHINERS
to this solution to a final concentration of 0,6M. Finally it resonators with new shape and plasmonic properties.
was stirred for 3h, centrifuged and redispersed in water. Using such nanoparticles we were able to measure Raman
Raman measurements were carried out using a Horiba signal from the cell wall of yeasts.
Jobin-Yvon Labram HR800 spectrometer equipped with
He-Ne (632.8 nm) and Nd:YAG (532 nm) lasers. REFERENCES
Saccharomyces boulardii yeasts were bought in the 1. Z. Tian et al, Nature 2010, 464, 392395
pharmacy. 2. V. Kitaev et. al, ACS Nano 2009, 3, 2126
3. Ch. Mirkin, Adv. Mater. 2007, 19, 40714074
RESULTS AND DISCUSSION
Figure 1 shows UV-Vis spectra of spherical Ag@SiO2 ACKNOWLEDGMENTS
and decahedral Ag@SiO2 nanoparticles before and after This project was financed from the funds of the National
deposition of SiO2 layer and the TEM micrograph of Science Centre allocated on the basis of the decision
decahedral Ag@SiO2 nanoparticles. As can be seen in number DEC-2013/11/B/ST5/02224.
Fig. 1 obtained decahedral nanoparticles has different
33

A Three Dimensional Approach for Structural and Electrical Characterization of


Planar Sets of Gold Nanoparticles

Z. Zolnai1*, A. Dek1, N. Nagy1, D. Zmb1, S. Pothorszky1, and A. Nmeth2


1
Centre for Energy Research, Institute of Technical Physics and Materials Science, P.O.B. 49, H-1525 Budapest, Hungary
*
Presenting author e-mail: zolnai@mfa.kfki.hu
2
Wigner Research Centre for Physics, Institute for Particle and Nuclear Physics, P.O.B. 49, H-1525 Budapest, Hungary

Surface electric fields play important role in both the of VS. The angular dependence and 3D nature of these
preparation and operation processes of nanodevices. effects was monitored by two detectors placed at different
Accordingly, detailed knowledge on the morphology and tilt angles between 0o-70o with respect to the sample
behavior of individual nanoparticles and their sets in normal. The strength of VS was controlled with a tunable
presence of surface electric fields is essential for novel electron source. Besides 3D-RBS, AFM and FESEM
nanotechnology applications. In this work, based on ion analysis have been applied as complementary
beam analytical tools a quantitative 3D approach is shown characterization tool to monitor the surface morphology.
to induce and monitor in-situ surface potential buildup on
RESULTS AND DISCUSSION
planar sets of gold and gold-silica core-shell nanoparticles
The development of high surface potentials up to 70 kV
supported by or embedded in solid substrates. By
was found at the surface of Au nanobricks on a glass
switching on and off the surface potential detailed
substrate. In this case structural reorganization via
information can be obtained about the shape, size,
decreasing the amount of Au has been observed with
arrangement, and the behavior of the particles in the
increasing the applied ion fluence. The results suggest
changing electrical environment. Through this concept
that surface electric field-driven evaporation of the
surface reorganization processes like electric field-
uncovered gold particles may occur. Nevertheless, the
induced morphology changes, evaporation, sputtering, or
possible role of sputtering induced surface erosion and
rearrangement, can be followed.
thermal evaporation will be also discussed.
On the other hand, Au nanospheres embedded in silica
INTRODUCTION
shell or buried in glass substrate did not show significant
The development of ion-beam induced surface electric
change in the presence of a high surface potential, thus
potential (VS) on insulating planar surface layers has been
suggesting the protective nature of the cover layer. Note
successfully monitored with ion beam analysis1.
to our knowledge embedded nanostructures were not
Nevertheless, the power of the concept has not yet been
studied so far with the proposed concept.
exploited for individual nanoparticles. Recently we
reported the detailed 3D analysis of the shape, size, and
CONCLUSION
atomic composition for ordered sets of nanoparticles via
Our 3D-RBS study on the in-situ monitoring of surface
Rutherford Backscattering Spectrometry (RBS)2,3. Due to
morphology and ion-beam induced surface charging open
the small size and large surface curvature of spherical or
up the way for the detailed 3D analysis of individual
rectangular particles high electric fields may appear even
nanoparticles and their planar sets. Understanding surface
for low surface potentials. Accordingly, charging,
potential-particle and particles-particle interactions is
polarization, field evaporation or field induced dissolution
straightforward for many processes like field induced
of the particles may occur. In this work we combine the
electron or ion emission, reorganization4, shaping,
3D-RBS morphology analysis measured for VS = 0 with
transport, or the influence of high static electric fields on
the analysis of sample charging measured at high values
the plasmon resonance properties of metal nanoparticles.
of VS. Gold nanospheres, nanobricks, and gold-silica core-
shell nanoparticles deposited on or embedded in a glass REFERENCES
substrate are analyzed.
1. T. Nagatomi et al, J. Appl. Phys. 106, 104912 (2009)
EXPERIMENTAL/THEORETICAL STUDY 2. Z. Zolnai et al, Phys. Rev. B 83, 233302 (2011)
RBS experiments were performed in a vacuum chamber 3. Z. Zolnai, Appl. Surf. Sci. 281, 17 (2013)
by He+ analyzing ions with energy of 750 keV or 1.5 4. S. Lugomer et al, Thin Solid Films 574, 136 (2015)
MeV. For each element (Si, O, Au) in the sample VS can
be calculated from the shift of the leading edges of the ACKNOWLEDGMENTS
RBS spectrum on the energy scale. In addition, for gold This work was supported by grants from the Hungarian
VS can be also determined from its effect on the Au peak Scientific Research Fund (OTKA K 112114, OTKA PD
integral due to acceleration/deceleration of the analyzing 105173) and for A. D. by the Jnos Bolyai Research
ions and the bending of the ion trajectories in the presence Fellowship from the Hungarian Academy of Sciences.
34

Exciton and trion features in MoS2/WS2 heterobilayers: Theoretical study

Imen Ben Amara1, Emna Bensalem1 and Sihem Jaziri1


1
Laboratoire de Physique de la Matire Condense, Facult des Sciences de Tunis, Universit Tunis El Manar Campus
Universitaire, 1060 Le Belvdre, Tunisia
imen.benamara5@gmail.com

INTRODUCTION electronic devices based on the herein heterobilayers .The


In the recent years, two-dimensional (2D) materials have real and imaginary dielectric functions are also elucidated
attracted an increasing interest due to the ability to fulfill and help to identify the optical direct interbands
the future demands of the nanoelectronic device and their transitions occurring from VB to CB in the present
potential applications in the next generation low-cost material, and to predict the dielectric constants. DFT-
solar cells [1]. Monolayers of group-VI transition metal results offer the crucial parameters to our analytical model
dichalcogenides (TMDs) have recently emerged as a new in which the potential takes in account the electron-hole
class of direct-gap semiconductors in the two-dimensional interaction. Our results show that absorption spectrum
(2D) limit and the visible range band gap further makes evolves gradually from an additive spectrum, that is,
these 2D semiconductors ideal platforms for MoS2 and WS2 monolayers contribute separately to the
optoelectronics and light-harvesting applications [2]. absorption spectrum of the heterostructure, to coupled
Stacking different TMDs monolayers to form van der spectrum due to the strength coupling. By explaining the
Waals heterostructures opens open up venues to creating charge transfer mechanism, we have explained and
new material systems exploited at nanoscale, with rich calculated the neutral excitons and trion states.
functionalities and novel physical effects. Importantly,
MX2 heterostructures are predicted to form type II
heterojunctions in which the conduction band minimum
and valence band maximum reside in two separate
materials giving an efficient separation of electrons and
holes [3]. Very Recently, MoS2/WS2 heterobilayers have
been realized by Sefaattin Tongay and collaborators [3]
using CVD grown monolayers. They have highlighted
that the PL spectrum of the herein heterobilayers changes
versus annealing time, from additive PL to renormalized
one. This is manifested in the PL spectrum by the
appearance of multiple-peak and gradual reduction of
others. These peaks correspond to neutral and charged Fig.1. Bands structure of MoS2/WS2 heterobilayers
exciton coming from the constituent monolayers.
CONCLUSION
THEORETICAL STUDY DFT calculations illustrate the type II-alignment band for
To provide an insight on the observed phenomena, we the heterobilayers (MoS2/ WS2) that highlight the
suggest a theoretical investigation based on two and three- significance of interlayer coupling and charge transfer in
body Hamiltonian, in which the electron-hole interaction the absorption spectrum of TMD material and offer a
is taken in consideration. To propose the key parameters general route to prepare large-area TMD structures for
for the analytical model, we have carried out Density fundamental study as well as electronic and photovoltaic
Functional Theory (DFT) calculations [4] on the present applications.
heterostructure MoS2, /WS2.
REFERENCES
RESULTS AND DISCUSSION [1] C. C. Neto and K. S. Novoselov, Mater. Express 1, 10
DFT-bands structure shows the formation of type II- (2011).
alignment band for the heterobilayers (MoS2/ WS2). The [2] A. Splendiani et al, Nano Lett 10, 127 (2010).
computed partial densities of states (PDOS) indicated the [3] S. Tongay et al Nano Lett.14, 3185 (2014).
d-character of momentum contribution and the presence [4] P. Hohenberg and W. Kohn Phys. Rev B.136,
of a charge-transfer exciton shared by two different layers 864(1964).
constituents. Furthermore, we have given an insight about ACKNOWLEDGMENTS
the change in the effective mass values from monolayers
(ML) constituents to heterobilayers structure. The Authors acknowledge the WIEN2k team.
calculations highlight the lower carrier effective mass of
MoS2/WS2 and thus may offer large carrier mobility in
35

Theoretical study on silicon photonic crystal microcavity biosensor


with improved sensitivity

A. Benmerkhi, M.Bouchemat, and T.Bouchemat

Dpartement d'lectronique, Universit des frres Mentouri, Algrie

email. hm_bouchemat@yahoo.fr

INTRODUCTION by infiltrating one functionalized row localized at each


Biosensors based on photonic crystal (PC) waveguides side of the line defect with water, up to all rows. We
incorporated with microcavities [1] have some advantages demonstrated that the sensitivity of the design varies from
over the biosensors mentioned above in compactness, 160.60 nm/RIU (R = 1) to 206 nm/RIU (R= all). Next, we
high sensitivity, easy extension to sensor arrays, various have further enhanced the sensitivity by adjusting the size
choices of materials, and capability of parallel of the holes around the cavity to a value of r=0.29a, and
measurement. They can offer sensitivity of 175 nm/RIU the hole dimension of the defect line surrounding
and a limit of detection (LOD) of 7x10 -5 RIU [2]. alternated holes are reduced to r'=0.25a (see Fig.1a). A
The photonic crystal sensor arrays make the detection of 159 nm wavelength position of the resonance shift was
different analyte simultaneously on a single platform observed corresponding to a sensitivity of
possible. Considering the multiple sensing performance 374.24 nm/ RIU (see fig.1b). Also, there is a linear
and label-free biomolecular detection, photonic crystal dependency between resonant wavelength shift and the
sensor array is a better choice. Examples of such refractive index changes.
(a) (b)
structures include the work of Liu et al. who proposed a
novel nanoscale photonic crystal biosensor arrays r'=0.33a
platform for label-free biosensing. The simulation results r'=0.29a
demonstrated that the refractive index sensitivity of
r'=0.28a
sensor array varies from 66.67 to 136.67 nm/RIU
r'=0.27a
corresponding to the number of functionalized air holes
r'=0.26a
ranged from 4 to 21[3]. Another sensor was introduced
by Liu et al. [4]. They report the results of a study of an r'=0.25a
optical sensor based on a channel-drop configuration with r'=0.24a
a reflector and an additional photonic crystal cavity. The r r'
sensor keeps a high sensitivity in RI sensing. A minor Fig. 1. (a) PC waveguide with a cavity on a side, the water
difference of 0.12 in the RI between water and oil fills all the air holes, (b) The sharp drop fraction of output
samples results a resonant wavelength shift of 18.3 nm in transmission spectrum of TE-like polarized light wave of the
experiment, which is in excellent agreement with the defect line surrounding alternating holes to different values.
calculated shift of 20.0 nm. This real wavelength shift
results in an index sensitivity of 153 nm RIU 1. Yang et CONCLUSION
al. demonstrated a nanoscale photonic crystal sensor array We propose a final structure where the optimized design
on monolithic substrates using side-coupled resonant is created by reducing the hole dimension around the
cavity arrays [5]. cavity and reducing the hole dimension of the defect line
surrounding alternated holes. We succeeded to obtain a
RESULTS AND DISCUSSION new sensitivity value of 374.24 nm/RIU. The designed
Figure 1a shows schematically the basic structure of the structure has high sensitivity, which is an important
channel drop filtering devices under consideration, which parameter in biosensing applications.
are based on 2D PC consisting of a triangular lattice of air
REFERENCES
holes in a 0.6a thick silicon (Si) slab. The PC has a lattice
[1] S. Mandal et al. Opt. Express 16, 16231631
constant "a" and a pore radius of 0.33a.The refractive
(2008).
index of Si is approximately 3.4 at a wavelength of
[2] E. Guillermain et al, Proc. of SPIE 7167, 71670D-1
1.55m. The central row of air holes are removed in order
(2009).
to form a line defect (W1) waveguide, with a simple
[3] Q. Liu et al. Sensors and Actuators A 216, 223-230
cavity formed by missing a single hole in the PC
(2014).
structure. The PC waveguide and cavity are put together;
[4] Y. Liu et al. J. of Light. Tech. 33, 3672-3678
the cavity mode can be excited by the waveguide.
(2015).
In the first step, a microcavity filled with water is coupled
[5] D. Yang et al., Opt. Express 19, 2002320034
with the waveguide. In this case the sensitivity is equal to
(2011).
60.60 nm/RIU. This sensitivity could be further improved
36

Investigation of Growth Parameters on Hydrogen Defect Formation in


Nanocrystalline Diamond Films Grown by Microwave Plasma Chemical Vapour
Deposition

C.J. Tang1,2*, Shuilin Tu1, A.J.S. Fernandes2, Haihong Hou1, X.F. Jiang1, J.L. Pinto2
1*
Department of Physics, Jiangsu Key Laboratory for Advanced Functional Materials, Changshu Institute of Technology,
Changshu 215500, Peoples R China, tang.chunjiu@cslg.cn and tang.chunjiu@ua.pt
2
Department of Physics, I3N (Institute for Nanostructures, Nanomodelling and Nanofabrication), University of Aveiro,
Campus Universitrio de Santiago, 3810-193 Aveiro, Portugal

In this work, we carry out a systematic study of the A series of nanocrystaline diamond films of various
effect of growth parameters on hydrogen impurity microstructure, orientation and texture, were obtained
incorporation in nanocrystalline diamond (NCD) films through nitrogen and oxygen addition into
grown at high microwave power ranging from 2000 to methane/hydrogen plasma using high power ranging from
4000 W. The NCD samples were obtained by a small 2 kW to 4 kW. Hydrogen impurity in the nanocrystalline
amount of nitrogen and oxygen addition into diamond films were analyzed based on their FTIR spectra.
conventional methane and hydrogen plasma. The
morphology, grain size, microstructure, orientation or The growth mechanism of nanocrystalline diamond films
texture, and crystalline quality are characterized by was discussed based on small perturbation through
using scanning electron (SEM) microscopy, X-ray nitrogen addition to the standard diamond growth
diffraction, and micro-Raman spectroscopy. Hydrogen mechanism by CVD. The incorporation mechanism of
impurity in the NCD films is analyzed by using hydrogen impurity in NCD films is discussed based on
Fourier-transform infrared (FTIR) spectroscopy. The the modification of the standard model of CVD
growth rate and hydrogen impurity content of the diamond [3] upon nitrogen and oxygen addition.
NCD films strongly depends on the growth conditions
The role of microwave power (and substrate
temperature), the amount of nitrogen and oxygen CONCLUSION
addition, and deposition time is analyzed. The In this work, it has been demonstrated that the growth
formation mechanism of hydrogen defects in NCD parameters such as microwave power, the amount of
films is discussed nitrogen and oxygen and deposition time has strong effect
on the growth of nanocrystaline diamond films and its
INTRODUCTION hydrogen impurity incorporation when a small amount of
In one hand, hydrogen plays significant role on the nitrogen and with or without oxygen addition is used. The
conventional growth of CVD diamond. On the other hand, incorporation form, distribution and content of hydrogen
hydrogen is an important impurity of diamond [1], impurity in nanocrystaline diamond films were studied
because it can drastically influence its electrical and and compared with that of large-grained microcrystalline
electronic properties. Hydrogen is a ubiquitous impurity diamond films to understand the incorporation mechanism
of CVD diamond films, due to the rich hydrogen of hydrogen impurity in nanocrystalline diamond films.
atmosphere during growth. It is well-known that high
power MPCVD systems are efficient for producing high
REFERENCES
quality diamond films of high uniformity, large area and
high growth rate [2]. In this work, we perform a
1 Y.R. Chen, et. Al, J. Chem. Phys. 119, 10626 (2003)
systematic study of the effect of many growth parameters
2 V. Ralchenko, et. Al. Diamond Relat. Mater. 8, 189
on hydrogen impurity incorporation in nanocrystalline
(1999)
diamond (NCD) films grown at high power ranging from
3 J.E. Butler, et. Al, J. Phys. Conden. Matt. 21, 364201
2000 to 4000 W using a 5 kW MPCVD reactor.
(2009)
EXPERIMENTAL/THEORETICAL STUDY
ACKNOWLEDGMENTS
A 5 kW ASTeX PDS-18 MPCVD system was used for
This work is supported by project PEst-
diamond growth on silicon substrates. A variety of
C/CTM/LA0025/2011 by FCT Portuguese Science and
techniques such as SEM, Raman, XRD and FTIR
Technology Foundation. The financial support by the
spectroscopy were used for characterization of the
National Science Foundation (NSF) of China under grant
produced diamond films.
No. 51102027 is also acknowledged. In addition, we
acknowledge the partial financial support by the European
RESULTS AND DISCUSSION Union under Grant Agreement 295208 (CarbonNASA).
37

Simulations of biophysically detailed neurons connected with nanoscale memristors


Joo Reis1, Catarina Dias1,2, Joo Ventura1,2 and Paulo Aguiar3,4,*

1
Department of Physics and Astronomy, Faculty of Sciences, University of Porto, Portugal, joao.alexandre1993@gmail.com
2
IFIMUP and IN-Institute of Nanoscience and Nanotechnology, Portugal
3
i3S Instituto de Investigao e Inovao em sade, Universidade do Porto, Portugal.
4
INEB Instituto de Engenharia Biomdica, Universidade do Porto, Portugal

INTRODUCTION
Memristors are a research topic with very high interest
nowadays1. They are a passive electronic element with the
useful characteristic of integrating the input to change its
resistance value, which enables some very promising
solid-state memory developments. More recently they
have also been used on the context of neuromorphic
devices to create artificial synapses. The use of electronic
circuitry to mimic biological neural networks2 has already
a long history but previous attempts have proven to be Fig. 1 Voltage of stimulated neuron in red while black
inadequate3, without the necessary scalability and power represents the other neuron, connected via memristor.
consumption that memristors appear to have. This work
explores the neuromorphic properties of memristors by memristor needs to receive several inputs (a spike train) to
targeting a promising field: neuro-electronic hybrid produce this effect. An inductor and a memristor in series
systems where biological neurons connect to implanted also exhibits interesting learning properties: a spike train
memristors to modulate neuronal populations activity. with a short period simulates not only the output of the
same neuron but also that the connection resistance, which
METHODS will only change if the spikes are not isolated.
Numerical simulations of simple hybrid systems were
performed, exploring the dynamics of neuron models with
high biophysical detail connected with memristors. The
simulations were carried out in the NEURON simulation
environment4, a standard tool in the field of computational
neuroscience. In this tool, two neurons were modeled and
simulated using the Hodgkin-Huxley (HH) equations for
the membrane potential dynamics. A simple non-linear
nanoscale memristor of the type5
= () + ( 1) Fig.2 Resistance change in connection with an inductor-
was added to the simulation environments library of memristor, after 4 spikes with 5 ms separation.
mechanics by writing code in NEURONs modeling
programming language. In this model i is the current, x a CONCLUSION
dimensionless state parameter and V the voltage; all other Interesting dynamics can be achieved with even simple
parameters change the effective resistances of the two circuits combining memristors with HH neurons.
states of the memristor. An external source was used to
injected current into one of the neurons to drive the REFERENCES
system. This hybrid system was explored under different 1. S. Dmitri et. al., Nature 453.7191 (2008): 80-83.
parameterizations. 2. C. Mead and M. Ismail, Analog VLSI Implementation
of Neural Systems , pp.239 -246 , 1989
RESULTS 3. G. Snider, Advances in Neuromorphic Memristor
The memristor model mimics a non-associative learning Science and Applications, Chapter 1, 2012
rule, where consistent activation of the pre-synaptic 4. M. Hines and N. Carnevale, Neural Computation
neuron progressively increases the strength of the 9:1179-1209, 1997
connection. This leads to neuronal synchronization. The 5. J. Yang et al, Nat. Nanotechnology 3, 429 - 433 (2008)
38

Fullerene-Clad Ultra-Long Carbon Nanotubes

Nikita Kazennov1, 2 *, Ekaterina Zhukova1, Sergey Urvanov1, Aida Karaeva1, 2 and Vladimir Mordkovich1, 2 *
1
Technological Institute for Superhard and Novel Carbon Materials, Moscow, Russia
2
INFRA Technology Ltd., Moscow, Russia
*
mordkovich@infratechnology.com

INTRODUCTION C-O bonds, the oxygen concentration in general and


Fullerene-like nanostructures are usually considered apart healing some of the surface defects. XPS study
from their relatives of fibrous nature such as carbon fibers manifested partial transition of sp2-hybridized carbon into
or carbon nanotubes (CNT). Indeed, the properties of sp3-hybridized form as a result of immobilization.
fullerenes are very different, especially spectroscopic and
chemical features. However, the very difference may
become a source of new properties born from
combination of molecular fullerene C60 and fibrous
carbons. It is known from literature1 that fullerenes do
have affinity to grapheme, in particular to nanotubes,
although this property is usually manifested by forming
peapods not by interacting with CNTs outer surfaces.
The possible use of C60 as a fibrous carbon outer surface
modifier has been extensively studied in our lab for recent
years.
This work represents both conceptual and experimental
study of modification of ultra-long carbon nanotubes,
which were recently synthesized in our lab2, with Fig. 1 Double-walled nanotubes: as-synthesized (left);
fullerenes. fullerene-clad (right)

EXPERIMENTAL STUDY The C60 content in such nanocomposites may reach 37 %


The CNT were synthesized as centimeter-long double- weight. It was also shown that the combination of
walled nanotubes by continuous catalytic process, which fullerenes with fibrous carbons in such immobilized
is described in detail elsewhere2. The CNT in as- composites leads to drastic alteration of mechanical
synthesized form were deep-black, light-weight (density properties as well as of chemical durability. Enhance,ent
of 0.1 to 0.2 g/cm3 only) unwoven threads cut to 10-cm of electrical conductivity was registered as well.
pieces. The C60 adsorption on the surface was
experimentally realized through impregnation of CNT CONCLUSION
with fullerene solution in toluene or in CS2. Since as- Ultra-long double-walled carbon nanotubes (CNT) were
deposited fullerenes are soluble, it is necessary to grown in a scaled-up continuous reactor. These nanotubes
immobilize then on the CNT surface. It was found out were transformed into fullerene-clad form by two-step
that the most efficient technique for immobilization is process of impregnation and immobilization. The 2-3 nm
intensive irradiation by continuous-wave green laser thick C60 covering was closely-packed and tied strongly
(wavelength 514 nm, power 10.3 W/cm2). The resulting by covalent bonds. It has been established that the new
fullerene-clad CNT were investigated by scanning and properties can be reached in such nano-composites. As a
transmission electron microscopy (SEM and TEM), XPS, result, the new fullerene-clad centimeter-long nanofibers
AES, Raman spectroscopy thus establishing structure, were synthesized as a basis for novel nanomaterials.
morphology, surface coverage, etc.
RESULTS AND DISCUSSION REFERENCES
Investigations of fullerene-clad CNT by transmission 1. H. Guerine. J. Chem. Phys. 95, 561 (1998)
electron microscopy showed that the molecules of 2. V.Z. Mordkovich et al. Patent RU 2497752
fullerene formed a shell and covered CNT by bimolecular
closely-packed polymerized layers. The thickness of such
C60 layer was 2-3 nm only as shown in Figure 1. It is
interesting that immobilization of fullerne was
accompanied by visible film self-ordering.
The results of instrumental studies also showed that
fullerene molecules were immobilized with covalent
bonds effectively decreasing the surface concentration of
39

Thermally conductive graphene-polymer composites: size, percolation and synergy effects

Oren Regev1,*
1*
Department of Chemical Engineering, Ben-Gurion University of the Negev, Beer Sheva, Israel, oregev@bgu.ac.il

The rapidly increasing device densities in electronics calls GnP volume fraction () plot, revealing a signature of the
for efficient thermal management. If successfully thermal percolation threshold, t, at GnP = 0.17
exploited, graphene, which possesses extraordinary (intersection of the lines) [1]. The proposed composite
thermal properties, can be commercially utilized to reduces the operation temperature of a device by an order
produce polymer composites with ultrahigh thermal of magnitude (Figure 2) [2].
conductivity (TC). The total potential of graphene to
enhance TC, however, is restricted by the large interfacial
thermal resistance between the polymer-mediated
graphene boundaries. We report a facile and scalable
dispersion of commercially available graphene nano
platelets (GnPs) in a polymer matrix, which forms
composite with ultra-high TC of 12.4 W/mK (vs. 0.2
W/mK for the neat polymer). This ultra-high TC is
achieved by applying high compression forces during the
dispersion that results in the closure of gaps between
adjacent GnPs with large lateral dimensions and low
defect densities. We also found strong evidence for a
thermal percolation threshold. Finally, the addition of
electrically insulating nano-boron nitride (BN) to the
thermally conductive GnP-polymer composite
significantly reduces its electrical conductivity (to avoid
short circuit) and synergistically increases the TC. The
Figure 1. A thermal percolation phenomenon: TC vs.
efficient dispersion of commercially available GnPs in
(GnP). Intersection of the lines indicates the thermal
polymer matrix provides the ideal framework for
percolation threshold (red dashed arrow). Inset:
substantial progress toward the large-scale production and
logarithmic fit to the critical power low of TC
commercialization of GnP-based thermally conductive
GnP_network vs. r = (-t/1-t).
composites.
INTRODUCTION
Efficient thermal management has become a necessity in
next-generation miniaturized electronics, optoelectronics
and medical devices. As the electronic components of
these devices continuously become denser and faster, the
heat they generate could be effectively dissipated by a
polymer-based composite with enhanced thermal
conductivity (TC) as an alternative to conventional heat
removal solutions (e.g., metal heat sink). Figure 2. A diode (left), potted in neat epoxy (middle),
In this study, we chose an epoxy (TC = 0.19 W/mK), a and epoxy-graphene composite (right). The potted diodes
material commonly used in microelectronic applications, are operated and thermally imaged (FLIR) at steady state.
as a polymer matrix. We explored the structural
parameters of commercially available GnPs and their CONCLUSION
effects on the TC of the composite. We found that loading We used thermogravimetric analysis (TGA), beyond the
the epoxy with a GnP of large lateral dimensions and low conventional analysis track[3], to select the most efficient
defect density produced a ultra-high isotropic GnP types for TC enhancement. Hybrid composites of
enhancement of TC (12.4W/mK). Finally, we electrically conductive GnPs and electrically insulating
demonstrated that GnP-BN-epoxy hybrid composites had BNs were shown to form a 3-D network that had a
a synergistic effect on the TC. Since this hybrid may also synergistic effect on TC and that resulted in a tunable EC.
be electrical conductivity (EC) tunable, it is therefore REFERENCES
suitable for a wide spectrum of thermal management 1. Shtein, M., Nadiv, R., Buzaglo, M., Kahil, K., Regev,
applications. O., Chem. Mater. 2015, 27 2100.
RESULTS AND DISCUSSION 2. Shtein, M., Nadiv, R., Buzaglo, M., Regev, O., ACS
A thermal percolation phenomenon has not been Appl. Mater. Interfaces 2015, 7, 23725.
explicitly explained and remains a subject of intense 3. Shtein, M., Pri Bar, I., Varenik, M., Regev, O., Anal.
debate: Figure 1 shows a kink in the composite TC vs. Chem. 2015, 87, 4076-4080.
40

Intermediate phase in Bi1-xPrxFeO3 ceramics at the rhombohedral-orthorhombic


phase boundary

D.V. Karpinsky 1,2,*, M. Willinger 3, M.V. Silibin 1, A.A. Dronov 1, S.V. Dubkov 1, K.N. Nekludov 1, I.O. Troyanchuk 1
1
National Research University of Electronic Technology MIET, 124498 Moscow, Zelenograd, Russia
2
Scientific-Practical Materials Research Centre of NAS of Belarus, 220072 Minsk, Belarus
3
Fritz-Haber-Institut der Max-Planck-Gesellschaft, D-14195 Berlin, Germany
*
karpinski@ua.pt

Pr-doped BiFeO3 ceramics with compositions across the room temperature is characterized by the coexistence of
rhombohedral-orthorhombic phase boundary have been the R- and O2- phases (with ratio 9:1). The temperature
studied by X-ray diffraction and transmission electron diffraction data have evidenced a diminution of the
microscopy measurements. The investigations have orthorhombic phase and at temperatures above 200C the
specified concentration- and temperature- driven crystal structure becomes single phase rhombohedral. At
structural transition from the polar rhombohedral phase to T = 450C small intensity reflections specific to the O1-
the non-polar orthorhombic one. Transmission electron phase have been observed. Above this temperature the
microscopy measurements have disclosed a revival of the structure has been successfully refined using
anti-polar orthorhombic phase with temperature increase centrosymmetric space group Pnma. In order to clarify
prior to formation of the non-polar orthorhombic phase. the observed structural peculiarities we have performed
high resolution transmission electron microscopy
INTRODUCTION
measurements (HRTEM) (Fig. 1).
It is known that chemical substitution of bismuth ions in
The FFT images
BiFeO3 by large rare-earth elements (La - Sm) drives
calculated for the
structural transition from the rhombohedral phase (R-
data recorded at
phase) to antipolar orthorhombic one (O2) and then to
T=400C and 450C
nonpolar orthorhombic phase (O1) [1, 2]. The compounds
reveal the appearance
within the R - O2 morphotropic phase boundary (MPB)
of new spots
are of particular interest as they possess specific structural
(denoted as (002) and
state associated with enhanced physical properties
(040)) associated
promising for device applications. It is known [3, 4], that
with the antipolar
chemical substitution with lanthanum and praseodymium
ortho-rhombic phase
ions leads to stabilization of the phase coexistence state in
(Fig. 1b,c). Further
wide concentration range (as compared to a substitution
temperature increase
by other rare-earth elements) thus allowing its detailed
leads to the Fig.1. FFT images of the HRTEM
study.
stabilization of the data calculated for the x=0.125
EXPERIMENTAL nonpolar ortho- compound at different temperatures:
Nanosize ceramic samples of Bi1-xPrxFeO3 system with rhombic phase (Fig. 100C (a), 400C (b), 450C (c),
dopant concentrations x=0.10 - 0.25 were prepared by the 1d). 500C (d). The diffraction spots
two-stage solid-state reaction followed by application of assosiated with the intermediate
CONCLUSION orthorhombic phase are marked by
external pressure of 5 GPa [5]. X-ray diffraction
Thermal diffraction the arrows.
measurements were performed with a PANalytical XPert
data have allowed to
MPD PRO diffractometer (Cu-K radiation) equipped
clarify the single phase and the phase coexistence regions.
with an Anton Paar (HTK 16N) heating stage. High
The HRTEM measurements have disclosed stabilization
Resolution Transmission Electron Microscopy (HRTEM)
of the anti-polar orthorhombic phase at temperatures prior
measurements have been performed using FEI TITAN
to formation of the non-polar orthorhombic phase.
80-300 microscope.
REFERENCES
RESULTS AND DISCUSSION 1. I. Levin, et al., Chem. Mater. 23, 2166 (2011)
Room temperature XRD data obtained for Bi1-xPrxFeO3 2. D.V. Karpinsky, et al., J Mater Sci 49, (2014)
solid solutions testify rhombohedral (R) to anti-polar 3. D.V. Karpinsky, et al., Phys. Solid State 56, (2014)
orthorhombic (O2) phase transition via two-phase region 4. I. O. Troyanchuk, et al., Phys. Rev. B 83, 054109 (2011)
(0.12<x<0.15). Further increase of the dopant 5. I. O. Troyanchuk, et al., J. Am. Ceram. Soc. 94, 4502 (2011)
concentration leads to a stabilization non-polar
ACKNOWLEDGMENTS
orthorhombic structure (O1). We have focused structural
This research project has been supported by RSF (grant
investigations on the temperature evolution of
15-19-20038).
Bi0.875Pr0.125FeO3 compound whose crystal structure at
41

(ANM)Advanced Nanomaterials (topic include: nanomaterials) Poster


Controlling Densities of Oxygen Vacancies in TiO2 Nanocrystals: Thermal annealing and Acidity of the Medium

Anielle Christine A. Silva1* and Noelio O. Dantas1*


1
Laboratrio de Novos Materiais Isolantes e Semicondutores - LNMIS, Physics Institute, Federal
University of Uberlndia, Uberlndia, MG, Brazil, , email: acalmeida@ufu.br
INTRODUCTION This decay is associated with the transformation of the
Titanium dioxide (TiO2) is a semiconductor with a wide anatase phase to the rutile phase, which has a greater
bandgap (3.0 eV - rutile and 3.2 eV - anatase) and high density of oxygen vacancies, favoring charge transfers
photochemical stability.1 This material is commonly used from the conduction band to defect levels (energy
in various technological such as lithium-ion batteries2. diagram). The excitonic fluorescence intensity of the R1
TiO2 is a polymorphic material with three allotropic sample annealed at 500oC/1h decreased more than that of
forms: anatase, brookite, and rutile. Anatase, brookite and the other samples annealed at this temperature. This effect
rutile are, respectively, tetragonal (I41/amd), orthorhombic is associated with a higher percentage of rutile phase.
(Pbca) and tetragonal (P42/mnm).3 We controlled phase by (a) (b)
varying acid concentration and thermal annealing.
Understanding the effects of these synthesis parameters
on the physical properties of the TiO2 nanocrystals enables
optimal use of these nanocrystals in various
nanotechnological applications. The changed the
structural properties by Raman spectroscopy and
luminescence properties by fluorescence spectroscopy
(PL).
EXPERIMENTAL/THEORETICAL STUDY
TiO2 nanocrystals were synthesized at room-temperature
in an aqueous solution with varying concentrations of
nitric acid at ratios of 10:2:x of H2O:Ti:HNO3, where x
was 1 (Route R1), 2 (Route R2) and 3 (Route R3). Micro-
Raman spectra were obtained from an Ocean Optics
spectrometer and using 780 nm line. Fluorescence spectra
were recorded with a Cary Eclipse spectrophotometer
(Varian) using a 325 nm wavelength from a xenon lamp
as the excitation source. All characterizations were carried
out at room temperature.
RESULTS AND DISCUSSION
Fig. 1 shows (a) micro-Raman spectra (b) VO and
excitonic fluorescence intensity graphs of the TiO 2 NCs.
Fig. 1. (a) micro-Raman spectra and (b) energy diagram
In the Raman spectra annealed at 100oC/24h show bands
for all transitions related to the PL spectra, VO and
characteristic of anatase phase.3 However, higher
excitonic fluorescence of the TiO2 NCs synthesized as a
annealing temperatures observed a band at approximately
function of annealing temperature.
450 cm-1 that is associated the rutile phase. This band is
CONCLUSION
more intense in the Raman spectra of the by route R1 with
We concluded that the optical and structural properties of
a lower acid concentration. Annealed at 650oC/1h shows
TiO2 NCs can be controlled via acid concentration and
transformations from anatase to the brookite phase that
annealing temperature. Thus, these NCs are candidates for
resulted from higher concentrations of acid in the
uses in various applications as fluorescent markers and
synthesis process. Annealed at 800oC/1h clearly show
photocatalysts.
vibrational modes of the brookite phase, and a lower
REFERENCES
percentage in the R1 route. The VO fluorescence intensity 1
. P. V. Kamat, J. Phys Chem. C 116, 11849-11851,
increased at higher annealing temperatures for all
(2012).
samples. These increased occurred because of phase 2
. X. Su et al. J. Mater. Sci. 47, 2519-2534, (2012).
transformations from anatase to rutile and brookite to 3
. D. Reyes-Coronado et al. Nanotechnology 19, 1,
rutile. Higher concentrations of acid in the synthesis
(2008).
process inhibited the formation of the rutile phase, as
ACKNOWLEDGMENTS
confirmed by Raman spectra, resulting in lower VO
The authors gratefully acknowledge CAPES, FAPEMIG,
fluorescence. The excitonic fluorescence intensity
MCT/CNPq.
decayed in all samples at higher annealing temperatures.
42

(ANM)Advanced Nanomaterials (topic include: nanomaterials)- Poster

Synthesis of Simonkolleite Nanocrystals and Control of Transformation to Zinc Oxide by Thermal


Annealing

Noelio O. Dantas1* and Anielle Christine A. Silva1


1
Laboratrio de Novos Materiais Isolantes e Semicondutores - LNMIS, Physics Institute, Federal
University of Uberlndia, Uberlndia, MG, Brazil, , email: noelio@ufu.br

INTRODUCTION 800C is attributed the vaporization of ZnCI2. As


Zinc oxide (ZnO) is a group II-VI semiconductor with a annealing temperatures increase to 250C and 500C, the
hexagonal wurtzite crystal structure, a broad energy band thermodynamic processes shift to lower temperatures,
(3.37 eV), high bond energy (60 meV) and high thermal confirming simonkolleite decomposition. This result
and mechanical stability at room temperature.1 ZnO can explains the diffraction peaks from simonkolleite (Fig.
be used in various applications such as piezoelectric 1a).
devices2. Simonkolleite (Zn5(OH)8Cl2H2O) results from (a) (b)
the natural weathering of Zn-bearing mine slags in
the German region of Michelsdorf 3. It is also known as
zinc chloride hydroxide monohydrate and has numerous
applications supercapacitor applications4. Furthermore, it
is electrically and chemically (electrochemically) active
due to surface oxygen vacancies that significantly
increase conductivity 4,5. In this study, we modulation
amounts of simonkolleite and the ZnO as a function of
thermal annealing temperature.
EXPERIMENTAL/THEORETICAL STUDY
An aqueous 6M zinc chloride solution was prepared.
Next, an 8 M sodium hydroxide solution was added to
raise the overall pH to 7. Finally, the precipitate was
microwave- annealed/15min, 250C/5h, 500C/5h,
750C/5h and 1000C/5h. X-ray diffraction (XRD)
patterns obtained at room temperature using an XRD-
Fig. 1. (a) X-ray diffraction patterns and (b) DTA
6000 Shimadzu diffractometer Cu-K1 radiation ( =
thermograms of samples subjected to thermal annealing.
1.54056 ). Differential thermal analysis (DTA) was
performed on a 50 mg sample in a nitrogen atmosphere
CONCLUSION
with a Shimadzu DTA Analyzer (model DTA-50) at a
Therefore, we have demonstrated a method for
rate of 20oC/min.
modulation amounts of simonkolleite and the ZnO.
RESULTS AND DISCUSSION
Finally, the results obtained via this methodology pave
Fig. 1 shows the (a) XRD patterns and (b) DTA
the way for significant development of new mixed
thermograms of the synthesized samples submitted to the
materials for electronic devices.
annealing treatments. The Bragg diffraction peaks in the
REFERENCES
diffraction pattern of the sample subjected to microwave 1
A. Kolodziejczak-Radzimska et al Materials 7, 2833
confirmed the formation of simonkolleite structure
(2014).
(JCPDS No. 070155)6. Higher annealing temperatures 2
M. R. Hasan et al Acs Appl Mater Inter 7, 5768 (2015).
facillitated the transformation of simonkolleite into zinc 3
S. M. A. Moniem et al. Process Saf Environ 95, 247
oxide7. We zoomed in on the Bragg diffraction peaks to
(2015).
demonstrate that the principle simonkolleite peaks only 4
S. Khamlich, A. Bello et al. J Solid State Electr 17, 2879
disappeared at temperatures greater than 750C. The DTA
(2013).
thermograms of the samples subjected to microwave 5
J. Sithole et al. Appl Surf Sci 258, 7839 (2012).
thermal annealing show all of the thermodynamic events 7
I. Rasines and J. I. Moralesdesetien, Thermochim Acta
associated with the decomposition of simonkolleite. The
37, 239 (1980).
peaks at 145C and 186C are associated with the loss of
ACKNOWLEDGMENTS
water molecules and partial decomposition of
The authors gratefully acknowledge CAPES, FAPEMIG,
simonkolleite. The peaks at 225C and 554C are
MCT/CNPq.
associated with the total decomposition. The peak at
43

Composite -AgVO3@V5+1.6V4+0.4O4.8 hydrogels and xerogels. Protonic conduction


and pollutant sequestration.

Roberto Fernndez de Luis,1 Ana Martnez-Amesti,2 Edurne S. Larrea,3 Anthony R. West,4 Mara Isabel Arriortua.1,3
1
BCMaterials (Basque Centre for Materials, Applications & Nanostructures),Technological Park of Zamudio, Camino 5 de
Ibaizabal, Bndg. 500-1st, 48160, Derio, Spain. roberto.fernandez@bcmaterials.net
2
Servicios Generales de Investigacion SGIker, 3Departamento de Mineralogia y Petrologia, Facultad de Ciencia y
Tecnologia, Universidad del Pais Vasco, UPV/EHU. Apdo. 644, E-48080 Bilbao. Spain.
4
Department of Materials Science and Engineering, University of Sheffield, Sir Robert Hadfield Building
Mappin Street, Sheffield, S1 3JD.

INTRODUCTION To study the thickness and shape of a single nano-ribbon


Nanostructured silver vanadium oxides (SVO) and a 3D reconstruction was done by electron tomography
vanadium oxides (VO), and concretely -AgVO3 nano- (Fig. 1(b)).
ribbons have received considerable attention in the last
decade [1] One of the most amazing consequences of the
crystallization of this 1D nano-structures is that -AgVO3
nano-ribbons can form inorganic hydrogels establishing a
3D non-covalent cross linked framework, which traps
water within its pores. In addition to the unique physical
properties of VO and SVO, inorganic hydrogels possess
an intrinsic porous structure, which opens the possibility (a) (b)
of their use for pollutant sequestration. [2] Herein, we Fig. 1 (a) TEM micrograph of an hydrogel. (b) Electron
tomography. 3D reconstruction of a single nano-ribbon.
report a facile and fast method for the synthesis of nano-
structured SVO and slightly reduced VO hydrogel The dried hydrogels possess moderate surface areas (100
composites with the (-AgVO3)@(V5+1.6V4+0.4O4.8) gr/cm2) and the porous size depends on the hydrogels
formula, hereafter SVO@VO. Moreover, the pollutant initial composition. Despite their small surface area, both
adsorption capacity and the electric and protonic the hydrogels and the xerogels trap very efficiently
conduction properties of the dried hydrogels have been different pollutants dyes, such as methylene blue, crystal
also studied. violet and Iodide. For the specific case of erythrosine of
EXPERIMENTAL STUDY rhodamine 6G, the dyes are selectively trapped by the
Synthesis: The SVO@VO hydrogels are synthesized at composite xerogels containing VO nano-ribbons.
room temperature by the mixture of NaVO3 and AgVO3 The dried SVO hydrogel shows protonic conduction
solutions. Characterization: Atomic emission capacities dependent on the humidity of the atmosphere.
spectroscopy (ICP-AES), powder X-ray diffraction, Above 100C, a protonic conduction, probably associated
infrared and Raman spectroscopies, thermogravimetry, with the silver cations has been also observed. For the
Electron microscopy (SEM-TEM). Electron tomography SVO@VO composites, their electronic conductivity is
of a single ribbon was done using a FEI Titan Cubed G2 increased with heat treatments, due to the activation of
60-300 transmission electron microscope. Adsorption new electron carriers.
capacity: The absorption capacities of the hydrogels were CONCLUSION
determined by UV-vis spectroscopy. Ionic/Electronic The SVO@VO hydrogels are new promising materials for
conductivity: Impedance spectroscopy measurements pollutants sequestration due to the reactive nature of the
were carried out on a Solatron ModulaXm equipment at nanoribbons, and the porous structure of the hydrogels.
different temperatures and under different atmospheres.
REFERENCES
RESULTS AND DISCUSSION 1. F. Cheng, J. Chen, J. Mater. Chem. 21, 9841 (2011)
The synthetic conditions, and more concretely, the 2. (a) C. Mondal, G. Ganguly, J. Pal, R. Sahoo, A. K. Sinha, T.
volume of nitric acid added during the synthesis, control Pal, Chem. Commun. 49, 9428 (2013). (b) R. Fernndez de
not only the composition of the final hydrogel, but also its Luis, A. Martnez-Amesti, E. S. Larrea, A. T. Aguayo, L.
Lezama, M. I. Arriortua. J. Mater. Chem. A. 3, 19996 (2015)
porous structure, and hence the porous structure of the
xerogels that is obtained from it. In this regard, the ACKNOWLEDGMENTS
This work has been founded by the Ministerio de
addition of nitric acid increases the volume of the VO
Economa y Competitividad (MAT2013-42092-R) and
nanoribbons in the SVO@VO hydrogels. The SEM and
the Basque Government (ELKARTEK-2015, grupos de
TEM micrographs reveal that the hydrogels are formed by
investigacin del sistema universitario vasco (IT630-13)),
entangled ribbons with micrometric lengths (1000-
and the university of the Basque Country UPV/EHU (UFI
100m) and nanometric widths (10-300 nm) (Fig. 1 (a)).
11/15).
44

Design Porous Co3O4 Ribbon for Electromagnetic Wave Absorption

Fa-Nian Shi*, Yue Hu, Xingdan Sun, Guimei Shi and Xiaolei Wang*

School of Science, Shenyang University of Technology, China, fshi96@foxmail.com

INTRODUCTION which is even better than the reported composite


Recently, the research on electromagnetic wave absorbing C@Co3O4 in the literature4.
materials has developed rapidly. One of most such
CONCLUSION
interesting materials is Co3O4 and its composites. In order
The porous Co3O4 ribbon was synthesized by thermal
to obtain an excellent absorbing properties of Co3O4, the
treatment of cobalt oxalate at 450 oC in air. The unique
researchers have made a variety of attempts, including
morphology leads to an excellent electromagnetic wave
altering the morphologies of Co3O41, changing the particle
absorbing properties.
sizes from the range of micrometers to nanometers2, even
assembling complex components into composites3. All of REFERENCES
these efforts indeed affect the electromagnetic wave 1. X. B. Li, S. W. Yang, J. Sun, P. He, X. P. Pu, G. Q.
absorbing properties. Here we wish to report that a porous Ding, Synthetic Met. 194, 5258 (2014)
Co3O4 ribbon material prepared from cobalt oxalate is
2. P. -B. Liu, Y. Huang, and X. Sun, ACS Appl. Mater.
with a very good performance of electromagnetic wave
absorption. Interfaces 5, 1235512360 (2013)
3. H. J. Wu, Q. F. Wu, L. D. Wang, Mater. Charact. 103,
EXPERIMENTAL/THEORETICAL STUDY
110 (2015)
The cobalt oxalate as the precursor was directly heated at
450 oC to obtain black porous Co3O4 ribbon. PXRD was 4. F. S. Wen, H. Hou, J. Y. Xiang, X. Y. Zhang, Z. B.
employed to the phase of Co3O4, and SEM technique was Su, S. J. Yuan, Z. Y. Liu, Carbon 89, 372 377
used to do the morphology characterization. The (2015)
performance of absorbing wave was also analyzed on a
vector network analyzer (Agilent E5071C, between 1.0
and 18 GHz). ACKNOWLEDGMENTS

RESULTS AND DISCUSSION Authors acknowledge the project 21571132 is supported


The SEM image in Fig. 1 shows that after calcined at 450 by National Natural Science Foundation of China.
o
C the product became porous on the particle surface with
the pore size within 100 nanometers and the in situ
morphology of the cobalt oxalate precursor remained.

Fig. 1 As-synthesized Co3O4 is with a unique porous


ribbon morphology

Owing to the unique porous ribbon morphology, the as-


synthesized Co3O4 material displayed a remarkably
enhancement on the microwave absorption properties
45

Hexamethyldisiloxane Based Plasma Polymeric Nanomaterials for Gas Sensors


Application
Ekaterina Radeva

Acoustoelectronics Laboratory/Georgi Nadjakov Institute of Solid State Physics, Sofia, Bulgaria,


eradevak@gmail.com

Plasma polymers were synthesized from hexamethyldisiloxane by capacitively coupled radio frequency
glow discharge under different operating conditions of glow discharge current density, monomer flow
rate, polymer film thickness and modification of the polymer surface in an ammonia plasma. The
chemical structures of the obtained nanomaterials were investigated by FTIR spectroscopy. The
spectroscopic study revealed that the plasma parameters significantly influence the chemical structure of
the polymers. The result of the current density increase and the monomer flow rate decrease has an
effect of elongated and additionally cross-linked polysiloxane chain. The ammonia plasma post
treatment led to creation of additional Si-O-Si bridges in the polymer network. The higher oxygen
content contributed to the enhanced sorptive characteristics of the plasma polymer films with respect to
the studied gas molecules. It is probably due to the creating intermolecular forces between oxygen atoms
and sorpted substances, which results in a better performance of the sensors element. The influence of
the same parameters on the gas sensing properties of the polymers is studied by a quartz crystal
microbalance (QCM). The sensitivity of the films to humidity and NO2 detected by polymer-QCM
system was enhanced by working at the highest current density and monomer flow rate and by raising
the film thickness and exposure to the ammonia plasma. The results are very promising for development
of thin plasma polymer film - QCM systems suitable for humidity (from 20 to 100 % relative humidity)
and N2 detection (in the concentration interval within the limits from 100 ppm to 5000 ppm).
46

Physical Vapour Deposition of Transparent Conducting Oxides and Barrier Layers


for Large Area Optoelectronic Devices
Parnia Navabpour1, Kevin Cooke1, Joanne Stallard1, Paolo Melgari2, (Sam) Yun Fu Chan2, Phil Hollis2, Alexander Goruppa3,
Katrin Zorn3, Manuel Auer-Berger4, Andreas Klug4, Meilan Guo5 and Guosheng Shao5
1
Teer Coatings Limited, Miba Coating Group, United Kingdom, parnia.navabpour@miba.com
2
Centre for Process Innovation, United Kingdom
3
High Tech Coatings, Miba Coating Group, Austria
4
NanoTecCenter Weiz Forschungsgesellschaft mbH, Austria
5
University of Bolton, United Kingdom

INTRODUCTION Successful OLED devices were produced using the TCO


Flexible electronic devices such as organic light emitting and barriers developed (Fig. 2).
diodes (OLEDs) and organic photovoltaic (PV) devices
require a number of elements including the anode, a hole
injection layer, emissive layer and the cathode. Metal
grids are often needed to enhance the conductivity. In
order to preserve the device and prevent damage caused
by the absorption of water, a barrier layer with very low
water vapour transmission rate (10-6 - 10-4 g m-2day-1
depending on the device) is required. PVD process has
been used for the deposition of these critical elements in
order to obtain high-efficiency, transparent devices.

EXPERIMENTAL
Both TCO and barrier coatings were deposited using
Closed Field UnBalanced Magnetron Sputter Ion Plating Fig. 1 Schematic of a CFUBMSIP coating system
(CFUBMSIP)1.
Green phosphorescent OLED stack,
TCO/NPD/TpBi:Ir(ppy)3/LiF/Al was optimised from 2
2 mm2 to 200 200 mm2 by scaling up the process using
CPIs Large Area Coating Equipment (LACE) The LACE
system comprises of three atmosphere-controlled modules
allowing to deposit metallic thin films and organic small
molecules layers in isolated chambers without breaking
vacuum and hence avoiding cross contamination.
Following OLED stack deposition, the device is
encapsulated in LACE controlled atmosphere module
using produced barriers. Fig. 2 Silver grid deposited onto the substrate
RESULTS AND DISCUSSION CONCLUSION
AZO-based transparent conducting oxide (TCO) coatings TCO and barriers for large area optoelectronic devices
with resistivity in the order of 1 10-4 cm and light were deposited using CFUBMSIP. Successful devices
transmittance in visible range of greater than 85% were were fabricated using these elements.
deposited on polyethylene naphthalate (PEN) using
CFUBMSIP (Fig. 1). REFERENCES
1. K. Laing et al., Surf. Coat. Technol. 112, 177 (1999)
Metal grids were produced on PEN substrate by
magnetron sputtering from an Ag target. The grids had ACKNOWLEDGMENTS
honeycomb pattern with line width 100 m and thickness This work was part of the OLAE+ project FLEXIBILIS.
up to 0.1 m. The authors would like to acknowledge the support from
Innovate UK and the Austrian Research Promotion
Barrier coatings were deposited using PVD and showed a Agency FFG).
water vapour transmission rate (WVTR) of less than 5
10-4 g m-2 day-1.
47

Generation of Stainless Steel Nanoparticles with Tuned Composition

Calle Preger, Linus Ludvigsson, Bengt O Meuller, K Deppert and Maria E Messing*

Solid State Physics, Lund University, Sweden


Maria.messing@ftf.lth.se

INTRODUCTION sintering of metal particles. Furthermore, by using a


The number of nanoparticle-based products on the market Ar/H2 gas mixture the sintering temperature could be
is expected to increase considerably during the coming lowered.
decades. This forces industry to have highly meticulous
manufacturing of large amounts of nanoparticles using
cheap and environmentally friendly methods. In the case
of metal oxide particle generation methods that meet these
demands are relatively well established. However, for
pure metal particles no recognized method is used today
but physical production via spark discharge is considered
highly promising.1,2 In this work we present for the first
time generation of stainless steel nanoparticles using this
method.

EXPERIMENTAL/THEORETICAL STUDY
Nanoparticle generation by spark discharge where the
formation of a plasma channel between two conducting
electrodes leads to a spark discharge that evaporate
material3 is reasonably energy efficient. Other advantages
with this method includes a continuous generation Fig. 1 Particles sintered at 1200 o
C under nitrogen
process, high cleanliness of the nanoparticles, avoidance atmosphere.
of chemical precursors and the possibility to easily
manufacture alloy and mixed metal particles including CONCLUSION
particles of materials that are immiscible in bulk form.4 By using pre-alloyed stainless steel electrodes, it is
The spark discharge generator consists of a chamber possible to generate nanoparticles with different
housing two opposing electrodes that are separated by a chromium composition. This results indicate that it should
small gap. Nanoparticles are formed when material be possible to generate particles of any type of stainless
ablated from the electrodes via the spark, are transported steel alloy which enables numerous interesting
away from the heated gap region by means of a carrier applications.
gas. To create a spark discharge between the electrodes a REFERENCES
self-pulsed circuit is used, consisting of a capacitor bank References must be numbered. Keep the same style.
driven by a high voltage DC power supply connected in
parallel to the electrode gap. Several parameters can be 1. www.buonapart-e.eu
adjusted to affect and control the particle production 2. L. Ludvigsson et. al, J. Phys. D 448, 314012 (2015)
including the capacitance, the discharge frequency (by the
out-put current), the electrode distance, the electrode 3. S. Schwyn et. al, J. Aerosol Sci. 19, 639 (1988)
material, the carrier gas flow rate, the type of carrier gas 4. N. S. Tabrizi et. al, J. Nanopart. Res. 12, 247 (2010)
and the geometry of the spark discharge generator.
RESULTS AND DISCUSSION ACKNOWLEDGMENTS
To generate stainless steel particles pre-alloyed electrodes This work was performed within NanoLund at Lund
with different chromium content was used, and resulted in University. The research leading to these results received
particle formation. To reach a stable continuous funding from the Swedish Research Council and the
generation an electrode gap distance of 2 mm and an European Union Seventh Framework Programme
output current of 10 mA was found to be optimal settings. (FP7/20072013) under Grant Agreement n 280765
The as-produced particles are in the form of agglomerates (BUONAPART-E). This publication reflects only the
and to form compact particles sintering of the as-produced authors/ authors view(s), and the community is not
particles was performed. It was shown that under nitrogen liable for any use made of the information contained
atmosphere the particles compacted at around 1200 oC therein.
(Fig. 1), which agrees well with previous reports of
48

Preparation and characterization of non-toxic Er3+/Yb3+ doped strontium


lanthanum aluminate phosphors

K. Pavani 1, J. Suresh Kumar 1, K. Srikanth 2, E. Pereira 2, T. Monteiro 1, M.J. Soares 1, A.J. Neves 1, M.P.F. Graa 1*
1
I3N & Physics, University of Aveiro, 3810-193 Aveiro, Portugal
2
CESAM-Centre for Environmental and Marine Studies & Department of Chemistry, University of Aveiro, Aveiro, Portugal
email presenting author: mpfg@ua.pt

Strontium lanthanum aluminate (SrLaAl3O7) phosphors, 0.1)Al3O7:Er0.01Yb0.09.


The molar ratio between the metal
doped with Er3+ and Er3+/Yb3+ were prepared by the sol- ions and citric acid was 1:1 and the pH was adjusted to
gel method, where the pH and treatment temperatures 1.0, 3.5 and 6.5, using ammonium hydroxide. After
were the parameters analyzed in order to optimized the drying, the powders were heat-treated (HT) at several
structure. temperatures. The powders HT at 800 C for 6 h were re-
The structural and morphological properties of the milled thoroughly by mixing acetone, pressed into pellets
products were analyzed by X-ray diffraction (XRD), and studied.
Raman spectroscopy and Scanning electron microscopy
RESULTS AND DISCUSSION
(SEM) respectively. Upconversion and prompt
The powders prepared with pH > 3 present a XRD pattern
luminescence (down conversion) in visible and near
with pure tetragonal SrLaAl3O7 phase with space group
infrared regions were measured. The dependence of the
P421m. The microstructure analysis revealed crystallites
integral intensity on the pumping energy of laser was
sizes between 40-60 nm and the SEM micrographs
measured. The upconversion photoluminescence intensity
showed grains, with a spherical habit, with average size
in low temperature range was described using
between 100-200 nm (Fig.1a).
fluorescence intensity ratio (FIR) technique, determining
their sensing behavior and efficiencies.
Cytotoxicity of the prepared phosphors were evaluated
using BF-2 fish cell line (ATCC # CCL91) originating
from the caudal fin tissue of the bluegill sunfish (Lepomis
macrochirus) to check the viability of cells.
INTRODUCTION
Interest on rare earth photoluminescence (PL) is not only
because of the efficient down conversion (DC) PL but a) b)
also due to the wide range application of their Fig. 1: (a) SEM micrograph of the SLA:Er sample (b)
upconversion (UC) in the fields of color displays, LEDs, Photoluminescence excitation and emission spectra of
bio-imaging, temperature sensors etc.. In particular for SLA:Er phosphor with xenon excitation
bio-imaging analysis, normally the studies are done at
room or low temperatures and hence the estimation of the Fig. 1(b) shows the excitation and emission spectra of
temperature of the bio-material is essential. SLA:Er phosphor. Excitation spectrum has been recorded
by monitoring the emission 4S3/2 4I15/2 at 547 nm. It
In this work, strontium lanthanum aluminate, SrLaAl3O7 consists of well-resolved sharp peaks attributed to the
(SLA), which is one of the complex compound direct excitation of Er3+ from the ground 4I15/2 level to
crystallizes in the tetragonal melilite-like structure (space higher excited levels.
group P421m) with a general chemical formula ABC3O7
(where A = Ca, Sr, Ba; B = La, Gd, Y and C = Al, Ga) CONCLUSION
was analyzed. It is already known that it has good Excitation spectrum shows a host band in the UV region
mechanoluminescence properties due to various studies which when excited emits in the region 350 - 450 nm. The
done in this aspect in the host material as well as in the origin of these bands is assigned to oxygen defects.
Eu3+ doped ones. Cytotoxicity evaluated for SLA sample shows minimum
toxicity and can be classified as non-toxic by nature.
EXPERIMENTAL STUDY
The SLA, SLA:Er and SLA:Er/Yb phosphors were ACKNOWLEDGMENTS
synthesized by Pechini method using strontium, Authors acknowledge UID/CTM/50025/2013 for the
lanthanum, aluminium, erbium and ytterbium nitrates as financial support to this work.
raw materials, citric acid as complex agent and ethylene
glycol as chelating agent. The SLA:Er prepared phosphor
has the molar composition SrLa(1-0.01)Al3O7:Er0.01 and the
SLA:Er/Yb the molar composition SrLa(1-
49

TSDC and dielectric characterization of Hydroxyapatite/-Tricalcium Phosphate


bioceramics
P.R. Prezas1, B.M.G. Melo1, M.J. Soares1, M.C. Lana2, L.F.V. Pinto3, F.N.A. Freire4, M.P.F. Graa1*
1
i3N and Physics Department, University of Aveiro, 3810-193, Aveiro, Portugal
2
Cenimat i3N/Department of Materials Science, FCT/UNL, Campus da Caparica, 2829-516 Caparica, Portugal
3
Altakitin S.A., Rua Jos Gomes Ferreira, 1-Arm. D 2660-360 So Julio do Tojal, Portugal
4
Mechanics Engineering Department, Cear Federal University, Fortaleza, Brazil
email presenting author: mpfg@ua.pt

INTRODUCTION samples was also performed, as a function of the


Bone grafting is actually a big business, generating more temperature between room temperature and 1000 C, and
than $2.5 billion per year. Worldwide, autografts (bones of the frequency between 100 Hz and 1 MHz.
obtained from another anatomic site in the same patient)
RESULTS AND DISCUSSION
or allografts (bones from another subject) are applied in
Among the studied samples, the biphasic revealed very
approximately 2.2 million orthopaedic procedures
interesting features, namely stored charge densities in the
annually. Currently, autografts and allografts remain the
order of 10-3 C/cm2 and long depolarization times at the
dominant materials applied for bone repair, substitution
physiological temperature (~ 37 C). The IS
and augmentation. However, autografts usage is limited
measurements revealed the high capacity of the samples
by donor-site morbidity and supply, whereas allografts
to store charge, with very low losses at lower
drawbacks include immunogenic response by the host to
temperatures, as fig. 1 displays.
the foreign bone tissue and the possibility of disease
5
transmission. Thus, these limitations are leading to 100 C 200 C 300 C
4.5
development of new biomaterials to be applied as bone 400 C 500 C 600 C
4 700 C 800 C 850 C
substitutes. 900 C 950 C 1000 C
3.5
Synthetic Hydroxyapatite [Hap, Ca10(PO4)6(OH)2] based
Loss tangent

3
bioceramics have been highlighted over the last four
2.5
decades due to their structural and compositional
analogousness with the biologic Hap1,2, i.e. the one which 2
occurs naturally in our organism and is the main 1.5
component of bones (65 to 70 wt%). These biomaterials 1
display bioactivity and osteoconductivity processes2. 0.5
However, the rate at which Hap-based bioceramics 0
promote the growth of new host bone, which is related 1000 10000 100000 1000000
with the osteoconductivity and resorption processes, is Frequency [Hz]
still considered unsatisfactory. Among the methods being Fig. 1 Temperature and frequency dependency of the loss
researched to enhance host bone formation, the electrical tangent for a biphasic sample.
polarization of these materials is the one with the most
remarkable results, accelerating considerably the host CONCLUSION
bone growth3. The biphasic samples revealed very appealing features
regarding potential applications in the bone tissue
EXPERIMENTAL/THEORETICAL STUDY engineering field. Further studies must be conducted
In the present work the electrical polarization of pure Hap taking in account the potentialities of the biphasic
and biphasic (75Hap-25-TCP wt%, -TCP, - samples, because the polarization of Hap/-TCP biphasic
tricalcium phosphate, -Ca3(PO4)2) bioceramics was samples is still not common in the literature
analyzed by measuring thermally stimulated
depolarization currents (TSDC). The samples were REFERENCES
thermo-electrical polarized at temperatures between 250 1. W. Wang et. al, Acta Biomater. 5, 3132-314 (2009)
and 500 C. At such temperatures, with external electrical 2. R.Z. LeGeros, Chem. Rev. 108, 4742-4753 (2008)
field amplitudes in the order of 1-5 kV/cm, the ionic 3. H. Sagawa et. al, Artif. Organs 34(6), 491-497 (2010)
mobility is activated, enabling stored charge densities in
the order of 10-8-10-3 C/cm2 to be achieved. From the ACKNOWLEDGMENTS
TSDC spectra, the total stored charge density for a given Authors acknowledge UID/CTM/50025/2013 for the
polarization temperature (Qp) and the depolarization time financial support.
at a given temperature (T) were calculated. The dielectric
characterization (impedance spectroscopy, IS) of the
50

Plasma-assisted atomic layer deposition of TiO2 thin films: effect of direct plasma
exposure during deposition on film structure and morphology

William Chiappim1, Giorgio Ernesto Testoni2, Rodrigo Svio Pessoa1,2, Mariana Amorim Fraga3*, Homero Santiago Maciel1,2
1
Nanotechnology and Plasmas Processes Laboratory, Universidade do Vale do Paraba (Univap), Brazil.
2
Plasma and Processes Laboratory, Instituto Tecnolgico de Aeronutica (ITA-DCTA), Brazil.
3*
Associate Laboratory of Sensors and Materials, National Institute for Space Research, Brazil, mafraga@ieee.org

INTRODUCTION
The titanium dioxide (TiO2) has a wide range of
applications both as thin film or bulk material due to
many attractive properties such as wide band gap, high
dielectric constant, and photocatalytic activity. As thin
film several applications can be cited as photovoltaics and
sensors [1]. Recent studies have shown that modification
of stoichiometry, crystalline structure, morphology and,
consequently, the optical/electrical properties of TiO2
films can be finely tuned by appropriately altering plasma
enhanced atomic layer deposition (PEALD) process
parameters, e.g. plasma power, gas flow rate and pressure
and plasma exposure (direct or remote plasma) [2]. In this
work, we report about the effect of direct plasma exposure
during deposition on film structure and morphology of
PEALD TiO2 thin films using TiCl4 precursor. For this, a
remote capacitively coupled 13.56 MHz oxygen plasma
was used as co-reactant during ALD process and the
plasma power was varied from 50 W to 200 W for a fixed Fig. 1 . FESEM images and respective GIXRD spectrum
process temperature of 250 C. In order to improve the of TiO2 films deposited under rf power of (a) 50 W and
discussions, thermal ALD of TiO2 films were performed (b) 150 W for both electrode grid configuration
at similar process conditions.
It is observed that the removal of the grid causes a
EXPERIMENTAL decrease in grain size, and consequently of TiO2 film
The samples were deposited using a Beneq TFS 200 ALD crystallinity. GIXRD analyzes show that all TiO2 films
tool equipped with a capacitively coupled plasma reactor are in anatase phase and the intensity of the main peak
that can be separated from substrate stage by a grid. orientation (100) is influenced by the electrode grid.
Pieces from a 350 m thick Czochralski Si wafer (p-type,
4 .cm, (100)-orientation) were used as substrates. TiO2 CONCLUSION
films were grown using 0.25s TiCl4 (99.95%, Sigma- From the experimental results, it was evidenced the effect
Aldrich) and 2s O2 (99.99%, White Martins) plasma or of electrode grid on reducing the action of plasma ions
0.25s deionized water (thermal ALD). For the studies of during capacitively coupled PEALD process. In addition,
this work, the spacing between the upper plate and the could be highlighted that PEALD allows to easily control
grid was 30 mm and between the grid and the substrate the TiO2 film structure and morphology for a fixed
holder was 12 mm. The depositions were carried out with process temperature.
plasma power ranging from 50 W to 200 W in 50 W
increments. Finally, the purge step consisted of 2 s of N2 REFERENCES
pulse during all experiments. 1. R. S. Pessoa et al., Materials Science in Semicondutor
Processing 29, 56-68 (2015).
RESULTS AND DISCUSSION 2. H. B. Profijt et al., Journal of Vacuum Science and
The experiments were performed with and without the Technology A 29(5) 050801 (2011).
grid for two RF power: 50 W and 150 W. The number of
reaction cycles was set to obtain films with thickness of ACKNOWLEDGMENTS
approx. 100 nm. Figures 1 presents FESEM images of the The financial support of Brazilian agency program
surface of TiO2 films for both reactor geometries. FAPESP/MCT/CNPq-PRONEX (grant n 2011/50773-0),
Furthermore, in the right side of the figures is showed the FAPESP (grant n 2015/05956-0 and n 2015/10876-6),
GIXRD spectrum of each sample. and CNPq (grant n 305496/2012-3 and 446545/2014-7)
are strongly acknowledged.
51

Synthesis of colloidal dispersions of gold-oxocarbons nanocomposites by


atmospheric CO2 recycle during pulsed laser ablation in water
TommasoDel Rosso1, O. Pandoli 2,
1
Department of Physics, Pontifical Catholic University of Rio de Janeiro, Brazil, tommaso@puc-rio.br
2
Department of Chemistry, Pontifical Catholic University of Rio de Janeiro, Brazil

Stable colloidal dispersions of gold-oxocarbons shows the presence of different OC on the NCs, with the
nanocomposites (NCs) have been synthesized by pulsed predominance of the Au-carbonyl line detected at about
laser ablation (PLA) of a gold disk in water using 532 nm 2120 cm-1and the classical D and G band of amorphous
ns-pulses without the addition of any stabilizing agent. carbon [3,4]. Total Organic Carbon (TOC) measurements
UV-Vis spectroscopy, SERS spectroscopy, NMR performed on similar colloids using NaOH in the place of
spectroscopy and High Resolution Transmission electron KOH confirm the introduction of new carbon based
Microscopy (HRTEM) confirm the production of NCs material in the final colloidal solution, up to 6 times of the
composed by an Au core and an oxocarbon shell initial concentration [4]. Furthermore, NMR
(Au@OC NCs). The results suggest a fundamental role of measurements on the NCs reveal a clear carbonyl band
the recycle process of atmospheric CO2 in the creation of located at ~220 ppm, absent in the original water used to
the OC shell. perform PLA, confirming the presence of new organic
material in the colloidal solution.
INTRODUCTION
An easy and green way to produce a dielectric shell
around the core of metal NPs is strongly desired by the
scientific community, in order to overcome instability
problems in high ionic media and to have an external
surface with chemical groups ready to interact with
molecules of biological interest [1]. In literature we can
find only one reference relative to the encapsulation of
AuNPs in carbon shell by chemical methods, and there
are no attempts to produce this kind of NCs by PLA. Fig.1: a) HRTEM image of a typical NC. b) SERS
response of a deposition of NCs on glass substrate excited
EXPERIMENTAL at 783 nm.
We performed PLA at a pulse fluence of about 6 J/cm2, in
a water solution with pH=7 and enriched of CO2 by the CONCLUSION
addition of KOH. The extinction spectra of the colloids We point out an easy and one step procedure to synthesize
has been measured using an UV-Vis spectrophotometer Au-oxocarbon NCs by PLA. The NCs are marked by ~ 10
model Lambda 950 from Perkin Elmer and their chemical nm blue-shift of the LSPR band, we associate to the
composition has been analyzed by an NMR spectrometer presence of Au-carbonyl [4] at the interface between the
at 400 Mhz. The chemical composition of the dried NCs Au core and the OC shell. The new carbon based organic
has been studied by the use of a Micro Raman apparatus material is generated by reactions happening to dissolved
at the wavelength of 783 nm and the details of their CO2 during the PLA process. This new class of green
structure has been observed by the use of a FEI Titan 80- synthesized NCs has a unique and rich surface
300TM microscope operating at 300 kV. composition, which makes them particularly attractive in
bio-related applications [4].
RESULTS AND DISCUSSION
The NCs synthesized using the monovalent hydroxide are REFERENCES
stable and present a circular shape with an average 1. J. Zhou et. al, J. Colloid. Interface Sci., 286, pp. 526-
diameter of about 9 nm. In comparison with bare AuNPs, 535, (2005)
these NCs present a marked blue-shift in the position of 2. P. Mulvaney, Surface Plasmon Spectroscopy of
the localized surface plasmon resonance (LSPR), Nanosized Metal Particles, Langmuir, 12, pp. 788-800,
indicating electronic interaction between the Au core and (1996)
the ligands constituting the shell of the NCs [2]. HRTEM 3. K.V. Kong et. al, Angew.Chem.Int. Ed., 51, pp. 9796-
image of Fig. 1a evidences a shell around the Au core, 9799, (2012)
which EDX measurements (not shown) confirm to be 4. T. Del Rosso et. al, Nanotechnology, Submitted,
constituted by C and O atoms. SERS measurements have (2016)
been performed on nanoislands films of NCs created by
drying drops of the colloids on a glass substrate. The ACKNOWLEDGMENTS
spectra excited at 783 nm is represented in Fig. 1b, and The Authors wish to acknowledge FAPERJ and CNPq.
52

Micro and Nanoscale Mapping of Electrical Characterization of Graphene and


Semiconductor Heterostructures

Benjamin Robinson1, Ghazi Alsharif1,2* and Oleg Kolosov1

Department of Physics, Lancaster University, Lancaster LA1 4YB, UK


1
2
Department of Physics, Taibah University, Madinah, Saudi Arabia
*
Email: g.alsharif@lancaster.ac.uk
ABSTRACT
Graphene and 2D materials have proven to be promising RESULTS AND DISCUSSION
materials to be used to fabricate heterostructures, and also Here, we perform nanoscale measurements on InAsNWs,
promising candidate to be used in combination with both topographically and electrically by SSRM, as well as
optoelectronic devices, due to their unique electronic captured (I-V) curves with/without illumination. Bottom
properties1. Here, the electrical properties of figure (right) shows graphene/MoS2/graphene layers
heterostructures, as well as the specific contacts area onto stacks on each other performing by PSM with changing
graphene are investigated by using properly designed test backgate.
patterns. We firstly use PlayStation micro-probing (PSM)
for macroscopic characterisations. Secondly, High- spatial
resolution current mapping needed to provide an insight
into the nanoscale mechanisms of electrical transport. We
use scanning probe microscopy (SPM) as well as
scanning gate microscopy (SGM), with a conductive
diamond tip directly access to nano-resolution structures
both topographically and electrically, with illumination
and dark regimes. Additionally, we plan to report
measurement in 2D materials heterostructures and their
photoresponse on this regimes.
EXPERIMENTAL STUDY
(I-V) curves for different bottom gate voltages
5

1. Micro scale-probing Station (PSM) Measurements


0

The electronic transport -5

Current (uA)
properties of heterostructures -10 probes Vg=-0.5V

have been characterised on the gr(top)


Vg=0V
Vg=5V

macroscopic scale by electrical -15 Vg=10V


MoS2 Vg=15V
gr (bottom) Vg=20V
measurements by Imina -20 Vg=25V
Vg=30V
probes, as in Fig.1 -25
-5 -4 -3 -2 -1 0 1 2 3 4 5

2. Nanoscale- probing (SPM) Voltage (V)

Measurements Fig. The top (left) shows topographic image on InAsNWs,


top right image shows conductivity contrast, (I-V) curves
We have implemented an performed by SSRM on InAsNWs, and bottom (right)
experimental set up based on image microscale measurements on heterostructures
scanning Probe Microscopy materials performed by PSM.
(SPM), by using a modified
CONCLUSION
commercial atomic force We have shown different methods to probe
microscope with a conducting heterostructures in micro- and nanoscale regimes to
probe and an appropriate investigate electrical properties which lead to assist in the
method to measure and development of electrical transport characterization
interpret the electrical transport properties of 2D materials methods and, of new electronic nanodevices. We plan to
such as graphene at the nanoscale regime. Our system report measurement in 2D materials heterostructures and
allows nanoscale resolution measurement of local their photoresponse.
physical properties such as mapping of spreading
REFERENCES
resistance of graphene layers under environment 1. K. S, Novoselov et. al, Science. 306, 666-669
conditions. This technique can provide new insight into (2004)
the electrical transport properties at the nanoscale of 2D
material nanostructures. The research objective is to assist ACKNOWLEDGMENTS
in the development of electrical transport characterization
Ghazi Alsharif would like to thank Taibah University for
methods and, of new electronic nanodevices.
their financial support.
53

Lithium intercalation in Carbon Nanotube/Bone Charcoal Composite coating with


Metals Nanoparticles

Matsubara, Elaine Yoshiko and Rosolen, Jose Mauricio

Department of Chemistry, University of So Paulo Ribeiro Preto, Brazil, elainematsubara@yahoo.com

INTRODUCTION

Li-ion battery (LiB) can be prepared with several


carbonaceous, oxides and alloys. However, in case of
commercial LiB whose demand is still growing, the main
materials employed in its preparation coming from
minerals (e.g. Li, graphite, Co, Mn, Ni, V), an industry
which can provoke serious environmental impact as
recently occurred in Brazil. For this reason studies about
Li intercalation materials resulting from biomass, animal Fig. 1 CNT/BC granule decorated with about 1 wt % of
wastes are become relevant to industry of LiB. In the Ag nanoparticles.
present study we have considered the bone charcoal with
carbon nanotubes cover with metallic Ag nanoparticles The galvanostatic discharge/charge cycles of electrodes
for Li intercalation. Carbon nanotubes and carbonaceous reveals distinguishable increase of energy stored in
constituent materials present a Li specific capacity (SC) CNT/BC (SC = 232 mAh g-1) with light Ag NPs coating.
which can be higher or near of natural graphite (320-370 In fact, at 0.22 A.g-1 the specific capacity of the CNT/BC
mAh.g-1)1-2. On the other hand, Ag nanoparticles are is most twice with Ag coating. In addition, the
employed as coating in industry of LiB battery. CNT/BC/PVDF electrode was able to provide 314 mAh.g-
1
with coulombic efficiency near to 99% at higher
EXPERIMENTAL gravimetric current 0.86 A.g-1 as well.

The composite CNT/BC was prepared from direct CONCLUSION


growing of CNT on the surface of granules of bone
charcoal obtained from pyrolyses of bone of cattle. To The CNT/BC composite appears as renewable and green
coating on CNT/BC with Ag nanoparticles or Cu Li-host with potential to development of novel hybrid
nanoparticles were employed well known methods composite materials to LiB. Its specific capacity can be
published elsewhere. More details about the CNT growth increased with coating of Ag nanoparticles or Cu
on bone charcoal are in reference 3. The electrodes of nanoparticles. Moreover, the variation of specific
CNT/BC (90 wt. %) were prepared with PVDF (10 wt. %) capacity of CNT/BC with Ag coating suggests, together
and Cu foils3. The electrochemical characterization of with other studies about Li intercalation into CNT-NP
CNT/BC/PVDF/Cu foil electrodes was obtained using electrodes, the presence of a galvanic coupling3 between
swagelock type electrochemical cells with Li metallic the CNTs and nanomaterials which can help understand
(auxiliary electrode and/or reference) in commercial the electrochemical performance of this class of
electrolytes (e.g. 1 M LiPF6 EC/DMC). composite.

RESULTS AND DISCUSSION REFERENCES


Figure 1 shows the scanning electron microscopy (SEM) 1. E.Y.Matsubara, S.M. Lala, J.M.Rosolen. Journal
pictures of a typical granule of CNT/BC coating with Ag Brazilian Chemistry Society, 21, 1877 (2010).
nanoparticles. The picture in Figure 1 was collected in 2. L.Montoro, E.Y.Matsubara, J.M.Rosolen, Journal of
backscattering mode to show the Ag NP on surface of Power Sources, 257, 205 (2014).
CNT/BC (lightest spot in inserted Figure). The SEM 3. E.Y. Matsubara, G.Takahashi, N. Guerra, J.M.Rosolen.
analysis reveals which Ag nanoparticles are adsorbed Journal of Electroanalytical Chemistry, 2016 (in press).
predominantly on surface of CNT network which cover
all surface of BC. For CNT/BC with Cu nanoparticles the ACKNOWLEDGMENTS
decoration were found similar.
The authors would like to thank FAPESP (2010/07681-5),
and CNPq (308106/2013-0) for the partial financial
support and CAPES for the Postdoctoral fellowship.
54

Nanoparticles of MOF-545/PCN-222: Synthesis and Phototoxicity

Daniel Bek1,2, Jan Demel1, Kaplan Kirkaci1, Jaroslav Zelenka3, Tom Ruml3 and Kamil Lang1
1
Institute of Inorganic Chemistry of the Czech Academy of Sciences, e, Czech Republic, buzek@iic.cas.cz
2
Faculty of the Environment, Jan Evangelista Purkyn University, st nad Labem, Czech Republic
3
University of Chemistry and Technology Prague, Praha, Czech Republic

INTRODUCTION the nanoparticles have the potential for PDT treatment


Metal-organic frameworks (MOFs) are porous activated by visible light illumination.
coordination polymers consist of coordinated metal atoms
forming secondary building units (SBU) connected by
organic linkers. MOFs are extensively used for gas
storage, separation, drug delivery, catalysis, and sensing
applications.1 Porphyrin containing MOFs attract
attention due to their rigid geometry, variable structure,
and the use in catalysis or light sensitive materials. We
reported recently that porphyrin containing MOFs
produce singlet oxygen, O2(1g), an excited form of
oxygen.2 Singlet oxygen is one of reactive oxygen species
which inactivates tumor cells in photodynamic therapy of
cancer (PDT). In the present work, we describe the
synthesis, characterization, photophysical and
photochemical properties, and phototoxicity of
nanoparticles made of MOF-545/PCN-222 composed of
tetracarboxyphenyl porphyrin linkers and Zr6O4(OH)4
SBU.
Fig. 1: SEM image of the MOF-545/PCN-222
nanoparticles. The average lateral size is approximately
EXPERIMENTAL/THEORETICAL STUDY
350 nm.
Nanosized MOF-545/PCN-222 was synthesized by the
solvothermal method. The variation of the amount of a
crystallization modulator allowed tuning the nanoparticles
CONCLUSION
size. All materials were characterized by powder XRD,
We prepared the nanoparticles of MOF-545/PCN-222 in
scanning (SEM) and transmission (TEM) electron
the pure hexagonal phase. These nanoparticles showed
microscopy, adsorption isotherms of nitrogen, absorption
promising phototoxicity towards tumor cells under
and luminescence spectroscopy. Dark toxicity as well as
irradiation with visible light.
phototoxicity of the nanoparticles upon light irradiation
was studied using tumor human cell lines SHSY5Y
(neurobastoma) or PaTu (pancreatic cancer).
REFERENCES
1. W.-X. Zhang. Coordination Chemistry Reviews. 293-
294 (2015) 263.
RESULTS AND DISCUSSION
We were able to prepare different sized of the MOF- 2. J. Demel, et. al. Inorg. Chem. 52 (2013) 2779.
545/PCN-222 nanoparticles. The smallest nanoparticles
have an average size 35 nm, middle sized nanoparticles
95 nm in average, and the large nanoparticles 350 nm in ACKNOWLEDGMENTS
average. The powder XRD patterns document the
presence of the pure MOF-545/PCN-222 phase. The This work was supported by Czech Science Foundation
(No. 16-02098S)
morphology and size distribution was determined by SEM
and TEM measurements (Figure 1). The images show the
needle-type nanoparticles with a broader center.
Absorption and luminescence measurements of
nanoparticle dispersions indicated the stability on the
nanoparticles in several organic solvents, capability of
O2(1g) generation under visible light irradiation, and the
suitability of these dispersions for the internalization into
cells. The elucidations of in vitro experiments proved that
55

Resistive Switching of Si/Ag interfaces with different layer thicknesses

C. Dias1, H. LV2, P. Aguiar3,4, S. Cardoso2, P. P. Freitas2 and J. Ventura1


1
IFIMUP and IN Institute of Nanotechnology, and Department of Physics and Astronomy, Faculty of Sciences, University
of Porto, Porto, Portugal
2
INESC-MN and IN - Institute of Nanoscience and Nanotechnology, Lisboa, Portugal
3
3i3S Instituto de Investigao e Inovao em sade, Universidade do Porto, Portugal
4
INEB Instituto de Engenharia Biomdica, Universidade do Porto, Portugal c.dias@fc.up.pt

INTRODUCTION
Present computer processing capabilities are becoming a
restriction to meet modern technological needs.
Therefore, approaches beyond the von Neumann
architecture are imperative and the brain's operation and
structure are truly attractive models1. Memristors are
nanodevices characterized by a nonlinear relationship
between current history and voltage2, exhibiting a
nonvolatile resistive switching and properties resembling
those of neural synapses3. These properties have huge
interest for applications in fields such as nonvolatile
memories and artificial neural networks, respectively.
Silicon is widely used in semiconductor industry and so it
is a good choice to integrate in new systems since the
processes can be easily adapted. Fig. 1 I-V characteristics of a Pt/Si/Ag/TiW sample
EXPERIMENTAL/THEORETICAL STUDY including voltage and current distributions over 50 cycles
Here, we present a study on resistive switching in (the inset shows ON and OFF resistances over the cycles).
Pt/Si/Ag/(Pt, Ta or TiW) structures deposited by
magnetron sputtering. Silicon and silver thicknesses are CONCLUSION
variable in the range of 2 - 20 nm, with a thicker layer of We achieved bipolar resistive switching using
the first than the later. Circular top electrodes of 100, 200 Pt/Si/Ag/(Pt, Ta, TiW) structures. We studied the
and 300 m in dimeter and 100 nm thick were defined by transport mechanisms involved in the switching and the
optical lithography. The current-voltage (I-V) statistical distribution of both the SET and RESET
characteristics of the devices were measured using voltages, and the ON and OFF resistances.
tungsten micro-probes connected to a Keithley
REFERENCES
SourceMeter 2400 at room temperature. All 1. Y. Shimeng e.t al, IEEE Trans. Electron Devices 58, 8
measurements were performed applying the bias voltage (2011).
on the top electrode (Pt, Ta or TiW) with the bottom 2. L. Chua, IEEE Trans. Circuit Theory 18, 5 (1971).
electrode grounded (Pt). A current compliance (CC) was
3. M. Prezioso et. al, Nature 521, 6164 (2015).
used to avoid damaging the sample.
RESULTS AND DISCUSSION
ACKNOWLEDGMENTS
We observed bipolar resistive switching with low (< 1 V)
SET and RESET voltages and small statistical
The authors acknowledge funding from FEDER and ON2
distributions in up to 100 cycles (Fig. 1). A constant
through Project Norte-070124-FEDER-000070 and from
applied voltage input is also able to switch the structure
FCT through the Associated Laboratory, IN. J.V.
and the switching time inversely depends on voltage
acknowledges financial support through FSE/POPH. C.D.
amplitude. The phenomenon was attributed to the
is thankful to FCT for Grant SFRH/BD/101661/2014.
formation (for positively biased top electrode) and rupture
(negatively biased) of metallic filaments inside the Si.
The typical dependences of the low resistance value on
the current compliance during the SET process were
obtained and both resistive states are stable over cycles
and time.
56

High Adhesion of Ultrananocrystalline Diamond Coatings to WC-Co Substrate

Mariana Fraga1, Andr Contin1, Jos Vieira1, Raonei Campos2, Divani Barbosa1, Evaldo Corat1 and Vladimir Trava-Airoldi1
1
National Institute for Space Research, So Jos dos Campos, Brazil, email: mafraga@ieee.org
2
Federal Institute of So Paulo, Jacare, Brazil

INTRODUCTION RESULTS AND DISCUSSION


CVD diamond coatings have shown great potential The nanostructured morphology of the as-deposited
to improve lifetime and service performance of hard metal UNCD coating can be observed in Fig. 1(a).
cutting tools. Several studies have discussed the adhesion In Fig. 1(b), it is shown the FEG-SEM image of the
of CVD diamond on WC-Co substrates1. Most of these UNCD coated WC-Co substrate after indentation. As can
works are focused on microcrystalline and nanocrystalline be noted, there is no coating delamination, which
diamond1, 2. Here we report the high adhesion of indicates a high adhesion between the UNCD coating and
ultrananocrystalline diamond (UNCD) grown by hot- the WC-Co substrate.
filament chemical vapor deposition (HFCVD) on
pretreated WC-9%Co substrates. The choice of use
UNCD coatings was motivated by their unique
microstructure comprised of nanometer-sized diamond
grains that provide remarkable material properties such as
high hardness, extreme fracture toughness, low coefficient
of friction, chemical inertia and low surface roughness.

EXPERIMENTAL
UNCD coatings were deposited on WCCo disks (91%
WC and 9% Co composition, 9 mm in diameter and 3 mm
thick) by the conventional hot-filament technique using a Fig. 1 FEG-SEM images: (a) UNCD film and (b) UNCD
gas mixture of methane (9%) and hydrogen (91%). Prior coated WC-Co substrate after indentation
to deposition, the substrates were pretreated as follows: (i)
first they were etched by Murakami solution (10 g This high adhesion confirms that the UNCD coating
K3[Fe(CN)6]+10g KOH+100ml H2O) for 10 min in an exhibits high quality and low residual stress which was
ultrasonic bath, (ii) the surface Co was etched in aqua also observed by Raman measurements.
regia solution (HNO3/HCl = 1:3) for 5 min and (iii) the
etched substrates were seeded in water slurry containing 4 CONCLUSION
nm diamond nanoparticles dispersed by PSS (sodium4- We have evaluated the the adhesion between the UNCD
styrenesulfonate) polymer. The pretreated WC-Co coating and pretreated WC-Co substrate. The indentation
substrate was placed at 5 mm from five tungsten filaments tests under a load of 150 kgf showed that there is no
(0.125 mm in diameter and 100 mm long). The UNCD delamination of the UNCD coating. A set of new UNCD
samples were grown at a temperature of 600C measured samples with different thicknesses will be prepared to
by a thermocouple fixed at the bottom of the substrate. perform more studies to achieve a full elucidation of the
Deposition parameters were kept as follows: CH4 flow adhesion mechanisms.
rate (9 sccm), H2 flow rate (91 sccm), pressure (30 Torr)
and deposition time (120 min). REFERENCES
The UNCD coatings were characterized by Raman 1. Q. Wei et. al, Appl. Surf. Sci. 256, 4357 (2010).
spectroscopy, atomic force microscope (AFM), x-ray 2. M. A. Fraga et. al, Mater. Res.
diffraction (XRD) and scanning electron microscopy Express 3, 025601 (2016).
(FE-SEM, Tescan Mira 3 FEG) coupled with Energy-
dispersive X-ray spectroscopy (EDS or EDX). In order to
evaluate the adhesion level of the CVD diamond coating, ACKNOWLEDGMENTS
indentation tests using a diamond stylus Rockwell C with
a conical diamond indenter (120 cone angle and 0.2 mm We would like to thank FAPESP (processes number:
tip radius) were performed. The samples were tested by 12/15857-1, 14/18139-8 and 13/25939-8).
applying a load of 150 kg at the diamond indenter.
57

Zero-Dimensional Hybrid OrganicInorganic Halide Perovskite Modeling:


Insights from First Principles

Giacomo Girogi and Koichi Yamashita

Department of Chemical System Engineering, The University of Tokyo,


7-3-1 Hongo, Bunkyo-ku, Japan
E-mail: yamasita@chemsys.t.u-tokyo.ac.jp

INTRODUCTION tendency of recombination once the cluster is excited. It


We have identified and characterized models of zero- is also extremely appealing that both electron and hole are
dimensional (cluster) hybrid organicinorganic halide readily accessible at the surface of the cluster as both
perovskite systems. Interesting properties of such clusters Figures 1 and 2 clearly evidence.
that have been extensively investigated include their
charge distribution, bandgap, wave function localization,
and reduced effective mass. These properties are obtained
by cutting the bulk of MAPbI3 perovskites. Interesting
trends, including the function of the orientation, surface
termination, and the organic/inorganic cation ratio have
been found. It emerged that surface termination is crucial
in determining the structural and optoelectronic properties
of this overlooked, dimensionally reduced class of
materials. Analogies and differences with the bulk are
discussed. The aim of this study is to pave the way for
further investigations of clusters with different
orientations, terminations, and compositions. Fig. 1 (a) Side and (b) top view of the VBM wavefunction
of the trajectory of s cluster extracted after 2.05ps. (c) and
THEORETICAL STUDY (d) same for the CBM.
By means of a combined ab initio molecular dynamics
(AIMD) and scalar relativistic Density Functional based
calculations, we theoretically characterize bulk cut
nanoclusters of increasing sizes, focusing on their
structural and electronic properties. We have performed
several AIMD simulations by means of the SIESTA code.
The generalized gradient approximation for the exchange
and correlation functional (GGA/PBE) has been used in
conjunction with the norm-conserving pseudopotentials
for the description of the core electrons.
RESULTS AND DISCUSSION
Figure 1 shows the top and the lateral view of the band-
edges for the structure at 2.05 ps. In this case both VBM
and CBM are spread along the surface edge as a Fig. 2 (a) Side and (b) top view of the VBM wavefunction
consequence of a more uniform Pb-I bond-length of the trajectory of s cluster extracted after 2.85ps. (c) and
distribution. In the case of the trajectory characterized by (d) same for the CBM. [Grey, Pb; Purple, I; Brown, C;
smaller gap (2.85 ps) the VBM is mainly localized into a light blue N, White, H atoms. Isosurface level 0.04 eV/].
single PbI6 octahedron at the surface. Very interestingly
we observe that reducing the OIHP dimensionality, MA CONCLUSION
orbitals participate to the VBM with a small, but non In summary we have for the first time reported results of
negligible, contribution, in clear contrast with the bulk clusters (0D) modelling of hybrid Organic-Inorganic
case. On the other hand, the CBM is more spread along Halide Perovskites (OIHPs). Our modelling is motivated
one of the Pb-I-Pb edge in the the z-direction. by the lack of experimental and theoretical results about
Similar distribution of the wavefunction (along one Pb- OIHP nanostructures in view of their fundamental
I-Pb edge) holds for states above the CBM itself. An property investigations. The present study represents the
interesting feature in this case is the quantitative presence first analysis focused on electronic and structural
of I orbitals which in the case of the bulk are present only properties of OIHP clusters. Further analysis to tune
in traces. Regardless the bandgap, we observe that an electronic properties of such clusters based on their
efficient electron (CBM)-hole (VBM) separation takes size/facet reconstruction relationship is nowadays in
place for both the structures witnessing a reduced progress.
58

Development of e-nose biosensors based on organic semiconductors towards low-


cost health care diagnosis in gynecological diseases

H. Cruz1, A.J. Califrnia2, A. Pinto2, J. Fonseca2, J. Gomes2, A. Palmeira-de-Oliveira3, J. Martinez-de-Oliveira3 and L.


Pereira1*
1
Department of Physics and i3N Institute of Nanostructures, Nanomodelling and Nanofabrication, University of Aveiro,
Portugal, luiz@ua.pt
2
CeNTI Centre for Nanotechnologies and Smart Materials, Portugal
3
Faculty of Health Sciences and CICS-UBI - Centre of Research in Health Sciences, University of Beira Interior, Portugal

INTRODUCTION was proven to be problematic since the sensors exhibited


The increase of organic electronics and consequently, the some sensitivity to the water and in fact in most of the
development of sensors based on organic polymers have cases it was very difficult to distinguish not only the
attracted a lot of attention of the scientific community. reaction of the sensors to both vaginal fluids but also to
Intrigued by these multifunctional, easily processed and the water. The sensitivity of this type of sensors to the
low cost materials, it has started to develop odor water is definitely an important parameter to take into
biosensors (electronic nose e-nose - concept) for account. By other side, it was shown that sometimes is
different applications, including medical field and the difficult to distinguish the vaginal fluids from each other
detection of various diseases. The present work, is with different sensors of the same type, mainly because
focused in the scaling-up of a devoted laboratory the differences between different sensors response and
approach, in particular concerning the development of the results fluctuation linked to the sensors sensitivity to
organic odor biosensors based on a conductive polymer these analytes. However, with only one sensor it was
(PEDOT:PSS) in a pre-industrial approach. A detailed proven that not only its possible to distinguish water
characterization of sensor heads with different geometry from the vaginal analytes, that its clear that the sensors
is reported on a specific case of gynecological diseases react differently to the analytes with a clear pattern. It is
caused by Lactobacillus infection. also possible to notice that the resistance and capacitance
increase healthier vaginal fluid which has 20 % less
EXPERIMENTAL/THEORETICAL STUDY
concentration of lactobacillus than the infected fluid. The
The e-nose system consists in two chamber, one for the
variation of sensor parameters such as width, length and
analyte and another for the sensor head, which is forced to
number of fingers, seems not to have considerable
contact the analyte odor by means of a simple aspiration
influence in the sensors behavior. However, its clear that
process. The sensor heads were fabricated in flexible
the variation of geometrical parameters such as the gap
substrates with carbon microelectrodes with different
width and the fingers width influences considerably the
geometrical parameters and produced by means of
resistive and the capacitive response. These variations are
printing techniques, such as screen printing and slot die
very important, since for different applications may be
Roll-to-Roll, that was applied to coating the PEDOT:PSS
more useful to use the capacitive or the resistive mode
film over the microelectrodes. The sensor responses were
and in that case its possible to choose the best parameters
analyzed in resistive and capacitive modes with
for the sensors.
environment parameters control.
RESULTS AND DISCUSSION CONCLUSION
The sensors were morphologically characterized by Simple, low-cost, disposable and sensitive sensors based
optical microscopy, atomic force microscopy, on organic semiconducting polymers was developed in
perfilometry and electrically identified by the two points high-output pre-industrial systems and successful applied
probe method. The sensors were tested with the use of to diagnosis gynecological diseases. The good results,
different analytes with the main focus on Lactobacillus allied to the developed techniques to processing the
gynecological analyte, in a standard medical vaginal fluid. electrical responses, allows the use of such sensor to
The resistive and capacitive electrical sensor responses efficient diagnosis and opened the possibility for the
for the analytes were analyzed and discussed in depth. home care concept.
Important results were obtained with regard to the
influence of the geometrical parameters of the carbon
ACKNOWLEDGMENTS
microelectrodes and also to the polymer thickness (from
The authors would like to acknowledge the financial
217 to 382 nm). The vaginal fluid simulators in this work
support from i3N - UID/CTM/50025/2013.
had a different concentration of lactobacillus in the
solution. Both of these analytes are not very volatile
aqueous solutions and have a big volume of water. This
59

Bulk-Heterojunction Organic Solar Cells area-dependent parameters fluctuation

A.J. Trindade and L. Pereira*


1
Department of Physics and i3N Institute of Nanostructures, Nanomodelling and Nanofabrication, University of Aveiro,
Portugal, luiz@ua.pt

INTRODUCTION necessary dependent on the solar cell area. Gains in the


The efficiency of a solar cell is clearly dependent on the VOC from the initial area can add up to +0.2 V on the final
active area and such relationship can be a constrain in the device behavior, providing a significant increase in the
upscale factor when thinking on possible market device power production. The observed losses in FF
applications. In this work, a detailed study of an organic results on a serious crop on the performance of the device.
bulk-heterojunction (HBJ) solar cell with active layer As more intrinsic defects play a role on the current
based on poly(3-hexylthiophene) P3HT and 1-(3- production once these get exposed to the incident
methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 PCBM is radiation, it can be seen through the curve shape how the
made. The results are discussed pointing the main device gradually loses its ability to maintain a good FF.
physical influences for the observed efficiency data. From the initial 55.7% of FF as the active area rises, the
rectification of the device decreases rapidly substituting
EXPERIMENTAL
the desired L-shape of the J-V curve by a line that
The solar cells were fabricated by spin-coating on glass
resembles a linear J-V behavior. In our case, the active
substrates with Indium Tin Oxide as anode. The structure
area increasing causes a nearly-exponential drop of
was a 50 nm tick PEDOT:PSS hole-injection layer
efficiency going from the initial 2.28% to 0.47%.
followed by and active layer (200 nm tick) composed of
Considering now the overall figures of merit from our
P3HT and PCMB on a ratio 1:1. The Aluminum cathode
devices, we can see that both JSC and FF decrease
(200 nm) was thermally evaporated on the top of the
significantly while VOC as remains relatively constant.
active layer. Current-Voltage (J-V) data was acquired at
The reduction of the J SC can be easily attributed to the
room temperature using an AM1.5 Global Solar
possible existence of pin holes and / or inhomogeneities
Simulator. The active area increase was performed using
in the thin film morphology. Taking into account such
black cardboard masks avoiding edge effects as only the
possible non-uniformities in the active area that increases
nominal active area is tested. The area changed from 10-2
the series resistance it seems to be also correct to list the
to 2 cm2.
decrease of efficiency as arising from the FF behavior.
RESULTS AND DISCUSSION Considering the final market applications, a suitable
The figures of merit of the solar cell were extracted from physical model comprising the nanostructured HBJ solar
the equivalent circuit using a genetic based algorithm, and cells vs active area is proposed.
their relationship with the active area was compared. It is
observed that the efficiency drops significantly with the CONCLUSION
active area increase (as the fill-factor FF) while the In this study we approached the active-area growth from a
parallel and series resistance seems to be relatively typical lab-scale to a manufacturing-scale using the
constant and linearly increase respectively. As the voltage simplest architecture for a BHJ device. The results were
open circuit (VOC) and diode ideality factor changes with successfully modeled using our algorithms and allowed
the active area increase, we conclude that the physical for a comparison of the cell behavior-evolution with the
properties at nanoscale dimension of the cells are related area increase. There seems to be always a trade-of
with the active area. The short circuit current (JSC) and the whenever considering the advantages of small-area cells
generated photocurrent also drop significantly with the and large-area cells, and from the reported experimental
active area increase, showing a similar behavior. It is data, that has been proved. Further studies and
clear a global drop in current production and a small gain optimizations to the morphology of these devices must
in VOC. Naturally that these behaviors changes consider the data here analyzed to decide strategies to
significantly the overall solar cell figures of merit. The approach these materials / architecture limitations.
simulated total photocurrent by the device is always
paired with the JSC. Increases in the measured JSC causes
ACKNOWLEDGMENTS
the algorithm to recognize a higher produced photocurrent
The authors would like to acknowledge the financial
from the device, resulting in a better overlap of the
support to the project PTDC/108701/2008 Photovoltaics
experimental curve and the simulated J-V curve. With the
from Organic Materials PhotOM and the i3N support
active area increase, the extra-produced photocurrent still
from UID/CTM/50025/2013.
surpasses the lost photocurrent due to recombination in
the device, and seems to slowly decay for areas superior
to 1.82 cm2. Regarding the VOC, this parameter is not
60

A novel nanostructured complex adsorbent from aluminosilicate binders

David Kolousek1*, Barbora Dousova1, Martina Urbanova1, Jiri Brus1

1
Institute of Chemical Technology Prague, Czech Republic
2
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Czech Republic
david.kolousek@vscht.cz

INTRODUCTION was measured between 570 2 (step 0.05 2/s) for


qualitative identification of phases.
Geopolymers with specifically synthesized nano-sized
domains of zeolites are not only perspective materials for RESULTS AND DISCUSSION
building industry, but also promising systems for sorption
of various toxic contaminants. These nanostructured and First, activation of Zeolite A in the AAA matrix by the
nanocrystalline materials offer enhanced physicochemical solution of 0.6 M solution FeSO4.7H2O leads to the
properties thanks to an extremely large interfacial area of considerable transformation of aluminosilicates network.
nanosized zeolite domains. Zeolites are commonly used The structure of zeolite is strongly destructed. From the
as selective sorbents of cationic particles, such as metal recorded NMR spectra it is apparent that AlIV tetrahedral
ions or ammonium ions due to ion exchange. A simple sites are transformed to AlVI units. Moreover homogenous
pre-treatment of these materials with Fe ions causes the broadening of the AlVI signal observed in 27Al 3Q/MAS
change of surface charge (pHZPC), which significantly NMR spectra indicates that Fe2+/Fe3+ ions of complex
improves the sorption affinity to anionic contaminants, adsorbent are present close Al-Si interlayers. Second, the
such as phosphates, arsenates, etc. Nalsit model system undergoes limited structural
In the presented study the aluminosilicate geopolymer transformation, as evidenced by the recorded NMR
binders containing controlled fraction of zeolite phases spectra. Activation of Nalsit by the solution of 0.6 M
(zeolite A) were prepared from waste Czech solution FeSO4.7H2O leads to only partial transformation
aluminosilicate materials (AAA). Adsorption properties of tetrahedral AlIV units to hexacoordinated AlVI sites.
of the prepared materials were tested, and compared with This may be explained by the formation of nanozeolitic
the behavior of two model zeolite phases based on domains located in the inter-layered area of layered
hydroxysodalite and Nalsit. Structural changes in these aluminosilicate phase; and direct incorporation of
materials induced by the sorption process were Fe2+/Fe3+ ions into the aluminosilcate matrix in which
subsequently characterized in detail by a range of solid- formally substitute Al atoms in the newly formed
state NMR experiment combined with XRPD analysis. octahedral. In addition we also suppose presence of
Fe2+/Fe3+ ions filling the voids in vicinity of AlO45-
EXPERIMENTAL tetrahedra. Third, structure of hydroxysodalite model
Preparation of anion-active sorbents was done by the system is entirely maintained. Fe2+/Fe3+ ions are adsorbed
surface modification the following materials: i) Zeolite A exclusively on the surface of hydroxysodalite particles.
27
in the AAA (alkaline active aluminosilicates) matrix; ii) Al 3Q/MAS NMR indicates negligible transformation
Nalsit (synthetic zeolite of type A); iii) Hydroxysodalite. AlIV units to AlVI units.
All the used zeolite systems were modified with Fe ions
in the same manner; the pre-treatment with FeII salts CONCLUSION
consisted of the agitation of raw sorbent with 0.6M We investigated complex adsorbents prepared from
(0.3M) FeSO4.7H2O/0.6M (0.3M) FeCl2.4H2O (20 g.l-1) nanosilicates binders (nanozeolites of type A). Fe(II)
in a sealed polyethylene bottle at laboratory temperature modification with 0.6M FeSO4.7H2O was found as an
(20 C) for 24 hours. The prepared samples were tested optimal procedure for nanostructured aluminosilicates.
on phosphate adsorption. All tested zeolite phases are selective anionic sorbents.
After activation of samples by the 0.6 M solution
Solid-state NMR spectra were measured using a Bruker FeSO4.7H2O nanozeolites of type A was completely
Avance 500 NMR spectrometer. The following structurally transformed; Nalsit-based systems exhbited
techniques were applied: i) 27Al and 29Si MAS NMR partial structural transformation; whereas the
experiments, ii) two-dimensional multiple-quantum hydroxysodalit systems underwent negligible structural
experiments 27Al 3Q/MAS NMR for detailed description transformation.
of these systems.
Powder X-Ray Diffraction data were recorded using a
3000P Seifert device using CoKa radiation. Every sample ACKNOWLEDGMENTS
The authors thank the Czech Science Foundation (GA13-
24155S).
61

Ammonolytical conversion of bulk wafers of gallium arsenide GaAs to polytype


specific nanopowders of the gallium nitride GaN semiconductor

Jerzy F. Janik* and Mariusz Drygas

AGH University of Science and Technology, Faculty of Energy and Fuels; Al. Mickiewicza 30, 30-059 Krakow, Poland;
*janikj@agh.edu.pl

INTRODUCTION
There is still a need for development of a simple and high 900 C/6 h
yield synthesis of nanocrystalline powders of the gallium interior
nitride GaN wide bandgap semiconductor. The
metathetical ammonolysis of readily available gallium
pnictides GaE (E = As, P, Sb), GaE + NH3 GaN + EH3,
is one of the plausible pathways to reach such a goal. We 900 C/6 h
have already published reports on the feasibility of this crust
approach for E = P1 and Sb2 and, now, presented is part of interior crust
our recent study on E = As.
EXPERIMENTAL
Chunks of [100] oriented GaAs wafers of commercial
quality were generously acquired as waste material from
the Institute of Electronic Materials Technology,
Warszawa, Poland. They were nitrided as received in the 950 C/6 h
stream of flowing ammonia NH3 at 900 or 950 C for 6 h.
In the 900 C-conversion, a few pieces of a thin (2-3 m)
transparent yellowish crust could be carefully separated
from a gray yellowish interior powder of the product. The
XRD patterns and SEM pictures were obtained both for
such a crust-enriched material and for interior. A
representative part of the product (crust plus interior) was
averaged out by gentle grinding to yield the XRD data Fig. 1. XRD patterns (left panel) and SEM images (right
that were used to calculate the parameters in Table 1. In panel) of GaN prepared from GaAs wafer at 900 C/6h
the 950 C-conversion, the product was a homogeneous (top rectangle) and 950 C/6h (bottom rectangle).
gray yellowish powder (no crust was discernible). Herein,
the results of the XRD and SEM determinations are Table 1. Polytype make-up and crystallite characteristics.
discussed. A thorough materials characteristics includes
also the XPS, Raman, and UV-vis spectral analyses. Nitridation Phase, content Lattice Av. size
(temp/time) [%] a [], c [] [nm]
RESULTS AND DISCUSSION
h-GaN, 76 a=3.19, c=5.20 30
The 900 C /6 h or 950 C/6 h single-step ammonolysis 900 C/6 h
c-GaN, 24 a=4.51 33
conditions were sufficient for complete nitridation of the
GaAs wafer to mostly nanocrystalline GaN products. All 950 C/6 h h-GaN, 100 a=3.18, c=5.18 22
by-products were conveniently removed from the reaction
zone by flowing gases/sublimation phenomena. The CONCLUSION
formation of GaN was additionally confirmed by the The ammonolysis of GaAs wafers at 900-950 C/6 h can
Raman and UV-vis spectroscopy analyses. At 900 C, the yield either nanocrystalline mixtures of the polytypes or
product was a mixture of the hexagonal and cubic GaN pure hexagonal polytype of GaN. The 900 C-conversion
polytypes whereas at 950 C the exclusive formation of leads to formation of a few micrometer thick transparent
hexagonal GaN was observed. The 900 C conversion crust made of mechanically coherent polycrystalline GaN.
provided also with a 2-3 m thick surface crust layer
REFERENCES
which was mechanically coherent and transparent
1. M. Drygas et al., RSC Adv., 5, 106128-106140 (2015).
supporting high purity and textured growth of the GaN
2. M. Drygas et al., RSC Adv., 5, 82576-82586 (2015).
crystallites. The GaN polytype make-up results from an
interplay of the thermodynamic and topochemical factors. ACKNOWLEDGMENTS
The study was supported by the Polish National Science
Center (NCN), Grant No. 2013/09/B/ST5/01223.
62

New carbon phases obtained from C70 at high-pressure and high-temperature

Leonel Marques1*, Yuriy Skorokhod2 and Rosrio Soares3


1*
Departmento de Fsica and CICECO, Universidade de Aveiro, Portugal, lmarques@ua.pt
2
Institute of Physics of the Czech Academy of Sciences, Prague, Czech Republic
3
Laboratrio Central de Anlises and CICECO, Universidade de Aveiro, Portugal

INTRODUCTION
Nanostructured carbon materials prepared using
fullerenes precursors under extreme conditions of
pressure and temperature display outstanding mechanical
properties1,2. On the other hand, ordered fullerene
networks created by assembling C60 building blocks at
milder conditions of pressure and temperature display
unique physical properties such as low-compressibility,
superhardness, electron conductivity and high-
temperature ferromagnetism 3,4. We show that oval- Fig. 1 One-dimensional zigzag C70 structure (left panel)
shaped C70 building blocks assembled at high-pressure and two-dimensional hexagon C70 structure (right panel).
and high-temperature can also form ordered network
structures, in contrast to earlier results.
EXPERIMENTAL/THEORETICAL STUDY CONCLUSION
The new C70 phases were synthesized at high-pressure The present work definitely establishes C70 molecules as
and high-temperature using a Paris-Edinburgh press very efficient building blocks, on the same footing as C60
equipped with WC/sintered-diamond anvils. The and in opposite to old ideas, to create novel
structures of the new phases were determined by Rietveld nanostructured carbon phases. Mapping the reaction
analysis of the X-ray diffraction data combined with pressure-temperature diagram for C70, as it was
density functional theory modeling. thoroughly carried out for C60, should lead to the
discovery of other new fullerene network structures.
RESULTS AND DISCUSSION
Two new C70 phases have been synthesiszed at 9GPa and
270C (1D phase) and at 7Gpa and 600C (2D phase). REFERENCES
Their structures, both monoclinic, were determined by 1. Q. Huang et al, Nature 510, 250; (2014)
combining powder x-ray diffraction, which provided the
lattice parameters and symmetry, and density functional 2. L. Wang et al, Science 337, 825 (2012)
calculations, which in turn gave the optimized atomic 3. L. Marques et al, Science 283, 1720 (1999)
positions used subsequently in Rietveld analysis of the
experimental diffractograms6,7. The structure of the 1D 4. S. Yamanaka et al, Phys. Rev. Lett. 96, 076602 (2006)
phase consists of zigzag polymerized C70 molecules while 5. T. Makarova et al, Nature 413, 716 (2001)
the 2D phase consists of layered polymerized C70
molecules arranged in puckered hexagons, in which each 6. L. Marques et al, Carbon 82, 599 (2015)
molecule is bonded to three neighboring molecules (see 7. L. Marques et al, Phys. St. Sol. RRL 9, 535 (2015)
figure 1). Such networks have never been observed in
related phases, particularly in C60-based networks. ACKNOWLEDGMENTS
The present study also demonstrates the role played by
the layer displacements on the phase transformations of L. Marques and Y. Skorokhod acknowledge Fundao
C70 at high-pressure. Antiparallel displacements of the para a Cincia e Tecnologia (FCT) and EU/FEDER
compact layers lead to short interfullerene distances and COMPETE (Project PTDC/FIS/104310/2008 and
promote covalent bonding between the molecules. contracts PEST-C/CTM/LA0011/2013 and FCOMP-01-
0124-FEDER-037271) for financial support..
63

Space Charge Induced Electrostatic Doping of Two-Dimensional Materials:


Graphene as a Case Study
Andrea Paradisi1, Johan Biscaras1 and Abhay Shukla1
1
Institut de Minralogie, de Physique des Matriaux et de Cosmochimie, UPMC Univ. Paris 06, UMR CNRS 7590, MNHN,
IRD UMR 206, 4 Place Jussieu, F-75005 Paris, France, andrea.paradisi@upmc.fr

INTRODUCTION surface) or holes (depletion of Na+) to doping levels up to


We introduce a technique that we call Space Charge 1.21014 cm-2 for the case of electron doping. The
Doping1 for electrostatic doping of 2D materials. This minimum attained sheet resistance value was 225 / for
technique exploits the presence of mobile ionic species in CVD graphene.
glass to induce a charge imbalance at the glass-material With the Space Charge Doping we are able to finely
interface. Ionic mobility in glass is species dependent and control the doping level, as shown in Figure 1 (right side),
also dependent on the temperature and the applied electric where the Rs vs ns characteristic of graphene is shown.
field. Mobility of positive sodium ions is increased by Each point of the curve is obtained by heating the sample
heating and an applied electric field causes ion drift. The with a gate voltage applied while monitoring the sheet
polarity of the electric field results in accumulation or resistance and, when the desired value of Rs is reached,
depletion of sodium ions at the glass surface inducing, the sample is rapidly cooled down to room temperature
respectively, electron or hole doping in the material where the ions mobility is negligible.
placed on the surface, in this case graphene. Extremely
high doping levels are reached (>1014 cm-2) without
compromising graphene quality and with reversibility,
bipolarity, and stability in time.

EXPERIMENTAL
For this work we used commercial CVD graphene
transferred on commercially available glass (borosilicate
or soda-lime glass) through the standard PMMA transfer
technique2 and graphene realized with the Anodic
bonding technique3 directly on the glass substrate. The
samples are contacted in the van der Pauw geometry, as
schematically shown in Figure 1 (left side). The Space Fig. 1 (Left) Schematization of a graphene sample on a
Charge Doping and sheet resistance measurements were glass substrate. (Right) Sheet resistance of graphene as a
performed in a custom-built system with a continuous function of doping. Each point of the curve is obtained
liquid He flow cryostat capable of reaching temperatures with the Space Charge Doping.
in the range 3420K under high vacuum conditions (<10-6
mbar). The doping concentration is measured in situ with The quality of graphene, as its transparency, are not
the Hall effect using an external 2 T electromagnet. altered by the doping process.
Raman spectroscopy is used to check the quality of the
graphene film before and after the doping. CONCLUSION
The Space Charge Doping is a new technique with
RESULTS AND DISCUSSION potential industrial applications (in the field of
The Space Charge Doping uses the presence of positive Transparent Conductive Electrodes for example) as well
sodium ions in the glass substrate to create an as fundamental applications like insulating to
accumulation (depletion) of ions at the glass/material superconducting transition4.
interface. The ions mobility in the glass is negligible at
room temperature and increases exponentially with the REFERENCES
temperature. At high temperature an electric field across 1. Paradisi et al., Appl. Phys. Lett. 107, 143103 (2015).
the glass causes the ions drift and the accumulation
2. X. Li et al., Nano Lett. 9, 4359 (2009).
(depletion) layer is created. This charged layer is
preserved back at room temperature even without the 3. A. Balan et al., J. Phys. D: Appl. Phys. 43, 374013
applied electric field. The Space Charge Doping is (2010).
performed at moderate temperatures (T<420 K) and
4. Biscaras et al., Nature Comm. 6, 8826, (2015).
voltages (VG<285 V).
For the case of graphene, we were able to routinely dope
graphene with electrons (accumulation of Na + at the glass
64

Formation of stanene on SiC surfaces: An ab inito study

Filipe Matusalem1*, Friedhelm Bechstedt2, Marcelo Marques1 and Lara K. Teles1


1
Department of physics, Technological Institute of Aeronautics, Brazil, filipematus@gmail.com
2
Institut fr Festkrpertheorie und -optik, Friedrich-Schiller-Universitt, Germany

INTRODUCTION In Fig. 2 the band structures are shown for 1x1 stanene,
The deposition of overlayers 1,2 on 4H-SiC(0001) stanane and fluorostanene on 3x3(0001) SiC substrate.
substrates is studied by means of density functional The BZ of the 3x3 surface and the BZ of the 11 sheets
theory, including van der Waals interaction and are identical because of the assumed strained systems.
approximate quasiparticle3,4 electronic structure Interestingly, stanene-derived linear bands survive at the
calculations. Geometries, formation energies and bands K point and near the Fermi level independent of the
structures are computed and discussed. The influences of surface and the mixed covalent/vdW or the pure vdW
the Sn overlayer geometry, the surface passivation by H bonding of the stanene overlayer. Despite of a partial Si-
and F as well as the chemical functionalization of the Sn Sn bonding in Fig. 2 (a) the Dirac cones of stanene at the
layer by fluorine and hydrogen are investigated in detail. K point survive. This behavior is also observed for 2x2
The overlayers are characterized by their energies, strain stanene-like derived sheets on 3x3(0001) SiC substrate.
and electronic states, especially the occurrence of Dirac-
like bands in the fundamental gap of SiC.
EXPERIMENTAL/THEORETICAL STUDY
The total-energy and force calculations are performed in
the framework of the DFT as implemented in VASP.
Exchange and correlation are simulated in the framework
of the optB86b-vdW functional including van der Waals
(vdW) interaction. Also the excited states correction
method DFT-1/23,4 is applied. The simulations of the SiC Fig. 2: DFT-1/2 band structures of 11 overlayers on (a)
surfaces and their adsorbates are performed within the clean, (b) H-passivated and (c) F-passivated 4H-
repeated slab approximation. The stanene-like sheet of Sn SiC(0001)3x3 substrates. The Sn-derived bands are
atoms is deposited on top of the Si-terminated (0001) SiC shown as blue dots, whereas the bulk SiC bands are
surface, which can or cannot be passivated with H or F indicated by the shaded regions. The Fermi level is
atoms. indicated by a red solid lines.
RESULTS AND DISCUSSION
CONCLUSION
In Fig. 1 the total energy of the slab systems per atom is
The studied systems give rise to local minima on the total
plotted versus the corresponding distance. For the clean
energy faces. The reactivity of the clean SiC surfaces
surface the pronounced minimum indicates a strong
widely destroys the band structures of freestanding
covalent bonding between overlayer and substrate. The
stanene or stanane, but Dirac cones survive at K point for
situation is similar for stanane, although the energy
passivated substrate systems. To prepare Sn-based 2D
minimum is less pronounced.
honeycomb crystals stanene, stanane or fluorostanene we
recommend further growth experiments, in particular such
on less reactive, almost passivated SiC substrates.

REFERENCES
1. C.-C. Liu, et. al., Phys. Rev. B 84, 195430 (2011).
2. B. V. D. Broek, et. al., 2D Mater. 1, 021004 (2014).
3. L. G. Ferreira, et. al., Phys. Rev. B 78, 125116 (2008).
4. L. G. Ferreira, et. al., AIP Adv. 1, 032119 (2011).

ACKNOWLEDGMENTS

This work was supported by the Brazilian funding agency


CAPES, grants No. 23038.005810/2014-34 and No.
Fig. 1: Total energy per atom in terms of the distance of 88881.068355/2014-01, and So Paulo Research
the 2D Sn-derived 22 sheet on 33 SiC substrate. Foundation (FAPESP), grants No. 2012/50738-3 and No.
2014/13907-7.
65

Estimation of Polymer Stretching Degree Arising During Electrospinning

Arkadii Arinstein1, Michael Burman2, Gleb Vasilyev1, and Eyal Zussman1


1
Department of Mechanical Engineering, TechnionIsrael Institute of Technology, Israel, mearin@technion.ac.il
2
LMEE, Universit dvry Val d'Essonne, Paris, France

INTRODUCTION
It is commonly accepted that polymer matrix inside of The comparison of the contraction kinetics of single
electrospun nanofibers is at non-equilibrium state. Such a electrospun fibers (see Fig. 2) and pre-stretched films (see
non-equilibrium microstructure formed during the Fig. 2, the final stage after 60 min) allows us to estimate
electrospinning process, is characterized by a high the stretching degree of electrospun nanofibers.
stretching rate and rapid evaporation. Although the
formed stretched polymer structure can partially relax due -10
to some residual solvent, the final state of polymer
nanofibers remains noticeable stretched. It is clear that the
stretching of polymer macromolecules is accompanied by

Strain (%)
-20
increasing their orientation.
In order to characterize the stretched state of polymer
1
macromolecules, several research groups measured the -30
molecular orientation via, birefringence, Raman
spectroscopy, etc1. Unfortunately, the interpretation of
these results can be ambiguous. The point is that stretched 2
macromolecules should demonstrate some orientation, -40
2 4 6 8
while an orientational ordering can also be observed even Time (min)
in non-stretched systems, for example, in liquid crystals.
In spite of that, there are no doubts that the molecular Fig. 2. Contraction of single electrospun nanofibers at
orientation, observed in the above measurements, is 63C for fiber at 1.14 (1) and at 1.81 (2) kV/cm.
related to the polymer matrix stretching. Nevertheless,
direct measurements (or even estimation) of a stretching CONCLUSION
degree is still demanding. The proposed method is founded in the analysis of the
RESULTS AND DISCUSSION contraction kinetics of electrospun polymer nanofibers
An experimental procedure allowing one to estimate the upon heating and comparison of this phenomenon to the
stretching degree in TPU (thermoplastic polyurethane) contraction of a polymer film, subjected to programming
segmented block-copolymer electrospun nanofibers, is and allows one the quantitative characterization of the
proposed. The estimation method is based on the degree of stretching of polymer matrix inside electrospun
phenomenon that upon heating, nanofibers, as well as pre- nanofibers, including both plastic and elastic deformation
stretched films began to massively contract2 (see Fig. 1). modes. The degrees of stretching of a polymer matrix in
TPU electrospun nanofibers, fabricated with electrical
field strengths of 1.14 and 1.81 kV/cm, were estimated to
90
Strain (0.3 min) be 250% and 1400%, respectively. Such a high stretching
100 Strain (5 min) 80 level of the second nanofiber reflects the fact that with the
Strain (10 min)
increase in the spinning voltage, the degree of plastic
Temperature (oC)

Temperature 70
75 Temperature deformation of the spinning polymer system related to
Strain (%)

Temperature 60 reorganization of the entanglement network, also


50
increases; and when the voltage achieves a critical value,
50
disturbing the spinnability conditions, the system
40 elongation will be so high that the connectivity of the
25 entanglement network will be broken.
30
REFERENCES
0
0 20 40 60 80 100 120 140 1. M. Richard-Lacroix and Ch. Pellerin, Macromolecules
Time (min) 46, 9473 (2013).

Fig. 1. Contraction phenomena in TPU cast film after 2. D. Alhazov, et. al, J. Polym. Sci., Part B: Polym. Phys.
high-temperature stretching for different time period at 53, 1254 (2015).
90C.
66

Effect Of Annealing Process In TiO2 Thin Films: Structural, Morphological, And


Optical Properties
Anderson Dussan1*, Andres Bohrquez1 and Heiddy Quiroz1
1
Departmento de Fsica/Grupo de Materiales Nanoestructurados y sus Aplicaciones, Universidad Nacional de Colombia -
Bogot, Colombia, adussanc@unal.edu.co

ANM-nanomaterial-Poster increase in the crystallinity due to the annealing


processes, allowed identifying this phase in the
This work presents a study of the structural, preferential plane (101). Fig. 1 presents the SEM
morphological, and optical properties of titanium dioxide micrograph of the sample with T = 353K; the presence of
thin films prepared via chemical bath deposition method, nanoflowers is observed. These types of nanostructures
after being submitted to annealing processes and varying were formed when the pH of the chemical bath was
the temperature from 373 to 723 K. The presence of the around of 1.0. With increased pH, these nanostructures
Rutile phase in all the samples was identified by using X- tend to disappear.
ray diffraction measurements. When the annealing
temperature increased to 723 K, the presence of the
Anatase phase was observed. From scanning electron
microscopy measurements (SEM), the formation of
nanoflowers was also observed; these flower-like
structures are composed of nanorods of around 10 nm in
length. With increased annealing temperature, these
structures disappear transforming into platelets distributed
over the whole surface.

INTRODUCTION
Physical properties1,2 of the titanium dioxide (TiO2) has
been studied in the last decades on diverse applications,
like: gas sensors3, photovoltaic devices (solar cells)4, UV
light sensors5, and some biomedical applications5.
However, their properties change depending of the Fig. 1 SEM micrograph of the TiO2 sample with T = 353
fabrication method. K. The figure inset shows a nanoflower structures.
Titanium dioxide thin films have been synthesized by
using the innovative chemical bath deposition (CBD) CONCLUSION
method. Temperature of solution, deposition time and pH TiO2 thin films were fabricated via the CBD method. All
solution, were studied. Structural, morphological and the samples showed the presence of the rutile phase and
optical properties were correlated with parameter when the annealing temperature was increased to 723 K,
synthesis from X-ray diffraction (XRD), scanning the Anatase phase was also found. Similarly,
electron microscopy and reflectance measurements. topographical changes, caused by temperature variations,
were evident in the disappearance of the nanoflower
EXPERIMENTAL/THEORETICAL STUDY structures formed at T = 353 K, giving way to
TiO2 films were fabricated by CBD method using soda agglomerate-like structures.
lime glass like substrates. Samples were fabricated in a
solution of distilled water mixed with titanium chloride REFERENCES
(III) (TiCl3), obtaining an acidic solution with pH equal to 1. T. Amna et al, Colloids Surf. B: Biointerfaces 101, 424
1.3. The substrate was vertically submerged into the (2013).
solution by using a mechanical support and the bath was 2. P. Naira et al, Appl. Surf. Sci. 257, 10869 (2011).
heated initially to 353 K, the agitation was reduced to 100 3. S.J. Ramadossa et al, J. Alloys Compd. 561, 262(2013).
rpm for 8 h, keeping the pH. After the deposition process, 4. P.S. Musavi Gharavi et al, Sol. Energy Mater. Sol.
the samples were heated to 373, 573, and 723 K to study Cells 137, 113 (2015).
changes in their structural, morphological, and optical 5. C. Grimes and G. Mor, TiO2 Nanotube Arrays:
properties. Synthesis, Properties, and Applications (Springer US,
New York, 2009), p. 217.
RESULTS AND DISCUSSION
Anatase and rutile phases were identified by XRD ACKNOWLEDGMENTS
patterns. The Anatase phase present in the sample with T This work was supported by Universidad Nacional de
= 723 K can be associated to the segregation of crystalline Colombia.
phases in the samples of different TiO2 polymorphs. An
67

Natural Photonic Nanostructure of Greta Otto Butterfly


Heiddy Quiroz1*, Claudia Barrera2, Rafael Rey2 and Anderson Dussan1
1
Departmento de Fsica/Grupo de Materiales Nanoestructurados y sus Aplicaciones, Universidad Nacional de Colombia -
Bogot, Colombia, hpquirozg@unal.edu.co
2
Departmento de Fsica/Grupo de ptica e Informacin Cuntica (GOIC), Universidad Nacional de Colombia - Bogot,
Colombia

ANM-nanomaterial-Poster electric field amplitude in the holes of the triangular


lattice, and hexapole mode (Fig. 1d).
In this work, we present an experimental and theoretical
study about the optical and morphological properties of
wing butterfly Greta Otto. From reflectance
measurements it was possible to observe a shift in the
maximum of the reflectance spectra towards lower values
of lambda when the angle of the incident light increases
from 20 to 60. To explore this correspondence, we
implemented the simulation of butterfly wing from
experimental results, like a triangular system formed by
Chitin with air. We obtained the photonic band structures
and the profiles to the electric field intensity. The
simulation was done using the MIT PhotonicBands
(MPB) package, the calculations were realized using the
plane wave bases, the code does a direct computation of
the eigenstates and eigenvalues of Maxwell's equations,
using a plane wave basis. Photonic properties of the wings
and its iridescent effects are explored.
Fig. 1 Scheme of the real part of the z component of the
INTRODUCTION electric field to TM for the first four bands in the direction
In recent years, a theoretical compression about of the
of point of high symmetry K for the system of triangular
photonic crystal, methods of fabrication and
lattice chitin-air: a) TM 1, b) TM 2, c) TM 3 d) TM 4.
characterization have been developed due to understand
its optical and physical properties1-3.
The degradation in color indicates the change in
In this work at the compositional, topographical and
amplitude values (inset Fig. 1).
morphological characterization of the structures in the
wings of the butterfly are presented through energy
CONCLUSION
dispersive X-ray spectroscopy (EDXS) measurements,
scanning electron microscopy (SEM) and specular The simulated photonic crystal of the butterfly wing
reflectance. From the optical measurements evidence of structure, allowed calculating the photonic band structure,
iridescent character of butterfly wings and their similarity exhibiting a partial gap for transverse electric (TE) mode.
with periodic structures associated with photonic crystals. Introducing a disorder in the theoretical model was
possible to find the photonic band structure and mode
EXPERIMENTAL/THEORETICAL STUDY frequency located in the gap partial electric transverse
The development of photonic system simulation was mode.
performed with the MIT Photonic-Bands (MPB) package.
This code calculates the eigenmodes of photonic crystals REFERENCES
by the plane wave expansion method. The algorithm used 1. C. Sibilia, T.M. Benson, M. Marciniak, T. Szoplik
calculates the actual values of the frequency in periodic (eds.), Photonic Crystals: Physics and Technology
structures and allows working with newspapers and (Springer, Verlag, 2008), p. 1.
anisotropic dielectrics. 2. R. Hovden et al, Nat. Commun. 6, 1 (2015).
The Greta Otto butterfly from Santa Marta City 3. Di Zhang et al, Prog. Mater Sci. 68, 67 (2015).
Colombia, was provided by the Instituto de Ciencias
Naturales of the Universidad Nacional de Colombia. ACKNOWLEDGMENTS
This work was supported by Universidad Nacional de
RESULTS AND DISCUSSION Colombia DIB project Code Quip No. 201010020493.
Fig. 1 shows the patterns for the electric field of the TM Financed by COLCIENCIAS project code Quip No.
quadrupole degenerate mode (Fig. 1a), dipolar 201010019609 and Universidad Nacional de Colombia
degenerated mode (Fig. 1b), monopolar mode (Fig. 1c), DIB project Code Quip No. 19023
which forms a pattern due to variation of the sign of the
68

Evidence of Iridescence in TiO2 Nanostructures: an Approximation in Plane Wave


Expansion Method
Heiddy Quiroz1*, Claudia Barrera2, Rafael Rey2 and Anderson Dussan1
1
Departmento de Fsica/Grupo de Materiales Nanoestructurados y sus Aplicaciones, Universidad Nacional de Colombia -
Bogot, Colombia, hpquirozg@unal.edu.co
2
Departmento de Fsica/Grupo de ptica e Informacin Cuntica (GOIC), Universidad Nacional de Colombia - Bogot,
Colombia

ANM-nanomaterial-Poster 20 and 60. The values of 500, 543, 565, and 562 nm
for the frequencies indicated in the figure.
The TiO2 traces appeared on the surface of the Ti
substrate upon removing the TiO2 nanotubes from it by
using mechanical stress. This study used Uv-Vis
spectroscopy to obtain the optical response of the sample
when varying the angle of the incident light from 20 to
60. This behavior could be associated with the
iridescence phenomena on the traces, which could present
a relation with photonic effects. To explore this
correspondence, we implemented the simulation of the
traces from experimental results, like a triangular system
formed by TiO2 in the Anatase and Rutile phases with air.
The simulations were performed by using the
approximation of expansion in plane wave method, Fig. 1 a) Absorbance spectra of the TiO2 traces varying
obtained photonic band structures and present their the light incident angle from 20 to 60. b) Scheme the
relation with iridescent effects. reflectance-absorbance measurements.

INTRODUCTION Fig. 1a correspond to the colors: blue (450 500 nm) and
Titania nanoarrangements can be obtained by chemical green (500 570 nm), respectively. The changes in
and physical-chemical processes, like Sol-gel method1, absorbance can be associated to iridescence effects in the
electro-chemical attack2, hydrothermal synthesis3, and material due to the concavity of the traces and/or to the
electrochemical anodization technique4. interaction between radiation and surface traces (Fig. 1b).
This work presents a theoretical-experimental study of the
optical properties of traces obtained by the fabrication of CONCLUSION
TiO2 nanotubes via electrochemical anodization. From From SEM measurements, it was possible to observe that
measurements of spectral absorbance as a function of the the traces have a self-organized concave structure,
frequency varying the incident angle of the light, permit- forming a hexagonal lattice or honeycomb.
ting identification of the UV region corresponding to the Theoretical study shows the absence of total gaps to
TiO2. A correlation between experimental measurements simulate the system as a bidimensional photonic crystal.
and the model presented allow associating the optical phe- In the case of separate traces appear partial gaps to the TE
nomenon to iridescence effects of photonic materials. modes, in concordance of absorbance spectra in the
region visible frequency spectra, where are evidence the
EXPERIMENTAL/THEORETICAL STUDY iridescent phenomena.
The traces were obtained by mechanical stress of TiO2
nanotube foils fabricated by electrochemical anodization REFERENCES
in a solution of ethylenglicol, distilled water, and 1. S. Pazokifard et al, Prog. Org. Coat. 7, 36 (2015).
ammonium fluoride (NH4F)5. 2. A. Adalberto et al, Thin Solid Films 587, 20 (2015).
Photonic systems are characterized as compound 3. H. Song et al, J. Mater. Sci. Technol. 31, 23 (2015).
materials of different dielectric functions exhibiting novel 4. L. Diamandescu et al, Appl. Catal. A 325, 270 (2007).
optical properties. The simulations were performed by 5. Heiddy P. Quiroz et al, Revista Momento 49, 35
using the approximation of expansion in plane wave (2014).
method with MPB (MIT Photonics Band) code.
ACKNOWLEDGMENTS
RESULTS AND DISCUSSION This work was supported by Universidad Nacional de
Fig. 1a presents the dependence of the absorbance with Colombia DIB project Code Quip No. 201010020493.
the incident angle of the light. A shift in the maximum of Financed by COLCIENCIAS project code Quip No.
the absorbance curves towards smaller values was 201010019609 and Universidad Nacional de Colombia
observed when the angle of the light increased between DIB project Code Quip No. 19023
69

A Hierarchical Structure of Tb3+ functionalized MOF Coatings on ZnO


Micronano Arrays for Highly Selective Sensing Acetone
Yi Wang, Yangyi Yang*
KLGHEI of Environment and Energy Chemistry, School of Materials Science and Engineering, Sun Yat-Sen University, Guangzhou,
510275, P.R. china.
*Corresponding authors: E-mail: cesyyy@mail.sysu.edu.cn. Tel: 86-20-84112977

ANM-nanomaterial-Oral/Poster Right: SEM of MOF-5/ZnO (a), film 1(b), cross section of the
film 1(c) and EDS of the film 1(d).
INTRODUCTION Luminescent sensing small molecules
Lanthanide metalorganic frameworks (MOFs) have
emerged as very important multifunctional luminescent
materials in the past decade due to their unique
luminescence properties, such as large Stokes' shifts,
high color purity, and long luminescence lifetimes,
make them especially attractive for sensing
applications.1,2 For practical sensor applications, it is
necessary to fabricate MOFs as thin films on different
Left: Emission spectra of the film 1 after being immersed
types of substrates.3 These MOF films are almost in small molecules (excited at 299 nm).
always based on transition metal MOFs and cannot Right: Plot of I0/I of the film 1 (at 546 nm) vs.
satisfy all the applications in sensing usage. As many concentration of acetone in lower concentration ranges (0-
of lanthanide complexes have poor film forming ability, 1 vol%) (up to 0.14 M, 1 vol%).
few investigations concerning the growth of Ln-MOF
films for luminescent applications were achieved so CONCLUSION
far.4 It is still a great challenge to prepare Ln-MOF In summary, a series of hybrid luminescent
films on supports in an easy and simple way. Tb@MOF/ZnO coatings were achieved on the
ordered ZnO micronano arrays by using solvothermal
EXPERIMENTAL/THEORETICAL STUDY synthesis and post-synthetic modification approach, A
A series of luminescent thin films based on Tb3+ doped highly characteristic green emission of Tb3+ ion was
in metallic organic frameworks with different obtained through doping few Tb3+ into the hybrid
carboxylic acids [1,4-benzenetricarboxylate,1,3,5- micronano coating of MOF-5/ZnO (Zn:Tb = 100:1).
benzenetricarboxylate, 2,6-naphthalenedicarboxylic We first demonstrate the hybrid luminescent coating
acid] are fabricated on ordered ZnO arrays. The devices of Tb@MOF-5/ZnO to be utilized as probe
luminescent thin films Tb@MOF/ZnO (Tb doped in for detecting small organic molecule. Our research
MOF/ZnO) are synthesized by solvothermal synthesis provides a new strategy for fabricating luminescent
and postsynthetic modification (PSM) approach. The coatings or films.
structure, composition and morphology of Tb@MOF-
5/ZnO (1) are characterized by XRD, EDS, SEM and REFERENCES
ICP. This kind luminescent coating was first prepared [1] Y. Zhu, et al. J. Mater. Chem. A, 1, 11312
and used as a small molecule sensor successfully. (2013).
[2] M. Zheng et al. Acs Appl. Mater. Interfaces 5,
RESULTS AND DISCUSSION 1078 (2013).
The fabrication and morphology of Tb@MOF-5/ZnO [3] S. Dou et al. J. Am. Chem. Soc. 136, 5527
(2014).
[4] Y. Yang et al. J. Mater. Chem. C , 2, 8683
(2014).

ACKNOWLEDGMENTS
The authors acknowledge the financial support of the
National Natural Science Foundation of China
(51472275, 20973203 and 91022012) and Guangdong
Natural Science Foundation (2014A030313207).
Left: Scheme of the prepared luminescent thin film
Tb@MOF-5/ZnO
70

Introducing Nanoscaled Surface Morphology into Mesoporous Silica Films

Emke Albert1, Pter Basa2, Andrs Dek3, Attila Nmeth4, Zoltn Osvth3, Gyrgy Sfrn3,
Zoltn Hrvlgyi1, and Norbert Nagy3*
1
Budapest University of Technology and Economics, Department of Physical Chemistry and Materials Science, Hungary
2
Semilab Semiconductor Physics Laboratory Co. Ltd., Hungary
3
Centre for Energy Research, Institute of Technical Physics and Materials Science, Hungary; *nagyn@mfa.kfki.hu
4
Wigner Research Centre for Physics, Institute for Particle and Nuclear Physics, Hungary

INTRODUCTION fluences applied. For CTAB-templated films the degree of


Inorganic sol-gel materials attracted great attention due to densification was significantly higher than in the
their unique properties. Among them mesoporous silica is Pluronic-templated ones. The HRTEM analysis revealed
utilized as low-k and low refractive index material, that the pore structure remained intact where the silica
antireflective and self-cleaning coating, functional spheres were non-transparent for the bombarding ions.
membrane, in the field of catalysis, sensorics, drug The pore structure remained interconnected near the Si
delivery, and corrosion protection. Surface nanostructures substrate surface at the lowest fluence. Contrarily, at the
play determining role in catalysis, sensorics, antibacterial, highest fluence, the regions surrounding the intact porous
superhydrophobic, and superhydrophilic surfaces. In this columns were fully densified thus forming non-porous
study we aimed to combine the advantages of mesoporous border zones.
character and surface morphology at the sub-micron scale.
EXPERIMENTAL
Mesoporous silica thin films were prepared by sol-gel
method with ordered and disordered pore system using
Pluronic PE 10300 and CTAB as molecular templates.
Hexagonally ordered LangmuirBlodgett (LB) films of
spherical silica particles were applied as mask against ion Fig. 2 AFM images of irradiated mesoporous films
irradiation. The ion energy was chosen according to measured (a) at the edge of the particulate LB mask and
Monte-Carlo simulations to achieve high lateral contrast (b) at the border of irradiated and unirradiated regions.
in ion transmittance. The surface morphology was created
by the ion hammering effect, i.e., the bombarding ions
densified the material where they could penetrate through
the particulate mask. The resulted surface morphology
and pore structure were studied by AFM, profilometry,
HRTEM, confocal fluorescent imaging, and ellipsometric
porosimetry.

Fig. 3 Cross-sectional HRTEM images of (a) Pluronic-


and (b) CTAB-type coatings irradiated with fluences of
0.1 1016 cm-2 and 1.0 1016 cm-2, respectively.
CONCLUSION
The disordered pore system proved to be more resistant
against ion bombardment. The main character of the pore
system can be tailored to be interconnected or separated
by controlling the ion fluence. By increasing the fluence
value, however, separated porous volumes can be created
Fig. 1 Schematics of the ion bombardment through a at the expense of the total pore volume.
masking SiO2 sphere (left); and the key steps of sample
preparation (right). ACKNOWLEDGMENTS
The financial support of TMOP-4.2.4.A/2-11/1-2012-
RESULTS AND DISCUSSION 0001 National Excellence Program, Jnos Bolyai
The aspect ratio of resulted morphology was proved to be Research Fellowships of HAS, REA # 334377, TMOP
high; the created surface structures were very similar 4.2.1/B-09/1/KMR-2010-0002, OTKA K 112114 and
irrespectively of the type of template molecules and ion PD 105173 is highly appreciated.
71

Corrosion and Biological properties of Oxide and Nanooxide Layers on the


Ti13Nb13Zr Alloy
Agnieszka Ossowska, Andrzej Zielinski,

Department of Materials and Bonding Engineering, The Gdansk University of Technology, Poland,
agnieszka.ossowska@pg.gda

INTRODUCTION RESULTS AND DISCUSSION


Titanium alloys are widely used for implants in the Fig. 1 shows microstructure obtained after thermal
orthopedics and dental fields because of their oxidation, which clearly reveals the presence of
superior biocompatibility, corrosion resistance, and oxide scale throughout the surface without
specific strength compared with other metallic spallation at a different temperature. Fig. 2
implant materials [1]. Very important factor in the demonstrates anodic polarization curves for
formation of bonds between the implant and the thermally unoxidised (Fig. 2a) and oxidised
bone is a surface topography. The best properties to specimens in a solution adjusted to different pH: 3,
cells adhesion, proliferation, and migration are 5, 7. The specimens oxidised electrochemically
demonstrated by anatase-until structural mix [2]. showed similar behaviour. For the specimens, two-
One of the surface modification treatments that stage oxidized the appearance of nanotubular oxide
changes the structure of surface layer is thermal layer was dependent on the thickness of the
oxidation [3]. The result of thermal oxidation previous oxide layer. The biological tests
treatment of titanium alloys is a titanium dioxide demonstrated good biocompatibility.
(TiO2) layer, which appears in three crystal phases:
anatase, rutile, and brookite. The thermally oxidized a) b)
surface of titanium shows better properties than the
others since it produces a thick, highly crystalline
oxide film. This method was already investigated
with a focus to improve the hardness and wear
resistance [4]. So far, the effects of thickness,
continuity, structure, and morphology of thickness
of the oxide layers on the corrosion behavior of
thermally oxidized titanium alloy Ti13Nb13Zr were Fig. 2. Polarization curves of the surface: a)
not investigated. unoxidised; b) thermally oxidized specimen in
different pH
EXPERIMENTAL STUDY
Tests were performed on two-phase titanium alloys CONCLUSION
Ti13Nb13Zr. Some specimens were oxidized in The oxide layers after gas oxidation are uniform,
laboratory air at three different temperature: 700C, continuous and well adjacent to the substrate. The
900C, and 1100C for 5, another electrochemical layer obtained at 700C consists of the mix of
in 1N H2SO4 with an addition of HF, and the last rutile-anatase, and at temperature 900C and 1100
part oxidised first in gas and then in solution. The C only of rutile crystals. After electrochemical
oxide layers` microstructure, corrosion resistance oxidation, the nanotubular layer appears. The
in Ringer's solution, and wettability angle and biochemical performance of all layers is
biological behaviour in vitro were examined. The satisfactory.
XRD method was used to detect the phases.
REFERENCES
a) b) 1. Kim W.-G., Choe H.-Ch., Trans. Nonferr. Met.
Soc. China 19, 1005-1008 (2009).
2. Wang Y., Tao J., Ling W., HE P., Tao W.,
Trans. Nonferr. Met. Soc. China, 18, 631635
(2008).
3. Ossowska A., Sobieszczyk S., Supernak M.,
Zielinski A.,Surf. Coat. Tech.; 258, 1239-1248
(2014).
Fig.1. The microstructure (SEM) of the surface of 4. Siva Rama Krishna D, Brama YL, Sun Y.
the sample after thermal oxidation in air at 5h: a) Tribol. Int. 40, 32934 (2007).
700C; b) 900C
72

Intracellular sulfidization of silver72nanoparticles by microglia inhibits


nanoparticle toxicity and reduces inflammation and neurodegeneration
Daniel Gonzalez-Carter1,2,*, Bey Leo1, Pakatip Ruenraroengsak1, 3, Shu Chen1, Angela Goode1, Ioannis Theodorou1, Fan Chung3, Raffa Carzaniga4, Milo Shaffer1 , David
Dexter2, Mary Ryan1, Alexandra Porter1
1
Department of Materials, 2Centre for Neuroinflammation and Neurodegeneration, 3 National Heart and Lung Institute, Imperial College London, UK; 4Electron Microscopy
Unit, The Francis Crick Institute, London, UK *Presenting author, daniel.gonzalez-carter08@imperial.ac.uk

Introduction (a) (b) (c) 200 (d) 0.8


Silver nanoparticles (AgNPs) accumulate in the brain following Control AgNP *
inhalation and cause neuronal death1. Microglia (brain-resident 150 0.6 ***

CSE/ -Actin
immune cells) phagocytose and process nanomaterials2. In

CSE (MFI)

O.D. ratio
100 0.4
addition, microglial inflammation contributes to neuronal death
seen in Alzheimers disease (AD)3. Hence, it is important to 50 0.2

understand how AgNPs are processed by microglia, and how they 0 0.0
affect microglia inflammation and neurotoxicity to better predict Control AgNP
(50 g/mL)
Control AgNP
(50 g/mL)
their bioreactivity and role in neurodegeneration. We demonstrate
Fig. 2 Confocal microscopy of (a) control and (b) AgNP-treated microglia
microglia reduce AgNP toxicity in vitro by sulfidizing and
(green, pink, blue = CSE, AgNPs, DAPI). (c) Quantification of CSE intensity in
capturing released Ag+ ions by formation of silver sulfide (Ag2S) confocal images. (d) Quantification of CSE expression by Western blotting.
through reaction with hydrogen sulfide (H2S), a mechanism which
correlates with a decrease in microglia inflammation and Results and Discussion
microglia-mediated neurotoxicity. Microglia internalized AgNPs into endosomes and the cytosol.
Analytical microscopy and spectroscopy revealed sulfur
deposition and Ag2S formation on and around AgNPs (fig. 1),
probably mediated by reaction of Ag+ with H2S, as AgNPs
increased the expression of the H2S-synthezising enzyme CSE
(fig. 3). The sequestration of released Ag+ by formation of Ag2S
acted as a detoxifying mechanism, as AgNP treatment did not
affect membrane integrity, metabolic activity or mitochondrial
potential at doses shown to be toxic to other cell types4.
Furthermore, AgNP treatment induced a reduction in LPS-
induced inflammation (fig. 5) (probably due to the known anti-
inflammatory effect of H2S5), which translated into a reduction
in LPS-induced microglial neurotoxicity.

(a) (b) (c)


1.5
200 6
*** ***
*** ** * *

TNFng/mL
150
Nitrite (M)

1.0
(% control)

4
ROS

100

2 0.5
50

0 0
Control AgNP Control AgNP 0.0
Control AgNP
LPS LPS
LPS
Fig. 3 AgNP treatment reduces LPS-induced microglia inflammation, as
measured by production of (a)ROS, (b) nitrite and (c) TNF.
Fig. 1 (a) TEM of internalized AgNP into microglia. (c) EDX spectra indicating
sulfur deposition around AgNP marked in (b). (e) FFT indicating Ag2S coating of Conclusion
AgNP regions marked in (d).
Formation of Ag2S by induction of H2S production to capture
released Ag+ prevents AgNP toxicity towards microglia, with a
Methods concomitant decrease in inflammation and microglia-mediated
Microglia (N9 cell line) were treated (1hr pulse, 24 hr chase) with
neurodegeneration. The current results provide novel insights
citrate-capped AgNPs (50 nm diameter, 50 g/mL), with or into the bioreactivity and stability of brain-penetrating AgNPs,
without lipopolysaccharide (LPS). Internalization and processing and indicate AgNPs may be employed to inhibit inflammation-
were examined by TEM, EDX spectroscopy and FFT patterns. Cell induced neuronal death in AD.
death was quantified by measuring metabolic activity, cell
membrane integrity and mitochondrial potential. Inflammation References
was determined by measuring reactive oxygen species (ROS), 1
Sun et al. Toxicol Sciences, 108:2 (2009). 2Goode et al. Biomaterials, 70:57-70
nitrite and TNF production. Microglia-mediated neurotoxicity (2015). 3Mosher et al. Biochem Pharmacol,88:11 (2014). 4Vrcek et al. Environ
Toxicol, 10.1002/tox.22081 (2014). 5Sivarajah et al. Shock, 31:8 (2009)
was examined by co-incubating AgNP/LPS-treated microglia with
the neuronal cell line N27 (48 hr) and quantifying membrane
integrity and metabolic activity.
73

Sol-gel preparation of size-controlled spherical silicified-liposomes


particles

Hye Sun Lee, Jingming Zhao and Jeong Ho Chang*

Center for Convergence Bioceramic Materials, Korea Institute of Ceramic Engineering and Technology, Koreaa,
Email: jhchang@kicet.re.kr

The amphiphilic natural structure of lipids was exploited These findings confirm our understanding of silica
to assemble hydrolyzed TEOS at the bilayer/water adsorption on liposome surfaces and the formation of an
interface and ensuing condensation within the hydrophilic interfacial layer with increased surface coverage at high
shell of the lipid bilayer drives silica formation, producing silica: lipid ratio compared to the low. It is not benefit for
a novel class of silicified-liposomes. A novel and simple spherical liposomes formation with high TEOS
route was developed without chloroform for spherical concentration. The size of silicified-liposomes decreased
silicified-liposomes formation in this study. Structure with increasing reaction time. This significant decreased
characterization was confirmed by scanning electron in particle size is a good indication of the incorporation of
microscopy that the spherical liposome formed by this silica and suggest that the TEOS formed a close
new and simple preparation, and DSC-TGA and FT-IR association with the liposome matrix materials.
measurements provide evidence for the amount of lecithin
and silica coating.

INTRODUCTION
We provide a simple route to prepare a class of liposomes
by exploiting interfacial sol-gel chemistry confirmed to
the hydrophilic bimolecular structure of the lipid bilayer
wall of the liposomes. The bilayer of the vesicular wall
results from self-assembly of amphiphilic lipids
consisting of a hydrophilic head and a pair of
hydrophobic tails. The bilayer is formed by self-assembly
of phospholipids with their tails pointing toward the
center of the sheet when phospholipids are exposed to
water as a consequence of the so-called hydrophobic
effect. The central core of the bilayer is hydrophobic and Fig. 1 Influence of reaction time on size distribution of
thus oil-soluble, while the interface of the bilayer with the silicified-liposomes particles
aqueous environment is hydrophilic producing a well-
hydrated shell. An important consequence of the bilayer CONCLUSION
assembly is that the liposomes are able to encapsulate We have demonstrated a novel and simple route to
hydrophilic molecules within their aqueous lumen and the preparing spherical silicified-liposomes without
hydrophobic one within the core of the bilayer lipid chloroform. The available range of silica-based
membrane. nanomaterials increases continuously, MSNPs having
become the preferred choice for delivery purposes. On the
RESULTS AND DISCUSSION other hand, compact SNPs, as well as nanomaterials
A more spherical shape was observed for the silicified- coated with compact silica shells, find their place in
liposomes with higher concentration of TEOS than for applications where the active ingredients must be kept
lower concentration of TEOS, suggesting a possible separated from the biological surroundings
external structural reinforcement of the ultra deformable
lipid bilayer by the silica shell. But the silicified- ACKNOWLEDGMENTS
liposomes with too high concentration of TEOS (2 g) This work was supported by a grant from the R&D
showed a non-smooth spherical structure, while the silica program funded by the Ministry of Trade, Industry and
coated liposomes exhibited a dense and spherical Energy (MOTIE), Republic of Korea.
structure with rough surfaces. All the particles aggregated
together, and its not easy to separate them. In the other
hand, the silicified-liposomes with 1 g TEOS showed a
smooth and separated spherical structure, indicating the
presence of silica nanoparticles distributed across the
liposome surface.
74

Controlled astaxanthin release with silicified phospholipids assembled


boron nitride complex for cosmetic application
Hye Sun Lee and Jeong Ho Chang*

Center for Convergence Bioceramic Materials, Korea Institute of Ceramic Engineering and Technology, Koreaa,
Email: jhchang@kicet.re.kr

This work demonstrates the controlled release of anti- phospholipids-coated boron nitride revealed the
oxidant astaxanthin from the synthesized nanoporous disappearance of the ordered lamellar structure in the
silicified phospholipids particles assembled boron nitride boron nitride powder as a result of the liquid
(nSPLs@BN) powder for various application such as phospholipids coating. However, the initial lamellar
cosmetic and drug carrier. The nanoporous silicified structure on the powder was formed by the silicification
phospholipids (nSPLs) were obtained by silicification caused by the interaction between the hydrophilic heads
with tetraethyl orthosilicate (TEOS) on the hydrophilic of the phospholipids and silica precursor.
region of phospholipid bilayers and the process involves
the co-assembly of chemically active phospholipid
bilayers within the porous silica matrix. Controlled
release of anti-oxidant astaxanthin was achieved with
nSPLs@BN powder as a function of release time and the
used concentration for the cosmetic applications.

INTRODUCTION
Boron nitride (BN) is a ceramic material that had a
structure of a plate-shaped. Hexagonal BN was first used
in cosmetics around 1940 in Japan. Its use was revitalized
in the late 1990s with the optimization h-BN production
processes, and currently h-BN is used by nearly all
leading producers of cosmetic products for foundations,
make-up, eye shadows, blushers, kohl pencils, lipsticks
and other skincare products. Because of its excellent
thermal and chemical stability. However, the
characteristic of this fast initial release behavior has most
of the plate-like powder. Such being the case, the reason
that the surface processed even though many advantages
of BN. Herein, we report the novel and simple step for Fig. 1 SEM images of boron nitride powders (BN),
anti-oxidative phospholipid nanocomposite by a magnesium chelated boron nitride (BM) phospholipids-
silicification process with a silica precursor of tetraethyl coated boron nitride powders (BML), and nanoporous
orthosilicate. The phospholipid astaxanthin silica-boron silicified phospholipids-coated boron nitride powders
nitride was achieved by combining a sequential (BMLT)
measurement of field-emission scanning electron
microscopy (FE-SEM). In addition, the controlled release CONCLUSION
application was demonstrated with astaxanthin on In summary, hybrid Astaxanthin loaded silicified lipid
nanoporous silicified phospholipids. boron nitrides and their application for antioxidant and
sustained release. The method provides a simple, low cost
RESULTS AND DISCUSSION and easy-to-handle approach for the fabrication of nano-
The synthesized product of the nanoporous silicified composites due to the anti-oxidative activity and easily
phospholipids was achieved by a solgel reaction. The functional materials release. We describe the approach for
results of the FE-SEM image shows synthesized Boron applications in various fields, including drug delivery,
Nitride (BN)/Silicate precursor, non-treatment Boron optical material or cosmetic.
Nitride (BN) of the nanoporous silicified phospholipids-
coated boron nitride powder, where the boron nitride ACKNOWLEDGMENTS
powder has endured magnesium chelation, phospholipids
coating, and a silicification process. It is showed the This work was supported by a grant from the R&D
comparative results after the phospholipids and program funded by the Ministry of Trade, Industry and
silicification coating processes: the image of the Energy (MOTIE), Republic of Korea.
75

Thermoresponsive Elimination of Hexavalent Chromium with PNIPAm grafted


Amino-functionalized Mesoporous Silica

Jin-Won Kim, Hye Sun Lee and Jeong Ho Chang*

Center for Convergence Bioceramic Materials, Korea Institute of Ceramic Engineering and Technology, Koreaa,
Email: jhchang@kicet.re.kr

In this study, the effective elimination of Cr(VI) was However, it swells at 40 C and allows the release or
achieved by thermo-responsive polymer-grafted amino- uptake the molecules. The Cr(VI) was rapidly adsorbed in
functionalized mesoporous silica (MS@APTES@ the first 5-10 min, and then the adsorption rate decreased
PNIPAm) in aqueous solution. The MS@APTES@ at 25 C. While the adsorption equilibrium of Cr(VI) was
PNIPAm was successfully synthesized by the coupling of attained within the first 200-360 min at 40 C, the
3-MOP and N-isopropyl acrylamide (NIPAm) in 3- adsorption rate decreased gradually. This result can be
aminoproyltriethoxysilane (APTES) grafted mesoporous attributed to the multistep adsorption process or the
silica surface. The thermo-responsive elimination of intraparticle diffusion of Cr(VI) ions.
Cr(VI) was demonstrated at various pH levels and at
room temperature and 40C, respectively. The maximum
adsorption of hexavalent chromium on MS@APTES@
PNIPAm in aqueous solution was 127 mg/g at 40C in pH
2.5.

INTRODUCTION
Poly(N-isopropyl acrylamide) (PNIPAm) is one of the
most extensively studied thermo-responsive polymers,
which has a lower critical solution temperature (LCST) of
32oC. Grafting of PNIPAm on the silica nanoparticle can
be performed by copolymerization with 3-(trime
thoxysilyl)propyl methacrylate (MOP) which is Fig. 1 Scheme for the preparation of thermo-responsive
commonly used in the preparation of organic-inorganic mesoporous silica for the efficient elimination of
hybrid compounds as a silane coupling agent. Generally, hexavalent chromium
organic-inorganic hybrid compounds have several
benefits, such as improvement of both mechanical CONCLUSION
strength and thermal stability. Thermo-responsive elimination of hexavalent chromium
In this work, we prepared the thermos-responsive was successfully achieved with thermo-responsive
mesoporous silica materials for the selective elimination polymers-grafted mesoporous silica (MS@APTES@
of hexavalent chromium in aqueous solution through the PNIPAm) materials at various reaction times,
PNIPAm polymerization within the amino-functionalized temperatures and pH levels. The synthesized MS@
mesoporous silica, and demonstrated this at various pH APTES@PNIPAm materials were characterized in detail
levels and at room temperature and 40C. Furthermore, by FT-IR, TGA, N2 desorption-adsorption BET, and SEM
we conducted the additional kinetic experiments to analysis. The BET surface area, pore volume and average
determine the adsorption behavior of hexavalent pore diameter of MS@APTES@PNIPAm were 28.5
chromium on MS@APTES@PNIPAm. m2/g, 0.04 cm3/g and 3.61 nm, respectively. SEM images
showed the rod-like structure of MS@APTES@PNIPAm.
RESULTS AND DISCUSSION The elimination of hexavalent chromium was
To elucidate the influence of reaction time, we soaked the demonstrated as a function of reaction time, and the
MS@APTES@PNIPAm materials in Cr(VI) aqueous elimination efficiency rates of 79.7% and 38.6% were
solution for various time durations ranging from 5 to 1200 achieved at pH 2.5 and the initial temperature of 40 and
min. The elimination of Cr(VI) as a function of reaction 25C, respectively.
time and elimination efficiency values were 79.7 and
38.6% at the initial temperatures of 40 and 25C, ACKNOWLEDGMENTS
respectively. At 25C, the adsorption capacity of Cr(VI)
was lower than that at 40 oC because of swelling and This work was supported by a grant from the R&D
shrinking transformation of PNIPAm on the inner surface program funded by the Ministry of Trade, Industry and
of MS, as shown in Scheme 1. The PNIPAm shrinks at Energy (MOTIE), Republic of Korea.
25C and prevents the release or uptake of the molecules.
76

Photoluminescent and electrical properties of ZnO thin films subjected to the


thermal annealing and a hydrogen plasma treatment

Khabibulla Abdullin1, Maratbek Gabdullin1, Lesya Gritsenko1,2, Serik Kumekov2 and Zhanar Mukash2
1
National Nanotechnology Laboratory of Open Type, Kazakh National University after al-Farabi, Kazakhstan
2
Department of General and Theoretical Physics/Institute of Hi-Tech and Sustainable Development, Kazakh National
Research Technical University after K.I. Satpaev, Kazakhstan, presenting author
gritsenko_lv@mail.ru

INTRODUCTION Therefore, we can conclude that the increasing of the


NBE intensity occurs due to the formation of oxygen-
Zinc oxide (ZnO) has unique properties such as wide hydrogen-related complexes, which are formed on the
band gap of ~3.37 eV, large exciton binding energy (~60 grain boundaries. Moreover, the intensity of the NBE
MeV), effective ultraviolet photoluminescence, which band shows behavior similar to that of persistent
makes it attractive for practical application. Currently, photoconductivity in ZnO. Namely, the NBE intensity,
ZnO is one of the actively studied wide band gap which increased by two orders after annealing in air
semiconductor. High exciton binding energy makes ZnO followed by hydrogen plasma treatment, gradually
promising for creation of new generation of bright decreases after storage for several days after the plasma
optoelectronic devices such as light-emitting diodes based treatment. However, NBE intensity can be fully restored
on hetero-structures1 and homo-structures2,3. by exposure under UV light with a wavelength of ~360
Improvement of photoluminescent properties and nm.
conductivity of ZnO thin films can be achieved by
thermal and plasma treatments. Therefore, development CONCLUSION
of methods for controlling properties of ZnO films by
various treatments is significantly important. The near band edge PL intensity increases after annealing
in the range of 200-325 due to the decrease of the
EXPERIMENTAL/THEORETICAL STUDY carrier concentration, and then NBE intensity sharply
decreases at annealing temperature higher than 325C due
Photoluminescence (PL) spectra and electrical properties to the surface band bending which leads to the destruction
of boron-doped ZnO thin films were investigated in of excitons.
dependence on annealing temperature in the range 100-
500C in the air as well as the RF hydrogen plasma It was found that the gas atmosphere during the exposure
treatment. with UV light and subsequent aging significantly affects
the intensity of the NBE band. The response of
photoluminescence to UV light and gas atmosphere is
RESULTS AND DISCUSSION similar to the effect of persistent photoconductivity in
Annealing in an oxidizing atmosphere leads to resistivity ZnO.
increasing due to the enrichment of the surface with
oxygen and capturing conduction electrons by oxygen- REFERENCES
related grain boundary states. As a result of annealing in
air, the bulk carrier concentration decreases, and the 1. M.-C. Jeong, et. al, Appl. Phys. Lett., 88, 202105
carrier mobility dramatically reduces due to scattering on (2006)
the charged grain boundaries. 2. F. Zhuge, et. al, Appl. Phys. Lett., 87, 092103 (2005)
3. S.J. Jiao, et. al, Appl. Phys. Lett., 88, 031911 (2006)
It was found that plasma treatment in hydrogen
atmosphere leads to the increase both of carrier ACKNOWLEDGMENTS
concentration and carrier mobility. Hydrogen-induced
passivation of charged states on the grain boundaries This work was financially supported by the Grant
completely eliminates the grain boundary scattering. The Financing of scientific research of Ministry of Education
intensive near band edge (NBE) PL emission also appears and Science of the Republic of Kazakhstan (Grant
after plasma treatment in hydrogen atmosphere. It was #3825/GF4 and #1677/GF4).
established that the intensity of NBE band after hydrogen
treatment of zinc oxide films depends on the time and
temperature of the preliminary annealing in the air.
77

Synthesis of fullerenes by arc discharge

M.T. Gabdullin1, T.S. Ramazanov1, Kh.A. Abdullin1, D.V. Ismailov1, D.G. Batryshev1,2, S.A. Sarbay1,2,
D.S. Kerimbekov1,2, Z. Smakova1, K.M. Amirkhanova1, D.V. Schur3
1
Al-FarabiKazNU, NNLOT, Almaty, Kazakhstan
2
Al-Farabi KazNU, LEP, Almaty, Kazakhstan
3
I. M. Frantsevich Institute for Problems of Materials Sciences, Kiev, Ukraine
saltanat.sarbay@mail.ru
INTRODUCTION
Nowadays, fullerenes attract much attention of
scientists all over the world. This material has a very
high potential for using as additives in various
industries1.
Fullerenes can be synthesized by a variety of
methods, but only two of them are used for the
synthesis of traditional metal-fullerenes, and only one
of them is used for production of trimetallic nitride
endohedral metal-fullerenes. The most common
method of producing fullerenes and metal-fullerenes
is based on the use of arc evaporation of a graphite
rod under the action of AC or DC current in the Fig.1. SEM image of fullerene crystals
working helium atmosphere at a temperature above
3000 C. For traditional production of metal-
fullerenes, a hollow graphite rod is filled with a metal
oxide/graphite mixture, which is subjected to arc
evaporation under the same conditions as those used
to obtain usual carbon fullerenes. During rod
combustion, the carbon black is formed in the process
and collected from the bottom of the generator2.
EXPERIMENT
In the experiments on arc spraying of graphite
in helium medium, the products of plasma chemical
reaction were obtained at the following discharge
parameters: p=300 rr, U = 30 V and I = 300 A. It
was found that in the synthesis reaction during anode Fig.2. Raman spectra of fullerene crystals
evaporation, a deposit of different configurations was
formed on the cathode. This deposit can grow CONCLUSION
coaxially to the cathode and with deviation from its In this work, the carbon fullerenes, multi-
axis, but coaxially to the anode. It is found that the walled nanotubes and graphene planes and rings were
cross-section of the deposit has two zones - loose and synthesized in helium arc discharge. Investigation of
smooth zones. synthesis process of fullerene and its derivatives
As the reaction products, there were obtained allows us to development a mechanism of their
fullerene soot deposited on the reactor wall and the growth.
deposit material formed on the cathode electrode. REFERENCES
After filtration and benzene evaporation, surface 1. D.V. Schur, M.T. Gabdullin, S.Yu.
morphology, chemical composition and phase Zaginaichenko, T.N. Veziroglu, M.V. Lototsky,
structure of the obtained samples (fullerite crystals) V.A. Bogolepov, A.F. Savenko Experimental SET-
were studied by using scanning electron and probe UP for investigations of hydrogen-sorption
microscopes (Fig. 1 and 2). characteristics of carbon nanomaterials // Int. J.
The samples, obtained as a result of graphite Hydrogen Energy, 10.1016/j.ijhydene.2015.08.087.
decomposition in the arc discharge, were studied by 2. Douglas A Knight, Joseph A Teprovich Jr,
the scanning and transmission electron microscopy Andrew Summers, Brent Peters, Patrick A Ward,
and Raman scattering method. It was found that the
Robert N Compton and Ragaiy Zidan. Synthesis,
samples consisted of multi-walled carbon nanotubes,
graphene planes and rings. Using these results, we characterization, and reversible hydrogen sorption
explained the mechanism of growth of fullerenes and study of sodium-doped fullerene // Nanotechnology.
their derivatives in the arc discharge plasma. 2013. Vol. 24. P. 455601.

ACKNOWLEDGMENTS
This work has been supported by the grant
3227/GF4/2016 of the Ministry of Education and
Science of RK.
78

On the filling of Nanotubes New 1D HeteroNanostructures

Francis Leonard Deepak 1,*


1
International Iberian Nanotechnology Laboratory, Avenida Mestre Jose Veiga, Braga 4715-330, Portugal
email: leonard.francis@inl.int

The hollow interiors of nanotubes could host the growth


or filling of foreign elements/compounds to obtain hetero-
structures. The growth of these materials in the confined
one dimensional space lead to novel properties. There are
different routes to obtain the filling of nanotubes. Among
these capillary filling serves as a suitable method to
enable filling of carbon nanotubes (CNTs) and inorganic
nanotubes including those of BN and WS2.1, 2 In this talk
the synthesis, structure and novel properties/applications
of such 1D heteronanostructures will be discussed.
Various suitable examples will be highlighted. These Fig. 1 a) Volume rendering of EDS-STEM tomograms of
GdI3@WS2 nanotube. b) Vertical orthoslice of the
include recent work on filling of Gd based compounds nanotube. c) and d) Orthoslices along the nanotube cross
within WS2 Nanotubes and CNTs. In such complex section. Greyscale images represent HAADF. The
elements are color coded as blue for W, yellow for Gd,
heterostructures, the precise determination of the structure green for S and red for I.
and composition is detrimental in its further application.
REFERENCES
Thus the investigation of the structure, morphology and
1. Ronen Kreizman, Andrey N. Enyashin, Francis
chemical composition of filled nanotubes investigated Leonard Deepak, Ana Albu-Yaron, Ronit Popovitz-Biro,
using aberration corrected scanning/transmission electron Gotthard Seifert, and Reshef Tenne, Adv. Funct. Mater.,
20 24592468 (2010).
microscopy and associated spectroscopic techniques
(EELS and EDS) will be outlined. The three dimensional 2. Elok Fidiani, Pedro M. F. J. Costa, Anja U. B. Wolter,
Diana Maier, Bernd Buechner, and Silke Hampel, J. Phys.
structure of such systems can be elucidated using electron Chem. C, 117 1672516733 (2013).
tomography. However in such cases obtaining the three
3. Georg Haberfehlner, Angelina Orthacker, Mihaela
dimensional composition information is non-trivial due to Albu, Jiehua Li and Gerald Kothleitner, Nanoscale, 6
1456314569 (2014).
the presence of multiple high atomic number elements.
4. F. L. Deepak, A. Mayoral, R. E. and Arenal (Eds.),
Therefore, EDS-STEM tomography which is a novel and Advanced Transmission Electron Microscopy:
emerging technique, employed to map the chemical Applications to Nanomaterials, Springer 2015.
composition in three dimensions will be highlighted.3 In 5. E. A. Anumol, Andrey Enyashin, Nitin M. Batra, Pedro
order to reduce the beam induced effects on the specimen, M. F. J.Costa and Francis Leonard Deepak, Submitted,
2016.
tomography experiments are usually carried out at 80
kV.4 The experimental observations in these systems are ACKNOWLEDGMENTS
FLD would like to thank Prof. Reshef Tenne (WIS) and
adequately supported by carrying out Molecular Dr. Alla Zak (HIT) for providing the WS2 nanotubes.
Dynamics Simulation in order to elucidate and understand FLD acknowledges the financial support provided by the
ERDF (ON.2 - O Novo Norte Program).
the difference in behavior of the various compounds
towards their affinity to fill the interior of the Nanotubes.5
79

Synthesis of high purity Ca(OH)2 nanoparticles with improved


properties for consolidation of cultural heritage materials
Marcos Lanzn1, Juan Antonio Madrid2.
1
Departamento de Arquitectura y Tecnologa de la Edificacin, Universidad Politcnica de Cartagena,
Espaa, presenting autor, e-mail: marcos.lanzon@upct.es
2
National Center of Reference for Chemical VET, Cartagena, Spain
above 60%. Finally, TEM examination showed
INTRODUCTION
2D hexagonal plates nanoparticles ranging in
Limewater and nanolime suspensions are
size from 300 to 600 nm. The lowest dimension
commonly used in materials consolidation. In
detected in TEM was about 6 nm. These
the synthesis of Ca(OH)2 an important amount
findings suggest the nanoparticles are
of NaCl is generated. Besides, effective
appropriate for consolidation of porous
strategies to remove NaCl are poorly addressed
substrates.
in the scientific literature. This paper describes a
method to obtain pure and, therefore, more P
respectful Ca(OH)2 suspensions. In addition, the

Counts, a.u
effect that the number of washings has on the
yield of the synthesis is reported for the first P
time. P
P
P P
PP

10 20 30 40 50 60 70
2 angle
Fig. 2. XRD; all peaks match with portlandite P.
CONCLUSION
In the synthesis pure Ca(OH)2 nanoparticles, the
number of washings plays a fundamental role.
The yield of the synthesis is sufficient to scale
up the process to industrial level.
The obtained suspensions are more respectful
Fig. 1. Ca(OH)2 synthesis and TEM analysis. and compatible with heritage materials.
EXPERIMENTAL STUDY TEM examination confirms the small size of the
The experimental setup used for the nanoparticles and their physical stability.
nanoparticles synthesis is shown in Fig. 1. Pure REFERENCES
N2 atmosphere was used to avoid carbonation. 1. E. Doehne, C.A. Price. The Getty
The NaCl removal was performed using Milli-Q Conservation Institute, Los Angeles CA (2010).
ultrapure water. The electrical conductivity and 2. V. Daniele, G. Taglieri, J Cult Herit 11
concentration in Na+ and Cl- were monitored by (2012) 102-106.
ionic chromatography. The yield of the method 3. C. Rodriguez-Navarro, A. Suzuki, E. Ruiz-
was evaluated to determine the influence of the Agudo, Lagmuir 36 (2013) 11457-11470.
washings. XRD and TGA analyses were used to 4. G. Borsoi, B. Lubelli, R. Van Hees, R. Veiga,
study the purity of the suspensions in Ca(OH)2. A. Santos, L. Colla, L. Fedele, P. Tomasin,
After that, the nanoparticles were dispersed in Colloids Surface A 497 (2016) 171-181.
2-propanol, sonicated and examined by TEM to 5. M.J. Varas-Muriel, E.M. Prez-Montserrat,
investigate their size. C. Vzquez-Calvo, R. Fort, Constr Build Mater
RESULTS AND DISCUSSION 95 (2015) 611-622.
The XRD spectra showed that portlandite was 6. M. Lanzn, V. Cnudde, T. De Kock, J.
the only component in the suspension. Traces of Dewanckele, A. Piero, Eng Geol 171 (2014)
calcite were detected in TGA analysis due to 21-30.
residing time of the samples in the auto-sampler 7. P. Lpez-Arce, L.S. Gomez-Villalba, L.
(natural carbonation). The electrical Pinho, M.E. Ferndez-Valle, M. lvarez R.
conductivity was substantially reduced after Fort, Mater Charact 61 (2010) 168-184.
four washings, although five to six washings 8. V. Daniele, G. Taglieri, R. Quaresima, J Cult
were necessary to reach the lowest values. In Herit 9 (2008) 294-301.
these conditions, the yield of the synthesis was
80

Testing the efficiency of diluted nanolime suspensions in consolidating


heritage materials: a case study for stone, plasters and adobe samples.
Marcos Lanzn1, Juan Antonio Madrid2.
1
Departamento de Arquitectura y Tecnologa de la Edificacin, Universidad Politcnica de Cartagena,
Espaa, presenting autor, e-mail: marcos.lanzon@upct.es
2
National Center of Reference for Chemical VET, Cartagena, Spain
INTRODUCTION suspensions. The phenolphthalein tests showed
the consolidant penetration was higher in the
The use of nanolime suspensions is widely
stone (up to 6-8 mm). Moreover, the samples
accepted in consolidation of soft and porous
colour was not perceptibly altered due to the
materials. This paper describes the efficiency of
low concentration of Ca(OH)2.
diluted nanolime suspensions in consolidating
diverse architectural heritage materials.
EXPERIMENTAL STUDY
The nanoparticles were synthesised in a glass
reactor using pure N2 atmosphere to avoid
carbonation. The isolated Ca(OH)2 was mixed
with 2-propanol at concentrations of 5 g/l and
sonicated (Fig. 1).

Fig. 1. Glass reactor used for the synthesis and


Tyndall effect of nanolime 5g/l suspensions.
Fig. 2. Top: Roman Theatre of Cartagena and
The consolidation method varied depending on peeling test performed on the same type of rock.
the nature of the treated materials. The Bottom: spraying system used for plasters.
calcarenitic rock was cut in slices and
impregnated in nanolime suspensions for 24h. CONCLUSION
The slices were put on a wipe and left for one Diluted nanolime suspensions are effective in
week under laboratory conditions to allow consolidating architectural heritage materials.
carbonation to happen. Due to the rapid Particles agglomeration is less probable and the
softening of gypsum and adobe, these samples mixture is easily re-dispersed by sonication.
were not immersed but sprayed four times with The original colour of the substrate is practically
the suspension. Again, the consolidant was left unaltered.
to harden for one week under laboratory Using diluted suspensions fewer pores are
conditions. Phenolphthalein solutions were used obstructed at the surface.
to check the consolidant diffusion through the REFERENCES
pores of the specimens. Finally, peeling and 1. M. Lanzn, V. Cnudde, T. De Kock, J.
ultrasonic tests were conducted on consolidated Dewanckele, A. Piero, Eng Geol 171 (2014)
samples and compared with non-treated ones. 21-30.
RESULTS AND DISCUSSION 2. V. Daniele, G. Taglieri, R. Quaresima, J Cult
Herit 9 (2008) 294-301.
The suspensions were stable for several days as 3. C. Rodriguez-Navarro, A. Suzuki, E. Ruiz-
confirmed by Tyndall effect tests (Fig. 1). The Agudo, Lagmuir 36 (2013) 11457-11470.
peeling tests confirmed that stone, gypsum 4. E. Doehne, C.A. Price. Stone Conservation:
plasters and adobe samples can be effectively An overview of current research, The Getty
consolidated using diluted Ca(OH)2 Conservation Institute, Los Angeles, CA, 2010.
81

Optimization of synthesis conditions for high electrical conductivity of polypyrrole


nanotubes

Jan Proke1, Martin Varga1, Jitka Kopeck2, Duan Kopeck2 and Martin Vrata2
1
Faculty of Mathematics and Physics, Charles University in Prague, Czech Republic, vargam@kmf.troja.mff.cuni.cz
2
Faculty of Chemical Engineering, University of Chemistry and Technology Prague, Czech Republic

INTRODUCTION with even higher template concentration, composite of


Conducting (conjugated) polymers promise a wide range polypyrrole and methyl orange is formed. The overall
of applications such as chemical sensors, batteries, solar conductivity is thus lower although well-conducting PPy
cells, anticorrosive coatings, field effect transistors1. From is present as confirmed by temperature dependence of
that perspective, it is essential to understand influence of conductivity. Clearly, for achievement of the highest
various synthesis conditions on their final properties, conductivity the neat nanotubular state is essential.
mainly electrical conductivity. Polypyrrole (PPy) Moreover, its quality is enhanced when polymerization
nanotubes prepared using methyl orange (MO) as temperature is lowered and more ordered state is
template has recently attracted considerable attention with obtained. We believe that besides the optimization of
properties superior to its granular counterpart2. In the conditions these findings can provide more general
previous studies it was found that template-to-monomer insight to synthesis of such nanostructured conducting
ratio3 and oxidant4 affect the final thickness and materials.
conductivity of nanotubes. In the present study we focus
on the structure-property relationship and optimization of CONCLUSION
synthesis conditions to increase electrical conductivity by We have found non-monotonic dependence of
changing polymerization temperature alongside with the conductivity of polypyrrole on concentration of methyl
molar concentration of methyl orange. orange. The maximum is characteristic for the neat
nanotubular state while other concentrations of template
EXPERIMENTAL lead to composite, either with less conducting granular
Pyrrole was chemically polymerized with iron(III) polypyrrole or insulating template itself. This maximum
chloride hexahydrate in the presence of methyl orange as was furthermore found higher and slightly shifted to
template3. Polymerization temperature varied from 5 to lower concentrations for low polymerization
35C and concentration of methyl orange from 0.5 to temperatures.
25 mM. Morphology and chemical composition of
samples were studied by scanning electron microscopy
REFERENCES
and energy-dispersive X-ray spectroscopy, respectively.
1. A. J. Heeger, Rev. Mod. Phys. 73, 681 (2001)
Electrical conductivity, within temperature range 77
318 K, was measured by the four-probe method in van der 2. Y. Z. Long et. al, Prog. Polym. Sci. 36, 1415 (2011)
Pauw configuration.
3. J. Kopeck et. al, RSC Adv. 4, 1551 (2014)
4. M. Varga et. al., J. Polym. Sci. B: Polym. Phys. 53,
RESULTS AND DISCUSSION
1147 (2015)
Dependence of electrical conductivity on concentration of
MO was found non-monotonic with maximum slightly
shifted to higher concentrations with increasing ACKNOWLEDGMENTS
temperature and the corresponding conductivity Financial support of Czech Grant Agency (1300270S,
decreases, from about 70 S/cm at 5C to about 16 S/cm at 1410279S) is fully acknowledged.
35C. Traces of residual MO were observed by chemical
analysis and increased substantially with increasing molar
concentration. On the other hand, content of chloride
(indicating protonation level) decreased monotonically.
Generally, the effect of increasing template concentration
was found twofold. Firstly, the ratio of nanotubular to
globular phase in sample is increasing up to the fully
nanotubular state. In the recent study, protonation level,
internal order and conductivity of nanotubular PPy
oxidized with iron(III) chloride was found higher that in
case of granular one4. Therefore with increasing content
of nanotubes overall conductivity increases. Secondly,
82

High-purity alumina production technology: hydrothermal oxidation of aluminum


and following thermal treatment

Andrey Zhuk, Mikhail Vlaskin


Joint institute for high temperatures of Russian academy of sciences, Moscow, Russia

Table. 1. Impurity content in produced high purity


The lack of efficient and clean technologies for the
aluminum oxide.
production of high purity alumina hinders the
development of innovative areas of technological Impurity Limit of analysis (LA) Measured value
development: optical and semiconductor industry, K ppm 1 < LA
quantum electronics, energy, material engineering etc. Na ppm 2 < LA
High purity alumina is used, for example, for synthesis of Fe ppm 4 < LA
high-quality optical ceramics and leucosapphires, which Ni ppm 0,6 < LA
has a wide range of applications: LED production, Cr ppm 5 < LA
substrates of chips, laser diodes, implants and artificial
Ca ppm 2 < LA
joints, microsilica, protective glasses, jewelry, etc.
Mg ppm 1 < LA
Currently, to obtain the high-purity aluminum oxide Ti ppm 4 < LA
hydrolysis of aluminum isopropylate [1], thermal V ppm 0,1 4,3
decomposition of aluminum alkoxides [2] and thermal Cu ppm 1 < LA
decomposition of aluminum nitrate [3] are used. Alcohol- Zn ppm 0 < LA
based alumina production technology is the main
Zr ppm 1 < LA
industrially integrated method for obtaining raw material
Y ppm 0,02 0,033
for the production of alumina mono crystals [4].
Mn ppm 0,1 < LA
In this study a simple technology of high purity alumina Ga ppm 0,2 < LA
production is presented. The synthesis process consists of
three steps: i) hydrothermal oxidation of aluminum in the REFERENCES
water; ii) calcinations of Al hydroxide in atmosphere at [1] Grinberg EE, Saradzhev VV, Levin YI, Ryabenko EA.
1400 K; iii) high temperature vacuum processing of Preparation of Fine Alumina Powders by Hydrolysis of
aluminum alpha oxide at 2100 K. Aluminum Isopropylate. Russian Journal of Applied
At hydrothermal oxidation industrial aluminum micron Chemistry. 2002;75:245-7.
powder of technical purity (99.8 %) and distilled water [2] Mekasuwandumrong O, Silveston PL, Praserthdam P,
are used as starting materials. No other chemical agents Inoue M, Pavarajarn V, Tanakulrungsank W. Synthesis of
are added. Hydrothermal oxidation of Al powder is thermally stable micro spherical -alumina by thermal
carried out at 300 0 and 15 MPa. The reactor provides decomposition of aluminum isopropoxide in mineral oil.
continuous and large-scale production of hydroxide. The Inorganic Chemistry Communications. 2003;6:930-4.
reaction products are gamma-AlOOH and steam- [3] Pacewska B, Keshr M. Thermal transformations of
hydrogen mixture. Conversion degree of aluminum is of aluminium nitrate hydrate. Thermochimica Acta.
about 100 %. Steam-hydrogen mixture can be utilized as 2002;385:73-80.
working body in heat engine, for example in steam or gas [4] Fujiwara S, Tamura Y, Maki H, Azuma N, Takeuchi
turbine [5] . Y. Development of New High-Purity Alumina.
SUMITOMO KAGAKU. 2007;2007-I:1-10.
The product of hydrothermal oxidation AlOOH [5] Vlaskin M.S., Shkolnikov E.I., Bersh A.V., Zhuk
(boehmite) then go through thermal treatment deleting the A.Z., et al. An Experimental Aluminum-Fueled Power
impurities from the product (aluminum oxide). Impurity Plant // J. Power Sources. 2011;196: 8828 8835.
content in produced high purity aluminum oxide is
presented in table 1. It shows that proposed method allow ACKNOWLEDGMENTS
producing high-purity aluminum oxide of 5N grade This work was performed with financial support from the
(99,999 %). Aluminum oxide, synthesized by means of Ministry of education and science of the Russian
the proposed method, meets the requirements of industrial Federation in the implementation of applied research and
manufacturers of high grade sapphire. experimental development agreement grant No.
14.607.21.0082 (Unique identifier of the project
is RFMEFI60714X0082).
83

Influence of operating parameters and ion doping on the photocatalytic activity of


mortars containing titanium dioxide nanoparticles

Sandra S. Lucas1,2
1
Department of Engineering Science, University of Greenwich, United Kingdom
2
University of Aveiro, CICECO, Portugal
s.lucas@gre.ac.uk

INTRODUCTION concentrations of 0.7 and 0.5 ppmv. It can be concluded


In, self-cleaning materials for construction, titanium that for pollutant concentrations below 1 ppmv the NOx
dioxide nanoparticles have been amongst the most degradation rate increases, however this photocatalytic
studied. Its incorporation in building materials has shown efficiency enhancement is not directly proportional to the
promising results for self-cleaning and depolluting pollutant concentration.
applications. Indoor air quality in buildings is now going The analysis of the titanium dioxide powder shows that
far beyond the simple indoor temperature regulation. the co-precipitation method was effective. The samples
Other aspects like contamination of the indoor air by were prepared with 1% of iron-doped TiO2 and showed a
pollutants, are gaining importance and researchers are photocatalytic activity almost 10% higher compared to
trying to develop methods to mitigate the impact of such the non-doped mortars.
pollutants, to reduce adverse effects on human health.
Internal sources are usually the main cause of
contamination: wall paints, materials and coatings applied
in furniture, tobacco smoke, fireplaces and stoves;
consequently, different types of contaminants (VOC,
NOx, SOx, formaldehyde, etc.) can be present inside the
buildings, sometimes in higher concentrations than
outside. Titanium dioxide (TiO2) exhibits good efficiency
to remove several air pollutants, presenting itself as a
suitable solution for indoor air cleaning [1]. Although the
photocatalytic activity is quite high even with levels of
incorporation as low as 5%, the use of nanoparticles in
mortars is complex and can have a detrimental impact in
their mechanical strength [2]. The photocatalytic efficiency
is dependent on external factors like humidity and Fig. 1 Iron-doped titanium dioxide
pollutant concentration. Modification of the
photocatalytic additive by ion doping can also be used to CONCLUSION
increase performance. To reduce the content of In this work it has been investigated the influence of
photocatalytic additive and maintain the same level of operational conditions in the photocatalytic efficiency of
efficiency, ways of increasing TiO2 catalytic activity and titanium dioxide nanoparticles (TiO2). It was also studied
the impact of the external factors have been studied. the effect of iron doping in photocatalysis and it was
EXPERIMENTAL/THEORETICAL STUDY demonstrated that the efficiency improved without the
Commercial titanium dioxide nanoparticles were mixed need of a higher content of nanoparticles.
with cement and lime-based mortars. The influence of REFERENCES
different operating parameters in the photocatalytic [1] M. V. Diamanti, R. Paolini, M. Rossini, A. B.
activity has been studied [3]. Factors such as the Aslan, M. Zinzi, T. Poli, M. P. Pedeferri, Construction
deactivation time, the initial pollutant concentration and and Building Materials 2015, 96, 270.
the effect of metal doping have been investigated. [2] S. S. Lucas, V. M. Ferreira, J. L. B. d. Aguiar,
Titanium dioxide nanoparticles were doped with iron ions Cement and Concrete Research 2013, 43, 112.
(Fe3+) by co-precipitation. The efficiency of these mortars [3] H. Dong, G. Zeng, L. Tang, C. Fan, C. Zhang, X.
to degrade NOx was studied and compared with samples He, Y. He, Water Research 2015, 79, 128.
with non-doped titanium dioxide.
RESULTS AND DISCUSSION ACKNOWLEDGMENTS
The deposition of reaction products on the surface of the The author acknowledges the Foundation for Science and
mortar can contribute to the temporary deactivation of Technology (FCT) for the financial support
some of the active sites of the catalyst. In order to (PTDC/ECM/72104/2006) and the University of
evaluate the photocatalytic efficiency for concentrations Greenwich for the support through the FES2015 REF
below 1 ppmv the samples were analysed using pollutant competitive fund.
84

Correlation Between Metal Doping (Ti, Al and Ag) and Basic Properties of DLC
Films Produced by DC and HiPIMS Magnetron Sputtering

Gabriela Leal1, Mariana Amorim Fraga2*, Argemiro Soares da Silva Sobrinho3 and Marcos Massi1

Science and Technology Institute, Federal University of So Paulo, Brazil


1
2
Associated Laboratory of Sensors and Materials, Nacional Institute of Spatial Research, Brazil
3
Plasma and Process Laboratory, Technological Institute of Aeronautics, Brazil, *mafraga@ieee.org

INTRODUCTION quantity of metal in these samples was slightly higher


Considerable research efforts into diamond-like carbon than in samples deposited with DC power supply,
(DLC) technology have been focused on the ability of reinforcing the idea that films deposited with HIPIMS can
control their properties by the varying deposition be denser than those deposited using DC. The Ag-DLC
conditions1. Many desirable properties for a variety of thin films showed a different behavior in RBS analysis. It
applications have been achieved by the introduction of a was observed a second thin film formed only by silver
metal element in deposition process, for example the over an Ag-DLC thin film. The Ag-DLC film cannot be
mechanical, electrical and biological properties for quantified because its peak was covered by the silver
applications as coatings tools, sensor material and in peak. FEG-SEM investigation (Fig.1) confirm the RBS
medical devices2-4. results, where it can be observed an Ag thin film over a
DLC thin film. It is known that Me-DLC thin films is
formed by metal clusters or metal carbide cluster in a
EXPERIMENTAL
DLC matrix and because of silver high sputtering yield,
Me-DLC thin films were deposited on n-type (100)
the cluster coalesced forming another thin film. While
silicon wafers by co-sputtering of graphite and metal (Ti,
that, FEG-SEM images of the Al-DLC and Ti-DLC films
Al, Ag) targets in argon atmosphere. The DC power
showed that these materials did not present the same
applied to graphite target was fixed at 300W whereas the
behavior observed for the Ag-DLC films. These films are
metal target was varied from 10 to 30W varying also the
formed by carbon grains with metal.
power supplies (DC and HiPIMS). The film thickness and
chemical composition were determined by mechanical
profilometry using a Dektak 3030- Veeco Instrument and
by Rutherford Backscattering Spectroscopy (RBS) using a
Pelletron-Tandem 5SDH- NEC accelerator, respectively.
The surface morphologies of the Me-DLC films were
examined by field emission scanning electron microscope
(FE-SEM, Tescan Mira 3 FEG).
200nm

RESULTS AND DISCUSSION Fig. 1 FEG-SEM image of Ag-DLC samples with 300k
The mechanical profilometry analysis showed that the times magnifying
film thickness increases with the increase in the power
applied to the metal targets (Ag, Al and Ti). The Ag-DLC
CONCLUSION
films presented the greatest film thickness (from 117 to
In summary, different Me-DLC thin films were
609nm) followed by Al-DLC (from 110 to 301nm) and
characterized in terms of metal element and power supply
Ti-DLC (from 86 to 119nm). This occurs because the
type used. It was observed an influence in thin film
silver sputtering yield can be also 7 times higher than the
thickness and composition with the metal sputtering yield
carbon while aluminum can be almost 2 times higher and
and the Ag higher sputtering yield caused the formation
titanium has almost the same sputtering yield compared
of a silver film over an Ag-DLC film. The results showed
with carbon. The use of DC power supply resulted in a
also a probably denser films deposited by HiPIMS.
greater thickness for samples of Ag-DLC and Al-DLC,
whereas no significant difference was observed for Ti-
DLC. The lower sputtering rate using HiPIMS can be a REFERENCES
consequence of its known higher density films. The 1. B. Pandey et. al, Appl. Surf. Sci. 261, 789 799 (2012)
composition of the films were determined by RBS 2. A. Amanov et. al, Tribol. Int. 62, 4957 (2013)
analysis and showed a variation from 2 to 20% of metal in 3. J. Chen et. al, Thin Solid Films 518, 7320-7323 (2010)
Al-DLC and from 0.5 to 6.0% of metal in Ti-DLC 4. L. Cui et. al, Thin Solid Films 475, 279 282 (2005)
samples. The Ti-DLC samples presented lower amount of
metal compared to Al-DLC samples, probably because of ACKNOWLEDGMENTS
titanium lower sputtering yield. In spite of the smaller We thank FAPESP (grant 2013/17045-7) and Brazilian
thickness of the films deposited with HiPIMS, the Space Agency (AEB) for the financial support.
85

The CNTs-Re nanocomposites observed under electron microscopes

Anna D. Dobrzaska-Danikiewicz1, Weronika Wolany1, Klaudiusz Goombek1, Dariusz ukowiec1


1
Faculty of Mechanical Engineering, Silesian University of Technology, Poland, anna.dobrzanska-danikiewicz@polsl.pl

INTRODUCTION In the SWCNTs nanotubes were formed numerous


Rhenium is a heavy metal, possesses very high melting rhenium nanowires with diameter about 12nm,
and boiling point, good thermal, electrical and catalytic especially visible during the study using transmission
properties, so is used in the developing industries such as electron microscopy (Fig. 2) and Re nanoparticles on the
space, electrical, petrochemicals, chemicals ones. carbon nanotubes surface. The outcomes of EDS
Searching for new uses of Re, including as a component examinations confirm each time the occurrence of carbon
of nanocomposites composed of carbon nanotubes is in the investigated materials and rhenium peaks are also
purposeful and interesting1,2,3. Single- and multiwalled visible originating from Re nanoparticles.
carbon nanotubes can be modified in a different way to
enhance their application possibilities. The main goal of
this paper is to present a method for manufacturing of the
nanocomposites consisting of SWCNTs or MWCNTs
decorated with Re nanoparticles. A decoration process
was started with covalent functionalization of carbon
nanotubes. Then the material was dispersed in ethanol and
added a rhenium precursor (HReO4). In the next step
carbon nanotubes was sonicated in ultrasonic bath, dried
and inserted it in quartz vessel. Finally the material was
heated in the atmosphere of H2 and in the shield of inert
gas Ar.
EXPERIMENTAL/THEORETICAL STUDY
The microscope examinations of the SWCNTs-Re and
MWCNTs-Re nanocomposites were carried out with the
SEM and also S/TEM using an HAADF detector. An Fig.2. STEM image of SWCNTs-Re nanocomposite
energy dispersive spectroscope (EDS) was employed to
determine chemical composition of the materials. CONCLUSION
The development of different kinds of carbon nanotubes
RESULTS AND DISCUSSION decorated with Re nanoparticles has concerned intensive
The outcomes of the undertaken microscope examinations interest in the last decade because of their outstanding
visibly indicate that the applied fabrication methods of sensing properties. The functionalisation and the
presented nanocomposites are effective and allow to nanocomposites fabrication method are essential for the
permanently attach carbon nanotubes with nanocrystals morphology of the presented carbon-metal materials.
and/or nanowires of rhenium. In the MWCNTs-Re Generally, CNTs-based gas sensors are attractive because
nanocomposite Re nanoparticles are usually spherical or of their small size, low weight, low power consumption
oval shaped, but some of them are irregularly (Fig. 1). and very high sensitivity.
Generally, rhenium nanoparticles possess diameter below
20 nm, but the presence of agglomerates was also noticed. REFERENCES
1. Patent application P.407887, Polish Patent Ofce
2. W. Wolany, PhD Thesis: The structure and properties
of nanocomposites composed of carbon nanotubes
decorated with rhenium nanoparticles, Silesian University
of Technology, Gliwice 2016, work in progress
3. A.D. Dobrzaska-Danikiewicz et. al, Phys. Status
Solidi (b) 251/12, 2485 (2014)
ACKNOWLEDGMENTS
The publication was financed from a statutory grant of the
Faculty of Mechanical Engineering of the Silesian
University of Technology in the framework of BK_16
Fig.1. SEM image of MWCNTs-Re nanocomposite project.
86

Flame retardant polyurethane composites with addition of carbon nanotubes

Kamila Mizera1*, ukasz Kaniuk1, Milena Zieleniewska1, Monika Augucik1, Joanna Ryszkowska1, Kamil Lipert2, Justyna
Czech-Polak3
1
Faculty of Materials Science and Engineering, Warsaw University of Technology, Woloska 141, 02-507, Warsaw, Poland,
*
kpietrzak@inmat.pw.edu.pl
2
Asma Polska Sp. z o.o Company, 10 Mostw Street Wola Ducka 05-408 Glinianka near Warsaw, Poland
3
Faculty of Chemistry, Rzeszow University of Technology, Al. Powstancow Warszawy 6, 35-959 Rzeszow, Poland

INTRODUCTION RESULTS AND DISCUSSION


The reasons of the great demand for polyurethanes (PUR) The results of physical and mechanical properties are
are their functional properties, i.e. good resistance to given in Table 1. The characteristic of density is very
abrasion and to oil, grease and weather conditions. The similar for all samples. The density increased with the
properties are the result of their segmented structure [1]. increase of carbon nanotubes, and is higher for PUR with
The usefulness of the polyurethanes for use as part of the 5% of ecopiren. The hardness have the same
construction of an enclosure determines its susceptibility characterisation, but in PUR with 5% PNX the lowest
to fire. In order to increase resistance to fire the most used value is for sample with 0.1% of carbon nanotubes. The
are chlorine compounds. However, in recent years to resilience decreased in both PUR groups.
reduce the potential for fires during dioxins and furans are
introduced restrictions on the use of chlorine and Table 1. Physico-mechanical properties, results from CC
bromine. Therefore, studies are undertaken to limit their and oxygen index test of selected PURs
use. The aim of the study was to verify the suitability of Samples , g/cm3 H, ShA , % HRRr, LOI
additives reducing flammability of polyurethane, selection kW/m2
of the number and verification of properties of P1 1.1099 88.6 35.5 182.1 28.7
commercial mixtures containing polyurethane them. P2 1.1072 89.5 35.2 188.5 28.4
P3 1.1272 90.6 34.2 106.4 28.6
EXPERIMENTAL/THEORETICAL STUDY 1.0877 86.7 34.2 217.3 28.7
P4
The subject of the study was to perform syntheses of
P5 1.0788 83.9 33.7 164.3 28.9
polyurethane nanocomposites in a one-stage process with
P6 1.0884 87.0 33.4 223.5 28.7
carbon nanotubes.
For the manufacture of PUR nanocomposites the
polyurethane ASMAPRENE A with hardness 90ShA The average heat release (HRRr) decrease for PUR with
was used. The technical carbon nanotubes NANOCYL 0.25% carbon nanotubes and 5% ecopiren (Table 1). In
NC7000 TM were used a filler. As a flame retardant were PURs with 5% of PNX, the lowest value of HRRr is for
used: magnesium hydroxide - ECOPIREN 10, Torimex- PUR P5 with 0.1% carbon nanotubes. Oxygen index
Chemicals Ltd. Sp z o.o. and phosphorus compound - shows that all samples meet the criteria of slow-burning
Fyrol PNX- ICL Industrial Products. materials specified by the standard (IO>26%) (Table 1).
The structure description of PUR was carried out using
CONCLUSION
density () (determined via hydrostatic weighing in
The introduction of carbon nanotubes to polyurethanes
conformity with the norm ISO 2781). Hardness (H) was
causes changes in chemical structure and consequently in
determined using durometre Shore A according to ASTM
the properties of the materials produced. This is probably
D2240-75. Resilience () was tested by Schobe method
because the addition of fillers changes the reaction
according to PN-71/C-04255. Flammability tests were
between the reactive groups of individual substrates. Use
made using a cone calorimeter (CC) under the heat flux
a different flame retardants can reduce the flammability of
equal to 50 kw/m2. The CC test was performed in
the produces materials.
accordance with ISO 5660. Inflammability was assessed
by LOI at ambient temperature according to Standard PN-
REFERENCES
EN ISO 4589-2:2006.
1. R. Jayakumar, S. Nanjundan, M. Prabaharan React.
The samples were marked as P1PUR with 0.05%
Func. Polym. 66, 299-314 (2006)
nanotubes and 5% ecopiren, P2PUR with 0.1%
nanotubes and 5% ecopiren, P3PUR with 0.25%
nanotubes and 5% ecopiren, P4PUR with 0.05% ACKNOWLEDGMENTS
The study has been financed by the National Research
nanotubes and 5% PNX, P5PUR with 0.1% nanotubes
and Development Centre within the framework of the
and 5% PNX, P6PUR with 0.25% nanotubes and 5%
project DOB-BI06/02/2014.
PNX.
87

Size Effect and Geometric Thermal Stability of Hollow Pt3Ni Nanospheres:


A Molecular Dynamics Study

Serap SENTURK DALGIC

Department of Physics, Trakya University, TURKEY, serapd@trakya.edu.tr

The size dependent morphological stability of hollow MD sample of hollow Pt3Ni NP with an average diameter
Pt3Ni nanoparticles(NPs) have investigated. The thermal 15nm and wall thickness of 10nm is shown in Fig.1. All
stability of hollow Pt3Ni ordered alloy nanospheres with NPs are constructed from the big fcc crystal cube with
different sizes up to an average outer diameter of 15nm ordered L12 structure.
were studied by Molecular Dynamics (MD) simulation
method. Geometric thermal phase diagram (GTPD) has
obtained at various temperatures as a function of aspect
ratio and wall thicknesses. Additionally, surface
segregation of Ni atoms was observed and analysed by
computing the surface energy and the existence of
stacking faults in interior and exterior shells of hollow
particles. These results can be used as a guide for the
synthesis of Pt3Ni hollow structures.

INTRODUCTION
Hollow interior materials have attracted increasing
interest in fields of catalysis, biomedical applications, and
electronics. Among them, Pt-based hollow structures are
critical materials in fuel cells and metal-air batteries as Fig. 1 The initial state snapshot of the hollow Pt3Ni
electrocatalysts. Zhou et. al.1 reported catalytic activities nanoparticle; blue spheres Pt atoms and red spheres are Ni
hollow Pt-Ni nanospheres at different compositions. In atoms.
recent experiments, it has been noted that PtNi3 solid
polyhedral shaped NPs are transformed into hollow Pt3Ni The developed GTPDs show that hollow spherical Pt3Ni
nano frame catalysts2. On the other hand, nano polyhedral ordered NPs are energetically stable with some critical
Pt3Ni nanocatalysts (NCs) have the high electrocatalytic inner diameters. As reported by experiments, the shell
activity. Up to now, intense research efforts have been thickness decreases, and particle size increases, hollow
focused on developing the most active electrocatalysts; NPs became stable.
less is known about their morphologies. Controlling of CONCLUSION
the hollow structure nanocatalysts such as shrinkage or In this work, we investigated the size effect on the
collapse mechanism is difficult clearly exposed thermal stability of Pt3Ni HNPs. This study provides an
experimentally and will strongly affect their physical and approach to the investigation of size-dependent surface
chemical properties especially their catalytic performance. properties of the hollow Pt3Ni intermetallic spherical
The main aim of this study is to present a theoretical work nanoparticles by atomistic simulations. However, future
based on computer simulations in exploring the phase research will be needed to compare the catalytic
stability diagram of hollow nanocatalysts within activation energies of a hollow truncated octahedral
spherical geometry. shaped Pt3Ni NPs.
METHOD
REFERENCES
The MD simulation package DLPOLY3 was used in
1. X. Zhou et al., J. Power Sources, 196, 5844 (2011).
present work. The pair interactions were established with
the quantum corrected Sutton-Chen (Q-SC) potentials. 2. C. Chen et al., Science 343, 1339 (2014).
Surface energy and the number of Ni atoms at the
3. DL_POLY: an MD simulation package was written by
outermost layer have calculated from the MD results. The
W. Smith, T.R. Forester, and I.T. Todorov obtained from
stacking faults have determined from the common
the website:http://www.ccp5.ac.uk/DL_POLY
neighbor analysis (CNA) method using OVITO5.
4. A. Stukowski, Modelling Simul. Mater. Sci. Eng. 18,
015012 (2010)
RESULTS AND DISCUSSION
In this work, first, we are focused on the thermal stability
ACKNOWLEDGMENTS
of hollow Pt3Ni nanospheres. GTPD deduced from MD
The author thanks, Trakya University for supporting the
simulations at different temperatures are given to obtain
attendance of the ANM 2016 Conference.
the stable, metastable and unstable structures. The initial
88

Molecular Dynamics Simulations of AgPd Nanorings

Serap SENTURK DALGIC1, Gulsen TEZGOR2*


1
Department of Physics, Faculty of Science, Trakya University, Edirne-TURKEY
2
Department of Physics, Faculty of Science, Trakya University, Edirne-TURKEY,gulsentezgor@trakya.edu.tr

Recently, among bimetallic electrocatalysts, Ag-Pd diameter ( 5nm : 15nm) and wall thicknesses greater
hollow nano frames, especially the structures of AgPd than 2nm. The created initial MD sample of AgPd
nanorings/nanoshells become an increasingly pressing nanoring is illustrated in Fig. 1 using OVITO5. We have
topic. AgPd nanorings are created as the larger cavity size also calculated the self-diffusion coefficients of Ag and
with a thin shell thickness of Ag-Pd alloys. In this study, Pd atoms in AgPd alloy.
we prepared different sizes of Ag-Pd nanorings from the
atomically ordered structure of AgPd with an Ag/Pd ratio
of 1:1. Molecular dynamics (MD) simulations are
established first to investigate the size-dependent
properties of AgPd nanorings. We focus on computing the
stable hollow structure having suitable cavity size with
the appropriate shell thickness. It has found that diffusion
of both Ag and Pd atoms is strongly dependent on the
particle size and inner radius. These results can exhibit a
role for designing the electrocatalysts with high catalytic
performance.

INTRODUCTION

The Pd-based nanomaterials such as nanoparticles, Fig. 1 Snapshot of an initial MD sample of AgPd
nanowires, nanorods and another shape of nanomaterials nanoring with an average diameter of 21nm and a wall
have been investigated as potential catalysts.For thickness of 5.5nm.
nanostructured electrocatalysts, their catalytic properties
are strongly dependent on the surface structure and shape It has found that AgPd nanorings become more stable by
of the nanomaterials. Recent experiments show that increasing the outer diameter and wall thickness.
nanomaterials with hollow interiors are of great interest in However, Ag and Pd atoms located in the ring-shaped
the application of catalysts because of the large surface to structures with larger cavity size and outer diameter are
volume ratio compared to solid catalysts1. Although the more active than that of the hollow spheres at the same
hollow Pd-Ag or Ag-Pd nano frames synthesized by size.
different experimental methods2,3, theoretical and MD
studies on Ag-Pd alloy are not sufficient to understand the CONCLUSION
nanoscale behaviors of these nanostructures. In this work, We have noted that the strain induced segregation are
we present first a computational model to compute the more pronounced for larger size AgPd nanorings than
size-dependent thermal and geometric stability of AgPd others. As the interesting line of future research, there is a
alloy nanorings. possibility of designing the nano frames to utilize this
segregation.
THEORETICAL STUDY
REFERENCES
The ring-shaped AgPd alloy nanostructures are 1. M. Tsuji et al., CrystEngComm., 16, 2684 (2014).
investigated by classical MD simulations using the 2. M. Liu. et al., Adv. Funct. Mater., 23, 1289 (2013).
DLPOLY simulation code4. The Sutton-Chen (SC) many
body potential are used to describe interatomic 3.G-T. Fu et al., Sci. Rep., 5, 13703 (2015).
interactions in the system. We assume that this potential is 4. DL_POLY: an MD simulation package was written by
transferable for hollow AgPd nanostructures. To the W. Smith, T.R. Forester, and I.T. Todorov obtained from
identification of structure type of the system after the website:http://www.ccp5.ac.uk/DL_POLY
simulations near room temperature, we have used the 5. A. Stukowski, Modelling Simul. Mater. Sci. Eng. 18,
common neighbor analysis (CNA) method of OVITO5. 015012 (2010)
RESULTS AND DISCUSSION ACKNOWLEDGMENTS
The authors thank Trakya University for supporting the
In this work, we have calculated the total change in attendance of the ANM 2016 Conference.
cohesive energy of nanorings with various inner:outer
89

Self-assembly of Hierarchical Nanomaterals with High Activity and High Stability

Jie Ying, Yu-Xuan Xiao, Hao Wei and Xiao-Yu Yang*

State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology,
Wuhan, China, xyyang@whut.edu.cn

INTRODUCTION
Self-assembled nanomaterials, which are formed from
interatomic and intermolecular interactions, may represent
building blocks in the 21st century. The most significant
problems with the applications of these nanomaterials
have been property changes over time duo to poor
stability. Recently advances in self-assembly technique
enabled precise control synthesis of nanomaterials, which
has significant impacts in the development of self-
assembled nanomaterials.
RESULTS AND DISCUSSION
We present our recent work on design of a series of self-
assembled hierarchical nanomaterials at micro/nano scale,
which their activity and stability can be greatly enhanced. Fig. 2 (a, b) TEM images of PtPd@MCF at low
Firstly, hierarchical micro-meso-macroporous materials magnification and high magnification, respectively. (c, d)
with zeolite architectures (Fig. 1) have been designed and HAADF-STEM images of PtPd@MCF sample at low
synthesized by using self-assembly method1, 2. These magnification and high magnification, respectively.
materials exhibit high activity and high stability in
catalysis, which can be attributed to the unique and stable
hierarchically porous structure. Then, metal nanocrystals
have been stabilized and encapsulated in a unique one
particle@one cell structure (Fig. 2) by the viscosity-
adjusting method using mesocellular foam.3, 4. Metal
nanocrystals in mesocellular foam exhibit high activity,
high stability and high durability for oxygen reduction
reaction. Furthermore, we also succeed to use self-
assembly method for cell protection. Living cells with
nanoporous biohybrid shells (Fig. 3) can be rational
designed5, 6. The self-assembled biohybrid shells endow
the cells with enhanced stability and extra functionalities.
Fig. 3 Schematic illustration of Au@L-cysteine biohybrid
layer formation and bilayer shell-encapsulation process: A)
native cell, B) cell with the precursor of the nanosized
biohybrids, C) cell with the bio-interface, D) bio-
interfacing cell with the precursors of nanoporous silica,
and E) cell within a bilayer shell.

CONCLUSION
It is believed that our methods could be useful for the
preparation and stabilization of nanostructured materials
with multiple functionality.
REFERENCES
1. X. Y. Yang et. al, Adv. Mater. 12, 1368 (2009)
2. L. H. Chen et. al, Angew. Chem. Int. Ed. 50, 11156
Fig. 1 Schematic of the synthetic procedure for (2011)
hierarchically micromesomacroporous catalysts 3. J. Ying et. al, Nanoscale 22, 13370 (2014)
constructed from zeolite TS-1 nanocrystals by a quasi- 4. J. Ying et. al, Nano Energy 8, 214 (2014)
solid-state crystallization process. 5. N. Jiang et. al, Chem. Sci. 6, 486 (2015)
6. N. Jiang et. al, Small 11, 2003 (2015)
90

Aging Time Effect On ZnO Thin Films Photocatalytic Activity Synthesized By Sol-
Gel Dip Coating Method
R. Tala-Ighila,b,* M. Toubaneb,c , F. Bensouicib,c, M. Bououdinad, M. Souier f, W. Caie,S. Liue , A. Iratnib
a
Institute of Electrical and Electronic Engineering, University M'hamed Bougara Boumerdes, 35000 Boumerdes, Algeria.
b
URMPE Unit, University M'hamed Bougara Boumerdes, 35000 Boumerdes, Algeria.
c
Physics Department, Faculty of Sciences, University M'hamed Bougara Boumerdes, 35000 Boumerdes, Algeria.
d
Department of Physics, College of Science, University of Bahrain, PO Box 32038, Kingdom of Bahrain.
e
Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, Centre for
Environmental and Energy Nanomaterials, Institute of Solid State Physics ,Chinese Academy of Sciences, Hefei 230031,
P.R. China.
f
Physics Department, College of Sciences, Sultan Qaboos University, Po Box 36, Sultanate of Oman.
Corresponding author: t_razika@hotmail.com
ABSTRACT Fig.1 .X-ray diffraction patterns of ZnO ten layers deposited on
In this work ZnO thin films were prepared by sol-gel dip glass substrate for various aging time
coating method onto glass substrates. Zinc acetate 100
a
100

dehydrate, ethanol and Diethanolamine (DEA) were used 80 2 days


10 days
80

Transmittance (%)

Reflectance (%)
30 days
as starting material, solvent and stabilizer respectively. 60

40
341nm
60

40

The aging time effect of the starting solution (2, 10 and 30 20


20

days) on structural, morphological and optical properties 0

300 450 600 750 900 1050 1200


0
1350 1500 16501800

as well as photocatalytic efficiency was deeply wavelength(nm)

investigated. The crystal structure was checked with X- Fig.2. Optical transmittance T() and reflectance R() spectra
ray diffraction (XRD), the optical transmittance and for different sol aging time
reflectance were measured with a spectrophotometer and (a) (b)
Morphological observations were performed using
scanning electron microscopy emission gun scanning
electron microscope (FESEM) equipped with electron
dispersive x-ray (EDX) spectrometer for chemical
analysis, the film surface roughness was investigated by
Multimode-8 atomic force micro- scope (AFM) from
Bruker. X-ray diffraction analysis indicates that all
prepared thin films exhibit a Zincite structure with a
preferred grains orientation along (002). The preferred
orientation factor (POF) increases with aging time while
the crystallite size decreases. A high transparency is
observed for all ZnO thin films, ranging from 90 up to
100%. The field emission scanning electron microscopy
(c)
observations reveals nanorods morphology. The length of
Fig.3 SEM images of ZnO thin films deposited for different
ZnO nanorods decreases as a function of aging time while aging time a) 2 days b) 10 days c) 30 days and DES analysis
adopting a random orientation. It was found that CONCLUSION
Methylene Blue (MB) dye photocatalytic degradation ZnO nanorods were successfully synthesized by a sol-gel
increases with aging time, reaching almost 94% after 10 h dip coating method. It was found that structural,
under UV irradiation. The reaction rate (Kapp) obtained by morphological, optical properties and photocatalytic
Langmuir-Hinshelwood model increases with aging time efficiency were directly affected by sol aging time. The
from, from 0.218 h-1 for 2 days then reaching a steady length of ZnO nanorods decreases as a function of aging
-1
state around 0.270 h . time with random orientation. All the films showed a high
RESULTS AND DISCUSSION transparency and good crystallinity improved by the aging
Intensity( arb.units)

0 2 4 6 8 10
10
3500 time.
(101)
60 days
a
120

100
(002) 8
3000
Acknowledgements
Intensity (arb.units)

(100)
80 6
2500
60
(110) 4

(002) 40

20

0
(013)
(112)
2

0
2000

1500
Dr. Mohamed Bououdina would like to thank Chinese Academy of
(002) 30 40 50 60 70
2()
1000 Science (CAS) through CAS Presidents International Fellowship
(103) 500

0 Initiative Grant No.2015 VTA016.


(002)

(100)
(101)
(100) (101)
(102)
(103)
(201)
2B days
REFERENCES
1
(102) (110) (103)
(201)
10
D days
H.T. Ng et al., Nano Letters, 4 (2004) 1247-1252.
2
30
C
days
. zgr et al., Journal of applied physics, 98 (2005) 041301.
30 40 50 60 70 3
2
M. Miki-Yoshida et al., Thin Solid Films, 419 (2002) 60-64.
4
D. Abou-Ras et al., Thin Solid Films, 480 (2005) 118-123.
5
K. Ramamoorthy et al., Journal of crystal growth, 226 (2001) 281-286.
91

A Nano Zeolite Modified Carbon Paste Electrode


forElectrocatalyticOxidation of Hydrogen Peroxide in Alkaline
Media
Maryam Abrishamkar 1,*,Fatemeh Kiani2
1
Department of Chemistry, Ahvaz Branch, Islamic Azad University, Ahvaz, Khouzestan, Iran.
*E-mail: m.abrishamkar@umz.ac.ir
2
Department of Chemistry, Khouzestan Science and Research Branch, Islamic Azad University, Iran.

Abstract carbone paste electrode (CPE), used for


comparison, was prepared in the same way but
In this work theuse ofsynthesizedY omitting the zeolite addition step. In order to
zeoliteforpreparation of modified carbone paste incorporate Ni () ions into carbon paste
electrode for electrocatalytic oxidation of electrode [CPE]. The oxidation of hydrogen
hydrogen peroxide was investigated. In order peroxide was studied at CPE,NiCPEand
topreparetheelectrodes, the nickelions were NiZSM-5/CPE by cyclic voltametric experiment
doped to Y zeolite framework through ion in 0.1 M NaOH solution.
exchange mechanism and the electrochemical
behavior of proposed modified electrode studied RESULTS AND DISCUSSION
using cyclic voltammetry.
Cyclic voltammetry (CV) is considered to be a
Keywords: electrocatalytic, modified electrodes, suitable tool to indicate the capacitive behavior
hydrogen peroxide, Y zeolite of any material. Fig. 1, is shown the
electrochemical response of CPE and
INTRODUCTION Ni/NZMCPE in the0.1 M
Hydrogen peroxide is the product ofthe NaOHelectrolytesolution. As can be seen,
reactions catalyzed by a large number of whereasneither oxidation nor reduction took
oxidizes[1].The determination of hydrogen place on CPE (Fig. 1 (c)), awell-defined stable
peroxide is of considerable interest, because redox peaks were observed for
hydrogen peroxide isnot only an important Ni/NZMCPE(Fig. 1 (a)).
analyte in food, pharmaceutical, clinical,
industrial and environmental analyses but also
playing a key role as the product of the
enzymatic reaction in coupled enzyme
systems[2]. Studies showthat nickel-based
electrodes exhibit high stability in alkaline
solution together with excellent catalytic
efficiency foroxidation of various organic
materials[3]. Zeolite molecular sieves are a well-
known category of hydrated crystalline and
porous aluminosilicate with pores and channels REFERENCES
of various shapes, sizes, and topologies that
[1] R. Ojani,J. B. Raoof,B.Norouzi, J Solid State
control the reactivity and shape-selective
Electrochem, 14:621631(2010).
properties of these materials [4].Application of
[2] G. Li , X. Hui, Sensors, 7: 239-250(2007).
zeolite modified electrodes (ZMEs) for
[3]M. Abrishamkar,N.Azizi,J. B.Raoof,
electroanalytical purposes has attracted much
attention [5].Transition metal-containing MonatshChem, 143:409-412(2012).
[4] Ojani R, Raoof JB,B.Norouzi, Int. J.
zeolites were found to exhibit a high catalytic
Electrochem. Sci.7: 1852 1863(2012).
activity[6].
[5]M. Abrishamkar ,F. BagherfardKahkeshi,
Microporous and Mesoporous Materials,
EXPRIMENTAL
167:51-54(2013).
A mixture of 0.015g of NiY, 0.35g of graphite [6]J. B. Raoof, N. Azizi ,R. Ojani, S. Ghodrati
powder and paraffin was blended to prepare the ,M. Abrishamkar ,F. Chekin, International
zeolite modified carbon paste [NZMCP]. The journal of hydrogen energy, 36: 13295-
resulting paste was then inserted in a glass tube. 13300(2011).
The electrical connection was implemented by a
copper wire lead fitted into the glass tube. The
92

First principles study on the electronic properties of BN nanowires

Sena Gler zkap1*, Bar zkap1 , Harun zkii2 and Seyfettin Dalg3
1*
Vocational School of Technical Sciences, Trakya University, Turkey, senaguler@trakya.edu.tr
2
Kean Yusuf apraz School of Applied Sciences, Trakya University, Turkey
3
Department of Physics, Trakya University, Turkey

a)
INTRODUCTION
One-dimensional (1D) nanostructure systems and their
unique properties make them very promising applications
for nanoelectronic devices1. Electronic, optic and
mechanical properties of this structure are different from
their bulk structures due to quantum confinement, surface
and geometric effects. Boron nitride (BN) is an important
semiconductor material that has a wide band gap, low b)
dielectric constant, high melting point, etc. It has several
crystalline forms such as zinc blende, wurtzite and
hexagonal. Besides nanotube and nanowire structures can
be constituted for BN2. These nanostructures exhibit very
interesting physical properties depending on their sizes.
Therefore, the studies on structural and electronic
properties of nanowires attract a great deal of attention.
BN nanotube studies were done by theoretical c)
calculations3 and their synthesis studies were performed4
in 1994 and 1995, respectively. Since then, many
experimental and theoretical studies have been carried
out. While there are a lot of theoretical studies about BN
nanotubes and other semiconductor nanowires, BN
nanowires studies are very limited5. In the present work,
structural and electronic properties of zinc blende BN
nanowires with different diameters have been investigated Fig. 1 Electronic band structure and dos of BN nanowires
by using first principles method. with different diameters a) 0.72 nm, b) 0.92 nm, c) 1.45
THEORETICAL STUDY nm, respectively. (Blue atoms:B, purple atoms:N)
In this study, structural and electronic properties of BN
nanowires oriented along (001) direction have been CONCLUSION
investigated by using Plane Wave Self Consistent Field The results show that the band gap increases slightly with
(PWSCF) program based on Density Functional increasing diameter for 0.72 nm and 1.45 nm BN
Theory6,7. Perdew-Burke-Ernzerhof (PBE) ultrasoft nanowires. However, the band gap of BN nanowire with
pseudopotantial and GGA approach have been used8. The 0.92 nm diameter is larger than the other nanowires. We
energy cutoff of the plane wave basis set is set 40 Ryd to can say that this situation results from type of the atoms
ensure accurate results. The summation over the Brillouin (B or N) on the surface of nanowires.
zone is performed by the Monkhorst-Pack grid with
1x1x8 k points. REFERENCES
1. M.M.J. Treacy et al, Nature 381, 678 (1996)
RESULTS AND DISCUSSION
Initially bulk BN have been modelled in zinc blende 2. A. Rubio et. al, Phys. Rev. B 49, 5081 (1994)
structure and then cut from the bulk BN crystal in 3. X. Blas et al, Europhys. Lett. 28, 335 (1994)
nanowire forms with different diameters. Electronic
structure of BN nanowires have been presented and the 4. N. G. Chopra et al, Science 269, 966 (1995)
dependence on nanowire diameter and shape have been 5. K. H. He et al, Solid State Commun. 150, 701 (2010).
examined. We can say that lattice constant is stable with
increasing diameter. Also calculated band gaps are 1.31 6. P. C. Hohenberg et al, Phys. Rev. B 136, 864 (1964)
eV, 2.72 eV, 1.50 eV for BN nanowires with 0.72 nm, 7. W. Kohn et al, Phys. Rev. A 140, 1133 (1965).
0.92 nm and 1.45 nm diameters, respectively.
8. J.P. Perdew et al, Phys. Rev. Lett. 77, 3865 (1996).
93

SIS-CCTO polymer matrix composites for embedded capacitors


F. Amaral1,2*, J. Santos2, M. Graa2, Z. Spitalsky3, M. Ilcikova3, K. Czanikova3, J. Mosnacek3

Polytechnic Institute of Coimbra, Portugal, filipe.amaral@estgoh.ipc.pt


1*
2
I3N, Physics Department, University of Aveiro, Portugal,
3
Polymer Institute, Slovak Academy of Sciences, Bratislava, Slovakia,

ABSTRACT RESULTS AND DISCUSSION


In this work we studied the dielectric behavior of styrene- Dielectric measurements performed to the composites
isoprene-styrene-CaCu3Ti4O12 (SIS-CCTO) composites to shown that the best results were obtained for the films
be used as embedded film capacitors in printed circuit prepared with CCTO particles obtained from solid state
boards (PCBs). Films were prepared with growing reaction. The results of dielectric constant (), at room
CCTO/SIS volume ratio using a doctor-blade based temperature, are presented at figure 1.
method. In order to study the influence of particle size on
the dielectric behavior of these composites, two different %CCTO 0 15 30 45 60
methods were used for the synthesis of CCTO powder:
Power of peel-off 0,293 0,133 0,113 0,047 0,023
solid state reaction and sol-gel method1. [N/mm]
Tab. 1 Power of peel-off measured for SIS-CCTO
INTRODUCTION composites, prepared by doctor-blade based method.
The need for production of more efficient electrical
appliances and their miniaturization has been one of the T=300 K
main purposes of the electronic industry. In this context 35 15%
30%
came the need to improve the performance of the PCBs, 30 45%

reducing noise while making them more flexible and 25


60%
0%
stable in the face of sudden changes in temperature and in
order to operate in a wide range of frequencies and 20

powers. With this purpose, it has been considered the


'

15
incorporation of passive components, including
10
capacitors, as film, directly inside the polymeric card2. In
order to maintain a high dielectric constant and low 5
dielectric loss, while maintaining the flexibility associated 0
with the polymer, a polymeric matrix composite has been
created. In this work we prepared and studied the 102 103 104 105 106 107

morphology and dielectric behavior of styrene-isoprene- Frequncia (Hz)

styrene-CaCu3Ti4O12 (SIS-CCTO) composites. Fig. 1 Dielectric constant () of the SIS-CCTO samples


prepared by doctor-blade based method.
EXPERIMENTAL STUDY
Composites were prepared with the following CCTO-SIS CONCLUSION
volume ratio 0%, 15%, 30%, 45%, 60%, dissolved in Thick SIS-CCTO composite films (<50 m) were
toluene. After adding the particles, mixing speed was set successfully prepared using copper plate as substrate.
to 1200 rpm and the mixture was stirred for 3 hours at presents a significant variation along the studied
room temperature. After that, the high viscous solution of frequency range. Even so, the high (>30) found for the
polymer with CCTO particles was poured out on copper 45% vol. sample at the low frequency region can be
plates and spread with dispensing ruler to wet film with useful for embedded capacitors. The results obtained for
thickness of 0,24 mm. The finally, the brown films of these samples compare well with other commercially
composites were dried at room temperature and then available polymer-ceramics nanocomposites.
under vacuum overnight. In the dielectric characterization
the value of the dielectric constant and losses for all films REFERENCES
prepared at room temperature (300 K) was studied and the 1. F. Amaral et. al, Phys. Status Solidi A 208, 2284
study at variable temperature (200 - 400 K) was used to (2011).
determine whether or not the existence of sub vitreous 2. W. Jillek et. al, Int. J. Adv. Manuf. Technol., 25, 350
and vitreous relaxations and thereby calculate the glass (2005).
transition temperatures and activation energies,
respectively. Adhesion tests were performed and the ACKNOWLEDGMENTS
dynamic mechanical analysis technique applied to obtain This work was supported by bilateral project SK-PT
the glass transition temperature. 0012-12.
94

Ferroelectricity of CsRbPb2I6 superlattice

Amirbekova Gulzhanat1, Abdykadyrov Baurzhan1 and Takibaev N. Zh.1


Physics department, al-Farabi Kazakh National University, Kazakhstan, abkxat@gmail.com
ANM-nanomaterial-Poster superlattice spontaneous polarization direction is related
with moving of PbI layers.
INTRODUCTION
MAPbI3 perovskites has been considered as promising -
material for low-cost, high-efficiency solar cells1 Many 3.
studies have followed with the aim of investigation the
40
fundamental properties of perovskites. Theoretical
calculations suggested the possibility of ferroelectricity of 0
MAPbI32.

THEORETICAL STUDY
In this study, we have performed ab-initio calculations of
CsRbPb2I6 halyde perovskites. Used approach is density
functional calculations with the PBE-GGA3. The
momentum space integrations were performed using a
5 4 4 -centered Monkhorst-Pack k-mesh4. We have
applied a linearized form of the investigation of total
polarization of a crystal. This method combines Berry
Phase born effective charges and displacements of ions Figure 2. Berry phase polarization calculation from
from ideal positions5. undistorted tetragonal phase to a fully distorted
orthorhombic phase of (a) [001] projection of CsRbPb2I6
RESULTS AND DISCUSSION and (b) [111] projection of CsRbPb2I6.
The unit cell of perovskite contains 20 atoms. Space
group of [001] layered supercell is Pmc21, [111] rocksalt The total polarization of [001] ordered superlattice is
supercell`s space group is Pna21, this is actually a polar ~0.825 with approximately 93% of that value
space groups shown in Fig. 1. owing contributions from the CsI/RbI layers and the
remainder from the two PbI2 layers(Fig. 2a)..
Secondly we examined the spontaneous polarization
(a) [001] layered (b) [111] rocksalt for the [111] ordered superlattice (Fig. 2b). The total
polarizarion of [111] superlattice is 1.114 . Partial
polarization calculations showed, that The total structural
distortion for the PbI2 compounds is larger than CsI and
RbI compounds. The ferroelectric instability is larger for
the PbI2 compounds.

CONCLUSION
We have examined ferroelectric properties of CsRbPb2I6
superlattices. Spontaneous polarization was commonly
found in [001] and [111] directions. The observed
spontaneous polarization is expected to be one of the
important properties which determines efficiency of
Orthorhombic Orthorhombic perovskite based solar cells.
Figure 1. Structure of CsRbPb2I6 superlattices in [001]
and [111] directions6 REFERENCES

The value of spontaneous polarization is calculated 1. Kim, H.-S. et. al, 2 (2012)
from the born effective charge of each atom in- the 2. Liu, S. et. al, J. Phys. Chem. Lett., 6 (2015)
0.
different Wyckoff positions and the atomic displacements 3. Kresse G., Joubert D., Physical Review B., Vol.59.
03
from equilibrium position of high symmetry phase. Figure (1999)
2(a) shows the spontaneous polarization in [001] ordered
4 4. H.J. Monkhorst, J.D.Pack, Phys. Rev. B, 13 (1976)
superlattice along the b-axis (Ps) which is closely related 5. Yip S., Handbook of materials modeling (2005)
with moving CsI and RbI layers. In [001] ordered 6. Abdykadyrov B., ANM abstracts (2015)
95

Competitive binding between polymer and protein


onto carbon nanotubes as probed by diffusion NMR

Ricardo Fernandes1,2, Matat Buzaglo3, Oren Regev3, Eduardo Marques1* and Istvan Fur2
1*
CIQ-UP, Dept. of Chemistry and Biochemistry, University of Porto, Portugal. efmarque@fc.up.pt
2
Applied Physical Chemistry, Dept. of Chemistry, KTH Royal Institute of Technology, Stockholm, Sweden
3
Dept. Chem. Eng. & Ilse Katz Inst. for Nanotechnology, Ben-Gurion University, Beer-Sheva, Israel.

INTRODUCTION dispersion, the protein is replaced at the SWNT surface.


Pristine carbon nanotubes are hydrophobic in character Consequently, the polymer binds to the nanotube surface
and hence do not disperse in water, requiring either more strongly than the protein.
covalent surface modification or addition of dispersing
agents.1-2 In the latter case, the binding strength of
dispersants to the CNT surface is of great importance for
dispersion efficiency and potential applications. For
instance, the separation of different sorts of nanotubes
(e.g. metallic or semiconducting) can be made possible by
different binding affinity of the dispersants. This affinity,
however, is difficult to assess experimentally and thus
data are scarce on the subject. Here, we present diffusion
NMR results for dispersions of single-walled carbon
nanotubes (SWNTs) prepared with either the triblock
copolymer F127 or the protein bovine serum albumin
(BSA).3,4 NMR allowed to quantify the fraction of Fig. 1. Main findings: (a) lateral diffusion of polymer
dispersant adsorbed, and to detect the surface along the nanotube and surface residence times; (b)
displacement of dispersant. competitive adsorption of polymer and protein onto the
nanotube surface.
EXPERIMENTAL SECTION
The SWNT powder was dispersed in polymer F127 or
CONCLUSION
protein BSA solution using probe sonication followed by NMR diffusion data showed that the polymer F127
centrifugation to remove undispersed materials. The exhibits a stronger binding to the nanotube surface than
concentration of CNT dispersed in the supernatant was protein BSA. We hence provide a way to gauge
quantified by a combined TGA/UV-vis methodology.3,4 adsorption strength of dispersing agents. The preference
1
H NMR experiments were carried out in a spectrometer of one dispersant over another could is extremely relevant
equipped with a z-gradient diffusion probe. The for nanotube applications, such as composite materials
stimulated echo pulse sequence was used. The important and sensing, where high CNT concentration and
parameter is the time delay between gradient pulses, (of selectivity are required.
the order of 10-1,000 ms), the diffusion time.
REFERENCES
RESULTS AND DISCUSSION 1. P. Angelikopoulos et al. Phys. Chem. Chem. Phys. 14,
Protein and polymer molecules exchange between their 9546 (2012).
respective surface-adsorbed and bulk states. With 2. O.V. Kharissova et al., RSC Adv. 3, 24812 (2013).
diffusion NMR experiments like the ones performed here, 3. R.M.F. Fernandes et al., J. Phys. Chem. C 118, 582,
we detected double-exponential diffusional decays for 2014.
polymer F127. From those and their variation with the set 4. R.M.F. Fernandes et al., J. Phys. Chem. C 119, 22190
diffusion time, , we obtained important insights on the (2015).
dynamic equilibrium and surface coverage of F127 on
SWNTs. Two distinct molecular populations were
ACKNOWLEDGMENTS
identified, one diffusing fast (free polymers) and one with Suppor f o o oo
much slower diffusion (CNT-bound polymers). The data (FCT, Portugal) PEst-C/QUI/UI0081/2013 (CIQ-UP) and
also showed that only a minor fraction of the total the Swedish Research Council VR is gratefully
polymer (a few percent) is adsorbed at the surface. acknowledged.
As will be presented in detail, the NMR experiments
further showed that when protein BSA is added to a FI27
dispersion of SWNTs it leaves the adsorbed polymer
coverage intact. However, when F127 is added to BSA
96

Molecular trends in the non-covalent functionalization


of carbon nanotubes with surfactants

Brbara Abreu1, Brbara Claro1, Ricardo Fernandes1,2, Matat Buzaglo3,


Oren Regev3, Istvan Fur2 and Eduardo F. Marques1*
1*
CIQ-UP, Department of Chemistry and Biochemistry, University of Porto, Portugal. efmarque@fc.up.pt
2
Applied Physical Chemistry, Department of Chemistry, KTH Royal Institute of Technology, Stockholm, Sweden
3
Dept. Chem. Eng. & Ilse Katz Inst. for Nanotechnology, Ben-Gurion University of the Negev, Beer-Sheva, Israel.

INTRODUCTION
Due to their high aspect ratio and strong tube-to-tube van and respective surfactant concentration at that point,
der Waals attraction, carbon nanotubes (CNTs) form dispersion effectiveness and efficiency. The effects of
highly entangled bundles and ropes. Hence, CNTs are nanotube morphology and surfactant propertiesnamely
very difficult to be individually dispersed in liquids, a pre- aromatic rings, chain length, headgroup charge and cmc
requisite for many applications.1 In water, non-covalent could be assessed and rationalized, both in terms of
dispersion using adsorbed amphiphilessurfactants, dispersed nanotube mass and surface area.
polymers and proteinsis a suitable approach to
overcome this problem.1,2 Yet, the process is still not well
understood at molecular level. There is lack of systematic
data on dispersibility, partly due to the wide variation and
lack of control of processing conditions leading to large
discrepancies.2,3 In this work, our goal was to investigate
in a systematic way the ability of several ionic surfactants
(Fig. 1) to disperse SWNTs and MWNTs in water using a
stringently controlled methodology and thus obtain
molecular insight on the dispersion process.3

n-2

SDS n = 12
SDBS STS n = 14
Fig. 2 Dispersibility curves for SWNTs and MWNTs
n-2
using (a) anionic and (b)-(c) cationic surfactants; (d)
general curve profile.
DTAB n = 12
TTAB n = 14
CTAB n = 16 CPyCl CONCLUSION
Main conclusions: (i) CNT-surfactant aggregation shows
Fig. 1. Molecular structure of the ionic surfactants used. very different features than other equilibrium processes
governed by hydrophobicity namely micellization; (ii)
EXPERIMENTAL SECTION comparing MWNTs and SWNTs, curvature does not
The exfoliation and de-bundling of CNTs is achieved by a affect much the surface coverage at saturation (iii)
rigorously controlled ultrasonication-centrifugation surfactant aromatic rings and chain length clearly enhance
procedure in presence of surfactant solution. This is dispersion performance; (iv) presence of micelles in the
followed by accurate quantification of the concentration exfoliation process is not crucial for dispersibility.
of dispersed CNTs by combining thermogravimetric
analysis and UV-Vis absorption spectroscopy.3 REFERENCES
1
T. Premkumar et al. Small 8, 1299 (2012).
2
RESULTS AND DISCUSSION A.J. Blanch et al. Carbon 49, 5213 (2011).
3
Single and multi-walled carbon nanotubes (SWNTs and R.M.F. Fernandes et al. Langmuir 31, 10955 (2015).
MWNTs) were employed, covering a wide range of
surfactant concentration, below and above the critical ACKNOWLEDGMENTS
micelle concentration (cmc) of each surfactant (Fig. 2). We kindly acknowledge support from FCT, Portugal,
The dispersion curves obtained allowed us to define and through PEst-C/QUI/UI0081/2013 (CIQ-UP) and the
extract quantitaive metrics, viz. the critical dispersion Swedish Research Council VR.
concentration, maximum dispersed CNT concentration,
97

Study on Nanosize and Temperature Effect on a Bioglass-ceramic Grossular


Ca3Al2Si3O12 Cubic Nanoparticle by Molecular Dynamics Simulations

Serap SENTURK DALGIC 1,*, Vildan GUDER2


1
Department of Physics, Trakya University, TURKEY, serapd@trakya.edu.tr
2
Department of Physics, Trakya University, TURKEY, vildanguder@hotmail.com

The size effect and temperature-induced phase containing 24c, 16a, 24d and 96h ions,
transformations in a cubic Grossular nanoparticle (CGNP) respectively,according to te Wyckoff notation. The
with 4.7nm size have first investigated by molecular heating process in MD simulations ranging from 0K to
dynamics simulation method. The structural evolution of 3500K has established using the NVT ensemble.
the nanoparticle in the presence of vacuum has also RESULTS AND DISCUSSION
studied at the high-temperature range. The predicted The initial MD sample of cubic Ca3Al2Si3O12 NP with an
thermodynamic properties such as temperature dependent average size 5nm is shown in Fig.1.
cohesive energy, heat capacity are compared with that of
the bulk system in order to understand the nanoscale
effect and melting point depression phenomena. The
liquid and amorphous phases of CGNP have determined
from the computed pair distribution functions and
energetics of surfaces. It has been observed that the
melting point of CGNP is lower than that of the bulk
system. The presented computational model is described
well the structure and thermodynamics of a Grossular
cubic nanoparticles in a vacuum.
INTRODUCTION
.Grossular is a member of the silica-garnet group which is Fig. 1 Snapshot of the MD sample of a cubic Grossular
classified as a bioglass-ceramic. It has high degradability nanoparticle with 10240 atoms.
and biocompatibility. There have been many studies to
derive mixing properties of garnet solid solutions from The temperature dependent cohesive energy of CGNP has
phase equilibrium experiments and atomistic calculated and compared with those obtained for bulk
simulations1. Among these, very few studies on physical grossular described in our previous paper2. The calculated
properties of grossular2, especially on grossular NPs. radial distribution functions have detailed information
However, bioceramic nanoparticles are expected to have about the nature of structure and melting process of
improved bioactive properties, due to their high aspect grossular cubic nanoparticles in a vacuum.
ratio exhibited by the nano-materials3. CONCLUSION
The purpose of this study is to present a computational In this work, we have investigated the size effect on the
model in exploring the size and temperature dependent grossular cubic nanoparticles by comparing with bulk
some physical properties of grossular bioceramic properties. The temperature-induced phase transformation
nanoparticles. Because of its high melting point, the cubic has found. This study provides an approach to the
shape NPs (nano boxes) are preferred as MD samples to investigation of size and temperature dependent properties
be able to predict the thermodynamic behaviour of of the grossular bioceramic NPs. The obtained results
grossular in nanoscale.It has known that cubic NPs are may be helpful to understand the behaviour of bioceramic
more energetic nanomaterials than spherical ones but less small nanoparticles. However, the shape effect on the
than polyhedral shape NPs. energetic properties of grossular NPs is needed to be
METHOD investigated in future research.
In this work, structure optimization of the system was *corresponding author; e-mail: serapd@trakya.edu.tr
performed with GULP (General Utility Lattice Program) REFERENCES
MD simulation code4. We also use the LAMMPS MD 1. V. Haigis et. al, Chem Geol. 346, 14 (2013).
Simulator5 for computing the some nanoscale physical 2. S. Senturk Dalgic et. al, Acta Phys.Pol. A (in 2016).
properties of CGNPs. The pair interactions were modelled 3. C. Covarrubias et. al, Appl. Surf. Sci., 363, 286(2016).
with short range ionic potentials and a long-range 4. J. D. Gale, A.L. Rohl, Mol. Siml. 29, 291(2003).
Coulombic interaction term. MD sample of Grossular NPs 5.S.Plimpton, J.Comp. Phys. 117, 1 (1995).
have created from a unit cell, 4x4x4 repeated periodically. ACKNOWLEDGMENTS
It is known that bulk Grossular crystallizes in the Ia3d The authors thank Trakya University and OYP
space group in a cubic system. In the structural formula of Programme for supporting the attendance of the ANM
Ca3Al2Si3O12 , where the Ca, Al, Si and O atoms 2016 Conference.
98

Electrospun nanofibers of Poly(vinyl alcohol) Thiolated Loaded with Cisplatin


Romero-Garca Jorge1*, Zavala-Betancourt, Sara1 and Ledezma-Prez Antonio1 , Torres-Lubian, Romn
1
Centro de Investigacion en Qumica Aplicada, Saltillo Coahuila, Mexico.

INTRODUCTION for other thiolated polymers. It is worth mentioning that


during storage of the thiolated PVA at differente
The cis-platinum (cis-diamminedichloroplatinum (II) temperatures decreased over time the solubility of this
(CDDT), is an inorganic compound whose therapeutic polymer. This we attributed to the possible formation of
activity is well known. Over the last 40 years, platinum- bridges or -S-S- intrachain and form interchain reticulated
containing drugs have been the main chemotherapeutic structures due to humidity and temperature.
agents used in the treatment of different cancers Figure 1 show the PVA and PVA-SH electrospun
(testicular cancer, cervical, ovarian, bladder, lung, nanofibers loaded with 5 % of CDDT. The best results
stomach, etc.)1. Although, this drugs are very potent in were obtained when the distance from tip of the needle to
the treatment of various cancers, this has certain the aluminium collector was increased up to 20 cm.
disadvantages, such as the development of resistance by a b c
The flow of the solution was kept 0.3mL/h and a
tumorogenic cells2. Various strategies have been voltage of 20 kV.
suggested to avoid these drawbacks. Among them, the
synthesis of new Pt (II) coordinated complexes3 and
synthesis of prodrugs based on coordinated Pt (IV).
However, these agents still show certain toxic effects,
which are associated with the effective dose and form of Figure 1. SEM micrographies of PVA and PVA-SH
therapeutic administration. The design of safe methods, electrospun nanofibers: a)Neat PVA, b) PVA-SH and
controlled and targeted release of these drugs has emerged PVA-SH CDDT loaded
as an alternative to counteract the side effects and at the The neat PVA electrospun nanofibers observed by SEM
same time maximize their efficacy4. The polymeric show a cylindrical morphology, flawless and with an
nanostructures are a few examples of such carriers for average diameter of 211 nm (Fig. 1a),However, the
drug release. Recently, electrospinning of polymer preparation of nanofibers using PVA-SH causes the
nanofibers has emerged as a platform where research is formation of drops or defects and slight a diameter
being conducted for the controlled and targeted release of increase (Fig. 1b). The electrospun nanofiber CDDT
biomolecules and drugs5. loaded have an increase in their diameter up to 238 nm
PVA has an outstanding feature due to the presence of The increased content of PVA-SH causes the formation of
OH groups and that allows to perform certain types of We assume that the diameter increase could be due to
chemical modifications, such as the thiolation, where the increased content of PVA-SH used in the manufacture of
addition of -SH free groups in its structure, leads to nanofibres and likely the closer proximity of the polymer
dynamic changes from -S-S- to SH with other chains in the solution promote formation of bringing S-
molecules that contain free thiol groups. S- reaction.
This work, describes the conditions to obtain and
characterize electrospun nanofibers of PVA, PVA-SH, CONCLUSION
and PVA-SH loaded with CDDT. PVA-SH and PVA-SH CDDT loaded electrospun
nanofibers was achieved. We are in the process to
EXPERIMENTAL/THEORETICAL STUDY evaluate kinetics od CDDT release from the nanofibers.
Materials. The PVA-SH (125,000 g / mol, PVA-SH125K)
was synthesized in this work7. All the reagents were REFERENCES
obtained from Sigma-Aldrich, except colloidal silver 1. N. P. Farrell. Chem. Soc. Rev., 44, 8773
adhesive, which was obtained from Electron Microscopy (2015).N. P. Farrell, Drugs Future, 37, 795
Science (PA, USA). (2012).
Preparation of PVA-SH nanofibers loaded with cisplatin. 2. A. Samanta, et al., RSC Adv., 4, 43516 (2014).
A prepared PVA-SH solution was used to fabricate 3. E. Schreiber-Brynzak, et al., Metallomics, 2016,
electrospun PVA-SH and PVA-SH cisplatin loaded Advance Article, DOI: 10.1039/C5MT00312A.
nanofibers. The PVA, PVA-SH and electrospun nanofiber 4. O. Vrana Oldrich, et al., Chem., Eur.J. 22, 2728
were characterized by SEM and SEM-EDX, microscopic (2016).
techniques, DSC, TGA, UV/Vis and FTIR 5. I.E. Moreno-Cortez, et al., Mat. Sci. Eng. C, 52
spectroscopies. 306 (2015).
ACKNOWLEDGMENTS
RESULTS AND DISCUSSION
The Laboratorio Nacional de Materiales Grafnicos,
The PVA modification by the thiolation reaction
thanks the finantial support granted by CONACYT
indicates that 220.7 M of -SH groups/g of polymer were
incorporated. Values in these ranges have been reported
99

Application of carbon nitride nanofibers as cathode catalyst in microfluidic fuel cell


Amandeep Jindal and Suddhasatwa Basu*

Department of Chemical Engineering, Indian Institute of Technology New Delhi-110016, India


*Email: sbasu@iitd.ac.in

INTRODUCTION microscopic image of the MFC at Y-junction. Figure 1 (b)


shows the MFC polarization curve for different cathode
Research momentum for microfluidic fuel cells (MFC) catalysts, e.g., Au, Pt and CNx nanofibers. It is seen that
has increased recently due to growth in demand of power CNx nanofibers shows improved peak power density of
source for portable devices. In MFC, the laminar flow of 3.4 mW cm-2 as compared to Au, 2.7 mW cm-2, and Pt,
the fuel and the oxidant flow is maintained within a 3.1 mW cm-2. Corresponding current density increases
microfluidic channel. In order to increase the commercial from 6 mA cm-2 for Au and 6.2 mA cm-2 for Pt to 9.8 mA
feasibility of MFC, research work is being carried out to cm-2 for CNx nanofibers. OCP for all the cathode catalysts
replace Pt catalysts with non-precious ORR catalysts1. In remained constant, 1.1 V.
our previous studies, it was shown that the electrospun
carbon nitride (CNx) nanofibers showed ORR activity 1,2 4
comparable to Pt/C catalysts2,3. In the mentioned study3, (a) (b)

Power density (mW cm-2)


linear sweep voltammetry for ORR showed that CNx/PAN 0,8
3

nanofibers, improved with carbon black and Nafion

Voltage (V)
2
fillers, (referred as CNx nanofibers) showed onset
potential (0.95 V) and peak current density (6.32 mA cm - 1000 m 0,4
CNx nanofibers 1
2
) similar to Pt/C catalysts (0.97 V, 6.41 mA cm-2). In the Pt
present study, CNx nanofibers are employed as the ORR 1000 m 0
Au
0
catalyst in MFC. 0 5 10
Current density (mA cm-2)

EXPERIMENTAL STUDY Fig. 1 (a) Microscopic image of Y-junction of the


microchannel of microfluidic fuel cell, (b) polarization
MFC presented in this work is composed of the glass slide and power density curve at flow rate of 300 L min-1 for
containing the electrodes and the PDMS Y-shape different cathode catalyst
microchannel, used to introduce the fuel and the oxidant.
The microchannel is fabricated using the master template CONCLUSION
made of SU-8 photoresist patterned on silicon wafer. SU-
8 photoresist pattern is defined by UV-lithography on Si CNx nanofiber utilized as cathode catalyst in MFC, marks
wafer. PDMS microchannel is peeled off from the master significant improvement in power density and current
template. In order to fabricate the electrodes, anode and density of MFC as compared to MFC that utilizes Au and
cathode films, placed parallel to each other on the glass Pt as cathode catalysts. Even though there is not much
slide, is patterned using UV lithography. CNx nanofiber, change in OCP, 1.1 V, for MFC tested with CNx
the cathode catalyst, is synthesized using electrospinning. nanofiber, Au and Pt as cathode catalysts, maximum
The ORR catalytic activity of CNx nanofibers is compared power density is observed for CNx nanofibers (3.4 mW
with Pt and Au by comparing the current-voltage plots of cm-2) followed by Pt (3.1 mW cm-2) and Au (2.7 mW cm-
MFC employing the aforementioned cathode catalysts. Pt 2
).
layer is used as the anode. The PDMS microchannel is
aligned and soft-bonded to the metallized glass slides. It is
made sure that the electrodes lie within the microchannel REFERENCES
width.
Fuel is composed of 0.5 M H2SO4 and 2.1 M HCOOH. [1] A.S. Gago et al. J. Power Sources 196, 1324
Oxidant is composed of 0.5 M H2SO4 and 0.144 M (2011)
KMnO4. The fluid flow for all MFC tests is pressure [2] A. Jindal, S. Basu et al. RSC Adv. 5, 69378
driven. The flow rates of the fluid are controlled by the (2015)
syringe pump. The flow rate of the fuel and the oxidant is [3] A. Jindal, S. Basu, Int. J. Hydrogen Energy
maintained 300 L min-1. Tungsten probes is utilized to (2016) in press,
make the electrical connection from the electrodes. http://dx.doi.org/10.1016/j.ijhydene.201.
RESULTS AND DISCUSSION ACKNOWLEDGMENTS
MFC is fabricated with channel dimensions of 800 m
(W) x 125 m (H) x 37 mm (L). Figure 1 (a) shows the
Authors would like to acknowledge DIT, Government of
India for funding the project.
100

In-situ Solid State Synthesis of Silver and Nickel Doped g-C3N4 for Efficient
Photoelectrocatalytic Water Splitting

Nimai Bhandarya,b, Pravin. P. Ingolea, Suddhasatwa. Basub*


a
Department of Chemistry, Indian Institute of Technology Delhi, New Delhi-110016
b
Department of Chemical Engineering, Indian Institute of Technology Delhi, New Delhi-110016
Email: sbasu@iitd.ac.in

INTRODUCTION both Ag and Ni ions incorporation it shows large


Development of a suitable low cost, efficient, visible-light hypsochromic shift which proves a decrease in band gap
active photocatalyst for environmental protection and that is beneficial for visible light absorption in
solar fuel has remained a challenge for global photocatalytic. TEM analysis proves after Ag and Ni
researchers.1 Since the first report by Fujishima and nanoparticles are embedded on layered carbon nitride
Honda2 as photoinduced water splitting catalyst on TiO2 building block which is helpful for enhanced activity.
semiconductor based electrode, various photocatalysts PEC data suggests both the Ag and Ni metal ion
emerged as efficient catalyst. In spite of significant embedded g-C3N4 samples photoanode showed much
advancement with TiO2 as photocatalyst, its application is higher photocurrent 1.29 mA/cm2 at 1.0 V versus
restricted due to wide band gap of 3.2 eV which hinders Ag/AgCl, than the all other prepared samples which
visible solar light utilization.3 Tremendous efforts have suggests that the co-doping of metal ions in g-C3N4
been made to modify TiO2 with metal doping or dye promotes enhanced visible light absorption due to
sensitization and coupling with another semiconductor for synergic effect of Ag and Ni ions and encourage the fast
heterojunction which can enhance solar light utilization separation of photogenerated charge carrier
and improve photocatalytic performance but still it has 5 g-C3N4
1.4
6
g-C3N4 under dark g-C3N4
8
g-C3N4
not reached the expectation of technologist in this field. In 1.2 g-C3N4 under Light Ag-g-C3N4 7

JP (A/cm2)

1/C2x 1010 (cm4 F-2)


Ag/g-C3N 4 Ag/g-C3N4
Ni-g-C3N4

this regards g-C3N4 has attracted much more interest due


4 Ni/g-C3N4 1.0 2 6 Ni/g-C3N4
AgNi-g-C3N4
2

AgNi/g-C3N4 AgNi/g-C3N
[F(Roo)h]

5
its suitable band gap of 2.7 eV which is capable of

JP (mA/cm2)
0.8 0
3
2 -2 4
F = (1-R) /2R
absorbing sunlight efficiently.4 Its graphitic carbon
0.6 -0.2 0.0 0.2 0.4 0.6 0.8
E (V vs Ag/AgCl)
2 3
0.4
(b)
nitrogen network have revealed many visible light driven 1
(b) 0.2
(a) 2

photocatalytic applications like degradation of organic


1
0.0
0 0
pollutants in water, solar H2 generation, conversion of 2.0 2.5 3.0
h (eV)
3.5 4.0 0.4 0.5 0.6 0.7
E (V vs Ag/AgCl)
0.8 0.9 1.0 -1.5 -1.0
E (V
-

CO2 to useful fuel etc. Herein, we report in-situ Fig. (a) I-V plot in 1.0 M NaOH (b) UV-Vis DRS.
(c)
incorporation of Ag and Ni ions in g-C3N4 matrix by 500

direct solid state heat treatment method. CONCLUSION 400

Photoelectrochemical (PEC) water splitting is studied In summary, a novel Ag-Ni/g-C 3N4 photocatalyst is
Zimg ()

g-C3N4
300
Ag/g-C3N4

with such catalyst which exhibits excellent activity with synthesized based on in-situ200solid state heat treatment Ni/g-C3N4

respect to photocurrent density. route. The catalyst is demonstrated to present excellent


AgNi/g-C3N4

100
EXPERIMENTAL photoelectrochemical activity 0 for solar water splitting.
Graphitic carbon nitride was prepared by simple heat The catalyst holds great promise0
as 400
200
future
600
material
800
in
1000 1200
Zr ()
treatment. Briefly 5.0 g of melamine is heated at 550 C energy conversion devices.
in a quartz tube kept in muffle furnace under flow of
nitrogen gas with a heating rate of 5 degree/min. Metal
ions doped g-C3N4 is prepared following the same REFERENCES
procedure but by adding metal precursor. A desired 1. A. J. Nozik, M. C. Beard, J. M. Luther, M. Law,
weight ratio of melamine and metal nitrate are taken. R. J. Ellingson and J. C. Johnson, Chem. Rev.,
After they are grinded well with mortar and pestle a 2010, 110, 68736890.
homogeneous fine particles of the mixture is obtained 2. A. Fujishima, K. Honda, Nature, 1972, 238, 37.
which is then heat treated following the same route as 3. F. Zuo, K. Bozhilov, R. J. Dillon, L. Wang, P.
mentioned earlier for pure carbon nitride. Smith, X. Zhao, C. Bardeen, P. Feng Angew.
Chem. Int. Ed. 2012, 51, 6223 6226
RESULTS AND DISCUSSION 4. Y. Wang, X. Wang, M. Antonietti, Angew.
Chem. Int. Ed. 2012, 51, 6889
The optical absorption and energy band gap structure of
g-C3N4 changes significantly after introduction of metal ACKNOWLEDGMENTS
ions into carbon nitride network as apparent from the UV- Authors would like to acknowledge DST, Government of
Vis diffuse reflection spectra, After incorporation of Ag India for funding the project.
ion a slight hypsochromic shift of the photoabsorbtion
edge in comparison to pure g-C3N4 is observed. After
101

Nanostructured transition metal oxides as co-catalyst anodes for direct ethanol fuel cells

Youling Wang, Haixia Wang, Amel-Tabet Aoul and Mohamed Mohamedi*

nergie, Matriaux et Tlcommunications (EMT), Institut National de la Recherche Scientifique (INRS), Universit de
Recherche, 1650 Boulevard Lionel Boulet, Varennes, Qubec, J3X 1S2, Canada, mohamedi@emt.inrs.ca

INTRODUCTION SEM images of few examples of TMOs-Pt


Several transition metal oxides (TMOs) are cheap, nanocomposites.
abundant and environmentally benign. Due to particular
native properties and functions of their own, some TMOs
are emerging as a new class of electrode materials for a
large range of applications such as energy conversion
devices like polymer electrolyte fuel cells (PEFCs),1
photoelectrochemical cells,2-3 and energy storage systems,
including rechargeable batteries and capacitors.4
The future of such energy technologies is dependent on
the readiness of improved synthesis routes that allow
tailor-designing, and architecturing TMOs in a specific
way to enhance particular functional properties mainly
when they are combined with other functional materials.
In continuation of our efforts to develop new catalysts
based on nanostructured metal oxides that enable or
Fig. 1 Few examples of TMOs films grown with one
provide enhanced catalytic performance towards ethanol beam laser PLD onto CNTs. (a) CNT/SnO2, (b)
oxidation reaction, we will addresses the challenges and CNT/TiO2, (c) CNT/MnO2 and (d) CNT/CeO2.
the developments of anode catalysts for Direct ethanol
fuel cells (DEFCs). In particular, we will emphasize our
recent results obtained with TMOs (CeO2, SnO2, TiO2,
MnO2)-Pt grown onto carbon nanotubes (CNTs) substrate
nanocomposite anode. Correlations between surface
morphology and electroactivity towards ethanol oxidation
reaction (EOR) will be discussed.
EXPERIMENTAL/THEORETICAL STUDY
Nanostructured TMOs-Pt films are grown onto CNTs at
room temperature by an asymmetric cross beam pulsed
laser deposition (CBPLD) geometry, which permits to
mix TMOs and Pt directly in the laser plasma. The gas
atmosphere in the deposition chamber was also varied in
order to produce various morphologies of the TMOs-Pt
films. Such synthesized CNT/(TMOs-Pt) materials are Fig. 2 Few examples of CBPLD-grown (TMOs-Pt) films
comprehensively characterized with SEM, XRD, XPS, onto CNTs. (a) CNT/(MnO2-Pt), (b) CNT/(CeO2-Pt), (c)
micro Raman spectroscopy, and TEM (HR-TEM) CNT/(SnO2-Pt) and (d) CNT/(TiO2-Pt).
techniques. The electroactivity and durability of
CNT/(TMOs-Pt) as well as catalytic promoting properties CONCLUSION
of TMOs towards EOR were studied with cyclic Given proper synthesis conditions, CBPLD developed
voltammetry and chronoamperometry, respectively in 0.5 TMOs-Pt thin films demonstrated remarkable durability
M H2SO4+ 1M Ethanol solution. and provided electrochemical performance much greater
RESULTS AND DISCUSSION than the Pt catalyst.
Figure 1 shows SEM images of few examples of TMOs REFERENCES
grown under He atmosphere onto CNTs using one laser 1. Z. Zhang et al, Energy Environ. Sci. 7, 2535 (2014)
beam PLD. Depending on the interaction with CNTs, 2. K. Singh et al, Chem. Soc. Rev. 42, 1961 (2013)
different morphology can be observed, i.e., highly porous 3. N. Nuraje et al, Curr. Inorg. Chem. 2, 124 (2012)
SnO2 film (Fig. 1a), TiO2 with forest-like structure (Fig. 4. Y. Ren et al, Chem. Soc. Rev. 41, 4909 (2012)
1b), segmented MnO2 film into clusters of particles (Fig.
1c), and cauliflower like CeO2 (Fig. 1d). Fig. 2 shows
102

Carbon nanotubes synthesis through laser ablation in ionic liquids and their surface
properties tuning ability in a HDPE matrix

Catalin Croitoru1*, Silvia Patachia2, Alexandru Pascu1, Ionut Roata1, Elena Manuela Stanciu1 and Mircea Tierean1
1
Department of Materials Engineering and Welding, Transilvania University of Brasov, Romania, c.croitoru@unitbv.ro
2
Department of Product Design and Mechatronics, Transilvania University of Brasov, Romania

INTRODUCTION of the carbon nanotubes with the ionic liquid cation


moieties, as determined from XRD diffractograms. The
Carbonaceous nanomaterials have attracted great interest
presence of nanotubes in the polyolefin matrix determined
due to their wide range of useful and tunable mechanical,
a surface energy ranging from to 30.5 to 40 mN/m,
optical and electrical properties, while embedding them
depending on the type of ionic liquid used.
into various types of matrix (organic, ceramic, metallic)
[1-3]. Carbon nanotubes reinforced polymer composites CONCLUSIONS
currently present a large variety of applications, among
Carbon nanotubes have been obtained through laser
which the most important is represented by their low
ablation in ionic liquids. HDPE-carbon nanotubes
density, where mechanical reinforcement or increased
composites were prepared by using twin-screw melt
electrical conduction are required [2]. In order to obtain
compounding. The electron microscopy results have
composites with improved properties, the nanotubes must
indicated that the nanotubes are well distributed and
be uniformly distributed and dispersed throughout the
dispersed in the HDPE matrix, with both individual as
polymer matrix, and secondly, an improved interfacial
well as agglomerations of nanotubes being evident. XRD
interaction/wetting between the polymer and the
spectroscopy has evidenced the possible functionalization
nanotubes must be obtained [4]. Liquid phase laser
of the carbon nanotubes with the dominatingly
ablation in ionic liquids has been proven as an efficient
hydrophobic cation, which owes for an improved
method of obtaining nanotubes with improved properties,
compatibility with the dominatingly dispersive polyolefin
or in functionalization of nanotubes [4].
matrix.
EXPERIMENTAL/THEORETICAL STUDY
REFERENCES
Carbonaceous nanoparticles have been obtained through 1. M.L. Polo-Luque et al, TrAC Trends in Analytical
laser ablation of graphite in two different types of ionic Chemistry, 47, 99110 (2014)
liquids, namely 1-hexyl-3methylimidazolium chloride and 2. Y. Shim et al, ACS Nano, 3 (7), 16931702 (2009)
trihexyltetradecylphosphonium chloride, by using a diode 3. M. Mohammadi et al. Physical Chemistry Chemical
1 kW (wavelength of 970 nm) laser, with a 2 mm Physics, 7, 2482-2494 (2013)
diameter defocused spot at different power densities. The 4. S. Kanagaraj et al, Composites Science and
irradiation time was kept constant at all experimental Technology, 67, 30713077 (2014).
synthesis tests. The obtained nanotubes have been
characterized through scanning electron microscopy,
ACKNOWLEDGMENTS
FTIR, UV-VIS spectroscopy and XRD, in order to
determine the morphology, compositional and structural This work was supported by the Romanian National
information about the synthesized material. The obtained Authority for Scientific Research and Innovation, CNCS-
nanomaterials have been embedded into HDPE by using UEFISCDI, project number PN-II-RU-TE-2014-4-0173.
various ratios of nanomaterial, reported to the matrix. The
distribution of the nanomaterial in the matrix and the
compatibility between the two components has been
determined by SEM and FTIR spectroscopy. The surface
properties have been evaluated by contact angle
determinations and AFM microscopy.
RESULTS AND DISCUSSION
The obtained nanomaterial can be clearly identified and is
uniformly dispersed, either as single nanotubes or as
aggregates of varying dimensions. The embedding of the
carbon nanotubes into the HDPE matrix has led to the
obtaining of a uniformly distributed nanomaterial, as
demonstrated from the AFM and SEM microscopy
results. This could be due to the possible functionalization
103

Optomagnetism and ultrafast spintronics in Carbon-based materials via optical


vortices
Jonas Wtzel1, Alexander Schffer1, Michal Ingolt2, and Jamal Berakdar1*
1
Institut fr Physik, Martin-Luther-Universitt Halle-Wittenberg, Halle, Germany
2
Department of Physics and Medical Engineering, Rzeszw University of Technology, Rzeszw, Poland
*
presenting author, email: jamal.berakdar@physik.uni-halle.de

INTRODUCTION
Over recent years remarkable advances were made in the
fabrication and control of optical vortices, i.e. light beams
carrying orbital angular momentum. Nowadays such
beams are routinely produced in a wide range of
frequencies, intensities, and duration1. When interacting
with matter optical vortices can transfer a definite and
controllable amount of orbital angular momentum1 and
offer so a new way for light-assisted, ultrafast spintronics,
particularly in spin-orbit coupled systems2. Fig. 1 (left) irradiating C60 with light carrying orbital
angular momentum (blue ring) drives charge loop
currents on C60 in the plane perpendicular to the
THEORETICAL STUDY propagation direction. The associated magnetic pulse can
In this contribution we aim at triggering via optical steer an encapsulated magnetic structure (arrow) or
vortices an orbital charge current in Carbon-based locally control the magnetism of a spin-active substrate.
materials such as endohedral molecular magnets3, (Right) the generated loop current density after the pulse
graphene, or graphene nanostructures, as well as in the plane of the vertex.
semiconductor nanostructures with a strong Rashba spin
orbit coupling. We evaluate the associated magnetic field CONCLUSION
pulses and envisage the possibility of controlling these Vortex light pulses offer qualitatively new opportunities
pulses by tuning the light parameters. These internal for optomagnetics and ultrafast spintronics. The
magnetic field pulses serve then for steering the local spin topological charge of the vertex beam is a new feature
dynamics or spin polarized currents on a femtosecond with which the amount of the angular momentum transfer
time scale. to the sample can be controlled.
REFERENCES.
RESULTS AND DISCUSSION
Our quantum full-fledge numerical and analytical studies4
1. D. L. Andrews, Structured light and its applications:
for the carrier propagation in vertex beams show that
An introduction to phase-structured beams and
indeed an optical vertex beam can orbitally magnetize
nanoscale optical forces (Academic Press, 2011).
endohedral fullerenes by generating loop currents on the
surface (cf. Fig.1) that are controllable by the frequency, 2. G. F. Quinteiro, P. I. Tamborenea, and J. Berakdar,
Opt. Expr. 19, 26733 (2011).
the topological charge, and the intensity of the light. The
3. J. Crose et al. Nat. Mater. 7, 884 (2008); R.
loop currents generate in turn internal magnetic pulses
Westerstrm et al., J. Am. Chem. Soc. 134, 9840
that can be utilized to steer the spin dynamics of
encapsulated magnetic structures. Further examples, to be (2012)
4. J. Wtzel, Y. Pavlyukh, A. Schffer and J. Berakdar,
presented at the conference, evidence the potential of
Carbon 99, 439-443 (2016)
these beams for steering the orbital and spin degrees of
5. J. Wtzel, and J. Berakdar, Scientific Reports 6,
freedoms in structured, semiconductor-based two-
dimensional electron gas5 and graphene. First experiments 21475 (2016)
6. M. A. Noyan, and J. M. Kikkawa, Applied Physics
with vortex light interacting with semiconductors6
Letters 107 (2015).
highlight the quantitatively new features of the dynamics
driven by optical vortices.
ACKNOWLEDGMENTS

This work was supported by the Deutsche Forschungs-


gemeinschaft under SPP 1840.
104

Sputtering of Cu2ZnTiS4 thin films for solar cells

Derya Kaya1, Murat Toku2, Yusuf Selim Ocak3,*, Mustafa Fatih Genisel3 , Omer Celik4, Ahmet Tombak5
1
Department of Physics, Institute of Applied Science Dicle University, Diyarbakir, Turkey,
deryak545@gmail.com
2
Department of Biophysics, Faculty of Medicine, Cukurova University, Adana, Turkey
3
Department of Science, Faculty of Education, Dicle University, Diyarbakir, Turkey,
yusufselim@gmail.com
4
Department of Physics, Faculty of Education, Dicle University, Diyarbakir, Turkey
5
Department of Physics, Faculty of Science, Batman University, Batman, Turkey

INTRODUCTION 0388 for CZTS. Furthermore, the Raman spectroscopy


Cu2ZnSnS4 (CZTS) is one of the most exiting peaks were coherent with the peaks of CZTS thin films.
quaternary semiconducting compound materials for solar The optical band gap values of all films were recorded
cell applications as an absorber layer. The band gap of lower than 1.5 eV. The results implies the successful
the CZTS is about 1.5 eV. Many studies have been formation CZTiS thin films by co-sputtering technique
reported to control electrical and optical properties of with lower band gap compared to conventional CZTS thin
CZTS thin films by changing the elements in the films Furthermore, the photovoltaic properties of the cell
structure. Ti is one of the rare abundant materials. Wang fabricated using CZTiS films obtained various substrate
et al [1] calculated the electronic structure of the temperature were compared to each others.
Cu2ZnTiS4 compound between 1.1 and 1.3 eV. They also
reported that the optical absorption coefficient of CZTiS
compound is higher than the conventional CZTS thin
films. Various approaches have been reported to obtain
CZTS layers including thermal co-evaporation,
sputtering, sol-gel methods and pulsed laser deposition.
Co-sputtering allows us to deposit homogeneous thin
films on different substrates using more than one source
at the same time.
In this study we have deposited CZTiS thin films by
co-sputtering technique and determined morphological,
structural and optical properties.

EXPERIMENTAL/THEORETICAL STUDY
CZTiS thin films were deposited on glass and Mo
coated glass substrates by co-sputtering technique using
ZnS, Cu and Ti target as sources. Thin films were
deposited at various substrate temperatures (100, 175 and
250 C). The obtained films were also annealed at 400 C
in H2S+Ar atmosphere to increase the quality of the films.
The structural, morphological and optical properties of Fig. 1 XRD patterns of CZTiS thin films deposited at
CZTiS thin films were analyzed by means of x-ray various substrate temperatures
diffraction (XRD), Raman spectroscopy, scanning
electron microscopy (SEM), energy dispersive
spectroscopy (EDS) and uv-vis data. After analyzing thin CONCLUSION
films, CdS, ZnO and Al doped ZnO layers were sputtered In this study, CZTiS based solar cell obtained by
to obtain solar cells. The photovoltaic properties of the deposition of CZTiS thin films using co-sputtering
cells were determined under a solar cell with AM.1.5 technique.
filter.
REFERENCES
RESULTS AND DISCUSSION 1. X. Wang, J. Li, Z. Zhao, S. Huang, W.Xie, J. Appl.
The SEM images showed that the increase in Phys. 112, 023701 (2012)
temperature increased the aggregation on the surface and
EDS results showed that the films were Cu rich and Ti ACKNOWLEDGMENTS
poor. The CZTS peaks were observed for all films. The This study is supported by TUBITAK with 114F363
XRD data were coherent with ICDD card number 04-005- Grand Number.
105

Conversion from p- to n-type conductivity in copper (II) oxide thin films by cobalt
doping

Silan Baturay1, Derya Kaya2, Ahmet Tombak3, Yusuf Selim Ocak4,*


1
Department of Physics, Institute of Applied Science Dicle University, Diyarbakir, Turkey,
2
Department of Physics, Faculty of Science, Dicle University, Diyarbakir, Turkey
3
Department of Physics, Faculty of Science, Batman University, Batman, Turkey
4
Department of Science, Faculty of Education, Dicle University, Diyarbakir, Turkey,
yusufselim@gmail.com

INTRODUCTION RESULTS AND DISCUSSION


Due to its unique electrical and optical properties, No clear changes in the XRD peak positions were
copper (II) oxide (CuO) potentially has a wide variety of evident in the diffraction data; the few additional peaks in
applications. It is commonly known that CuO has p-type the spectra, which were believed to be associated with the
conductivity; however, we report observations of n-type peaks of Co atoms, were so weak that they vanished in
conductivity in thin CuO films for the first time. We regions with a noisy signal. The peaks of all of the films
achieved n-type electrical conductivity in CuO films with exhibited a wurtzite structure, with no other peaks in their
cobalt (Co) doping. Pure and Co-doped CuO thin films line limit.
were fabricated using a spin coating technique. Electrical SEM and AFM analyses indicated that the Co-doped
parameters, specifically, the charge carrier concentration, CuO nanoparticles formed crystal grains that were
sheet resistance, and conductivity type were investigated spherical in shape. The size of the grains depended on the
using a van der Pauw Hall measurement system. The concentration of the Co-doping solution and increased
effects of metal doping on the width of the optical band from 18 to 47 nm as the concentration of the Co solution
gap were investigated using ultraviolet-visible increased from 0% to 10%, respectively.
spectrometry over the wavelength range of 300 to 1100 A slight increase in the optical band gap was
nm. The optical band gaps for undoped and 10% Co- observed with Co-doping. For undoped thin films, the
doped thin CuO films were 1.70 and 1.83 eV, band gap was 1.70 eV; the band gap increased to 1.83 eV
respectively. in films prepared with a Co solution concentration of 10
wt%.
EXPERIMENTAL/THEORETICAL STUDY Finally, The electrical properties at room temperature
Pure and Co-doped CuO films were deposited of pure and Co-doped CuO thin films obtained from
onto soda lime glass substrates at room temperature by deposition of solutions with various concentrations of Co
means of spin coating technique using pure copper (II) were studied. The values measured for the resistivity at
acetate (Cu(CH3COO)2H2O) and CoCl2.6H2O solutions. each concentration are shown in Table 3. A magnetic
Thin Co-doped CuO films were prepared with the field of 1070 G was applied to the films during the
following Co-doping concentrations: undoped/pure (0 measurements. The electrical properties of the thin Co-
wt%) CuO, and 2, 2.5, 3, 3.5, 4, 6, and 10 wt% Co. All of doped CuO films was affected by the Co concentration
the films were annealed at 500C for 1 h in a furnace to used for doping. Pure, undoped CuO films have p-type
obtain a crystalline structure. conductivity; however, a transition to n-type conductivity
The crystalline properties and phase purity of was observed in conjunction with Co-doping.
pure and Co-doped CuO films were characterised by
XRD over a range of 2 values. The surface
morphologies and structural characteristics of the films CONCLUSION
were investigated with SEM and AFM. The electrical We investigated the optical, electrical, and structural
properties of the prepared films were examined using a properties of undoped and cobalt (Co)-doped thin copper
van der Pauw Hall measurement system at room oxide (CuO) films, fabricated at room temperature using a
temperature. The electrical properties of the films were of spin coating technique. It was observed the Co doping
particular interest, because the Co-doped CuO films with changes the conductivity type of CuO thin films.
doping concentrations of 3, 3.5, 4, 6, and 10 wt% Co
exhibited n-type conductivity. The values of the
reflectance, absorbance, and transmittance coefficients of
the pure and Co-doped CuO films were analysed using a
UV-Vis spectrophotometer over the wavelength range of
3001100 nm.
106

Characterization of Ultrasonically Sprayed Cu2CdSnS4 Thin Films For Solar Cell


Applications
A.Tombak1, Y.S. Ocak,2,3,* T. Kilicoglu,1
1
Batman University, Faculty of Science & Technology, Department Physics, Batman, Turkey
2
Dicle University, Faculty of Education, Department of Science, Diyarbakr, Turkey
3
Dicle University Science & Technology Application & Research Center, Diyarbakr, Turkey
email of presenting author:yusufselim@gmail.com

INTRODUCTION absorption coefficient, which is larger than 104 cm-1 in the


visible wavelength region indicating the value is suitable
The need for energy has been increasing day by day in the for solar cell applications of thin films. The optical band
world. Fossil fuels which are used to eliminate the need gap energy of the Cu2CdSnS4 film can be estimated from
both they are depleted and cause environmental disasters. the (h)2 versus h graph by extrapolating the linear
These environmental disasters cause irreversible damages absorption edge part of the curve. The result shows that
for example global warming and air pollution. For this the optical bandgap of the Cu2CdSnS4 film is around 1.38
reason, the need for new and renewable energies is eV.
constantly increasing and countries, scientists focus on the
important issues. In this respect, solar energy among
renewable energies is the most important candidate
resource. In recent years, studies on this issue are very
important and exciting. Kesterite phase of Cu2ZnSnS4
(CZTS) occurs in nature and is the most likely alternative
to Cu(In,Ga)Se2 (CIGS) thin film solar cells which started
to spread increasingly in all over the world by
commercially. Cu2CdSnS4 (CCTS) is a semiconductor
with a band gap of 1.37 eV and a large absorption
coefficient over 104 cm1 is also considered as a possible
photovoltaic material owing to its similar structure with
CZTS.

EXPERIMENTAL STUDY Fig. 1 SEM image of Cu2CdSnS4 thin film grown at


320C
Ultrasonic Spray Pyrolysis (USP) is very powerful
technique to get homogenous, repeatable and large area Table 1. Band gaps of CCTS samples (eV)
thin films. In this work, cheap and abundant material
containing Cu2CdSnS4 (CCTS) starting to find its place in Substrate Unannealed Annealed Annealed
solar cell production, quaternary semiconductor films Temperatures at 400 C at 500 C
were produced on glass substrates by the ultrasonic spray (C) H2S H 2S
pyrolysis method at different substrate temperatures. The ambient ambient
structural features of thin films were determined by X-ray 280 1.32 1.38 1.40
diffraction (XRD), the molecular structure by Raman 320 1.25 1.39 1.39
spectroscopy, surface morphology by the Atomic Force 360 1.28 1.40 1.39
Microscope (AFM) and Scanning Electron Microscopy 400 1.25 1.40 1.38
(SEM). Light transmittance and absorbance of the films
were used for determining of absorption properties by CONCLUSION
UV-VIS-NIR as absorber layers in photovoltaic
applications and after determining optical band gap of the The results showed that ultrasonically sprayed CCTS thin
device were detected. Important electrical parameters of with 1.38 eV which is lower than CZTS thin films (1.51
solar cells such as charge carrier density, conductivity eV) and high conductivity is very suitable for high
type and resistivity were measured by Hall effect efficient solar cell fabrication
measurement system.
ACKNOWLEDGMENTS
RESULTS AND DISCUSSION
Authors would like to acknowledge TBTAK for
It can be seen that the annealed film has a large optical financial support with a grant number of 115F234.
107

Effect of electron-surface scattering and thiols adsorption on the electrical resistivity of


metallic ultra thin films

Ricardo Henriquez1*, Claudio Gonzalez1, Jonathan Correa-Puerta2, Valeria Del Campo1, Marcos Flores2, and Patricio
Hberle1.
1*
Physics Department, Universidad Tcnica Federico Santa Mara, Chile, email: ricardo.henriquez@usm.cl
2
Physics Institute, Pontificia Universidad Catlica de Valparaso, Chile.
3
Physics Department, Universidad de Chile, Chile.

INTRODUCTION specularity parameter P, whereas the effect of electron-


The miniaturization of circuits in current technology has grain boundary scattering, by a reflectivity parameter of
highlighted the old problem of how are affected the grain boundary R. MS dependence on the thickness or
physical properties of a sample when its dimensions on the grain diameter of the resistivity is used to adjust
achieve the nanometric scale, or simply, how the physical values of P and R.
properties are affected by the size effects. From electric
transport viewpoint, today this discussion has achieved RESULTS AND DISCUSSION
characteristic lengths of a few tens of nanometers, Seeking to grow large grains, we fabricated gold ultrathin
orienting the traditional study in thin films to ultrathin films 10 nm thick at different substrate temperature TS.
films1. The deposition of a chromium seed layer 0.8 nm thick,
One of the fundamental questions about electric transport allowed us increase the mean grain diameter keeping low
in metallic films is the effect of the different microscopic resistivity, compared with the value measured in Au/mica
electronic scattering mechanisms on the resistivity samples at room temperature and with the adjustment due
measured macroscopically. The resistivity of a metallic to MS theory.
film at room temperature (RT) can be understood through The measurement of the resistivity increase due to thiol
the presence of three electronic mechanisms: electron- adsorption allowed us to determine conditions that
phonon, electron-surface and electron-grain boundary enhance the electron-surface scattering. Samples
scattering. deposited at 360 K, which showed large grains and
In this work, we present a fabrication method of ultrathin lowest surface roughness, present the highest resistivity
gold films on mica, using a seed layer of chromium. Also, increase due to thiol adsorption.
we characterized the contribution of the electron-surface
scattering to electrical resistance by a method based on CONCLUSION
the resistivity increase due to thiol adsorption on the film In this work, we determined fabrication conditions of gold
surface. ultrathin films that maximize the contribution of electron-
surface scattering on the electrical resistance.
EXPERIMENTAL/THEORETICAL STUDY
Samples preparation was performed through thermal REFERENCES
evaporation in a High Vacuum System (Base Pressure 1. www.itrs2.net
3x10-5Pa) enabled for evaporation of two or more 2. A.F. Mayadas, M. Shatzkes. Phys. Rev. B 1, 1382
materials sequentially. Evaporation rate and film (1970).
thicknesses of gold (99.999% purity) and chromium
(99.99% purity) were measured with quartz ACKNOWLEDGMENTS
microbalances, previously calibrated. The morphology of This work was partially financed by project Fondecyt de
the gold films was characterized by scanning tunneling Iniciacin n11140787.
microscopy (STM). Through these measurements we
obtained two characteristic values mean grain diameter
and surface roughness.
The electrical resistance was monitored by the four-
contacts method injecting a current of 15A and 540 Hz.
Voltage signals were acquired using computer controlled
830's LIA built by Stanford Research. Resistance was
monitored during the thiol adsorption process.
For the theoretical part of this study we used the theory
published by Mayadas and Shatzkes (MS) in 19702. This
is the most widely used theory among those that include
the three scattering mechanisms. In this theory, the effect
of electron-surface scattering is represented by a surface
108

Silver nanoparticles surpass antibiotic-resistance and enhance antibiotics activity

Roberto Vazquez-Muoz1,2, Nina Bogdanchikova3* and Alejandro Huerta Saquero1


1
Department of Bionanotecnology/Center of Nanoscience and Nanotechnology (CNyN), UNAM,
Mxico presenting author
2
Center of Scientific Research and Higher Education of Ensenada (CICESE), Mxico
3
Department od Catalysis//Center of Nanoscience and Nanotechnology (CNyN), UNAM, Mxico
*nina@cnyn.unam.mx

INTRODUCTION
Microorganisms may cause several problems in daily life. Also, AgNPs showed a synergistic effect with some
They are among the leading causes of death worldwide. In antibiotics. Our results showed that synergy could be
food sector, cause millions in losses throughout the attributed to AgNPs-cell interaction, rather than AgNPs-
process chain1. Multi-resistant microorganisms against antibiotics interaction.
conventional treatments is a serious problem worldwide CONCLUSION
and it is cause of great concern2,3. Despite biological differences between microorganisms,
AgNPs have significant antimicrobial properties. The
Developing new antimicrobial agents is critical.
inhibitory capacity of AgNPs and AgNPs is independent
Antimicrobial nanomaterials (nanoantibiotics) are a viable
of antibiotic susceptibility. Nanoantibiotics could be used
alternative to solve this problem. The most promising are
as a first-line treatment for some infections and other
silver nanoparticles (AgNPs), due to their antimicrobial
related health problems. The synergistic effect could
and antiviral properties 46. AgNPs surpass microbial
improve the effectiveness of current treatments, even
resistance against antibiotics and show synergistic effect
allowing reuse of antibiotics that have fallen into disuse
when combined with certain antibiotics 7.
due to antibiotic-resistant microorganisms emergence.
EXPERIMENTAL/THEORETICAL STUDY Nano-antibiotics could have a major social and economic
Microbial strains and culture conditions: Bacteria: E. coli, impact, allowing a more efficient fight against pathogenic
S. enterica serovar Typhimurium, S. aureus and B. bacteria and fungi.
subtilis. Fungi: C. albicans, C. glabrata and F.
oxysporum. AgNPs and Antibiotics. AgNPs from Vector
Vita Ltd. Antibiotics: Kanamycin, Chloramphenicol, REFERENCES
Biapenem, Aztreonam, Amphotericin B, fluconazole, 1. R. Tauxe et al Int. J. Food Microbiol. 139 Suppl , S16
caspofungin, Ampicillin (Sigma-Aldrich). Microbial 28 (2010).
viability assays: M07-A9 and M27-A3 protocols from the
2. E. Silbergeld et al. Annu. Rev. Public Health 29, 151
CLSI. AgNPs-antibiotic combined treatments were
169 (2008).
studied through a microdilution assays. Ultrastructural
analysis: TEM & EDX analysis were performed on a 3. N. Paphitou et al. Int. J. Antimicrob. Agents 42, S25
JEOL ARM 200F. S28 (2013).
RESULTS AND DISCUSSION 4. A. Huh et al. J. Control. Release 156, 128145 (2011).
AgNPs used are spheroids of 35 15 nm in diameter,
stabilized with PVP. MIC of AgNPs for bacteria and 5. M. Rai et al. Biotechnol. Adv. 27, 7683 (2009).
fungi is within the range of 101 g/ml. Although each 6. B. Borrego et al. Nanomedicine (2016).
microbial strain showed different susceptibility to
antibiotics, AgNPs antimicrobial effectivity is the same 7. R. Vazquez-Muoz et al. PLoS One 9, e108876 (2014).
for all strains. AgNPs were found inside and outside the
cells, and attached to the cell wall (fig. 1). ACKNOWLEDGMENTS
We acknowledge CONACYT for the doctoral scholarship
for M.C. Roberto Vazquez-Muoz; To Dr. Miguel Jose
Yacaman (UTSA, USA), To the International
Bionanotechnology Network. To the DGAPA grant
project IN204815.

Fig. 1 TEM image of miicrobial cells with AgNPs S.


aureus (left) and C. albicans (right).
109

Abstract

NFFA-Europe: enhancing European competitiveness in nanoscience research and


innovation.
F.Carsughi, Forschungszentrum Jlich, Germany

NFFAEUROPE is an European open access resource for experimental & theoretical


nanoscience and sets out a platform to carry out comprehensive projects for multidisciplinary
research at the nanoscale extending from synthesis to nanocharacterization to theory and
numerical simulation. Advanced infrastructures specialized on growth, nano-lithography,
nano-characterization, theory and simulation and fine-analysis with Synchrotron, FEL and
Neutron radiation sources are integrated in a multi-site combination to develop frontier
research on methods for reproducible nanoscience research and to enable European and
international researchers from diverse disciplines to carry out advanced proposals impacting
science and innovation. NFFAEUROPE will enable coordinated access to infrastructures on
different aspects of nanoscience research that is not currently available at single specialized
ones and without duplicating their specific scopes. Approved user projects will have access to
the best suited instruments and support competences for performing the research, including
access to analytical large scale facilities, theory and simulation and high-performance
computing facilities. Access is offered free of charge to European users and users will receive
a financial contribution for their travel, accommodation and subsistence costs. The users
access will include several installations and will be coordinated through a single entry point
portal that will activate an advanced user-infrastructure dialogue to build up a personalized
access programme with an increasing return on science and innovation production. The own
research activity of NFFAEUROPE will address key bottlenecks of nanoscience research:
nanostructure traceability, protocol reproducibility, in-operando nano-manipulation and
analysis, open data.
110

Optimized fabrication of ZSM-5 zeolite nano sheets for catalytic applications

A. Bagheri Garmarudi, F. Farsi, M. Khanmohammadi


Chemistry Department, Faculty of Science, Imam Khomeini International University, Qazvin, Iran
bagheri@sci.ikiu.ac.ir

A novel approach has been introduced for fabrication of experimental parameters and template:SiO2 - H2O:SiO2,
MFI zeolite nano-sheets utilizing new surfactants based template:SiO2 - SiO2:Al2O3 and template:SiO2 - aging
on a bicyclo organic structure. In order to assess the time for the interactions. The most important two-way
impact of various parameters on the morphology, crystal interaction variable is template:SiO2 - H2O:SiO2. As f-test
structure, surface area and sheet layer thickness of nano- response for the main factors is much more than two-way
sheets, an experimental design was developed based on interactions thus it can be concluded that the main factors
fractional factorial method. Synthesized nano-sheets were are more effective.
characterized by XRD, TEM, FE-SEM and BET. The
layer thickness was determined between 5.5-10.34 nm
and the mean surface area considering the experimental
design was 355.5

INTRODUCTION
Recently nano-sheet zeolites have been fabricated to
overcome these problems. Different structures of
mesoporous zeolites have been synthesized by suitable
surfactants via micelles formation [1], in which micelles
are the porogen in the mesoporous material, whereas a Fig. 1 typical TEM image of prepared nano-sheet
single molecular template is the porogen for microporous
zeolite. Several templates such as, amphiphilic CONCLUSION
organosilanes, which contain the tetra-alkyl ammonium Hydrothermal method using reflux was studied as a
cation (zeolite template) and hydrophobic long alkyl helpful approach for synthesis of ZSM-5 zeolite nano-
chains (mesopore director) in the same molecule, have sheet using 1,4-Diazabicyclo [2.2.2] octane based
been employed for the synthesis of hierarchical zeolites surfactant templates. While both symmetric and
[2,3]. Recently, efforts have been focused to prepare high- asymmetric surfactants were appropriate for synthesis of
surface-area MFI zeolites with pillared nano-sheet ZSM-5 nano zeolite, only the symmetric one (C10-D-
morphology using multi quaternary ammonium salts as C10) would utilize the formation of sheet morphology.
structure-directing agent (SDA). Several variables may Considering the importance of optimizing the
influence the outcome of a ZSM-5 synthesis. experimental parameters, a fractional factorial model was
employed by which the best nano-sheet could be
EXPERIMENTAL/THEORETICAL STUDY synthesized.
Sodium silicate, Al2 (SO4)3, NaOH, (C10D-C6), H2SO4
and distilled water were mixed to obtain the initial gel REFERENCES
composition of NaO2:Al2O3:SiO2:(C10-D-C10) or (C10D- [21] M. Choi, H. S. Cho, R. Srivastava, C. Venkatesan, D.
C6):H2O. The molar rations of the reaction chemical H. Choi, R. Ryoo, Amphiphilic, Nature Materials 5(2006)
components were of importance to be optimized. 718 723.
Obtained gel was transferred to a round-bottomed flask [22]V. N. Shetti, J. Kim, R. Srivastava, M. Choi, R. Ryoo,
being refluxed for 5-12 days. After crystallization, the Assessment of the mesopore wall, Journal of Catalysis,
zeolite product was filtered, being washed with distilled 254 (2008) 296 303.
water and dried at 120C. The product was calcinated at [23] C. J. H. Jacobsen, C. Madsen, J. Houzvicka, I.
550C for 5 h under air flow. A fractional factorial design Schmidt, A. Carlsson, Mesoporous Zeolite
of experiments was applied to optimize the synthesis Single Crystals J. Am, Chem. Soc, 122 (29) (2000) 7116
process of MFI zeolite nano-sheets. 7117.

RESULTS AND DISCUSSION


Analysis of variance was used to analyze how the
experimental factors affecting ZSM-5 nano-sheet layer
thickness. Statistical results are present in Table 6, where
p-value was used to determine effective factor (p-value
<0.05). The order of the importance is template:SiO2,
SiO2:Al2O3, H2O:SiO2 and aging time. For the
111

A comparative Study of TiO2 Surfaces with Different Topographies on Osteoblast Behavior

Zdenka Fohlerova1*, Katerina Prikrylova1, Katerina Polakova1 and Jaromir Hubalek1


1
Faculty of Electrical Engineering and Communications, Brno University of Technology, Czech Republic

INTRODUCTION
Besides chemical modifications, the nanoscale surface
topography of titanium dioxide and other metals becomes
a crucial factor to be recognized as an attractive and
promising for orthopedic and dental implants
osseointegration1. Up to now, there is an increased
evidence of improved cellular responses on TiO2
nanostructures with different micro- and
nanotopographies2. Some physical and chemical
modifications of titanium surfaces enhancing bioactivity
of cells were also extensively studied3. Futher, there is Fig. 1 SEM images of titanium dioxide nanodots (a) and
also the evidence of the effect of various phases of TiO2 nanorods (b) with inserts of actin filaments stained with
on cell behavior4 etc. ActinGgreen after 24 hours.
Many works in this area were performed on nanotubes
and undefined surfaces with different roughness. The activity of alkaline phosphatase was measured at 48
Therefore, we aimed our work primarily on other and 72 hours (observed confluency). ALP activity tends
structures such as dots and rods. Thus, here we present to decrease on nanostructured surfaces which might
our results arising from comparative study of flat, nanodot corresponds with decreasing of cell number and well as
and nanorod based TiO2 surfaces in amorphous phase to that our introduced nanostructures are unfavorable to
osteoblast adhesion, proliferation and maturation. differentiation of MG-63 cells. However, even when the
decrease of cells at 72 hours was observed on flat surface,
EXPERIMENTAL/THEORETICAL STUDY the ALP activity significantly increased. This might be
The titanium dioxide based nanodot and nanorod surfaces caused by the fact that, despite the cells stopped
in amorphous form were prepared via anodic oxidation of proliferation they increase expression of ALP. The other
alumina and titanium layers. The process ran at 40V in fact we observed is that nanodots surface is more
oxalic acid to get alumina template, followed by potential favorable for cell proliferation than nanorods which can
increase to 80V to obtain nanorods. Alumina was etched correspond with higher roughness.
in mix of HF, CrO3 and water for 5 min at 55C. Surfaces
were characterized by SEM and contact angle CONCLUSION
measurement after one hour UV treatment. The Our results from the interaction of MG-63 cells with three
biocompatibility of nanostructured surfaces was tested on TiO2 surfaces of different nanotopographies indicate that
MG-63 cells by means of adhesion, proliferation and the flat TiO2 surface was more favorable for cells than
alkaline phosphatase activity. surfaces based on nanodots and nanorods. This might be
the indicator of more precise investigation of stability UV
RESULTS AND DISCUSSION treated surfaces in time, to prepare other TiO2 phases for
TiO2 nanodots and nanorods prepared by anodic oxidation comparison as well as to prepare highly ordered
via alumina template are shown in Fig. 1. The diameter nanostructures with different parameters and
and contact angle of dots were 506 nm and 35 and 255 modifications to improve the cell-substrate interaction.
nm with 39 wettability for rods. The flat surface
exhibited with 69 wettability. MG-63 cells adhesion REFERENCES
showed good adhesion at 24 hours. However better spread 1. H. Matsuno et. al, Biomaterials 22, 1253-1262 (2001)
cells were observed on flat TiO2, where filopodia could be 2. J. Park et. al, Nano Lett. 7, 1686-1691 (2007)
well seen. More round or elongated shape was observed 3. D. M. Rivera-Chacon et. Al, J. Biomed. Nanotechnol.
on nanostructures probably due to the induction of stress 9, 1092-1097 (2013)
conditions for cells which is in a good agreement with 4. J. He et. al, J. Mater. Sci: Mater. Med. 19, 3465-3472
literature. The adhesion was also confirmed with the MTT (2008)
test of proliferation. The nanostructured surfaces induced
cells to death in 72 hours, in opposite to the flat surface.
The gradual decrease of cells on flat surface was noticed ACKNOWLEDGMENTS
in 72 hours. Research described in this paper was financed by the
National Sustainability Program under grant LO1401. For
the research, infrastructure of the SIX Center was used.
112

Studies on Synthesis and Optical-Electrical Features of Zn0.5Cd0.5S Quantum Dot


Dispersed Magnesium Niobate Nanocrystals
D. Pukazhselvan1, Nivas Babu Selvaraj2, Igor Bdikin1, R. Sakthi Sudar Saravanan3, Suresh Kumar4 and Duncan Paul Fagg1
1
Nanotechnology Research Division, Department of Mechanical Engineering, University of Aveiro, 3810-193, Portugal.
2
CICECO, Department of Materials and Ceramic Engineering, University of Aveiro, 3810-193, Portugal.
3
Department of Physics, Chikkanna Government Arts College Tiruppur 641602, Tamilnadu, India.
4
Department of Physics, University of Aveiro, 3810-193, Portugal.
Email: dpuksel@gmail.com, nivasbabu@gmail.com

Presence of a small amount of Zn0.5Cd0.5S (10 wt.%) QD restricts the obtained luminescence intensity of QD mixed MNB is
dielectric constant of Magnesium Niobate (MNB) from 23 to 4, with
smaller than the PL intensity of both Zn0.5Cd0.5S QD and
almost no dielectric loss over 30 150 C. The photoluminescence
intensity of Zn0.5Cd0.5S dispersed MNB is much smaller as compared MNB. Moreover, the electrical analysis suggests that, the
to the PL intensity of both Zn0.5Cd0.5S and MNB. These observations value of the QD loaded mixture is significantly different
ensure promising applications in optoelectronic device engineering. as compared to the value of pure MNB. The value of
pure ZnS is 4.5 whereas the value of pure MNB is 22
INTRODUCTION 24 within the temperature range of 20 150 C. The
Dielectric constant () of neat Magnesium Niobate value of 10 wt.% Zn0.5Cd0.5S additive mixed MNB is 4.4,
(MNB) is quite high (~22) whereas the loss is much but no dielectric loss was observed in this material. The
smaller. Reports in the literature suggests that the dielectric nature of MNB is strongly influenced by the
dielectric characteristics of MNB can be modulated by additive, Zn0.5Cd0.5S QD.
employing dopants1-2. Herein we suggest that apart from
dopants (lattice substituted), certain additives (existing as
secondary surface) can also significantly influence the
optical-electrical features of MNB. The band gap value of
MNB ceramics (3.6 eV) is closer to the band gap value of
the promising II-VI semiconductor quantum dot, Zn-Cd-S
(3.7 3.8 eV). However, unlike MNB, the dielectric
constant of ZnS is small ( of Zn-Cd-S: ~4 eV; of MNB:
~22 eV) and the dielectric loss is higher than MNB. In
view of these, it is of interest to know the optical and
dielectric behavior of MNB supported by Zn-Cd-S QD
structure as an additive. In the present study, we have
initially optimized the phase pure synthesis of MgNb 2O6
and Zn0.5Cd0.5S and then dispersed a 10 wt. % of
Zn0.5Cd0.5S with MNB. We have observed roughly 6
times smaller with negligible dielectric loss for the
Zn0.5Cd0.5S with MNB over 30 150 C. Fig. 1 PL spectrum of 10 wt.% Zn0.5Cd0.5S dispersed MNB. For
comparison, the PL spectra of MNB and QD are also given in the figure.

EXPERIMENTAL STUDY
CONCLUSION
For the synthesis of MNB, the required reactants MgO
The value of MNB is restricted by a factor of 6 when the
and Nb2O5 (Alfa Aeser) were taken in 1:1 ratio and ball
surface is enclosed by Zn0.5Cd0.5S QD additive. It is also
milled for 30h using N2 and etanol medium. Milling was
interesting that the mixture show nearly a zero dielectric
performed at 350 rpm with a ball to powder ratio of 1:75.
loss factor. The distinct PL intensity observed for the
Synthesis of Zn0.5Cd0.5S quantum dot was performed by
Zn0.5Cd0.5S dispersed simple as compared to its
solovothermal microwave irradiation technique. XRD
counterparts suggest a role of surface interaction between
measurements were carried out by using Rigaku X-ray
QD and MNB.
diffractometer (wavelength = 1.541 , step width: 0.03
within every 2 seconds. Photoluminescence (PL) REFERENCES
measurements were carried out at room temperature using [1] Swartz SL, Shrout TR, Schulze WA, Cross LE. J. Am.
a Perkin Elmer LS 55 model luminescence spectrometer Ceram. Soc. 1984 1;67(5):311-4.
having a pulsed Xenon lamp as excitation source. [2] Fang TH, Hsiao YJ, Chang YS, Ji LW, Kang SH. Curr.
Opin. Solid State Mater. Sci. 2008 30;12(3):51-4.
RESULTS AND DISCUSSION
The PL spectrum of a 10 wt.% Zn0.5Cd0.5S dispersed ACKNOWLEDGMENTS
MNB is shown in Fig. 1. Since the 10 wt.% Zn0.5Cd0.5S Pukazh acknowledges FCT (Portugal) for the post-
mixture is a blend of two wide band gap semiconductors, doctoral grant (SFRH/BPD/88756/2012). NBS
the spectra exhibits two absorption edges. As seen, the acknowledges FCT (Portugal) for the post-doctoral grant
(SFRH/BPD/82158/2011).
113

Y doped CeO2 nanopowder: Synthesis, structural and optical properties

Ajay Kaushal1*, Chandan Bhardwaj2, Ishu Sharma3, Budhendra Singh4, Reza Zamiri1 and J.M.F. Ferreira1
1*
CICECO-DEMaC, University of Aveiro, 3810-193 Aveiro, Portugal, presenting author: meetuiitr@gmail.com
2
NSCBM Govt. College Hamirpur, Himachal Pradesh University, Shimla-05, India
4
Department of Physics, Amity University, Dubai, UAE
3
TEMA-NRD, Aveiro Institute of Nanotechnology (AIN), University of Aveiro, 3810-193 Aveiro, Portugal

This paper reports the synthesis and characterization of times with distilled water to complete removal of
Yttrium-doped ceria (YDC) nanopowder by a simple unwanted Na+, Cl-, NO3- ions. The washed precipitates
chemical co-precipitation method. The prepared YDC were then dried at 353 K for 3 h.
nanopowder was characterized for structural and optical
RESULTS AND DISCUSSION
properties. The XRD, FTIR, and SEM data were analyzed
XRD patterns shows cubic phase for prepared pure and y
systematically for structural properties of YDC
doped CeO2 nanopowder. No impurity phase was
nanopowder. UVvis spectroscopy was also performed to
observed in the X-ray diffraction pattern for pure CeO2.
study the optical properties of the synthesized
SEM image (Fig 1) shows agglomerated CeO2 s making
CeO2 sample. The CeO2 nanopowder showed an increase
it difficult to estimate the real particles size. The
in the amount of oxygen vacancies with an increase in the
crystallite size of the synthesized particle were further
Y concentration. The FTIR spectrum of prepared CeO2
calculated and estimated from Hall-Williamson plot and
nanopowder showed absorption bands at 400 cm-1 to 450
TEM analysis. TEM analysis revealed the size of
cm-1 regime, that correspond to CeO2 stretching vibration.
prepared nanopowder between 510 nm. The optical band
gap of prepared nanopowder was determined by
INTRODUCTION
extrapolating the function of (h)2 in terms of h. UV-
Nanomaterials with crystal sizes less than 100 nm have
visible spectrum of the CeO2 nanopowder shows a distinct
been reported to exhibit optical, electrical, catalytic,
absorption band at ~370 nm. The optical band gap of Y
thermal and mechanical properties that significantly differ
doped CeO2 nanopowder was found to be lower than that
from those observed for their microcrystalline
of pure CeO2.
counterparts1. In recent years, cerium (IV) oxide (CeO2,
also known as ceria) nanoparticles have received much
attention because of its many interesting characteristics,
such as unique UV absorption ability, high stability at
high temperature, high hardness and reactivity. Thus,
CeO2 and CeO2-based materials have been extensively
used in a wide variety of applications such as solid oxide
fuel cells (SOFCs), catalysis, luminescent materials, gas
sensors, and ferromagnetic oxides and so on2.
Various chemical route methods have been reported on
the synthesis of CeO2 oxide nanoparticles such as
reversed micelles route, co-precipitation, hydrothermal Fig. 1 SEM image of pure CeO2 nanopowder prepared by
synthesis, solvo-thermal synthesis, solgel process, chemical co- precipitation method.
pyrolysis, electrochemical method, and sono-chemical
methods. In this work, we report on synthesis of CeO2 CONCLUSION
nanopowder by a facile and single one-pot template-free Pure and Y doped CeO2 nanopowder were successfully
precipitation route without any need of capping ligands prepared by applying simple chemical rout method. The
and other additives. structural, and optical properties of the prepared CeO2
nanopowder samples were systematically investigated.
EXPERIMENTAL STUDY TEM analysis revealed the prepared nanopowder size
Pure and Y doped CeO2 nanopowder were prepared by a range between 510 nm. The Y doped CeO2 showed low
wet chemical co- precipitation method. Ce(NO3)3.6H2O optical band gap energy.
and Yttrium (III) nitrate hexahydrate were chosen as a
source material for Ce and Y, respectively. High purity REFERENCES
aqueous solution of starting precursors in their 1. Gleiter H., Acta Mater., 48, 1 (2000)
stoichiometric ratio was prepared by dissolving in de- 2. Zamiri et al, PLoS ONE, 10(4), e0122989 (2015)
ionized water. The dissolved solution was then added
drop wise into a beaker containing 100 mL of 0.4M ACKNOWLEDGMENTS
NaOH (Merck, Germany) solution at room temperature. Authors AK, BS and RZ acknowledge financial support
The centrifuged precipitates were further washed several from FCT, Portugal.
114

Enhanced local piezoelectric response in the Erbium-doped ZnO nanostructures


prepared by wet chemical synthesis

Reza Zamiri1, Avito Rebelo1, Budhendra Singh2, Igor Bdikin2, Ajay Kaushal1*, J.M.F. Ferreira1
1*
CICECO-Aveiro Institute of Materials & DEMaC, University of Aveiro, 3810-193 Aveiro, Portugal
3
TEMA-NRD, Aveiro Institute of Nanotechnology (AIN), University of Aveiro, 3810-193 Aveiro, Portugal
Presenting author: meetuiitr@gmail.com

Pure and Erbium (Er) doped ZnO nanostructures were response of the sample. In present study, a commercial
prepared by we chemical precipitation technique. The AFM (Ntegra Prima, NT-MDT) equipped with an
samples were characterized by X-ray diffraction (XRD), external lock-in amplifier (SR830, Stanford Research)
scanning electron microscopy (SEM) and Energy and a function generator (FG120, Yokogawa), were used
dispersive X-ray spectroscopy (EDX). For assessing in order to apply both ac and dc voltages to the surface of
piezoelectric properties, the synthesized powders were the crystals for poling and piezoresponse image
pressed in pellet form and piezoresponse imaging was acquisition 2.
performed to characterize the piezoelectric properties
RESULTS AND DISCUSSION
before and after sintering. The out-of-plane (effective
Upon evaluating out-of- plane (OPP) or in-plane (IP)
longitudinal) and in-plane (effective shear) coefficients of
images of pure and Er-doped samples (Figure 1) it could
the samples were estimated from the local piezoresponse.
be found that in comparison with pure ZnO the contrast is
higher for Er-doped ZnO nanostructure and became even
INTRODUCTION
more stronger after sintering of the pellet.
Zinc oxide (ZnO), a direct wide bandgap compound, is
widely exploited and extensively used as a piezoelectric
material because of high piezoresponse when compared to
other II-VI tetrahedrally bonded wurtzite compound
semiconductors like ZnS, CdS, and CdSe. The lack of
center of symmetry combined with the large
electromechanical coupling in ZnO results in a strong
piezoelectric response. The piezoelectric properties of
ZnO, are exploited in a wide spectrum of applications like
transducers, sensors, and actuators.
It is well known that the various properties of
semiconductor material can be enhanced and/or modified
on doping with proper ions in host lattice. It has been Fig. 1 ZnO PFM images: (a-d) OPP images. (e-h) IP
found that doping ZnO with various element has a images. (a) and (e) pure ZnO before heating. (b) and (f) -
pronounced effect on both microstructure and pure ZnO after heating at 500 C. (c) and (g) Er-doped
piezoelectric properties of ZnO. Piezoelectric properties ZnO before heating. (d) and (h) Er-doped ZnO after
evaluated for ZnO films doped with Ni, Cu, Fe and Co heating at 500 C.
showed a variation in the longitudinal piezoelectric
coefficients from 5 to 14 pm V1. Further, the significant CONCLUSION
increase in d33 (up to 110 pm V1) has been observed for Pure and Er-doped ZnO nano structures were synthesised
V-doped ZnO. In this work we prepared pure and Er- by wet chemical method. It was observed that the sample
doped ZnO nanostructures by wet chemical method. Their with 7 wt. % Er-doped displays stronger piezocontrast in
local piezoelectric properties has been systematically comparison to pure ZnO. In addition a significant
analyzed from their piezoresponse force microscopy enhancement in the effective piezoresponse value was
(PFM)1 response. observed for Er-doped sample when annealed at 500 C.
The obtained results suggest the applicability of Er-doped
EXPERIMENTAL STUDY samples for potential industrial application.
The ZnO nanostructure powders were pressed in
cylindrical shape of 10 mm diameter with thickness of ~2 REFERENCES
mm and visualized by using contact mode AFM and PFM 1. M.-H. Zhao et. al, Nano Letters, 4, 587 (2004)
methods. The PFM technique is based on the detection of 2. N. Balke et. al, J Am Ceram Soc, 92, 1629 (2009)
the mechanical response of the sample to an applied
electric voltage due to the converse piezoelectric effect. A ACKNOWLEDGMENTS
conductive Si cantilever (Nanosensors, with a nominal Author RZ, BS and AK acknowledge financial support
force constant of 15 N/m) was used to both apply the from FCT, Portugal.
voltage to the surface and to measure the mechanical
115

Anti-Bacterial Biofilm Activity of Magnesium Ferrite Thin Film


Atul Kumar1, Rakesh Dhar1*, Jyoti2, Rajesh Thakur2
1
Deptt. of Applied Physics, Guru Jambhshwar University of
Science and Technology, Hisar.
2
Deppt. of Bio&Nanotechnology, Guru Jambhshwar University of
Science and Technology, Hisar.
atul26787@gmail.com

ABSTRACT
In the present work, thin film of Magnesia
ferrite (MgFe2O4) has been synthesized on a b
glass substrate by using thermal
evaporation technique and studied their
anti-bacterial biofilm activity against gram
negative and gram positive bacteria. Thin
film deposition rate was 102 /Sec and the
thickness of the film was 100nm which was
d c
annealed at 600OC. X-ray Diffraction reveals
the crystalline structure, SEM analysis show
the morphological characteristic and TEM
used to find the particle size and shape of
the magnesium ferrite. The model
organisms for anti-bacterial biofilm activity
were E.coli (gram negative) and S. aureus
(gram positive). Fluorescent microscope Fig. Fluorescent image of biofilm growth on
has used to observe biofilm growth on coated and uncoated glass slide coated; (a)
MgFe2O4 coated glass slide and uncoated E.coli biofilm growth on uncoated glass
(glass slide as a positive control). It is found slide, (b) S.aureus biofilm growth on
that the MgFe2O4 coated glass slide exhibit uncoated glass slide, (c) E.coli biofilm
minimum bacterial growth (both negative growth on MnFe2O4 coated glass slide, (d)
and positive bacteria) with compare to S.aureus biofilm growth on uncoated glass
uncoated glass slide. slide.

KEYWORDS: Magnesium ferrite, Thin Film,


Anti-Bacterial Biofilm, XRD, SEM, TEM,
Fluorescent Microscope.
116

Atomic Layer Deposition for TiO2 and TiN Nanometer Films

Zeke Insepov1,2*, Ardak Ainabayev1, Farabi Bozheyev1, Maria Lukasheva3 , Kurbangali Tynyshtykbayev
1
National Research and Innovation System, Nazarbayev University, Astana, Kazakhstan
2*
Purdue University, West Lafayette, IN, USA, zinsepov@purdue.edu
3
TESKAN Performance in Nanospace, Saint Petersburg, Russia

Experimental results of atomic layer deposition for TiO2 that the roughness is decreased with increasing number of
and TiN films on Si substrates are presented (Fiji G2, layers (thickness).
Ultratech Cambridge, NURIS, Nazarbayev University).
For deposition of TiO2 and TiN films the precursor Table. Ellipsometer parameters
TDMAT [(CH3)2N]4Ti (Sigma Aldrich) was used. The Layer Element Thickness Density Roughness
atomic layer deposition of thin films were performed on (nm) (g/cm3) (nm)
100 mm diameter silicon wafers Si(111), p-type 1 Ti 1.10 2.10 0.66
(Siemens), which had been previously cleaned up with 2 Ti 9.34 2.33 0.34
acetone in an ultrasonic bath, afterwards rinsed with Substrate Si 0.00 4.36 0.443
deionized water and dried in N2 stream. For deposition of
TiO2 and TiN films, the Si-substrate and precursors were Determination of the elemental composition of the TiO2
heated up to 150 C and 75 C, respectively. For synthesis and TiN films was carried out directly by using energy
of the film with a 10 nm thickness 100 precursor cycles dispersive spectrometer (EDS), AZtecEnergy Automated
were performed. For deposition of TiN films additionally (X-MAX 150, SDD, Oxford Instruments). Determination
a plasma module was used, where the N2 was of the thin thicknesses was not possible by EDS, since the
decomposed under the influence of the plasma on layers were much thinner than the spatial resolution of
radicals. The thickness of the resulting film was EDS-analysis. However, after convolution of separate
monitored by in-situ quartz crystal measurements (QCM). spectra from each structural component, it is often
possible to see a significant predominance of certain
elements in the same spectrum as compared to the others,
which leads to the conclusion that the component is
analyzed not quantitatively, but qualitatively.
Figure 2 shows the spectrum of the elemental composition
For investigation the back of TiO2 and TiN films obtained by superimposing of two
side of the wafer was chosen, wherein three areas are EDS-spectra collected under the same conditions.
allocated - central (1), intermediate (2) and periphery (3).

Fig.2. EDS spectrum of the elemental composition of


TiO2 and TiN films.

Fig. 1. SEM images of front (a) and back (b) sides of the In the spectrum it is seen a clear predominance of Ti and
wafer surface: 1 - central region, 2 - intermediate layer, 3 N, i.e., the spectrum consists of titanium nitride, high
- peripherals. concentration of C, and low concentration of O. Platinum
presents in all spectra as protective layer to conserve all
The thicknesses of the TiO2 and TiN films were measured adjacent layers even the thinnest layers of the sample
by ellipsometer in Rigaku Smart Lab diffractometer. The cross section. Gallium occurs due to the injection of
results of the measurements show that the film thickness gallium ions to the sample during the etching process by
is about 10 nm (see Table). From the table it is obvious the liquid gallium ion source (SEM TESCAN LYRA).
117

Multiscale modelling of fluid flow in nanopump


Zamart Ramazanova1, Kumiszhan Dybyspayeva1, A. Ainabayev1 , A.F. Vyatkin2 and Zeke Insepov1,2,4*

*zinsepov@purdue.edu

INTRODUCTION
The fluid flow manipulation in nanotubes has
fundamental interest due to its potential application in
the field of nanotechnology particularly for progress in
development and optimization of nanopumps, nanoarrays,
and nanomembranes based devices. The idea of using
surface acoustic waves (SAW) for ascuating miscoscopic
flows (nanopumping) was proposed in our previous paper
[1]. In this work the nanopump was developed further.
The fluid flows in carbon nanotube were simulated with
large scale parallel molecular dynamics (MD) and finite
elements (Comsol). Fig.1 MD models of nanotube flows in 2D and 3D,
respectively.
MD SIMULATION
Fluid flows through nano- and microtubes under SAW Fig. 2 shows our simulation results for propagation of
were studied using Large-scale Atomic/Molecular liquid flow inside a nanotube.
Massively Parallel Simulator (LAMMPS). LAMMPS is
one of the tools of MD that can run in parallel, which
substantially reduces computation time.
Nanotube was modeled using data files generated by
VMD tools. Interactions between carbon atoms were
described by Tersoff potential. SAW was generated using
a function that moves carbon atoms radially with desired
frequency. Water was selected as a fluid in simulations.
The current models compute atomic and average flow
rates of the fluid as a function of SAW frequency.
Fig. 2 - The total displacement and velocity magnitude
COMSOL SIMULATION
The problem was studied numerically using COMSOL Flow rates via nanotube were calculated as a function of
Software, where a CFD and an acoustics modules were fluid density, wave frequency of SAW and the efficiency
implemented simultaneously. of the nanopumping is discussed.
A fluid flow in nanochannel was activated using an
Acoustic-Shell Interaction, Transient and Laminar flow REFERENCES
models in COMSOL Multiphysics. As it is seen in Figure 1. Zeke Insepov, Dieter Wolf and Ahmed Hassanein,
1, the model geometry consists of a tank and a nanotube Nano. Lett. 101, V.6, 063104 (2006)
with the length and diameter equals 100 and 20 nm,
respectively. The tube is connected to the tank. The
ACKNOWLEDGMENTS
material of nanotube is made of graphite sheet. The
This work has been supported by the Ministry of
nanotube shell is filled with liquid and the tank contains
Education and Sciences of the Republic of the Kazakhstan
air.
(Contract No. 265 -12.02.2015). Z.I. is indebted to the
Nazarbayev University World Science Stars program,
RESULTS AND DISCUSSION
under grant No. 031-2013 of 12/3/2013.
118

Effect of multiwall carbon nanotubes electrochemical modification on the electrical


properties of the epoxy carbon nanotube composites

Milena Kurkowska 1, Stefan Awietjan1 , Rafa Kozera1 and Anna Boczkowska 1


1
Faculty of Materials Science and Engineering, Warsaw University of Technology, Poland presenting author,
milenakurkowska88@gmail.com
Faculty of Materials Science and Engineering, Warsaw University of Technology, Poland,

INTRODUCTION A B
The composites of epoxy resin as a matrix with carbon
nanotubes as a filler are used in many industries, most
commonly in the aerospace industry. The selection of
these components is due to good commercial availability
of a wide range of resins of varying viscosities and
mechanical properties. The use of carbon nanotubes as a
filler improves not only the mechanical properties but also
thermal and electrical conductivity. The best electrical
properties have single wall carbon nanotubes (SWCNT, Fig. 1 Nanotubes with Ni-P coating : (A) first
= 105 S/m) . Unfortunately, due to their high prices and experiments, (B) after a series of process modifications.
low availability we decided to use the multi wall carbon
nanotubes (MWCNT). The main task of this work is to Purification in mixture of acids leads to the reduction of
obtain a composite with anisotropic properties in respect CNTs length. The length of the nanotubes has a
of electrical conductivity. Improvement of magnetic significant impact on the value of the electrical
properties of nanofiller (coating Ni-P) will provide the conductivity. Therefore, the conductivity decreases to a
alignment of nanotubes in the polymer matrix using an value of 10-4 S/m. For the preparation and deposition
external magnetic field (B = 0.5T). ultrasounds were applied. That improved the availability
of surface area of nanotubes and reduced the
EXPERIMENTAL/THEORETICAL STUDY agglomerates of nanotubes. Unfortunately a reduction the
The interaction between the tubes in MWCNTs, surface length of the CNTs was observed. Therefore CNT/Ni-P
defects and contamination after the production (CCVD) composite had conductivity of 10-6 S/m.
leads to the reduction in electrical conductivity.
MWCNTs were surface modified in order to improve
CONCLUSIONS
their electrical conductivity and magnetic properties.
A method of surface preparation is important for the
Nanotubes were decorated with a coating of Ni-P by the
quality of the deposited coating. Initial purification of
application of electroless deposition. As a nickel source
carbon nanotubes, suitable homogenization and uniform
nickel sulfate and as a reducing agent sodium
sensitization and activation are important steps in the
hypophosphite (sodium phosphate) was used. In addition,
preparation of the substrate. Homogenization of the epoxy
glycine (Gly) was used as buffer- complexing agent and
resin with carbon nanotubes using a calander provides a
additional components such as stabilizer (Thiourea) and
good dispersion of nanofiller in the matrix. The addition
surfactant (CTAB). Homogenization of the solution was
of carbon nanotubes significantly improves electrical
ensured by the use of an ultrasonic cleaner and
conductivity. Reducing the length of the CNTs results in
disintegrator. Calender was used to homogenize the
deterioration of electric conductivity in relation to the raw
mixture of the epoxy resin and the filler. Finally, in order
CNTs.
to examine the electrical conductivity a Keithley
6221/2182 nanovoltometer was used.
REFERENCES
RESULTS AND DISCUSSION [1] Sandler J. et. al. Polymer 40:5967-5971, (1999);
Proper preparation of carbon nanotubes before electroless [2] Tessonnier J. et. al., Carbon 47:1779-1798, (2009);
deposition has a significant impact on the quality of the [3] Gojny F.H. et. al., Compos. Sci. Technol. 65:2300-
coating (uniformity). The first deposition experiments 2313, (2005);
lead to deposition of large agglomerates irregularly on the [4] Hussain F. et. al., J. Compos. Mater. vol. 40, 17:1511-
surface of carbon nanotubes. Modification of the 1575, (2006);
activation step and homogenization resulted in uniform [5] Kong F.Z. et. al., Surf. Coat. Tech. 155:33-36, (2002);
coating (Fig.1). The conductivity of the epoxy resin is 10- [6] Wang F. et. al., Carbon 43:1716-1721, (2005).
15
S/m. The addition of the raw, non-modified carbon ACKNOWLEDGMENTS
nanotubes in epoxy resin increases the conductivity up to This work was financially supported by the National
10-2 S/m. Science Centre of Poland DEC-2011/03/D/ST8/04921.
119

Nanofillers Reinforced Polymer Composites Fabricated by Melt Compounding for


Biomedical Application

Azadeh Motealleh1*, Siamak Eqtesadi1, Rune Wendellbo1, Marco Scatto2, Paolo Scopece2, Alessandro Patelli2, Michele
Sisani3 ,Maria Bastianini 3 and Hugo Perera4
1
Abalonyx AS, Forskningsveien 1, 0373 Oslo, Norway, am@abalonyx.no

2
Nadir S. r. l., Italy
3
Prolabin & Tefarm, Via dell'Acciaio, 9, 06134 Perugia, Italy
4
Departamento de Ingeniera Mecnica, Energtica y de los Materiales, Universidad de Extremadura, Escuela de Ingenieras
Industriales, Avda. de Elvas s/n, 06006 Badajoz, Spain.

.
INTRODUCTION
Graphene has attracted tremendous attention in recent
CONCLUSION
years owing to its exceptional thermal, mechanical, and
electrical properties. One of the most promising
applications of this material is in polymer The dispersion of GP in polymeric matrix can be
nanocomposites, polymer matrix composites which improved by using hydrotalcite like nonofillers as well as
incorporate nanoscale filler materials1. Good dispersion of melt mixing. The flexural strength of composites are
graphene (G) in the polymer matrix is essential for affected by the amount of the nanofillers.
achieving desired physical and mechanical properties2.
Melt mixing has been used for incorporating G-derived
fillers into a variety of polymers while some restacking of
the platelets may be occur that may deteriorate the
functionality of the composite. In this work we attempt to REFERENCES
1. T.K.Das et. al, Polymer-Plastics Technology and
solve this problem through the combination of graphene
Engineering, 52: 319331(2013).
particles with other nonofillers using a special melt
2. S. Kumar, J Biomed Mater Res B Appl Biomater.
mixing system. The microstructural and mechanical
104(4): 732-49(2016).
characterization of fabricated composites will be reported.
EXPERIMENTAL/THEORETICAL STUDY ACKNOWLEDGMENTS
Reduced graphene nanoplatelets (rGNP) are synthesized
The research leading to these results has received funding
from reduction of graphene oxide (GO) which is produced
from the European Union Seventh Framework
according to a modified Hummers method. This
Programme (FP7) under grant agreement n 685825.
produces GNP with a unit sheet thickness of about 0.3 nm
and tuneable length/width ranging from 0.05 m - 50 m.
Different amount of GNP/hydrotalcite and GNP/ZrHPO4
nonofillers were mixed in the molten polymers. The
structural evaluation of composites will be done by
scanning electron microscopy (SEM). The mechanical
characterization will be done by 3 point bending test.
RESULTS AND DISCUSSION
Mixing GO in molten polymer is problematic due to
chemical reduction of GO at high temperatures which
results in formation of carbonaceous gases. On the other
hand rGNP has a poor affinity for dispersion in polymers
because of van der waals forces. Mixing GNP with
Hydrotalcite nono fillers is a solution for tackling this
problem.
The microstructural and mechanical characterization will
be ready after the abstract submission deadline and we
would appreciate it if the reviewers consider this matter.
120

Laser light-triggered formation of SnO2/PMMA nanocomposites

Athanassia Athanassiou1, Despina Fragouli1, and Gianvito Caputo1*


1
* Smart Materials, Nanophysics, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy
email: gianvito.caputo@iit.it

INTRODUCTION
In recent years, the field of organic-inorganic
nanocomposites has attracted great consideration due to
the possibility to combine some characteristic features of
both organic polymers and inorganic materials exploitable
for various applications such as gas sensing and
environmental protection.1 However, one of the most
important drawbacks associated with the nanocomposite
formation is related to the filler dispersion inside the
polymeric matrix to achieve homogeneous materials. In
order to circumvent this issue, a possible strategy can be
represented by the so-called in situ synthesis of
nanoparticles in solid polymeric films in which the
desired material is directly synthesized in a polymeric
structure avoiding particles aggregation.2 This innovative
and unconventional approach allows at the same time to Fig. 1 SEM images related to SnO2/PMMA
form metal and metal oxide nanoparticles and to embed nanocomposite formed at 355 (a,b) and 532 nm (c,d),
them into the polymer matrix, eventually leading to the respectively.
final nanocomposite material.3,4
EXPERIMENTAL/THEORETICAL STUDY
Thin films of polymethylmetacrylate (PMMA) and tin CONCLUSION
precursors were prepared by drop casting from a toluene The in-situ methodology has been used as a tool for the
solution. The prepared samples were irradiated using creation of SnO2/PMMA hybrid system. The method
second and third harmonics (=532 and 355 nm, proposed can pave the way for the formation of
respectively) of a Nd:YAG nanosecond laser (Spectra- nanocomposites exploitable in several fields such as
Physics, Quanta-Ray, 6 ns pulse duration) on a spot with catalysis and gas-sensing.
diameter of 1 cm, at a repetition rate of 10 Hz using 100
and 30 mJcm-2 as a fluence for the green and blue REFERENCES
irradiation, respectively. The irradiation process was
carried out at room temperature. 1. S. Sarkar et al., J. Nanoparticle Res. 14, 2 (2012)
2. G. V. Ramesh et al., Chem. Soc. Rev. 2646, 38 (2009)
RESULTS AND DISCUSSION 3. D. Fragouli et al., Nanotechnology 20, 155302 (2009)
In this contribution, the localized in situ formation of tin 4. F. Spano et al., Langmuir 3911, 28 (2012)
dioxide (SnO2) nanoparticles embedded in PMMA films
will be presented. This is achieved by the photo-induced
reduction of the metal oxide precursor included in the ACKNOWLEDGMENTS
polymeric films, through controlled UV and Visible
pulsed laser irradiation. Interestingly, SnO2 particle The authors thank Alice Scarpellini for SEM analysis and
formation follows the same formation pathways with both Marco Scotto for the technical support.
laser wavelengths.
By using a combination of structural, morphological and
spectroscopic techniques (XRD, TEM, SEM, UV-Vis),
we will demonstrate that the pulsed laser irradiation at
355 and 532 nm generates the reduction of the metal
oxide precursor leading to SnO2 particle formation
homogeneously distributed in the polymeric film, as
displayed in the representative SEM images (Figure1).
121

Electronic band structures of Te-doped GaN nanowires


Harun zkii1, Bar zkap2*, Sena Gler zkap2 and Seyfettin Dalg3

Kean Yusuf apraz School of Applied Sciences, Trakya University, Turkey


1
2*
Vocational School of Technical Sciences Trakya University, Turkey, barisozkapi@trakya.edu.tr
3
Department of Physics, Trakya University, Turkey

INTRODUCTION the undoped GaN NWs, the band gap values are found as
Gallium Nitride (GaN) is an important III-V 0.899 eV, 0.756 eV, 0.621 eV for Te-doped GaN NWs with
semiconductor material for electronic device technology radii of 0.57 nm, 0.76 nm and 0.94 nm, respectively in both
due to its electro-optical properties such as high electron cases.
mobility, tunable band-gap and direct wide energy band r =0.57 nm r =0.76 nm r =0.94 nm

gap of approximately 3.4 eV. GaN has a potential to be a)


used for a wide range of applications like blue light )
emitting diodes and laser diodes1. With the developments
of experimental techniques such as metal organic chemical
vapor deposition (MOCVD), chemical vapor deposition
(CVD) and hydride vapor phase epitaxy (HVPE), GaN
nanowires (NWs) can be obtained successfully2-6. It is well
known that physical properties of nanostructures can be
changed by doping with various elements. Recently, in r =0.57 nm r =0.76 nm r =0.94 nm

addition to the experimental studies, some research groups b)


have carried out theoretical studies on doped GaN
nanowires. Nannan et al. have investigated electronic
properties of P-doped hydrogen saturated GaN nanowires7,
Zhen et al. have studied the electronic and optic properties
of Ti-doped GaN nanowires8 and Zhang et al. have
reported field emission properties of Te-doped
pseudohydrogen passivated GaN nanowires for wurtzite Fig.1. The band structures of a) pure and b) Te-doped GaN
structure9. In this work, we present electronic structures of nanowires. The energy at the Fermi level is set to zero.
Te-doped zinc blende GaN nanowires oriented with [001]
direction.
CONCLUSION
THEORETICAL STUDY In summary, using first-principles method, we have
In this study, we have investigated electronic structures of calculated the electronic band structures of pure and Te-
Te-doped GaN NWs with three different radii using the doped GaN NWs. The results show that the energy band
Quantum ESPRESSO code10, which is based on the density gap values reduce when nanowires are doped with Te atom.
functional theory (DFT). The exchange-correlation Also, it is seen that while band gap values of pure NWs
interaction is described via generalized gradient increase with increasing nanowire radius, band gap values
approximation (GGA) with the Perdew-Burke-Ernzerhof of doped NWs decrease with increasing wire radius.
(PBE)11 ultra-soft pseudopotential. The cutoff energy for
the plane wave basis set is 400 eV. The Brillouin zone is
sampled by a set of k-point grid 1 x 1 x 6 Monkhost-Pack REFERENCES
Scheme. 1. N. Bouarissa et al. Mater. Chem. Phys. 73 51-56 (2002)
2. T. Kuykendall et al. Nano Lett. 3 1063-1066 (2003)
RESULT AND DISCUSSION 3. Z. H. Zhong et al. Nano Lett. 3 343-346 (2003)
4. P. G. Li et al. Alloys. Comp. 475 463-468 (2009)
Firstly, the structure optimizations are performed for bulk 5. E. L. Li et al. Appl. Surf. Sci. 257 10850-10854 (2011)
ZB GaN and obtained lattice constant a0 is 4.548 , in 6. C. S. Xue et al. Alloys. Comp. 484 33-35 (2009)
agreement with experimental values of 4.49812. Then, the 7. F. Nannan et al. J. Alloys Comp. 596 92-97 (2014)
initial structures of the GaN NWs along the [001] direction 8. C. Zhen et al. Mater. and Design 96 409-415 (2016)
are generated from a bulk zinc blende (ZB) GaN supercell. 9. Y. Zhang et al. Comp. Mat. Sci. 83 277-281 (2014)
The relaxed structures, total energies and electronic band 10. P.Giannozzi et al. J. Phys. Cond. Mat. 21 39 (2009)
structures of pure and Te-doped GaN NWs are calculated. 11. J.P. Perdew et al. Phys. Rev. Lett. 77 3865 (1996)
Fig.1. shows electronic band energies of pure and Te- 12. K. Kim et al. Phys.Rev.B 56 7018 (1997)
doped GaN NWs with three different radii which are 0.57
nm, 0.76 nm and 0.94 nm. While the energy band gap
values are found as 0.956 eV, 1.455 eV and 1.534 eV for
122

Materials for implantable bioelectronic devices

Ana Mestre1,2, Pedro C. Incio1,2, Carmen Freire3, Quirina Ferreira2 Maria Medeiros4, Fabio Biscarini5 and
Henrique L. Gomes1,2*
1
Universidade do Algarve, FCT, Campus de Gambelas, Faro, Portugal.
2
IT-Instituto de Telecomunicaes, Av. Rovisco, Pais, 1, Lisboa, Portugal; presenting author
3
CICECO- Aveiro Institute of Materials, Department of Chemistry University of Aveiro
Campus de Santiago, 3810-193, Aveiro Portugal
4
IT-Instituto de Telecomunicaes, Departamento de Engenharia Eletrotcnica e de Computadores, Universidade de
Coimbra, 3030-290 Coimbra, Portugal;
5
Life Science Dept. - University of Modena and Reggio Emilia,Via Campi 183, I-41125 Modena, Italy.
(*)
hgomes@ualg.pt

INTRODUCTION was tested in-vivo in a mouse model of contusion thoracic


Transplantation of stem cells or stem cell-derived SCI. The device is made of PLGA substrates with
progenitors represents a promising therapeutic solution to interdigitated gold electrodes for electrical stimulation
repair the damaged brain or nerve. These cells are able to and recording of signals from the tissue and microfluidic
develop into functional neurons to integrate synaptically channels to deliver drugs/chemicals (such as
into the host brain circuitry. This approach requires Minocycline) at the site of implantation. The device was
implantable multifunctional devices suitable for developed within the project iONE-FP7.
engrafting neural stem/precursors cells. Devices should A flexible cellulose substrate with ink-jet printed polymer
have long-term stability associated to high electrodes is shown in Fig.1 (c). These devices were used
biocompatibility and safety. Since stem cell commitment to record bioelectrical activity form neuronal cells.
is governed by a combination of topo-electro-chemical
stimuli, the device should be able to mimic the local
microenvironment for stem cell differentiation. This
requires possibility to perform local stimulation with
tunable electric fields; local delivery of growth factors,
neurotransmitters, and drugs. The integration of highly
sensitive transducers in the implanted device would allow
monitoring the status of the regenerating nerve cells.
The fabrication of these bioelectronic implants requires
emergent materials. The choice of an organic
semiconducting polymers integrated into soft and flexible
substrates endows the device with interesting features,
namely, softness and density matched to that of the host
tissue, minimal immune-inflammatory response,
adaptivity to the local geometry by shape conformality
and mechanical compliance.
In this contribution we report the fabrication and testing
of polymer based electrodes deposited by ink-jet printing
on nanofibrous bacterial cellulose and in poly(D,L-
lactide-co-glycolide) (PLGA). An implantable device was
fabricated. Soft electrodes were also tested in vitro using
small organs and several types of neuronal cells. It is
shown that they can record bioelectrical activity over Fig. 1. (a) Schematic of an AMID to repair a nerve with a
extended periods (weeks) without degradation and with a broken connection. (b) photograph of the prototype tested
good signal-to-noise-ratio. in a mouse model. (c) printed PEDOT:PSS electrodes on
The electrodes used were based on poly(3,4- bacterial cellulose and (d) AFM photograph of the
ethylenedioxythiophene) doped with poly(styrene sulfonic cellulose nanofibrous structure.
acid) (PEDOT:PSS). .
ACKNOWLEDGMENTS
RESULTS AND DISCUSSION This work received financial support from European
Fig.1 shows the schematic diagram and a photograph of Community Seventh Framework Programme (FP7/2007-
an Active Multifunctional Implantable Device (AMID) 2013) trough the project iONE-FP7 grant agreement n
developed to repair a spinal cord injury (SCI). The AMID 280772. PROJECT WEBPAGE URL: http://ione-fp7.eu.
123

Manipulation of Electrical Conductivity of Graphene Oxide Films


by Addition of Carbon Nanotubes and Thermal Treatment

O. Okhay1, Gil Gonalves1, C. Dias 3, J. Ventura3, E. Titus1 and A. Tkach2


1
Nanotechnology Research Division, Center for Mechanical Technology and Automation (TEMA), Department of
Mechanical Engineering, University of Aveiro, 3810-193 Aveiro, Portugal, olena@ua.pt
2
CICECO Aveiro Institute of Materials, Department of Materials and Ceramic Engineering, University of Aveiro, 3810-093
Aveiro, Portugal
3
Institute of Physics of Materials of the University of Porto (IFIMUP), 4169-007 Porto, Portugal

Electrical conductivity of graphene oxide (GO) was conductivity of GO films was slightly changed by
changing from insulator to semiconductor behaviour by addition of CNT (one to tree orders of magnitude
simple addition of carbon nanotubes. However, depending on CNT concentration), however it changes
significant changing in current values was observed after significantly after heat treatment at 180oC under vacuum
thermal treatment: from 0.07mA to 500mA at applied 5V (4 orders).
for GO with 20% CNT annealed at 180oC.

INTRODUCTION
Low-dimensional carbon structures such as carbon
nanotubes (CNTs) and graphene holds great promise for
potential sensor applications because of their unique
nanoscale features, large specific surface area, high
carrier mobility and facile chemical functionalization.1,2
Thus, the combination of these two carbon nanostructures
allows to obtain carbon hybrid materials with high
mechanical stability and with interesting electrical
properties. At the same time, reduced graphene oxide
(rGO) has not such ideal structure as graphene but show
good electrical properties and its preparation is simple.3 It
was observed here, that addition of conductive CNT to
insulator GO can lead to semiconductor electrical
properties and after thermal treatment leads to full
reducing of composite GO with CNT with high electrical
conductivity.
EXPERIMENTAL
Light-brown GO solution was prepared from graphite
powder by Hummer-based method. Commercial single
wall carbon nanotubes (SWCNT) was added to GO Fig. 1 IV data of GO (a), GO with 20%CNT (b) and
solution in different concentrations (1%, 5%, 10%, 20% GO with 20%CNT after reducing at 180oC.
and 50%) and ultrasonicated at room temperature.
Corresponding solution was filtered with Millipore filters CONCLUSION
(0.22 m) and dried at room temperature in order to This work shows an easy way to change the insulating
obtain films of GO and GO + SWCNTs with different properties of GO (electrical conductivity 10 -5A at applied
compositions for further study of electrical properties. At 10V) by combining the addition of SWCNTs (slightly
the same time, identical samples were thermal treated in conductive material) with the thermal treatment in
vacuum at 180oC to study the influence of reduction of vacuum (highly conductive, 500mA at applied 5V for GO
GO and concentration of SWCNTs on the electrical with 20% CNT).
properties. The structure of the samples was analysed by REFERENCES
XRD and SEM. Current-voltage (I-V) measurements 1. A. Modi et al., Nature 424, 171, (2003)
were done at room temperature. 2. S. Park et al. Nat Nanotechnol.4, 217 (2009)
3. G. Eda et al. Adv. Mater. 22, 2392 (2010)
RESULTS AND DISCUSSION
XRD spectra show GO, rGO peaks as well as SWCNTs ACKNOWLEDGMENTS
response in the corresponding samples. SEM images O. O. acknowledges FCT (FRH/BD/77704/2011) for
present free standing continuous layered films. Electrical financial support.
124

SiO2(111) SURFACE OPTIMIZATION BY DFT CALCULATIONS

G. Romn1, A. Daz Compay2, A. Juan3, S. Simonetti4


1
UNS, Argentina.
2
CIC, UNS-CONICET, UTN, Argentina.
3
UNS-CONICET, Argentina.
4
UNS-CONICET, UTN, Argentina.

The development of modern theoretical surface science provides an opportunity to investigate

structures on the atomic scale with useful applications in industrial technologies. Due to their high surface

areas and pore volumes, mesoporous silicas have attracted great attention in novel applications.

Calculations reported in this work were performed in the framework of the Density Functional

Theory (DFT) using the Vienna Ab-initio Simulation Package. In this code plane wave basis sets are used

to solve the KohnSham equations. The electron projector augmented wave (PAW) method was used and

the generalized gradient approximation (GGA) with the PerdewBurkeErnzerhof (PBE) functional was

utilized. The fixed convergence of the plane-wave expansion was found with cut-off energy of 750 eV. A

set of 331 Monkhorst-Pack k-points was used to sample the Brillouin Zone. The ground state was

found by a Methfessel-Paxton smearing of 0.2eV.

The SiO2(111) surface model is obtained from bulk -cristobalite, saturated with OH groups and

optimized by DFT calculations. The result is a silica surface model whose density of silanols is close to

the experimentally measured value for fully hydroxylated surface. The SiO 2(111) surface was represented

with a periodically repeated slab containing five layers of atoms (the optimum number of layers was

previously tested) separated in the normal direction by a vacuum region. The width of this gap was

optimized to avoid the interaction between slabs.


125

Synthesis of well dispersed Pd nanoparticles on reduced graphene oxide for


electrocatalytic oxidation of ethanol

Rahul Krishna1,2*, Elby Titus1


1
Center for Mechanical Technology and Automation (TEMA), Department of Mechanical Engineering, University of Aveiro,
Portugal.
2
I3N Department of Physics, University of Aveiro, 3810-193 Aveiro, Portugal. *rahulkrishna@ua.pt

growth process. In this work, we used the Pd(OAc)2 as a


In the present study, we report a facile synthesis of precursor and methanol as solvent and reducing agent. At
crystalline, small size Pd nanoparticles (NPs) on reduced moderate temperature and under sonication condition
graphene oxide (RGO) abbreviated as Pd/RGO for
methanol provided the reducing species H2 which reduces
electrocatalytic oxidation of ethanol. In this synthesis, first
graphene oxide (GO) was reduced by the green method the Pd2+ ions. Fig. 1 sows the high resolution transmission
using L-ascorbic acid and citric acid and further Pd NPs electron microscope (HRTEM) image of the Pd/RGO
were decorated on RGO by a facile method without using nanocomposite, which clearly exhibited the uniform
any reducing agents. To evaluate the catalytic activity of dispersion of Pd NPs onto the graphene sheets with a
Pd/RGO nanocomposite towards the electrocatalytic narrow size distribution. The electrocatalytic activity of
oxidation of ethanol the cyclic voltammetric (CV) technique
Pd/RGO nanocomposite was evaluated towards the
was used.
ethanol electro-oxidation in presence of 1 M KOH,
INTRODUCTION depicted their promising behavior for electro-oxidation
reaction without losing their activity after 50 CV cycles.
Recently, Pd/RGO based electrocatalysts received
enormous interest for the electrocatalytic oxidation of ethanol
due to their superlative characteristics such as high
catalytic activity, selectivity and stability during the
catalysis reactions [1]. However, synthesis of uniform Pd
NPs (in the size range of 2-3 nm) without using of any
expensive reagents, surfactant and reducing agent is
highly desirable to make them as energy vector. Here, we
demonstrate a facile synthesis of well dispersed Pd NPs
on RGO for ethanol electro-oxidation.

EXPERIMENTAL

In this work, GO was synthesized as previous [1]. To


synthesize the Pd@RGO nanocomposite, first RGO was Fig.1. HRTEM image of Pd/RGO nanocomposite.
synthesized by the green reduction of GO using L-
ascorbic acid and citric acid at 80 C for 12 h. After
CONCLUSION
completion of reaction, product was centrifuged at 3000
rpm and several times washed with Milli-Q water and
Pd/RGO nanocomposite was successfully synthesized by
methanol to remove the impurities and dried in vacuum
a facile method for ethanol electro-oxidation.
oven at 250 C for 8 h. Then after, Pd NPs were decorated
on them by a safe and convenient method without using
ACKNOWLEDGMENTS
any specific reducing agents. Pd2+ ions were reduced to
Pd (0) in presence of anhydrous methanol (CH 3OH) under
R.K. acknowledges FCT for financial support (SFRH/BD/
sonication.
80105/2011).
RESULTS AND DISCUSSION
REFERENCES
In this work, Pd NPs were decorated on surface of
[1] R. Krishna, D. M. Fernandes, J. Ventura, C. Freire and
RGO without using any specific reducing agents and they E. Titus. Int. J. Hydrogen Energy, 41 (2016) pp.11811-
were synthesized only in presence of anhydrous methanol 11822.
at 45 C. This strategy led the formation of crystalline,
uniform Pd NPs on RGO due to the controlled reduction
of Pd2+ ions from the solution and slow nucleation and
126

Investigation on the effect of Weld Defect on the Fatigue Behavior of Welded Structures
Ramu M 1, Prabhu Raja V 2, Thyla P R 2, Devaraj Ramasamy4*, Sathiskumar Jothi 3, Somu C 2
1
Department of Mechanical Engineering Amrita School of Engineering, Coimbatore, Amrita Vishwa Vidyapeetham, Amrita
University, India.
2
Department of Mechanical Engineering, PSG College of Technology, Coimbatore-641 004, India .
3
College of Engineering, Swansea University, Bay Campus, Fabian Way, Swansea SA1 8EN, UK
4*
Centre for mechanical technology and automation, department of mechanical engineering, University of Aveiro, 3810 193
Aveiro, Portugal.
*devaraj.ramasamy@ua.pt

INTRODUCTION radiographic testing(Fig.2).Weld defects like lack of


The present work is to predict the fatigue life of penetration, lack of fusion, porosity are incorporated as
symmetric structures like pressure vessels in the presence elliptical crack at weld zone for further crack growth
of common welding defects such as Lack Of Fusion analysis(Fig.3).
(LOF), Lack Of Penetration (LOP) and Porosity. A ring
type specimen which replicates the stress pattern in the
pressure vessel is considered for the study of severity of
weld imperfections. Initial dimensions of weld defects are
arrived by performing NDT inspection. Crack growth
analysis is carried out to determine the remaining life of
the welded joint with defects

PREDICTION OF FATIGUE CRACK GROWTH


A semi-elliptical surface crack with dimension 2a and
2c in a finite plate of dimension 2b x 2h x t (Fig.1) with
initial dimensions of a = c = 1 mm in a finite geometry of Fig. 2 Radiographic image of specimen
2b = 2h = 100 mm and t = 10 mm shown in Fig. 1 is
considered for the study.

Fig. 1 Semi elliptical surface crack in a finite body Fig. 3 FEM of ring specimen with crack
Final crack size or the critical crack length is considered CONCLUSION
as 60% of total thickness of the plate that cause an Fracture analysis of ring type specimens was carried out till the
unstable fracture. Stress of 100 MPa is applied at the critical crack length of 4 mm beyond which the crack
boundary parallel to semi elliptical crack and the life for propagation will be unstable and the results are shown in Fig. 3.
the propagation of crack at the increment of 0.5 mm upto From the results, it could be noted that Lack of Fusion is the
6 mm is determined by Paris law. Also the problem is most influencing defect on the fatigue life compared to other
two defects.
modeled in Franc3D software with crack and the
calculated value of number of cycles for each incremental
crack length is estimated.

PREDICTION FCG IN NON-STANDARD


GEOMETRY
Possibility of defective weldments causes severe impact
on the structural integrity of the pressure vessel as the
weld defect leads to the origin of crack. In order to simply
the computational and experimental effort of the fatigue
analysis of the pressure vessel, it has been proposed to
Fig.3 Fatigue life of ring type specimen
design an equivalent ring type specimen which exactly
simulates the global stress pattern of the vessel.
Weldments are tested for any weld defects using
127

Effect of homogenization on Mechanical Property of newly developed self-healing


alloy

Titus Thankachan1, K. Sooryaprakash1, Devaraj Ramasamy2* and Sathiskumar Jothi3


1
Department of Mechanical Engineering, Anna University, Regional Campus, Coimbatore 641046, India
2*
Centre for Mechanical Technology and Automation, Department of Mechanical Engineering, University of Aveiro, 3810
193, Aveiro,Portugal.
3
Material Research Center, College of Engineering, Swansea University, Bay Campus, Fabian Way, Swansea, SA1 8EN,
UK, * devaraj.ramasamy@ua.pt

INTRODUCTION The effective density in gm/cm3 and hardness in BHN


Aluminum alloys well known for its high strength, calculated using the Maxwell Garnett effective medium
excellent formality and good corrosion resistance with approximation is provided in the figures 1 and 2.
low density are major candidates for aerospace and
automobile body panel applications. Even though
researches on the aluminum alloyed tin and its corrosion
resistance was widely studied the Aluminum-Tin alloy as
a self healing material was not investigated to a high
level1, 2. Self healing materials are a new class of
materials where the material once exposed with a crack
heals itself or by an external process such as heat
treatment3. This research focuses on the development of
Aluminum-Tin based self-healing alloys of varying
weight percentage and the effective density and hardness Fig. 1 Predicted Hardness of the self healing alloy
was modeled based on the MaxwellGarnett effective
medium approximation.
EXPERIMENTAL/THEORETICAL STUDY
The aluminum 6061- T6 was taken as the base material
of chemical composition Cr 0.04-0.35%, Cu 0.15-0.4%,
Mg 0.8-1.2%, Si 0.4-0.8%, Fe 0.7, Ti 0.15%, Zn 0.25% at
maximum and others at a maximum of 0.15 by weight.
Tin (Sn) being the alloying element with purity 98% was
acquired. Stir casting was opted for the casting process as
the continuous stirring of the base metal has to be carried
out to preclude segregation. Aluminum was heated in a Fig. 2 Predicted Density of the self healing alloy
crucible to its liquidus temperature and once the molten
condition is attained the stirring set up was introduced to From the figures it is clear that the hardness of the
create a vortex to which the tin element was introduced. material decreased with the introduction of the tin ass
The tin weight percentage was varied from 5 to 50% alloying element. It can be stated from the results that the
respectively. The Maxwell Garnett effective medium tin being a soft material reduced the hardness of the
approximation was employed in this study to effectively developed self healing alloy. Similarly the density of tin
model the effective hardness and density of the developed being 7.31 g/cm3 increased the density of the developed
alloy were the volume fraction of the base metal and self healing alloys with tin inclusion.
alloying element along with its densities and hardness
were used to discover the same. The Maxwell Garnett CONCLUSION
effective medium approximation method used in this The property modeling of the developed self healing
study is given as equation 1 &2 respectively4. composites was successfully carried out employing
Maxwell Garnett effective medium approximation and the
density was found increasing and hardness decreasing
with Tin inclusion.
REFERENCES
1. S. Gudic et. al, J. Alloy Compd. 505, 54-63 (2010)
2. Juan Tan et. al, Corros. Sci. 76, 219-230 (2013)
3. A.D. Moghadam et al, JOM, 66, 872-881 (2014)
RESULTS AND DISCUSSION 4. S. Jothi et al, Compos. Struct. 108, 555-564 (2014).