EnergEn 2018

National R-D Institute for
Ministry of Research and Cryogenics and Isotopic Technologies

Innovation - ICSI Rm. Valcea -
nd
The 22 nd National Conference
with International Participation
NEW CRYOGENIC AND ISOTOPE TECHNOLOGIES FOR

ENERGY AND ENVIRONMENT
EnergEn 2018
Book of Abstracts
Vol. 1/2018
ROMÂNIA
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Baile Govora, Romania

October 24-26, 2018
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““New C
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Eneerrgyy aand E Ennvirronnmeennt”
–– EnergEn 2018 –
Book of Abstracts
Vol. 1/2018
Băile Govora, Romania

October 24-26, 2018
Senior Editor: Roxana IONETE - National Research and Development Institute
for Cryogenics and Isotopic Technologies – ICSI Rm. Valcea,
Romania
Editor: Vasile STANCIU – National Research and Development Institute for
Cryogenics and Isotopic Technologies – ICSI Rm. Valcea,
Romania
Technical box:
Layout: Camelia ASPRITA
Cover: Camelia ASPRITA
ISSN: 2601-9965
The conference is organized with the financial co-support of

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XXII nd National Conference with International Participation
New Cryogenic and Isotope Technologies for Energy and Environment
24–26 October 2018, Băile Govora, Romania
CONTENTS
ENERGY STORAGE AND HYDROGEN TECHNOLOGIES

ESHT 1-O Norbert Wagner, Alexander Kube, Frieder Warth, Andreas
Kaspar Friedrich
Post Li‐Ion batteries 15
ESHT 2-O Krum Banov, Ilya Popov, Dimka Ivanova, Ludmi Fachikov,
Branimir Banov
Advanced lithium ion batteries 17
ESHT 3-O Mathilde Bangoura
Valorization of a local energy resource: Hydrogen applications 19
ESHT 4-O Aishui Yu, Siyang Liu, Congcong Zhang
NCMs as cathode materials for lithium – ion batteries 20
ESHT 5-O Silvia Bodoardo
Lithium sulphur batteries: strategies to increase the cycle life 22
ESHT 6-O Aurelio Somà, Francesco Mocera, Elena Vergori
The role of energy storage in low consumption working vehicles 23
ESHT 7-O Natalia-Silvia Asimopolos, Laurentiu Asimopolos
Study on geothermal energy on romanian territory 26
ESHT 8-O Damian Axente, Cristina Marcu
Nuclear assisted hydrogen production 28
ESHT 9-O Mihaela Aneta Dumitrescu
Li‐ion battery manufacturing in europe: italian initiative 29
ESHT 10-O Adrian Bot, Vasile Rednic, Nicolae Aldea
α‐SETS software for analysis, modelling and simulation of the
stirling engine 30
ESHT 11-O Vasile Rednic, Robert Gutt, Emil Bruj, Gabriel Roșca, Radu Pop,
Sergiu Pogăcian, Dan Zotoiu and Adrian Bot
Thermal receptor for concentrated solar power. An experimental
and simulated efficiency study 31
ESHT 12-O Andreea Oprisa, Nikolay Djourelov, Victor Leca, Doru Dinescu
Techniques based on positrons at ELI‐NP 32
ESHT 13-O Ioan Iordache, Dorin Schitea, Alexandru Floristean, Ioan
Stefanescu, Nicolas Brahy
Hylaw ‐ Project presentation 33
3
ESHT 14-O Shin Ki-Yeol, Cristian Hoarca

Optimum slope and azimuth angles for solar collector and PV
module 35
ESHT 15-O Elena Carcadea, Varlam Mihai, Jianu Catalin, Patularu Laurentiu,
Dorin Schitea
PEM fuel cells ‐ on the way from modeling to reality 37
ESHT 16-O Constantin Filote, Daniel Fodorean, Claudia Martis, Filip Carlea,
Mihai Rata, Maria Simona Raboaca
Smart conductive charging station, fixed and mobile, for electric
vehicles (SMiLE‐EV) 40
ESHT 17-O Valentin Vlad, Mihai Rata, Constantin Filote, Alexandru Lavric,
Maria Simona Raboaca
Interfaces and communication protocols for electric car
charging station 42
ESHT 18-O Mihai Rata, Gabriela Rata, Constantin Filote, Ana Maria
Cozgarea, Andreea Raluca Felseghi, Maria Simona Raboaca
An EV charging station demonstrator 44
ESHT 19-O Ciprian Afanasov, Constantin Filote, Valentin Vlad, Gabriela Rata,
Maria Simona Raboaca
DC‐DC converter for fast charging of electric vehicles 46
ESHT 20-O Daniel Fodorean, Maria Simona Raboaca, Rares Catalin Nacu,
Aron Attila Popp, Constantin Filote, Filip Cirlea
Modelling of fuel cell, battery and ultracapacitor as energy
sources for EV charging stations 49
ESHT 21-O Filip Carlea, Maria Simona Raboaca
European local energy ownership in energy transition 51
ESHT 22-O Iurie Bosneaga, Elena Agarwal
Sustainable solutions for public terrestrial transportation 53
ESHT 23-P Carmen Maria Moraru, Iulia Stefan, Florentina Magda Enescu
Study about smartgrid in Energy 55
ESHT 24-P Krum Banov, IlyaPopov, Dimka Ivanova, Ludmi Fachikov,
Branimir Banov
NMC cheap and prospective cathode material for EV&HEV 56
ESHT 25-P Mihail Culcer, Mircea Raceanu, Mariana Iliescu, Adrian Enache,
Nicu Bizon, Mihai Varlam
Hydrogen mobility demonstrator – Hy‐DeMo 57
ESHT 26-P Mirela Draghia, Madalina Ivanovici, Gheorghe Pasca, Alin Fuciu
Hydrogen production based on glycerol steam reforming process
performed in a membrane reactor 59
4
ESHT 27-P Adrian Armeanu, Elena David, Violeta Niculescu, Claudia Sandru
Hydrogen‐rich gas production by biomass conversion in a free‐
fall reactor promoted by Fe/CaO catalyst 60
ESHT 28-P Radu Pop, Vasile Rednic, Oana Raita, Emil Bruj, Daniel Banyai,
Liviu Vaida, Adrian Bot
Hydraulic Simulation, Concerning Optimization of Water Flow
Capture for micro‐hydro power plants in order to increase the
energy production 62
ESHT 29-P Robert Gutt, Vasile Rednic, Emil Bruj, Adrian Bot
Stirling engine burning chamber design and simulation in ANSYS
fluent 63
ESHT 30-P Emil Bruj, Vasile Rednic, Robert Gutt, Radu Pop, Sergiu Pogăcian
and Adrian Bot
Heat recovery system for stirling engine flue gases 64
ESHT 31-P Mariana Iliescu, Mihail Culcer, Florian Stefanescu, Marian
Curuia, Elena Carcadea, Nicu Bizon, Mihai Varlam
Small high temperature superconducting coil as energy storage
unit for spacecraft power systems 65
ESHT 32-P Ioan Iordache, Dorin Schitea
Electrochemical Hydrogen Separation 67
ESHT 33-P Constantinescu Marius, Bucura Felicia, Ionete Roxana, Zaharioiu
Anca, Ciucure Corina, Oancea Simona
Disposal and energy recovery from sewage sludge 69
ESHT 34-P Gabriel Rasoi, Mihai Culcer, Mariana Iliescu, Maria Simona
Raboaca, Dan Mocanu, Adrian Armeanu
Integrated solar power plant system based on Dish Stirling
technology for sustainable energy generation 72
ESHT 35-P Laurentiu Patularu, Mihai Varlam, Elena Carcadea, Eusebiu
Ionete, Dan Mocanu, Adrian Armeanu
Development of a hydrogen filling station for fuel cell electric
vehicle at ICSI Rm Valcea 73
ESHT 36-P Alexandru Ciocan, Alexandru Rizoiu, Alexandru Badita
Thermal behavior investigation of a Li‐Ion pouch cell 75
ESHT 37-P Athanasios Tiliakos, Alexandra M.I. Trefilov, Elena Dutu, Eugenia
Tanasă, Adriana Balan, Ioan Stamatin
First results on laser‐induced graphene foam as gas diffusion
layer for PEM Fuel Cells 77
ESHT 38-P Mihaela Buga, Alexandru Vlad, Adnana Spînu-Zăuleț, Alexandru
Rizoiu, Radu Ene
Cathode materials with mixed high energy density and pulse
power capability for Li‐ion batteries ‐ preliminary results 80
5
ESHT 39-P Mariea Deaconu, Ion Furtuna, Alice Dinu, Maria Mihalache
Studies On Hydrogen Interaction With Uranium Alloys 82
CRYOGENIC TECHNOLOGIES
CRYT 1-O Silvano Tosti
Pd‐membranes applications from tritium separation to pure
hydrogen production 83
CRYT 2-O Petar Dalakov, Maxim Kupriyanov, Jürgen Klier
The technological chain of enrichment of 3He 85
CRYT 3-O Vitaly Bondarenko, Iurii Symonenko, Dmytro Tyshko, Borys
Pylypenko
Production of light gases stable isotopes by cryogenics method 86
CRYT 4-O Vitaly Bondarenko, Artem Chyhrin, Hlib Bashkirov
Cryogenic support of rectification units for the neon isotopes
production 88
CRYT 5-O Catalin Stelian Tuta, Cristian Postolache, Aurelia Celarel,
Constantin Cenusa, Viorel Fugaru, Mihail-Razvan Ioan
Characterization of gamma radiation fields emitted by 60‐Co
sources inside of the chambers for simulation of specific outer
space conditions 90
CRYT 6-O Ion Zabet, Iulian Nita, Raluca Fako, Gratiela Maria Tarlea
Mathematical model of a heat exchanger working with different
refrigerant fluids 91
CRYT 7-O Sebastian Brad, Alin Lazăr, Mihai Vijulie
Studies of cryogenic distillation equipments and process 93
CRYT 8-P George Bubueanu, Cristian Postolache, Viorel Fugaru, Catalin
Stelian Tuta
Radiological characterisation of resulted materials from
refurbishing of Tritium Laboratory 94
CRYT 9- P József-Zsolt Szücs-Balázs, Ștefan Bugeac, Codruța Mihaela
Varodi, Claudia Lar, Mariana Cristina Marcu, Mihai Liviu Gligan
Experimental plant for carbon isotopes separation by carbon
monoxide cryogenic distillation 95
ISOTOPES OF HYDROGEN AND ITS APPLICATIONS

ISHA 1-O Zhang Dongxun
Fabrication and hydrogen permeation of Al2O3/Er2O3 coating
by MOD method 96
6
ISHA 2-O Kris Dylst, Yves D’Joos, Herman Lodewyckx, Anisia Bornea,
Marius Zamfirache
Dismantling an obsolete tritium installation 97
ISHA 3-O Luo Wenhua, Luo Deli, Meng Daqiao, Li Rong, Huang Zhiyong,
Song Jiangfeng, Huang Guoqiang, Chen Chang-an, Deng
Xiaojun, Qin Cheng, Qian Xiaojing, Zhang Guikai
R&D of Tritium technology for CFETR: progress and prospect 99
ISHA 4-O Chen Chang'an
Progress of tritium related materials for fusion system 100
ISHA 5-O Zhang Xinjian
Introduction of Institute of Materials, CAEP 100
ISHA 6-O Song Jiangfeng
Progress of HCCB TBM system 100
ISHA 7-O Li Peilong
Progress of WDS technology in CAEP 100
ISHA 8-O Cristian Postolache, Viorel Fugaru, Catalin Stelian Tuta,
Bubueanu George
Synthesis of labelled compounds with tritium using
organometallic compounds as intermediates 101
ISHA 9-O Octavian G. Duliu, Carmen Varlam
Time series analysis of 18 years of continuous observation of
tritium content in Ramnicu Valcea precipitations 103
ISHA 10-O Iulian Nită, Mariea Deaconu, Raluca Fako, Sorin Meglea, Dan
Bujoreanu
Overview of tritium activity in the nuclear fission reactors 106
ISHA 11-O Carmen Varlam, Ionut Faurescu, Dorin Schitea, Ionut Spiridon,
Alin Chitu, Diana Costinel, Laurentiu Patularu, Daniela Ion-
Ebrasu, Irina Vagner
Polymer electrolyte membrane used in tritium enrichment of
aqueous sample ‐ preliminary results 107
ISHA 12-O Liviu Stefan, Anisia Bornea, Marius Zamfirache, Nicolae Bidica,
Iuliana Stefan
Cernavoda tritium removal facility – connection to fusion R&D 109
ISHA 13-O Nicolae Bidica
Non‐steady‐state modelling of the permeation of multi‐
component hydrogen isotopes through metals 111
ISHA 14-O Carmen Varlam, Irina Vagner, Ionut Faurescu, Denisa Faurescu
Capabilities of ICSI Tritium Laboratory in providing accurate
estimation of tritium level in the uncontaminated environment 114
7
ISHA 15- P Tatiana Voronina, Daria Tugusheva

Tritium activityon on‐line monitoring in the pik reactor water
coolants by using flow‐through radiometer Wilma 116
ISHA 16- P Tatiana Voronina, Daria Tugusheva
On‐line monitoring of the deuterium content in heavy water
reflector at pik reactor 118
ISHA 17- P Ana-Maria Iordache, Stefan-Marian Iordache, Eusebiu Ilarian
Ionete, Ioan Stamatin
Electrochemical investigation of Pd/CNT composite for
hydrogen isotope identification 120
ISHA 18- P Diana Chiper, Cristian Postolache, Viorel Fugaru
The usage of the polymeric gel "Decongel" for the
radiochemical decontamination 122
ISHA 19- P Viorel Fugaru, Cristian Postolache, Mihaela Enachescu,
Catalin Stan-Sion, Andrei Antohe, Catalin Stelian Tuta,
Diana Chiper, George Bubueanu
Titanium hydrides with controlled H/T ratio for ams facilities
calibration 125
ISHA 20- P Alina Niculescu, Toma Constantin, George Ana
Dynamic simulation of a multicomponent distillation column
for D‐T separation 127
ISHA 21- P Viorel Fugaru, Cristian Postolache, George Bubueanu, Catalin
Stelian Tuta, Diana Chiper
The area measurements in the tritium laboratory within NIPNE
Magurele 128
ISHA 22- P Anisia Mihaela Bornea, Marius Zamfirache, George Ana, Alina
Niculescu, Liviu Stefan, Toma Constantin, Ovidiu Balteanu,
Ciprian Bucur
Advanced technology for tritiated water waste processing
based on the CECE separation process 129
ISHA 23- P Nadia Paun, Gheorghe Titescu, Ioan Stefanescu, Arian
Armeanu, Constantin Ciortea, Cristian Mladin
Ordered packing dedicated to deuterium depleted water
production 131
MATERIAL SCIENCE FOR ENERGY AND ENVIRONMENT

MSEE 1-O Laurentiu Asimopolos, Natalia-Silvia Asimopolos, Violeta-
Carolina Niculescu
Remarks on the thermal properties of rocks and the
treatment of geothermal waters 132
8
MSEE 2- O Jasmina Grbović Novaković, Sandra Kurko, Sanja Milošević

Govedarović, Tijana Pantić, Bojana Paskaš Mamula, Mirjana
Medić, Nikola Novaković
Theoretical and experimental approach to destabilization
methods for improvement of hydrogen sorption kinetics in Mg
based systems 134
MSEE 3- O Diana Lazar, Monica Dan, Maria Mihet
Biogas up‐grading to Syngas catalyzed by alumina supported
nickel catalysts 136
MSEE 4- O Abdelmalek Malouche, Oana Grad, Dan Lupu, Claudia Zlotea,
Gabriela Blanita
The interaction of hydrogen with nanosized Pd clusters 138
MSEE 5- O Izabell Crăciunescu, Alexandrina Nan, Gabriel Roşca, Adrian
Bot
Dye‐sensitized solar cells fabricated on plastic and glass
substrates 139
MSEE 6- O Marius Rada, Mioara Zagrai, Jing Zhang, An Pengfei, Simona
Rada
XAS and XRD studies on the structure of vitroceramic
eletrodes based on lead‐lead dioxide‐manganese dioxide 141
MSEE 7- O Raluca Fako, Adriana Olteanu, Iulian Nită
Aspects regarding material history effect (manufacturing &
operation) on damage phenomena of certain stainless steel
grades 143
MSEE 8- O Adrian E. Ion, Sergiu Shova, Marius Andruh, Simona Nica
Development of azulene tailored π‐conjugated systems: solution
and solid‐state characterization 145
MSEE 9- O Adriana Marinoiu, Elena Carcadea, Mircea Raceanu, Mihai
Varlam
Synthesis of well dispersed gold nanoparticles on reduced
graphene oxide and application in PEM Fuel Cells 148
MSEE 10- O Mirela Dragan, Stanica Enache, Amalia Soare, Konstantin
Petrov, Mihai Varlam
LaCoO3 perovskite‐type oxide: synthesis and characterization
towards practical applications 150
MSEE 11- O Ciprian Iacob, Atsushi Matsumoto, Tadashi Inoue, James
Runt
Charge transport and glassy dynamics of polymerized ionic
liquids in bulk and in unidirectional silica nanopor 153
9
MSEE 12- O Daniela Ion-Ebrasu, Bruno G. Pollet, Adnana Spinu-Zaulet,

Amalia Soare, Elena Cacadea, Dorin Schitea, Alin Chitu, Mihai
Varlam, Konstantin Petrov
Graphene modified fluorinated cation‐exchange membranes
proton exchange membrane water electrolysis 155
MSEE 13- O Constantin Bubulinca
Fabrication technology of self‐standing binder free
LiMn2O4/MWCNT electrode by vacuum filtration method 157
MSEE 14- O Wycliffe Kiprop Kipnusu, Mohamed Elsayed, Reinhard
Krause–Rehberg, Friedrich Kremer
Glassy dynamics polymethylphenylsiloxane in one‐ and two‐
dimensional nanometric confinement—A comparison 159
MSEE 15- O Stanica Enache, Mirela Dragan, Amalia Soare, Konstantin
Mastering electronic percolation threshold of metal‐oxide
composites towards highly porous solid‐state catalysts 161
MSEE 16- P Adriana Dehelean, Simona Rada, Marius Rada, Ramona Suciu
The change of the local environment of samarium ions in
lead‐borate glasses and vitroceramics 163
MSEE 17- P Adriana Vulcu, Camelia Berghian-Grosan, Diana Lazar,
Sebastian Porav, Gheorghe Borodi, Teodora Radu
Sulfur – doped reduced graphene oxide decorated with
platinum nanoparticles as electrocatalyst for methanol
oxidation 164
MSEE 18- P Violeta Niculescu, Mihaela Iordache, Marius Miricioiu,
Laurentiu Asimopolos
Phosphorus removal from wastewater in the presence of
mesoporous materials 166
MSEE 19- P Marin Gheorghe, Simona Gheorghe
Bifacial solar cells 167
MSEE 20- P Elena David, Claudia Sandru, Violeta Niculescu,
Adrian Armeanu
Development of mesoporous materials for catalytic
conversion of residual biomass 168
MSEE 21- P Gabriel Roşca, Izabell Crăciunescu, Alexandrina Nan, Adrian Bot
Development and basic research on flexible dye‐sensitized
solar cell 170
MSEE 22- P Simona Rada, Mioara Zagrai, Marius Rada, Lidia Magerusan,
Ramona Suciu, Maria Suciu
Electrochemical performances of lead‐lead dioxide‐copper
oxide glasses and vitroceramics as electrodes for batteries 172
10
MSEE 23- P Mioara Zagrai, Simona Rada, Ramona Suciu, Marius Rada,
Adrian Bot
Spectroscopic and electrochemical properties on the lead‐
lead dioxide‐manganese dioxide vitroceramics 174
MSEE 24- P Claudia Lar, József-Zsolt Szücs-Balázs, Monica Violeta Cîrcu,
Anca Cristina Petran, Codruța Mihaela Varodi, Ștefan Bugeac,
Aurel Bâldea
Synthesis of a new labeled 15N organic compound based on
2‐nitromalonaldehyde 15N core 176
MSEE 25- P Adriana Dehelean, Dana Alina Magdas, Cezara Voica,
Gabriela Cristea, Ioana Feher
Multi‐element and 13C analysis for assessing quality of meat 177
MSEE 26- P Ancuţa Dinu, Constantin Apetrei
Development of voltammetric sensors based on conducting
polymers for the detection of amino acids 179
MSEE 27- P Gheorghe Ionita, Amalia Soare and Ionut Spiridon
Aspects concerning increasing of wetability of mixed
catalytic packing for hydrogen‐water isotopic exchange 180
MSEE 28- P Radu Dorin Andrei, Adriana Marinoiu, Felicia Bucura, Anca
Zaharioiu, Violeta Niculescu, Claudia Sisu, Elena Carcadea
A new method to synthesize electrospun polyacrilonitrile
nanofibers 181
MSEE 29- P Claudia Sisu, Radu Dorin Andrei, Adriana Marinoiu, Claudia
Sandru, Marius Constantinescu, Irina Petreanu, Elena
Carcadea
Electrochemical stability investigation of platinum on
graphene oxide catalyst using cyclic voltammetry method 183
MSEE 30- P Felicia Vasut, Anisoara Oubraham, Adriana Marinoiu, Amalia
Soare
A new method to obtain Pt on graphene oxide using
microwave reactor 185
MSEE 31- P Adriana Marinoiu, Felicia Vasut, Anisoara Oubraham, Radu
Dorin Andrei, Irina Vagner, Amalia Soare, Catalin Capris,
Elena Carcadea
Synthesis of gold nanoparticles supported on reduced
graphene oxide by microwave procedure 186
MSEE 32- P Mirela Dragan, Stanica Enache, Amalia Soare, Konstantin
Perovskite‐type lanthanum cobaltite for use as a catalyst:
synthesis and characterization 188
11
MSEE 33- P Michail-Liviu Craus, Vitalij Turchenko, Valerij Simkin, Tat'jana

Evgenievna Konstantinova, Anelija Savin
Structural modification in Zr1‐x (Ge/Y)x complex oxides 191
MSEE 34-P Alice Dinu, Mariana Tunaru
Characterization of Biofilms Developed on Carbon Steel Using
X‐Rays Micro‐Diffraction 192
LIFE QUALITY AND ENVIRONMENT TECHNOLOGIES

LQET 1- O Karel Lemr
Mass Spectrometry in Forensic Analysis 193
LQET 2-O Jerzy W. Mietelski
Nuclear jet engines tests make new challenges for studies of
radioactivity in environment 196
LQET 3-O Ashok Vaseashta
Smart and connected system for ecological monitoring and
situational awareness 197
LQET 4-O Nina Ciocarlan, Alexandru Ciocarlan, Ion Dragalin, Aculina
Aricu, Inga Zinicovscaia, Svetlana Gundorina
GC–MS and neutron activation (NAA) analysis of medicinal
Teucrium L. species 199
LQET 5-O Vasile Patrascu, Codruț Cherestes, Maria Tomescu, Silvia
Serban
Preliminary results in Rn monitoring at INCDM Constanta 201
LQET 6-O Radu Tamaian
Virtual screening of trabenazine and its deuterated analogue
against the synaptic vesicular amine transporter 203
LQET 7-O Elisabeta-Irina Geană, Corina Teodora Ciucure, Raluca
Popescu, Diana Costinel, Roxana Elena Ionete
Alternative analytical approaches for detecting adulteration
of honey 206
LQET 8-O Aurel Mircia Toderici
Multidimensional chromatography coupled with high speed
mass spectrometry. Progress in orthogonal acceleration
time‐of‐flight mass spectrometry 209
LQET 9-O Roxana Elena Ionete, Diana Costinel, Raluca Popescu, Oana
Botoran
Stable isotope ratio of O‐H‐C bioelements and its applicability
in verifying the origin of wine 211
LQET 10-P Desislava Gerginova, Yavor Mitrev and Svetlana Simova
Wines produced in Bulgaria ‐ chemical profile via 1H NMR 213
12
LQET 11-P Nicolae Enaki, Tatiana Paslari, Marina Turcan, Sergiu Bazgan,
Starodub Elena, Ashok Vaseshta
Manipulation of spontaneous emission of long living isomers
using UV‐C radiation 215
LQET 12-P Alexandru Ciocarlan, Aculina Aricu, Mariana Deleanu
Comparative spectroscopic and chromatographic
quantification of nicotine in moldavian tobacco 217
LQET 13-P Bubueanu Elena Corina, Pavaloiu Ramona
HPTLC identification of some mushroom and vegetal species
for quality control of derived products 219
LQET 14-P Ramona Ooana Gunache (Roşca), C. Apetrei
voltammetric sensor for the analysis of electroactive
compounds from gingko biloba based pharmaceutical products 220
LQET 15-P Iurie Bosneaga, Elena Agarwal
Non‐equilibrium (cold) plasma as an energy‐efficient method
of microbiological decontamination and heat and mass
transfer intensification 221
LQET 16-P Damian Axente, Ştefan Bugeac, Ştefan Gergely, Mihai Gligan,
Cristina Marcu, Zsolt Szücs, Codruţa Varodi
The 15N separation by isotopic exchange in nitrox system at
pressure 225
LQET 17-P Ionela Ramona Aranghel, Nuşa-Crenguţa Mădgălin, Simona
Măchiţă, Bogdan Blănaru
Aspects concerning the environmental impact assessment
procedure for a heavy water management facility 226
LQET 18-P Alina Stancu
Preliminar studies about the beta‐cyclodextrin encapsulation
of Eugenia caryophyllata essential oil and eucalyptol 228
LQET 19-P Raluca Popescu, Diana Stegarus, Claudia Sandru, Mihaela
Iordache, Felicia Bucura, Anca Zaharioiu, Elisabeta-Irina
Geana, Corina Ciucure, Diana Costinel, Roxana-Elena Ionete
Influence of the agricultural practices on the compositional
profile of vegetables – Coventional versus organic 229
LQET 20-P Dana-Alina Magdas, Simona Cinta Pinzaru, Ioana Feher,
Bogdan Ionut Cozar
Spectroscopic and chemometric methods for wine
classification 231
LQET 21-P Claudia Sandru, Mihaela Iordache, Andreea Radulescu,
Violeta Niculescu, Roxana Elena Ionete
Geochemical characterization of river Olt, Romania using of
piper and Durov diagrams 232
13
LQET 22-P Carmen Varlam, Nicolae Sofilca, Ionut Faurescu, Alin Chitu,
Irina Vagner, Mihaela Iordache, Diana Costinel, Denisa
Faurescu
Database of drinking water sources monitoring in Babeni‐
Valea Mare area – preliminary results 234
LQET 23-P Elisabeta-Irina Geană, Corina Teodora Ciucure, Raluca
Popescu, Constantin Apetrei
Application of spectroscopic techniques coupled with
multivariate statistical analysis for wines authenticity
assessment 236
LQET 24-P Corina Teodora Ciucure, Elisabeta-Irina Geană
Characterization and classification of honeys with different
botanical sources based on organic acids and water‐soluble
vitamins in conjunction with chemometric analysis 239
LQET 25-P Ioana Feher, Dana-Alina Magdas, Adriana Dehelean,
Costel Sarbu
Geographical, vintage and variety fingerprinting of wines
based on elemental content and chemometric approach 242
LQET 26-P Corina Teodora Ciucure, Elisabeta-Irina Geană
Impact of adulteration with different sugar syrups on honey
organic acids and water‐soluble vitamins 244
LQET 27-P Aurel Mircia Toderici
Shifting retention time in gas‐chromatography. practical
problems for analytical method development of urethane in
the alcoholic distillates by GC‐MS 246
LQET 28-P Andreea Iordache, Mihaela Iordache, Claudia Sandru, Cezara
Voica, Ramona Zgavarogea, Roxana Elena Ionete
Aspects on advanced isotopic and multiparametric
investigation of surface waters as support in environmental
processes 247
LQET 29-P Relu Dobrin, Cristian Dulama, Crina Bucur, Valentina Neculae
Measurement of Ra‐226 via Rn‐222 in Water Samples by LSC 249
LQET-30-P Oana Iuliana Popescu, George Serbanescu, Mihaela Vitan,
Simona Budan, Alexandru Florea
CANDU 600 Failed fuel location system. Analysis of BF3
delayed neutron detectors ageing 251
14
POST LI-ION BATTERIES
Norbert Wagner, Alexander Kube, Frieder Warth, Andreas Kaspar Friedrich
German Aerospace Center (DLR), Institute for Engineering Thermodynamics,

Pfaffenwaldring 38‐40, 70569 Stuttgart, Germany
Corresponding author: norbert.wagner@dlr.de
In the last decades, the investigation of new secondary cells has been increased
considerably. Very promising battery systems are the so called “Post Li-ion batteries”
with metal anodes: metal-sulfur and metal-air (oxygen) batteries, in particular Li-sulfur,
Mg-sulfur, Zn-air and Li-air batteries.
Li-sulfur battery is a promising system, due to its high theoretical capacity (1675
mAh/gsulfur), energy density (2500 Wh/kg), the low cost and non-toxicity of sulfur.
Nevertheless, some of the drawbacks of lithium-sulfur batteries are the poor
rechargeability and high self-discharge rates. Due to the low electrical conductivity
of sulfur, electrical conductive material has to be added in order to encourage the
electrochemical reaction. Furthermore, polysulfides of high order (Li2Sn with 2 ≤ n
≤ 8) dissolve in the electrolyte and can diffuse to the anode and react directly with
lithium metal. This so-called shuttle mechanism causes irreversible loss of sulfur.
Carbon aerogels are a highly promising material to be used as matrix for sulfur
to fabricate cathode for lithium-sulfur batteries. Resulting from organic resorcinol-
formaldehyde aerogels, carbon aerogels exhibit highly porous structure with
porosity up to 97%, high surface area about 500-3500 m²∙g-1, large pore volume
about 2-3 cm³∙g-1, and good electronic conductivity. Additionally, the important
advantage of carbon aerogel is its tunable porous structure and pore size
distribution. In the presentation actual results will be discussed.
Zinc based metal-air batteries have the advantage of high energy density, because
oxygen from ambient air is used without in-cell storage. As a consequence, lighter
batteries are produced with the reversible available Zinc as the only limiting factor.
However, before Zn-air batteries can be used as secondary elements some
obstacles have to be overcome. The low cyclability of state of the art Zn-air batteries is
caused by the passivation rate and dendrite growth of zinc, carbonate formation in the
alkaline electrolytes, corrosion of cathode materials and flooding of the cathode.
The flooding of the cathode has different origins; one is the increase of
electrolyte pressure inside the cell, due to the volume expansion of the zinc anode.
To mimic this behavior, different hydrostatic pressures from 5.2 mbar to 26 mbar
were applied during measurement of the polarization curves and electrochemical
impedance spectra (EIS).
Bifunctional Ni/Co3O4 based electrodes (Wittmaier et al., 2014 a; Wittmaier, et al.,
2014 b) were produced by the RMR technique (Gülzow, et al., 2003) and the porous
structure was varied by applying different pressures (4 bar, 6 bar and 10 bar) during
production of the electrodes by hydraulic hot pressing. These electrodes were used to
15
investigate how the electrolyte penetration depth influences the electrochemical

performance and how this behavior can be influenced by the porous electrode structure.
The electrochemical measurements during oxygen reduction reaction (battery
discharging mode) were performed in a 7.5 M KOH solution, at 25°C with neat oxygen
using a homemade hydrostatic half-cell, a RHE reference electrode (Hydroflex from
Gaskatel, Germany) and a Pt counter electrode. Electrochemical impedance spectra
(Fig. 1) were recorded at different current densities in the frequency range from 20 mHz
to 100 kHz.
The equivalent circuit used for the evaluation of the measured spectra consists of a
series combination of charge transfer resistance and diffusion impedance element
(Nernst impedance) in parallel to the double layer capacity imbedded in the porous
electrode model of Göhr and in series with the electrolyte resistance and inductance
from wiring.
90
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electrode produced at 4 bar, hydrostatic electrolyte pressure 4 mbar at different current densities
References
D. Wittmaier, T. Danner, N. Wagner, K.A. Friedrich, (2014 a), Screening and further investigations on
promising bi‐functional catalysts for metal‐air batteries with an aqueous alkaline electrolyte,
Journal of Applied Electrochemistry, 44:73-85
D. Wittmaier, S. Aisenbrey, N. Wagner, K. A. Friedrich, (2014 b), Carbon‐free nickel‐cobalt oxide
cathodes for lithium‐air batteries with an aqueous alkaline electrolyte, Electrochim. Acta,
149:355-363
E. Gülzow, N. Wagner, M. Schulze, (2003), Preparation of gas diffusion electrodes with silver
catalysts for alkaline fuel cells, Fuel Cells – From Fundamentals to Systems, 3:67-72
N. Wagner, (2005), Electrochemical power sources – Fuel cells in Impedance Spectroscopy: Theory,
Experiment, and Applications, 2nd Edition, Edited by Evgenij Barsoukov and J. Ross Macdonald,
John Wiley&Sons, Inc., ISBN: 0-471-64749-7, pp. 497-537
16
ADVANCED LITHIUM ION BATTERIES
Krum Banov1,2, IlyaPopov1, Dimka Ivanova2, Ludmi Fachikov2,

Branimir Banov*1,3
1
Institute of Electrochemistry and Energy Systems, IEES,“Acad. G. Bonchev” str. BL10, 1113 Sofia
2
University of Chemical Technology and Metallurgy – UCTM, bul. “Kl. Ohridski” N:8, 1756 Sofia
3
European Polytechnical University, EPU, “Ciril and Methodius” str. N:23, 2300 Pernik
Corresponding author: bbanov@iees.bas.bg
The lithium batteries take larger place over the classical electrochemical systems,
due to their extremely high specific performances. The lithium cobaltate and nickelate
are widely distributed cathode materials for secondary lithium batteries. The high
toxicity of both nickelate and cobaltate is not discussed, thus many investigators have
oriented their efforts towards finding an effective replacement. The other
disadvantage of these materials, especially for he cobaltate, is its relatively high cost.
The lithium batteries possess a number of advantage characteristics as high and stable
discharge voltage, wide working temperature region, high specific characteristics and
long storage life. A distinct tendency is noticed in the field of synthesis and
investigations of nanostructured electrochemically active compounds aiming the
enhancement of their specific characteristics to the theoretical ones.
Lithium ion batteries are the best choice for energy storage due to their
electrochemical characteristics – high discharge voltage from 2.75 to 4.1V, wide
operating temperatures range from – 40oC up to +85oC, long shelf life, up to 10 years,
for the primary electrochemical systems, with capacity losses les than 10% at the end
of the period. The lithium ion systems possess another big advantage to allow
discharging and especially charging at negative temperatures- on the other hand the
widely used lead acid batteries can not be charged at all at temperatures lower than -
5oC. Specific characteristics determine lithium elements as a reliable and promising
source for storage and conversion of energy. Electrochemical power sources are the
only ones that allow energy storage so efficiency - for classic electrochemical systems it
is about 85-90% and lithium reaches over 95%. This fact is especially important now in
the time of growing global energy crisis.
Different ways to improve the electrochemical characteristics by modifying the
active cathode materials are shown. Еlectrochemical characteristics of promising
cathode materials based on manganese dioxide are presented and discussed. The latter
are suitably modified to stabilize the crystal structure, electrochemical parameters and
improvement of reversibility, as resulting characteristics were compared to baseline.
The problems of different active cathode materials are discussed and a model
experiment to solve them is proposed. On the basis of the results obtained has been
17
developed a complex method for improving and stabilizing the characteristics of

different active electrode materials - anode and cathode.
In the present the widely used active electrode material for lithium ion batteries
are lithium LiCoO2, lithium LiNiO2 or NCA. Nickel manganese cobalt NMC with general
chemical formula LiNixMnyCozO2 with x+y+z=1 became more and more investigated,
especially of EV&HEV applications. Special attention is devoted to the NMC with high
manganese content higher than 50%, thus diminishing the total price of active cathode
material. The price of cobalt is 27, the nickel -17US$ but the manganese is only 1.5 US$
per kilogram. Preparing a high voltage cathode material based on high manganese
content with the following stoichiometry LiNixMnyCozO2 NMC 1:1:3 preserving the high
voltage performances and delivered capacity of about 180 mAh g-1 the price of
obtained active cathode material will be more than 30% less. Additional use of
manganese replacing the toxic nickel and cobalt is the way for new and
environmentally friendly active electrode materials for advanced lithium ion batteries.
Silicon is very attractive as prospective active electrode material - anode for high
capacity lithium ion batteries. The big problem of this material is the volume changes
exceeding 300%. These big changes in volume could not be compensated easily so
special structures are proposed to compensate and eliminate this problem. The IEES
R&D team successfully develops complex technique for preparation of microscopic
particles with “grass” structure thus developing the specific surface area of active
anode material and using the fine microstructure as “free” volume to accommodate
the volume changes. Silicon composite with specific capacity of 1280 mAh g-1 at the
first cycle is successfully obtained and tested for up to 100 cycles displaying stable
reversible capacity of 1140 mAh g-1. The lost of capacity is lower than 10% witch is
promising as starting point of developing the high capacity composite anode material.
The proposed work is oriented to the main investigated and developed lithium
electrochemical systems by the IEES’ team. Obtained results in this direction are
compared with the worldwide R&D achievements. Successful solving of the tasks and
their modeling could offer a new methodology for development of promising
electrodes for lithium ion batteries, to find in the future widespread use in electric
vehicles EV, full and hybrid HEV & PHEV and highly efficient storage and conversion of
energy from renewable energy sources RES.
In the present lecture will be communicated the last achievements of IEES
team in the field of developing high voltage cathode materials with reduced nickel and
cobalt content and composite anode material based on silicon composite with special
structure. Both active electrode materials are developed for take place in real
production of advanced lithium ion batteries.
Keywords: lithium ion batteries, high voltage NMC cathode materials, high capacity
silicon composite anode materials
18
VALORIZATION OF A LOCAL ENERGY RESOURCE: HYDROGEN APPLICATIONS
Mathilde Bangoura*, Frédéric Thiebaud, Dominique Perreux, Benoit Delobelle,

Pascal Robinet, David Chapelle
MAHYTEC, 6 rue Léon Bel, 39100 Dole, France

Corresponding author: mathilde.bangoura@mahytec.com
Phone: +33.384.80.17.20; Mobile: +33.699.62.81.97
When it comes to managing the final consumption of energy, local energy

production comes as a strong link of the energy transition to contribute to the
development of a carbon-free economy across a region.
Local renewable energy production will undoubtedly flourish, especially since the
heart of renewable energies is local by nature. Solar plants, wind farms are being
installed as close as their end-users ; it is even more true since decentralized production
has been promoted by most European governments who see into this new energy
generation method the way to respond to local demand more environmentally friendly.
The storage of these intermittent renewable energies by the use of hydrogen
technologies is then becoming more and more relevant.
Local energy resources can also be fatal energy (waste, co-product) and should
follow the same dynamism. Chemical industry for instance is a big consumer of
dihydrogen but also a big producer, and the balance being what is produced and what is
used into their manufacturing process is globally positive. Moreover, this is a significant
resource; in France, in 2016 out of the 922.000 tons of hydrogen production, 314 000
tons are a result of co-productions, that is about 34% of the hydrogen production that
stems from the production of ethylene, styrene, coke plants or electrolysis… For these
industries comes the question on what to do with the hydrogen and how to make it
more valuable, to reach the optimum of a green circular economy.
Some local institutions have been and still are pushing forward regional projects to
demonstrate the potential of local energy resource. It is in particular the case of the
Region Bourgogne Franche-Comté in East of France where several projects have been
implemented to use either renewable energies or an industrial hydrogen source to
participate to the expansion of an hydrogen society.
The article exemplifies three main projects related to hydrogen and fuel cell
technology which confirm that hydrogen is a local energy resource that can be valuable
when it comes to energy storage and clean mobility.
Keywords: H2 technologies, hydrogen production, hydrogen storage, hydrogen

transport, green mobility, energy storage
19
NCMS AS CATHODE MATERIALS FOR LITHIUM – ION BATTERIES
Aishui Yu, Siyang Liu, Congcong Zhang
Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials,

Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Institute of New Energy,
Fudan University, Shanghai 200438, China
Corresponding author: asyu@fudan.edu.cn
The rapid development of electric vehicles has stimulated the demand for
lithium-ion batteries with higher gravimetric and volumetric energy densities. Ni-
rich layered oxide cathodes LiNi1-x-yCoxMnyO2 (NCMs, 1-x-y ≥ 0.6) are promising
cathodes to satisfy such requirements due to their higher specific capacity
(200~220 mAh g-1), higher energy density (>800 Wh kg-1) and lower cost (Zheng et
al., 2018). However, several technique challenges, such as fast capacity fading, high
voltage instability, and poor storage property, hinder their large-scale application.
To overcome these problems, we developed several surface modification methods,
and compared the effects of coating and doping. Meanwhile, we revealed their
capacity fading mechanisms at elevated temperature.
For example, we proposed a facile method to reconstruct the surface structure
of LiNi0.6Co0.2Mn0.2O2 (NCM622) via Nb modification, which integrated the merits of
partial Nb5+ doping in the pristine structure and surface Li3NbO4 coating (Liu et al.,
2018 a). The presence of Nb5+ in the Li layer exhibited positive effects on stability of
layered structure, and the surface Li3NbO4 coating layer increased interfacial
stability, which resulted in superior electrochemical performance at high voltage.
A facile ball-milling method was proposed to remove the lithium residues and
enhance the electrochemical performance of NCM622 (Zhang et al., 2018). After
NH4VO3 treatment, a lithium ion-conductive Li3VO4 coating layer was found on the
NCM622 surface at heat-treatment temperatures of 300 and 450°C, with a small
part of vanadium ions diffusing into the surface lattice. When the temperature
surpassed 600°C, almost all vanadium ions doped into the bulk structure.
Electrochemical tests showed that 0.5 wt% NH4VO3 treated NCM622 at 450 °C
exhibited much improved cycling stability (96.1% cycling retention at 0.5C after 100
cycles and 97.2% after 50 cycles at 55°C), rate capability (117.0 mA h g−1 at 5C), and
storage property (4683 ppm lithium residue amount after storing in air for 7 days).
Two kinds of cathode materials (Zr-doped NMC622 and ZrO2-coated NMC622)
were synthesized, and the effects of doping and coating on the structural stability
and electrochemical performance were investigated (Liu et al., 2018 b). Zr-doped
NMC622 exhibited superior electrochemical performance with 98% capacity
retention after 50 cycles between 3.0 and 4.5 V at 55°C. In contrast, pristine and
20
ZrO2-coated NMC suffered continual capacity decay during cycling. Ex situ analyses
revealed that the performance improvement originated from the structure
stabilizing effects of Zr doping and the robust interfacial film on the cathode surface
during cycling, suggesting that lattice doping was a key factor in obtaining excellent
cycling performance at high temperatures.
We investigated the electrochemical performance of NCM622 and examined
the corresponding degradation mechanisms (Liu et al., 2018 c). The results
highlighted that the capacity degradation of the NCM622 was the result of multiple
factors, including the structural transformation of cathode materials as well as the
adjustment of the cathode/electrolyte interface. On one hand, phase
transformations and surface structural deterioration were responsible for the
increase in charge transfer impedance upon repeated cycling. On the other hand,
electrolyte decomposition and the interactions between the cathode and
electrolyte rendered the electrode surface accumulation of LiF and NiF2 species,
resulting in increased surface film resistance and reduced Li+ diffusion kinetics.
Keywords: LiNi1‐x‐yCoxMnyO2, at elevated temperature, at high voltage, coating,

doping, capacity fading mechanisms
References
J. Zheng, P. Yan, L. Estevez, C. Wang, J.G. Zhang, (2018), Nano energy, 49:28-548
S.Y. Liu, X. Chen, J.Y. Zhao, J.M. Su, C.C. Zhang, T. Huang, J.H. Wu, A.S. Yu, (2018 a) J. Power Sources,
374:149-157
C.C. Zhang, S.Y. Liu, J.M. Su, C.G. Chen, M.M. Liu, X. Chen, J.H. Wu, T. Huang, A.S. Yu, (2018),
Nanoscale, 10:8820-8831
S.Y. Liu, Z.Y. Dang, D. Liu, C.C. Zhang, T. Huang, A.S. Yu, (2018 b), J. Power Sources, 396:288-296
S.Y. Liu, J.M. Su, J.Y. Zhao, X. Chen, C.C. Zhang, T. Huang, J.H. Wu, A.S. Yu, (2018 c), J. Power Sources
393:92-98
21
XXIInd National Conference with International Participation
LITHIUM SULPHUR BATTERIES: STRATEGIES TO INCREASE THE CYCLE LIFE
Silvia Bodoardo
Electrochemistry Group – Politecnico di Torino

Corresponding author: silvia.bodoardo@polito.it
The talk will focus on new battery technologies based on lithium and in
particular on Lithium-Sulphur. Results obtained by the Electrochemistry Group of
Politecnico di Torino (Italy) will be presented with particular focus on strategies
applied on the cathode protection to reduce and block the polysulphides shuttling.
Two main strategies are followed: the cathode confinement and the use of an
interlayer.
The use of TiO2 based systems permit to well adsorb polysulphides and
increase the cycle life
Finally the use of an interlayer based on C3N4 is presented and allowing to

block polysulfides shuttling
The results obtained guarantee high cyclability and good capacity retention
even at high Crate.
The presented research activities are carried out in ALISE European funded
project.
22
THE ROLE OF ENERGY STORAGE IN LOW CONSUMPTION WORKING VEHICLES
Aurelio Somà, Francesco Mocera, Elena Vergori
Department of Mechanical and Aerospace Engineering (DIMEAS), Politecnico di Torino,

Corso Duca degli Abruzzi 24, 10129 Torino, Italy
Corresponding author: aurelio.soma@polito.it
Energy storage is a very hot topic today and the main reason for this is energy
transition (Etacheri et al., 2011; International Energy Agency, 2018; Nitta et al.,
(2015; Peters et al., 2017). During years, primary sources of energy produced other
kind of energy such as gasoline, electricity and heat. We used this kind of energy,
but we also produced waste and gasses such as CO2. These waste and excess of
gasses are now producing their effect causing global warming. Many researchers
are focusing on renewable energy. The main problem with this kind of energy is
that it is not reliable, because of large fluctuations and variability during the day
and within seasons and year, because of the intrinsic intermittent nature of
renewables. The energy demand is not uniform within the year among different
places on the earth. In this scenario, energy storage has a fundamental role,
allowing to store energy when surplus energy is available. Energy storage also
allows to store energy when it is cheap to be produced and to sell it when it is
expensive, so it is an active way to influence the energy prices.
Table 1. Different types of energy storage systems

Energy storage device Energy storage technology
Fossil fuels, Hydrogen, fuel cells, electrolyser Chemical storage
Heat batteries, Sensible/latent heat storage Thermal storage
Electroch emical batteries, flow batteries Electro-chemical storage
Flywheel, compressed air, pumped hydro Mechanical storage
Supercapacitors, superconducting magnetic Electromagnetic storage
Each type of storage in Table 1, is characterized by different discharge

duration, that can be microseconds, seconds, minutes, hours, days, weeks and
finally months. Another classification must be made according to the capacity these
technologies can store (Farmann et al., 2015).
If batteries can be the solution depends on the application. For sure, batteries
have some theoretical limitation. Using the standard potential table, it is possible to
combine cathodic materials with anodic materials to find out the cell voltage, and
the maximum theoretical reachable limit is about 5 V.
23
Another theoretical limitation is specific capacity and specific energy, which

depend on the chemistry of the battery system. Finally, batteries are always a
compromise solution between available energy and power.
In this big transition period, the market is providing its answer. Batteries cost is
decreasing over the years and according to forecast the batteries price, today
about 250 $/kWh, will reach 100 $/kWh within the next 20 years. Lithium-ion
batteries are dominating the market today, and the same will be within the next
years. Among them, various chemistries exist and continuously research is
conducted to find out more stable and cheap materials, efficient and with longer
life. When dealing with vehicles, the short-term environmental solution seems to
be batteries powered vehicles. This solution is particularly important in urban
centres, because it allows to reduce the local CO2 production.
In the Non-Road Mobile Machineries (NRMMs) field, the need for more efficient
and less pollutant industrial machines have pushed manufacturers towards
research and development efforts for new innovative architectures. To satisfy
emissions regulations, after-treatment gas systems have been widely adopted, but
they have quickly showed to be not the best solution (Reşitŏglu et al., 2015). With
stricter regulations, the size of these systems has grown exponentially leading to
serious problems in the on-board integration from the manufacturer side. This is
the main reason why new electrified battery-based architectures started to be
considered also in this field (Emadi et al., 2003; Somà et al., 2016; Somà, 2017;
Katrăsniket al., 2007; Lajunen et al., 2018).
In this scenario, our research group is working to give its contribution in this
transition stage. Through the experience gained in this field in several years, the
system engineering approach to the electrification lead to a special design
approach based on the hybridization factor of the architecture.
These machines are characterized by the fact that during their life, they may be
called to accomplish several tasks, different from each other in terms of power
demand and duty cycle. This is the main reason why the group worked hard in the
characterization of the Working Cycle (WC) of several industrial machines and
agriculture applications. Starting from the WC of the machine, electrified
architectures can be designed finding the best solution between energy storage
and charge sustaining solutions (Mocera and Somà, 2017). This allows to
accomplish the tasks the machine was designed for, without the need of oversized
energy storage devices.
Several prototypes were designed by the research group during the last
decades, collaborating with industrial partners which strongly believe that an
energy transition will soon or later involve also the NRMMs field. Thanks to several
remote monitoring devices developed by the group itself, it is possible to have a
“Real Time” view of the machine performance directly on a cloud platform. A
specifically designed interface allows users to have a complete overview of all the
main electric parameters to be monitored. This means that also battery
24
performance can be studied under high stress working conditions and diagnostic
actions can be performed (Vergori et al., 2018; Wang et al., 2016).
Keywords: Energy transition, energy storage, lithium‐ion batteries, diagnostic,

hybrid electrification, working vehicles.
References
V. Etacheri, R. Marom, R. Elazari, G. Salitra, D. Aurbach, (2011), Challenges in the development of
advanced Li‐ion batteries: a review. Energy & Environmental Science, 4, 3243
International Energy Agency, (2018), Global EV Outlook 2018: Towards cross-modal electrification
N. Nitta, F. Wu, J. T. Lee, G. Yushin, (2015), Li‐ion battery materials: present and future. Materials
Today, 18(5), 252-264
J. F. Peters, M. Baumann, B. Zimmermann, J. Braun, M. Weil, (2017), The environmental impact of Li‐
Ion batteries and the role of key parameters – A review. Renewable and Sustainable Energy
Reviews, 67:491-506
Farmann, W. Waag, A. Marongiu, D. Uwe Sauer, (2015), Critical review of on‐board capacity
estimation techniques for lithium‐ ion batteries in electric and hybrid electric vehicles. Journal of
Power Sources, 281:114-130
Reşitŏglu, K. Altinişik, A. Keskin, (2015), The pollutant emissions from diesel‐engine vehicles and
exhaust aftertreatment systems. Clean Technologies and Environmental Policy, 17:15-27
Emadi, M. Ehsani, J. M. Miller, (2003), Vehicular Electric Power Systems: Land, Sea, Air and Space
Vehicles CRC Press 1 edition
Somà, F. Bruzzese, F. Mocera, E. Viglietti, (2016), Hybridization Factor and Performance of Hybrid
Electric Telehandler Vehicle. IEEE Trans. on Ind. Appl 52:5130-5138
Somà, (2017), Trends and Hybridization Factor for Heavy‐Duty Working Vehicles, Hybrid Electric
Vehicles Teresa Donateo, IntechOpen, 3-32
T. Katrăsnik, F. Tranc, S. Rodman Oprěsnik, (2007), Analysis of the energy conversion effciency in
parallel and series powertrains. IEEE Trans. Veh. Technol. 56(6), 3649–3659
Lajunen, P. Sainio, L. Laurila, J. Pippuri-Mkelinen, K. Tammi, (2018), Overview of Powertrain
Electrification and Future Scenarios for Non‐Road Mobile Machinery. Energies 11:1184-1206
F. Mocera, A. Somà, (2017), Study of a Hardware‐In‐the‐Loop bench for hybrid electric working
vehicles simulation. 2017 Twelfth International Conference on Ecological Vehicles and
Renewable Energies (EVER), 1-8
E. Vergori, F. Mocera, A. Somà, (2018), Battery Modelling and Simulation Using a Programmable
Testing Equipment. Computers, 7(2):20-44
Q. Wang, B. Jiang, B. Li, Y. Yan, (2016), A critical review of thermal management models and
solutions of lithium‐ion batteries for the development of pure electric vehicles. Renewable and
Sustainable Energy Reviews 64:106-128
25
STUDY ON GEOTHERMAL ENERGY ON ROMANIAN TERRITORY
Natalia-Silvia Asimopolos, Laurentiu Asimopolos
Geological Institute of Romania, Caransebes Street, 1, Bucharest, 012271, Romania

Corresponding author: natalia.asimopolos@igr.ro
Geothermal energy is an unconventional renewable energy source with

enormous potential for exploitation, of which only a very small part is currently
used today.
Worldwide, countries with a high geothermal potential are Iceland, New
Zealand and in Europe are Hungary, Romania, Serbia. In these countries, as well as
in many others, there are geological conditions that allow to geothermal
phenomena to manifest on the surface of the Earth. The limited exploitation of this
energy resource is still limited by existing technologies and by the high cost of
deep-water equipment.
For the future, geothermal energy is considered to be Earth's most important
energy resource, given the estimate that the temperature in the centre of the Earth
is equal to the temperature at the surface of the Sun. The problem lies in finding
the most suitable technologies for exploitation both in areas with geothermal
phenomena on surface and in areas with these manifestation in underground
(Veliciu, 1998).
The main geothermal systems discovered on the Romanian territory are found
in porous permeable formations such as sandstones interbedded with clay and
shales or carbonate formations of Triassic age in the basement of the Pannonian
Basin and Aptian age in the Moesian Platform.
Geothermal reservoir Oradea is located in the Triassic limestone and dolomites
at the depths between 2200m to 3200m on an area of about 75Km2 with a total
flow rate of 140 l/s geothermal water with temperatures at the head of 70-105
degrees Celsius. Recharge area is in the Northern edge of the Padurea Craiului
Mountains and the Borod Basin. Although there is a significant recharge of the
geothermal system, the exploitation with a total flow rate of 300 l/s generates
pressure draw down in the system (Cohut, 1998).
The Bors geothermal reservoir is a tectonic closed aquifer with a surface area
of 12km2, situated at about 6 km norh-west to Oradea with geological framework is
completely different from the Oradea geothermal reservoir although the reservoirs
in the same fissured carbonate formations.
For a good image of Romania's geothermal potential, we present, in our
paper, the temperature map at 3000 m deep and the geothermal flow map on the
26
surface. These maps we made with the Surfer program, based on the data
presented on geophysical portal on the WEB page of the Geological Institute of
Romania.
Keywords: environment, geothermal, renewable energy, geophysical portal.
Acknowledgments: This work was supported by a grant of the Romanian Ministry

of Research and Innovation, CCCDI – UEFISCDI, project Nr.16PCCDI/2018:
Institutional capacities and services for research, monitoring and forecasting of risks
in extra‐atmospheric space”, within PNCDIII.
References
Cohut I., (1998), Utilisations of Geothermal resources in Romania. Romanian Journal of Geophysics
Veliciu S., (1998), Dezvoltari recente in exploatarea geofizica a resurselor geotermale in Romania.
Romanian Journal of Geophysics
27
NUCLEAR ASSISTED HYDROGEN PRODUCTION
Damian Axente, Cristina Marcu
National Institute for Research and Development of Isotopic and Molecular Technologies
67‐103 Donat Str., 400293 Cluj‐Napoca, Romania, Tel. 0264 584037
Corresponding author: Damian. Axente@itim‐cj.ro
Nuclear generated hydrogen has important advantages over other sources that
will be considered for a growing hydrogen share in a future world energy economy. Still
there are technical uncertainties in nuclear hydrogen processes that need to be
addressed through a research and development effort. Safety issues as well as
hydrogen storage and distribution are important areas of research to be undertaken to
support a successful hydrogen economy in the future.
Hydrogen will play a large and growing role in the refining of petroleum products,
means of storing electrical energy during periods of weak consumption and restore
them during times of peak power demand.
Centralized energy production in large quantities favours the use of nuclear plants.
A principal advantage of nuclear based energy supply is: eliminating supply uncertainty
and sensitivity of energy prices to volatility of natural gas and other fuel prices; virtually
no emission of airborne pollutants.
The potential of three hydrogen production processes under development for the
industrial production of hydrogen using nuclear energy are compared and evaluated in
this work: advanced electrolysis; steam reforming; sulfur-iodine water splitting cycle.
Water electrolysis and steam reforming of methane are proven and use extensively
for the production of hydrogen today. The sulfur – iodine cycle (S – I), a thermochemical
water splitting process is of particular interest because it produces hydrogen efficiently
with no CO2 by product. If heated with nuclear source it could be an ideal
environmental solution to hydrogen production.
The overall thermal efficiency of the electrolysis includes the efficiency of the
electrical power generation and of the electrolysis itself. The electrolysis process
efficiency is about 75% and of electrical power generation is only 30%, the overall
thermal efficiency for hydrogen generation being about 25%.
Steam reforming process consists of reacting methane (or natural gas) and steam in
a chemical reactor at 800-900oC with a thermal efficiency of about 70%. In a reforming
process with heat supplied by nuclear reactor the heat must be supplied by a secondary
loop from the nuclear side and be transferred to the methane/steam mixture via a heat
exchanger type reactor.
Steam reforming remains the cheapest hydrogen production method based on the
latest estimates, even when implemented with nuclear reactor.
The S – I cycle offers a close second and electrolysis is the most expensive of the
options for industrial hydrogen production.
28
Li-ION BATTERY MANUFACTURING IN EUROPE: ITALIAN INITIATIVE
Mihaela Aneta Dumitrescu
Lithops s.r.l, Strada del Portone 61, 10137 Torino

Corresponding author: aneta.dumitrescu@lithops.it
The market of Li-ion batteries is continuously growing due to the progresses

made at technological level and in the same time due to the policies adopted by
several countries and at European level. In Norway, the government’s transportation
plan targets that all new passenger cars and vans sold in 2025 should be zero-
emission vehicles. According to the International Energy Agency at least 10 other
countries have electric car sales targets in place. One of the questions that rises is if
the European cell manufacturers can compete with well established Asian producers
or the new giga-factory in USA. European Commission is actively supporting the
European battery cell competitiveness through establishing “European Battery
Alliance” (EBA). One of the declared goals is to avoid the technological dependency
with respect to a critical component: cells. In Europe the market is driven by
automotive sector but the applications are numerous, starting with consumer goods
like batteries for smartphones and laptops and going to larger applications like
stationary energy storage systems and not forgetting aerospace and medical sectors.
In which market will invest the new European players?
Lithops s.r.l is the first Italian Li-Ion Technology Developer. It was founded in
Torino in 2010 and since December 2015 is part of Seri S.p.A, under the direct
presidency of FIB, owner of the historical Italian brand of lead-acid batteries FAAM.
Currently, FIB is establishing in Italy a manufacturing base with a capacity of
200MWh/y. In this presentation will be highlighted the strategy employed for a
successful initiative.
Keywords: Li‐ion battery, manufacturing, competitiveness.
29
α-SETS SOFTWARE FOR ANALYSIS, MODELLING AND SIMULATION OF THE

STIRLING ENGINE
Adrian Bot, Vasile Rednic, Nicolae Aldea
National Institute for Research and Development of Isotopic and Molecular Technologies,
67‐103 Donat, 400293 Cluj‐Napoca, Romania
Corresponding author: nicolae.aldea@itim‐cj.ro
Type the body of the abstract text (including tables and figures – if considered)
justified single-spaced in 11-point Times New Roman regular fonts. Abbreviations
should be defined at first mention and used consistently thereafter. Cite references in
the text by name and year in parentheses.
The Stirling engine works with hot gas such as air, helium or hydrogen on a closed
regenerative thermodynamic cycle with external heat input between minimum and
maximum temperatures.
The aim of our contribution consists in development of the computer code written
in MAPLE 2018 language, used in modelling, analysing and simulation of the alpha
Stirling engine. Main parts of computer code are based on distinctly procedures and
they have the following functions: (i) input data for many type geometries of cooler,
heater, regenerator, compression and expansion spaces, (ii) isothermal analysis based
on Schmidt model, (iii) adiabatic analysis of the compression and expansion space, (iv)
scaling parameter approach based on real simulation of cooler, regenerator and heater
furnishing all technical information of engine. The test run was done on technical
information of Genoa03 and Ford Philips 4 - 215 Stirlig engines.
The computer code αSETS is a powerful tool in analysis, modelling and simulation
of α Stirling engine. To proof this a demo presentation will be done eventually.
The main conclusions can be summarized as: (i) simulation results obtained using
αSETS software are in good agreement with the experimental measured parameters of
investigated engines, (ii) the IT product can be fully considered as a technology
transfer with application in science, technology and production of α Stirling engine, (iii)
it can be used in scientific and technological research by universities and scientific
researchers to understand the operation and design of α Stirling engine, (iv) in the
near future we will try to bring it into IT products market.
Keywords: Stirling engine, isothermal analysis, adiabatic analysis, scaling parameter

approach, efficiency.
Acknowledgments: Financial support from the MCI, Core Programme, Project PN 18

03 01 02 is gratefully acknowledged.
30
THERMAL RECEPTOR FOR CONCENTRATED SOLAR POWER. AN EXPERIMENTAL

AND SIMULATED EFFICIENCY STUDY
Vasile Rednic, Robert Gutt, Emil Bruj, Gabriel Roșca, Radu Pop, Sergiu Pogăcian,
Dan Zotoiu and Adrian Bot
National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103
Donat, 400293 Cluj-Napoca, Romania
Corresponding author: vasile.rednic@itim‐cj.ro
The growing interest in the use of alternative energy sources, both to reduce
pollution and to cover the increase in global energy demand, has led to intense
research and technology development in this field. Together with hydro and wind
powers, solar power is the most important renewable energy source in terms of
globally capacity. Concentrated solar power can be used as heat source for Stirling
engine but the capture and conversion of solar energy is not an easy task. We
investigate, through simulation and experiment, different designs of thermal
receptors in order to increase their efficiency. The experimental design use Fresnel
lens as solar concentrators, mounted on a two-axis solar tracking system. The
numerical simulation used in this research are performed in ANSYS software, using
Fluent to simulate working fluid flow, temperature distributions and both energy
loss and energy transferred through the thermal receptor.
Keywords: Concentrated solar power, Thermal receptor, Energy conversion, Thermal

simulation, ANSYS Fluent.
Acknowledgments: Financial support from the MCI, Core Programme, Project PN

18 03 01 02 is gratefully acknowledged.
31
TECHNIQUES BASED ON POSITRONS AT ELI-NP
Andreea Oprisa, Nikolay Djourelov, Victor Leca, Doru Dinescu
ELI‐NP, “Horia Hulubei” National Institute for Physics and Nuclear Engineering, 30 Reactorului Street,
RO‐077125, Bucharest‐Magurele, Romania
Corresponding author: andreea.oprisa@eli‐np.ro
We present a brief description of the techniques based on positrons that we

want to develop at ELI-NP (Extreme Light Infrastructure-Nuclear Physics). ELI-NP is
a new European Research Infrastructure that is currently built in Magurele-
Bucharest (Romania), and where a moderated positron beam with an intensity of
~ 1x 106s-1, will be obtain by pair production in a tungsten converter target, using
an intense γ - beam of 2.4x1010 γ/s with energies up to 3.5 MeV (Djourelov et al.,
2016 a; Djourelov et al., 2016 b). The moderated positrons will be used to
implement some particular experimental tools based on positron annihilation,
which are useful in materials research.
Due to the limited  - beam time at ELI-NP dedicated to positron production,
we foresee to use also a commercial 22Na positron source, which will allow full
year operation of the laboratory.
At ELI-NP, the access will be possible for scientists interested on study of
materials by application of the positron beam with spectroscopy instruments that
will be implemented.
Keywords: Gamma beam, positron production, moderated positron beam, simulation.
References
N. Djourelov et al., (2016 a), Positron Production by Gamma Beam at ELI-NP, Romanian Reports in
Physics, 68:S735-S797, Supplement
N. Djourelov, A. Oprisa, V. Leca, (2016 b), Source of slow polarized positrons using the brilliant
gamma beam at ELI-NP. Converter design and simulations, Nucl. Instr. Meth. A, 806:146-153
32
HYLAW - PROJECT PRESENTATION
Ioan Iordache1, Dorin Schitea1, Alexandru Floristean2,

Ioan Stefănescu1, Nicolas Brahy2
1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI
Rm. Vâlcea, Code 240050, Rm. Vâlcea, Uzinei Street no. 4, PO Box Râureni 7, Vâlcea, Romania;
2
Hydrogen Europe, Avenue de la Toison d’Or 56‐60, 1060, Brussels, Belgium
Corresponding author: iordache.ioan@icsi.ro
HyLaw is a flagship project aimed to removal the legal and administrative

barrier to the effective utilization and commercial deployment of fuel cells and
hydrogen. Effective results of the project are available at www.hylaw.eu.
The project brings together 23 partners from Austria, Belgium, Bulgaria,
Denmark, Finland, France, Germany, Hungary, Italy, Latvia, Norway, Poland,
Romania, Spain, Sweden, Portugal, the Netherlands and United Kingdom and is
coordinated by Hydrogen Europe.
The HyLaw partners have identified in first stage the legislation and regulations
relevant to fuel cell and hydrogen applications and legal obstacles to their
commercialisation. Now, in the second stage were provide specific benchmarks and
recommendations on how to remove these barriers (Iordache, 2018, Iordache, 2017;
Møller-Holst, 2017).
HyLaw sets up a long-term consolidation of National Association not only on
the project period of time. By bringing together these national associations and all
of Hydrogen Europe’s members, it’s the first time ever that the entire European
FCH sector is brought together with a clear and common ambition.
Table 1. Project partners
Parti-
Name Country
cipant
1(Co.) Hydrogen Europe Belgium
2 Austrian Energy Agency (AEA) Austria
3 Waterstofnet Vzw Belgium
4 Bulgarian Academy of Science (BAS) Bulgaria
5 Danish Hydrogen & Fuel Cell Partnership (DPHFCP) Denmark
6 German Hydrogen and Fuel Cell Association (DWV) Germany
Research Centre For Natural Sciences, Hungarian Academy Of
7 Hungary
Sciences (MTA TTK)
National Agency For New Technology, Energy and Sustainable
8 Italy
Economic Development (ENEA)
33
National Research and Development Institute for Cryogenics and

9 Romania
Isotopic Technologies (ICSI)
10 The Scottish Hydrogen And Fuel Cell Association (SHFCA) UK/Scotland
Foundation For The Development Of New Hydrogen Technologies
11 Spain/Aragon
In Aragon (FHa)
12 Hydrogen Sweden Sweden
13 Greater London Authority (GLA) UK/London
14 Technology Research Centre (VTT) Finland
15 Atomic Energy and Alternative Energies Commission (CEA) France
16 Dutch Standardisation Institute (NEN) Netherlands
17 Energy Institute (IEn) Poland
18 Dutch Hydrogen and Fuel Cell Association (NWBA) Netherlands
19 STI Industrial Technical Systems (STI) Portugal
20 Stiftelsen (SINTEF) Norway
21 Latvian Hydrogen Association (H2LV) Latvia
22 French Hydrogen And Fuel Cell Association (AFHYPAC) France
23 UK Hydrogen and Fuel Cell Association (UKFHCA) UK
In Romania, HyLaw project activities has comprised data collection from interviewees
and review the public sources. A national workshop and a national policy paper were
provided.
Keywords: FCH, HyLAW, LAP, LIS.
Acknowledgments: The HyLAW project has received funding from the Fuel Cells and
Hydrogen 2 Joint Undertaking under grant agreement No 737977. This Joint
Undertaking receives support from the European Union’s Horizon 2020 research
and innovation programme.
References
Iordache I., (2018), HYLAW – a project designed to accelerate the hydrogen technology implementation in
Europe - https://asociatiaenergiainteligenta.ro, accessed at 1/05/2018
Iordache I., Kraus N., Schitea D., Skiker S., Ștefănescu I., Brahy N., (2017), HyLAW – a project
designed to reduce vulnerabilities of the hydrogen economy in Europe, EFC2017 - European
Fuel Cell “Piero Lunghi” Conference & Exhibition, Naples, Italy, December 12-15, 2017
Møller-Holst S., (2017), HyLAW, https://www.sintef.no/en/projects/hylaw/ accessed at 1/12/2017
34
OPTIMUM SLOPE AND AZIMUTH ANGLES FOR SOLAR

COLLECTOR AND PV MODULE
Shin Ki-Yeol1, Cristian Hoarca2

1
School of Mechanical Engineering, Yeungnam University, 280 Daehak‐ro, Gyeongsan, Gyeongbuk,
38541, Republic of Korea;
2
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
Valcea, Code 240050, Uzinei Street no. 4, P.O. Box Râureni 7, Valcea, Romania
Corresponding author: shinky@ynu.ac.kr
In this paper the optimum condition of installation of PV module has been studied.
The optimization algorithm of sun-tracking system has been developed to find out how
to maximize solar power generation (Bazyari et al., 2014; Yadav and Chandel, 2013).
The slope and azimuth angle of a solar-energy system are important variables to
calculate maximum solar-energy collection. Surface angle is one of the installation
specifications, which depends on the seasonal path of the sun (Gebremedhen, 2014).
The accurate determination of the optimum azimuth angle for the installation is
important for the maximum energy production by the solar power system. The
variation effects of slope and azimuth angles for solar collector were studied by using
Typical Meteorology Year data set for Buk-Gangleung area in Korea. The beam and
diffuse radiations are also analysed according to various installation conditions from
total solar radiation for a year. For the PV power calculation, 14kW power PV module
set was designed and produced yearly based power generation. As a result, the
amount of solar-energy collection depends on the azimuth angles but changed as each
seasons. There is maximum power generation condition of surface direction to the sun
and it can be also applied to the control algorithm of sun-tracking system.
Figure 1. Annual total solar radiation by azimuth (β) and slope (α) variations
35
Figure 2. Annual average PV power generation by azimuth (β) and slope (α) variations
Keywords: Solar Energy, Photovoltaic, Optimum Installation, Sun Tracking.
Acknowledgments: This work was supported by the National Research Council of

Science & Technology (NST) grant by the Korea government (MSIP) (No. CRC‐15‐01‐
KIST).
References
Bazyari, S., Keypour, R., Farhangi, S., Ghaedi, A., & Bazyari, K., (2014), A study on the effects of solar
tracking systems on the performance of photovoltaic power plants. Journal of Power and Energy
Engineering, 2(04):718-728
Gebremedhen, Y. B., (2014), Determination of Optimum Fixed and Adjustable Tilt Angles for Solar
Collectors by Using Typical Meteorological Year data for Turkey. International Journal of
Renewable Energy Research, 4(4):924-928
Yadav, A.K. and Chandel, S.S., (2013), Tilt angle optimization to maximize incident solar radiation: A
review. Renewable and Sustainable Energy Reviews, 23, pp. 503-513
36
PEM FUEL CELLS - ON THE WAY FROM MODELING TO REALITY
Carcadea Elena, Varlam Mihai, Jianu Catalin, Patularu Laurentiu, Dorin Schitea
National Research and Development Institute for Cryogenics and Isotopic Technologies ‐ ICSI Rm.
Valcea, Uzinei Street no. 4, P.O. Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: elena.carcadea@icsi.ro
Fuel cell is unanimously considered the core of the hydrogen – based energy
revolution. It promises to impact environmental and economic issues facing the world
every day. Modern lifestyles, high prices for diminishing supplies of fossil fuels, and the
environmental impact of energy production have all made alternative power
generation technology like fuel cells a necessity.
Electrochemical energy conversion involves complex developments of materials
and designs due to the close link between fluid flows, charge transport, corrosion
processes and performance. Advances in the development of bipolar plates, gas
diffusion layers and catalysts are required in order to reduce the main technological
barriers, which hinder the commercialization of PEMFC at large sale.
An essential component in developing the PEM fuel cell stacks is represented by
the design and manufacturing of bipolar plates with the flow field channels grooved.
80% of the total weight of a fuel cell stack and around 45% of the manufacturing costs
are coming from the development of bipolar plates. The complexity of designing and
producing bipolar plates consists in the fact that they are multifunctional elements that
must distribute uniformly the reactants to the active electrodes, eliminate the excess
heat from the active areas, sweep the current to and from the fuel cell as well as
prevent leakage of reactants. At present, a global overall effort is to find the right
materials and architecture to perform these functions, and at the same time to be light
and have low manufacturing costs.
(b)
(a)
(c)
Figure 1. (a) Bipolar plate with 3 serpentine channels (b) semi-circular, (c) rectangular profile
37
Flow field design has an important influence on fuel cell performance. A

homogeneous flow distribution, a minimal pressure loss, a uniform profile for the
species mass fraction and current distribution are few of the main goals when
developing bipolar plates for PEM fuel cells. A complete 3D PEM fuel cell model
was used to study the effect on the cell performance of a rectangular and semi-
circular flow field channel designs, as can be seen in Fig. 1. The simulations results
are plotted as I-V curves in Fig. 2. For the same channel length and pattern, the
rectangular cross section shows a better performance as compared to semi-
circular, especially in the concentration losses area of the polarization curve. The
pressure drop in the channels investigated is reported in Fig. 3. It can be seen that a
higher pressure drop of 499Pa is obtained in the semi-circular profile as compared
with 273Pa from the rectangular channels. Since the pressure drop is a good
indicator of the amount of water in the channels of fuel cells and of the flooding
phenomena, the performance drop noticed in Fig. 2 for the fuel cell with semi-
circular profile can be explained. Usually the semi-circular channel keeps the
condensed water at the bottom leading to accumulation, whereas the rectangular
shape break the surface tension of the water film formed due to the sharp corners.
Such investigations could help in choosing the optimum configuration for a specific
application or product in order to achieve an improved performance.
1.2
1.1
1 semi-circular
Voltage (V)
0.9 rectangular
0.8
0.7
0.6
0.5
0.4
0 0.1 0.2 0.3 0.4 0.5 0.6
Current density (A/cm2)
Figure 2. Polarization curves for the fuel cell with semi-circular and rectangular channels
Two different flow field geometries: a semi-circular and a rectangular 3-serpentine

channels have been investigated. The numerical model was developed based on the
commercially available ANSYS MULTIPHYSICS software in order to analyse the
influence of the flow field design on the fuel cell performance. The best configuration
will be manufactured and tested experimentally and the results will be compared with
the numerical results for model validation.
38
Figure 3. Pressure drop (Pa) in the channels for (a) semi-circular profile, (b) rectangular profile
Keywords: bipolar plates, fluid flow channels, CFD modelling, performance

evaluation.

of Research and Innovation, CCCDI‐UEFISCDI, project number PN‐III‐P1‐2‐PCCDI‐
2017‐0194 /25PCCDI/2018, within PNCDI III.
39
SMART CONDUCTIVE CHARGING STATION, FIXED AND MOBILE,

FOR ELECTRIC VEHICLES (SMiLE-EV)
Contantin Filote1, Daniel Fodorean2, Claudia Martis2, Filip Carlea3, Mihai Rata1,
Maria Simona Raboaca4
1
Stefan cel Mare University of Suceava, Suceava, Romania;
2
Technical University of Cluj‐Napoca, Romania, Cluj‐Napoca, Romania;
3
National Institute of Economic Research, Bucharest, Romania;
4
Valcea, Uzinei Street no. 4, P.O. Box 7 Râureni, 240050, Râmnicu Vâlcea, Romania
Corresponding authors: filote@eed.usv.ro, simona.raboaca@icsi.ro
Climate change and the desire to improve breathing air quality in urban areas
are the main factors that have led to legislative changes in the use of green energy
sources, including in the field of individual transport. The SMiLE-EV project
proposes the deployment of fixed and mobile EV & PHEV charging stations for
electric vehicles in order to obtain and develop clean energy applications, of Green-
to-Green type.
In Romania there are a number of legislative facilities designed to encourage
the sale of electric propelled vehicles (EV & PHEV) by providing checks on the
purchase of such a new car, or tax exemptions/reductions. One of the reasons why
the number of EV&PHEV units sold in Romania is not higher is also due to the fact
that the number of charging stations is not sufficient and without proper regional
coverage.
The SMiLE-EV project proposes the deployment of fixed and mobile EV & PHEV
charging stations to meet the mobility needs of tomorrow's society and to prepare
active/potential industrial partners for knowledge/technology transfer at the
component or system level in prepare launching new products.
Thus, 4 Romanian research entities, 2 universities and 2 institutes (covering the
three historical regions of the country), as well as 10 potential industrial partners
benefiting from the resulting technologies/products, joined in this effort. Moreover,
the SMiLE-EV project is an opportunity for (re)launching the research activities of the 4
partners in areas such as: fast EV&PHEV charging solutions, H2-based energy sources
integrated into charging stations, energy management of the mobile station, the
exploitation of the available energy in the public transport network, efficient
propulsion solutions, the connection/adjustment of the Romanian energy/
environment legislation to the new challenges posed by the use of EV&PHEV stations.
(Aschilean et al., 2018a; Aschilean et al., 2018b) Through the involvement of a
40
young/mixed workforce, the SMiLE-EV project contributes to the formation of

researchers oriented towards products with high marketing potential.
The implementation of the multidisciplinary research activity within the SMiLE-
EV project is expected to produce the following results:
• construction of a stationary charge station of electric vehicles for multiple
modes of operation (Ricaud, P. Vollet, 2017);
• construction of a PEM fuel cell testing bench dedicated to electric transport;
• construction of a mobile charging station for light electric cars and scooters,
using a mixed power supply and energy management study in the mobile station;
• propulsion system for the mobile station and the study of other auxiliary
consumers that affect the autonomy of the mobile station;
Keywords: charging station, electric vehicle, EV&PHEV
Acknowledgment: This work was supported by a grant of the Romanian Ministry of

Research and Innovation, CCCDI ‐ UEFISCDI, project number PN‐III‐P1‐1.2‐PCCDI‐
2017‐0776 / No. 36 PCCDI / 15.03.2018, within PNCDI III.
References
Aschilean I., Rasoi G., Raboaca M.S., Filote C., Culcer M., (2018a), Design and Concept of an Energy
System Based on Renewable Sources for Greenhouse Sustainable Agriculture. Energies. 11:1201,
doi: 10.3390/en11051201
Aschilean I., Varlam M., Culcer M., Iliescu M., Raceanu M., Enache A., Raboaca M.S., Rasoi G., Filote
C., (2018b), Hybrid Electric Powertrain with Fuel Cells for a Series Vehicle. Energies. 11:1294, doi:
10.3390/en11051294
C. Ricaud, P. Vollet, 17.06.2017, Connection method for charging systems – a key element for electric
vehicles, Schneider Electric
41
INTERFACES AND COMMUNICATION PROTOCOLS FOR

ELECTRIC CAR CHARGING STATION
Valentin Vlad1, Mihai Rata1, Constantin Filote1, Alexandru Lavric1,

1
Stefan cel Mare University of Suceava, Suceava, Romania;
2
Corresponding authors: vladv@eed.usv.ro, mihair@eed.usv.ro, filote@eed.usv.ro,
lavric@eed.usv.ro, simona.raboaca@icsi.ro
This paper analyses the ways in which the electric vehicle charging stations
interface with human users or other information systems during the charging
process. The interfaces discussed include the human-machine interface (HMI),
allowing users to configure and start/stop the charging process, the interface for
users’ authentication (mainly based on RFID), the interface for communication with
a central server or a local application and the interface for communication with the
electrical vehicle.
The electric vehicles become nowadays more and more widespread,
determining a continuous development of the charging points infrastructure. There
is a variety of charging stations, from the simple home charging points, to the
public complex stations, allowing user authentication, different payment options
and multiple kinds of charging.
Public stations have user interfaces, in the simplest form consisting of several
buttons and LEDs, which provide the user with a minimal control and information
regarding the charging process. More advanced user interfaces include a
touchscreen display with various facilities for configuration, control and monitoring
of the charging process.
The users can pay for the battery charging using a prepaid system, through a
mobile phone operator or cash. A prepaid system is based on a contactless card,
through which the user is identified. Using the information on the card, the
charging station can check the user account from a central database and enable or
not the charging process (Vaidya and Mouftah, 2018; Aschilean et al., 2018a).
The communication between the charging station and other information
systems like a central server may be done through the protocol OCPP (Open Charge
Point Protocol). The goal for the Open Charge Point Protocol (OCPP) is to offer a
uniform solution for the method of communication between charge point and
central system. With this protocol it is possible to connect any central system with
42
any charge point, regardless of the vendor (Pate and Ho, 2017; Panatarani, 2016;
Gianluca et al., 2014).
A charging station must also have an interface to communicate with the
vehicle in order to verify the presence of a compatible electrical receptacle and
know type of battery and its condition (Aschilean et al., 2018b).
Keywords: electric vehicle, charging station, HMI, RFID.

References
M. Pate, M. Ho, (2017), Charging ahead toward an EV support infrastructure, Texas Instruments
S. Sojoudi, S. H. Low, 2011, Optimal charging of plug‐in hybrid electric vehicles in smart grids, in
Proc. IEEE PES Gen. Meet., 24–29 Jul.
C. Panatarani, (2016), Design and Development of Electric Vehicle Charging Station Equipped with
RFID, AIP Conference Proceedings, 1712, 030007, doi: 10.1063/1.4941872.
R. Gianluca, G. De Maso-Gentile, C. Scavongelli et al., (2014), Active role of a NFC enabled
smartphone in EV‐EVSE charging process, IEEE International Electric Vehicle Conference (IEVC),
Florence, Italy, December 17-19
B. Vaidya, H. T. Mouftah, (2018), Deployment of Secure EV Charging System Using Open Charge
Point Protocol, 14th International Wireless Communications & Mobile Computing Conference
(IWCMC), pp. 922-927
Aschilean I., Rasoi G., Raboaca M.S., Filote C., Culcer M., (2018a), Design and Concept of an Energy
System Based on Renewable Sources for Greenhouse Sustainable Agriculture, Energies,
11:1201, doi: 10.3390/en11051201
Aschilean I., Varlam M., Culcer M., Iliescu M., Raceanu M., Enache A., Raboaca M.S., Rasoi G., Filote
C., (2018b), Hybrid Electric Powertrain with Fuel Cells for a Series Vehicle, Energies, 11:1294,
doi: 10.3390/en11051294
43
AN EV CHARGING STATION DEMONSTRATOR
Mihai Rata1, Gabriela Rata1, Constantin Filote1, Ana Maria Cozgarea1, Andreea
Raluca Felseghi2, Maria Simona Raboaca3
1
Stefan cel Mare University of Suceava, Suceava, Romania
2
Civil Engineering Researcher, AIB Consulting, 400497, Cluj ‐ Napoca, Romania
3
Corresponding authors: mihair@eed.usv.ro; gabrielar@eed.usv.ro; filote@eed.usv.ro;
anamariacozgarea@eed.usv.ro; andreea.felseghi@gmail.com; simona.raboaca@icsi.ro
Because of the problems associated with hydrocarbon-fueled vehicles (damage

to the environment caused by their emissions, and the sustainability of the current
hydrocarbon) at the beginning of the 21st century, the interest in electric and other
alternative fuel vehicles has increased
In the last years, the environmentally friendly products became an issue.
Among them, cars have been electrified and some drivers already drive hybrid
vehicles or electric vehicles (Lee et al. 2016). The electric and hybrid electric
vehicles are a very important factor for improvement of traffic and for a healthier
environment, due to their beneficial effect on environment. The emissions from
conventional vehicles are increased, leading to increased pollution and global
warming (Patel et al., 2016; Collin et al., 2016).
Using an electric vehicle on a regular basis requires safe and easy-to-use
charging installations. Moreover, these charging infrastructures allow the user to
charge his/her vehicle whenever he/she makes a stop (home, workplace, shopping
centers, car parks, etc.) and should not require him/her to stop just to charge: the
concept of electric vehicle charging is charging when we stop and not stopping to
charge; unlike thermal vehicles! Different types of charging infrastructures are
therefore necessary to strike a balance between the complete charging of the
vehicle and the user’s habits related to the places where he/ she stops:
• for long stops (overnight at home, daytime in the workplace), complete
charging in 6 to 8 hours can be achieved;
• for shorter stops of 1 to 2 hours (car park, shopping center, parking on a public
road, lunch break, etc.), quick-charging with a specific terminal is necessary;
• There are still cases where the user has to stop to charge (during a long trip
or after intensive professional use, like taxis or certain vehicle fleets); here,
very quick-charging in 15 to 20 minutes is necessary (Ricaud and Vollet,
2017).
In all cases, the safety of the charging operation for people, for the vehicle and
for the installation to which it is connected, is essential. It is this factor, for
example, that limits the performance and use of existing electrical sockets during
44
home charging. The different charging modes that have been defined by
international standards offer solutions to solve this situation.
In this paper the authors present an EV Charging Station Demonstrator that
work in three charging modes according IEC 61851-1 standard “ELECTRIC VEHICLE
CONDUCTIVE CHARGING SYSTEM”.
In this case the charging station has a charging controller that, checks the
following before starting the charging process: if is connected correctly booth EV to
the station and the earthing
system of EV protection circuit
of the station, if the power in
the cable, the vehicle and the
charging circuit are consistent.
What is the maximum charging
power that will be allocated to
the vehicle. All these checks
are carried out and
communicated through a
specific wire, called PILOT Figura 1. Experimental results
WIRE. In Fig. 1 is illustrated the communication signal between charging station
demonstrator and EV.
Keywords: electric vehicle, electric motors, charging station

References
Ha Jeong Lee, Ho Yeong Lee, Chang Geun Heo and Gwan Soo Park, (2016), A study on the magnetic
resonant wireless charging system for electrical vehicles, IEEE Transportation Electrification
Conference and Expo, Asia-Pacific (ITEC Asia-Pacific), Busan, pp. 630-634
N. R. Patel, V. A. Shah and M. M. Lokhande, (2016), Design and performance analysis of radial flux C‐
core switched reluctance motor for in‐wheel electrical vehicle application, IEEE Transportation
Electrification Conference and Expo (ITEC), Dearborn, MI, pp. 1-6
A.J. Collin et al., (2016), Survey of harmonic emission of electrical vehicle chargers in the European
market, International Symposium on Power Electronics, Electrical Drives, Automation and
Motion (SPEEDAM), Anacapri, pp. 1208-1213
C. Ricaud, P. Vollet, (iunie 2017), Connection method for charging systems – a key element for
electric vehicles, Schneider Electric
***, IEC 61851-1 standard “ELECTRIC VEHICLE CONDUCTIVE CHARGING SYSTEM
45
DC-DC CONVERTER FOR FAST CHARGING OF ELECTRIC VEHICLES
Ciprian Afanasov1, Constantin Filote1, Valentin Vlad1, Gabriela Rata1,

1
Stefan cel Mare University of Suceava, Suceava, Romania
2
Corresponding authors: aciprian@eed.usv.ro; filote@eed.usv.ro; vladv@eed.usv.ro;
gabrielar@eed.usv.ro; simona.raboaca@icsi.ro
Due to the increasing popularity of electric vehicles, there is an urgent need to

shorten the charging time. This involves the development of high-power charging
stations with fast chargers so as to reduce the waiting time of drivers. With fast
charging stations that can recharge a vehicle battery in minutes, the range
limitation can be overridden in principle. For such fast charging stations, compact
and efficient DC-DC converters with a high output power are required.
In recent years, major changes have been made to the automotive industry
with regard to electric vehicle transport. Several companies have produced Electric
Vehicles (EVs) and Plug-in Hybrid EVs and are currently on the market offering a
clean and environmentally friendly alternative to conventional vehicles.
The range of electric cars is still quite limited due to the distance that can be
traversed and the long charging times. To reduce the charging time, various types
of fast chargers, usually off-board solutions located in public spaces, are being
developed.
Also another important element when it comes of electric vehicles it is
represented by the infrastructure and the number of charging stations which are
available “on the road”. In the last two years at least in Europe a lot of countries
decided to focus on infrastructure, electric vehicles and charging stations to offer a
good alternative to vehicles with internal combustion engines. It is not enough to
have as many charging stations as possible but also it is necessary like a charging
station to have some characteristics: charging capacity, multi brand compatibility
and cost of charging.
For such fast charging stations, compact and efficient DC-DC converters with a
high output power are required. The charger has the purpose to convert ac to dc
current from the charging station into direct current and limits the current to the
maximum acceptable by the cable and charging station combination. Because of
power ratings, fast chargers impose several challenges. Level III or fast dc charging
46
is not suitable as an on-board solution, as the higher power capacity will be strongly
limited in terms of cost, space and weight (M. Yilmaz and Krein, 2013). On the other
hand, from the grid point of view it also represents a challenge, as the penetration
of Plug-in Electric Vehicles increases, the electric system will not be able to provide
the demand of power, particularly at peak charging hours. In addition, fast chargers
are not suitable for residential use, as a higher power charger is more likely to be a
three-phase solution (Dickerman and Harrison, 2010). Besides, the transformers in
these areas are not rated to withstand the sudden connection of several fast
chargers. For these reasons, the concept of a commercial charging station with
installed off-board high power chargers, similar to conventional gas filling stations
located at public places (parking lots, work, shopping locations, etc.) appears as a
viable solution to enable Plug-in Electric Vehicles fast charging (Rivera et al., 2013).
The fast charging station utilizes an intermediate storage battery, in order to
avoid power pulsations at the grid and to provide additional functionality as e.g.
energy storage for renewables. By splitting the intermediate storage battery, the
voltage ratings of the semiconductor devices used in the high power DC-DC
converter can be reduced, which increases the system efficiency (Christen et al.,
2012). To achieve a high power density as well as to implement ripple cancelation
on the output current, several power electronic modules must be parallel
interleaved. High-power charging is a challenging task due to high currents of
several hundred amperes as well as a wide output voltage range. In order to
simultaneously achieve a high efficiency and a high power density, non-isolated DC-
DC converters are the most suitable topologies, since the isolation to the grid is
realized in the AC-DC stage (Aschilean et al., 2018a; Aschilean et al., 2018b).
Keywords: DC‐DC converter, electric vehicle, high power charging stations

References
M. Yilmaz and P. Krein, (2013), Review of Battery Charger Topologies, Charging Power Levels, and
Infrastructure for Plug‐in Electric and Hybrid Vehicles, Power Electronics, IEEE Transactions on,
28(5):2151-2169
L. Dickerman and J. Harrison, (2010), A New Car, a New Grid, Power and Energy Magazine, IEEE,
8(2):55-61
Sebastian Rivera, Bin Wu, Jiacheng Wang and Hussain Athab, (2013, Electric Vehicle Charging Station
using a Neutral Point Clamped Converter with Bipolar DC Bus and Voltage Balancing Circuit,
IEEE Transactions on, pp. 6219–6626
47
D. Christen, S. Tschannen, J. Biela, (2012), Highly Efficient and Compact DC‐DC Converter for Ultra‐
Fast Charging of Electric Vehicles. 15th International Power Electronics and Motion Control
Conference, EPE-PEMC 2012 ECCE Europe, Novi Sad, Serbia
Aschilean I., Rasoi G., Raboaca M.S., Filote C., Culcer M., (2018 a), Design and Concept of an Energy
System Based on Renewable Sources for Greenhouse Sustainable Agriculture. Energies 11:1201,
doi: 10.3390/en11051201
Aschilean I., Varlam M., Culcer M., Iliescu M., Raceanu M., Enache A., Raboaca M. S., Rasoi G., Filote
C., (2018 b), Hybrid Electric Powertrain with Fuel Cells for a Series Vehicle. Energies 11:1294,
doi: 10.3390/en11051294
48
MODELLING OF FUEL CELL, BATTERY AND ULTRACAPACITOR AS ENERGY SOURCES

FOR EV CHARGING STATIONS
Daniel Fodorean1, Maria Simona Raboaca2, Rares Catalin Nacu1, Aron Attila
Popp1, Constantin Filote3, Filip Carlea4,
1
Technical University of Cluj‐Napoca, Cluj‐Napoca, Romania
2
3
University „Stefan cel Mare” of Suceava, Suceava, Romania
4
National Institute of Economic Research, Bucharest, Romania
Corresponding author: Daniel.fodorean@emd.utcluj.ro
The paper proposes the modelling of a triple source which can be used as
energy supplying unit inside a charging station for electric vehicles (EVs). The triple
source contains a fuel cell unit, a lithium type battery an ultra-capacitor (UC)
storage pack. These energy sources are to be integrated into an EV charging
station, to assure the supply of light electric vehicles found in urban areas. In the
paper will be presented the mathematical model of each energy source unit, some
details of the schematic modelling blocks elaborated in Matlab/Simulink, the
operation of each unit for specific load conditions and their mixed operation inside
the charging station. (Iranzo et al., 2010; Wang et al., 2015; Giaouris et al., 2012;
Wang et al., 2017; Wang et al., 2014; Thounthong et al., 2008; Wang et al., 2005;
Bellache et al., 2018)
Keywords: fuell cell, battery, ultracapacitor; EV charging station; modelling.

Reference
Iranzo A., Munoz M., Rosa F., Pino J., (2010), Numerical model for the performance prediction of a
PEM fuel cell. Model results and experimental validation, Int. J. Hydrogen Energy,
35(20):11533-11550
Y-X. Wang, K. Ou, Y-B. Kim, (2015), Modeling and experimental validation of hybrid proton exchange
membrane fuel cell/battery system for power management control, International Journal of
Hydrogen Energy, 40(35)
D. Giaouris, F. Stergiopoulos, C. Ziogou, D. Ipsakis, S. Banerjee, B. Zahawi, et al., 2012, Nonlinear
stability analysis and a new design methodology for a PEM fuel cell fed DC–DC boost converter,
International J Hydrogen Energy, 37(23):18205-18215
49
Guorui Zhang, Weirong Chen, Qi Li, 2017, Modeling, optimization and control of a FC/battery hybrid
locomotive based on ADVISOR, International Journal of Hydrogen Energy, 42(29):18568-18583
Wang Y. X., Yu D. H., Chen S. A., Kim Y.B., 2014, Robust DC/DC converter control for polymer
electrolyte membrane fuel cell application, Journal of Power Sources, 261:292-305
Thounthong P., Rael S., Davat B., 2008, Control algorithm of fuel cell and batteries for distributed
generation system, IEEE Transactions on Energy Conversion, 23(1):148-155
C. Wang, M. H. Nehrir, S. R. Shaw, 2005, Dynamic models and model validation for PEM fuel cells
using electrical circuits, IEEE Trans. Energy Convers., 20(2):442-451
K. Bellache, M. B. Camara, B. Dakyo, 2018, Transient Power Control for Diesel‐ Generator Assistance
in Electric Boat Applications Using Supercapacitors and Batteries, IEEE Journal of Emerging and
Selected Topics in Power Electronics, 6(1), March 2018
M. B. Camara, B. Dakyo, 2016, Real time energy management for hybrid electric boat applications
Using variable speed diesel generator and lithium‐battery, IEEE International Conference on
Automation, Quality and Testing, Robotics (AQTR), DOI: 10.1109/AQTR.2016.7501371
50
EUROPEAN LOCAL ENERGY OWNERSHIP IN ENERGY TRANSITION
Filip Cârlea1, Maria Simona Răboacă2

1
National Institute of Economic Research, Bucharest, Romania
2
Corresponding author: Filip_carlea@yahoo.com
The reasons and opportunities that motivate local authorities to embark on

community energy projects are revitalising the local economy, creating a close
connection with citizens, managing local public services in a more integrated way,
fostering cooperation and partnerships with other players, accessing new markets,
etc. Local energy ownership models allow the existence of various forms of local
energy communities where benefits are shared locally bringing communities closer
to the concept of energy democracy. Local energy communities can be
partnerships, cooperatives, non-profit organisations or entities owned by the local
authorities. The organisational structures of community energy initiatives include
different legal forms such as partnerships (including public‐private partnerships
(PPPs) with local authorities), cooperatives, community trusts and foundations,
limited liability companies, non-profit customer-owned enterprises, housing
associations and municipal ownership. Energy cooperatives have several key socio-
economic impacts, some of which are also shared with some of the other types of
local energy ownership models. Community energy is sufficient distinct from
traditional energy market participants and can thus warrant different treatment in
accessing the grid. Local energy communities can offer a variety of benefits to the
local community – from strengthened ownership and democratic participation in
the energy market, to economic and environmental benefits for the local
community and wider national or EU level. European Union legislation has an
important role for setting a level-playing field and minimum requirements for the
promotion of local energy communities and leading by example. EU legislation and
policy should not limit the possibilities for Member States to continue supporting
RE with market based and market independent financial support measures. It is
important to recognise the role of local energy communities in the energy
transition at the EU level through the definitions and provisions in the clean energy
package proposals. National policy-makers might assess the potential contribution
of such communities in meeting the national energy policy goals and define
concrete objectives for the community energy (Angel, 2016; Assimakis and Kitsilis,
2017; Balkan Green Energy News, 2017).
51
Keywords: energy cooperatives, local energy communities, public‐private partnerships,

municipalisation, devolution

References
Angel J., (2016), Towards Energy Democracy: Discussions and outcomes ‐ workshop, Amsterdam, 11-
12 February, Workshop Report May 2016
Assimakis D. and Kitsilis M., (2017), Shifting to auctions for renewable energy capacity in Greece,
Norton Rose Fulbright, April 2017
Balkan Green Energy News, (2017), Greek energy communities draft bill awaits ratification, 15
December 2017
52
SUSTAINABLE SOLUTIONS FOR PUBLIC TERRESTRIAL TRANSPORTATION
Iurie Bosneaga1, Elena Agarwal2

1
Institute of Applied Physics, Chisinau, Republic of Moldova
2
University Dimitrie Cantemir, Chisinau, Republic of Moldova
Corresponding author: iubosneaga@gmail.com
We consider mainly common (public) transport - because of its clear sustainable

perspectives, especially for urban transportation. (Nevertheless, the similar solutions -
for the off-track and railway transport - could be applied).
One of the important advantages of the modern electric vehicles, especially for
urban traffic, is the increased energy efficiency - especially, due to the use of the
regenerative (recuperative) brakes. The “classical” trolleybus (which uses traction
current delivered by overhead wires) ensures, in fact, totally “green” transportation,
but it has a limited range and even cannot maneuver around obstacles and broken
overhead transmission wires. Installation of expensive and heavy accumulators (usually
combined with supercapacitors) mitigates this shortage, but the range still remains
limited and insufficient for many cases.
A hybrid vehicle offers the best solution: additional installation of the internal
combustion engine (ICE), which ensures independent generation of electricity - when it
is necessary (inclusively, for reverse electricity supply to the power grid). Such a hybrid
trolleybus possesses the functions of the electro-bus, plus - the important function of
the maneuverable, remotely controlled power generator (being a valuable SMART
GRID component).
In fact, hybrid electrical vehicles have a long history of combining internal
combustion engine and electrical transmission - as it is in a diesel-electric powertrain.
Our improvement consists of the use of liquid natural gas (LNG) as ecologically friendly
fuel in the LNG-based ICE, combined with the complex use of the LNG’ cryogenic
potential. Cryogenic potential of the LNG is used for the electric motor cooling (with
the eventual perspective of superconductive effects utilization), for air-conditioning
and carbon dioxide emissions prevention (CO2 capturing). Application of the
semiconductor thermocouple batteries as an “active wall” in low-temperature heat
exchangers is also considered (for the rational use of the cryogenic potential).
A particular case of the hybrid trolleybus (electro-bus) for operation in
conditions of extremely hot weather is considered. In such conditions the special
liquid nitrogen tank is necessary for ensuring air-conditioning and safe functioning
of the vehicle at high temperatures, inclusively - for cooling photovoltaic (PV) solar
batteries. (These PV batteries - installed on the roof and partly on the lateral sides
of the vehicle - contribute to air-conditioning charge reduction, inclusively due to
53
their additional electric power generation). Also we investigate the use of

radionuclides (coming from the spent nuclear fuel reprocessing) - for pre-burning
dissociation of methane (Boşneaga Iu., 2015).
The program is - to implement gradually the above-described conception of
electric hybrid transport, beginning with ICE on compressed natural gas (CNG),
stored in safe reduced-pressure vessels (with “solar” activated carbon - as
absorbent), and finishing with totally “green”, sustainable LNG vehicle.
Keywords: sustainable public transport, LNG’ cryogenic potential, radionuclides for

pre‐burning dissociation of methane
References
Boşneaga Iu. (2015), Huge non‐spent potential of the “spent fuel”‐ the ways of its utilization.
International Conference on Management of Spent Fuel from Nuclear Power Reactors - An
Integrated Approach to the Back-End of the Fuel Cycle, Vienna, Austria, 15-19 June 2015
54
STUDY ABOUT SMARTGRID IN ENERGY
Carmen Maria Moraru1, Iulia Stefan1, Florentina Magda Enescu2

1
2
Department of Environmental Engineering and Sciences Applied Engineering ‐ University of Pitesti,
Street Targu din Vale, no. 1, Pitesti, Romania
Corresponding author: carmen.moraru@icsi.ro
In this article will be discuss the future trends in the energy sector, specifically
will address topics such as blockchain and Smart Grid. What is blockchain and what
does smartgrid mean in energy, how much theory is it and how much do these
concepts apply in Romania and in the world? Summarily, blockchain is a technology
that wants to replace the old centralized energy model to trade energy on a new
decentralized, modern platform where transactions can be made more easily
between the producer and the consumer. Smartgrid is a well-known concept,
already implemented in many countries, including Romania. Smart Grid is
considered an "Energy Internet" because it provides consumers with real-time
energy information, enabling them to make smart choices. Intelligent network
technology is a set of network control and management systems, sensors and
communication and information tools that incorporate both traditional and state-
of-the-art features. It combines software and hardware elements to significantly
improve the way how the current electrical system is operated, while offering the
possibility of further upgrading.
Keywords: Blockchain, Smart Grid, Energ
References
I. Dumitrache, (2012), Cyber Physical Systems ‐ New Challenges for Science and Technology, in First
International, Workshop on Cyber Physical Systems
I. Dumitrache, N. Constantin, and O. Stoica, (2013), Some Challenges for the Cyber ‐ Physical Power
System, București
M. Amin and B. Wollenberg, (2008), Toward a Smart Grid, IEEE Power and Energy Magazine, 3:34-38
55
NMC CHEAP AND PROSPECTIVE CATHODE MATERIAL FOR EV&HEV
Krum Banov1,2, IlyaPopov1, Dimka Ivanova2, Ludmi Fachikov2, Branimir Banov1,3

1
Institute of Electrochemistry and Energy Systems, IEES, “Acad. G. Bonchev” str. BL10, 1113 Sofia
2
University of Chemical Technology and Metallurgy – UCTM, bul. “Kl. Ohridski” N:8, 1756 Sofia
3
European Polytechnical University, EPU, “Ciril and Methodius” str. N:23, 2300 Pernik
Corresponding author: k.banov@iees.bas.bg
Lithium batteries occupy the largest market place of batteries to conventional

electrochemical power sources thanks to* its exceptional qualities, especially in
cases where the specific energy performance play a role - namely, portable
electronic devices, aerospace, special and military applications recently EV electric
and hybrid vehicles HEV & PHEV. Their role in the direction of the storage of
renewable energy, however, is becoming more and more significant.
The main objectives in the research of lithium ion batteries (LIB) are the
increase of the energy density and the cost reduction. The material characteristics
related to energy and power, cycle life and safety play a big role. For this purpose
manganese spinel, pure and doped, as NMC cathode materials are promising
materials with higher energy densities, safety and cycle life.
The field of electric mobility reveals great application opportunities for lithium
ion batteries. However, substantial improvements are required with regard to the
energy density, the cycle life and safety. Due to the high operating potential (4.5V),
LMO and NMC represents a promising next generation cathode material for
advanced lithium ion batteries (LIB). On the other hand new silicon based anode
material appears as promising anode material which in combination with high
energy density cathode materials will be the big success for the new generation LIB.
The main topic is developing new ways of cheap environmentally friendly
synthesis procedure for obtaining promising electrode materials for new
generation LIB based on NMC with high manganese content higher than 50-60%. In
the present work is investigated new class of high voltage materials with large
application in EV and advanced energy storage systems for home or industrial
applications. The electrochemical characteristics of two high voltage active
electrode materials, LiNixMnyCozO2 NMC 1:1:3 and NMC 1:1:4 are investigated.
Samples of NMC active electrode material are prepared by solid-state reaction and
physicochemical and electrochemically characterized. A capacity of 165-182 mAh g-
1
is obtained at the 50 cycle depending from the preparation way.
Keywords: NMC cathode, high voltage cathode material, nickel, manganese, cobalt
oxides.
56
HYDROGEN MOBILITY DEMONSTRATOR – HY-DEMO
Mihail Culcer1, Mircea Raceanu1, Mariana Iliescu1, Adrian Enache1,

Nicu Bizon2, Mihai Varlam1
1
National Research and Development Institutefor Cryogenics and Isotopic Separation – ICSI Rm.
Valcea, Uzinei Street, no. 4, PO Box 7 Raureni, 240050, Valcea Romania;
2
University of Pitesti, Street Targu din Vale, no. 1, Zip Code 110040 Pitesti, Arges County, Romania
Corresponding author: mihai.culcer@icsi.ro
Starting from the decisive challenge facing humankind - to protect our planet and
its inhabitants from catastrophic climate change, and considering that in 2015, the
transport sector contributed 21% of total EU-28 greenhouse gas emissions, the
European Commission has identified fuel cell electric vehicles (FCEVs) among the
technologies needed for Europe to meet its ambitious energy security objectives and to
deliver a minimum 60% reduction of greenhouse gas emissions from transport by 2050.
On this line are included the researches carried out within the National Center for
Hydrogen & Fuel Cell of the National Research and Development Institute for
Cryogenics and Isotopic Technologies Ramnicu Valcea on the direction of Hydrogen
mobility, by proposing a new hydrogen-based hybrid powertrain for automotive
applications.
Among alternative fuels, hydrogen seems to be the most promising, being also the
most challenging energy vector, compared to liquid eco-friendly fuels such as ethanol or
biodiesel. So, there was foreseen a change in the powertrain system structure of the
usual electric vehicle, by including a hybrid multiple power source with a major
component based on Hydrogen fuel cell stack (FCS) and an additional supply with a
Lithium ion battery.
This new hydrogen hybrid electric powertrain was developed and implemented on
a low-power electric vehicle, a Hydrogen Mobility Demonstrator (HyDeMo) being built
and characterized on the basis of our team expertise.
The diagram of this powertrain architecture having two energy flows, is shown in
Figure 1.
The objectives of this hybrid configuration are:
- minimizing hydrogen consumption;
- protecting the fuel cell from the fast load transients;
- storing energy in a rechargeable battery pack;
- maintaining the set voltage value on DC Bus;
- minimizing costs.
These objectives are achieved by implementing an efficient energy management
strategy based on efficiency map. HyDeMo's optimized control system aims to provide
in any moment the energy to comply with load demand by controlling the energy flow
between DC Bus and the energy sources, FCS and Battery, by means of PI control loops.
Following a cost / performance analysis, an optimization method based on the GES
(Global Extremum Seeking) control of the DC-DC boost converter and on load tracking
57
by fuel (Hydrogen) flow control is the most advantageous over the entire power range
in terms of power efficiency and fuel efficiency (measured by fuel economy) (Bizon,
2017; Bizon, 2018).
Figure 1. Block diagram for HyDeMo
The Hydrogen Mobility Demonstrator, HyDeMo, presented in Fig. 2, validates in

laboratory environment a hybrid electric propulsion technology with hydrogen fuel
cells, which has to support the increase of public acceptance for this technology and to
pave the way for the introduction of such a concept of mobility on the domestic market.
Figure 2. The HyDemo Demonstrator
Acknowledgement: This work was supported by a grant of the Research and

Innovation Ministry, Program PN III, within contract PED 53/2017.
References
1. Nicu Bizon, (2017), Energy optimization of the Fuel Cell System using the Global Extremum Seeking
algorithm, Applied Energy. 206:458-474
2. Nicu Bizon, Gabriel Iana, Erol Kurt, Phatiphat Thounthong, Mihai Oproescu, Mihai Culcer, Mariana
Iliescu., (2018), Air Flow Real‐Time Optimization Strategy for Fuel Cell Hybrid Power Sources
with Fuel Flow Based On Load‐Following, Fuel Cell. 2018 (under review)
58
HYDROGEN PRODUCTION BASED ON GLYCEROL STEAM REFORMING PROCESS

PERFORMED IN A MEMBRANE REACTOR
Mirela Draghia, Madalina Ivanovici, Gheorghe Pasca, Alin Fuciu
SC I.S.TECH SRL, Timisoara, Romania

Corresponding author: mirela.draghia@istech‐ro.com
Hydrogen has the potential to be a significant fuel for the future, with a wide
range of uses, capable to meet the high energy demand. In present most of the
hydrogen produced in the industry comes from the reforming of natural gas.
In the last years, the interest for the green hydrogen production has grown in
various industrial companies and academic organizations that are exploring the
possibilities that hydrogen can be an option for a low-carbon future. Glycerol
obtained as waste in biodiesel production process is a cheap raw material that can
be a viable alternative for hydrogen production.
This paper aims to present a technology for hydrogen production from
glycerol, using a membrane steam reforming reactor that allow concomitant
conversion of glycerol into hydrogen and separation of hydrogen from the mixture
of reaction products resulted in the glycerol steam reforming process. The
configuration is a combination of a membrane steam reforming reactor and two
microreactors used for the oxidation of hydrogen, carbon monoxide and methane
in order to reduce the emissions of toxic gases into the atmosphere and to recover
the generated heat by the oxidation reactions.
The proposed configuration for the technological process performing has
developed in such way to reduce the conventional energy consumption during the
glycerol conversion process and to minimize greenhouse gas emissions in the
atmosphere.
Keywords: hydrogen, glycerol, steam reforming.
59
HYDROGEN-RICH GAS PRODUCTION BY BIOMASS CONVERSION IN A FREE-FALL

REACTOR PROMOTED BY Fe/CaO CATALYST
Adrian Armeanu, Elena David, Violeta Niculescu, Claudia Sandru

1
Valcea, Uzinei Street, no. 4, PO Box 7 Raureni, 240050, Valcea Romania
Corresponding author: Adrian.armeanu@icsi.ro
Natural resources are rapidly exhausted, resulting in the release of huge

amounts of pollutants (Acharya et al., 2010; Muangrat et al., 2010). On the other
point of view, the hydrogen is proposed as a potential energy vector owing to its
clean high-energy yield (Zhao et al., 2010). However, the predominant method of
producing hydrogen from natural gas or other fossil fuel sources requires high
energy consumption and results in the emission of a significant amount of green
house gases into the atmosphere (Bru et al., 2007; Mustafa, 2008).
Biomass energy, a type of renewable energy,is an abundant and environmentally
friendly resource and thus, its use as an energy source through thermochemical
conversion technology is expected to play an important role in hydrogen production.
Consequently, this paper presents the biomass gasification for hydrogen production
and this was performed in a continuous-feeding free-fall reactor with the use of
Fe/CaO catalysts. The relationship between catalyst properties and biomass
gasification process efficiencies was studied. The results showed that only CaO was
involved in the enhancement of char gasification, resulting in an increased hydrogen
amount into gas production.
However, CaO was also easily deactivated by biomass tar also resulted by
process. The results indicated that when CaO was impregnated with Fe,Ca2Fe2O5
formed on the surface of the support and Ca2Fe2O5 decomposed polyaromatic tar
but was not effective in char gasification process. The synergistic effects between
Fe and CaO that effectively enhanced biomass gasification mainly involved
combustion and pyrolysis, and the biomass gasification products, i.e., char and tar,
were further gasified, indicating that tailor-made Fe/CaO catalysts prevented the
process of the CaO deactivation by tar and thus promoting biomass gasification
process and hydrogen-rich gas production.
Keywords: biomass, Fe/CaO catalyst, char, tar, gasification, hydrogen‐rich gas.
60
Acknowledgments: The financial Support of this research was provided by the

Ministry of Research and Innovation from Romania, National Plan of Research &
Development in Energy and Environmental field. Project no. PN 18 12 03 01/2018.
References
Acharya B., Dutta A., Basu P., (2010), An investigation into steam gasification of biomass for
hydrogen enriched gas production in presence of CaO, Int J Hydrogen Energy, 35:1582-1589
Bru K., Blin J., Julbe A., Volle G., (2007), Pyrolysis of metal impregnated biomass: an innovative
catalytic way to produce gas fuel, J Anal Appl Pyrolysis, 78:291-300
Muangrat R., Onwudili J.A., Williams P.T., (2010), Influence of alkali catalysts on the production of
hydrogen‐rich gas from the hydrothermal gasification of food processing waste, Appl Catal B
Environ, 100:440-449
Mustafa B., (2008), Potential importance of hydrogen as a future solution to environmental and
transportation problems, Int J Hydrogen Energy,33:4013-4029
Zhao B., Zhang X., Chen L., Qu R., Meng G., Yi X., et al., (2010), Steam reforming of toluene as model
compound of biomass pyrolysis tar for hydrogen, Biomass Bioenerg, 34:140-144
61
HYDRAULIC SIMULATION, CONCERNING OPTIMIZATION OF WATER FLOW

CAPTURE FOR MICRO-HYDRO POWER PLANTS IN ORDER TO INCREASE THE
ENERGY PRODUCTION
Radu Pop1,2, Vasile Rednic1, Oana Raita1, Emil Bruj1, Daniel Banyai2, Liviu Vaida2,
Adrian Bot1
1
Cluj‐Napoca, Donat Street, no. 67‐103, Cluj‐Napoca, Romania
2
Technical University of Cluj‐Napoca, Faculty of Mechanical Engineering, Cluj‐Napoca, Romania
Corresponding author: radu.pop@itim‐cj.ro
The water intake from the micro-hydro power plant captures water in two
ways, namely, in summer through a surface grill and in winter by “winter intake”,
which is immersed in water below freezing level. The water flow captured for
energy production is influenced by the river and fish ladder flow. From technically
reasons, the fish ladder flow is bigger than is necessary (in our case more than
0,202 m3/s [Regulament de Exploatare pentru MHC Racatau R1 – 2014]), because
should ensure a minimum servitude flow for all the river flows. The paper presents
a simulation [Technical project, power plant MHC Valea Racatau] concerning
optimization of water flow capture for micro-hydro power plants in order to
increase the energy production. This optimization should be made by keeping a
constant and a minimum flow though the fish ladder and use the surplus to
produce more electrical energy. The increase on the efficiency as a function of the
river flow will be presented.
Keywords: water intake, energy production, servitude flow, efficiency
Acknowledgments: Financial support from the MCI, Core Programme, Project PN

18 03 01 02 is gratefully acknowledged.
References
4C Proct Consulting SRL “Regulament de Exploatare pentru MHC Racatau R1 – 2014” (private
document)
4C Proct Consulting SRL “Technical project, power plant MHC Valea Racatau” (private document).
62
STIRLING ENGINE BURNING CHAMBER DESIGN AND

SIMULATION IN ANSYS FLUENT
Robert Gutt, Vasile Rednic, Emil Bruj, Adrian Bot
Cluj‐Napoca, Donat Street, no. 67‐103, Cluj‐Napoca, Romania
Corresponding author: robert.gutt@itim‐cj.ro
Due to the rising interest in the optimisation of the Stirling engine, this work
considers a simulated design of a Stirling engine burning chamber and discusses the
thermal parameters, such as the heater temperature, the energy loss of the
burning cavity as well as the ejected stream heat. The numerical results are
performed in ANSYS Fluent, in order to obtain the temperature distribution, the
velocity profiles and the heat flux. The initial setup is based on an existing burning
chamber for a Stirling engine, such that the numerical results are compared to
experimental measurements. Based on this model, different structures for the
burning chamber are considered in order to increase the heat input in the Stirling
engine, such that a higher efficiency can be obtained by the engine.
Keywords: Stirling Engine, Thermal simulation, ANSYS Fluent
Acknowledgments: The authors acknowledge the financial support from the MCI,
Core Programme, Project PN 18 03 01.
63
HEAT RECOVERY SYSTEM FOR STIRLING ENGINE FLUE GASES
Emil Bruj, Vasile Rednic, Robert Gutt, Radu Pop, Sergiu Pogăcian, Adrian Bot
National Institute for Research and Development of Isotopic and Molecular Technologies, 67‐103
Donat, 400293 Cluj‐Napoca, Romania
Corresponding author: emil.bruj@itim‐cj.ro
In the combustion processes an important part of the thermal energy is lost

through the exhaust gases. In order to recuperate the lost energy, heat exchangers
are used to reduce the temperature of exhausted gases by recovering part of its
thermal energy. In this study we propose a design of heat exchanger for Stirling
engine exhaust pipe. The design is correlated with the technical characteristics of
Stirling engine burning chamber and its efficiency dependence on its parameters is
simulated using ANSYS Fluent software. Based on the simulations, the experimental
model is constructed and tests are performed.
Keywords: Stirling engine, Heat exchanger, Thermal simulation, ANSYS Fluent
Acknowledgments: Financial support from the MCI, Core Programme, Project PN 18

03 01 02 is gratefully acknowledged.
64
SMALL HIGH TEMPERATURE SUPERCONDUCTING COIL AS ENERGY

STORAGE UNIT FOR SPACECRAFT POWER SYSTEMS
Mariana Iliescu1 , Mihail Culcer1, Florian Stefanescu2, Marian Curuia1, Elena

Carcadea1, Nicu Bizon3, Mihai Varlam1
1
Valcea, Code 240050 ‐ Rm. Valcea, Uzinei Street no. 4, P.O. Box Râureni 7, Valcea, Romania;
2
PFA Stefanescu Florian, Craiova, Romania; 3University of Pitesti, Street Targu din Vale, no. 1, Zip
Code 110040 Pitesti, Arges County, Romania
Corresponding author: Mariana Iliescu@icsi.ro
Storing the necessary amount of energy remains a great challenge for space
power technologies. Depending on the energy and power demand, different
technologies were considered, including several types of primary and secondary
batteries and fly-wheels.
In SMES (Superconducting Magnetic Energy Storage) technology, the energy is
stored in the magnetic field generated by a DC current flowing through a
superconducting coil, cryogenically cooled to a temperature below its superconducting
critical temperature, at which its resistivity becomes “zero”. Ideally, once the
superconducting coil is charged, the current will not decay and the magnetic energy
can be stored indefinitely. Practically, the unavoidable external heat input has to be
compensated, otherwise the superconducting coil temperature rise could determine
quenching. Also local thermal transient heating could produce subsequent quenching.
On the way to achieve a “proof- of- concept” of a magnetic energy storage system
based on HTS (High Temperature Superconductor) coil, and to validate this technology
for space applications at ICSI Ramnicu Valcea, the activity started by evaluating the
possibility of using an existent Standard HTS DC Coil, made in Japan by Sumitomo
Electric Industries Ltd., presented in fig. 1.
Figure 1. The Sumitomo Electric Industries Ltd. Standard HTS DC Coil
This coil is made of DI-BSCCO (Dynamically- Innovative Bismuth Strontium

Calcium Copper Oxide) multi- filamentary superconducting wires, manufactured by
controlled overpressure sintering method by the same Sumitomo Electric.
65
The most important parameter of a coil used as SMES is its inductance, which
depends exclusively on how it is built: coil geometry (dimensions), number of turns,
core magnetic material.
Unfortunately, the Sumitomo Standard HTS DC Coil was not accompanied by
inductance data, so the paper deals with both theoretical and experimental work
carried out in order to characterize the aforementioned HTS coil.
Using a simplified geometry of the coil and a finite element approach, through
FEMM 3.4.2 (Finite Element Method Magnetics) software (Meeker, 2015), together
with data on the value of the central magnetic field in liquid nitrogen (77 K) at
atmospheric pressure provided by the CERT2015-001 Test Certificate of the coil, a
theoretical value of 18 mH was obtained.
In order to validate this value, the voltmeter-ammeter method was chosen to
measure the coil impedance and resistance, followed by the inductance calculation.
The value obtained from the experimental work (27 mH) being quite different from
the theoretical one, future activities will be deployed in order to increase the
model accuracy by improving the coil geometry and finding shield and core
material characteristics closer to real ones.
Keywords: magnetic energy storage, high temperature superconductor, inductance.
Acknowledgment: This work was supported by a grant of the Romanian Space

Agency, within contract STAR 167/2017.
REFERENCES
Mathew Aneke, Meihong Wang, (2016), Energy storage technologies and real life applications – A
state of the art review, Applied Energy, 179:pp. 350-377
Chr. Janot, (1986), Les amorphes métalliques et leurs propriétés magnétiques, Revue de Physique
Appliquee, 21:635-647
S. L. Lalitha, (2017), Low resistance splices for HTS devices and applications, Cryogenics, 86:7-16
David Meeker, (2015), Finite Element Method Magnetics – Version 4.2 User’s Manual, 161 p.
Sumitomo Electric Industries, (2015), Ltd., Specifications SAP2-15-015 and CERT2015-001
66
ELECTROCHEMICAL HYDROGEN SEPARATION
Ioan Iordache, Dorin Schitea, Rasoi Gabriel
Valcea, Code 240050 ‐ Rm. Valcea, Uzinei Street no. 4, P.O. Box Râureni 7, Valcea, Romania
Corresponding author: ioan.iordache@icsi.ro
This work presents the first results of the project entitled “Hydrogen,
alternative energy vector; electrochemical separation and storage of hydrogen, a
new and emerging technology”.
The project approaches the electrochemical separation and storage of the
hydrogen and comes with solutions to integrate these new and emerging
techniques. In this context there are capitalized the intermittent sources of energy
by means of innovative processes that have as their starting point Romania's
energy specificity and foresees the increase of the renewable and nuclear
generation capacities. There are identified the solutions for the accommodation of
three elements in the national energy system: renewable energy, nuclear energy
and energy storage.
The main idea of the project has appeared in the context of the hydrogen
technology development and the transition to a new renewable dominated energy
market.
Until now, has been designed a functional hydrogen electrochemical
separation system up to 1L / minute with the storage possibility of the products.
The electrochemical mono-cellular hydrogen separation system has the
following technical characteristics:
- ensure the overall electrochemical separation by means of ion-exchange
membrane electrochemical cell of the hydrogen from the gas mixtures at an
optimum flow rate of about 0.5 l/ minute as the process gas;
- the maximum system pressure is 13.5 bar;
- the maximum operating temperature 50 oC.
Electrochemical Monoclonal Hydrogen Separation System contains:
- water circuit for membrane hydration;
- hydrogen blower;
- power supply;
- electrochemical cell assembly;
- dryer;
- ventilation system;
- hydrogen sensor.
67
The gas flow system has the following routes (pipelines): nitrogen line, inlet gas
mixture line (process gas), product gas line (hydrogen), residual output gas line, and
safety emergency line.
Figure 1. 3D Overview for the Electrochemical Hydrogen Separation Equipment.
The equipment can be used to process a wide range of gases, from pure
hydrogen to highly diluted hydrogen in a mixture. Hydrogen gas is fed to the anode
of the electrochemical cell where hydrogen is electrochemically pumped to its
cathodic side and can be compressed up to 13.5 bar. The system allows the user to
control the flow of process gas input. The system has external connections for
process gas inlet, nitrogen inlet, deionized water (DI), process gas outlet, product
outlet, ventilation and power (230 VAC, 50 Hz). A 3D overview of the system is
presented in Fig. 1.
Keywords: Electrochemical hydrogen separation (EHS), hydrogen, hydrogen

storage.
Acknowledgments: This work was supported by the grant of Ministry of Research

and Innovation (Romania), Contract no. 1 N /16.03.2018, Project PN 18120103.
68
DISPOSAL AND ENERGY RECOVERY FROM SEWAGE SLUDGE
Marius Constantinescu1,2, Felicia Bucura1, Roxana Ionete1; Anca Zaharioiu1,

Corina Ciucure1,2, Oancea Simona2
1
2
Lucian Blaga University of Sibiu, 10, Victoriei Bd., Sibiu, 550024, România
Corresponding author: marius.constantinescu@icsi.ro
The evolution of modern society through everything that means urbanization has
inevitably led to an exponential increase in waste levels. Legislative changes in the
recent years at European level have compelled Romania to rethink the waste disposal
process, including for sewage sludge from the water treatment plants.
Until now, the solution for sewage sludge reuse was in agriculture as fertilizer, for
the restoration of degraded land and production of biogas following fermentation
process. Another possible solution in the elimination of waste sludge is their
combustion, thus capitalizing on its huge energy potential. This alternative has been
tested on sewage sludge (SS) alone, SS in combination with different biomass matrices,
and SS with solid fossil fuels (Sopper et al., 1993; Williams, 2005; Zsirai, 2011; Calvo,
2013; Kirchmann, 2017). In-depth research on sewage sludge has still to be done
before the most appropriate disposal mode to be established.
In this work an advanced characterisation of sewage sludge is done before a
disposal solution to be proposed, considering that the main drawback for SS potential
as fuel is its extremely high humidity, Wt. ~70%. The study has successfully revealed
the possibility of drying the SS in a solar device, thus eliminating much of the humidity
without a very high energy consumption. For thus, 7 samples of SS were taken in
different sampling campaigns from a water treatment plant.
The experiment was developed in a greenhouse made from plastic, equipped with
wicking sewage sludge filtering equipment guided through Wi-Fi, the fan system so
arranged as to be able to effectively remove water. A mobile weather station installed
on the SS drying device registered the meteorological data (ex. temperature,
humidity). Additional analytical investigation of SS, before and after drying, were
performed. The level of heavy metals was assessed by atomic absorption spectroscopy
(AAS), the content of dioxin and furans by gas chromatography coupled with mass
spectrometry (GC-MS), and PAHs by high performance liquid chromatography (HPLC).
Since we intended to use SS as an alternative fuel a series of tests on the elementary
composition, as well as calorimetric tests were carried out. The elementary analysis,
C/H/S/N/O content (Table 1), made with EA Flash2000 (Thermo Scientific, UK), gave us
69
valuable information on the level of potentially energetic elements (C/H/O), but also
about potentially polluted elements, respectively C → COx, N → NOx, and S → SOx.
Tabel 1. Assessments of sewage sludge

Sewage Sludge
Proximate analysis
I II III IV V VI VII STDEV Average RSD%
V-% 52.38 50.32 57.77 55.53 43.34 55.03 45.95 5.28 51.47 0.10
A-% 43.07 44.51 45.94 40.72 48.21 41.72 46.87 2.75 44.43 0.06
Wt. - % 75.00 77.90 74.75 78.84 67.31 78.04 72.50 4.04 74.91 0.05
Ultimate analysis
C-% 27.34 26.44 25.66 29.03 23.70 27.93 24.65 1.87 26.39 0.07
N-% 4.48 4.62 4.44 4.52 3.83 4.42 4.34 0.26 4.38 0.06
H-% 4.26 4.26 4.13 4.42 3.78 4.32 3.91 0.23 4.15 0.06
S-% 0.82 0.65 0.59 0.58 0.75 0.59 0.65 0.09 0.66 0.14
O-% 20.03 19.52 19.24 20.73 6.45 20.66 19.59 5.14 18.03 0.28
Qsup - 2951 2915 2671 3113 2611 2903 2695 181.846 2837.000 0.064
MJ/m3
Qinf - MJ/m3 2718 2698 2297 2695 2390 2495 2479 167.312 2538.857 0.066
An IKA5000 (IKA, Germany) calorimeter equipped with an oxygen bomb, was

used to evaluate the calorific power of the sewage sludge in the analysis state. In
the study conducted over a 12-month period of the same year, several samples of
depletion sludge were taken gradually. A series of gravimetric ash-containing,
volatile matter analyses overlapped the TGA/DSC type. Considering the more
efficient way of combustion treatment of the sludge, a pellet prototype, made
exclusively from sludge was made. The emission factor (Fig. 1), the required
parameter to assess the emission level in the case of a fuel combustion, was
evaluated according to the lower calorific power.
Figure 1. Evolution of emission factor
Validation of SS as alternative fuel was done by its combustion in a cast iron

burner and by monitoring the released emissions.
70
Keywords: sewage sludge, alternative fuel, pellet, energy
References
Sopper, W.E. (1993), Municipal sludge use land reclamation - 1ª Ed. Pennsylvania: Ed. Lewis
Publishers, 163p.:il.
Kirchmann H., Börjesson G., Kätterer T., Cohen Y., (2017), From agricultural use of sewage sludge to
nutrient extraction: A soil science outlook. Ambio.;46(2):143-154.
J.H. Williams, G. Guidi, P.L’Hermite, (2005), Long‐term effects of sewage sludge and farm slurries
applications, Elsevier Applied Science Publishers, London, New York
I. Zsirai, (2011), Sewage sludge as renewable energy, Journal of Residuals Science & Technology, 8(4)
L.F. Calvo, A.I. García, M. Otero, (2013), An Experimental Investigation of Sewage Sludge
Gasification in a Fluidized Bed Reactor, The Scientific World Journal, 1-8
71
INTEGRATED SOLAR POWER PLANT SYSTEM BASED ON DISH STIRLING

TECHNOLOGY FOR SUSTAINABLE ENERGY GENERATION
Gabriel Rasoi, Mihai Culcer, Mariana Iliescu, Maria Simona Raboaca, Dan Mocanu,
Adrian Armeanu
Corresponding author: gabi.rasoi@icsi.ro
Concentrating solar power plant CSP DISH STIRLING represents an unique

energetic and ecological device, which effectively uses renewable sources of energy.
This power plant is built on modern technologies, which are able to use
concentrated solar radiation.
The thermo-electrical system (CSP Dish Stirling) are designed to produce electricity
and heat, from renewable sources with low levels of pollution such as solar energy,
which was developed and implemented within of a research project.
Concentrating Power Plants plants based on Stirling technology is an innovative
concept for combined production of electricity and heat, which are environmental
equipment in operation using only renewable energy.
Parabolic concentrator with mirror surface reflects solar radiation to the focal
point where is the PCU - power conversion unit.
This system provides an annual period of about five months during the summer,
heat and electricity from renewable energy, such as solar, and has the ability to store
electrical energy over a long period, as chemical energy using the hydrogen that is
obtained through water electrolysis, and it will be used to generate energy when the
weather conditions are not favourable for solar energy use.
The system features fully automatic controlling and positioning of the
concentrator in two axis and meets the requirements in order to be built and engaged
in harsh conditions.
Individual concentrating solar power plants can be connected and used as
standalone systems, or can be integrated into off-grid solution, with output ranging
from tens of kw to tens of MW.
Dish Stirling system can be installed on terrain with high slope tolerance.
The electrical energy can be used for immediate consumption, can be
accumulated through battery system, or can be stored as hydrogen, which can be used
at any time in the systems of fuel cells to produce electricity.
Keywords: solar power plant, sustainable energy, CSP dish stirling, renewable sources,
parabolic concentrator, heat and electricity
72
DEVELOPMENT OF A HYDROGEN FILLING STATION FOR FUEL CELL ELECTRIC

VEHICLE AT ICSI RM. VALCEA
Laurentiu Patularu, Mihai Varlam, Elena Carcadea, Eusebiu Ionete, Dan Mocanu,
Adrian Armeanu
Corresponding author: laurentiu.patularu@icsi.ro
Hydrogen fuel-powered Fuel Cell electric vehicles offer great potential to eliminate
high emissions associated with the combustion of gasoline and diesel fuels. In order to
propel a vehicle, hydrogen is converted to electric power with the help of fuel cell
powertrains. Hydrogen fuel cell vehicles are typically capable of long trips (over 500
kilometers or 300 miles) and a short refueling time that is comparable to conventional
vehicles. Today hydrogen storage technology for automotive field is based on 350bar
and 700 bar pressures delivered in composite Type 3 or Type 4 tanks.
An intermediary step in the development of a facility for ultrapure hydrogen
production, intermediary storage, compression, dispensing and final storage stage at
350 bar unit for Fuel Cell Electric Vehicle (FCEV) is presented. The architecture of this
installation is based on a “low flow” principle, based on a 160 bar outlet H2 pressure,
gas generator PEM electrolyzer type, metallic pressure cylinders battery as 160 bar
buffer tank, an extremely reliable double diaphragms compressor who boost the
pressure from 160 up to 350 bar and 700 bar allowable pressure, and Type 4
composite vessels as FCEV hydrogen reservoir. Low flow hydrogen filling principle is
based on the maximum discharge flow of a compressor that pumps hydrogen into the
FCEV tank. In this way we eliminate the chilling stage of hydrogen from the “high flow”
principle, the main drawback of this scenario is the increase of filling time.
The working principle of this installation is based on the high pressure of PEM
electrolyzer Hogen HP40, who is able to supply the buffer tank up to 160barg. With
the range of 28-200 barg inlet pressure, the compressor will pump up the pressure
73
to the desired value (up to 350barg) directly in the Fuel cell tank. The tank filling
time is based on the hydrogen pressure at the inlet of compressor.
The Fuel cell tank has its own protection against pressure and also NTC
temperature sensor integrated into the pressure valve body. Hydrogen safety
aspects for each stage from hydrogen production to final storage are also
presented.
74
THERMAL BEHAVIOR INVESTIGATION OF A Li-ION POUCH CELL
Alexandru Ciocan, Alexandru Rizoiu, Alexandru Badita
Corresponding author: alexandru.ciocan@icsi.ro
Lithium-ion batteries are widely used in many portable applications and are the
most promising energy systems for future mobility and stationary applications.
Worldwide extensive research efforts focus on the development of high performance,
low cost and more sustainable materials for advanced lithium ion batteries. In the last
years lithium – ion batteries have seen a major introduction to small scale hybrid and
fully electric vehicles. As larger battery cells have become cheaper, larger li-ion based
batteries are currently seen to be introduced to large scale electric and hybrid electric
vehicles. As larger vehicles take batteries into use, larger battery packs are needed and
more intense cycles are applied.
This paper is focused in reporting a modelling methodology to predict the effects
of operating conditions on the thermal behavior of a lithium – ion battery module. The
potential and the current density distribution on the electrodes of a Li-ion battery cell
are predicted as a function of discharge time based on the principle of charge
conservation. The modelling software used for analysis was chosen to be Ansys/Fluent.
This soft includes in its tools two mathematical models in the field of batteries and
these models are function of their mathematical complexity divided in four sub-
models. Therefore in this paper the model used in battery cell modelling is a pseudo –
two – dimensional model, which is the most complex model delivered by Ansys, –
based on four electrochemical kinetics transport equations which take in to account
the Lithium ions concentration in solid state at electrodes, in liquid state in electrolyte
and the electric potential in liquid and solid states.
Different battery chemistry could be analyzed in Ansys/Fluent from: lithium-iron-
phosphate (LFP), to lithium-manganese-oxide (LMO), to nickel-manganese-cobalt
(NMC), to lithium-cobalt-oxide and others. In the following figures from 1 to 6 are
presented the cathode/anode profile from potential perspective, the discharge
evolution for four scenarios of discharge rate and as well the static temperature
evolution for the same working scenarios of discharge rate. The analyzed battery is a
pouch cell 500 mAh, LFP, and the role of the battery simulation is for a better
understanding of: its behavior, its performance and to see in which measure can
deliver the required performance and which are the directions to be followed for
performance improvement.
The infrastructure that ICSI Rm. Valcea owns allow to build battery cells from
mAh to units of Ah and to test it. However the challenge is to develop simpler and
faster models which predict faithfully the behavior of Li-ion batteries having in the
end an important role from economic point of view. The modelling results can be
compared and adapted to that results obtained from the testing part.
75
Keywords: Li‐Ion battery, energy storage, pouch cell, thermal runaway.
Figure 1. Profile of negative electrode (V) Figure 2. Profile of positive electrode (V)
Figure 3. Profile of static temperature (K) Figure 4. Profile of current density colored by
2
magnitude (A/m ) during discharge process
Figure 5. Potential profile for different Figure 6. Static temperature profile in electrolyte
discharge C-rate zone for different discharge C-rate
References
Buga M., Bubulinca C., Badea S., Rizoiu A., Stanica E., Balan M., Ciocan A., Varlam M., (2018), Study of
LiFePO4 electrode morphology for Li‐ion battery performance, REV.CHIM. 69(3):549-552
Kim U. S., Shin C. B., Kim C-S., (2008), Effect of electrode configuration on the thermal behavior of a
lithium polymer battery, Journal of Power Sources, 180: 909-9016
76
FIRST RESULTS ON LASER-INDUCED GRAPHENE FOAM

AS GAS DIFFUSION LAYER FOR PEM FUEL CELLS
Athanasios Tiliakos1, Alexandra M.I. Trefilov1, Elena Dutu1, Eugenia Tanasă2,

Adriana Balan3, Ioan Stamatin3
1
National Institute for Lasers, Plasma and Radiation Physics, 409 Atomistilor Street,
Bucharest‐Măgurele MG‐36, 077125, Romania
2
Polytechnic University of Bucharest, Faculty of Applied Sciences, Department of Physics,
313 Splaiul Independenței Street, 060042, Bucharest, Romania
3
University of Bucharest, Faculty of Physics, 3Nano‐SAE Research Centre, 405 Atomistilor Street,
Bucharest‐Măgurele MG‐38, 077125, Romania
Corresponding author: thanos.tiliakos@inflpr.ro
Porous nanocarbons have been established as materials of choice in the

manufacturing of gas diffusion layers (GDLs), microporous layers (MPLs), and catalyst
supports for proton-exchange membrane fuel cells (PEM-FCs), with the requirements
of presenting high material stability and efficient flow management to secure adequate
power densities. With inexpensive materials of low-quality resulting in poor
mechanical and chemical stabilities, obtaining high-quality nanocarbons at a
competitive yield-to-cost ratio constitutes an important objective, with pyrolytic
techniques having shown promise for the bulk production of such carbonic
nanopowders.
In this report, we present the first results of laser-induced graphene (LIG) foam as
the GDL in PEM-FCs. The LIG method employs low-cost IR laser engravers (10.6 μm CO2
laser with 14 μs pulse duration) for the laser pyrolysis of commercial polyimide
substrates (poly 4-4' oxydiphenylene pyromellitimide, PMDA-ODA) into graphene-
based foams with distinctive 3D porous networks (Tiliakos et al., 2016). During laser
pyrolysis of polyimides, sp3 carbons are photothermally converted to sp2 carbons via
the violent expulsion of volatile elements (CO2, CO) and the rapid condensation of
escaping aromatic groups (cyclohexylmethane, N-vinylphthalimide, N-cyclohexyl-N-
ethylacetamide) into interconnected graphenic cells of micronic dimensions.
Similarly to direct laser printing, the LIG method allows for the versatile control of
the geometry of such graphenic structures attached to the flexible polymeric
substrate.
For the purposes of GDL construction, the challenge of retaining the
mechanical integrity of the LIG foam network after detachment from the substrate
was overcome by using a reverse decal method: after impregnating the LIG foam
with a Nafion solution acting as a binder, an MPL/catalyst layer consisting of Nafion
and suspended platinum particles was deposited on the LIG surface; an elastomeric
Nafion membrane was sandwiched under mechanical pressure around two
catalyst-bearing LIG units serving as anode and cathode, allowing for the successful
77
removal of the polymeric substrates on either side and resulting in an integrated

membrane-electrode assembly (MEA).
The LIG assembly was tested on a BT-552 Membrane Conductivity and a BT-
112 Single Cell Test Systems, showing power performance comparable to Ketjen®
black and graphene-coated carbon black references, but lower than a high-cost
pyrolyzed carbon-black reference system (Trefilov et al., 2017) – the LIG system
presented significantly higher potential and current density ranges, but suffered
from high overpotential and impedance losses. This will need to be rectified by
readdressing the parameters of the reverse decal method (Nafion content, applied
pressure, MPL/catalyst layer deposition) to neutralize such performance obstacles,
while retaining and enhancing the positive aspects of LIG GDLs: elevated working
potential and current ranges coupled with impeccable fuel crossover performance
for a low-cost system resulting from a highly scalable, inexpensive, and rapid
manufacturing method.
Figure 1. SEM images of LIG porous network (left), catalyst layer (center), and
catalyst layer deposited on the LIG GDL (right)
Figure 2. TEM images of Pt-impregnated LIG, with SAED pattern in the inlet
78
Figure 3. Polarization graphs of LIG (left), Ketjen black (center), and

graphene-coated carbon black (left)
Keywords: laser‐induced graphene, laser pyrolysis, gas diffusion layer, PEM fuel
cells
Acknowledgments: The authors acknowledge the support granted for this work by
the UEFISCDI ‐ National Authority for Scientific Research and Innovation, within the
frame of contract PN‐III‐P1‐1.2‐PCCDI‐2017‐0194 (25PCCDI/2018).
References
Tiliakos A., Ceaus C., Iordache S. M., Vasile E., Stamatin I., (2016), Morphic transitions of
nanocarbons via laser pyrolysis of polyimide films. Journal of Analytical and Applied
Pyrolysis, 121:275-286
Trefilov A. M., Tiliakos A., Serban E. C., Ceaus C., Iordache S. M., Voinea S., Balan A., (2017),
Carbon xerogel as gas diffusion layer in PEM fuel cells. International Journal of
Hydrogen Energy, 42(15):10448-10454
79
CATHODE MATERIALS WITH MIXED HIGH ENERGY DENSITY AND PULSE POWER
CAPABILITY FOR Li-ION BATTERIES - PRELIMINARY RESULTS
Mihaela Buga1, Alexandru Vlad2, Adnana Spînu-Zăuleț1,

Alexandru Rizoiu1, Radu Ene1
1
2
Universite Catholique de Louvain, 1348 Louvain‐la‐Neuve, Belgium
Corresponding author: mihaela.buga@icsi.ro
The massive infiltration of hybrid electric, plug-in hybrid electric, and battery
electric vehicles (HEVs, PHEVs, and BEVs) and renewable energy management calls for
higher performance electrochemical energy storage systems (Kitao et al., 2005).
Fundamentally, energy and power do not scale proportionally in these systems
although, ideally, they should be simultaneously as high as possible. Worldwide, many
initiatives are in progress to gradually improve the power or energy performance,
safety, life, and cost with different marketing or scientific schemes implemented
(Gallagher et al., 2011; Albertus and Christensen, 2009; Wohlfahrt–Mehrenes,
2011). The race for better electrochemical energy storage systems has triggered
intense multidisciplinary research over the past years. The two key characteristics -
high power and high energy density - are largely sought, but to simultaneously attain
both still possesses thermodynamic and kinetic limitations, hence leaving a large
performance gap between supercapacitors and batteries.
The present study focuses on the developing field of hybrids LIB chemistries from
a new perspective. One conceptual generation of hybrid composite and architecture is
targeted: high energy and pulse power compact system, through simplified
manufacturing and integration. Targeting a range of cathode materials (LiNi1-x-
yCoxMnyO2 (NCMs), LiFePO4 (LFP)), we proposed the roll-to-roll processing technology
for multilayer electrode for LIB, as a promising alternative to blending cathode. The
multilayer formulations are compared to physical mixing formulations (blending the
cathode materials) (Nam et al., 2009). Performed on lab-scale format (coin CR2032
cells) and pilot-line (pouch cells), the capacity, and rate capability of the materials
will be investigated in standard electrolyte formulations (LiPF6 and LiTFSI). At later
stages, the development of novel electrolyte formulations will be considered to
optimize the ionic properties, safety and interaction with the electrode materials.
The up-scaling process will be carefully considered and optimized as to provide the
composite materials in the amount needed for the realization of the final
prototype.
80
Keywords: lithium‐ion battery, cathode materials, high power, high energy density,
hybrid
References
H. Kitao, T. Fujihara, K. Takeda, N. Nakanishi, T. Nohma, (2005), Electrochem. Solid-State Lett. 8,
A87-A90
K.G. Gallagher, S.H Kang, S.U. Park, S.Y. Han, (2011), Journal of Power Sources, 196:9702-9707
P.Albertus, Z.S. Christensen, (2009), J. Electrochem. Soc., 156:A606-A618
M. Wohlfahrt –Mehrenes, (2011), J. Electrochem. Soc., 158:AS556-A561
K.W. Nam, W.S. Yoon, H. Shin, K.Y. Chung, S. Choi, X.Q. Yang, (2009), J. Power sources, 192:652-659
81
STUDIES ON HYDROGEN INTERACTION WITH URANIUM ALLOYS
Mariea Deaconu, Ion Furtuna, Alice Dinu, Maria Mihalache
Institute for Nuclear Research, Piteşti, Romania

Corresponding author: mariea.deaconu@nuclear.ro
This paper presents the studies and experimental research on the storage of
hydrogen isotopes as metal hydrides to promote new materials and the development
of storage technologies that can lead to systems of hydrides with superior properties.
Promoting research on the development of methods for reversible storage of
hydrogen isotopes is closely connected with the need to diversify energy sources and
with the interest of European Community regarding nuclear safety and radioactive
waste management. Although a huge amount of materials were analyzed in order to
use them for hydrogen storage, the development of fully functional storage system,
still require many years of research and development. In order to develop new
hydrogen storage materials, hydrogen absorption properties of U-Zr alloys were
examined. U-Zr alloys were prepared from the constituent elements by powder
metallurgy using depleted uranium U238 (<0.72%U235) of 99.0% purity and zirconium
sponge of 99.8% purity, both of nuclear grades and studied in as cast condition as
hydrogen storage materials. For investigating the structural, compositional and
morphological aspects of the alloys several techniques (X-ray diffraction, electronic
microscopy and differential calorimetry) were used. For the materials studied a
mechanism for hydrogen uptake was established by thermo-gravimetric (TG) analysis.
The specimens were thermal treated under constant flow of hydrogen, for
temperatures varying from 573K up to 873K at a hydrogen pressure slightly lower than
one atmosphere. Also, the quantity of absorbed hydrogen, the desintegration degree
and the formation of ternary hydrides were evaluated. For all the specimens, hydrogen
capacities were similar to or higher than of UHx or ZrHx hydrides. Hydrogen absorption
properties of uranium compounds were studied in order to identify ternary hydrides
but a clear ternary hydride was not identified. It is possible that the ternary hydride to
be a mixture of UHx and ZrHx.
Keywords: Hydrides, hydrogen storage, U‐ alloys, kinetics.
82
Pd-MEMBRANES APPLICATIONS FROM TRITIUM SEPARATION TO PURE

HYDROGEN PRODUCTION
Silvano Tosti
ENEA – FSN Department, C.R. ENEA Frascati, Via E. Fermi 45, Frascati (RM) I‐00044, Italy
Corresponding author: silvano.tosti@enea.it
Compared to the traditional separation treatments, the membrane processes

have introduced several advantages: continuous operation, reduced energy
consumption, modularity and easy scale-up. The Pd-alloys have been studied to
separate hydrogen from gaseous mixtures because of their high permeability and
resistance to embrittlement (Tosti, 2013). In particular, dense defect-free Pd-Ag
membranes exhibit complete (infinite) selectivity to hydrogen so that ultra-pure
hydrogen can be separated. At ENEA laboratory in the frame of the fusion fuel cycle
researches, thin-walled tubes have been produced via cold-rolling and diffusion
welding of Pd-Ag sheets (Tosti, 2010). These membranes have been used to
manufacture both permeators and membrane reactors for the recovery of tritium
from He and from tritiated water. Thanks to the small thickness (0.050-01.00 mm)
of these membranes, the devices developed have showed the achievement of high
detritiation factors, while the adoption of a proper mechanical design has ensured
the durability of the membranes (Tosti et al., 2006). In fact, as a consequence of the
hydrogen uploading into the metal lattice, the Pd-Ag alloy elongates significantly
(Fort and Harris, 1975): therefore, the thermal and hydrogenation cycling of these
membranes under the operating conditions typical of the hydrogen separation
processes (temperature up to 350-400°C, pressure of around 1 MPa) can produce
mechanical stresses capable to damage the thin-walled tubes. Membrane modules
adopting a finger-like configuration where pre-tensioned Pd-tubes have been
assembled have been designed, manufactured and successfully tested [Borgognoni
et al., 2010). The direct ohmic heating of the membrane tubes has been introduced
thus saving the heating power (about 50%) and reducing the temperature ramping
(Tosti et al., 2014).
Pd-membrane reactors have been used in several processes for the hydrogen
separation from tritiated water (Santucci et al., 2016; Santucci et al., 2013). The
efficient recovery of tritium from JET housekeeping waste has been demonstrated
(DF up to 10) by a membrane reactor made of a Pd-Ag thin wall tube of length 500
mm and diameter 10 mm (Liger et al., 2014).
The same Pd-membranes developed for the fusion fuel cycle have been studied
for the production of pure-hydrogen via dehydrogenation reactions of hydrocarbons,
alcohols and biomass. When a dehydrogenation reaction (i.e, water gas shift,
reforming, pyrolysis, etc.) occurs in a Pd-membrane reactor the continuous removal of
the hydrogen from the reaction zone into the permeate side promotes the reaction
conversion accordingly to the Le Chatelier’s principle according to the “shift effect” of
83
the membrane. A wide experimental work has been carried out by tubular Pd-
membrane reactors for testing the production of hydrogen via water gas shift,
reforming of methane and ethanol and reforming of biomass (Gallucci et al., 2007;
Mendes et al., 2010; Borgognoni et al., 2011). In particular, the olive mill waste water
(OMW) has been treated in a tubular Pd-Ag membrane reactor by recovering pure
hydrogen in the permeate (up to 2 kg of hydrogen per ton of OMW) plus a syngas
(namely CO2, H2 and methane) in the retentate (Tosti et al., 2016).
In all the tests of Pd-membranes, reaction conversions higher than those
obtained in traditional reactors have been observed. By scaling-up the lab setup,
membrane units producing ultra-pure hydrogen (up to 1 m3/h) for powering
polymeric fuel cells have been realized and tested as well.
Keywords: tritium recovery, Pd‐membranes, membrane reactors, pure hydrogen
References
S. Tosti, (2013), Membranes and Membrane Reactors for tritium Separation, Tritium in Fusion:
Production, Uses and Environmental Impact, ed. S. Tosti and N. Ghirelli, Nova Science
Publishers, Ch. 6, pp. 203-240
S. Tosti, (2010), Overview of Pd‐based membranes for producing pure hydrogen and state of art at
ENEA laboratories, International Journal of Hydrogen Energy. 35:12650-12659
S. Tosti, A. Basile, L. Bettinali, F. Borgognoni, F. Chiaravalloti, F. Gallucci, (2006), Long‐term tests of
Pd–Ag thin wall permeator tube, Journal of Membrane Science 284:393–397
D. Fort, I.R. Harris, (1975), The physical properties of some palladium alloy hydrogen diffusion
membrane materials, J. Less-Common Met. 41:313–327
F. Borgognoni, D. Demange, L. Dörr, S. Tosti, S. Welte, (2010), Processing test of an upgraded
mechanical design for PERMCAT reactor, Fusion Eng. Des. 85:2171-2175
S. Tosti, N. Ghirelli, F. Borgognoni, P. Trabuc, A. Santucci, K. Liger, F. Marini, (2014), Membrane
reactor for the treatment of gases containing tritium, European Patent Grant EP 2582618
(14.05.2014)
A. Santucci, M. Incelli, M. Sansovini, S. Tosti, (2016), Catalytic membrane reactor for tritium
extraction system from He purge, Fusion Engineering and Design 109–111 642–646
A. Santucci, C. Rizzello, S. Tosti, (2013), Computation and comparison of Pd‐based membrane reactor
performances for water gas shift reaction and isotope swamping in view of highly tritiated
water decontamination, Fusion Engineering and Design 88:2413-2416
K. Liger, P. Trabuc, J. Mascarade, M. Troulay, C. Perrais, S. Tosti, F. Borgognoni, (2014), Preliminary
results from a detritiation facility dedicated to softhousekeeping waste and tritium valorization,
Fusion Engineering and Design 89:2103-2107
F. Gallucci, A. Basile, S. Tosti, A. Iulianelli, E. Drioli, (2007), Methanol and ethanol steam reforming in
membrane reactors: An experimental study, Int. J. Hydr. En. 32:1201-1210
D. Mendes, V. Chibante, J-M. Zheng, S. Tosti, F. Borgognoni, A. Mendes, L.M. Madeira, (2010),
Enhancing the production of hydrogen via water gas shift reaction using Pd‐based membrane
reactors, Int. J. Hydr. En. 35:12596-12608
F. Borgognoni, S. Tosti, M. Vadrucci, A. Santucci, (2011), Pure hydrogen production in a Pd‐Ag multi‐
membranes module by methane steam reforming, Int. J. Hydr. En. 36:7550-7558
S. Tosti, M. Fabbricino, L. Pontoni, V. Palma, C. Ruocco, (2016), Catalytic reforming of olive mill
wastewater and methane in a Pd‐membrane reactor, Int. J. Hydr. En. 41:5465-5474
84
THE TECHNOLOGICAL CHAIN OF ENRICHMENT OF 3He
Petar Dalakov1, Maxim Kupriyanov2, Jürgen Klier1

1
Institut für Luft‐ und Kältetechnik gemeinnützige Gesellschaft mbH, Hauptbereich Kryotechnik
und Tieftemperaturphysik, Bertolt‐Brecht‐Allee 20, 01309 Dresden, Germany
2
Bauman Moscow State Technical University, Moscow, 107005, Russia
Corresponding author: Petar.Dalakov@ilkdresden.de
Currently, the most suitable raw material for the production of 3He is natural
helium, which is a natural mixture of 4He and 3He isotopes. Natural helium is
produced at large air separation plants. The concentration of 3He in natural helium
is only 1.4 ppm, but this is about ten times greater than the concentration of 3He in
natural gas fields.
The use of traditional technologies for the enrichment of 3He to high
concentrations is practically impossible because of the meager concentration of
3
He at the initial stage. Therefore, in order to enrich 3He in the first stage, it is
better to use filtration at a temperature level below a temperature of lambda
transition of liquid helium - Tl, at which the concentration of the 3He isotope can be
increased up to 103 ... 104 ppm. After the filtration process, a rectification or
adsorption can be used to further enrichment of 3He.
A technological chain for an enrichment of the isotope of 3He from the initial
low concentration with several ppm to high concentrations up to 95 ... 97 vol.% of
3
He, as well as the main economic indicators of the system is reported in this paper.
The proposed technological chain consists of 2 stages. The first stage, in which
3
He is preliminarily enriched (filtered), at a temperature below Tl. The second stage
uses a distillation column operating at a temperature level of 1.3 ... 3.0 K.
Keywords: 3He isotope, natural helium mixture, low temperature filtration, cryostating.
85
PRODUCTION OF LIGHT GASES STABLE ISOTOPES BY CRYOGENICS METHOD
Vitaly Bondarenko1, Iurii Symonenko2, Dmytro Tyshko3, Borys Pylypenko3

1
Moscow Bauman State Technical University, 2‐nd Baumanskaya Str., 5, 107005, Moscow, Russia
2
Cryoin Engineering, LTD, Mytna square, 1‐A, 65026, Odessa, Ukraine
3
Institute of Refrigeration Cryotechnology and Ecoenergetics n.a. V.S. Martynovsky,
Dvoryanskaya Str., 1/3, 65082, Odessa, Ukraine
Corresponding author: dtishko@cryoin.com, Tel: +380972211942
Nature neon consists of three isotopic components (Table 1). In 1913, J.

Thomson obtained first samples of neon isotopes by method of mass-spectrometry.
Separation of 20Ne and 22Ne isotopic pair for laboratory and industrial purposes is
also possible by thermal diffusion and chromatography methods. It is considered
that neon is at the limit of the rectification method application, which is effective at
the molecular weights less than 20. The rectification method is based on the
concentration discrepancy of liquid and gaseous phase in a theoretical plate.
However, deviations in the isotope components properties are hardly noticeable at
the same temperature. The ratio of saturated vapors elasticities of the isotope pair
20
Ne − 22Ne is shown at figure 1. At the neon rectification column work
temperature ТС = 28 K, the separation coefficient α is close to one, and equals
α=1,037.
Table 1. Isotope concentration in the nature
neon
Mass Concentration,
Isotope
number %
20
Ne 19,9924 90,48
21
Ne 20,9928 0,27
22
Ne 21,9914 9,25
Nature Neon 20,1797 100
Figure. 1. The temperature effect on the

separation coefficient of isotopes 20Ne − 22Ne
A considerable number of theoretical plates is required due to small values of

the coefficient α. Consequence there is large height of the column contact space.
Due to relatively small cross-section of such apparatus, their cryostatting at the
temperature level 28 K is associated with considerable difficulties. The ratio of the
column height to its diameter L/d is 600…800. It is very hard to transmit “cold”
from condenser to the distant L = 18 along the channel with the diameter 30 mm
even with the high-vacuum insulation and cooled screens. That’s why, the height of
86
the column contact space is reduced up to 3…6 meters. Due to the insufficient
separation factor, the secondary processing of the obtained fractions in the same
column is practiced (Bondarenko et al., 2016). In the next variant, a consistent
separation of neon is used in isotope columns cascade (Bondarenko et al., 2015).
The neon isotopes separations by rectification methods is very laborious and
inefficient. It is necessary to decrease gas losses in the process sequences
construction, because the energy costs for obtaining one normal liter of 20Ne and
22
Ne are 50…500 MJ.
Several types of rectification columns with different sizes of contact space
(from1.6 mm to 2.2 mm) have been tested (fig. 2). The results of the studies can be
used at the development of hydrogen isotopes rectification units. Despite the lower
work temperature, the phase separation conditions of Hydrogen are better than
conditions of isotope pair 20Ne − 22Ne. The separation coefficient α for Hydrogen-
Deuterium system is higher, and the boiling temperatures of H2 and HD differ by
almost two degrees.
Figure 2. Rectification unit for obtaining neon isotopes by cascade method

(each vacuum case contains three separate rectification columns)
Despite the technological difficulties, rectification method makes it possible to

obtain 20Ne and 22Ne with the concentration 99,995%. If 21Ne is the target product,
then this method doesn’t have any alternative (Bondarenko et al., 2013).
Keywords: neon isotopes, rectification column, transfer unit, separation factor
References
Bondarenko V. L., Symonenko I. M., (2015), U.S. Patent No 9,168,467. Assembly for separation gas
mixtures in fractionating columns.
Bondarenko V. L., Simonenko Yu. M., Tsvetkovskaya L. N., Matveev E. V., (2016), Separation of neon into
isotope components by rectification method in a single column. Industrial Gases, 16(6):57-66
Bondarenko V. L., Simonenko Yu. M., Diachenko O. V., (2013), Cascade units for neon isotopes
production by rectification method. Low Temperature Physics, 39(5):617-622
87
CRYOGENIC SUPPORT OF RECTIFICATION UNITS FOR THE

NEON ISOTOPES PRODUCTION
Vitaly Bondarenko1, Artem Chyhrin2, Hlib Bashkirov3

1
Moscow Bauman State Technical University, 2‐nd Baumanskaya Str., 5, 107005, Moscow, Russia
2
Cryoin Engineering, LTD, Mytna square, 1‐A, 65026, Odessa, Ukraine
3
Institute of Refrigeration Cryotechnology and Ecoenergetics n.a. V.S. Martynovsky,
Dvoryanskaya Str., 1/3, 65082, Odessa, Ukraine
Corresponding author: achigrin@cryoin.com, Tel: +380678275011
Neon has unique physicochemical properties, which have stipulated its use in
many areas of modern industry. In addition to neon, its isotope components 20Ne, 21Ne
and 22Ne and their mixtures find application in the science-intensive technologies.
These isotopes are required in medicine, nuclear physics, laser gyroscopes and mass
spectrometry. The production of inert gases and their isotopes isn’t limited by natural
resources. However, this process is accompanied by enormous energy costs. They are
measured by dozens of mega joules per cubic meter of neon, and hundreds of mega
joules per liter of its isotopes. Improving the technology for extracting these valuable
products is especially important in the condition of increased competition and
increased requirements to energy costs economy.
A number of common cycles, which can be based on an available equipment,
were considered, for a comparative analysis of cryostating methods. Among them:
neon and hydrogen high-pressure throttles cycles (Figure 1a), helium gas-
expanding cycle (Figure 1b), and the refrigeration cycle based on a 2-stage
cryogenic gas machine with the external heat removal circuit (Figure 1c). Neon or
hydrogen can be used as the working substance in the throttle cycle shown in
Figure 1-a. Two-stage membrane compressors with a pressure P = 220 bar were
used in the first case and the three-stage piston compressor with pressure P = 150
bar was used, when H2 is used as working substance. The main characteristics of
the investigated refrigerators are presented in Table 1.
Table 1. Comparison of refrigeration cycles at T = 28 K

The throttling cycle with Cryogenic
Gas-
Type of cycle cooling at temperature Gas
expander
level 66 … 78 К Machine
Designation scheme according to Figure 1; а) neon; а) hydrogen; b) helium; b) helium;
work substation; pressure in the circle, bar Р = 220 Р = 150 Р = 25 Р = 18÷42
Energy consumption NΣ, kW 15,0 7,8 18,1 22
Cooling capacity, Q, W 180 74 88 89
Relative energy consumption, NΣ/Q 83 106 206 247
88
Cooling of neon rectification columns by hydrogen and helium cycles should be

carried out indirectly. For these purposes, special heat exchanger capacitors are
placed in the upper part of the rectification units. Using of neon cycles gives the
right to choose: to use an isolated refrigerated cycle with a condenser or combine
the technological and refrigerant circuits. The second option is preferable, since it
simplifies the design and increases the heat transfer coefficient of the condenser.
The pure product (Ne) is obtained in the bottom of column section, upon
rectification of the Ne-He mixture. Therefore, the inclusion of a combined
refrigeration cycle in this case does not cause problems. It is required to remove
the heat from the top of the column where the fraction with a volume content of
Ne ≈ 98% is taken. After compression in the compressor, this stream is throttled
into the same zone in the form of a vapour-liquid mixture.
V C C ТН1 ТН2
N2 Q70K
V
VP N2
Q28K
HE1 HE1
VJ R2
L L
N2 N2
NB NB R1
HE2 HE2
Tr LD
D
Q28K Q28K
a) b) c)
Figure 1. Schemes of throttling (а), gas expanding (b) and Cryogenic Gas Machine
(c) circles for heat removing at the temperature level 28 К
NB – nitrogen bath; VP – vacuum pump; С – compressor; НЕ – heat exchanger; Tr – throttle valve; D – gas
expander; R1 and R2 – refrigerators of the first and second stages of the Cryogenic Gas Machine; VJ –
vacuum jacket; ТН1 and ТН2 − turbo pump of the external helium circuit of the 1-st stage (T ≈ 70 K) and
the 2-d (T = 28 K) stage; Q28 – heat from the rectification column at the temperature level T = 28 K; Q70 –
heat from the thermal insulation shields at the temperature level T ≈ 70 K.
The use of combined (non-condenser) circuits in the production of neon isotopes

involves a gradual change in the isotopic composition of the working substance. At the
launch time, neon with a natural ratio of isotopes (90.5% 20Ne) is in the refrigeration
circuit. After several days of column operating, the concentration of the light
component (20Ne) in the upper part of the column and in the refrigerating circuit to
99.9%. This allows to select 20Ne directly from the compressor discharge line.
The throttle neon cycle with pre-cooling of the working fluid with liquid nitrogen
at T = 66 ... 68 K is the preferred type of refrigeration cycle for providing rectification of
Ne. The using of neon as the working fluid makes it possible to combine the
refrigeration and technological circuits, eliminate the column condenser and reduce
irreversibility of the heat removal from the rectification columns.
Keywords: neon isotopes, rectification column, refrigeration cycles, cryogenic gas

machine.
89
CHARACTERIZATION OF GAMMA RADIATION FIELDS EMITTED BY 60-Co SOURCES

INSIDE OF THE CHAMBERS FOR SIMULATION OF SPECIFIC OUTER SPACE
CONDITIONS
Tuta Catalin Stelian, Postolache Cristian, Celarel Aurelia, Cenusa Constantin,

Fugaru Viorel, Ioan Mihail-Razvan
Horia Hulubei National Institute for Physics and Nuclear Engineering, 30,
Reactorului St., Magurele, Ilfov, Romania
Corresponding author: catalin.tuta@nipne.ro
Two multifunctional interaction chambers were designed built and tested to

establish the technical solution for future experimental facilities dedicated to simulate
the cosmic space environment at ELI NP/E5 Experimental Area, Bucharest-Magurele,
Romania.
The interaction chamber consists of:
– Cylindrical vacuum chamber, designed to work for a pressure range from
ambient pressure up to 10-4 Pa and temperature from -196°C to 150°C,
– High vacuum facility with vacuum measurement system (which can provide a
-7
10 Pa vacuum pressure)
– Ionising radiation sources for simulation of cosmic ray
For the simulation of cosmic rays, the researches were started by using of γ
radiation fields emitted by 60Co irradiator. The γ radiations are not representative
because they have a low value for LET, associated with reduced radio-induced effects
in electronic devices and biological systems. The advantages of the gamma radiations:
are slightly attenuated in materials, can be easily obtained extended high-density
particle flux, the dose/dose rate is easy to predict and determine. Gamma radiation
due not induce nuclear reactions. The exposed samples can be transferred without
restriction to other laboratories.
The gamma radiation fields, emitted by 60-Co sources were analysed in point of
view of axial and transverse dose distribution and uniformity of dose rate using:
electronic debit-meter UNIDOS T10021 type with Ionization Chamber TM 30013 type,
alanine tablet EPR dosimeters and EBT3 Gafchromic films.
Keywords: space, cosmic ray, testing facility, dosimetry.
Acknowledgments: This research is supported by the Core Project No 18 09 01 05

from Executive Unit for Financing Education Higher Research.
90
MATHEMATICAL MODEL OF A HEAT EXCHANGER WORKING WITH

DIFFERENT REFRIGERANT FLUIDS
Zabet Ion1, Nita Iulian1, Fako Raluca1, Tarlea Gratiela Maria2

1
Center of Technology and Engineering for Nuclear Project, 409, Atomistilor Street, Magurele, Ilfov,
Romania; 2Technical University of Civil Engineering Bucharest,66 Blv. Pache Protopopescu,
Bucharest, 021414, Romania
Corresponding author: zabeti@router.citon.ro
This paper involves building a model of a fin-and-tube heat exchanger geometry

using Mathcad software, creating a suitable geometry, setting up the cases (choosing
solvers, numerical solution methods, etc.), making the calculations with Mathcad, and
comparing results to known experimental data. Experiments done on fin-and-tube
heat exchangers and reported in the literature are used for validation. The model is
working on the refrigerant side with: R152a, R404A, R407C, R410A, R507A, R744, He
and with Air, H, T on the other side. The paper described the geometry and the
algorithm of the model. The mathematical model can calculate the next parameters:
capacity, global heat transfer coefficient, local heat transfer coefficients, Reynolds
number, Nusselt number, fluid velocity, Prandtl number, Colburn factor, friction factor
and pressure drop of the heat exchanger.
The mathematical model can calculate the pressure drop and Lockhart –
Martinelli parameter in biphasic flow. These two parameters can show the flow
regime inside the horizontal tubes.
One of the most important parameters in biphasic flow is Lockhart – Martinelli
parameter. Pressure drop in biphasic flow is calculated with Wang (2010) model
and use Bond, Reynolds and Weber numbers.
In the final of the paper it has been made a graphical comparison between
refrigerants for heat exchanger geometry.
This type of the heat exchanger is characterized by n-tubes arrange in line and
by aluminium fins. The input parameters are: air and refrigerant inlet temperature,
atmospheric pressure, air mass flow, refrigerant mass flow, displacement volume
and geometry. The output parameters are: capacity, global heat transfer
coefficient, local heat transfer coefficients, velocity of fluid, Prandtl number,
Colburn factor, friction factor and pressure drop. The heat exchanger are modelled
in the following flow types: counter flow, parallel flow, cross flow both unmixed
and cross flow one unmixed.
Keywords: cooling, heat exchanger, refrigerant, hydrogen, helium.
91
References
Zabet I., (2012), Contributions to the study regarding the increase of eco‐efficiency in refrigeration
systems, PhD Thesys, Bucharest
Baggio P., Fornasieri E., (1994), Air‐side heat transfer and flow friction: Theoretical aspects, in
Recent developments in finned tube heat exchangers. Energy Technology pp. 91-159
Gnielinski V., (1976), New Equation for heat and mass transfer in turbulent pipe and channel flow,
International Chemical Engineering, 359-368
L. Friedel, (1979), Improved friction pressure drop correlations for horizontal and vertical two‐phase
pipe flow, in: European Two-Phase Group Meeting, Ispra, Italy, Paper E2
Wang Chi-Chuan, Tseng Chih-Yung, Chen Youn, (2010), A new correlation and the review of two‐
phase flow pressure change across sudden expansion in small channels, International Journal of
Heat and Mass Transfer, 53:4287-4295
McQuiston F. C., (1978), Correlation for heat, mass and momentum transport coefficients for plate‐
fin‐tube heat transfer surfaces with staggered tube, ASHRAE Trans. 84:294-309
VDI Heat Atlas, (2010), Second Edition, Springer
92
STUDIES OF CRYOGENIC DISTILLATION EQUIPMENTS AND PROCESS
Sebastian Brad, Alin Lazăr, Mihai Vijulie
Valcea, Uzinei Street, no. 4, PO Box 7 Raureni, 240050, Valcea Romania
Corresponding author: sebi.brad@icsi.ro
Distillation is the process of separation of a homogeneous mixture of

liquids, based on the difference of the volatility of the components. Distillation is
also a repeated double process, composed by boiling of the liquid mixtures and
condensing the vapours. Therefore, in cryogenic distillation columns appear several
complex phenomena which should be treated very carefully, some of them must be
avoided and others are needed. Several times, in the cooling process of a cryogenic
distillation column, cannot be obtained a uniform cooling of all the parts of the
column. This situation could come from wrong system design or not proper
installation: insufficient cryogenic power, heat losses from design/construction or
from improper design/installation of the isolation systems, condenser with small
heat transfer surface or cryogenic power, column misalignment and column
internals not proper designed and installed, boiler affected, from construction, by
one of the undesired phenomena (the two-phase boiling and flow), feeding of the
column with high flow and/or high temperature, feeding and/or extraction points
from the column wrong positioned and wrong packing type. The effects of these
factors are often increased by not proper operation: improper cleaning and purging
of the installations, high inlet flow and/or pressure, accidentally heat inputs (e.g.
too much heat power in the boiler), wrong operation parameters of the equipment
(valves, pumps, compressors, turbo-expanders, J-T valves, etc.), improper purified
of the inlet streams.
93
RADIOLOGICAL CHARACTERISATION OF RESULTED MATERIALS FROM

REFURBISHING OF TRITIUM LABORATORY
Bubueanu George, Postolache Cristian, Fugaru Viorel, Tuta Catalin Stelian
“Horia Hulubei” National Institute for Physics and Nuclear Engineering, 30,
Corresponding author: cristip@nipne.ro
Determination of tritium content in solid samples can be achieved by total

combustion followed by LSC (Liquid Scintillation Counting) analysis of the resulting
tritiated water activity.
Radiological characterisation of solid wastes resulting in refurbishing step was
carried out using a total combustion plant constituted from:
- Pressure oxygen tub with pressure regulator and flow control Rota meter
- 2 tube furnaces with temperature controller (RT 50-250/11 Nabertherm
type), one for sample oxidation (with temperature gradient depending on the
nature of the analyzed material) and secondary for catalytic oxidation of resulted
gases at water and carbon dioxide (8000 C in presence of CuO wires)
- HTO collector
- Trapping unit for retention of tritiated water over siccative CaCl2
- Radioactive gas monitor (RGM) with Ionizing Chamber Overhoff type.
The equipment was used to radiological characterize the waste resulting from
the refurbishing phase of the tritium laboratory within IFIN HH (brick, plaster,
concrete, PVC false ceiling, linoleum, mineral oil, plastic tubes, glass, metals etc).
Keywords: Tritium, solid wastes, oxidizer, LSC

from Executive Unit for Financing Education Higher Research
94
EXPERIMENTAL PLANT FOR CARBON ISOTOPES SEPARATION BY CARBON

MONOXIDE CRYOGENIC DISTILLATION
József-Zsolt Szücs-Balázs, Ștefan Bugeac*, Codruța Mihaela Varodi, Claudia Lar,

Mariana Cristina Marcu, Mihai Liviu Gligan
Corresponding author: stefan.bugeac@itim‐cj.ro
A carbon stable isotopes separation plant, by carbon monoxide cryogenic

distillation was designed and built at National Institute for Research and Development
of Isotopic and Molecular Technologies from Cluj-Napoca. The experimental distillation
plant consists of three parallel, 7 meter high, packed separation columns, each of them
equipped with adequate boiler and condenser.
For the plant operation, a proper monitoring and control system was developed,
which allows the columns functioning both, in parallel and in series.
The performances of separation columns were determined in total reflux
condition; the preliminary experiments have shown for the theoretical plate height
promising values of 18, 21 and 20 mm for columns having the inner diameter of 20, 16,
and 12 mm, respectively. Moreover, for each separation columns we have determined
the overall separation factor; the obtained values stay in the interval 11-18.
Keywords: isotope separation, cryogenics, carbon monoxide.
95
FABRICATION AND HYDROGEN PERMEATION OF

Al2O3/Er2O3 COATING BY MOD METHOD
Zhang Dongxun
Shanghai Institute of Applied Physics, Chinese Academy of Sciences

Corresponding author: zhangdongxun@sinap.ac.cn
Reduced Activation Ferritic Martensitic Steel (RAFMS) is a structural material

for Test Blanket Module (TBM) in International Thermonuclear Experimental
Reactor (ITER).
hydrogen isotopes permeation barriers (HIPB) are used to reduce hydrogen iso
topes permeation, which may result in hydrogen isotopes leak and construction ma
terials brittleness. An oxide coating with a-Al 2O3 phase as a reference coating for
fusion reactors, has a high hydrogen permeation reduction factor, good electrical
insulation and radiation stability.
In this study, Al2O3 coating was fabricated on 316L substrate by the oxidation
of Fe-Al diffusion layer when Er2O3 coating as the outer layer was formed by metal
organic deposition (MOD) during the baking process. XRD patterns indicated that
good crystallinity of the Al2O3-Er2O3 multi-layer coatings was obtained for the
baking temperature of 600-700oC. Hydrogen permeability of the coated sample was
decreased by 1/1000 compared with the bare substrate in the temperature range
of 400-650°C. Meanwhile, microstructure of Al2O3-Er2O3 multi-layer coatings was
investigated by SEM.
Keywords: metal organic deposition, hydrogen isotopes permeation, coating,

diffusion
96
DISMANTLING AN OBSOLETE TRITIUM INSTALLATION
Kris Dylst1, Yves D’Joos1, Herman Lodewyckx1, Anisia Bornea2, Marius Zamfirache2
1
SCK•CEN – Boeretang 200 – 2400 Mol
2
ICSI – Rm. Valcea – 240050
Corresponding author: Kris.Dylst@sckcen.be
The irradiation device VNS (Variable Neutron Shield) provided the possibility to
vary the fission power produced in a fuel rod test in the BR2 reactor at SCK•CEN. It
consists of a fuel rod which was surrounded by an annular gas cap filled with He-3
gas (99% pure) (Falla, 1978), also called the He-3 shield. He-3 is a strong neutron
absorber and absorption of a neutron by the He-3 atom results in one hydrogen
and one tritium atom. The produced hydrogen and tritium were removed from the
in-pile section by sending the gas flow through titanium retention traps located in
the out-of-pile equipment mounted in a glovebox in the reactor building.
The maximum tritium retention capacity of the original VNS-1 installation was
about 3.7E14 Bq (10.000 Ci) of tritium. Currently the VNS-1 installation is de-
coupled from the in-pile-sections from the BR2 reactor. The VNS-2 installation has
the same basic structure as the VNS-1 installation and holds 3 Ti-getters for storing
the produced tritium. It is no longer operational as power cycling device. Part of the
installation is still pressurized with inert gas and regularly vented for controlled
tritium release. In total 5 titanium getter beds are present in the VNS installations
(VNS-1: 2 beds, VNS-2: 3 beds). The exact tritium inventory of each getter bed is
unknown.
To make things more complicated, a NaK getter is stored in the VNS-1
glovebox. This is an experimental liquid NaK getter in a stainless steel housing, with
a micro filter to optimize tritium trapping while passing through the liquid
(Delbrassine, 1994). NaK reacts vigorously with water and oxygen. This getter must
be handled carefully before and during dismantling. Besides the chemical risks, the
tritium content of this getter is also unknown.
The presentation will give an overview of the work that has been done until
now in order to prepare for the dismantling of the VNS installation.
Keywords: Tritium, obsolete installation, Dismantling, Getter, Titanium, NaK.
Acknowledgments: This work was funded by the European Commission via the
H2020 TRANSAT project.
97
References
Falla A., (1978), Power cycling of fuel rods in BR2 Test Reactor – Irradiation Device VNS, (SCK•CEN
reports No. RD.81/0304/02/AF). SCK•CEN - Studiecentrum voor Kernenergie/Centre d’Etude
de l’Energie Nucléaire
Delbrassine A., (1994), Proposition d’un systeme integré de piegage‐stockage du tritium généré par
un écran neutronique d’³He, (SCK•CEN reports No. TEC/50.C8229/19/Adel). Studiecentrum
voor Kernenergie/Centre d’Etude de l’Energie Nucléaire.
98
R&D OF TRITIUM TECHNOLOGY FOR CFETR: PROGRESS AND PROSPECT
Luo Wenhua, Luo Deli, Meng Daqiao, Li Rong, Huang Zhiyong,

Song Jiangfeng, Huang Guoqiang, Chen Chang-an, Deng Xiaojun, Qin Cheng,
Qian Xiaojing, Zhang Guikai
Institute of Materials, China Academy of Engineering Physics,

P. O. Box 9072, Mianyang 621908, Sichuan, China
Corresponding author: iterchina@163.com
China has decided to develop its own fusion engineering test reactor. Tritium
plant is one of the key systems of CFETR. A program supposed by China ministry of
Science and technology named Conceptual design and key technologies research
on tritium plant for fusion reactor was started on September,2011. After several
years research, we have finished the design of TEP,SDS,WDS,ISS and tritium safety
system. The key technologies such as hydrogen storage materials for SDS, catalysts
for WDS, palladium alloy membranes for TEP are under research. In this paper, the
progress and prospect of tritium technology for R&D of CFETR is introduced.
99
PROGRESS OF TRITIUM RELATED MATERIALS FOR FUSION SYSTEM
Chen Chang'an
Chinese Academy of Engineering Physics (CAEP), China

INTRODUCTION OF INSTITUTE OF MATERIALS, CAEP
Zhang Xinjian

PROGRESS OF HCCB TBM SYSTEM
Song Jiangfeng

PROGRESS OF WDS TECHNOLOGY IN CAEP
Li Peilong

100
SYNTHESIS OF LABELLED COMPOUNDS WITH TRITIUM USING

ORGANOMETALLIC COMPOUNDS AS INTERMEDIATES
Postolache Cristian, Fugaru Viorel, Tuta Catalin Stelian, Bubueanu George
Horia Hulubei National Institute for Physics and Nuclear Engineering, 30,
Typically labelled compounds with tritium are obtained by catalytic hydrogenation

reactions (the isotopic exchange method and chemical synthesis, respectively). A new
method for the synthesis of labelled compounds has been proposed which has the
following advantages: eliminates the need for presence of platinum catalysts in the
reaction system, labelling reactions are fast leading to products of superior purity, the
radioactive material use yields are over ten times higher than in the conventional
methods case. Another major advantage of the proposed method is that the
radioactive labelling material can be a tritium waste.
The new methodology consists in the use of gas mixtures resulting from treatment
of tritium-depleted sources (radio-luminescent sources, Ti/Zr absorbed tritium targets,
depleted raw materials, etc.) or tritiated water with low or medium mass activity.
The synthesis protocol consist of:
- Synthesis of organometallic compounds (Grignard organometallic-reagent
compounds) by reaction of Mg turnings with halogenated derivatives
CH3 CH3
H3C Si CH3
H3C Si CH3
O CH3 CH3 O
H O
I H3C Si N Si CH3 I
MgI
HN CH3 CH3 N N
CH3
Mg
CH3
O N H3C Si O N
H H3C Si O N
CH3
CH3
- Oxidation of gas mixtures to T2O or HTO using CuO catalysts. This type of
catalyst does not require the presence of oxygen, eliminating the risk of
uncontrolled oxidation reactions (explosion).
- Converting of resulted T2O / HTO to acetic acid marked on the carboxyl group
(CH3COOT). This allows double the marker yields and the control of the first steps
of the synthesis of the specific activities of the synthesized marked compounds.
101
- Reaction of organometallic compounds with acetic acid marked with rapid

obtaining of labelled compounds with minimization of self radiolytical processes
and significant reduction of resulting radioactive waste.
- The excess tritiated water is removed from the system using methyl
magnesium iodide with generation of tritiated methane.
Keywords: Tritium, labelled compounds, organometallic compounds, tritiated water.

102
TIME SERIES ANALYSIS OF 18 YEARS OF CONTINUOUS OBSERVATION OF TRITIUM

CONTENT IN RAMNICU VALCEA PRECIPITATIONS
Octavian G. Duliu1, Carmen Varlam2

1
Universuty of Bucharest, Faculty of Physics, Department of Structure of Matter, Earth and
Atmospheric Physics and Astrophysics, 405, Atomistilor str. 077125 Magurele (Ilfov), Romania
2
National R&D Institute for Cryogenics and Isotopic Technologies ‐ ICSI Rm. Valcea
4, Uzinei str, 240050, Rm. Valcea , Romania
Corresponding author: o.duliu@upcmail.ro
The monthly multi-annual (January 1999 – December 2017) precipitation levels

and tritium concentrations, as recorded by the Cryogenic Institute of Ramnicu Valcea,
Romania were analysed and compared with similar data of the Atomic Energy
International Administration Global Network of Isotopes in Precipitation (GNIP, 2018)
for Vienna, Berlin, Stuttgart, Regensburg and Krakow, i.e. localities where the influence
of the moist and depleted in tritium oceanic air is significantly reduced.
In all six cases, the precipitation level showed an annual variation pattern with a
maximum corresponding to the late spring – early summer period, reflecting the
common traits of Central European Continental Climate (Fig. 1A). On the other hand,
the multi-annual average values showed no decreasing tendency as the biplot
reproduced in Fig. 1B proves.
Figure 1. The monthly multi-annual (A) as well as the average annual (B) precipitation levels. It is
well evidenced that the monthly average level reach a maximum during the elate-spring-early
summer period (A) while the annual average corresponding to the 1990 – 2017 time interval
remained almost constant (B) (after Duliu et al. 2018)
A similar pattern concerning the monthly multi – annual was evidenced in

the case of tritium concentrations. Indeed, as the biplot 2A illustrates, the tritium
pattern presents the same late spring – early summer maximum, in concordance
with the Spring Leak mechanism (Clark and Fritz, 1997, Gat et al. 2001), the period
when the active transfer stratosphere-to-troposphere reaches a maximum.
103
Opposite to precipitation pattern, the multi-annual tritium concentrations showed

a continuous shrinkage with an annual rate of 1.4 ± 0.05 y-1, proving the fact that the
atmospheric contamination resulting from the ’60 atomic test has not reached the pre-
tests equilibrium status.
Figure 2. The monthly multi-annual (A) as well as the average annual (B) tritium concentrations.
Although the average level reach a maximum during the same period as the precipitation one (A),
the annual average corresponding to the 1990 – 2017 time interval showed a well evidenced
shrinkage (B). The small ellipses corresponds to the local Ramnicu Valcea tritium escape into
atmosphere (after Duliu et al. 2018)
Figure 3. The results of the Time Series Analysis performed on tritium concentrations (A, C) and
precipitation level (B, D). Both Power Spectra shows the same one year periodicity, better evidenced
in the case of tritium. The subsequent continuous wavelet transforms offer a most extended view of
the time evolution of both tritium (C) and precipitations (D) periodic or quasi-periodic components.
(After Duliu et al. 2018)
104
Totally differing by the precipitation pattern, the multi-annual tritium

concentrations showed a continuous shrinkage with an annual rate of 1.4 ± 0.05 y-1,
proving the fact that the atmospheric contamination resulting from the ’60 atomic
test has not reached the pre-tests equilibrium status.
The coincidence between the precipitation and tritium annual pattern suggests
the Spring Leak as the most probable mechanism which assure the cosmogenic
tritium transfer from stratosphere to troposphere and finally to the Earth surface.
All these assumptions were confirmed by the further Time Series Analyses of
both time series. Indeed, as the power spectra reproduced in Fig. 3 A and B, both
time series showed the same on-year maximum, better evidenced in the case of
tritium power spectrum (Fig.3A) than in the case of precipitations (Fig. 3B). In this
regard, a better representation of the time evolution of tritium concentrations and
precipitation levels is realized by the corresponding continuous wavelets
transforms reproduced in Fig. 3C and 3D respectively.
Indeed, while the tritium wavelet transform presented a single maximum
corresponding to a one year period, the precipitation wavelet transform showed a
most complex pattern, which in facts reflect the presence of multiple quasi-periodic
episodes of precipitations, a characteristic of the Ramnicu Valcea local atmospheric
conditions.
Acknowledgments: This work was partially done within the project PN 18 12 03 04,
part of Core Program ICSI 4E supported by the Romanian Ministry of Research and
Innovation, and monitoring program of Tritium Removal facility PESTD. OGD wish to
acknowledge that his contribution was partially done within the Cooperation
Protocol No. 4322‐4‐17/19 between the University of Bucharest and the Joint
Institute for Nuclear Research, Dubna, Russian Federation.
References
Clark I., Fritz P., (1997), Environmental Isotopes in Hydrogeology. CRC Press, Boca Raton, Florida
Duliu O. G., Varlam C., Schnawaw M.D., (2018), 18 years of continuous observation of tritium and
atmospheric precipitations in Ramnicu Valcea (Romania): A time series analysis. J. Environ. Rad.
190-191, 105-110
Gat J., Mook W., Meijer H., (2001), Tritium in the Atmosphere. In: Gatt, J., Mook, W.G., Meijer, H.A.J.
(Eds.), Environmental Isotopes in the Hydrological Cycle, Principles and Applications Vol. II
IAEAA, Vienna
GNIP, (2018), Global Network of Isotopes in Precipitation. https://nucleus.iaea.org/wiser/index.aspx,
Accessed date: 10 March 2018
105
OVERVIEW OF TRITIUM ACTIVITY IN THE NUCLEAR FISSION REACTORS
Iulian Nită1, Mariea Deaconu2, Raluca Fako1, Sorin Meglea1, Dan Bujoreanu2
1
Center of Technology and Engineering for Nuclear Projects (CITON),
Atomistilor Street, No. 409, Magurele, Judet Ilfov, Romania
2
Institute for Nuclear Research (ICN) Pitesti,
Campului Street, Nr. 1, POB 78, 115400 ‐ Mioveni, Arges, Romania.
Corresponding author: fakor@router.citon.ro
This paper will focus on assessment of tritium term sources relevant for fission
reactors from Europe. The purpose of this study is to estimate the quantity of
tritium production and its potential release ratio into the environment. The paper
studies tritium production aspects from fission reactors, in order to obtain a
preliminary estimate of the possible tritium source terms and identify areas where
barriers against tritium release could be upgraded. During the reactor operation
the tritium could be generated both as a fission product, by ternary fission, and as
an activation product from neutrons interacting with different elements of the
reactor core. Depending of reactor type generation of tritium it has different ways
and it's generated in different amounts. Depending on various reactor types, the
processes of tritium production and migration differ due to use of various fuel
types, structural materials of fuel cladding, temperature modes of operation, types
of the coolant and the systems that ensure radiation safety. Since the radiological
release of tritium (H3) can significantly impact human health and environmental
safety, the behavior of H3 in nuclear systems is of great concern in nuclear designs.
Tritium production in nuclear reactors has long been an item of concern, since
tritium can have significant biological impact if it is released into the environment.
For this reason, it is important to be able to predict how much tritium a reactor
produces, depending on the branch, what processes are important in its
production, and how we can improve protective barriers in order to keep H3 inside
in order to protect system operators and environment against radioactive H3
exposure.
Keywords: Tritium, nuclear fission, nuclear reactor.
106
POLYMER ELECTROLYTE MEMBRANE USED IN TRITIUM ENRICHMENT OF

AQUEOUS SAMPLE - PRELIMINARY RESULTS
Carmen Varlam, Ionut Faurescu, Dorin Schitea, Ionut Spiridon, Alin Chitu, Diana
Costinel, Laurentiu Patularu, Daniela Ion-Ebrasu, Irina Vagner
Corresponding author: ionut.faurescu@icsi.ro
Tritium level in the uncontaminated environment is now around 1-2 Bq/kg. The
REACH European directive (Registration, Evaluation, Authorization and restriction
on Chemicals, EC1907/2006) will have a huge impact of the liquid scintillation
cocktail performances, reflected for the tritium measurements in higher limit of
detection than the actual one. The tritium enrichment will be a usual procedure for
the environmental water.
Different studies (Muranaka et al., 2005) starting 2005, proposed the use of
Polymer Electrolyte Membrane (PEM) in the tritium enrichment of the
environmental water sample. The IAEA-H3 PEM system (Wassenaar et al., 2018)
which is an open source, gives a lot of details and permits adaptations to our
specific laboratory conditions. PEM was used initially for Hydrogen production for
combustion cell, but now this process is not essential, the “by-product”, residual
water is the main target for the tritium enrichment procedure. The advantages are
numerous: can be operated at the room temperature, no chemicals involved, and
no cross-contamination. The disadvantage of this procedure is the necessity of
deuterium content measurements of the initial and final water sample in order to
establish the enrichment factor, which is not a common measurement for a Tritium
laboratories.
The paper presents conceptual model, design, manufactured cell and
preliminary results of the PEM cell developed in our laboratory.
Keywords: polymer electrolyte membrane, tritium enrichment
Acknowledgments: This paper was prepared in connection with the work done for
project PN 18 12 03 04, part of Core Program ICSI 4E supported by the Romanian
Ministry of Research and Innovation, and monitoring program of Tritium Removal
facility PESTD.
107
References
Muranaka, T., Shima, N., Sato, H., (2005), A study to estimate tritium concentrations of 1 Bq/l or
lower in water samples, Fusion Science and Technology, 8:pp 516-519
Leonard I. Wassenaar, Liang-Feng Han, Thomas Schiefer, Gustav Kainz, Luis Araguas-Araguas,
Pradeep K. Aggarwal, (2018), A simple polymer electrolyte membrane system for enrichment of
low‐level tritium (3H) in environmental water samples. Journal Isotopes in Environmental and
Health Studies, 54(3):274-287, doi: 10.1080/10256016.2017
108
CERNAVODA TRITIUM REMOVAL FACILITY – CONNECTION TO FUSION R&D
Liviu Stefan, Anisia Bornea, Marius Zamfirache, Nicolae Bidica, Iuliana Stefan
Corresponding author: liviu.stefan@icsi.ro
ICSI has completed in 2015 the conceptual design of the Cernavoda Tritium
Removal Facility (CTRF). CTRF is located at CNE Cernavoda and is sized to process
40 kg/h heavy water from 2 CANDU reactors, with a detritiation factor of 100, over
40 years design life. CTRF removes tritium using liquid phase catalytic exchange
(LPCE) paired with cryogenic distillation (CD). The design of CTRF uses expertise
from ICSI (Pilot Plant for Tritium and Deuterium Separation) and from Canada
(Kinectrics), together with experience from Wolsung TRF project, research tritium
laboratories and industry. CTRF project is the most updated project for a TRF,
including last safety requirements for a tritium industrial facility, as specified by the
Romanian Regulator.
The objectives of CTRF will be to reduce operators’ internal doses and tritium
releases during refurbishment of units and normal operation, later to support
decommissioning of the reactors by reducing the tritiated heavy water quantities,
which otherwise will be radioactive waste.
Construction of CTRF in planned to start in 2020 and the detritiation of heavy
water from U1 reactor is scheduled to begin in 2026. After this date tritium stored
will become available to be used for fusion research and industrial facilities.
First phase of detritiation process is to reduce the moderator tritium content
from 65Ci/kg to 10Ci/kg, second phase to maintain the tritium concentration up to
10Ci/kg and third phase to use CTRF to reduce tritium content as low as possible
before decommissioning of the site.
The connection of CTRF with fusion R&D can be defined by two subjects. First
to be considered is an economical one, related to tritium sell for fusion activities.
Second one is represented by last technologies used for tritiated water treatment
(detritiation, tritium handling, software for process development, I&C, safety
approach).
More than that, ICSI Nuclear develop capabilities during the design of CTRF and
new opportunities for own R&D connected to fusion were investigated.
Since 2017 (2 years after CTRF design completion) new research strategy for ICSI
Nuclear was develop for R&D:
- Investigate new materials, tritium embrittlement and permeation
109
- Low tritium separation for environment purpose using combined

technologies (CECE, permeation)
- New types of catalyst with different shapes and material composition
- C-14 separation
- He-3 technologies
The paper will present the summary of technologies used for CTRF with
corresponding fusion application, a prediction of tritium production and an
overview of tritium quantities required by fusion and some considerations about
possible use of CTRF for supplying He-3, as a by-product of the detritiation process.
Future facilities in ICSI Nuclear for fusion application will be presented in
summary.
Keywords: Tritium, detritiation, TRF, fusion.
110
NON-STEADY-STATE MODELLING OF THE PERMEATION OF

MULTI-COMPONENT HYDROGEN ISOTOPES THROUGH METALS
Nicolae Bidica
Corresponding author: nicolae.bidica@icsi.ro
(Short Communication)
The control of tritium permeation through the structural materials and further
in the coolant of the fusion devices, in order to minimize tritium losses in the
environment, is one of the most important safety issues, because of the high
permeability of hydrogen isotopes through most structural metal structures of the
fusion reactors, and because tritium is radioactive. A brief review of the current
approaches to modelling the permeation of hydrogen isotopes through metals, and
about some models and experiments that had been carried out so far to estimate
the amount of tritium permeated in the key components of the fusion devices we
already pointed out in a previous work (Bidica, 2018). However, there are still
unresolved issues related to the modelling of synergistic isotope effects due to the
competition and the coupling of H, D, and T isotopes, when multi-isotope species
permeate through metals. These aspects are important because, for a reactor
based on deuterium-tritium fusion, both isotopes are fuel constituents and isotope
effects have to be taken into account. Thus, to further explore such issues, a
research project has been started at the Institute for Cryogenics and Isotopic
Technologies, ICSI Rm. Valcea. The aim of the project activities is to develop a
simulation tool that eventually will be benchmarked against the experimental
results, and this work presents the achievement of the first stage of this project in
progress.
The multi-isotope modelling which has been approached within several other
works so far, in connection with some experimental results (Kizu, Tanabe, 1998; Kizu,
Tanabe, 1999; Kizu et al., 2001; Zhang et al., 2017), were based on the kinetic theory of
the processes occurring at the interface between diatomic gases and metals, and
formulated for steady-state permeation, both in Surface Limited Regime (SLR, in which
the surface kinetic processes are prevailing over the fickian diffusion, which are
considered very fast) and DLR (Diffusion Limited Regime, in which the fickian diffusion
is prevailing). Also, these models were meant to explain co- or counter- permeation
experiments. Nevertheless, the same values, irrespective of the isotopic species, were
used for the kinetic coefficients of dissociation and recombination, respectively (i.e. no
intrinsic isotopic effect was considered).
111
The conclusions of these previous works were somewhat equivocal or contrary.

This is why, and also because no study describing non-steady-state models for
multi-isotope permeation was found in the literature, we decided to further
explore the co-existence of H , HD, and D species in the permeation processes by
a non-steady-state model based on the same kinetic theory of the surface
processes, as in previous models (i.e. dissociative-adsorption of the gas molecule
into the metal, and recombinative-desorption of the atoms dissolved in metal). A
pure Surface Limited Regime (SLR) of permeation has been considered into the
model, and thus expecting to better emphasize the effect of homo- and hetero-
isotope dissociations and recombinations on the effective permeation fluxes of
each isotope. The mass conservation law was applied for H and D atoms in the
membrane, in non-steady state and SLR, and the model was finally described by a
coupled system of two ordinary non-linear differential equations in and
, which are the momentary concentrations of H and D atoms, respectively,
into the metal bulk. We note that the mathematical model is invariant under a
change from co- to counter- permeation. The initial conditions were = 0 and
= 0, and to solve this Cauchy problem, a Runge–Kutta 4th-Order Method
was applied. The constant parameters of the system of ODE are: the thickness of
the membrane; the gas-phase partial pressures of the three species involved in
permeation (H , HD, and D ); the coefficients of dissociation and recombination,
corresponding to the three pairs HH, HD, and DD, respectively.
The simulations were performed by tacking different numerical values for
partial pressure of H , HD, and D , but always keeping the "effective" pressure of
deuterium ( = + ⁄2) constant at 0.1 Pa. Also, a mixture of only H and
D ( = 0), and pure D were considered. In the case of pure D2, an analytical
solution for could be found, and it was used to verify the numerical model.
Regarding the numerical values of the dissociation and recombination coefficients,
there are no data published in the literature for all those six parameters, for the
same material. So, basing on some theoretical approximations that give the
proportionality between these coefficients and the inverse of the square root of
the atomic mass (Esteban, 2002), a rule-of-thumb has been used to derive the
coefficients corresponding to HH and HD from those of DD, the latter being
calculated for a temperature of 500 K from the data published by Esteban (Esteban,
2002) for deuterium and Incoloy-800. We also performed simulations for the case
when the intrinsic isotope effect is not taking into account in dissociation and
recombination processes (i.e. the values of the dissociation/recombination
coefficients corresponding to HH and HD are equal to those corresponding to DD).
The simulations have shown the following main conclusions:
- The presence of hydrogen leads to a significant increase in the momentary
values of the permeated effective deuterium flux (relative to the case of
pure deuterium at the same „effective” pressure of deuterium) in the
transition period to the steady-state.
112
- If only H simultaneously permeates with deuterium (no matter if co‐ or

counter‐ current), then the permeated effective deuterium flux converges to
the same stationary value corresponding to the case of pure deuterium at
the same „effective” pressure of deuterium.
- If HD species is also present in the permeant mixture, then the stationary
values of the permeated effective deuterium flux will increase compared to
the case of pure deuterium at the same „effective” pressure of deuterium.
- These effects (by which hydrogen presence are influencing the permeated
deuterium flux) are more pronounced as the partial pressures of H and/or
HD species are higher.
- Deuterium concentration in metal falls down as hydrogen pressure is
getting higher.
- In the case when the intrinsic isotope effect is not taking into account in
dissociation and recombination processes, the permeated effective
deuterium flux converges to the same stationary value corresponding to the
case of pure deuterium at the same „effective” pressure of deuterium,
irrespective of the partial pressure values of HD.
References
Bidica N., (2018), Some issues in modelling of competing permeation of hydrogen isotopes through
metals ‐ A review, Progress of Cryogenics and Isotopes Separation, 21(1):5-15
Kizu K., Tanabe, T., (1998), Counter‐diffusion and counter‐permeation of deuterium and hydrogen
through palladium, Journal of Nuclear Materials, vol. 258-263, part 1, pp. 1133-1137
Kizu K., Tanabe, T., (1999), Deuterium permeation through metals under hydrogen counter flow,
Journal of Nuclear Materials, vol. 266-269, pp. 561-565
Kizu K. et al., (2001), Co‐permeation of deuterium and hydrogen through Pd, Journal of Nuclear
Materials, 289(3):291-302
Zhang H. et al., (2017), Characterization of Tritium Isotopic Permeation Through ARAA in Diffusion
Limited and Surface Limited Regimes, Fusion Science and Technology, 72(3):416-42
Esteban G. A., (2002), Diffusive transport parameters and surface rate constants of deuterium in
Incoloy 800, Journal of Nuclear Materials, 300:1-6
113
CAPABILITIES OF ICSI TRITIUM LABORATORY IN PROVIDING ACCURATE

ESTIMATION OF TRITIUM LEVEL IN THE UNCONTAMINATED ENVIRONMENT
Carmen Varlam, Irina Vagner, Ionut Faurescu, Denisa Faurescu
Corresponding author: carmen.varlam@icsi.ro
Tritium, the radioactive hydrogen isotope, can be found in the environment

as molecular tritium, tritiated water, or integrated in organic matter as organically
bound tritium (OBT). Before nuclear bomb tests of ‘60s, the tritium activity
concentration in rain was around 0.6 Bq/l (Clark, Fritz, 1997), and nowadays varies
around 1-2 Bq/l with occasionally peaks above (Varlam et al., 2016). If tritium
measurement of aqueous sample is a standardized procedure (ISO 9698, 2010),
tritium measurement of organic samples is not a routine procedure. Each
laboratory can develop its own procedure depending of the existing laboratory
equipment and of the wide range of tritium level found in the monitored area.
ICSI Tritium Laboratory is part of environmental monitoring program of
Experimental Cryogenic Pilot for Tritium and Deuterium Separation. Different types
of sample are frequently measured as water vapor, surface water, drinking water,
soil, wild vegetation, home grown vegetable, milk, meat. Quality assurance (QA)
system of Tritium Laboratory was evaluated and approved by the Romanian
Accreditation Body (RENAR), and the National Commission for Nuclear Activities
Control (CNCAN).
In order to obtain or maintain a quality assurance system in our Tritium
Laboratory is mandatory to participate at inter-laboratory exercises at least one
every three years. Three years is the period between QA system evaluations of the
Romanian Accreditation Body. Method validation (and verification) is one of the
important requirements of the QA system along with uncertainty budget of the
applied method. The easy way to evaluate and compare the laboratory
performance is to analyze reported results to intercomparison exercises. Results
obtained for proficiency tests during 2000-2017 period are used to verify and
validate measurements method of tritium specific activity in environmental
samples, focusing on the reported uncertainty of the method. If the linear
regression approach started to be used in biological routine analyzes (Meijer et al.,
2002), now Verrenzen et al. (Verrenzen et al., 2017) applied it for low level
radioactivity measurements of tritium and C-14. The long-term uncertainty method
114
(LTUM) was applied to Tritium Laboratory results in order to identify the constant
and proportional bias effects, random error and total error of the measurements.
facility PESTD.
References
Clark, I.D., Fritz, P., (1997), Environmental Isotopes in Hydrogeology. Lewis Publisher, 174-179
Varlam, C., Duliu, O.G., Faurescu, I., Vagner, I., Faurescu, D., (2016), Tritium time series in
precipitation of Rm. Valcea, Romania, Isotopes in Environmental and Health Studies, 52(4-
5):363-369
ISO 9698, (2010), Water Quality—determination of tritium activity concentration — liquid
scintillation counting method
Meijer P., de Maat M. P., Kluft C., Heverkate F., van Houwelingen H.C., (2002), Long‐term analytical
performance of hemostasis field methods as assessed by evaluation of the resultsof ah external
quality assessment program for antithrombin, Clin. Chem. 48(7):1011-1015
Verrenzen F., Vasile, M., Loots, H., Bruggeman M., (2017), Method validation and verification in
liquid scintillation counting using long‐term uncertainty (LTUM) an two decades of proficiency
test data, Journal of Radioanalitycal Nuclear Chemistry, 314:737-742
115
TRITIUM ACTIVITYON ON-LINE MONITORING IN THE PIK REACTOR WATER

COOLANTS BY USING FLOW-THROUGH RADIOMETER WILMA
Tatiana Voronina, Daria Tugusheva
NRC "Kurchatov Institute" ‐ PNPI, Gatchina, Leningrad region, Russia

Corresponding author: Tugusheva_DIU@pnpi.nrcki.ru
Currently, a high-flux research reactor PIK is under commissioning at NRC KI –

PNPI. The PIK reactor facility includes two heavy-water circuits. The rate of tritium
accumulation by the D (n, γ)T reaction in heavy-water reactors is equals to
2∙1011Bq/kg at year. This means that a significant part (up to 40%) of the reactor
staff radiation dose caused by tritium. Therefore, organization of tritium on-line
monitoring is important task.
Today, laboratory control of tritium at the PIK reactor is carried out by a
portable radiometer Triathler (HIDEX Oy). A technique for measuring tritium water
(Voronina et al., 2016) in the volumetric activity range (13.7∙103 - 22.2∙1010) Bq/kg
was developed at NRC KI – PNPI. It allows analyzing heavy water of the heavy-water
moderator (up to 7.4∙1010Bq/kg) and light water of the first circuit. However, off-
line control in laboratory has significant drawbacks: hand sampling, sample
preparation and recycling.
Therefore a permanent remote monitoring of tritium concentration should be
used in order to reduce laboratory staff radiation dose. For this purpose it is
decided to use a flow-through radiometer Wilma supplied by LabLogic (LabLogic …,
2014). Wilma is equipped with flow-through cells with a solid scintillator in addition
to standard liquid scintillator cells. A fine powder of CaF2 was used as the solid
scintillator. Solid scintillator will allow heavy water to be returned back to the
heavy-water circuit after measurement. Setup control and data processing will be
organized using a remote workstation. This will minimize time that personnel stay
in the radiation hazardous area of the PIK reactor.
Therefore, using a Wilma radiometer with a solid scintillator flow-through cells
solves two important tasks: manual tritium water sampling is not need; and return
heavy water after measurement back to the circuits. It is important, since heavy
water is an expensive special non-nuclear material.
In 2017, a certification test with determination of device basic metrological
characteristics was conducted at D.I. Mendeleyev Institute for Metrology VNIIM.
This led to including radiometer Wilma to the Register of measuring instruments of
Russian Federation with No. WIL / 0417/002.
Here presented the measurements made by Wilma with a 200 μl (0.2 ml) cell
with a solid scintillator. Actual volume of the cell (the volume of the sample) was 50
116
μl. Four calibrated tritium heavy water solutions were prepared for measurements.
Their activity was 4.07∙108 Bq/l; 4.29∙107 Bq/l; 4.44∙106 Bq/l; 4.44∙105Bq/l.
Chemically demineralized water was used as a background solution. A calibration
curve was obtained: Cm = 1.73∙105 ∙ I, where Cm is the sample tritium volume
activity (Bq / l), I is the radiometer count (imp/sec).
The parameters to have sufficient reproducibility and measurements accuracy
determined during the work were the next:
- filling time of the flow-through cell,
- sample discharge time,
- measurement time,
- washing time of the cell.
Wilma efficiency with a cell with a solid scintillator was 9%. Long-time
measurements of the same heavy water sample with an activity of 4.29 ∙ 107 Bq / l
show the stability of the flow radiometer. The obtained results indicate the
applicability of Wilma in the system of tritium on-line control.
Keywords: tritium, flow‐through radiometer, on‐line monitoring, the PIK reactor.
References
Voronina T.V., Romanova D.E., Tugusheva D. Yu, (2016), Determination of the volumetric activity of
tritium in the PIK reactor coolants by the liquid‐scintillation radiometry method, Main results of
scientific work 2015. Gatchina, pp. 106
«LabLogic Radiation Detection Online Water Quality Monitoring System», (2014), United States
Environmental Protection Agency, EPA/600/R-13/228
117
ON-LINE MONITORING OF THE DEUTERIUM CONCETRATION

AT HEAVY WATER OF REACTOR PIK MODERATOR
Tatiana Voronina, Daria Tugusheva
NRC "Kurchatov Institute" ‐ PNPI, Gatchina, Leningrad region, Russia

Corresponding author: voronina_tv@pnpi.nrcki.ru
This year, a high-flux research reactor PIK is under commissioning at NRC KI –

PNPI. Reactor PIK has unique parameters of neutron flux. Concentrated heavy water
D2O (> 99.8 %) is used as a moderator to reach 1.2∙1015n/cm2∙s. 1% decreasing of
deuterium concentration of heavy water reduces a neutron flux at 20% (Petrov, 1982).
Therefore permanent monitoring of deuterium concentration D2O is need.
The infrared spectrometry is convenient method for such control: it is not time
consuming, does not require high purity of D2O and allows for automatic permanent
measurements. Currently MIR Fourier spectrometer Tensor 37 (Bruker) is used for off-
line analysis of heavy water at the laboratory of reactor PIK. Measurement accuracy of
concentrated heavy water is 0.005 % and for wide range of D2O concentrations is 0.4 %
(Voronina, 2014]. The considerable drawbacks of the off-line control are hand sampling
and sample preparation, and the need for disposal of radioactive samples.
Therefore a permanent remote monitoring of deuterium concentration D2O
should be used after reactor PIK commissioning. For this purpose creation a flow-
through heavy water analyzer is carried out at NRC KI – PNPI. An obvious solution of
this task is to use the MIR Fourier spectrometer. This approach has its advantages:
- the most sensitive valence and deformation water vibrations are used for the
analysis,
- the analytical technique has already been worked out for laboratory MIR
spectrometer Tensor 37.
But this approach has significant drawbacks:
- "thin" cells (<1 mm) for the on-line measurements;
- a spectrometer would have to be placed directly into the technological circuit;
- there is no such analytical equipment suitable for operation in reactor conditions.
Therefore, it was decided to use NIR Fourier spectrometers. In this case, the
thickness of the flow cell can be increased to 5 mm. The NIR spectrometer has a
remote cell compartment. Such a device (MATRIX-F) is available from Bruker. It was
necessary to show that the NIR spectrometer (on the bands of overtones and
composite oscillations) could provide the necessary sensitivity of the analysis for
on-line monitoring of deuterium concentration D2O.
At first, the possibility of using a NIR spectrometry for accurate and reproducible
analysis of heavy water concentrations was shown by off-line spectrometer MPA. 18
D2O samples of various concentrations were prepared for the experiment. A sealed
118
flow circuit was assembled to avoid dilution of heavy water. Parameters and conditions
for measuring heavy water spectra were selected. As a result, two calibration models
were constructed: in a wide range of D2O concentrations (1-99 %) and for concentrated
heavy water (99.0-99.9 %). The measurement error of deuterium concentration was
not exceeding 0.003% in the range of the projected concentrations D2O. Such
measurement accuracy provides the necessary sensitivity of the analyzer for on-line
monitoring. A system for measuring the deuterium concentration of reactor PIK
moderator based on the NIR industrial spectrometer Matrix-F was proposed.
To continue the work, Bruker transferred industrial spectrometer MATRIX-F, an
industrial flow cell made of stainless steel (2 mm thick) and a fiber optic cable for the
test operation in PNPI. A prototype analyzer of the deuterium concentration D2O was
created in reactor PIK laboratory. 70 samples of heavy water were prepared for this
work. Figure 1 shows the spectra of heavy water, obtained on this prototype analyzer.
Six calibration models were constructed for different D2O concentration ranges. As a
result, was shown that the sensitivity of the industrial NIR spectrometer is sufficient for
on-line monitoring of deuterium concentration.
At present, the equipment has been purchased. Commissioning and calibration of
analyzers are planned before their installation into the technological circuit.
Figure 1. The spectra of heavy water calibration

samples in a wide concentration range (0.015 -
99.900) %, here ν is the wave number, D is the
optical density.
Keywords: deuterium, NIR spectrometer, on‐line monitoring, the PIK reactor.
References
Petrov Yu. V., (1982), Choice of reactor parameters for physical researches // LNPI preprint, pp. 62
Voronina T. V., Control organization of the heavy water isotope composition on the PIK reactor by IR
spectrometry. Materials of the VI STC "Problems and prospects of chemical and radiochemical
control development in nuclear power engineering"
119
ELECTROCHEMICAL INVESTIGATION OF Pd/CNT COMPOSITE FOR HYDROGEN

ISOTOPE IDENTIFICATION
Ana-Maria Iordache1, Stefan-Marian Iordache1, Eusebiu Ilarian Ionete2,

Ioan Stamatin1
1
University of Bucharest, Faculty of Physics, 3Nano‐SAE Research Center, 405 Atomistilor, P.O. Box
MG‐38, 077125, Magurele, Romania
2
Valcea, Uzinei Street no. 4, PO 7 Raureni, Rm. Valcea, 240050, Valcea, Romania
Corresponding author: anaducu@3nanosae.org
The field of hydrogen sensors is widely studied due to recent developments

related to hydrogen technologies, particularly in fuel cells and hydrogen storage,
but also in production and purification systems (Gupta et al., 2014; Chung et al.,
2012). Oxide semiconductors are the commonly used material for hydrogen
assessment, but the highest sensibility and selectivity is shown by palladium and
Pd-based composites (Oleksenko et al., 2014; Yoon et al., 2013; Lange et al., 2011).
Electrochemical sensors based on Pd nanoparticles have been used for the
detection and quantification of several rich in hydrogen analytical species, like
desipramine (Cincotto, et al., 2017) and hydrazine (Zhang, et al., 2017). However,
literature about electrochemical speciation of hydrogen isotopes in aqueous
solution is scarce (Schldiner, et al., 1958), (Lasser, et al., 1983). Since a large
attention is given to the identification of hydrogen isotopes in solutions (for
security in nuclear power plants, remote temperature sensing in underwater
volcanoes or geochemical analysis of rocks), more research is nedeed to investigate
the electrochemical behavior of Pd-Hydrogen isotopes.
In the present work, Pd-modified CNTs were used for the identification of two
hydrogen isotopes – Deuterium and Protium, in aqueous solutions. Pd nanoparticles
are deposited on MWCNT-OH using the micellization process. A modified electrode
was prepared by dropcasting the Pd/CNTs onto a screen printed electrode (SPE). The
Pd/CNT electrode was characterized using Raman spectroscopy, AFM microscopy and
cyclic voltammetry. The electrochemical characterization of the composite showed a
diffusion-controlled transfer process for both isotopes, with a faster reaction rate for
Protium isotope compared to Deuterium and a saturation process, which appeared at
high concentrations. An unexpected property was the ratio between
protons/electrons, which was calculated at m/n=1.5.
Keywords: Palladium, CNTs, electrochemistry, hydrogen isotopes
120
Acknowledgments (if applicable): This work was supported by a grant of the

Ministry of National Education and Scientific Research, RDI Program for Space
Technology and Advance Research‐STAR, project no.584 (143/2017). The authors
wish to express their gratitude to Dr. Diana Costinel, for preparing the 2H water
samples.
References
Chung M.G. et al., (2012), Flexible hydrogen sensors using graphene with palladium nanoparticle
decoration. Sensors and Actuators B: Chemical. 169:387-392.
Cincotto F. H. et al., (2017), Electrochemical sensor based on reduced graphene oxide modified with
palladium nanoparticles for determination of desipramine in urine samples. Sensors and
Actuators B: Chemical 239:488-493
Gupta D. et al., (2014), A low temperature hydrogen sensor based on palladium nanoparticles.
Sensors and aActuators B: Chemical. 196:215-222
Lange U. et al., (2011), Hydrogen sensor based on a graphene‐palladium nanocomposite.
Electrochimica Acta. 56:3707-3712
Lasser R. and Klatt K.-H., (1983), Sollubility of hydrogen isotopes in palladium, Physical Review B. 2,
28:748-758
Oleksenko L.P. et al., (2014), Study of influence of palladium additives in nanosized tin dioxide on
sensitivity of adsorption semiconductor sensors to hydrogen. Sensors and Actuators B:
Chemical. 196:298-305
Schldiner S. and Hoare J.P., (1958), Mechanism of hydrogen producing reactions on palladium.
Journal of the Electrochemical Society, New-York: [s.n.], pp. 278-284
Yoon J.-H. and Kim B.-J., Kim, J.-S., 2013), Sensing properties for a microhydrogen sensor with
modified palladium film, Sensors and Actuators B: Chemical., 187:540-545
Zhang Y. et al., (2017), A sensitive and selective amperometric hydrazine sensors based on palladium
nanoparticles loaded on cobalt‐wrapped nitrogen‐doped carbon nanotubes. Journal of
Electroanalytical Chemistry, 801:215-223
121
THE USAGE OF THE POLYMERIC GEL "DECONGEL" FOR THE RADIOCHEMICAL

DECONTAMINATION
Diana Chiper, Cristian Postolache, Viorel Fugaru
“Horia Hulubei” National Institute for Physics and Nuclear Engineering, Radioisotopes and Radiation
Metrology Department, Magurele – Ilfov Romania,
Corresponding author’s: dchiper@nipne.ro, cristip@nipne.ro, vfugaru@nipne.ro
We conducted an experiment for radiochemical decontamination of different

types of surfaces, equipment or technological spaces that can be encountered in a
radiochemistry laboratory. The purpose was to produce as little waste as possible, but
also to develop better protocols for radiological characterization and decontamination
in order to be able to take more suitable security mesures to decrese the risks in the
radiological field.
In the present paper there are presented data related to materials used in
radiochemistry laboratories when there were used tritium, Ir-192 or other
radioisotopes.
For the results shown in this paper there was used as decontaminant the
DeconGel® because it had several important advantages compared to other classical
ways of decontamination. Firstly, very important to mention is the fact that DeconGel
is non-polluting (environmentally friendly). It also presents a financial advantage
reducing the costs of expoitation, operating and storage, because it is easily handled
and applied to all kinds of surfaces, both vertical and horizontal as well as being
removed by only peeling. DeconGel is a polymeric hyrogel. Its working principle is
based on forming, at nano- or molecular level, more complexe chemical compounds
with the materials desired to be removed (dangerous) by encapsulating a wide
spectrum of chemical compouonds or radioisotopes using the method of binding by
traping. For the experiments realised we used three types of gels: DeconGel type 1102,
type 1108 and type 1128, which were procurated from "CBI Polymers", U.S.A.
The prelevating factor was determined by controlled contamination with
radioactive solutions followed by the step of prelevating the non-fixed contamination.
The surfaces of the chosen materials for the study were controlled contaminated or
there were used contaminated surfaces in hot cells. The working procedure is
represented by the complete coverage of the contaminated surfaces with a relatively
uniform layer of Decongel (all the types of DeconGel mentioned before were used,
each with a different type of contamination according to their properties). The
determination of the prelevating factor was made by reporting the activity originally
taken to the total prelevated activity (initial and repeated). The experimental results
122
were correlated with the conventional surface activity thus determining the
decontamination factors for each type of surface. Depending on the contamination
type and the contaminated radioisotope there may be necessary more than one
application of the gel.
After correlating the conventional surface activity with the experimental results it
was possible to determine the decontamination factors for each used surface.
The conclusions drawn from his experiment were that for the fixed radioactive
contamination with tritium, the polymeric gels Decongel 1102 and Decongel 1108 had
a decontamination factor of over 90% (even though the classical methods were
randered useless) and that it might be necessary to repeat the application of the gel
more than one time for obtaining the desired result in the case of some contamination
types or depending on the contaminated radioisotope that was used.
The device used to insert Ir-192 radioactive disks into the source capsule is
usually highly contaminated and requires repeated decontamination after each
batch of iridium sources. The gamma dose equivalent of the loading device was
mesured, the decontaminant gel was applied by brush (Fig. 2) and after 48h the gel
was peeled. The new rate was mesured again and a new layer of decontaminant gel
was applied. After the drying and peeling of the gel, the dose rate was reduced
almost 10 times. The peeling gel was analyzed using gamma spectrometry and it
put in evidence the presence of the radionuclides Ir-192. In conclusion, for better
decontamination of the device more layers of the Decongel 1108 decontamination
gel were needed. The decontamination time is still greatly reduced. The
decontamination factor for the polimerizable gel Decongel 1108 was over 90%,
even for fixed radioactive contamination.
The usage of DeconGel is safe because it creats a protective barrier between the
contaminant and human, being dust inhibitor. It does not require the usage of water so
the risk of further external contamination does not exist. This polymeric gel has a lot of
advantages: The decontamination factor is really high (90% - 100%), it is not corossive,
nor inflammable, it is biodegradable and it can e applied to both critical and hard-to-
acces infrastructures. One of the biggest advantage is the fact that it can used by
anybody, their profession or place of work being unrelated and they require no
qualification. This results in a decrease of the exposure and implicated work force up to
70%. Though it has to be noted that, as all the cleaning products, it can cause mild to
moderate skin irritation.
123
Figure 1. How to action the polymeric Figure 2. Charging device for Ir-92 sources
hydrogel Decongel after the decontaminating gel was applied
(source: https://www.slideshare.net
/Franklinss/decongel-overview)
Figure 3. – How to use the polymeric hydrogel Decongel

(sources: [pdf] DeconGel Strippable Decontamination Gel Manual - VWR International
https://us.vwr.com/assetsvc/asset/en_US/id/7037233/contents and
https://www.thomassci.com/EUGDPRStatement.htm)
Keywords: tritium, radiochemical decontamination, DeconGel, prelevating factor
Acknowledgments: This research is supported by the Nucleu Romanian National

Programme
References
www.decongel.com
https://en.wikipedia.org/wiki/DeconGel
https://www.firstlinetech.com/product/decongel‐1108
https://www.youtube.com/watch?v=LV3vCfPCoA0
https://www.crunchbase.com/organization/decongel
[PDF] CBI Polymers DeconGel® 1101 and 1108 for ... - Cfpub.epa.gov…, https://cfpub.epa.gov/si/si_
public_file_download.cfm?p_download_id=503590
EPA 600-R-11-084. June 2011. Technology Evaluation Report. CBI Polymers. DeconGel® 1101 and
1108 for. Radiological Decontamination ...
DeconGel | Galen Enterprise LLC, https://www.environmental-expert.com/products/decongel-
model-1102-gel-gel-for-oil-and-grease-clean-up-99744
https://www.slideshare.net/Franklinss/decongel-overview
[pdf] DeconGel Strippable Decontamination Gel Manual - VWR International
https://us.vwr.com/assetsvc/asset/en_US/id/7037233/contents
https://www.thomassci.com
124
TITANIUM HYDRIDES WITH CONTROLLED H/T RATIO FOR

AMS FACILITIES CALIBRATION
Fugaru Viorel, Postolache Cristian, Enachescu Mihaela, Stan-Sion Catalin, Antohe

Andrei, Tuta Catalin Stelian, Chiper Diana, Bubueanu George
Reactorului Street, Magurele, Ilfov, Romania
Annual tritium exposures can be determined for long time periods by analysis of
radioactive concentration in tree rings near nuclear facilities which can release tritium
in environment. Since the mass of analyzed samples is in milligrams order, the usual
method such as Liquid Scintillation Counting (LSC) cannot be applied. Recommended
method is: total combustion of the milligram sized samples, resulted HTO reduction at
tritiated hydrogen (HT) with identical H/T ratio, quantitative absorption in titanium
powder and H/T ratio determining using Accelerator Mass Spectrometry method
(AMS). For AMS detector calibration, titanium hydride standards with controlled H/T
isotope ratio are required.
Figure 1. Schematic view of tritiated hydrogen generation facility

DV- Dewar vessel; HTOA-Tritiated water ampoule; PTFEC-PTFE tube connection; HVV – HI-VAC valve,
PTFE, 90 Deg., W/Tip O-R ING, 0-8 mm bore range, 13 mm stem O.D: QT-Quartz tube, MgB-Mg
turning (Grignard grade) bed for total reduction of HTO; TF- Tubular furnace; CTF-Tubular furnace
controller; VG-Hi Vacuum Gauge; HTSV- Tritiated hydrogen storage vessel; HVP-Hivacuum pump
In this paper, the method for obtaining of titanium hydride standards with
different H/T isotopic ratio are described.
The titanium hydrides standards have been achieved by:
- Obtaining of HTO standards using Triple to Double Coincidence Ratio
primary national standard
125
- Designing and building of the HT generator constituted from: ampoule for

HTO standards, Mg column, tubular furnace, liquid nitrogen trap, flask for HT
storage, high vacuum valves and turbo-molecular vacuum pump
- Synthesis of HT standards
- Obtaining of titanium hydrides with controlled H/T isotopic ratio using
Tritium Manifold equipment.
Figure 2. Schematic view of tritiated Titanium hydride synthesis facility.

TF- Tubular furnace; CTF-Tubular furnace controller; QT-Quartz tube: QW –Quartz wool;
Ti-Titanium powder; PTFEC-PTFE tube connection; HVV – HI-VAC valve, PTFE, 90 Deg., W/Tip O-R
ING, 0-8 mm bore range, 13 mm stem O.D; VG-HiVacuum Gauge;
HTSV- Tritiated hydrogen storage vessel; HVP-Hivacuum pump
The Titanium hydride standards were used in calibration of AMS facility from
NIPNE Magurele Romania.
Keywords: Tritium, total combustion, isotopic ratio, metal tritides, AMS

from Executive Unit for Financing Education Higher Research
126
DYNAMIC SIMULATION OF A MULTICOMPONENT DISTILLATION

COLUMN FOR D-T SEPARATION
Alina Niculescu, Toma Constantin, George Ana
Vâlcea, Code 240050, Rm. Vâlcea, Uzinei Street no. 4, PO Box Râureni 7, Vâlcea, Romania
Corresponding author: alina.niculescu@icsi.ro
Cryogenic distillation (CD) process is being employed, among other

applications, in tritium separation technologies and in case of ITER is one of the key
processes in the fuel cycle. The ITER Isotope Separation System has to process by
cryogenic distillation various mixtures of H-D-T depending from the various torus
operation scenarios.
Cryogenic distillation has also been employed to separate and concentrate
tritium in a CANDU water detritiation system. Dynamic simulation of a distillation
column gives information on the behavior of the system when fluctuations in flow
feed or feed concentration may occur, with direct impact on the design of the
control system.
The objective of this work is to present a mathematical model for dynamic
simulation of a multicomponent distillation column for D-T separation. The
procedure of dynamic simulation is based on Lewis – Matheson method and
tridiagonal matrix method for design, respectively simulate a multicomponent
distillation column for D-T separation; the model is used to determinate the time
required to reach steady state into the entire distillation column, after the
occurrence of a process perturbation (e.g. modification of a feed flow, feed
concentrations).
Keywords: hydrogen isotopes, cryogenic distillation, dynamic simulation.
127
THE AREA MEASUREMENTS IN THE TRITIUM LABORATORY

WITHIN NIPNE MAGURELE
Fugaru Viorel, Postolache Cristian, Bubueanu George,

Tuta Catalin Stelian, Chiper Diana
Reactorului Street, Magurele, Ilfov, Romania
The tritium laboratory (TRITIULAB) from Horia Hulubei National Institute for
Physics and Nuclear Engineering, Magurele has been commissioned as part of
Radioisotope Research and Production Centre in 1976. At first, tritium laboratory
was designed for synthesis of labelled compounds. Later, the activities were
extended with tritium sealed sources obtaining, tritium detection and tritium
wastes management researches. In 2007-2014 period, the TRITIULAB was extended
and refurbished with maintaining the main research directions.
In this paper are showed the results of the radiological measurements in
TRITIULAB controlled area and adjacent zone for last three years.
The radiological characterization was performed by determination of removed
and fixed tritium contamination for the following surfaces; pavement, walls,
windows, radiochemical tables, radionuclide fume cupboards, glove boxes, sinks.
The determination of removable surface contamination has been carried out
by:
- Scanning of the radioactive contamination using tritium surface monitor LB
1230UMo with LB 1230 open window gas flow proportional counter detector,
Berthold type and
- Smear test using extruded polystyrene smears followed by the measurement of
removed activity at Liquid Scintillation Counter (LSC).
The air contamination determination was performed using tritium gas monitors
400SBDγC Overhoff, and CMS-H35L Lab Impex Systems types.
Keywords: Tritium, radiological characterisation, removable surface contamination,

radioprotection.

128
ADVANCED TECHNOLOGY FOR TRITIATED WATER WASTE PROCESSING BASED ON

THE CECE SEPARATION PROCESS
Anisia Mihaela Bornea1, Marius Zamfirache, George Ana, Alina Niculescu, Liviu
Stefan, Toma Constantin, Ovidiu Balteanu, Ciprian Bucur
Corresponding author: anisia.bornea@icsi.ro
The development of technologies used for the processing of low and highly
concentrated radioactive waste is a priority objective both in our country and
abroad.
The researches presented in this paper were promoted in order to develop an
advanced technology, followed by the construction of a multipurpose isotopic
separation plant. This installation could be used further in the case of nuclear reactors
which generate low concentrated tritiated water waste, in order to increase the
deuterium and tritium recovery rate (Bornea et al., 2018).
To demonstrate this technology at the laboratory level, the research will be
carried out in two stages. In the first stage the research is carried out in order to
develop the liquid isotope concentrator module (CECE). In the second stage, a gas
processing system will be developed by cryogenic permeation/distillation isotope
separation process, coupled to the CECE module, with the aim of concentrating
deuterium/tritium isotopes (in gas) at higher concentration for further extraction and
recovery.
The paper presents the early researches for the development of the tritiated
water waste processing module using the CECE isotopic separation technology.
A brief description of the CECE process is presented. For a better understanding of
the isotopic separation process is presented the mathematical model that contains the
interphase isotopic transfer equations.
It defines a tritium decontamination factor that represents the ratio between
the LPCE gas feed concentration and the gas concentration leaving the LPCE
column. The decontamination factor depends mainly on the efficiency of the LPCE
process under the operating conditions.
Another parameter to be watched is tritium/deuterium enrichment factor in
water and represents the ratio between the tritium concentration in water in the
LPCE column boiler and the tritium concentration in the CECE module feed water.
This parameter depends on the performance of the catalytic package and the molar
ratio between the LPCE column water and gas flow rate.
129
The gas flow rate is determined by the capacity of the electrolyzer and it is
considered to use the PEM electrolyzer in the PESTD, with the hydrogen flow being
2 Nm3/h. The water flow depends on the feed mode (directly in the electrolyzer or
on the column at certain calculated points). The CECE module will be designed and
built to allow both variants.
The paper presents the conceptual scheme of the CECE isotope separation
plant and a sizing of the main technological equipments.
Keywords: Tritium, Detritiation, Combined Electrolysis and Catalytic Exchange
Acknowledgments: This work was carried out by National Program Nucleu,

developed with the support of MCI, project no. PN18 12 02 02.
References
Anisia Bornea, Marius Zamfirache, Nicolae Bidica, 2018, Proposal for Combined Electrolysis and
Catalytic Exchange System (CECE) Development within the Pilot Plant FUSION10066, Fusion
Engineering and Design, https://doi.org/10.1016/j.fusengdes.2018.03.046
130
ORDERED PACKING DEDICATED TO DEUTERIUM DEPLETED WATER PRODUCTION
Nadia Paun1, Gheorghe Titescu1, Ioan Stefanescu1, Arian Armeanu1, Constantin

Ciortea1, Cristian Mladin2
1
2
Mecro System SRL, Timisoara Street 100P, Bucuresti, Romania
Corresponding author: nadia.paun@icsi.ro
The researches and experiments in the field of production and exploitation of

deuterium depleted water (DDW) were developed by ICSI Rm. Valcea during 2000-
2007. The activities resulted in developing a technology protected by an international
patent "Process and plant for obtaining biologically active water depleted of
deuterium-from natural water or water from heavy water manufacture". Product
valorisation was carried out in collaboration with recognized institutes from Romania,
obtaining favourable results regarding the bioactive properties of DDW.
The objective of this study was to develop an ordered packing, dedicated to
deuterium depleted water obtaining, using food stainless steel as the raw material.
This ordered packing can be used in the distillation columns of deuterium depleted
water facilities. The research consisted in laboratory tests on material selection, tests
on the materials surface wettability, elaboration of the geometric structure of the
ordered packing (Φ =100 mm), ordered packing design and isotopes separation
efficiency testing.
The final result of the study was the development of a new prototype of an
ordered packing made of food stainless steel. Since the raw material is very resistant to
chemical agents, the prepared packing can also be used in purification installations or
in industrial distillation/ separation chemical installations where corrosive fluids are
processed. Another area of use is cryogenic distillation plants, detritiation plants, which
can be equipped with such ordered packing.
Keywords: deuterium depleted water, food stainless steel, isotopes separation,

ordered packing.
Acknowledgments: The work has been funded by the Romanian Ministry of

Scientific Research and Innovation, UEFISCDI, Innovation checks PN‐III‐CERC‐CO‐CI‐
2017, Contract No. 5CI/2017.
131
REMARKS ON THE THERMAL PROPERTIES OF ROCKS AND THE TREATMENT OF

GEOTHERMAL WATERS
Laurentiu Asimopolos1, Natalia-Silvia Asimopolos1, Violeta-Carolina Niculescu2

1
2
Corresponding author: laurentiu.asimopolos@igr.ro
Geothermal resources can be considered renewable on the time-scales of

technological/societal systems and do not require the geological times of fossil fuel
reserves such as coal, oil, and gas (Rybach, 2003).
A geothermal research involves knowing the way heat is transferred to the studied
environment. There are three main processes of heat transfer (Kappelmayer and
Haenel, 1974): through conduction, by convection and by radiation.
Heat transfer by conduction takes place only in solid media by molecular
interaction. It is the main mechanism for transmitting heat to Earth's crust and
most importantly in geothermal research of wells.
Convective heat transfer is associated with the free movement of fluids
between two environments at different temperatures. It becomes important in
geothermal areas, in particular, in volcanic zones and in areas with active
groundwater circulation. The convection heat transfer mechanism has to be taken
into account in the geothermal research carried out in the drilling because it has a
significant weight in the modification of the natural thermal regime of the
geological formations traversed.
Heat transfer by radiation takes place on the Earth's surface, where
temperatures are conditioned by heat exchange between the Earth and the Sun,
and on the other hand in very hot rocks. For temperatures encountered at the
usual depths of wells, including deep wells, the radiation transfer is negligible. The
geothermal waters in our country are geothermal waters cantonized in
sedimentary formations, characterized by low pressures. They contain mainly
bicarbonates, sulphates, chlorides, hydrocarbons in the free and dissolved state.
The geothermal waters are subject to a treatment process in order to be exploited,
by which gas separation and eventually their valorization and reduction of the salt
crust formation capacity are achieved. In most countries, geothermal waters are
exploited in volcanic regions or seismic phenomena and are therefore rich in H2S
and SO2.
132
For water from sedimentary formations, various techniques are used, among
which the introduction of inhibitory substances to reduce deposits (sodium
polyphosphate), modification of the pH index to obtain neutral waters (by the
addition of HCl), ultrasonic treatment, magnetic flux treatment, etc.
Geopressured deposits are water tanks covered with waterproof coating,
subject to high pressures. The water contained in these tanks has a low salinity and
is saturated with natural gas. These systems have a wide spread and can be
exploited for both thermal energy and hydraulic power engineering.
Keywords: geothermal resources, renewable energy, conduction, convection, radiation.

of Research and Innovation, CCCDI – UEFISCDI, project Nr.16PCCDI/2018:
Institutional capacities and services for research, monitoring and forecasting of risks
in extra‐atmospheric space”, within PNCDIII.
References
Kappelmayer O., Haenel R., (1974), Geothermics with Special Reference to Application, Gebrüder
Borntrager, Berlin-Stuttgart, ISBN: 9783443130060
L. Rybach, (2003), Geothermal energy: sustainability and the environment. Geothermics, 32(4-
6):463-470
133
THEORETICAL AND EXPERIMENTAL APPROACH TO DESTABILIZATION METHODS

FOR IMPROVEMENT OF HYDROGEN SORPTION KINETICS IN Mg BASED SYSTEMS
Jasmina Grbović Novaković, Sandra Kurko, Sanja Milošević Govedarović, Tijana

Pantić, Bojana Paskaš Mamula, Mirjana Medić, Nikola Novaković
University of Belgrade, Vinča Institute of Nuclear Sciences, CONVINCE –Centre of Excellence for
Renewable and Hydrogen Energy, POB522, Belgrade 11000, Serbia
Corresponding author: jasnagn@gmail,com, jasnag@vin.bg.ac.rs
Magnesium hydride (MgH2) is considered as one of the most promising candidates

for solid state hydrogen storage due to its high theoretical hydrogen capacity (7.6
wt.%), good reversibility, and relatively low cost. MgH2 is also considered for thermal
energy storage applications. However, several factors have hindered its application: (1)
the thermodynamic stability of MgH2 leads to its dehydrogenation temperature being
as high as 350−400°C; (2) the kinec rates of both dehydrogenaon and hydrogenaon
reactions of Mg are usually poor and require high temperature conditions. The H
storage properties can be tailored by addition of small amount of transition metals (Ti,
V, Fe, Co, Ni, Cu and Pd), transition metal oxides (TiO2, CeO2, V2O5, WO3), halides (FeF3)
or borides (TiB2). We have used both, theoretical and experimental approach to study
reaction mechanism in powder and thin films material (Kurko, 2013; Montone, 2006;
Paskas Mamula, 2014).
Processes taking place during hydrogen desorption from Mg/MgH2 thin films
upon modification either by TiO2 capped layer or by ion irradiation were
investigated. Irradiation was used to produce controlled quantity of point defects
with well-defined depth distribution. It was shown that the size, shape, and
concentration of Mg nuclei formed during hydrogen desorption from MgH2 thin
films depend on the characteristics and distribution of the induced defects. In non-
irradiated samples the shape of Mg nuclei is spherical, while in irradiated samples it
is highly irregular. Variations in sample colour were observed during hydrogen
desorption and before the creation of Mg nuclei. DFT calculations showed that the
observed variations in the optical properties of samples can be explained by
changes in MgH2 electronic structure and the appearance of an H-vacancy band
within the MgH2 energy gap. On the other hand, the modification induced by
capping with TiO2 does not affect the shape of nuclei. The shape is rather spherical
and do not depend on film thickness. The size and concentration of nuclei is related
to the thickness of films. Both modifications (addition of additives or point defects)
lead to reduction of temperature onset for desorption and improved kinetics.
134
On the other hand it is well known that energetic ball milling of hydrides
substantially refines their particle size and forms nanometric grains within the
particles. In the mechanical (ball) milling process there is always a connected
reduction of the powder particle size which accompanies the reduction of grain size
of the phases residing within the particle. Those changes has an effect on
desorption properties of hydrides. This lecture will discuss in details those effects.
Keywords: hydrogen storage, magnesium based hydrides, DFT theory, ball milling,
ion irradiation, kinetics.
Acknowledgments The work is supported by Ministry of Education, Science and

Technological development under grant III45012 and III45003
References
Kurko S. et al., (2013), Int J Hydrogen Energy, 38(27):12199-12206
Montone A., et al., (2006), Mat.Sci Forum 518:79-84
Paskas Mamula B. et al., (2014), Int. J. Hydrogen Energy, 39(11):5874-5887
135
BIOGAS UP-GRADING TO SYNGAS CATALYZED BY ALUMINA

SUPPORTED NICKEL CATALYSTS
Mihaela D. Lazar, Monica Dan, Maria Mihet

National Institute for Research and Development on Isotopic and Molecular Technologies – INCDTIM,
67‐103 Donat Street, Cluj Napoca, Romania
Corresponding author: diana.lazar@itim‐cj.ro
The biogas is produced from vegetal and animal wastes by anaerobic

fermentation. After purification, its composition consists mainly in methane,
carbon dioxide and water vapors. Nowadays its main utilization is to be burned in
order to produce electricity and/or heat. One possible way to add more economic
value to the biogas would be its transformation in syngas, by reacting its
components in dry reforming of methane catalytic process. The main drawbacks of
this reaction are: (i) the carbon formation, especially on nickel-based catalysts
which leads to catalyst deactivation, and (ii) the low H2:CO ratio in the resulting
gasses which is not useful for further Fisher-Tropsch processes to obtain synthetic
fuels. In this work two ways to diminish the carbon formation and to increase
H2:CO ratio the will be employed:
(i) the addition of water in the reaction system resulting the so-called
combined steam and dry reforming of methane process (CSDRM);
(ii) the new catalysts design by confining the Ni nanoparticles in the pores of
alumina using a simple, accessible and template free preparation method obtained
by developing an already published method [Bao 2015].
Two catalysts were prepared: (i) Ni/Al2O3 BM having multi-modal pore size
structure and prepared by the modified co-precipitation method in different
reaction conditions, and (ii) Ni/Al2O3 DS prepared by double solvent impregnation
of mesoporous alumina obtained by the same preparation method.
The method developed for the preparation of Ni/Al2O3 BM consists in co-
precipitation of Al2O3 and NiO using NaOH as precipitating agent, followed by
suspension reflux for 24h. After Ni deposition all catalysts were calcined in Ar at
450°C and then reduced in H2 at 650°C. The low calcination temperature was
selected after testing several temperatures, in order to avoid the formation of Ni
aluminate species which are hardly reducible. The reduction temperature was
estimated from H2-TPR analysis.
All catalysts were subjected to the following characterization methods: X-Ray
diffraction (XRD) – to establish the crystallinity of the support and the size of Ni
crystallites; N2 adsorption-desorption isotherms – to calculate the surface area
using BET method and the porosity parameters using Dollimore-Heal model;
Temperature Programmed Reduction (TPR) – to estimate the strength of the metal-
support interaction; Electronic Microscopy (STEM) – to analyze the size and
dispersion of nickel nanoparticles; Temperature Programmed Desorption (H2-TPD)
to estimate the type and strength of catalytic active sites.
136
The results of catalysts characterization are presented in Table 1.

Table 1. The structural properties of Ni/Al2O3 materials
Catalyst St (m2/g) Rm (nm) DNi (nm) Tred (°C)
Ni/Al2O3 BM 271 4; 8; up to 60 5 553
Ni/Al2O3 DS 243 9 - 723; 800
St – total surface area; Rm – medium pores radius; DNi – nickel crystallites size (from XRD); Tred
– temperature reduction peak in H2-TPR
The characterization results showed that for Ni/Al2O3 BM the multi-modal pore
structure was achieved in the mesoporous range (pore size is 4 nm and 8 nm)
accompanied by a series of larger pores up to macropores. The temperature of the
H2-TPR peak, 553°C, indicates the existence of medium to strong interaction
between the Ni and the alumina. For Ni/Al2O3 DS catalyst, the Ni confinement in
alumina mesopores is suggested by the high temperature value and broad shape of
the reduction peak in the H2-TPR spectra (750-800°C) attributed to the intimate
contact of small NiO nanoparticles with alumina pores and not to the presence of
Ni aluminate spinel, which are not formed at such low reduction temperatures as
those used in this work. The absence or the very low intensity of Ni reflexions in the
XRD spectra are also attributed to the very small size and high dispersion of Ni
nanoparticles, re-enforcing the idea of nanoparticles confinement in the pores. The
surface area of the catalysts decreases in the order Ni/Al2O3 BM (271 m2/g) >
Ni/Al2O3 DS (243 m2/g). The higher surface area of Ni/Al2O3 BM is related to the
lower mezopores existent in its structure.
The catalytic performances of Ni/Al2O3 BM and Ni/Al2O3 DS were tested in
CSDRM
2CH4 + CO2 + H2O → 3CO + 5H2 (1)
in the following conditions: tubular reactor, atmospheric pressure, reaction
temperatures 600-750°C, reagents ratio CH4 : CO2 : H2O : Ar = 1 : 0.48 : 1.2 : 8.4.
The obtained results proved that the Ni/Al2O3 BM catalysts show superior
performances than Ni/Al2O3 DS catalysts. The very small NiNPs existent in the
structure of Ni/Al2O3 DS are oxidized in the reaction environment, the resulted NiO
presenting no catalytic activity for the desired process. The results obtained using
Ni/Al2O3 BM are very encouraging, CH4 conversion increasing from 63% at 600°C to
almost 100% at 750°C. The H2:CO ratio is around 2.8 at 600°C and 2.5 at 750°C. The
catalyst stability was tested for 24h time on stream, with no activity loss in this
period.
Keywords: biogas; syngas; combined steam and dry reforming; Ni catalysts.
Acknowledgments: We thank Romanian Ministry of Research and Innovation, CNCS ‐

UEFISCDI, for funding this research under project number PN‐III‐P2‐2.1‐PED‐2016‐0349,
within PNCDI III
References
Zhenghong Bao, Yongwu Lu, Jun Han, Yebo Li, Fei Yu, (2015), Applied Catalysis A: General, 491:116-
126
137
THE INTERACTION OF HYDROGEN WITH NANOSIZED Pd CLUSTERS
Abdelmalek Malouche1, Oana Grad2, Dan Lupu2, Claudia Zlotea1, Gabriela Blanita2
1
Institut de Chimie et des Matériaux Paris‐Est, CNRS‐UPEC, 2‐8 rue Henri Dunant, Thiais, 94320 France
2
National Institute for Research and Development on Isotopic and Molecular Technologies, 67‐103
Donat Street, Cluj Napoca, Romania
Corresponding author: Gabriela.Blanita@itim‐cj.ro
Sizing of metals at nano level become rapidly a promising route used to design
new materials with applications in fields like energy storage, catalysis, sensing etc.
A way to obtain and stabilize metal nanoparticles against coalescence and the
subsequent formation of large aggregates with bulk-like behaviour is to use
nanoporous scaffolds like metal-organic frameworks.
Metal-organic frameworks are a new class of crystalline materials that consist
of coordination bonds between metal ions or clusters and multidentate organic
linkers. They receive a worldwide attention due to their open rigid framework with
high surface area (up to 6000 m2/g) which make them very attractive for a wide
range of applications from gas storage and separation, catalysis and drug delivery.
The present work reports the synthesis and properties of hybrid materials
obtained dispersion of Pd nanoparticles within the MIL-101 pores.1 In fact, 1 nm Pd
clusters have been embedded into MIL-101 mesopores with different metal
loadings (5-20 wt.%). These clusters are crystalline with the archetypal fcc structure
of bulk Pd, as confirmed by both HR-TEM an in situ EXAFS.
Hydrogen absorption/desorption properties if 1 nm Pd nanoparticles have
been characterized by both laboratory and synchrotron facilities. Experimental
results revealed that hydrogen absorption kinetics and thermodynamics of Pd are
significantly modified by nanosizing.
Keywords: hydrogen absorption; Pd nanoparticles; metal‐organic frameworks; MIL‐

101.
Acknowledgments: This work was supported by a grant of the Romanian National

Authority for Scientific Research and Innovation, CNCS ‐ UEFISCDI, project number
PN‐II‐ID‐JRP‐RO‐FR‐2015‐0025.
References
A. Malouche, G. Blăniţă, D. Lupu, J. Bourgon, J. Nelayah, C. Zlotea, (2017), Hydrogen absorption in 1
nm Pd clusters confined in MIL‐101(Cr), J. Mater. Chem. A, 5:23043-52
138
DYE-SENSITIZED SOLAR CELLS FABRICATED ON PLASTIC AND

GLASS SUBSTRATES
Izabell Crăciunescu, Alexandrina Nan, Gabriel Roşca, Adrian Bot
Corresponding author: izabell.craciunescu@itim‐cj.ro
In comparison with high-cost conventional silicon solar cells, dye sensitized solar cells
(DSSCs) are well known as a cost-effective photovoltaic device due to their low-cost,
acceptable energy conversion efficiency, and some other unique characteristics (O’Regan
and Grätzel 1991; Chalkias et al. 2018). Dye-sensitized solar cells are composed of
titanium oxide (TiO2) as semiconductor, and the dye sensitizer that can be extracted from a
variety of natural resources with minimum costs. In addition, carbonaceous materials, such
as carbon nanotubes, graphite, and carbon black, has been suggested as a suitable
candidate material for fabrication of low-cost cathodes for DSSCs, replacing the platinum
catalyst which can further reduce the material cost. (Iefanova et al. 2014; Yue et al. 2013;
Wu et al. 2016).
Nowadays, flexible DSSCs based on thin polymer substrates or metal foils have
attracted wide attention, due to their lightweight, high flexibility, high impact resistance,
for use in a wide range of potential commercial applications, such as indoor or mobile
devices, as well as for building integrated photovoltaic modules and low-cost (Han et al.
2015; Huang et al. 2010; Li et al. 2012; Weerasinghe et al. 2010; Kuang et al. 2008).
However, when polymer substrates are used, a major challenge has been obtaining good
inter-particle connectivity similar to that can be achieved with high temperature sintered
on the glass-based electrodes.
In this study we envisioned to make a comparison between the glass DSSCs and
flexible DSSCs which were prepared from the same starting materials. The experiments
were carried out by using as substrates a glass fluorine-doped tin oxide (glass-FTO) and
indium tin oxide coated polyethylene terephthalate film (ITO-PET). The counter electrodes
were fabricated, by depositing the carbon on a conductive substrate (FTO and ITO-PET).
The ITO-PET substrate has a resistivity of 60 Ω/m2 and a thickness of 130 μm and the glass-
FTO substrate with thickness layer of 2.2 mm have the resistivity of 13 Ω/m2, both
substrates were squares with the size of 2.5 x 2.5 cm. As a semiconductor layer a
nanometric powder of TiO2 of ≤ 100 nm was used and was transformed into a
homogeneous paste by the addition of ethanol. The TiO2 coating on the substrates
were stretched in the form of controlled thickness layers using an MSK-AFA-III Thin
Film Coater, from the as synthesized TiO2 paste. Anthocyanin type natural extracted
from mature cranberry were used as dye for our experiments. The electrolyte solution
used in our experiments, was prepared by dissolving the required amounts of potassium
139
iodide (KI) and iodine (I 2) in ethylene glycol. For the construction of our DSSCs we used few
types of additives: polyethylene glycol (PEG), sodium lauryl sulphate (SLS), and acrylic acid.
For assembling the PET-ITO and glass-FTO cells the TiO2 layer were deposited at
various thicknesses and the dye were immobilized on the semiconductor surface, the
ensemble was impregnated with iodide solution (redox system) and coupled with the
counter electrode.
Through our research we looked also for a partial answer to the critical issue of the
flexible electronics: how to construct flexible electrodes with good mechanical stability
without sacrificing performance? Therefore, in this work the most efforts toward
fabricating flexible DSSCs have been focused on enhancing the connectivity of TiO2
nanopowder on the electrodes under low-temperature conditions (≤ 180 °C). We also
could conclude from our experiments, that by using acrylic acid as additive we can
increase the adherence of TiO2 on the surface of both substrates glass-FTO and the
ITO-PET.
Keywords: dye sensitizer, glass‐FTO, PET‐ITO, flexible DSSCs, TiO2 nanopowder.
Acknowledgments: This work was financially supported by the Ministry of Research

and Innovation through the Nucleus project PN 18 03 01 02.
References
Chalkias D. A., Laios A. I., Petala A., Papanicolaou G. C., (2018), Journal of Materials Science:
Materials in Electronics, 29:9621-9634
Han H.-G., Weerasinghe H.C., Kim K.M., Kim J.S., Cheng Y.B., Jones D.J., Holmes A.B. and Kwon T.-H.,
(2015), Scientific Reports, Vol. 5, 14645,
Huang X., Shen P., Zhao B., Feng X., Jiang S., Chen H., Li H., Tan S., (2010), Sol. Energy Mater. Sol.
Cells, 94:1005–1010
Iefanova A., Nepal J., Poudel P., Davoux D., Gautam U., Mallam V., Qiao Q., Logue B. and Baroughi
M.F., (2014), Thin Solid Films, 562:578–584
Kuang D., Brillet J., Chen P., Takata M., Uchida S., Miura H., Sumioka K., Zakeeruddin S.M., and
Grätzel M., (2008), ACS Nano, 2:1113–1116
Li Y., Lee D.-K., Kim J.Y., Kim B.S., Park N.-G., Kim K., Shin J.-H., Choi I.-S. and Ko M.J., (2012), Energy
Environ. Sci., 5:8950
O’Regan B. and Grätzel M., (1991), Nature, 353:737-740
Weerasinghe H.C., Franks G.V., Plessis J.D., Simona G.P. and Cheng Y.-B., (2010), J. Mater. Chem.,
20:9954-9961
Wu C.-S., Chang T.-W., Teng H. and Lee Y.-L., (2016), Energy, 115:513-518
Yue G., Wu J., Lin J.-Y., Xiao Y., Tai S.-Y., Lin J., Huang M. and Lan Z., (2013), Carbon, 55:1-9
140
XAS AND XRD STUDIES ON THE STRUCTURE OF VITROCERAMIC ELECTRODES

BASED ON LEAD-LEAD DIOXIDE-MANGANESE DIOXIDE
Marius Rada1, Mioara Zagrai1, Jing Zhang3, An Pengfei3 and Simona Rada1,2
1
National Institute for Research & Development of Isotopic and Molecular Technologies,
Cluj‐Napoca, 400293, Romania
2
Physics and Chemistry Department, Technical University of Cluj‐Napoca,
400020 Cluj‐Napoca, Romania
3
Beijing Synchrotron Radiation Facilities, Institute of High Energy Physics, Beijing,
People's Republic of China
Corresponding author: marius.rada@itim‐cj.ro
Lead acid batteries are typically used in the automotive industry, where they
provide a high current pulse to start the vehicle, in traction applications, where
they undergo periodic deep discharge and charge, and in stationary applications,
where they remain in charged state most of their life (Krivik, 2018).
According to statistics, approximately 3 million tons waste batteries are
generated every year and the production of lead-acid batteries will continue to rise
even more sharply with sustained and rapid development of economy. Lead-acid
batteries were consisted of electrolyte, lead and lead alloy grid, lead paste, and
organics and plastics, which include lots of toxic, hazardous, flammable, explosive
substances that can easily create potential risk sources. The materials contained in
lead-acid batteries may bring about lots of pollution accidents such as fires,
explosions, poisoning and leaks, contaminating environment and damaging
ecosystem (Zhang et al., 2016).
A new vitreous system based on manganese dioxide-lead-lead oxide was
prepared by melt quenching method. Structural and behavioural morphology of
samples were performed by XRD and XAS spectroscopy.
XRD patterns permits the identification of four crystalline phases: metallic Pb
with cubic structure, PbO with orthorhombic structure, PbO2 in the orthorhombic
structure and tetragonal PbO crystalline phase.
141
Figure 1: a) XRD patterns and b) XANES spectra of Mn at K edge for the samples having the
xMnO2∙(100-x)[4PbO2∙Pb] composition where x=0-20 mole % MnO2.
X-ray absorption near edge structure (XANES) is sensitive to local geometries

and electronic structure of manganese atoms. The Extended X-ray Absorption Fine
Structure (EXAFS) results show that the bond length sets of Mn-O shell have large
deviations by increasing of MnO2 content in the vitroceramic matrix. These
compositional evolutions suggests that the local structure around the Mn cation in
the samples are not similar to that the etalon sample, namely MnO2 crystalline
phase.
Keywords: electrodes, vitroceramics, lead dioxide, XRD, XAS
Acknowledgments (if applicable): This work was supported by grants of the

Romanian National Authority for Scientific Research and Innovation, project number
PN 18 03 01 02.
References
P. Krivik, (2018), Methods of SoC determination of lead acid battery, Journal of Energy Storage, v15,
15:191-195
J. Zhang, C. Chena, X. Zhang, S.Liua, (2016), Study on the Environmental Risk Assessment of Lead‐
Acid Batteries, Procedia Environmental Sciences, 31: 873-879
142
ASPECTS REGARDING MATERIAL HISTORY EFFECT (MANUFACTURING &

OPERATION) ON DAMAGE PHENOMENA OF CERTAIN STAINLESS STEEL GRADES
Raluca Fako, Adriana Olteanu, Iulian Nită
Center of Technology and Engineering for Nuclear Projects (CITON),

Atomistilor Street, No. 409, Magurele, Judet Ilfov, Romania
Corresponding author: olteanua@router.citon.ro
Stainless steel grades have an wide use in all industrial areas, mainly in chemical
and petrochemical industries. They are known for the capacity to withstand
successfully to uniform corrosion phenomenon in many service condition; it is
important to emphasize that with respect to their susceptibility to localized corrosion,
the service behavior must be judged from case to case, keeping in mind material
history and real operating parameters.
Corrosion is “the destruction of a material because of reaction with its
environment” (Fontana, 1987). Many factors (electrochemical, physical-chemical,
metallurgical and thermodynamic) are in fact responsible for failure of stainless steel.
For this reason, to quantify the contribution of each of these factors in case of
damage, it is important to use a failure methodology for root cause analyze.
Main environmental variables for corrosion kinetics and mechanisms are oxygen
and oxidizers (passive state could be altered by the presence of any oxidizing agents
into the system), velocity (generally, stainless steel is more resistant when the velocity
of the corrosive environment is high), temperature (usually, corrosion rate increases
with temperature), concentration (the behavior is depending on alloy – corrosive
system), and galvanic coupling.
As regards to metallurgical aspects, the susceptibility is strongly dependent on
product manufacturing route and further maintenance/repairs history.
From the point of view of a designer, corrosion allowances are based on
corrosion rate, but reflect only the general (uniform) corrosion rate of a metal in a
given environment. In case of stainless steels, localized corrosion phenomena are
responsible for the impairment of long term serviceability of equipment/ components
despite of a very good performance to uniform corrosion.
Depending on specific operating conditions, the material engineer will
recommend a specific material grade keeping in mind four basic principles to be
considered during selection: corrosion resistance, costs, fabricability and strength.
The alteration of passive state could be the cause for several localized corrosion
forms. Modification of metallurgical state due to sensitization of stainless steel grades
as result of manufacturing, maintenance and repair processes is the main cause for
occurrence e.g. of pitting or intergranular corrosion. For exemplification two failure
cases (Fako et al., 2015; RATEN CITON, Contract: 162/2016) will be discussed with
respect to root case determination.
143
An interesting failure case will demonstrate that improper maintenance/repair is

responsible for hydrogen induced cracking (HIC) or stress oriented hydrogen induced
cracking (SOHIC) adjacent to welded joints of 316L stainless steel grade – fig. 1.
Figure 1. Exemplification of HIC / SOHIC aspects in 316L stainless steel grade base material
(electrolytic etch 10% oxalic acid, X 100) (Fako et al., 2015)
The main cause for damage was improper preparation/cleaning of steel

surfaces prior to welding and the presence of a source of atomic hydrogen and
chlorite ions. Also, operating temperature (between 60-90oC) and residual stress
within material as result of manufacturing and repairs must be considered as
favoring factors for failure mechanisms.
In the second discussed case, failure occurred in cooling water as result of
intergranular corrosion (RATEN CITON, Contract: 162/2016). The sensitization of
the material (also, 316L stainless steel grade) was due to improper manufacturing
procedures that favored carbon pick-up and carburization. Details about this case
will be presented with highlights on methodologies considered worldwide to
decrease stainless steel susceptibility at intergranular corrosion.
Conclusion will be drawn to sustain the necessity for improvement of
competencies in the field of material science, in particular corrosion science, as
support of technologists and material engineers in case of new & particular service
situations in the power industry.
Keywords: Failure, stainless steel, material history
References
Raluca Fako, Liuba Damian, Andrei Neagu, (2015), Failure Case of a Drying Equipment in the
Petrochemical Industry, EUROCORR 2005, EFC Event no. 273, Proceedings, Lisbon Portugal
Mars G. Fontana, (1987), Corrosion Engineering. Third Edition, McGraw-Hill Book Company
*** Technical opinion for SC UZUC SA Ploieşti regarding failure analysis reports issued for several
seamless stainless steel tubes from QAFCO V Unit heat exchanger 152.E1201 UZUC-16216-ST,
rev. 0, RATEN CITON Contract: 162/2016
144
DEVELOPMENT OF AZULENE TAILORED π-CONJUGATED SYSTEMS: SOLUTION AND

SOLID-STATE CHARACTERIZATION
Adrian E. Ion1, Sergiu Shova2, Marius Andruh3, Simona Nica1

1
"C. D. Nenitzescu" Institute of Organic Chemistry, Romanian Academy, Splaiul Independentei, no.
202B, 060023, Bucharest, Romania
2
"Petru Poni" Institute of Macromolecular Chemistry, Aleea Grigore Gica Voda 41A, Romania
3
Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest, Str. Dumbrava Rosie
nr. 23, Bucharest, Romania
Corresponding author: simona.nica@ccocdn.ro
Supramolecular synthesis of organic materials is of significant interest in crystal

engineering due to the fascinating structural architectures as well as potential
applications in pharmaceutical industry, material science, gas storage, and host-
guest recognition (Desiraju, 2010; Desiraju, 1989). Although the crystal engineering
of organic molecules was initially introduced to study the stereochemistry of the
photochemical reactions (Jones, 1997), the ultimate goal is now the understanding
of the assembling processes that form supramolecular entities with functions
beyond the capability of the individual components. Supramolecular organic
materials can be constructed through several types of interaction, e.g. hydrogen
bonding, π-π stacking, halogen-halogen and van der Waals forces (Melendes and
Hamilton, 1998). One of the challenges of these processes is the selection of the
building blocks that allow molecular recognition, mainly through hydrogen bonding
interaction.
Azulene is a well-known chromophore with unique electronic and optical
properties such as large dipol moment, and unusual S2→S0 fluorescence emission
(Xin and Gao, 2017). Owing to this intrinsic feature, this organic scaffold can be
used to develop useful materials; examples include conducting polymers,
electrochromic materials, fluorescence switching materials and anion receptors
(Razus et al., 2011; Amir et al., 2011; Zielinski et al., 2008). The optical behavior of
the azulene derivatives is pH sensitive, the color being switchable in acid/base
environment (Murai et al., 2012).
Firstly, it will be discussed the supramolecular organization of 1,3-bis(4-
pyridyl)azulene (azbbpy) with various metal ions and additional organic ligands,
when the supramolecular architectures vary from 1-D to 2-D coordination polymers
(Ion et al., 2014). Secondly, there will be described the supramolecular interactions
of this azulene derivative as hydrogen bond acceptor with a variety of aromatic
hydrogen-bond donors yielding binary molecular co-crystals/salt (Ion et al., 2018).
Depending on the structure of the donors, co-crystals comprising zigzag and
145
interpenetrated channels were obtained. An interesting example is the co-

crystallization of azbbpy with trimesic acid, when two different systems - co-crystal
and salt - were isolated as a function of the used base percentage. In co-crystal, the
trimesic acid molecules are assembled in supramolecular helical chains which are
further connected by azbbpy through hydrogen bonding and π-π interactions into a
3D architecture with channels of 11.3 x 7.4 Å dimension, filled by crystallization
water molecules (Fig. 1). The second system obtained is a salt containing the
trimesic monoanion and monopyridinium cation of azbbpy. These are packed
through hydrogen bonding and π-π interactions generating a supramolecular 3D
architecture with channels running along the crystallographic a axis (Fig. 2).
Figure 1. Views of the helical chains formed by hydrogen bonded trimesic acid molecules (left) and the
crystal packing diagram along along crystallographic b axis showing the formation of channels (right).
Figure 2. Packing diagram of in salt of azbbpy with trimesic acid showing the formation of channels
as viewed along the crystallographic a axis
Further on, new fluorescent azulene materials will be disscused. These will
comprise photochromic azulene-based diarylethenes (Dragu et al., 2015) for which
the photocyclization occurred by irradiation with visible light and fluorescent 4’-
azulenyl 2,2’:6’,2”-terpyridines that are able to recognize poisoning metal ions
(Ion2016) (see below).
146
The studies were extended to novel multifunctional conjugated azulene bis-

carbohydrazones that can bind anions in a cleft-like fashion. Preliminary investigations
of the anion binding ability of these organic hosts showed that bis-thiocarbohydrazide
azulene derivative can accomodate small anions within the cavity.
Keywords: azulene, supramolecular architectures, photoswitching, fluorescence,

anion recognition.
References
Amir E., Amir R. J., Campos L. M., Hawker C. J., (2011), J. Am. Chem. Soc. 133, 10046
Desiraju G. R. (2010), Chem. Sci., 122, 667
Desiraju G. R. (1989), Crystal Engineering: The Design of Organic Solids; Elsevier: Amsterdam, The
Netherlands, 1989
Dragu E. A., Ion A. E., Shova S., Bala D., Mihailciuc C., Voicescu M., Ionescu S., Nica S., (2015), RSC
Adv., 5, 63282
Ion A. E., Madalan A. M., Maxim C., Julve M., Lloret F., Andruh M., (2014), CrystEngComm., 16, 319
Ion A. E., Madalan A. M., Shova S., Vallejo J., Julve M., Lloret F., Andruh M., 2014, Inorg. Chem., 54,
16
Ion A. E., Cristian L., Voicescu M., Bangesh M., Madalan A. M., Bala D., Mihailciuc C., Nica S., (2016),
Beilstein J. Org. Chem., 12, 1812.
Ion A. E., Dogaru A., Shova S., Madalan A. M., Akintola O., Ionescu S., Voicescu M., Nica S., Buchholz
A., Plass W., Andruh M., (2018), CrystEngComm, 20, 4463
Jones W., (1997), Organic Molecular Solids, CRC Press, New York, 1997
Mendeles R. E., Hamilton A. D., (1998), Hydrogen‐Bonded Ribbons, Tapes and Sheets as Motifs for
Crystal Engineering; 1998, 97-129
Murai M., Amir E., Amira R. J., Hawker C. J., (2012), Chem. Sci., 3, 2721
Razus A. C., Nica S., Cristian L., Raicopol M., Birzan L., Dragu E. A., (2011), Dyes Pigm., 91, 55
Xin H., Gao X. (2017), ChemPlusChem, 82, 945
Zielinski T., Kedziorek M., Jurczak J., (2008), Chem. Eur. J., 14, 838.
147
SYNTHESIS OF WELL DISPERSED GOLD NANOPARTICLES ON REDUCED GRAPHENE

OXIDE AND APPLICATION IN PEM FUEL CELLS
Adriana Marinoiu, Elena Carcadea, Mircea Raceanu, Mihai Varlam
Corresponding author: adriana.marinoiu@icsi.ro
One of the main current issues that inhibit the fuel cell technology through a
complete commercialization is the sluggish kinetics of the oxygen reduction
reaction (ORR), which causes significant voltage losses at the cathode. Thus the
actual research efforts are focused on the development and demonstration utility
of new highly active electrocatalysts for ORR process. The state-of-the-art of
developed Pt/C-based catalysts clearly indicates that these suffer from high price,
limited accessibility, as well as unavoidable critical and disputable long term
durability. Moreover, the specific environment during PEMFC operation demands
limited alternatives for materials that can be used as ORR electrocatalysts. The
actual research results of our group on development of ORR electrocatalysts with
enhanced electrochemical performances suggest gold nanoparticles decorated on
reduced graphene oxide (Au/rGO) as recommended co-catalyst for a novel cathode
for PEM Fuel Cells. Subsequently, the recent efforts employing Au/rGO in achieving
of improved ORR catalyst for acquiring highly efficient catalytic system to enhance
both activity and stability are discussed. However, there is still a significant
challenge in controlling the uniformity of graphene surface decoration with noble
metal nanoparticles and especially the strength of the attachment. In this study we
have developed a facile approach to create functional groups on the carbon surface
based on a polymer coating (poly-diallyldimethylammonium chloride - PDDA).
The surface morphology of prepared samples was investigated using scanning
electron microscopy (SEM) and specific surface area was determined using
Brunauer-Emmett-Teller methodology (BET), while structural properties were
investigated using Raman scattering spectroscopy, X-Ray photoelectron
spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR).
In respect to a representative surface morphology measurements, namely the
BET methodology (Figure 1), the lower pressure region and intermediate flat
region in the isotherms describe the adsorption behavior of porous adsorbents
indicating the presence of mesopores mainly, micropores and some macropores,
together with hysteresis behavior between the adsorption and the desorption
branch. A hysteresis appeared and was assigned to the process of capillary
148
condensation of nitrogen, relative to the presence of pores with the shape of thin
slots formed between two surfaces, indicating that the cleft-like pores were formed
by the aggregation of platelets-like particles.
Figure 1. Nitrogen adsorption-desorption isotherms and the corresponding

pore size distribution for Au/rGO
The electrodes containing Au/rGO were prepared, and electrochemical

measurements were performed in order to systematically characterization of the
electrical performances of catalytic system. The in‐situ electrochemical accelerated
stress tests (ASTs) were carried out as application in PEM fuel cells and analyzed as
comparison commercial Pt/C versus developed catalytic system. The results confirmed
that the developed Au/rGO nanoparticles proved enhanced electrocatalytic activity
and could be a valuable alternative as nanostructured electrodes.
PEM fuel cell accelerated test was focused on potential cycling between 0.0 – 1.2
VSHE, which theoretically could provoke a fast catalyst aging, in contrast to a constant
potential keeping test. Cyclic voltammogrames corresponding to electrocatalysts
exposure to potential cycling of 50 cycles between 0.02 – 1.2 V illustrate that the
membrane electrode assemblies (MEAs) including Au/rGO catalysts showed a good
stability in PEMFC durability tests. However, although it seems numerically easy to
evaluate the electrochemical surface area, the validity of this area approach is
questionable as it assumes that the contributions from the platinum and gold are
independent.
149
LaCoO3 PEROVSKITE-TYPE OXIDE: SYNTHESIS AND CHARACTERIZATION

TOWARDS PRACTICAL APPLICATIONS
Mirela Dragan1, Stanica Enache1, Amalia Soare1, Konstantin Petrov1,2,

Mihai Varlam1
1
2
Academician Evgeni Budevski Institute of Electrochemistry and Energy Systems; Sofia/Bulgaria
Corresponding authors: mirela.dragan@icsi.ro; stanica.enache@icsi.ro
As a result of chemical stability and superior electrolytic and ionic (O2-)

conductivity properties, lanthanum cobaltite (LaCoO3) is an industrial important
conductive ceramic material which finds a broad range of applications, such as
electrode material for solid-oxide fuel cells (SOFC) (Ding et al., 2015), gas sensors
(Rehman et al., 2018) and has been shown to have promising catalytic activity for
oxygen evolution reaction (OER) (Liu et al., 2018).
As the physical properties of the final lanthanum cobalt oxide powder material
obtained are strongly dependent on the method of preparation, the development
of a convenient method for the synthesis of lanthanum cobalt oxide is also
essential.
Lanthanum cobalt oxide polycrystalline powder was synthesized through
optimized solid-state reaction method, because of advantage given by simplicity
and the use of relatively inexpensive oxides as starting materials.
Various key properties of obtained lanthanum cobalt oxide material were
investigated such as morphological characteristics by scanning electron microscopy
(SEM) and the phase formation was determined by X-ray diffraction (XRD). The SEM
image on the sample of powder is presented in Fig. 1 and the X-ray diffraction
patterns indicating the formation of hexagonal nonstoichiometric LaCoO3 structure
(b) from initial raw material consisting in the mixture of oxide powder precursors
(a) are shown in the Fig. 2.
150
Figure 1. The SEM image of the LaCoO3 sample powder
(b) Product
(a) Precursors
in the mixture
Figure 2. The X-ray diffraction patterns of oxide precursors in the mixture (a) and the
reaction product (b)
To elucidate the reproducibility of our fabrication technique, the variations in

properties among the batch to batch samples were evaluated.
The prepared lanthanum cobalt oxide powder is essentially within a single
crystalline phase, with minimal traces of unreacted precursors. The results showed
that we realized good reproducibility of batch to batch powder properties, which is
one of the most important factors for commercialization.
151
We expect the findings of this work to serve as a lever to fine-tune or modify

the observed properties towards practical applications.
Keywords: LaCoO3; oxides powders; synthesis, catalyst
Acknowledgments: This work was supported by the Romanian Ministry of

Education and Research, project "RESTORE" - 117/16.09.2016 ID / Cod My SMIS:
P_37_595 / 104958
References
Jun-Chao Ding, Hua-Yao Li, Ze-Xing Cai, Xiao-Dong Zhang and Xin Guo, (2015), RSC Adv., 5:65668-
65673
Saeed Ur Rehman, Rak-Hyun Song, Tak-Hyoung Lim, Seok-Joo Park, Jong-Eun Hong, Jong-Won Lee
and Seung-Bok Lee, (2018), J. Mater. Chem. A, 6:6987-6996
Hao Liu, Xifeng Ding, Lixi Wang, Dong Ding, Shihua Zhang, Guoliang Yuan, (2018), Electrochimica
Acta, 259:1004-1010.
152
CHARGE TRANSPORT AND GLASSY DYNAMICS OF POLYMERIZED IONIC LIQUIDS IN

BULK AND IN UNIDIRECTIONAL SILICA NANOPORES
Ciprian Iacob1,2*, Atsushi Matsumoto3, Tadashi Inoue3, James Runt2

1
2
Department of Materials Science and Engineering, The Pennsylvania State University, University
Park, Pennsylvania 16802, United States
3
Department of Macromolecular Science, Osaka University, Toyonaka, Osaka 560‐0043, Japan
Corresponding author: ciprian.iacob@icsi.ro
Polymerized ionic liquids (PILs) combine the attractive mechanical

characteristics of polymers with the unique physicochemical properties of low
molecular weight ionic liquids (ILs) (Iacob et al., 2017; Iacob and Runt, 2016; Iacob
et al., 2011; Iacob et al., 2010). These properties make PILs appealing candidates
for various applications, such as electrolytes in electrochemical devices including
lithium ion batteries, supercapacitors, fuel cells, and dye-sensitized solar cells. High
ionic conductivity coupled with robust mechanical properties is one of the main
requirements of electrolytes for these applications. As a consequence, concerted
efforts have focused on establishing the link between the molecular structure,
morphology, and ionic transport in polyILs, with the aim of developing new
polymer electrolytes with high ionic conductivities. The impact of the chemical
structure on ion transport, nanoscale morphology, and dynamics in bulk
polymerized imidazolium-based ionic liquids is investigated by broadband dielectric
spectroscopy (BDS) and X-ray scattering, complemented with atomistic molecular
dynamics simulations. Anion volume is found to correlate strongly with Tg
independent ionic conductivities spanning more than 3 orders of magnitude. In
addition, a systematic increase in alkyl side chain length results in about one
decade decrease in Tg-independent ionic conductivity correlating with an increase
in the characteristic backbone- to-backbone distances found from scattering and
simulations. The quantitative comparison between ion sizes, morphology, and ionic
conductivity underscores the need for PILs with small counterions and short alkyl
side chain length in order to obtain polymer electrolytes with higher ionic
conductivity.
153
Figure 1: (a) Relationship between anion concentration-normalized dc conductivity at Tg/T = 1 and

repeat unit molecular volume Vm (including the counterion) for imidazolium-based polyILs with
various side chains and counterions as indicated. The dashed lines are to guide the eye. (b) Thermal
activation of the ionic conductivity for bulk and confined PEO600-Na and in silanized and
nonsilanized silica nanopores. VFT fits of bulk and confined data are also presented. Insets:
Characteristic rate of charge transport ωc and the local glassy state β-relaxation ωβ for bulk and
confined PEO600-Na. The dotted lines are fits to the Arrhenius equation. The local glassy state
dynamics of the confined ionomers coincide with that of the bulk.
When PILs are confined in nonsilanized unidirectional nanoporous membranes

(average pore diameter = 7.5 nm), the macroscopic transport quantities (dc
conductivity and characteristic frequency rate) are lower by about 1.4 decades
compared to the bulk. The remarkable decrease of transport quantities in nonsilanized
nanoporous membranes can be quantitatively explained by considering the
temperature dependence of the interfacial layer between the PIL and the silica
membrane surfaces. On the other hand, an enhancement of dc conductivity is
observed when the surfaces of the pores are treated with a nonpolar organosilane.
This effect becomes more pronounced at lower temperatures and is attributed to
slight changes in molecular packing density caused by the two-dimensional geometrical
constraint.
Keywords: broadband dielectric spectroscopy, polymerized ionic liquids, charge

transport, dc conductivity.
References
[1] Iacob, C., A. Matsumoto, H. Liu, S. Paddison, J. Sangoro, O. Urakawa, T. Inoue and J. Runt.
Polymerized Ionic Liquids: Correlation of Ionic Conductivity with Nanoscale Morphology. ACS
Macro Letters. (2017), 6, 941-946
[2] Iacob, C. and Runt, J. Charge transport of polyester ether ionomers in unidirectional silica
nanopores. ACS Macro Letters, (2016) 5, 476-480.
[3] Iacob, C., Sangoro, J. R., Kipnusu, W. K., Valiullin, R., Kärger, J. and Kremer, F. Enhanced charge
transport in nano‐confined ionic liquids. Soft Matter (2011), 8, 289-293.
[4] Iacob, C., Sangoro, J. R., Kärger, J. and Kremer, F. Charge transport and diffusion of ionic liquids in
nanoporous silica membranes. Phys. Chem. Chem. Phys., (2010), 12, 13798.
154
GRAPHENE MODIFIED FLUORINATED CATION-EXCHANGE MEMBRANES

PROTON EXCHANGE MEMBRANE WATER ELECTROLYSIS
Daniela Ion-Ebrasu1, Bruno G. Pollet2, Adnana Spinu-Zaulet1, Amalia Soare1,

Elena Cacadea1, Dorin Schitea1, Alin Chitu1, Mihai Varlam1, Konstantin Petrov1,3
1
2
Department of Energy and Process Engineering, Faculty of Engineering
Norwegian University of Science and Technology (NTNU) NO‐7491 Trondheim, Norway;
3
Acad. Evgeni Budevski Institute of Electrochemistry and Energy Systems, Bulgarian Academy of
Sciences, Acad. Georgi Bonchev Str., Block 10, 1113 Sofia, Bulgary
Corresponding author: daniela.ebrasu@icsi.ro
One of major current technical challenges in proton exchange membrane water

electrolysis (PEMWE) is limited proton conductivity. Nowadays, graphene is considered
one of the most promising candidates for improving the ionic transport properties,
isotopic selectivity and proton conductivity throughout the unique two-dimensional
structure. In this paper, we report on the development of graphene modified Fumapem
membranes with different graphene loadings for PEM electrolysis applications. The
membranes were characterized by Scanning Electron Microscopy (SEM) and thermo-
gravimetrical and differential thermal analysis (TGA-DSC). Properties of composite
membranes were investigated, including water uptake and ion-exchange capacity (IEC).
In plane four-electrode arrangement was used to determine the proton conductivity of
the composite membranes. The calculated activation energy (Ea) for proton conduction
was about 3.8 kJ mol-1 for the composite Fumapem®/grapehene membrane with 10 mg
graphene loading, lower than of the pristine polymer proton exchange membrane.
The graphene modified fluorinated cation-exchange membranes presented in this
study were synthesized by graphene uniformly distributed over the surface of
commercial 100 µm thick Fumapem® substrate membranes at various graphene
loadings. The graphene powder of high conductivity, rich porosity and multi-
dimensional electron transport pathway was purchased from Alfa Aesar. Nafion®
perfluorinated resin solution containing 5% water and 2-Propanol 99+% was purchased
from Alfa Aesar. Three loadings of graphene nanoplatelets, 5, 10, and 15 mg, were
added to 2.6 ml Nafion®/water/isopropanol solution accordingly (Table 1). These
mixtures were then ultrasonicated (ultrasonic bath, 80 kHz) for 12 hours in order to
form a homogenous solution. A compressed air spray brush was used to spray the
graphene solution over the Fumapem® membrane. A 3.3 × 3.3 cm2 Fumapem®
membrane was cut and the solution was then sprayed over one side of the dry
membrane using a compressed nitrogen spray brush at a pressure of 1.5 bar.
155
Table 1. Modified Fumapem® membranes and graphene loading

Graphene Graphene concentration over one side of
Membranes Support
loading (mg) the membrane (w/v %)
G1 5 0.19
G2 10 0.38 Fumatech® F-
G3 15 0.57 14100
Proton conductivity of the membranes to a large extent depends upon the

amount of water uptake and the ion exchange capacity. The proton conductivity
plots are presented in Fig. 1(a).
Figure 1. (a) Proton conductivity (a) and

(b) Arrhenius plot for the Fumapem® and G1-G3 membranes
Under fully humidified conditions (RH = 100%), the proton conductivity of the
composite membranes increases with temperature and graphene content. At a tem-
perature of ca. 80°C, a value of 115 mS/cm corresponding to 0.38 w/v % of graphene
loading can be achieved. For higher graphene loadings, the proton conductivity
decreases (membrane G3), which may be due to the excess amount of graphene,
hindering and disrupting proton pathway. The increased conductivity with the graphene
content may be explained by the additional conduction mechanism of protons through
nano-confined channels formed between the membrane surface and the graphene
layer. According to Figure 1(a), the proton transport can be achieved by the Grötthus
type proton transport mechanism through hydrogen bonding with water-filled ion
pores. From the Arrhenius plots (Fig. 1(b)), it was possible to calculate the activation
energy (Ea) for Fumapem® and composite membranes. It was found that the lowest Ea
value (3.8 kJ/mol) corresponds to membrane G2. The lower Ea of the G2 membrane
when compared to the Fumapem® value of 5.67 kJ/mol suggests that graphene loading
can improve the hopping mechanism. Moreover, the decrease of the energy barrier for
ion transfer from one free site to another can reduce the energy loss caused by the ionic
resistance of the membranes. Therefore, the presence of graphene may help to reach
an adequate hydration level and provide additional sites in the composite membranes
to maintain proton conductivity and decrease the activation energy.
Keywords: Membrane, Graphene, Fumapem®, Electrolysis, Conductivity.
156
FABRICATION TECHNOLOGY OF SELF-STANDING BINDER FREE LiMn2O4/MWCNT

ELECTRODE BY VACUUM FILTRATION METHOD
Constantin Bubulinca
Corresponding author: Constantin.bubulinca@icsi.ro
In last decades new types of smart electronics, wearable devices and rollup display
appear, which require new devices for energy storage with good electrochemical
properties and flexibility (Wang and Shi, 2015; Jia et al., 2012). Thus, fabrication of self-
standing electrodes with high mechanical and electrochemical features using
innovative methods is the key.
This paper present technology of fabrication and characterization of self-standing
binder free electrode base on LiMn2O4/CNT by vacuum filtration method trying to find
ecological, economical and energetically solution of problems regarding energy storage
for flexible devices. Mechanochemistry was used to increase specific surface area of
materials used for preparation of binder free self-standing electrode, reducing size and
improving distributions of active particles (Ning et al., 2004). Likewise, the proposed
technological fabrication method based on direct deposition (Lima et al., 2011) of
active material on carbon nanotubes network in reaction with surfactant (Cheng et al.,
2015) assisted by a vacuum filtration method. Direct construction of binder free
cathode using MWCNT is complicated but obtained results are promising. Moreover,
good control of range size and distribution of active particles implies in reaction
provide better intimate contact between MWCNT substrate and LMO spinel particles,
creating a self-standing electrode.
Figure 1. Schematic fabrication of binder-free flexible LiMn2O4/CNT network electrodes

through the dispersion and vacuum filtration processes
157
Schematic design of the fabrication process of binder-free self-standing

LMO/CNTs electrode is shown in Fig. 1. First, we reduced size of active particles by
ball milling, then we disperse LMO and MWCNT in surfactant like Triton X-100 and
demineralized water, where CNTs maintain their aspect ratio and create a
homogenously dispersion in solution. Materials will be after dispersed together and
filtrated using vacuum filtration method, washed to remove the surfactant and
finally dried and thermal threated.
For characterization of materials we used an X-ray diffraction (XRD), Raman
and laser diffraction method. Uniform distributed of particles, small chunks of LMO
and long conductive networks formed by MWCNT, as well dispersion of elements in
materials are revealed by field emission scanning electron microscopy (FE-SEM)
endowed with an EDX detector. Electrochemical properties of binder free cathode
base on LMO/CNT after 1 hour of ball milling measured by potentiostat galvanostat
device shows very good electrical conductivity (4,6x103 S/m), good dispersion of
materials and effective charge transport. Likewise, cyclic voltammetry shows the
presence of two oxidation/reduction peaks, stability of material and a high
reversibility.
Keywords: Li‐ion rechargeable battery, self‐standing electrode, binder free cathode,

vacuum filtration method.
Acknowledgments (if applicable): I thank to my colleague Ramona Mihaela BUGA

who provided me the materials implied in this study.
References
Cheng Y., Chen Z., M. Zhu, Y. Lu, Polyacrylic acid assisted assembly of oxide particles and carbon
nanotubes for high-performance flexible battery anodes, Adv. Energ. Mater., 5 (2015),
10.1002/aenm.201401207.
Jia X., Z. Chen, A. Suwarnasarn, L. Rice, X. Wang, H. Sohn, Q. Zhang, B.M. Wu, F. Wei, Y. Lu, High-
performance flexible lithium-ion electrodes based on robust network architecture Energ.
Environ. Sci., 5 (2012), pp. 6845-6849
Lima M.D., S. Fang, X. Lepró, C. Lewis, R. Ovalle-Robles, J. Carretero-González, E. Castillo-Martínez,
M.E. Kozlov, J. Oh, N. Rawat, Biscrolling nanotube sheets and functional guests into yarns,
Science, 331 (2011), pp. 51-55
Ning L., Y. Wu, S. Fang, E. Rahm and R. Holze, J. Power Sources, 2004, 133, 229–242.
Wang X. and G. Shi Flexible graphene devices related to energy conversion and storage Energ.
Environ. Sci., 8 (2015), pp. 790-823
158
GLASSY DYNAMICS POLYMETHYLPHENYLSILOXANE IN ONE- AND TWO-

DIMENSIONAL NANOMETRIC CONFINEMENT — A COMPARISON
Wycliffe K. Kipnusu1, Mohamed Elsayed2, Reinhard Krause–Rehberg2 and

Friedrich Kremer3
1
UJI, Institute of New Imaging Technologies, Universität Jaume I, 12071 Castellón de la Plana, Spain,
2 3
Department of Physics, Martin Luther University Halle, 06099 Halle, Germany, Institute of
Experimental Physics I, University of Leipzig, 04103 Leipzig, Germany
Corresponding author: wycliffe@uji.es
Glassy dynamics of polymethylphenylsiloxane (PMPS) is studied by broadband

dielectric spectroscopy in one-dimensional (1D) and two-dimensional (2D)
nanometric confinement; the former is realized in thin polymer layers having
thicknesses down to 5 nm, and the latter in unidirectional (thickness 50 m)
nanopores with diameters varying between 4 and 8 nm. Based on the dielectric
measurements carried out in a broad spectral range at widely varying
temperatures, glassy dynamics is analyzed in detail in 1D and in 2D confinements
with the following results: (i) the segmental dynamics (dynamic glass transition) of
PMPS in 1D confinement down to thicknesses of 5 nm is identical to the bulk in the
mean relaxation rate and the width of the relaxation time distribution function; (ii)
additionally a well separated surface induced relaxation is observed, being assigned
to adsorption and desorption processes of polymer segments with the solid
interface; (iii) in 2D confinement with native inner pore walls, the segmental
dynamics shows a confinement effect, i.e., the smaller the pores are, the faster the
segmental dynamics; on silanization, this dependence on the pore diameter
vanishes, but the mean relaxation rate is still faster than in 1D confinement; (iv) in a
2D confinement, a pronounced surface induced relaxation process is found, the
strength of which increases with the decreasing pore diameter; it can be fully
removed by silanization of the inner pore walls; (v) the surface induced relaxation
depends on its spectral position only negligibly on the pore diameter; (vi)
comparing 1D and 2D confinements, the segmental dynamics in the latter is by
about two orders of magnitude faster. All these findings can be comprehended by
considering the density of the polymer; in 1D it is assumed to be the same as in the
bulk, hence the dynamic glass transition is not altered; in 2D it is reduced due to a
frustration of packaging resulting in a higher free volume, as proven by ortho
positronium annihilation lifetime spectroscopy.
159
(a) Activation plots: A comparison of the relaxation rates of PMPS confine in thin films (1D) (half-
filed symbols) and in native (open symbols) and silanized (crossed symbols) nanopores (2D)
geometrical constraints. (b) The temperature dependencies of the free volume (Vf ) obtained from
PALS technique for PMPS sample in the bulk state and when confined in nanopores with mean pore
diameters of 4, 6, and 8 nm.
Keywords: Glass transition temperature, nanoconfinement, thin films, silica nanopores
References
Kipnusu W.K.K., Elsayed M.E., Krause-Rehberg R., Kremer F., (2017), Glassy dynamics of
polymethylphenylsiloxane in one‐and two‐dimensional nanometric confinement‐a comparison. J.
Chem. Phys., 146:203302
160
MASTERING ELECTRONIC PERCOLATION THRESHOLD OF METAL-OXIDE

COMPOSITES TOWARDS HIGHLY POROUS SOLID-STATE CATALYSTS
Stanica Enache1, Mirela Dragan1, Amalia Soare1, Konstantin Petrov1,2,

Mihai Varlam1
1
2
Academician Evgeni Budevski Institute of Electrochemistry and Energy Systems; Sofia/Bulgaria
Corresponding authors: stanica.enache@icsi.ro; mirela.dragan@icsi.ro
Standard catalysts are often dispersed on a porous support material in order to

increase the overall specific catalytic activity. In the process of making, binders are
involved to assure cohesion between constitutive parts at the expense of hindering
of catalytic centres. Additionally, self-standing catalytic electrodes based on binders
breath physically as their volume changes continuously while in action, modifying
local porosity and thus the effectiveness of the local catalytic reaction. In time,
repeated changes in the spatial distribution of active catalytic centres and binder
fatigue under stress results in electrode failure, eventually.
In this work, we show that it is not necessary to go on with a standard
approach for electrode manufacturing and we give a hint to what can be improved
in the process of electrode making so as premature electrode failure may be
avoided. For that, however, one has to be initiated into some aspects related to
composite materials comprising (f) parts by volume of metallic inclusions in a (1-f)
semiconducting matrix and re-define the electronic transport properties of the
entire system - the so called generalized Bruggeman theory for effective media. The
best example in this sense is a former study on some special complex metal-hydride
system that exhibits a continuous metal-to-semiconductor transition and also
behaves as both metal and semiconductor upon hydrogen absorption.
The Bruggeman theory for effective media is a special case to describe the
overall transport properties in composite media but it may not be that straight-
forward to formulate, especially when it comes to the shape of the metallic
inclusions. The best part of it is, however, that it can be triple-checked by different
methods (electrical, optical and local imaging), which also provide more insight into
the physical geometry of the constitutive parts. This statement holds strongly in
thin film geometry and it is not surprising in itself for, intuitively, the ac in-plane
electrical resistivity and out-of-plane transmission and reflection spectra should
overlap in the 0eV limit since the electrical field vector lays in the plane of the film
in both cases. This however, may not be restricted to thin film geometry, only.
161
With these given, we can show now that some special oxide catalysts mixed
with some other special metallic parts can be casted into self-standing highly
porous and highly conducting solid-state catalytic electrodes. The solid-state
electrodes are basically unbreakable and the constitutive parts rigid. We have
basically manipulated the ohmic drop over the electrode thickness over many
orders of magnitude and yet the catalytic activity survived. This is important for one
can now exploit the full catalytic capacity over the entire electrode thickness.
Moreover, it becomes trivial at one point that greater opportunities to tune further
the overall microscopic and macroscopic properties of solid-state electrodes arise
from simply choosing an appropriate preparation method.
Keywords: metal‐oxide composites, solid‐state electrodes; effective medium; metal‐

to‐semiconductor transition

Education and Research, project "RESTORE" ‐ 117/16.09.2016 ID / Cod My SMIS:
P_37_595 / 104958
162
THE CHANGE OF THE LOCAL ENVIRONMENT OF SAMARIUM IONS IN LEAD-

BORATE GLASSES AND VITROCERAMICS
Adriana Dehelean, Simona Rada, Marius Rada, Ramona Suciu
Donat Str., 400293, Cluj‐Napoca, Romania
Corresponding author: adriana.dehelean@itim‐cj.ro
Borate glasses have attracted much attention because of their electrochemical

and optical applications, namely as solid-state batteries, optical waveguides and
luminescent materials. Lead borate glasses are an optically transparent from the
visible to the near-infrared range, forming over a wide compositional region of PbO
concentration and creating an excellent host to incorporate trivalent rare earth
ions. Sm3+ doped glasses are of special interest because of their intense emissions
in the visible region through different emission channels. Especially, the reddish
orange emission originating from the 4G5/2 level of Sm3+ion possess strong
luminescence intensity, large stimulated emission cross section, high quantum
efficiency and very less probability for non-radiative decay, which are desirable
features for laser applications. From this point of view, structure and properties of
glasses and vitriceramics in the xSm2O3∙(100-x)[PbO∙4B 2O3] systems with x=0-20
mol % Sm2O3 have been analyzed in presented paper. The glasses were prepared by
conventional melt - quenching method and then the influence of Sm2O3 content on
the structure and properties of the glassy network was investigated using x-ray
diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), Raman,
ultraviolet visible (UV-Vis), photoluminescence (PL) and electron paramagnetic
resonance (EPR) spectroscopy.
Keywords: glasses, vitroceramics, lead‐borate, FTIR, UV‐Vis, EPR
Acknowledgments: The financial support of this work was provided by the National
Plan for Research‐Development, PN‐III‐P1‐1.1‐PD‐2016, Contract No. 33/2018
References
W. A. Pisarski, T. Goryczka, B. Wodecka-Duś, M. Płońska, J. Pisarska, (2005), Structure and properties
of rare earth‐doped lead borate glasses. Materials Science and Engineering: B, 122(2): 94-99
S. Mohan, S. Kaur, D. P. Singh, P. Kaur, (2017), Structural and luminescence properties of samarium
doped lead alumino borate glasses. Optical Materials, 73:223-233
163
SULFUR – DOPED REDUCED GRAPHENE OXIDE DECORATED WITH PLATINUM

NANOPARTICLES AS ELECTROCATALYST FOR METHANOL OXIDATION
Adriana Vulcu, Camelia Berghian-Grosan, Diana Lazar, Sebastian Porav, Gheorghe

Borodi, Teodora Radu
Donat Street, 400293, Cluj‐Napoca, Romania
Corresponding author: adriana.vulcu@itim‐cj.ro
Direct methanol fuel cells (DMFCs) represent alternative energy sources and
are employed in portable and electronic devices. The electric power is produced
directly using liquid methanol as fuel. The use of methanol as fuel has several
advantages such as transport and storage, easy to handle, low cost and high
theoretical energy density (Gomez et al., 2016; Sequeira et al., 2017). The major
disadvantage of DMFC is the high cost which comes from the use of platinum (Pt)
based catalysts (with high Pt loading) as electrocatalyst for methanol oxidation. The
extensive application of Pt catalysts is limited not only due to its high cost, but also
because is easily poisoned by the adsorption of CO intermediates (Li et al., 2016; Xu
et al., 2016). In this context, it is necessary to develop new catalysts with improved
stability and activity. Recently, graphene/reduced graphene oxide (RGO) have been
used as support for fuel cells catalysts, due to their excellent properties: high
surface are, high conductivity and electron mobility (Wang et al., 2013). Recent
studies revealed that doping graphene with heteroatoms (sulfur, nitrogen, boron)
can improve their electronic properties, chemical reactivity, the dispersion of the
metal nanoparticles, as well as, the interaction between metal and carbon support
(Chen et al., 2014; Higgins et al., 2014).
In this paper we report a simple and efficient solvothermal method to
synthesize sulfur-doped reduced graphene oxide decorated with platinum
nanoparticles (S-RGO-PtNPs). First, S-RGO was prepared, starting from graphene
oxide, using ethylene glycol as reducing agent and sodium sulfide as sulfur
precursor in a stainless steel autoclave at 180°C for 12 hours. Platinum
nanoparticles were deposited onto S-RGO in the presence of ethylene glycol and
hexachloroplatinic acid in a stainless steel autoclave at 180°C for 8 hours. After
cooling at room temperature the resulting suspension was filtered, washed with
double distilled water and ethanol, then frozen and lyophilized. The as prepared S-
RGO-PtNPs were characterized by transmission electron microscopy (TEM),
scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX), X-
ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR) and X-ray
164
electron spectroscopy (XPS). For the electrochemical measurements S-RGO-PtNPs

composite was dropped casted on a glassy carbon electrode (GC) and then tested
for methanol oxidation. The electrocatalytic activity in methanol oxidation reaction
(MOR) of the modified electrode was evaluated using cyclic voltammetry (CV).
Keywords: sulfur‐doped RGO, platinum nanoparticles, electrocatalyst, methanol

oxidation
Acknowledgments (if applicable)

This work was financially supported by Romanian National Authority for Scientific
Research and Innovation (ANCSI) by NUCLEU Program PN 18 03 02 02.
References
Chen Y., Li J., mei T., Hu X., Liu D., Wang J., Hao M., Li J., Wang J., Wang X. (2014), Journal of
Materials Chemistry A, 2:20714
Gomez J.C.C., Moliner R., Lazaro M.J. (2016), Catalysts, 6:130
Higgins D., Hoque M.A., Seo M.H., Wang R., Hassan F., Choi J.-Y., Pritzker M., Yu A., Zhang J., Chen Z.
(2014), Adv. Funct. Mater., 24:47325
Li J., Fu X., Mao Z., Yang Y., Qui T., Wu Q. (2016), Nanoscale Research Letters, 11:1
Sequeira C.A.C., Cardoso D.S.P., Martins M., Amaral L. (2017), AIMS Energy, 5:458
Wang R., Higgins D.C, Hoque M.A., lee D., Hassan F., Chen Z. (2013), Scientific Reports, 3:2431
Xu S., Ye L., Li z., Wang Y, Lei F, Lin S. (2016), Catalysts, 6:144
165
PHOSPHORUS REMOVAL FROM WASTEWATER IN THE PRESENCE OF

MESOPOROUS MATERIALS
Violeta Niculescu1, Mihaela Iordache1, Marius Miricioiu1, Laurentiu Asimopolos2

1
Valcea, Code 240050 ‐ Rm. Valcea, Uzinei 4, PO 7 Raureni, Valcea, Romania
2
Corresponding author: violeta.niculescu@icsi.ro
Phosphorus constitutes an important element widely used in agriculture as a

fertilizer and in industry as a detergent. The agricultural activities generate effluents
rich in phosphorous compounds, which constitute a major concern due to their direct
involvement in the eutrophication of the aquatic environments. Various Environmental
Protection Agencies have identified eutrophication, resulting from excess phosphorus
input, as the greatest threat to fresh water supply and leading to fish deaths and the
degradation of habitat.
The elimination of phosphorus compounds from waste effluents are
conventionally carried out by biological or physicochemical treatments which are long
and complex to be operated, their efficiency in removing phosphate being influenced
by several factors (pH, temperature, dissolved oxygen concentration, or the balance of
the nutrients in water). A promising alternative for phosphorus compounds removal
can be the adsorption process. Various adsorbents were developed and tested for
phosphorous compounds removal, but their adsorption capacity is still low and the
time to reach the equilibrium is relatively high.
Ordered mesoporous silica has proven to be good adsorbents for metal ions and
amino acids, due to their high specific surface area, controlled pore diameters and
controlled morphology. They are mechanically robust, non-toxic and environmentally
friendly. Mesoporous materials have significant potential for use as adsorbents for
removal of phosphate from water. In view of the above facts and in a continuous quest
for high capacity, selective, effective and regenerable adsorbents, the present work is
aimed to highlight the use of mesoporous materials for the removal of phosphorus
compounds from wastewater.
Keywords: environment, mesoporous materials, phosphorus, wastewater.
Acknowledgments: The work has been funded by the Romanian Ministry of Research
and Innovation, under 1N/16.03.2018 NUCLEU Program, PN 18 12 03 01 Project –
“Studies on the development of micro‐ and mesoporous materials with improved
catalytic properties for their use in solid, liquid and gaseous waste recovery processes”.
166
BIFACIAL SOLAR CELLS
Marin Gheorghe, Simona Gheorghe
NANOM MEMS srl Rasnov G. Cosbuc 9, 505400 Rasnov, Brasov County, Romania
Corresponding author: maringhe@nanom‐mems.com
Bifacial solar cells (Moehlecke et al., 2014; US Pat. No. 9893225/2018 ) are a
relative new type of photovoltaic devices which allow capturing the light from both
sides (front and rear). The advantages of this constructive solution comparatively
with monofacial face solar cells are the following:
- More light converted in electricity per area unit;
- Extended durability;
- Allow vertical positioning during exploitation;
The main disadvantage is price increasing.
Technological and design aspects, materials used for manufacturing these
devices and potential applications are analysed. Preliminary results for prototyping
bifacial solar cells will be reported.
Keywords: Thick film technology, Bifacial solar cell, Monofacial solar cell, Bifacial
efficiency
Acknowledgments: This paper is partially funded by the ROSA STAR contract No.
155/2016.
References
Adriano Moehlecke, Vanessa da Conceição Osório, Izete Zanesco, (2014), Analysis of Thin Bifacial
Silicon Solar Cells with Locally Diffused and Selective Back Surface Field, Materials Research.
17(5):1328-1335
US Pat. No. 9893225/2018, Bifacial solar cell
167
DEVELOPMENT OF MESOPOROUS MATERIALS FOR CATALYTIC

CONVERSION OF RESIDUAL BIOMASS
Elena David, Claudia Sandru, Violeta Niculescu, Adrian Armeanu
Valcea, Code 240050 ‐ Rm. Valcea, Uzinei 4, PO 7 Raureni, Valcea, Romania
Corresponding author: elena.david@icsi.ro
The substitution of non-renewable fossil resources by renewable biomass as a

sustainable feedstock has investigated with the aim to manufacture of biofuels
and new bio-based materials (Liu et al., 2014; Vassilev et al., 2013). Different solid
catalyst systems for the effective conversion of biomass feedstocks have been
investigated. The solid catalysts used in such applications are classified in four main
groups (Xu et al., 2016; Yoshioka et al., 2015; Wang and Xiao, 2015) considering
their substrate activation properties and structures as follows:(i) micro- and
mesoporous materials; (ii) metal oxides; (iii) supported metal catalysts, and (iv)
sulfonated polymers. The research is focused on the substrate activation path and
on the types of chemical reagents used to effect the activation of these groups of
nanomaterials ,and also the corresponding reaction mechanisms. In addition,
recent progress made in chemocatalytic processes for the production of
industrially important products such as bio-oil is presented. The second part of
paper presents our results obtained by the recycle of residual biomass as
precursors to generate new nanomaterials and biofuels. The prepared
nanomaterials can be used as catalysts and adsorbents materials for the green
diesel production from vegetable oil sludge. The experiments performed refer to
the extraction of silica and carbon from wastes by physico-chemical methods, use
of the silica and carbon extracted as precursors for the obtaining of new
nanomaterials such as (ZSM-5) and mesoporous materials (MCM-41, Al-MCM-
41,SBA-3); modification and functionalization of these new nano and meso-
structures by introducing of heteroatoms such as Al and Ti species; application of
these modified and functionalized materials as catalysts for the conversion of
vegetable oil sludge to green fuels (biodiesel) by thermal, pyrolysis and catalytic
cracking reactions.
Keywords: mesoporous materials; catalyst; pyrolysis; catalytic cracking reactions;

biofuels
168
Acknowledgments: The financial Support of this research was provided by the

Ministry of Research and Innovation from Romania, National Plan of Research
& Development in Energy and Environmental field. Project no. PN 18 12 03
01/2018
References
Liu M., Yokoi T., Kondo J. N., Tatsumi T., (2014), Synthesis of SFH‐type aluminosilicate zeolite with
14‐membered ring and its applications as solid acidic catalyst. Microporous and Mesoporous
Materials, 193:166-172
Meng X. J., Xiao F. S., (2014), Green routes for synthesis of zeolite. Chemical Reviews, 114(2):1521-
1543
Vassilev S. V., Baxter D., Andersen L K, Vassileva C G., (2013), An overview of the composition and
application of biomass ash. Part 2. Potential utilisation, technological and ecological advantages
and challenges, Fuel, 105:19-39
Xu S. D., Sheng H. D., Ye T., Hu D., Liao S. F., (2016), Hydrophobic aluminosilicate zeolites as highly
efficient catalysts for the dehydration of alcohols, Catalysis Communications, 78:75-79
Yoshioka M., Yokoi T., Tatsumi T., (2015), Development of the CON‐type alumino‐silicate zeolite and
its catalytic application for the MTO reaction, ACS Catalysis, 5(7): 4268-4275
Wang L., Xiao F. S., (2015), Nanoporous catalysts for biomass conversion, Green Chemistry, 17(1):
24-39
169
DEVELOPMENT AND BASIC RESEARCH ON FLEXIBLE DYE-SENSITIZED SOLAR CELL
Gabriel Roşca, Izabell Crăciunescu, Alexandrina Nan, Adrian Bot
Corresponding author: gabriel.rosca@itim‐cj.ro
Dye-sensitized solar cells (DSSCs) have gained much attention in recent years
(Law et al. 2005, Joly et al. 2014) due to their simple manufacturing process, low
cost of materials, light weight, flexibility, good photocurrent conversion efficiency,
short energy payback time and tuneable properties (Mathew et al. 2014).
A dye-sensitized solar cell is also known as the Grätzel cell, named after its
inventor, Michael Grätzel (Grätzel 2003). This cell is comprised of a porous TiO2
layer with an organic dye molecule adsorbed onto its surface that acts as the
sensitizer to absorb sunlight. An electron is transferred from the dye to the TiO2
and then an electrolyte acts to electrochemically regenerate the dye to complete
the circuit. This cell is typically made on a glass support substrate, but recent work
has demonstrated that it can easily be fabricated using a plastic substrate for
flexible devices.
Flexible dye-sensitized solar cells (DSSCs) built on plastic substrates have
attracted great interest as they are lightweight and can be roll-to-roll printed to
accelerate production and reduce cost. Moreover, processing and handling of
polymer foil devices in general is more difficult because plastic substrates such as
PET are permeable to water, oxygen and volatile electrolyte solvents, which is
detrimental to the cell stability. Another major challenge for the fabrication of
flexible solid-state DSSCs is the fabrication of good quality TiO2 films at low
temperature, because the plastic substrate is not resistant to high temperature.
Our research will focus first to investigate and identified the critical parameters
regarding the stability of the DSSCs on polymer foil (PET) and second to determine
and improve the efficiency of these solar cells by adapting the generally defined
standard test condition to our ambient and operating condition.
An indium tin oxide (ITO) polymer foil (PET) will be used as a substrate for DSSC
construction and the production process will be adapted taking in consideration the
low chemical and temperature stability of the polymeric foil. For that aqueous TiO2
paste without organic surfactants should be used and the sintering temperatures
will be 180°C, sufficient to produce mechanically stable TiO2 films. In order to avoid
the presence of air bubbles in the electrolyte layer, alternative sealing technology
170
can be used. Counter electrodes have been prepared by deposition of a thin layer
of graphite on the polymeric foil by the spray method.
Additionally, adapted measuring systems for this kind of solar cells will be
developed in order to overcome the limitations of non-precise measurement of
flexible dye-sensitized solar cells. These limitations are related to poor mechanical
and thermal stability and for this a solid mask will be built and integrated in the
measurement system where the solar cell will be placed for measurements. A
thermostatic cuvette will be placed between the solar cell and the irradiation
system to avoid overheating of the polymeric foil and surface modification.
Keywords: dye‐sensitized solar cells, PET‐ITO, flexible DSSCs.
Acknowledgments: This work was financially supported by the Ministry of Research

and Innovation through the Nucleus project PN 18 03 01 02.
References
Michael Graetzel, (2003), Journal of Photochemistry and Photobiology C: Photochemistry Reviews,
4(31):145-153
D. Joly, L. Pellejà, S. Narbey, F. Oswald, J. Chiron, J.N. Clifford, E. Palomares, R. Demadril, (2014), Sci.
Rep., 4:4033
M. Law, L. E. Greene, J. C. Johnson, R. Saykally, P. Yang, (2005), Nat. Mater., 4: 455-459,
10.1038/nmat1387
S. Mathew, A. Yella, P. Gao, R. Humphry-Baker, B. F. E. Curchod, N. Ashari Astani, I. Tavernelli, U.
Rothlisberger, M. K. Nazeeruddin, M. Grätzel, (2014), Nat. Chem., 6:242-247,
10.1038/nchem.1861
171
ELECTROCHEMICAL PERFORMANCES OF
LEAD-LEAD DIOXIDE-COPPER OXIDE GLASSES AND VITROCERAMICS
AS ELECTRODES FOR BATTERIES
Simona Rada1, 2, Mioara Zagrai1, 2, Marius Rada1,

Lidia Magerusan1, Ramona Suciu1, Maria Suciu1
1
National Institute for Research and Development of Isotopic and MolecularTechnologies,
2
Physics and Chemistry Department, Technical University of Cluj‐Napoca, 400020, Romania
Corresponding author: simona.rada@itim‐cj.ro
Glasses and vitroceramics having chemical composition of xCuO∙(100-

x)[4PbO2∙Pb] where x=0-70mol% CuO were prepared by conventional melt quenching
method. The samples were characterized by the investigations of analysis XRD and
SEM, UV-Vis spectroscopy and measurements of cyclic voltammetry.
Figure 1. a) SEM images, b) Compositional evolution of the optical gap energies,

c) Cyclic voltamograms for the three cycles of the samples in the xCuO∙(100-x)[4PbO2∙Pb]
composition where x=0-70 mol % CuO.
All diffractograms indicate the presence of two large halos characteristic

structure of amorphous samples. For sample with x=70mol% CuO a small
172
diffraction peak centered at about 35.40 assigned to the monoclinic CuO crystalline
phase was observed.
By introduction of higher CuO content (x≥40mol% CuO) in the host matrix, the
SEM micrographs evidenced inhomogeneous regions with some crystalline grains
with the spherical morphology formed on the surface. At higher CuO concentration,
copper oxide are unable to accommodate in the glass network and accumulate in
form of grains, which induces glass structure deformation for sample with
x=70mol% CuO. Cooper ions did not penetrate deep inside the matrix network and
diffuse out, which leaves traces in the structure of the sample.
An examination of the UV-Vis spectra reveals that with progressive CuO
addition a shift of the absorption edge toward longer wavelength side and an
increase in intensity in both of the UV and visible regions were identified.
Accordingly, the absorption edge and Cu +2 absorption band show different
dependences on the CuO concentration. These compositional evolutions suggest
that other species than Cu+2 ions alone such as Cu +1 ions contribute to the overall
absorption spectra.
Gap energy values were determined to evaluate the semiconducting properties
of the obtained samples. The values for the direct optical band gap energies are
observed to decrease from 2.85 to 2.05eV while for the indirect optical gap
energies are lying from 2.88 to 2.15eV with the increasing of CuO content up to
70mol% (Rada et al., 2017).
The increase of the number of non-bridging oxygen atoms as a function of CuO
content in studied samples leads the depolymerization of the host matrix, reduces
the stability of the network and favors the association of copper ions in clusters.
Samples used as working electrode in measurements of cyclic voltammetry
were demonstrated their electrochemical performances and the voltammograms
show the partial reversible processes.
Keywords: XRD, glasses and vitroceramics, electrode, cyclic voltametry
Acknowledgement: This research was supported by the “Core Program 2016” (Nr.
PN 16‐300205). The authors are gratefully acknowledged.
References
S. Rada, M. Zagrai, M. Rada, A. Popa, R. Suciu, S. Macavei, M. Suciu, Structure, electrochemical
characterization and the role of copper oxide in lead-lead dioxide glasses and vitroceramics,
2017, Journal of Non-Crystalline Solids,vol. 491, pag. 55-63
173
SPECTROSCOPIC AND ELECTROCHEMICAL PROPERTIES ON THE

LEAD-LEAD DIOXIDE-MANGANESE DIOXIDE VITROCERAMICS
Mioara Zagrai1, Simona Rada1,2, Ramona Suciu1, Marius Rada1, Adrian Bot1
1
National Institute for Research & Development of Isotopic and Molecular Technologies,
2
Physics and Chemistry Department, Technical University of Cluj‐Napoca,
400020 Cluj‐Napoca, Romania
Corresponding author: mioara.zagrai@itim‐cj.ro
Today lead acid batteries are the most commonly used energy storage
technology in material handling systems. Evaluation methods for the energy
efficiency of forklifts, traction batteries and chargers have gained in relevance in
this field. Generally, representative cycles are used to determine the energy
efficiency in order to avoid multiple long lasting cycle live tests. At first glance this
seems to be the adequate approach. However, for electrochemical storage systems
with significant side reactions - like lead acid batteries - this procedure leads, to
significantly lower values for energy efficiencies than in real life applications. While
these battery systems need some overcharging to reach fully charged state, an
overcharge is not necessary at every charge/discharge cycle (Büngele et al., 2018).
Manganese (IV) oxide was widely studied due to its technological importance
for catalytic and electrochemical applications.
In this paper, a new vitroceramic system in the xMnO2∙(100-x)[4PbO2∙Pb]
composition where x= 0 – 20 mol% MnO2 were prepared by melt-quenching
method. Structural investigations of prepared samples were performed by the SEM
analysis, FTIR and UV-Vis spectroscopies. The electrochemical properties of the
samples used as working electrodes were investigated by cyclic voltammetry
measurements.
The SEM micrographs evidenced inhomogeneous regions with some crystalline
grains formed on the surface.
The examination of the UV-Vis data show that the intensities of the bands
situated between 200 and 500nm were increased by adding of MnO2 contents in
the vitroceramics matrix. These compositional evolutions can be partly related to
the response of the manganese network because the characteristic visible peaks
due to the Mn+2 coordination geometry were modified in their position or number.
174
Figure 1. a) SEM images and b) Cyclic voltammograms of samples used as working

electrodes in the xMnO2∙(100-x)[4PbO2∙Pb] composition where x= 0 – 20 mol % MnO2
The cyclic voltammograms shows a good reversibility and offers an alternative

of performed electrodes for the rechargeable batteries. By addition of MnO2
contents in the lead-lead dioxide vitroceramic, the position of the process of the
water reduction reaction was not modified towards reactions of hydrogen
evolution and the passivation phenomena of the anodic electrode were
significantly reduced.
Keywords: SEM, electrode vitroceramics, UV‐Vis, cyclic voltammetry
Acknowledgments:This work was supported by grants of the Romanian National

Authority for Scientific Research and Innovation, project number PN 18 03 01 02.
References
J. Büngeler, E. Cattaneo, B. Riegel, D. UweSauerb, (2018), Advantages in energy efficiency of flooded
lead-acid batteries when using partial state of charge operation, Journal of Power Sources,
375:53-58
175
SYNTHESIS OF A NEW LABELED 15N ORGANIC COMPOUND BASED ON 2-

NITROMALONALDEHYDE 15N CORE
Claudia Lar, József-Zsolt Szücs-Balázs, Monica Violeta Cîrcu, Anca Cristina Petran,
Codruța Mihaela Varodi, Ștefan Bugeac, Aurel Bâldea
67‐103 Donat, 400293 Cluj‐Napoca, Romania
Corresponding author: claudia.lar@itim‐cj.ro
2- Nitromalonaldehyde is a useful intermediate for the synthesis of a variety

of heterocyclic nitro compounds which would be difficult to prepare by any
alternative procedure (Fanta and Stein, 1960). It is known that the reaction
between aromatic aldehydes with aminoderivatives leads to the formation of the
corresponding Schiff bases (McIntire, 1947). The condensation products formed
between carbonyl compounds and primary amino groups are usually instable,
however in the case of 2- Nitromalonaldehyde with an aromatic diamine there is a
possibility of stabilization of the obtained compound due the formation of
heterocyclic ring (Signor et al., 1971).
The target of this work was the synthesis and structural analysis of a new 15N
organic compound starting from 2-nitromalonaldehyde-15N and an aromatic
diamine; this compound beeing a valuable intermediate in synthesis of other
reagents who may develop applications in different fields (e.g.supramolecular
machines).
Keywords: 15N, 2‐nitromalonaldehyde, diamine, Schiff base
References
P. E. Fanta, R. A. Stein, (1960), Chem. Rec., 60:261
F. C. McIntire, (1947), J . Amer. Chem. Soc. 69:1377
A. Signor, G. M. Bonora, L. Biondi, D. Nisato, A. Marzotto,E. Scoffone, (1971), Biochemistry,
10(14):2748-2752
176
MULTI-ELEMENT AND 13C ANALYSIS FOR ASSESSING QUALITY OF MEAT
Adriana Dehelean, Dana Alina Magdas, Cezara Voica,

Gabriela Cristea, Ioana Feher
Donat Str., 400293, Cluj‐Napoca, Romania
Corresponding author: adriana.dehelean@itim‐cj.ro
The risk of heavy metal contamination in meat is of great concern for both
food safety and human health because of the toxic nature of these metals at
relatively minute concentrations. Some heavy metal ions that are known to be
potentially toxic include Al, As, Cd and Pb and also essential metals such as Fe, Mn,
Cu, Zn, Se, Ni and Co. The concentrations of these metals seem to vary among the
species or different tissue animals. Meanwhile, relative carbon stable isotope
abundance (δ13C) in meat samples, could provide valuable information about the
isotopic composition of the animals feed, fact that can lead to meat traceability in
the food chain.
In this light, the present study is focused on determination of elemental
distribution and 13C content in different meat tissues of two species animals (beef and
pork). The concentration of macro and micro minerals and toxic metals were measured
using Inductively Plasma of Mass Spectrometry (ICP-MS). The determination of δ13C
from meat samples were carried out on an Elemental Analyzer, coupled with an
isotopic ratios mass spectrometer.
The experimental data were subjected to analysis of variance (ANOVA),
Pearson correlation and principal component analysis (PCA). ANOVA analysis was
performed to reveal the parameters that could distinguish different animal species
(beef or pork) and type of animal tissues (muscles, leg, neck or chop). The
correlations between investigated parameters (elemental and 13C content) were
established using Pearson correlation analysis. PCA was applied to reduce the
number of variables to principal components and also to group the analysed
samples to their similarities. Furthermore, an attribution of influence upon every
principal component was performed.
Keywords: metals, 13C, ICP‐MS, chemometric method, animal species
Acknowledgments: The financial support of this work was provided by the National
Plan for Research-Development, PN18-03 02 02.
177
References
Salwa A. Abduljaleel, M. Shuhaimi-Othman and Abdulsalam Babji Salwa, (2012), Assessment of
Trace Metals Contets in Chicken (Gallus gallus domesticus) and Quail (Coturnix coturnix
japonica) Tissues from Selangor (Malaysia). Journal of Environmental Science and Technology
5(6):441-451.
Duruibe J.O., M.O.C. Ogwuegbu and J.N. Erwurugwu, (2007), Heavy metal pollution and human
biotoxic effects. International Journal of Physical Science 2:112-118.
178
DEVELOPMENT OF VOLTAMMETRIC SENSORS BASED ON CONDUCTING

POLYMERS FOR THE DETECTION OF AMINO ACIDS
Ancuţa Dinu1, Constantin Apetrei2

1
Department of Chemistry, Physics and Environment, Faculty of Science and Environment, “Dunărea
de Jos” University of Galati, Domnească Street, 47, Ro‐800008, Galati, Romania
2
Department of Chemistry, Physics and Environment, Faculty of Science and Environment, “Dunărea
de Jos” University of Galati, Domnească Street, 47, Ro‐800008, Galati, Romania
Corresponding authors: ancuta.dinu@ugal.ro; apetreic@ugal.ro
Conducting polymers were intensively studied as sensitive materials for the

development of different types of sensors. It is related to the different compounds
and materials, which can be obtained at the laboratory scale, with different
sensitivity properties.
In this studies were developed sensors based on polypyrrole doped with
different anions for the detection and quantification of amino acids. The
polypyrrole were electrosynthetised on the Pt surface, by chronoamperometry in
the presence of different doping agents. The characterization of the sensors was
carried out in KCl solution. The peaks observed are related to the oxido-rduction
processes of the polypyrrole. The peaks are influenced by the nature of the cation
and anion presents in the solution. Therefore, the detection of electroinactive
compounds is possible using this type of sensors. In potassium ferrocyanide and
catechol solutions, respectively, the voltammetric signals are complex, including
several peaks, both in anodic and in cathodic scan. The detection of electroactive
compounds from the aquous solution is possible.
The sensors were successfully employed in the detection of amino acids in
aqueous solutions, both from individual solution and from pharmaceutical products
(i.e. phenylalanine). The sensitivity is in the micromolar range and the excipients
interferences are insignificant.
Keywords: sensors, polypyrrole, voltammetry, amino acid
179
ASPECTS CONCERNING INCREASING OF WETABILITY OF MIXED CATALYTIC

PACKING FOR HYDROGEN-WATER ISOTOPIC EXCHANGE
Gheorghe Ionita, Amalia Soare, Ionut Spiridon
Vâlcea, R&D Department, Gas‐chromatography Lab., no. 4 Uzinei str. 240050, Rm. Vâlcea
Corresponding author: gheorghe.ionita@icsi.ro
A demonstration pilot for separation of tritium and deuterium based on cryogenic

distillation (CD) of hydrogen coupled with catalytic exchange in liquid phase (LPCE)
between hydrogen and water vapors is under testing at ICSI-Rm.Valcea (Romania). In
LPCE process, the isotopic exchange take place in two steps:
H2 (gas) + HTO (vapor) <-----> HT (gas) +H2O (vapor) (1)
H2 O (vapor) + HTO (liquid) <-----> HTO (vapor) + H2O (liquid) (2)
H2 (gas) +HTO (liquid) <-----> HT (gas) +H2O (liquid) (3)
Reaction (1) is a catalytic reaction and needs a hydrophobic catalyst which repels
the liquid water but allows the water vapor and hydrogen gas to reach the active
catalytic centers and to accelerate the isotopic transfer process. On the other hand, the
second process (2) is a conventional water distillation process and needs an efficient
contact element (hydrophilic packing) in order to increase the contact area between
water vapor and liquid water. ICSI Rm.Valcea has developed an improved mixed
catalytic packing based on the mixture in various ratio of hydrophobic catalyst and
hydrophilic packing, which play the key role in LPCE process.
The efficiency of hydrophilic packing in water distillation process strongly
depends on its wettability, therefore our research efforts have been focused on
increasing the wettability of the packing. The present study it’s focused on the ways to
increase the wettability of two hydrophilic packings manufactured in the same
geometry and structure (coded B-7 type) but made of different materials: bronze-
phosphorous and stainless steel; Two procedures, based on solution A and solution B
has been applied and tested at normal condition and at increased temperature. The
hold-up; wire size, roughness of wire and SEM image have been evaluated and
discussed as main parameters of treated packing in deep correlation with the
wettability of packing.
The results showed as the treatment based on solution B, at increased
temperature it is a promising idea and can be applied for the new improved mixed
catalytic packing which will equipped the isotopic exchange columns of the future
Tritium Removal Facility from Cernavoda Nuclear Power Plant. This procedure it is
also subject to be patented.
180
A NEW METHOD TO SYNTHESIZE ELECTROSPUN

POLYACRILONITRILE NANOFIBERS
Radu Dorin Andrei, Adriana Marinoiu, Felicia Bucura, Anca Zaharioiu, Violeta
Niculescu, Claudia Sisu, Elena Carcadea
Corresponding author: radu.andrei@icsi.ro
Nanotechnology is the science that implies the obtaining, manipulation and

characterization of functional structures composed of particles with at least one of
its dimensions measured in nanometers (Assis et al., 2012). Polymeric nanofibers
present various functionalities and have demonstrated the potential for
applications in many fields (Weiss et al., 2006) due to their mechanical, electrical
and thermal properties.
At present the electrospinning method receive great attention as the
cheapest path to perform organic nanofiber. The electrospinning is a technique
which implements high positive voltage (10 - 40 kV) to polymer fluid (nanofiber),
and spray it to a target who is charged negatively.
The electrospinning approach is the most widely used technique to form
polymer nanofiber owed to its repeatability, ease of scale-up the process and
fabrication of large and uninterrupted nanofibers. Likewise, this technique that
uses electrostatic forces to generate thin fibers from polymer solutions or melts
can produce fibers with a smaller diameter, ranging from 10 nm to 1000 nm, and a
higher surface area than those coming from common spinning techniques
(Bhardwaj and Kundu, 2010).
One of the key equipment present within the National Centre for Hydrogen
and Fuel Cells (CNHPC) department, namely a Nanofiber Electrospinning Unit from
Kato Tech Co, LTD was used to perform the synthesis of electrospun fibers.
Polyacrylonitril (PAN) polymer is the best precursor for the synthesis of
electrospun fibers and, subsequently for the carbon fibers production. Their
properties are due to a combination between tensile and compressive properties
and the carbon yield. Their thermal stability is a significant parameter to develop
more applications of these fibers (Park and Heo, 2015).
The polymer solutions of various concentration 4, 6, 8, 10, and 12%,
respectively (w/v) were prepared using N,N-dimethylformamide (DMF) as solvent.
The mixtures were ultrasonicated at 40°C until the polymer was completely
dissolved (usually between 4-5 h).
181
The as-prepared samples were carbonized at two different temperatures

1200°C and, respectively, 1400°C in order to observe the chemical composition. The
results are showed in Table 1. We can easily observe that if we increase the
carbonization temperature more carbon is obtained, ~95% at 1200°C against ~97%
at 1400°C. At the same time, when the carbonization temperature increases the
nitrogen and hydrogen concentrations slightly increase and the concentration of
oxygen easily decreases.
Tabel 1. The elemental composition of the sample carbonized at different temperature

Carbonization
Sample % PAN %C %N %O %H
temperature, °C
P1 4 1200 96.29 3.1 0.26 0.35
P2 6 1200 94.85 4.19 0.36 0.6
P3 8 1200 96.21 3.08 0.4 0.3
P4 10 1200 95.85 3.67 0.27 0.20
P5 12 1200 95.45 3.36 0.48 0.7
P6 4 1400 95.18 4.19 0.47 0.15
P7 6 1400 96.85 2.73 0.41 -
P8 8 1400 97.92 1.72 0.35 -
P9 10 1400 97.51 2.06 0.42 -
P10 12 1400 97.21 2.34 0.38 0.06
In conclusion, through this study, we were interested to synthesize electrospun

fibers from PAN precursor and N,N-dimethylformamide as solvent and to observe the
differences in chemical composition after carbonization treatment at two
temperatures. It was observed that a high temperature, 1400 °C is necessary to obtain
sample with more carbon in its composition. Moreover, the images after carbonization
treatment confirm that at 1400 °C the graphitization process take place.
References
Assis L., Zavareze E. R., Prentice-Hernandez C., de Souza-Soares L. A., (2012), Review: Charasteristics of
nanoparticles and their potential applications in foods, Brazilian Journal of Food Technology, 15(2),
99-109
Bhardwaj N., Kundu S. C., (2010), Electrospinning: A fascinating fiber fabrication technique, Biotechnology
Advances, 28, 325-347
Park S.J., Heo, G.Y., (2015), Chapter 2: Precursors and Manufacturing of Carbon Fibers, Carbon Fibers,
Springer Series in Materials Science, 210
Weiss J., Takhistov P., McClements D. J., (2006), Functional Materials in Food Nanotechnology, Journal of
Food Science, 71(9), 107-116
182
ELECTROCHEMICAL STABILITY INVESTIGATION OF PLATINUM ON GRAPHENE

OXIDE CATALYST USING CYCLIC VOLTAMMETRY METHOD
Claudia Sisu, Radu Dorin Andrei, Adriana Marinoiu, Claudia Sandru, Marius
Constantinescu, Irina Petreanu, Elena Carcadea
Corresponding author: claudia.sisu@icsi.ro
Cyclic voltammetry (CV) is the most widely used electrochemical technique to

investigate the reduction and oxidation processes of different atomic species. The
might of cyclic voltammetry comes from its ability to rapidly ensure considerable
information on the thermodynamics of redox processes and the kinetics of
heterogeneous electron-transfer reactions, and on coupled chemical reactions or
adsorption processes. In a cyclic voltammetry experiment the potential of working
electrode is ramped straight versus time. After the set potential is fulfilled in a CV
test, the potential of the working electrode is sloped in the reverse position to go
back to the original potential. These cycles of slope in potential could be repeated
so many times are necessary. The current at the working electrode is represented
against the applied voltage in order to obtain the cyclic voltammogram curve.
A CV system consists of an electrochemical cell, a potentiostat, a current-to-
voltage converter and a data acquisition system. The cell consists of a working
electrode, counter electrode reference electrode and electrolytic solution. The
working electrode's potential is varied linearly with time, while the reference
electrode maintains a constant potential. The counter electrode conducts
electricity from the signal source to the working electrode. The purpose of the
electrolytic solution is to provide ions to the electrodes during oxidation and
reduction. The CV's graphs can be used to determine the atoms that are
reduced/oxidized at the electrode during the reaction; find the area under the
curve of the cyclic voltammogram. If the area is divided by the scan rate this will
give the charge (Q/As) that is associated with the electron transfer in reaction.
In the present work, we evaluated the electrocatalytic activity of Platinum on
Graphene Oxide (Pt/GrO) catalyst by cyclic voltammetry (CV) of potassium
ferrocyanide (K4[Fe(CN)6]) as redox system. Series of voltammograms under several
experimental conditions were thoroughly analyzed in order to evaluate the stability
and durability of our catalysts.
Catalyst ink was prepared by dispersing the Pt/GrO catalyst with isopropyl
alcohol, deionized water and 5 wt% Nafion (Aldrich) dispersion and sonicated in
cold-water for 45 min. Thin catalyst film was deposited by dropping 10 µl of the
catalyst ink onto the polished gold disk electrode (4 mm diameter) followed by
drying at 40°C.
183
The electrochemical measurements were performed using a VersaSCAN

electrochemical workstation including two potentiostats VersaSTAT F and 3F from
Princeton Applied Research that is present in our institute and can be seen in the
National Centre for Hydrogen and Fuel Cells (CNHPC) department.
A classical three electrodes cell was used for the cell measurements, using an
Ag/AgCl electrode and a Pt wire as the reference and counter electrodes,
respectively. The prepared electrodes were tested on a solution of 5 mM
K3[Fe(CN)6] in distilled water, using KCl as indifferent electrolyte so that the
concentration was 100 mM. CV experiments were performed between -0.35 and 1
V vs Ag/AgCl with a sweep rate of 50 mV s-1. This test could be assigned as an
accelerated stability test (AST) using CV evaluation electrochemical method due to
drastic conditions in terms of potential. From Figure 1 it can be observed that at
more positive potential, a double layer region can be detected and in the potential
interval of 0.6 - 1 V vs. NHE, large peaks are presented and assigned to the
formation of platinum hydroxide and oxide in the anodic scan and reduction of the
platinum oxides in the return sweep (Flores-Rojas et al., 2016). Also, we can
observe that the catalyst is stable and no change in the shape of the voltammetry
curve is observed after 200 cycles.
6 -1 6 -1
Pt/GrO, 50 cycles, 50 mV.s Pt/GrO, 200 cycles, 50 mV.s
4 4
2 2
Current, µA
Current, µA
0 0
-2 -2
-4 -4
(a) (b)
-6 -6
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
Potential, V Potential, V
Figure 1. The accelerated stability tests of Pt/GrO catalyst after a) 50 cycles, b) 200 cycles
In summary, we presented the cyclic voltammetry analyzes of one electrode

prepared by depositing the catalytic ink on the electrode support. It was observed
that Pt-based catalysts are capable for electro-adsorbing/electro-desorbing of more
hydrogen and oxygen. Moreover, the accelerated stability tests (ASTs) of the
catalyst shown that all catalysts are stable even after 200 cycles.
References
Flores-Rojas, E., Cabaṅas-Moreno, J.G., Pérez-Robles, J.F., Solorza-Feria, O., 2016, Mechanochemical
synthesis of Co and Ni decorated with chemically deposited Pt as electrocatalysts for oxygen
reduction reaction, Materials Chemistry and Physics, 183, 101-109
WP3 “New binary/ternary catalyst systems” - Ex‐situ electrocatalyst tests. Defined electrochemical
test procedures for screening of catalyst activity” Authors: Edel Sheridan (SINTEF), Magnus
Thomassen (SINTEF), Nicolas Guillet (CEA)
184
A NEW METHOD TO OBTAIN PT ON GRAPHENE OXIDE USING

MICROWAVE REACTOR
Felicia Vasut, Anisoara Oubraham, Adriana Marinoiu, Amalia Soare

1
Corresponding author: felicia.vasut@icsi.ro
Graphene, a monolayer of sp2-bonded carbon atoms packed into a two-

dimensional honeycomb lattice has high surface area (2600 m2/g), high chemical
stability, and unique electronic and mechanical properties. It is a promising material for
application like nanoelectronics, composites, Li-ion batteries or sensors. Metal
nanoparticle deposed on graphene nanosheet have attracted considerable interest
because of the combination’s remarkable unusual properties of metal nanoparticles
with graphene and hence their synthesis has become scientific and technological
importance (Muszynski et al. 2008; Liu et al., 2010). Pt on graphene have been proven
to be a most promising material because Pt based materials exhibit high catalytic
activity and stability (Liu et al. (2011). The old method needs many steps and corrosive
chemical compounds (Tan et al., 2013). In the paper is presented a new method to
obtain Pt on graphene that involves only one step and non-corrosive substances.
Pt on graphene oxide has been prepared by a reduction method using
microwave processing using ethylene glycol or acetone for reduction of H2PtCl6 in a
graphene oxide solution. The analytic techniques like Field Emission Gun Scanning
Electron Microscope (FESEM), Brunauer, Emmett and Teller (BET) method have been
used to characterize the resulting materials. The material that was used to prepare Pt
on graphene oxide reduced are: graphene oxide powder produced by Abalonyx AS,
Norway, H2PtCl6 premion 99,9999% (metals basis) crystalline from Alfa Aesar, acetone
(99,92%) purchased from CHIMREACTIV SRL Romania, glycolic acid 99,99% purchased
from Alfa Aesar.
Keywords: platinum, graphene, preparation method, microwave
References
Muszynski R. et al., (2008), Decorating graphene sheets with gold nanoparticles. J. Phys. Chem. C.,
112(14):5263-5266
Liu S. et al., (2010), ‘‘Green’’ electrochemical synthesis of Pt/graphene sheet nanocomposite film
and its electrocatalytic property. J Power Sources, 195:4628-4633
Liu S. et al., (2011), Microwave‐assisted rapid synthesis of Pt/graphene nanosheet composites and
their application for methanol oxidation, J Nanopart Res, 13:4731-4737
Tan C. et al., (2013), Synthesis and applications of graphene-based noble metal nanostructures
Materials Today, 16(1/2):29-36
185
SYNTHESIS OF GOLD NANOPARTICLES SUPPORTED ON REDUCED GRAPHENE

OXIDE BY MICROWAVE PROCEDURE
Adriana Marinoiu, Felicia Vasut, Anisoara Oubraham, Radu Dorin Andrei,

Irina Vagner, Amalia Soare, Catalin Capris, Elena Carcadea
Corresponding author: adriana.marinoiu@icsi.ro
Microwave-assisted synthesis is considered a green chemistry approaches for

organic synthesis due to pollution free and eco-friendly nature. These synthesis
methods, which involves microwave exposure of reactants in presence or absence
of solvents offer high yields together with simplicity in processing and handling.
In contrast to the slow heating with traditional equipment (oil baths, heating
mantles), which creates hot surfaces on the reaction vessel where products,
substrates and reagents often decompose over time, microwave provide an
efficient heating of materials (by “microwave dielectric heating”) depending on the
ability of a specific material (solvent or reagent) to absorb microwave energy and
convert it into heat. With microwave heating, the energy can be applied directly to
the sample rather than conductively, via the vessel. Heating can be started or
stopped instantly, or the power level can be adjusted to match the required.
Graphene, one kind of two-dimensional nanomaterial, consisting on a single
or few layers of graphite, with a honeycomb C-C network has attracted great
interest due to its high electrical conductivity, excellent mechanical strength, large
specific surface area, thermal, optical and electromagnetical properties which offer
possible application in a series of top technology including energy storage, gas
sensors, electromagnetic interference shielding, composite or catalysis. The
dispersion of metal nanoparticles on graphene sheets may result in the production
of some excellent materials for various potential applications in many fields such as
catalyst, electronics, and biology. Au/rGO are remarkable properties but the
drawbacks for graphene-based hybrid materials are the nonuniform particle
diameters and the weak interaction between GO and AuNPs.
Microwave irradiation triggers the uniform and prompt heating of reaction
mixtures, thereby allowing simultaneous reduction of GO and metal ions, resulting
in the rapid formation of Au/rGO. Therefore, nanoparticles of very little size with
narrow size distribution can be achieved.
On the other hand, reduced graphene oxide characterized by moderate
hydrophilicity, interfacial defects and low degree of porosity is very often
186
recommended as catalytic support. This is due to its capability of anchoring noble

metal nanoparticles for the catalyst preparation for acidic media (e.g. for utilization
as electrocatalyst in PEM fuel cells).
The fast microwave heating provides homogeneous reaction environment
and offers good control of shape and size distribution of composites. According to
the obtained results, Au/rGO samples were produced at microwave power of 800
W, temperature 80 C for 30 minutes only.
Cyclic voltammetry experiment was used for the investigation of electrocatalytic
performance of Au/rGO. Support material rGO also plays an important role in
improving the activity of the catalysts. Specifically, the experimental parameters are as
follows: Ag/AgCl electrode and a Pt wire as the reference and counter electrodes; 5
mM K3[Fe(CN)6] in distilled water; KCl as indifferent electrolyte; 50 mV s-1 as scan rate
and −0.35 to +0.8 V as applied potential range.
The reduction and oxidation potential and peaks current showed a good
electrocatalytic activity of Au/rGO indicating that reduced graphene contributed to
the enhancement of the activity of Au (Fig. 1).
3 -1 3 -1
Au/rGO, 50 cycles, 50 mV.s Au/rGO, 200 cycles, 50 mV.s
2 2
1 1
Current, µA
Current, µA
0 0
-1 -1
-2 -2
(a) (b)
-3 -3
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8
Potential, V Potential, V
Figure 1. The cyclic voltammograms of Au/GrO-100 catalyst after a) 50 cycles, b) 200 cycles
In summary we synthesized graphene composites using assistance of

microwave irradiation could find application for energy – storage domain such as
fuel cells. Furthermore, this technique demonstrated real advantages such as
simple, quick, inexpensive, uniform could be used more and more in the next
future in order to prepare different materials with controlled size and shape for the
energy application.
187
PEROVSKITE-TYPE LANTHANUM COBALTITE FOR USE AS A CATALYST:

SYNTHESIS AND CHARACTERIZATION
Mirela Dragan1, Stanica Enache, Amalia Soare1, Konstantin Petrov1,2,

Mihai Varlam1
1
2
Academician Evgeni Budevski Institute of Electrochemistry and Energy Systems, Sofia, Bulgaria
Corresponding authors: mirela.dragan@icsi.ro; stanica.enache@icsi.ro
Nowadays the increasing of energy demands (Eurostat Database), concerns

about global climate changes associated with carbon dioxide emissions released by
the burning of fossil fuels (Climate Action) require new alternative fuels for
domestic heat and power as well as for transportation (Towards the broadest use
of alternative fuels).
Hydrogen is considered an ideal energy carrier that can be an alternative to
fossil fuels due to the fact that hydrogen is a clean and recyclable material (Horng
et al., 2012). Currently, the hydrogen production technologies include reforming of
natural gas (Maxwell, Gary, 2005) gasification of coal and petroleum coke (Collot,
2003) as well as gasification and reforming of heavy oil (Domenichini et al., 2010).
When compared to other available methods the electrochemical production
of hydrogen by alkaline water electrolysis is one of the most promising
environmentally friendly technology with great advantage of producing
environmentally friendly technology (>99.9%) (Chen et al., 2016).
For industrial large-scale systems of hydrogen production using water
electrolysis some improvements are needed. A great deal of work is devoted to the
development of electrodes for alkaline water electrolysis (Maruthapandian et al.,
2017; McCrory et al., 2013). Finding low cost electrode materials that are both
efficient and having long term stability is one of the remaining challenges within
the field of alkaline water electrolysis (Fabbr et al., 2014; Hall, 1981).
These circumstances open up many opportunities for research and
development leading to advancements towards industrial applications of alkaline
water electrolysis.
The effort of the present study was to develop non-precious metal-based
electrode materials for oxygen evolution reaction (OER) that can perform well
enough to replace precious and scarce metal-based catalysts.
The perovskite-based catalysts are a competitive alternative among the
noble-metal-free materials. These materials provide advantage over precious
188
metal-based catalysts not only from the aspect of low price but also the tolerance
during application.
The perovskite type oxide lanthanum cobaltite (LaCoO3), which is an industrial
important conductive ceramic material which finds a broad range of applications
and have promising catalytic activity towards oxygen evolution reaction in alkaline
media and it is the subject of this study.
The challenge is to develop a new technique that can overcome these
insufficiencies and is beneficial to both environmental protection and industrial
applications.
Taking in account these considerations a solid-state reaction process has been
developed in our laboratory to prepare the lanthanum cobaltite. The experiments
conducted for the work reported here indicate that, with proper improvement, the
solid-state reaction may also provide a new preparation method for perovskite-
type LaCoO3 powder.
Characterization of prepared lanthanum cobalt oxide material have been
studied by X-ray diffractometry (XRD), scanning electron microscopy (SEM),
thermogravimetry - differential thermal analysis (TG - DTA).
These analyses concluded the phase transformation process yielded a pure
binary oxide.
The most important factor for commercialization which is to produce again
same was analysed and showed good reproducibility of batch to batch powder
properties consistently.
This optimized method of synthesis offers a convenient, inexpensive,
environmentally friendly and effective method for the preparation of perovskite-
type lanthanum cobalt oxide powder material.
Keywords: LaCoO3; oxides powders; synthesis, water electrolysis, non‐noble metal

catalysts.

Education and Research, project "RESTORE" ‐ 117/16.09.2016 ID / Cod My SMIS:
P_37_595 / 104958.
References
Eurostat Database; http://ec.europa.eu/eurostat/data/database.
Climate Action, European Climate Change Programme; https://ec.europa.eu/clima/policies/eccp_en
Towards the broadest use of alternative fuels; https://www.actu-environnement.com/media/pdf/
news-30015-alternative-fuels-ue.pdf
Rong-Fang Horng, Huann-Ming Chou, Wei-Cheng Chiu, José Alexander, Lemus Avalos, Ming-Pin Lai,
You-Ming Chang, (2012), Energy Procedia, 29:216-224
Maxwell, Gary R., (2005), Hydrogen Production In: Synthetic Nitrogen Products, 47-162, Springer,
Boston, MA.
Collot A-G., (2003), Prospects for hydrogen from coal. Report CCC/78, Clean Coal Centre,
International Energy Agency
189
Domenichini R., Gallioa M., Lazzaretto A., (2010), Energy, 35(5):2184-2193

Long Chen, Xiaoli Dong, Yonggang Wang & Yongyao Xia, (2016), Nature Communications, 7, Article
number: 11741
V. Maruthapandian, M. Mathankumar, V. Saraswathy, B. Subramanian, S. Muralidharan, (2017), ACS
Applied Materials and Interfaces, 9(15):13132-13141
McCrory C.C.L., Jung S., Peters J.C., Jaramillo T.F., (2013), Journal of the American Chemical Society,
135(45):16977-16987
E. Fabbri, A. Habereder, K. Waltar, R. Kötz, T. J. Schmidt, (2014), Catal. Sci. Technol., 4:3800-3821
D. E. Hall, (1981), J. Electrochem. Soc., 128:740-746
190
STRUCTURAL MODIFICATION IN Zr1-x(Ge/Y)x COMPLEX OXIDES
Michail-Liviu Craus1,2, Vitalij Turchenko1,3, Valerij Simkin1, Tat'jana Evgenievna

Konstantinova3, Anelija Savin2
1
FLNP‐JINR, Dubna, Russia
2
National Institute of Research and Development for Technical Physics, Iasi, Romania
3
Institute of Physics and Technology “O. O. Galkin”, Donetsk, Ukraine
Corresponding author: craus_ml@hotmail.com; kraus@nf.jinr.ru
The substitution of the zirconium with various rare-earth elements and/or

transitions metals have large influence on the crystallographic transformation of
doped zirconia, implicitly, on the mechanical properties. Recently biomedical
implants from doped zirconia were used to restore the function of those body parts
deteriorated by trauma or desease. The material in use for femoral heads is 3Y-TZP
stabilized zirconia. However, because were reported a series of fractures of femoral
heads investigations of behavior of zirconia based ceramics, in various media were
performed. Another application field for doped zirconia is those of denta.
191
CHARACTERIZATION OF BIOFILMS DEVELOPED ON CARBON STEEL USING

X-RAYS MICRO-DIFFRACTION
Alice Dinu, Mariana Tunaru
Institute for Nuclear Research, Campului Street, No.1, Mioveni, Arges, Romania
Corresponding author: alice.dinu@nuclear.ro
Micro-diffraction technique was used to distinguish the different crystallographic

compounds present in bio-films that can be formed in restricted areas of secondary
side of CANDU NPP pipes. There were investigated small areas with different colour of
carbon steel SA106gr.B samples exposed for 90days in iron-oxidant bacteria
(4,2x1011bacteria cells/ml, pH=9, Vinogradski environment), respectively in sulphate-
reduction bacteria (5,5x1010 bacteria cells/ml, pH=8, Postgate environment). The X-rays
investigation was performed by using an X’Pert Pro MPD diffractometer, with a
ceramic X-ray tube (Cu anode, λCuKα=1.5412Å) and a mono-capillary of 0.1mm. The
analysed areas have a constant width of 142µm and a variable length between 820µm
at an incidence angle of 200, respectively 250µm at ω=700. On the samples exposed in
the Vinogradski environment was obtained that the bio-film is formed of K3P3O6(H2O)4,
Fe5(PO4)3(OH)5, NaPO3(H2O)2, NaNO3, H2Na(PO4), α–Fe2O3, ε–Fe2O3, β–Fe2O3, α–
Fe1.766O3, Fe, α–Fe. The area rich in hematite have a red colour. In the bio-films formed
on samples exposed in Postgate environment, two forms of FeS (with orthorhombic or
hexagonal crystallographic system), F1-xS (crystallised in hexagonal system), β”–Fe2O3 (a
form of hematite with hexagonal lattice) and maghemite (cubic crystallographic
system) are present. The red areas of bio-film are rich in hematite and maghemite,
while the yellow colour is given by the presence of FeS and F1-xS.
Keywords: X‐ray microdiffraction, microbiological corrosion, CANDU secondary side.
192
MASS SPECTROMETRY IN FORENSIC ANALYSIS
Karel Lemr
Regional Centre of Advanced Technologies and Materials,

Department of Analytical Chemistry, Faculty of Science,
Palacky University, 17.listopadu 12, 771 46 Olomouc, Czech Republic
Corresponding author: karel.lemr@upol.cz
Forensic analysis is an interesting area of application of analytical chemistry.

Importantly, it has to satisfy requirements for analytical processes but also
demands on the testimony. Applied methods have to be well proven and accepted
by courts. Elements, isotopes, small organic molecules or biomacromolecules
belong to target analytes. Forensic analysis can help in investigation of murders,
reveal smuggling of abused drugs, arson or food adulteration, just to mention a few
examples. Among used analytical techniques, mass spectrometry plays an
important role. Gas chromatography-mass spectrometry (GC-MS) is considered to
be a gold standard, high performance liquid chromatography-mass spectrometry
(HPLC-MS) or ultra-high performance liquid chromatography-mass spectrometry
(UHPLC-MS) are also routinely used today. The presented overview is focused on
less common techniques that might attract attention of analytical chemists,
toxicologists and forensic chemists.
Elemental analysis by laser ablation-inductively coupled plasma mass
spectrometry (LA-ICP-MS) can differentiate car paints (Deconinck et al. 2006),
origin of documents (Trejos et al. 2010) or natural and Be-treated sapphires with
artificially improved colour (Abduriyim and Kitawaki 2006). We applied LA-ICP-MS
to visualize latent fingerprints of persons manipulated with ammunition or a gun
(Pluháček et al. 2018). Gunshot residues particles detected on fingerprints can
provide the evidence that a suspect was shooting. Isotope ratio mass spectrometry
allows to discriminate between endogenous concentrations and concentrations
resulting from exposure an organism to control substances, e.g. gamma-
hydroxybutyric acid is a naturally occurring neurotransmitter but also a
psychoactive drug (Saudan et al. 2007).
Besides GC-MS, HPLC-MS and UHPLC-MS, small organic compounds can be
effectively separated and detected by supercritical fluid chromatography-mass
spectrometry (SFC-MS). We achieved sufficient fast separation of new psychoactive
substances (eleven cathinones and four phenylethylamines) in less than 1.6 min,
taking advantage of mass spectrometric detection (Pauk et al. 2015). We validated
UHPLC-MS and SFC-MS methods for quantitation of mentioned compounds in urine
(Borovcová, Pauk and Lemr 2018). In comparison to UHPLC, SFC showed higher
193
carryover but separated all isomers and provided more uniform matrix effects and
recoveries. Fast identification of controlled substances was also carried out using
ion mobility-mass spectrometry (Borovcová, Ondruchová et al. 2018). New
approach uses drift time but also profiles of arrival time distributions (mobility
peaks) in different drift gases as compound characteristics. Isobaric and isomeric
analytes were well discriminated. Capillary electrophoresis-mass spectrometry
analysis of lactoglobulins quantified the admixture of bovine milk in either ovine or
caprine milk and provided the evidence of milk adulteration (Müller et al. 2008).
Mass spectrometric analysis can also be carried out without chromatographic
or electrophoretic separation. We developed direct analysis of dyes to distinguish
indigo and Prussian blue in tiny samples of works of art (Pauk et al. 2013). It can
help to date historical paintings as indigo has been used for long time but Prussian
blue was synthesized in 18th century. Desorption nanoelectrospray designed in our
laboratory (Ranc et al. 2007; Hartmanová et al. 2016) belongs to ambient ionization
techniques. It was also tested for forensic applications. As an example colouring of
wine by elderberry extract can be recognized detecting anthocyanins (Hartmanová
et al. 2010). Desorption electrospray and MALDI are widely applied in mass
spectrometry imaging (MSI). MSI can visualize cocaine in a single hair (Porta et al.
2011) or chemical fingerprints. Although some limits have to be considered,
chemical fingerprints can confirm presence of abused drugs (Muramoto et al. 2015)
or manipulation with a condom (detection of lubricants) related to a sexual assault
(Bradshaw et al. 2011).
Many other examples can be found in the literature. Mass spectrometry is
routinely used in forensic laboratories but presented examples demonstrate rather
potential of mass spectrometry than routine procedures. In each case close
collaboration with investigators in sample collection and data interpretation is
essential.
Keywords: chromatography, ion mobility, abused drug, food adulteration,

fingerprint
Acknowledgments: Financial support from the Ministry of Education, Youth and

Sports of the Czech Republic (project LO1305).
References
Abduriyim A., Kitawaki H., (2006), Applications of LA-ICP-MS to gemology, Gems Gemol., 42:98
Borovcová L., Ondruchová J., Havlíček V., Lemr K., (2018 (a)), Profiles of arrival time distributions in
different drift gases as a tool for identification of isomers, International Mass Spectrometry
Conference, poster ThP 154, Florence, Italy, pp. 26-31
Borovcová L., Pauk V., Lemr K., (2018 (b)), Analysis of new psychoactive substances in human urine
by ultra‐high performance SFC and liquid chromatography: Validation and comparison, J. Sep.
Sci., 41:2288
194
Bradshaw R., Wolstenholme R., Blakledge R. D., Clench M. R., Ferguson L. S., Francese S., (2011), A
novel matrix‐assisted laser desorption/ionisation mass spectrometry imaging based
methodology for the identification of sexual assault suspects, Rapid Commun. Mass
Spectrom., 25:415
Deconinck I., Latkoczy C., Günther D., Govaert F., Vanhaecke F., (2006), Capabilities of LA‐ICP‐MS for
(trace) element analysis of car paints for forensic purposes, J. Anal. At. Spectrom., 21:279
Hartmanová L., Lorencová I., Volný M., Fryčák P., Havlíček V., Chmelíčková H., Ingr T., Lemr K.,
(2016), Lateral resolution of desorption nanoelectrospray: a nanospray tip without nebulizing
gas as a source of primary charged droplets, Analyst, 141:2150
Hartmanová L., Ranc V., Papoušková B., Bednář P., Havlíček V., Lemr K., (2010), Fast profiling of
anthocyanins in wine by desorption nano-electrospray ionization mass spectrometry, J.
Chromatogr. A, 1217:4223
Muramoto S., Forbes T. P., van Asten A. C., Gillen G., (2015), Test sample for the spatially resolved
quantification of illicit drugs on fingerprints using imaging mass spectrometry, Anal. Chem.,
87:5444.
Müller L., Barták P., Bednář P., Fryšová I., Ševčík J., Lemr K., (2008), Capillary electrophoresis‐mass
spectrometry ‐ a fast and reliable tool for the monitoring of milk adulteration, Electrophoresis,
29:2088
Pauk V., Havlíček V., Papoušková B., Sulovský P., Lemr K., (2013), Simultaneous identification of
historical pigments Prussian blue and indigo in paintings by ESI‐MS, J. Mass Spectrom., 48:927
Pauk V., Žihlová V., Borovcová L., Havlíček V., Schug K., Lemr K., (2015), Fast separation of selected
cathinones and phenylethylamines by SFC, J. Chromatogr. A, 1423:169
Pluháček T., Švidrnoch M., Maier V., Havlíček V., Lemr K., (2018), LA‐ICP‐MS imaging: A personal
identification based on a gunshot residue analysis on latent fingerprints, Anal. Chim. Acta,
1030:25
Porta T., Grivet C., Kraemer T., Varesio E., Hopfgartner G., (2011), Single hair cocaine consumption
monitoring by mass spectrometric imaging, Anal. Chem., 83:4266
Ranc V., Havlíček V., Bednář P., Lemr K., (2007), Desorption electrospray: A modern tool for organic
surface analysis, Chem. Listy, 101:524
Saudan C., Augsburger M., Mangin P., Saugy, M., (2007), Carbon isotopic ratio analysis by gas
chromatography/combustion/isotope ratio mass spectrometry for the detection of gamma‐
hydroxybutyric acid (GHB) administration to humans, Rapid Commun. Mass Spec., 21:3956
Trejos T., Flores A., Almirall J. R., (2010), Micro‐spectrochemical analysis of document paper and gel
inks by LA‐ICP‐MS and laser induced breakdown spectroscopy, Spectrochim. Acta Part B,
65:884
195
NUCLEAR JET ENGINES TESTS MAKE NEW CHALLENGES FOR STUDIES OF

RADIOACTIVITY IN ENVIRONMENT
Jerzy W. Mietelski1
Institute of Nuclear Physics Polish Academy of Science, Radzikowskiego 152, 31‐342 Krakow, Poland
Corresponding author: jerzy.mietelski@ifj.edu.pl
On 1st March 2018 Russian Federation President V.V. Putin announced that
Russia developed and tested nuclear jet engine as propulsion system to cruise class
missile (Putin, 2018). Although the technical detail how such engine works are
obviously classified one can consider general concept of such device. In open literature
various designs of nuclear rocket engines are discussed (Gabrielli and Herdich, 2015;
Nam et al., 2015). They all are thought to work in open space. For propulsion in
atmosphere more efficient are jet (turbojet) engines than rocket ones. Therefore
announced propulsion system is likely a modified turbojet engine where the
combustion chambers are replaced by the heat exchanger from nuclear reactor, or the
air directly goes through small reactor or that in combustion chambers highly
radioactive sources are located, similar to those used in Radioactive Thermoelectric
Generators (RTG). If it is a nuclear reactor the released contaminations are more or less
predictable regarding observed as result radionuclides. However tests of propulsion
systems based on a RTG–like radioisotopes can produce a novel and unexpected kind
of radioactive contamination with a high purity separated mono radioisotopes which
not necessarily emits gamma radiation. In October 2017 airborne Ruthenium-106
contamination was observed in large part of Europe. Its origin remains still a bit
mysterious It might be related to such test. The appearance of such contamination
makes urgent need for re-consideration of the measurement methods and techniques
used for radioactive monitoring of the air and in general – measurements .
Keywords: Monitoring of radioactivity, nuclear jet engine, RTG, propulsion reactors,

separated radioisotopes
References
Putin V. V. (2018), Presidental Address to the Federal Assembly, http://en.kremlin.ru/events/
president/news/56957
Gabrielli R.A., Herdich G. (2015) Review of nuclear thermal propulsion systems, Progress in
Aerospace Sciences 79, p. 92-113.
Seung Hyun Nam, Paolo Venneri, Yonghee Kim, Jeon Ik Lee, Soon Heung Chang, Yong Hoon Jeong
(2015) Innovative concept for an ultra-small nuclear theral rocket utilizing a new moderated
reactor, Nuclear Eng. Technol., 47 p. 678-699.
196
SMART AND CONNECTED SYSTEM FOR ECOLOGICAL MONITORING AND

SITUATIONAL AWARENESS
Ashok Vaseashta
International Clean Water Institute, Herndon, VA

NJCU – A State University of New Jersey, Jersey City, NJ USA
Ghitu Institute of Electronic Engineering and Nanotechnology, Academy of Sciences of Moldova,
Chisinau, Moldova
Corresponding author: prof.vaseashta@ieee.org
Although the correlation between environmental pollution and global warming is

debatable, the effects of pollution and its impact on human health are irrefutable.
Pollution in large cities has reached an alarming level and is widely perceived to be a
leading contributor to chronic and deadly health disorders and diseases affecting
millions of people each year. Furthermore, increased urbanization and use of fossil
fuels contribute to emission of GHG, widely believed and reported to be responsible
for global warming. In fact, a large sector of the world’s population does not have
access to fossil fuels yet suffer from the adverse effects of pollution due to transport
through air, water, and soil. Similarly, for water, there is a global shortage of clean and
potable water, despite the abundance of water worldwide. With mega cities merging
into mega regions, most water-stressed and lower per-capita income regions suffer
additional socio-political issues, such as gender-inequity, regional conflicts, and
agricultural system vulnerability. Sensing, detection and persistent monitoring of
ecological contaminants is crucial for both general purpose consumption and from
security standpoint. Conventional methods employed to sense/detect such
contaminants use commercial-off the shelf (COTS) systems and broad-spectrum
analytical instruments with interpretive algorithms to detect and characterize toxic
contaminants. With much at stake, it is prudent to challenge conventional wisdom and
investigate a new set of strategies to develop a future monitoring platform employing
a nexus of technological innovations, in conjunction with “acceptable” risk assessment
and a strategic transformation in “use, reuse, and recycle” as effective management
tools to address this grand challenge to design “future sustainability”.
The current environment requires detection of complex contaminant signatures
in addition to recycled pharmaceuticals, GMOs, and other by-products that are present
in food and water supplies, due to the fact that current filtration systems are not
designed to mitigate new variants of contaminants. However, rapid advancements of
molecular biology and its application in environmental microbiology represent a
significant advancement in the ability to rapidly detect microbial pathogens, may it be
waterborne or otherwise. Molecular methods coupled with high-throughput parallel
197
processes may provide a greater range of microorganism detection. The advances in

nanotechnology, bioinformatics and interdisciplinary fields of technologies have
brought in new and promising approaches that can be adapted and coupled with
detection methodologies.
The objective and motivation of this presentation is to provide an overview of a
GIS/GPS based Contamination Identification and Level Monitoring Electronic Display
Systems (CILM-EDS) prototype to sense/detect and spatially monitor contaminants in
real-time with the objectives that appropriate remediation strategies are exercised
before its entry in residential/commercial/industrial distribution. From sustainability
standpoint, it is crucial to note that a third of potable water is wasted due to leaks in
the water supply. The same system with appropriate sensors can monitor leaks and a
smaller version can be utilized along with smart home security monitoring system to
monitor and repair leaks to preserve water. The platform is also designed detect water
levels and hence is capable of producing flash-flood warning and other emergency
scenarios. This paper summarizes recent strategies to monitor flow, levels, and
contaminants in water, soil, and atmospheric monitoring system.
Keywords: Contamination Detection, Water Security, Situational Awareness
Acknowledgment: The investigation in part was supported by a NATO SPS award.
Figure 1. CILM-EDS Contamination Identification and Level Monitoring Electronic

Display Systems – Electronic display system
198
GC–MS AND NEUTRON ACTIVATION (NAA) ANALYSIS

OF MEDICINAL TEUCRIUM L. SPECIES
Nina Ciocarlan1, Alexandru Ciocarlan2, Ion Dragalin2, Aculina Aricu2,

Inga Zinicovscaia2,3,4 and Svetlana Gundorina3
1
National Botanical Garden (Institute) “Alexandru Ciubotaru”, Padurii str. 18, Chisinau MD‐2002,
Republic of Moldova
2
Institute of Chemistry, Academy of Science of Moldova, 3, Academiei str., Chisinau MD 2028,
Republic of Moldova
3
Joint Institute for Nuclear Research, Frank Laboratory of Neutron Physics, Joliot‐Curie str. 6, 141980,
Dubna, Russia
4
Horia Hulubei National Institute for R&D in Physics and Nuclear Engineering, 30 Reactorului Str.
MG‐6, Bucharest ‐ Magurele, Romania
Corresponding author: algciocarlan@yahoo.com
Teucrium L. (Lamiaceae family) is a large genus including more than 300

species widespread all over the world, from which almost 50 species are distributed
in Mediterranean region (Cantino et al., 1992; Tutin et al., 1972). The members of
this genus represent mostly perennial herbs, shrubs or subshrubs.
A large number of species belonging to the genus Teucrium L. are used in folk
medicine for treating mainly digestive and respiratory disorders. Externally some
Teucrium species are useful in diverse skin diseases, such as purulent eruptions,
wounds, mycosis, and skin abscesses. Many species of this genus have been found to
possess hypoglycemic, cicatrizing, hemostatic, diuretic, antispasmodic, anti-
inflammatory, detoxifying, antiseptic, purgative, antifungic, antibacterial and
antioxidant effects (Cantino et al., 1992; Ali and Ali Shah, 2011; Esmaeili and
Yazdanparast, 2004; Stancovic et al., 2011; Tariq et al., 1989).
Along with medicinal value many Teucrium L. species due to antimicrobial,
antioxidant and antifungal activities, are useful as natural preservative ingredients
very demandable today in food industry. T. polium has also an important insect
antifeedant activity against different species of insects (Bruno et al., 2003). In
addition, some Teucrium L. species are valued as ornamental plants and an
important pollen source. All these data reveal a significant medicinal and economic
importance of Teucrium L. species such that in recent decades they are the subject
of different studies.
This paper refers to four medicinal Teucrium L. (T. scordium, T. hircanicum, T.
polium and T. chamaedrys) species cultivated at experimental fields in the National
Botanical Garden (Institute). The allochthonous T. hircanicum species proved an
excellent growth with high vegetative expansion and abundant flowering in the
199
local climatic and soil conditions. The indicators of growth and development of
native T. polium and T. chamaedrys under ex situ conditions are very encouraging,
demonstrating their suitability for cultivation on a large scale.
The samples of Teucrium sp. essential oil were obtained by hydrodistillation
and then were subjected to GC-MS analysis. It must be mentioned that such results
for these species of Moldavian origin are reported for the first time. According to
GC-MS analysis, the main components of Teucrium sp. essential oils may be divided
in several groups according to their origin: monoterpene hydrocarbons (e.g. α- and
β-pinene, α- and β-thujene, β-myrcene, limonene); sesquiterpenes (e.g. β-cadinene,
germacrene, bicyclogermacrene, farnesan, β-farnesene, α-himacalene, α-
patchoulene) and their functional derivatives (myrtenal, spatulenol, eudesmol and
linalool).
The elemental composition of Teucrium L. was determined using neutron
activation analysis. Metal concentrations varied across studied species. The
concentrations of twenty-five major and trace elements were determined in all
species, while chromium was determined only in T. chamaedrys specie. The highest
concentrations of iron, manganese, cobalt and arsenic were found in T. polium, of
zinc in T. scordium and of molybdenum in T. hircanicum.
Keywords: Teucrium, GC‐MS analysis, neutron activation analysis, elemental

content.
References
Ali N., Ali Shah S. W., (2011), Antispasmodic activity of Teucrium stocksianum Boiss. Pakistan J.
Pharm. Sci., 24: 71-174
Bruno M., Maggio A.M., Piozzi F., Puech S., Rosselli S., (2003), Neoclerodane diterpenoids from
Teucrium polium and their antifeedant activity. Biochem. Syst. Ecol., vol. 31(9), p. 1051-
1056
Cantino P. D., Harley R. M., Wagstaff S. J., )1992), Genera of Labiatae: status and classification.
Advances in Labiatae Science, Royal Botanic Gardens, Kew, pp. 511-513
Esmaeili M. A., Yazdanparast R., (2004), Hypoglycaemic effect of Teucrium polium: studies with rat
pancreatic islets. J Ethnopharmacol, 95:27-30
Stancovic M. S., Curcic M. G., Zizic J. B., Topuzovic M. D., Solujic S. R., Marcovic S. D., (2011),
Teucrium Plant Species as Natural Sources of Novel Anticancer Compounds: Antiproliferative,
Proapoptotic and Antioxidant Properties. Int. J. Med. Sci., 12(7):4190-4205
Tariq M., Ageel A. M., al-Yahya M. A., Mossa J. S., al-Said M. S., (1989), Anti‐inflammatory activity of
Teucrium polium. Int. J. Tissue React., 11:185-188
Tutin T.G., Wood D., (1972),Teucrium. Flora Europaea, Cambridge: Cambridge University Press.,
III:129-135
200
PRELIMINARY RESULTS IN RN MONITORING AT INCDM CONSTANTA
Vasile Patrascu1, Codruț Cherestes2, Maria Tomescu3, Silvia Serban2

1
Institutul National de Cercetare‐Dezvoltare Marină ”Grigore Antipa”, Bd. Mamaia, nr. 300,
Constanta, Romania
2
Dositracker SRL, str. Atomiștilor 407, Măgurele, Ilfov, Romania
3
Centrul Meteorologic Regional Dobrogea, Bd. Mamaia, nr. 300, Constanta, Romania
Corresponding author: vpatrascu@alpha.rmri.ro
In order to ensure good living standards, all risk factors are considered in
ensuring work and life conditions. The urban lives we live can be influenced by the
quality of air both at work and at home.
Amongst environmental factors, air is essential to a good quality of life. A
component that demands close supervision is the radioactive gas Radon. It originates
both from natural radioactive constituents of Earth’s crust and construction materials.
This introduces variety to the places where Radon is found, both in terms of local
geological structure as well as building characteristics. Radon concentration levels in
inhabited buildings can also be influenced by the tenant’s daily habits. Both the
presence and measures of reducing the concentration of this radioactive gas require its
monitoring. The adoption of EU directive 2013/59/Euratom imposes the compulsory
protection to Radon exposure of the general population and indoor working personnel,
in buildings with public access and workplaces from any source of Radon infiltration,
whether originating from the ground or from construction materials.
The Radioecology Laboratory INCDM “Grigore Antipa” – Constanta initiated a
program of methodological testing and annual Radon monitoring. Preliminary results
of Radon concentration measurements through an active method range from 10-429
Bq/m3 (Fig. 1). Constant supervision is maintained in order to consolidate observations
of Rn concentration variation over time, as a function of meteorological parameters,
this potentially serving as a benchmark for measurements in coastal areas.
Keywords: air quality, radon, radon measurement, house, workplace.
201
Figure 1. Hourly variation of Rn Concentration and air Pressure at Cta
202
VIRTUAL SCREENING OF TRABENAZINE AND ITS DEUTERATED ANALOGUE

AGAINST THE SYNAPTIC VESICULAR AMINE TRANSPORTER
Radu Tamaian1,2
1 th
National Research and Development Institute for Cryogenics and Isotopic Technologies, 4 Uzinei
street, 240050 Râmnicu Vâlcea, Romania
2 th
SC Biotech Corp SRL, 4 Uzinei street, Office C52, 240050 Râmnicu Vâlcea, Romania
Corresponding author: radu.tamaian@icsi.ro
Tetrabenazine (TBZ) and its isotopic isomer, deutetrabenazine (DEU), are both
approved, investigational drugs. TBZ is an older drug used in present, primarily, for
the symptomatic treatment of various hyperkinetic disorders (Chen et al., 2012;
Kim et al., 2018; Solmi et al., 2018). Its analogue, DEU, is the first deuterated drug
recently approved by the US Food and Drug Administration for the treatment of
related movement disorders associated with Huntington’s disease (Schmidt, 2017).
In DEU, the two methoxy groups from TBZ structure are replaced by a pair of
trideuteromethoxy groups (Fig. 1) – incorporation of deuterium extends the half-
life of DEU in vivo and improve its toxicological profile (Claassen et al., 2017;
Rodrigues et al., 2017; Schmidt, 2017).
Figure 1. Skeletal formulae of TBZ (left side) and DEU (right side)
Both TBZ and DEU act as inhibitors of synaptic vesicular monoamine

transporter (VMAT2), also known as vesicular amine transporter 2 (Claassen et al.,
2017; Kim et al., 2018; Solmi et al., 2018; Stahl, 2018). VMAT2 belongs to the
vesicular transporter family and is a transport protein located on presynaptic
neurons. The precise mechanism of action is still unknown, but VMAT2 is
responsible for reducing the levels of monoamine neurotransmitters in the synaptic
regions – contributing to the drugs clinical efficacy (DeWitt and Maryanoff, 2018;
Stahl, 2018). This “gap” in understanding the underling mechanism of action of TBZ
and DEU is accentuated by the lack of structural information of VMAT2 in the RCSB
Protein Data Bank (Berman and Westbrook., 2000; Rose et al., 2017).
203
The aim of this paper was to use molecular docking, a cheminformatics tool,
to virtually screen TBZ and DEU against VMAT2 in order to predict the binding
conformations and the binding affinity (BA). Virtual screening was carried out with
PyRx 0.9.7 (Dallakyan and Olson, 2015), using AutoDock 4.2 as docking software
(Morris et al., 2009). Structural files of ligands (TBZ and DEU) were imported from
DrugBank 5.0 (Wishart et al., 2018), meanwhile for the target (VMAT2) was build a
homologue model with the help of SWISS-MODEL Workspace / GMQE
(Waterhouse et al., 2018).
Docking results indicates that DEU (BA = − 6.62 kcal/mol) is a stronger binder
than TBZ (BA = − 5.96 kcal/mol). Moreover, there are major diﬀerences between
binding modes of the investigated ligands: DEU does not make hydrogen bonds
(HBs) with the target (Fig. 2B.1), instead establishes strong steric interactions (SIs)
with the surrounding amino acids (AAs) residues of VMAT2 (Fig. 2B.2); on the other
hand, TBZ makes four HBs with AAs residues of VMAT2 (one with Ala352, one with
His353 and two with Ser401, see Fig. 2A.1) and additional SIs (Fig. 2A.2).
Figure 2. Best docking poses of TBZ (A.1) and DEU (B.1) within transmembrane helical domain of
VMAT2 and mapping of SIs established between ligands and VMAT2 (TBZ in A.2, respectively DEU in
B.2). Target is depicted as thin sticks with secondary structure drawn as cartoon backbone (A.1, B.1)
and ligands are figured as sticks (A.1-2, B.1-2). HBs are depicted as blue dashed lines (A.1). Strong SIs
are depicted as grey slender dashed lines between ligands and AAs residues (A.2, B.2), meanwhile
the weak SIs are depicted as red dotted lines between TBZ and Ala352 (A.2)
Both binding modes within transmembrane helix (UniProtKB keyword: KW-

1133) shows how TBZ and DEU inhibit the function of VMAT2, but further studies,
including here X-ray crystallography, are necessary to elucidate the complete
mechanisms of action of TBZ and its deuterated analogue.
Keywords: trabenazine, deutetrabenazine, isotopic isomer, deuterium, docking,

VMAT2
Acknowledgments: This work is part of the project PN 18 12 03 02 "Research on the

development of advanced analytical methods for the investigation of organic food
of plant or animal origin" financed by the Romanian Ministry of Research and
Innovation.
204
References
Berman H.M., Westbrook J., et al., (2000), The Protein Data Bank. Nucleic Acids Res. 28:235-242
Chen J.J., Ondo W.G., Dashtipour K., Swope D.M., 2012. Tetrabenazine for the Treatment of
Hyperkinetic Movement Disorders: A Review of the Literature. Clin. Ther. 34:1487-1504
Claassen D.O., Carroll B., et al., (2017), Indirect tolerability comparison of Deutetrabenazine and
Tetrabenazine for Huntington disease. J. Clin. Mov. Disord. 4:3.eCollection 2017
Dallakyan S., Olson A.J., (2015), Small‐molecule library screening by docking with PyRx. Methods
Mol. Biol. 1263:243-250
DeWitt S.H., Maryanoff B.E., (2018), Deuterated Drug Molecules: Focus on FDA‐Approved
Deutetrabenazine. Biochemistry 57:472-473
Kim A.P., Baker D.E., Levien T.L., (2018), VMAT2 Inhibitors: New Drugs for the Treatment of Tardive
Dyskinesia. Consult. Pharm. 33:201-209
Morris G.M., Huey R., et al., (2009), AutoDock4 and AutoDockTools4: Automated docking with
selective receptor flexibility. J. Comput. Chem. 30:2785-2791
Rodrigues F.B., Duarte G.S., Costa J., Ferreira J.J., Wild E.J., (2017), Tetrabenazine Versus
Deutetrabenazine for Huntington’s Disease: Twins or Distant Cousins? Mov. Disord. Clin. Pract.
4:582-585
Rose P.W., Prlić A., et al., (2017), The RCSB protein data bank: integrative view of protein, gene and
3D structural information. Nucleic Acids Res. 45:D271-D281
Schmidt C., (2017), First deuterated drug approved. Nat. Biotechnol. 35:493-494
Solmi M., Pigato G., Kane J.M., Correll C.U., (2018), Treatment of tardive dyskinesia with VMAT2
inhibitors: a systematic review and meta-analysis. Drug Des. Devel. Ther. 12:1215-1238
Stahl S.M., (2018), Mechanism of action of vesicular monoamine transporter 2 (VMAT2) inhibitors in
tardive dyskinesia: reducing dopamine leads to less “go” and more “stop” from the motor
striatum for robust therapeutic effects. CNS Spectr. 23:1-6
Waterhouse A., Bertoni M., et al., (2018), SWISS‐MODEL: homology modelling of protein structures
and complexes. Nucleic Acids Res. 46:W296-W303
Wishart D.S., Feunang Y.D., et. al., (2018), DrugBank 5.0: a major update to the DrugBank database
for 2018. Nucleic Acids Res. 46:D1074-D1082
205
ALTERNATIVE ANALYTICAL APPROACHES FOR DETECTING

ADULTERATION OF HONEY
Elisabeta-Irina Geană, Corina Teodora Ciucure, Raluca Popescu, Diana Costinel,

Roxana Elena Ionete
Corresponding author: irina.geana@icsi.ro, +40745752559
Honey was introduced in the list of products who are most exposed to the risk
of adulteration, in the most cases by the addition of sugars, as well as the false
declaration of botanical or geographical origin (Khan et al., 2018). In addition to
flavor and nutritional values, one of the most valuable qualities of honey is the
therapeutic potential given by low molecular biologically active compounds like
phenolic compounds, organic acids, volatile compounds, vitamins, amino acids, etc.
Direct incorporation of inexpensive sugar syrups to honey or indirect adulteration
of honey by bee-feeding with industrial sugars lead to deterioration of bioactive
constituent fingerprints (Soares et al., 2017). Ensuring traceability of the product in
the apiculture sector is essential and therefore, development of simpler, more
sensitive and more economical analytical methods able to determine the
authenticity and quality of honey represent an important issue (European
Commission, 2016).
The objectives of this study was to highlight the common analytical
instruments used to confirm the authenticity of honey in reference to detection of
direct and indirect adulteration of honey by addition of sugar syrups and to develop
new cost-effective methodologies based on fingerprinting honey bioactive
compounds. For this purpose, different authentic honeys and adulterated honeys
produced by direct incorporation of different percent of commercial sugar syrups
(from corn, rice and beet) in honey or produced by bees that had been fed
supplementary with sucrose syrup were analyzed.
Authenticity of different floral honeys (acacia, sunflower, linden, rape,
polyfloral and honeydew), in terms of adulteration identification was investigated
using basic physicochemical parameters (moisture, pH, electrical conductivity);
chromatographic methods for fingerprinting low molecular organic compounds
(phenolic compounds by UHPLC-ESI/MS, organic acids and vitamins by UHPLC-DAD)
and sugar composition by HPLC-ELDS; while bioactive properties (total polyphenols -
TP, total flavonoids – TF and antioxidant activity - % DPPH) were evaluated by UV-
Vis methods. Determination of δ13C in honey and δ13C in protein extracted from
206
honey by SCIRA method was used in order to establish the percent of adulteration
of honey with C4 plants sugar (e.g. cane, corn syrup). Screening spectroscopic UV-
Vis and NMR approaches were tested as alternative analytical methods used for
honey authentication. Statistical tools like ANOVA, PCA, LDA, AHC were used for
data processing.
Routine quality control methods for honey analysis in combination with
chemometrics, were found to be able to classify the pure honeys and adulterated
honeys resulted from deliberate addition of more than 30-40% sugar syrups.
Authentic honeys samples and commercial sugar syrups shows similar sugar
(fructose, glucose) content and for that, sugar profile cannot be used to distinguish
between adulterated and pure honeys than starting from 30% added sugar syrup to
honey.
δ 13C honey signature represent a reliable criteria for identification of honey
adulterated with sugars originating from C4 plants. By coupling δ 3C honey isotopic
signature with some physicochemical parameters and sugar composition a possible
prediction of honey adulteration with sugars originating from C3 plants can be
assured. Honey resulted by bee feeding with sucrose originating from C3 plants can
be discriminated based on physicochemical investigations, mainly based on sucrose
content.
Direct incorporation of sugar syrups in honey or intensive bee feeding with
sugar syrups has produced a decrease of honey bioactive compounds composition
and bioactive properties, but, within the natural range of variation for pure honeys,
some commercial sugar syrups showing bioactive compounds from added plant
extracts (Fig. 1).
Figure 1. Variation of bioactive properties in pure and adulterated sunflower honeys
Screening spectroscopic UV-Vis and NMR measurements coupled with

chemometric processing of the data seems to be more accessible approaches used
for rapid and economical honey authenticity assessments.
207
Keywords: honey adulteration, sugar syrups, analytical methods, chemometrics
Acknowledgements: This work was performed within the framework of the

research projects PN‐III‐P2‐2.1‐PED‐2016‐1656 – “Alternative analytical approaches
for detecting adulteration of honey with emphasis on its biologically active
compounds”, SAFE‐HONEY, 194PED/2017, supported by the Romanian National
Authority for Scientific Research and Innovation, CNCS – UEFISCDI.
References
European Commission, (2016), JRC Technical Report: Scientific support to the implementation of a
Coordinated Control Plan with a view to establishing the prevalence of fraudulent practices in
the marketing of honey. Results of honey authenticity testing by liquid chromatography-isoto
Khan S. U., Anjum S. I., Rahman K., Ansari M. J., Khan W. U., Kamal S., … Khan H. U., (2018), Honey:
Single food stuff comprises many drugs. Saudi Journal of Biological Sciences, 25(2):320-325,
http://doi.org/10.1016/J.SJBS.2017.08.004
Soares S., Amaral J. S., Oliveira M. B. P. P., & Mafra I., (2017), A Comprehensive Review on the Main
Honey Authentication Issues: Production and Origin. Comprehensive Reviews in Food Science
and Food Safety, 16(5):1072-1100. http://doi.org/10.1111/1541-4337.12278
208
MULTIDIMENSIONAL CHROMATOGRAPHY COUPLED WITH HIGH SPEED MASS

SPECTROMETRY. PROGRESS IN ORTHOGONAL ACCELERATION TIME-OF-FLIGHT
MASS SPECTROMETRY. A SHORT REVIEW
Aurel Mircia Toderici
Corresponding author: mircia.toderici@icsi.ro
Multidimensional chromatography represents a big step away in the

separation science field. In particularly, comprehensive two-dimensional gas-
chromatography (2D-GC or GCxGC) was permanently developed and improved in
the last two decades, comparing with two-dimensional liquid chromatography (2D-
LC or LCxLC), who became significant in the last years. That forced the producers of
chromatographic modulators, switch valves and secondary ovens to permanently
improve their products. On the introductory slides, a flash review about the
progress of comprehensive modulated two-dimensional gas (Tranchida et al., 2011)
and liquid chromatography (Egeness et al., 2016) are presented.
The compound detection also, both in comprehensive two-dimensional gas
or liquid chromatography involve a radically change in mass spectrometry design
and technical characteristics. The bigger limitation is the acquisition speed (number
of acquired spectra per second) but are more other improvements directions:
spectral precision, spectra stability and, for high-end mass spectrometers, the mass
resolution (M/∆M). The key for the big step away in high speed (or/and high
resolution) time of flight mass spectrometry is the development of orthogonal
acceleration sources (oaToFMS) (Guilhaus et al. 2000). A short review of mainly
developing steps and the last advanced in high frequency pulsed orthogonal
acceleration sources are presented.
Not only the orthogonal acceleration sources surfers drastically
improvements after the year of 2000 but the time of flight mass spectrometer
himself was significantly developed, especially by patented and continuously
developing of new folded-flight-path high resolution time of flight mass
spectrometer (FFP-HRToFMS) technology (Verenchikov, 2010). A brief review
containing the last developments in folded-flight path technology (multireflecting
time-of-flight) are also presented (Verenchikov et al., 2017).
209
Keywords: Multidimensional chromatography, GCxGC, LCxLC, orthogonal acceleration,

time‐of‐flight mass spectrometry, high resolution ToFMS, folded‐flight‐path,
multireflecting ToF.
References
P. Q. Tranchida, G. Purcaro, P. Dugo, L. Mondello, G. Purcaro, Trends in Analytical Chemistry, 2011,
30, 9, October, 1437-1461.
M.J. Egeness, M.C. Breadmore, E.F. Hilder, R.A. Shellie, LCGC Europe, 2016, 5, 29, 268–276.
M. Guilhaus, D. Selby, V. Mlynski, Mass Spectrometry Reviews, 2000, 19, 65-107.
A. Verenchikov, United States Patent, US 7,772,547 B2, Aug. 10, 2010.
A. Verenchikov, S. Kirillov, Y. Khasin, V. Makarov, M. Yavor, V. Artaev, Journal of Applied Solution
Chemistry and Modeling, 2017, 6, 1-22.
210
STABLE ISOTOPE RATIO OF O-H-C BIOELEMENTS AND ITS APPLICABILITY IN

VERIFYING THE ORIGIN OF WINE
Roxana Elena Ionete, Diana Costinel, Raluca Popescu, Oana Botoran
Corresponding author: roxana.ionete@icsi.ro
The wine composition is the result of interactions between various factors,

namely the terroir, the grape varieties and local oenological practices. The term
terroir combines the entire local climatic influences (e.g. temperature, precipitation,
insolation), geographic (e.g. altitude, latitude, distance to sea, slope - for hilly
regions) and geological (e.g. soil type, water, water retention in soil, soil drainage)
impacting on the quality and production of grapes and which virtually delimits the
suitable vineyard locations for the cultivation of certain varieties.
Since the isotopic ratios of the main bio-elements (O-H-C) in wine may be
locally enriched or depleted due to a variety of kinetic and thermodynamic factors,
their determination may be used to differentiate samples that otherwise would have
an identical chemical composition. Many natural phenomena, classified as
physicochemical effects such as evaporation and condensation, crystallization and
melting, or absorption and desorption, can lead to isotopic fractionation (measurable
changes in the ratio between the heavy and light isotopes of a given element). Thus,
measurements of their natural abundance will provide information on the plant
type/group (e.g. 13C/12C) or geographycal origin (e.g. 2H/1H, 18O/16O).
In other words, the distribution of stable isotopes in bio-molecules (eg ethanol
and water in wine) is controlled by biotic and abiotic fractionation processes that can
be used to authenticate a grape-origin product or to highlight fraud, like the addition
of exogenous water to wine, the addition of sugars before and after fermenting
grapes, including to verify the geographical origin declaration (Christoph et al., 2003;
Christoph et al., 2004; Schlesier et al., 2009, Costinel et. al, 2011, Sturza et al., 2017).
Geographic and climatic factors significantly affect the ratios of stable isotopes
(e.g. δ18O, (D/H)I and δ13C) in wine water and ethanol, which is why they can be
succesfully used to locate wine-growing areals according to climate (e.g. cold and dry,
cold and humid, warm and humid, or warm and dry). A decrease in the content of
isotopes of oxygen and to a lesser extent of the deuterium was observed in the wine
water, as it passes from warm/tropical climate areas to temperate climate zones and
from West to East. Also, strong trends in δ2H and δ18O in precipitation occur with
increase in latitude, altitude, and continentality. This climatic dependency is
transfered from rain-water to plant (vine) and to the fruit (grapes) and finnaly to the
fermentation product, the wine.
211
In the case of water extracted from fruits the oxygen and deuterium contents
are related to the local meteoric line, but in the final fermentation products the
hydrogen from sugars and ethanol change the composition in deuterium. The
fermentation process causes no enrichment in the δ18O in water. Therefore, the δ2H
and δ18O of the vegetation water of wines will reflect the provenance location of the
product.
An important role in isotope fractionation is given by the plant physiology (e.g.
the aperture/closing of stomata of phyton to adapt to the availability of water –
precipitation or soil water). The evapo-transpiration process that takes place during
the plant maturation is an isotopic fractionation factor that causes enrichment in 2H
and 18O of plant/fruits water, thus the δ 2H and δ18O values registered in plants water
and consequently in fruit waters and wine waters are higher than for meteoric
waters.
Also, due to the plants different photosynthetic pathways (C3, C4 and CAM)
that imparts different δ13C values to plants tissues (e.g. for C3 plants like grapes and
cane, average δ13C value of -27 ± 5‰; for C4 plants like beet and corn, of -13± 5‰)),
makes it a proper marker to establish the authenticity of wine (wine by definition is
100% from grapes).
Even each O-H-C stable isotopes assign a reliable information regarding the
wine origin, it was demonstrated that by considered toghether, due to the
complemetary data that offer, the authenticity of wine in respect of geographical and
botanical origin can be achieved.
Keywords: bioelements, light isotopes, wine authentication.
Aknowledgement: This study has been financed by the Romanian Ministry of Research and
Inovation, National Authority for Scientific Research, NUCLEU Program, under
Project 18120302/2018 ‐ "Studies regarding advanced analytical methods development for
organic food investigation".
References
Christoph N., Rossmann A., Voerkelius S., (2003), Possibilities, limitations of wine
authentication using stable isotope, meteorological data, data banks, statistical tests.
Part 1: Wines from Franconia, Lake Constance 1992 to 2002. Mitt Klosterneuburg
53:23–40.
Christoph N., Baratossy G., Kubanovic V. et al., (2004), Possibilities and limitations of wine
authentication using stable isotope ratio analysis and traceability. Part 2: Wines from
Hungary, Croatia, and other European countries. Mitt Klosterneuburg 54:144–158.
Costinel D., Tudorache A., Ionete R.E., Vremera R., (2011), The impact of grape varieties to
wine isotopic characterization. Analytical Letters 44(18): 2856-2864.
Schlesier K., Fauhl-Hassek C., Forina M., Cotea V., Kocsi E., Schoula R., van Jaarsveld F.,
Wittkowski R., (2009), Characterisation and determination of the geographical origin
of wines. Part I: overview. European Food Research and Technology, 230:1–13.
Sturza R., Gaina B., Ionete R.E., Costinel D., (2017), Autenticitatea si inofensivitatea
produselor uvologice. Metode de analiza si de prevenire a contaminarii, Universitatea
Tehnica a Moldovei, Chisinau, 264 p.
212
WINES PRODUCED IN BULGARIA - CHEMICAL PROFILE via 1H NMR
Desislava Gerginova, Yavor Mitrev and Svetlana Simova
Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of

Science, Acad. G. Bonchev str., bl. 9, 1113 Sofia, Bulgaria
Corresponding author: sds@orgchm.bas.bg
Combined use of instrumental and statistical methods during the past decade
has led to an increased number of applications on metabolomic problems with
NMR spectroscopy and mass spectrometry as leading methods. 1H NMR-based
metabolomics has proved its potential in medicine, pharmacy, environmental
chemistry, natural product chemistry and food science.
Wine is a favourite alcoholic beverage in the whole world, but one of the
frequently adulterated foods. Most often counterfeiting is related to declaration of
false botanical and/or geographical origin or vintage. NMR spectroscopy can be
used for authentication of botanical origin and quality control of wine in several
European countries (Godelmann et al., 2013), but rarely used in the region of South
East Europe. Bulgarian wine is famous for its aroma, taste, vinicultural traditions
and high quality, with antioxidant properties proved to be the highest among
European wines (Burn et al., 2000).
In our study we have used 1H NMR with water suppression, 2D HSQC and
TOCSY spectra to determine the chemical profile of several wines produced in
Bulgaria - Cabernet Sauvignon, Merlot, Syrah, Sauvignon Blanc and Chardonnay.
Identification and quantitation of more than 40 compounds has been achieved.
213
Data has been analyzed with the chemometric methods ANOVA and PLS-DA.
Differences in the concentration of 21 components allow unambiguous
determination of the botanical origin of the studied wines. Comparison of literature
data for wines from Slovakia, France, Brazil, Greece, China and Spain with data
from our study will be presented and discussed.
Keywords: 1H, NMR, wine, chemical profile, botanical origin.
Acknowledgments: Financial support of the Bulgarian National Science Fund (Projects

UNA‐17/2005, DRNF‐0213/2009 and DFNI B 02/22) is gratefully acknowledged.
References
Godelmann R., Fang F., Humpfer E., et al. (2013), Targeted and Nontargeted Wine Analysis by 1H
NMR Spectroscopy Combined with Multivariate Statistical Analysis. Differentiation of
Important Parameters: Grape Variety, Geographical Origin, Year of Vintage. J. Agric. Food
Chem. 61:5610-5619
Burns J., Gardner P., O’Neil J., et al., (2000), Relationship among antioxidant activity, vasodilation
capacity, and phenolic content of red wines. J. Agric. Food Chem., 48:220-230
214
MANIPULATION OF SPONTANEOUS EMISSION OF LONG LIVING ISOMERS USING

UV-C RADIATION
Nicolae Enaki1, Tatiana Paslari1 , Marina Turcan1, Sergiu Bazgan1,

Starodub Elena1, Ashok Vaseshta2
1
Institute of Applied Physics, Academy of Sciences of Moldova, Academiei str. 5, MD 2028
2
International Clean Water Institute, NUARI, USA
Corresponding author: tatianapaslari@gmail; prof.vaseashta@ieee.org
As is well known in the nuclear medicine use the radiation to provide

information about the functioning of a person's specific organs or to treat disease.
In most cases, the information is used by physicians to make a quick, accurate
diagnosis of the patient's illness. It is attractive from physical points of view, to
manipulate with the decay rate accompanied by the spontaneous emission of
gamma rays in the process of isotope disintegration, so that we can accelerate or
stop this emission in small regions of organic tissue in the human body.
From this point of view, we propose the interaction of powerful ultraviolet (or
X ray) laser with nuclear isotopes (or isomeric states of long living nuclei),
implanted in the special organic tissue regions. In this case the spontaneous
emission becomes selective and manipulated by the spatial distribution of the
amplitude of the standing wave of the laser field. This effect is well known in the
lasing problems of the Raman lasers , in which the Raman emission rate depends
on the intensity of the applied field, and the energetical distance between the
excited and intermediary states of the atom (or Nucley). In the case of Nuclei the
existence of such an intermediate state is possible (see for example isomers states
and upper shot living states) (Vučina and Lukić, 2002; Enaki, 2012a; Enaki, 2012b;
Dicke, 1954).
The contribution of this report consists in the established of the small sub-
wavelength regions of the standing wave laser field in order to manipulate with a
disintegration rate of isotopes from this space. In many case this is possible to be
founded from the experimental situation. (Enaki et al., 2017a; Enaki et al., 2017b).
Keywords: nuclear isotopes, Raman lasers, nuclear medicine, interaction of

powerful ultraviolet.
Acknowledgments: This paper was supported by the institutional project: No.

15.817.02.07F , NATO EAP SFPP 984890 and 18.80012.50.33A
215
References
Vučina J. and Lukić D., (2002), Radionuclidic generators for the production of technetium‐99M and
rhenim‐188, FACTA UNIVERSITATIS, Series: Physics, Chemistry and Technology, 2 (4):235- 243
Enaki N. A., (2012 a), Cooperative Resonance Interaction Between One‐and Two‐Photon Super‐
fluorescences Trough the Vacuum Field. Journal of Physics: Conference Series 338:012005
Enaki N. A., (2012 b), Mutual cooperative effects between single- and two-photon super-fluorescent
processes through vacuum field. Eur. Phys. J. D 66:98
Dicke R. H., (1954), Coherence in Spontaneous Radiation Processes, Phys. Rev. 93:99
N. A. Enaki, S. Bazgan, N. Ciobanu, M. Turcan, T. Paslari, C. Ristoscu, A. Vaseashta, I. N. Mihailescu,
(2017a), Improvement in ultraviolet based decontamination rate using meta‐materials,
Applied Surface Science, https://doi.org/10.1016/j.apsusc.2017.01.133.
Nicolae Enaki, Sergiu Bazgan, Tatiana Paslari, Ashok Vaseashta, (2017b), Control of decay rates of
nuclear isotopes by cooperative effects between the blocks of three radiators, ESIR 2017,
http://www.icsi.ro/esir2017/files/book_of_abstracts.pdf, pp. 153
216
COMPARATIVE SPECTROSCOPIC AND CHROMATOGRAPHIC

QUANTIFICATION OF NICOTINE IN MOLDAVIAN TOBACCO
Alexandru Ciocarlan1, Aculina Aricu1 and Mariana Deleanu2

1
Institute of Chemistry, Academy of Science of Moldova, 3, Academiei str., Chisinau MD 2028,
Republic of Moldova
1
Institute for Cellular Biology and Pathology "Nicolae Simionescu" of the Romanian Academy, B.P.
Hasdeu str. no. 8, 050568 Bucharest, Romania
Corresponding author: algciocarlan@yahoo.com
Tobacco is one of the oldest cultures known to mankind. It has its origins in
America and Asia, continents where the species was used for smoking or for
medical purposes two thousand years ago. In Bessarabia tobacco cultivation started
in 1612, and the branch grew intensively during the Balkan War of the years 1877-
1878.
Tobacco (Nicotiana tabacum L.) belongs to Solanaceae family, Nicotiana
genus, which includes more than 60 species. Most of these contain nicotine,
nornicotine, anabazine, and other alkaloids. More than three thousand tobacco
varieties are known in the world and are spread over 23 different types. (Jitcu et al.,
2001; Șkorupeev et al., 1976)
In this paper, we present the comparative results of the nicotine
quantification in the autochthonous selection of tobacco varieties by both the UV-
VIS spectrophotometric method and the Ultra High Performance Liquid
Chromatography Method (UHPLC) after methanolic extraction from tobacco leaves.
A Zorbax Eclipse Plus C18 column (2.1×150mm, 3.5µm, Agilent, USA) was used for
separation of compounds and the mobile phase consisted of methanol and
phosphate buffer, pH 7.9 in gradient elution. Detection was performed at 260 nm.
Ten tobacco varieties of Moldovan selection and Nicotiana rustica L. were analyzed.
Thus, the nicotine content in varieties analyzed by the UV-VIS method ranged from
1.24% (Virginia 401) to 2.74% (Moldavschi 456). Surprisingly, the nicotine content
of Nicotiana rustica L. (1.35%) was several times smaller than that described in the
literature (Moghbel et al., 2015; Murray, 2014).
Our HPLC method has a good sensitivity, accuracy, selectivity and
reproducibility and generally confirms the data obtained by the UV-VIS method.
Due to the selectivity and accuracy of the UHPLC analysis method, the nicotine
content values in the analyzed samples are somewhat lower. On the example
described above, its content ranged from 0.97% (Virginia 401) to 2.16%
(Moldavschi 456), with the exception of Moldavschi 272 (1.38% and 1.44%) and the
species Nicotiana rustica L. contains 1.08%.
217
Keywords: UV‐VIS spectroscopy, UHPLC, tobacco leaves, nicotine.
References
Jitcu T. G., Kulikova N. P., Osipova R. A., (2001), Kul’tura tabaka. Chișinău, Ed. Tipografia Centrală,
310 p.
Șkorupeev I. S., Șnirev V. A., Stașkov M. G., Verbițki N. F., (1976), Tabacovodstvo i tabac’naia
promișlennosti Moldavscoi SSR, Ed. Cartea moldovenească, Chișinău, 80 p.
Moghbel N., Ryu B.M., Steadman K. J., (2015), A reversed‐phase HPLC‐UV method developed and
validated for simultaneous quantification of six alkaloids from Nicotiana spp. Journal of
Chromatography B, 997:142-145
Murray J. L., (2014), Nicotine and what else?: HPLC elution optimization for the analysis of alkaloids
found in electronic cigarettes. Honors Theses. https://scholar.utc.edu/honors-theses/3
218
HPTLC IDENTIFICATION OF SOME MUSHROOM AND VEGETAL SPECIES FOR

QUALITY CONTROL OF DERIVED PRODUCTS
Bubueanu Elena Corina, Pavaloiu Ramona
National Institute for Chemical‐Pharmaceutical R&D (ICCF‐Bucharest), Vitan Road 112 Sector 3,
Bucharest, ROMANIA, Phone: +4021 321 2117; Fax: + 4021.322 2917
Corresponding author: corina.bubueanu@yahoo.com
Quality control of vegetal (including mushrooms) derived products must be

guaranteed for the safety of the consumers. Products that contain botanical
preparations are widely consumed in daily diets all over the world, because of the low
price comparatively with the synthetic drugs and also for the concept that “natural” is
“safe”. These types of products are characterized by complex (multicomponent)
mixtures with numerous natural compounds. In the present, there are a number of
complex and sophisticated analytical method for quality control of the these products
that contain high number of compounds, such as NMR, MS and IR combined with
chemometric tools. Fingerprint chromatography is now accepted by the World Health
Organization as a technique for identification and quality evaluation of vegetal raw
material (Alaerts, et al 2007). Because of the simplicity and accurately high-
performance thin-layer chromatography (HPTLC) has become one of the most
important tools for identification, authentication of species and quality control of
derived products (in the production steps). In the context of complex chemical
composition of vegetal (including mushroom) raw material, depending on the
cultivating region, the climate (temperature, humidity, light and wind), the harvest
time and plants part used, the chromatographic fingerprint can certify the species by
identification of active compounds and impurities. Given these, the present paper
aimed to show HPTLC chromatographic fingerprint (for -phenols – including
coumarin, sterols) of some mushroom and plant species as follows: Armillaria mellea-
honey fungus, Cantharellus cibarius – chanterelle, Echinacea purpurea (leaves) -
echinacea Armoracia rusticana (leaves) – horseradish, Lycium barbarum (leaves) – goji,
determined by HPTLC, species present in many derived products.
Keywords: mushroom, vegetal species, HPTC, fingerprint
Acknowledgments: This work was made with the support of MCI ‐ Nucleu Program ‐
Projects no 16 27 03 02 and 16 27 01 02
References
Alaerts G., Matthijs, N. Smeyers-Verbeke J., Vander Heyden Y., (2007) Chromatographic ngerprint
development for herbal extracts: A screening and optimization methodology on monolithic
columns. Journal of Chromatography A, 1172(1-8)
219
VOLTAMMETRIC SENSOR FOR THE ANALYSIS OF ELECTROACTIVE COMPOUNDS

FROM GINGKO BILOBA BASED PHARMACEUTICAL PRODUCTS
Ramona Oana Gunache (Roşca), Constantin Apetrei
Department of Chemistry, Physics and Environment, Faculty of Science and Environment, ”Dunarea
de Jos” University of Galati, Domneasca Street, 47, RO‐800008, Galati, Romania
Corresponding author: oana.gunache@ugal.ro
Pharmaceuticals products based on Gingko biloba are used in the practice for
the treatment of different diseases. These products can be used both as OTR and
under medical prescription. Some of these products are standardised and other are
not standardized. Therefore, the quantification of biologic active compounds from
these products is necessary.
The sensors based on carbon nanofibers using as detection technique the
cyclic voltammetry can be able to detect and quantify such compounds. Therefore,
in this study the sensors based on carbon nanofibers were used to study different
pharmaceutical products.
The optimization of the experimental parameters was carried out in order to
improve the sensitivity. These conditions include the pH, electrolyte, potential
range, and scan rate. The maximum of the sensitivity was obtained at pH of 7, the
electrolyte was KCl, the potential range was from -0.4 to +0.7V, and the scan rate
was 50 mV×s-1. The peaks observed in the voltammograms are related to the redox
processes of flavonoids from the Gingko biloba extract. The quantification of these
compounds has demonstrated the higher concentration in standardized products
comparing with unstandardized ones, even the label is indicating the contrary. It
fact can be also related with the quality of the Gingko biloba extract and the quality
of the raw matter. In conclusion, the voltammetric sensor could be successfully
used in the practical application in the pharmaceutical industry.
220
NON-EQUILIBRIUM (COLD) PLASMA AS AN ENERGY-EFFICIENT METHOD OF

MICROBIOLOGICAL DECONTAMINATION AND HEAT AND MASS TRANSFER
INTENSIFICATION
Iurie Bosneaga1, Elena Agarwal2

1
Institute of Applied Physics, Chisinau, Republic of Moldova
2
University Dimitrie Cantemir, Chisinau, Republic of Moldova
Corresponding author: iubosneaga@gmail.com
Non-thermal plasma is a perfect instrument for microbiological decontamination and heat

and mass transfer intensification. In the first case - it is due to the possibility of creation
extremely active oxidative atmosphere in plasma (Azharonok, 2011), and in the second - mainly
because the flux of the ionized gas, being placed in the magnetic field, becomes a dirigible one.
Creation of a sufficiently dense non-thermal plasma in an energy-efficient way - is a key
issue for ensuring high final cost-efficiency of the processes. We consider several methods for
energy-efficient dense non-thermal plasma generation: impulse microwaves (frequency range -
approximately 1 - 9 GHz); dielectric barrier discharge (DBD); short (nanosecond) high voltage
impulses; radionuclides (mainly coming from the spent nuclear fuel re-processing).
Non-thermal plasma is essentially non-equilibrium one because the ions’ (and neutrals)
temperature remains low, electrons’ temperature being very high (Te >> Tion = Tgas). The relative
number of ionized particles (molecules, atoms and radicals) is proportional to the electron
temperature and defines the intensity of the desirable oxidative and magneto-hydrodynamic
properties of plasma.
Energy‐efficient methods of non‐thermal plasma generation

Microwaves (MW) are one of the best methods of obtaining dense cold plasma: the
higher is the frequency and applied power, the higher is the grade of non-equilibrium and
plasma density. For the most typical microwave discharges plasma density (i.e., the
concentration of free electrons ne) is rather large, respectively electron plasma frequency
ω pe = ( ne e 2 / me ε 0 ) 1 / 2 (1)
is sufficiently high and surpasses the cyclic frequency of microwave generation ω (ω<ωpe).
So, the frequency of the electromagnetic field remains smaller than the plasma
frequency, and this corresponds to the condition of effective (high) absorption of microwave
energy by plasma. Also should be mentioned the advantages of microwave discharge plasma -
as electrodless process and which could be easily maintained at relatively high (inclusively,
atmospheric and higher) pressure - especially when impulse microwaves are applied.
The other two methods of non-thermal plasma generation - DBD and short (of order
- nanosecond) high voltage impulses - could be treated as of the same (as compared with
microwaves) mechanism of action - because periodic short impulses could be presented as
the sum of simple oscillating functions, namely sines and cosines (i.e., decomposed in
221
Fourier series) - of “microwave” range frequencies. So, for the generation of the non-
equilibrium (non-thermal) plasma it is not obligatory to use harmonic high frequency
oscillations. The same effect can be obtained as a result of application of the short (nano-
and, eventually, pico-second) high voltage impulses. In this case plasma parameters can be
controlled through the amplitude, duration and duty ratio of impulses. The main
differences come from the hardware design, which appears to be more complex in the case
of MW (see Fig. 1).
High-voltage MW Waveguide High-

Applicator Applicator
source generato system voltage
Figure 1. The scheme of microwave plasma installation as compared with

high voltage impulses variant
Radionuclides seem to be the most attractive instrument for non-thermal (“cold”)

plasma generation - because dense plasma of necessary ionization grade could be obtained
without any consume of high-potential (free) energy - but due to accumulated in
radionuclides nuclear energy [Boşneaga Iu., 2015]. All three (α, β, γ) ionizing factors could
be used, depending on the case. Of special interest are radionuclides coming from the
spent nuclear fuel re-processing - and strontium-90 (Sr90) is a good example. Strontium-90
is practically “pure” beta emitter with E = (0,546 MeV & 2,28 MeV) and is one of the most
abundant isotopes of uranium fission (about 4.5% of the total nuclear daughter products).
Chemical instability of strontium (it manifests extreme reactivity with oxygen and water)
can be annihilated - by a thin layer of aluminum oxide (Al2O3) coating, or by its
transforming into strontium titanate (SrTiO3). (Strontium titanate has high melting point, is
chemically stable and insoluble - due to its special stability quality it is used as a diamond
simulant). Besides ionization of gas components, radionuclides (it is especially
characteristic for α and β emitters) - additionally - ensure kinetic action (momentum) in the
direction of emission (propagation). The final value of this total momentum depends on
the radioactivity and quantity of the radionuclide(s) used (and, of course, on the grade of
construction’s optimization).
Magneto‐hydrodynamic effect and example of wind (éolien) magneto‐hydrodynamic

power generator
Magneto-hydrodynamic effect can be used for energy-efficient heat and mass
transformations. It is exemplified on the action of the wind (éolien) magneto-hydrodynamic
power generator.
Moving ionized atmospheric air (“ionized wind”) can generate electricity directly,
without any mechanical transformations - due to magneto-hydrodynamic effect: magnetic
field applied perpendicular to ionized air flux causes Lorentz force which separates moving
charges:
F = Q [vB] (2)
On Fig. 2 is presented (schematically) the wind MHD power generator.
222
Ionizing camera with electrodes-

collectors
S
Figure 2. The scheme of the wind (éolien) MHD power generator. No moving parts. Charge
separation occurs under the action of the Lorentz force F = Q [v×B]. The main ionizing agents –
radionuclides, which are placed in the ionizing camera
Magneto‐hydrodynamic steam condensation improvement

Cold plasma can be used in heat and mass transfer intensification. Nowadays most of the
electric power is generated by means of thermodynamic cycles which predominantly use
steam turbines. Respectively, evacuation of the waste heat through water vapor condensation
is an extremely widespread, economically and ecologically sensitive technological process. The
main feature of the proposed technology of dirigible energy-efficient condensation -
transformation of the neutral water vapour from the output of the turbine into cold (non-
equilibrium) plasma of sufficiently high density. Such “activated” flux of steam allows
transformation of a certain part of its thermal and kinetic energy into electricity - due to the
relevant magneto-hydrodynamic (MHD) cycle. As a result of magnetic field application
(perpendicular to vapour flux) there appears Lorentz force (2) which separates charges.
Additional power production is beneficial itself, but it is more important that for
condensation there will be necessary to absorb much less amount of heat. As a collateral
positive effect, in the presence of the proper catalysers, there can be achieved partial water
dissociation - with obtaining desirable products (H2, O2, H2O2, O3) on the electrodes-collectors.
In dependence of the applied methods of dense plasma generation, the components of
the “steam” plasma (molecules, atoms, radicals - and there electric charges) vary, the dominant
remaining hydroxyl radicals (OH), hydroxide ions (OH-), hydrogen atoms (H) and their ions (H+),
oxygen atoms (O) and their ions (O+, O-).
Table 1. Dissociation and ionization energies of water vapour and descendant products
Molecule,
radical, H 2O HO O2 H2 H O O3
atom type
Bond (dissoc.)
energy, eV H2O+ hν→ O3 + hν →
HO + hν→ O2+ hν→ H2 + hν→
(kJ/mol) OH + H O2 + O
O+H O+O H+H
5,19 (498,7) 1,11 (107,0)
&respec.rad.λ 4,45 (427,8) 5,12 (493,6) 4,49 (432,1)
λ max= 239,1 nm N/A N/A λ max =1117,3
(λ max disso-ciation λ max = 278,9 nm λ max= 242,4 nm λ max = 276,3 nm
nm
limit)
Ionization energy H2O+ hν→ HO + hν→ O2+ hν→ H2 + hν→ H + hν→ O + hν→ O3 + hν→
+ + + + + +
(for atoms, H2O + e OH O2 + e H2 + e H +e O +e O3 + e
molecules), eV 12,61 18,9 12,08 15,42 13,60 13,62 12,52
223
As it comes from the Table 1, ionization energy (for plasma atoms, molecules,
radicals) exceeds the dissociation one practically in all cases. It means that the concurrent
processes of inevitable positive ions’ recombination (transformation into neutral particles -
due to electrons’ re-absorption) cause dissociative recombination - a process where a
positive molecular ions recombine with electrons, and, as a result of energy emission, the
neutral particles - mostly molecules - dissociate. So, ionization means also dissociation.
Without any doubt, the presence of charged particles additionally contributes to
facilitation of water vapour condensation (through stimulation of nucleation) and
consequent reduction of resistance to phase transition.
Improved cold plasma magneto-hydrodynamic steam condensation is particularly
beneficial for Nuclear Power Plants - because of the possibility additionally to use the spent
nuclear fuel for cost-efficient cold plasma generation. (Spent nuclear fuel is always easily
accessible directly on the Nuclear Power Plant’s site, and it disposes of - both useful -
ionizing and thermal potentials).
Keywords: non‐thermal plasma, microbiological decontamination, microwave discharge

plasma, dielectric barrier discharge, radionuclides
References
V. Azharonok, I. Filatova, Iu. Bosneaga, M. Bologa, O. Shedikova, (2011), Non‐thermal plasma sterilization
in RF and MW discharges. Romanian Journal of Physics, 56(Supplement), pp. 62-68
Boşneaga Iu., (2015), Huge non‐spent potential of the “spent fuel”‐ the ways of its utilization.
International Conference on Management of Spent Fuel from Nuclear Power Reactors - An
Integrated Approach to the Back-End of the Fuel Cycle, Vienna, Austria, 15-19 June 2015
224
THE 15N SEPARATION BY ISOTOPIC EXCHANGE IN NITROX SYSTEM AT PRESSURE
Damian Axente, Ştefan Bugeac, Ştefan Gergely, Mihai Gligan,

Cristina Marcu, Zsolt Szücs, Codruţa Varodi
National Institute for R and D of Isotopic and Molecular Technologies

67 – 103 Donat Str., 400293 Cluj‐Napoca, Romania, Tel. 0264 584037
Corresponding author: Damian. Axente@itim‐cj.ro
The 15N separation cascade (two packed columns connected in series) by

isotopic exchange in NITROX system at pressure of 0.7 bar was experimentally
tested.
The operation was stable at total reflux and in production although the HNO3
10M feeding flow in the first column, packed with triangular stainless steel wire
helices 2.3 x 2.3 x 0.2 mm, were 47 and respectively 33% higher than that utilized at
atmospheric pressure. The nitric acid flow rates in the same column were 3.12
mL/cm2∙min and respectively 2.83 mL/cm2∙min for operation at pressure compared
to 2.12 mL/cm2∙min at atmospheric pressure.
The HNO3 10M flow feeding the second separation column, packed with the
same type packing, (1.8 x1.8 x 0.2 mm) were 324 mL/h and 264 mL/h, being 62 and
respectively 32% higher than those utilized at atmospheric pressure. The HNO3
10M flow rates in the second separation column were 3.05 mL/cm2∙min and 2.49
mL/cm2∙min, compared to 1.86 mL/cm2∙min at atmospheric pressure.
The HETP (height equivalent to theoretical plate) achieved in both separation
columns are smaller in the case of operation at pressure of 0.7 bar compared to the
values obtained at atmospheric pressure, although the both columns were
operated at higher flow rates.
The fact that it was possible to utilize higher HNO3 10M flow rates in the 15N
separation columns and that the HETP values are smaller than those achieved at
atmospheric pressure is an argument for operation at pressure of the separation
cascade.
Keywords: 15N separation, isotopic exchange, NITROX system, packed columns,

pressure.
225
ASPECTS CONCERNING THE ENVIRONMENTAL IMPACT ASSESSMENT PROCEDURE

FOR A HEAVY WATER MANAGEMENT FACILITY
Ionela Ramona Aranghel, Nuşa-Crenguţa Mădgălin,

Simona Măchiţă, Bogdan Blănaru
Technologies for Nuclear Energy State Owned Company ‐ Center of Technology and Engineering for
Nuclear Projects, 409 Atomistilor Street, Magurele, Romania
Phone: +40 21 404 6050, Fax: +40 21 457 4431;
Corresponding author: aranghelr@router.citon
Heavy water, a material of nuclear involvement, having as primary uses, the role
of primary heat and moderator in CANDU reactors, is not radioactive or toxic, is slightly
dangerous in the event of ingestion, is not irritating to the skin and eye.
Heavy water management generally consists of a series of actions that relate to:
• keeping the quality parameters of heavy water stored;
• ensuring the storage of heavy water quantities from each container;
• preventive and corrective measures relating to the finished product and
storage vessels;
• nuclear safeguards according to NGN-01, Norms on the Control of Nuclear
Safeguards.
Heavy water warehouse must ensure the following objectives:
• storage space and technological operations, QC and marketing;
• energy and technological and microclimate utilities;
• physical protection.
The environmental impact assessment identifies, describes and evaluates, the
direct and indirect effects of a project on the following factors:
a) human, fauna and flora;
b) soil, water, air, climate and landscape;
c) material goods and cultural heritage;
d) the interaction between the factors referred to point a), b) and c).
The Environmental Impact Assessment procedure is carried out in stages, as
follows:
a) the stage of project assignment in the environmental impact assessment
procedure;
b) the stage of defining the scope of the assessment and the implementation of
the environmental impact report;
c) the quality review stage of the environmental impact report.
Requesting and obtaining the environmental agreement shall be mandatory for
public or private projects or for modifying or extending existing activities that can have
a significant impact on the environment. In order to obtain the environmental
226
agreement, public or private projects likely to have a significant impact on the

environment, by their nature, size or location, shall be subject to environmental impact
assessment by the competent authority for the protection of environment.
Licensing process is a continuous process during the lifetime of a facility, a process
involving successive iterations between the Regulatory Authority and the applicant, a
process requiring continuous updating to comply with the new requirements.
Keywords: heavy water, management, environmental impact assessment procedure,

environmental agreement.
227
PRELIMINAR STUDIES ABOUT THE BETA-CYCLODEXTRIN ENCAPSULATION OF

EUGENIA CARYOPHYLLATA ESSENTIAL OIL AND EUCALYPTOL
Alina Ionela Stancu1, 2, Elena Pincu1, Gabriela Ioniță2, Anca Ruxandra Leontieș,
Eliza Oprea1
1
University of Bucharest, Faculty of Chemistry, 4–12 Regina Elisabeta,
RO‐030018 Bucharest, Romania
2
Institute of Physical Chemistry"Ilie Murgulescu" 202 Splaiul Independentei,
060021, Bucharest, Romania
Corresponding author: alina.stancu1995@gmail.com
Beta –cyclodextrin (BCD) is a cyclic carbohydrate which has the ability to form
inclusion complexes with essential oils and volatiles. Complexation has been used in
order to improve the stability of terpenes, essential oils and other compounds (Bilia,
2014).
The essential oil of Eugenia caryophyllata (Chaieb, 2007) and also eucalyptol
(Piletti, 2017) have proved broad-spectrum antibacterial and antifungal activity and
their encapsulation may increased the physical and/or chemical stability.
The present study was undertaken to obtain inclusion complexes of BCD with
Eugenia caryophyllata and eucalyptol by several methods. Eucalyptol was purchased
from Aldrich and the cloves essential oil was extracted with Neo Clevenger apparatus
(British Pharmacopoeia, 2003). There were used four methods for the preparation of
inclusion complexes for each: kneading, co-precipitation, freeze-drying and a
combination of methods from literature (Marques, 2010). This method consisted of co-
precipitation followed by freeze-drying.
Evidence for obtains inclusion complexes was done by some analytical techniques:
differential scanning calorimetry (DSC), UV–visible absorption and FT-IR spectroscopy.
Keywords: cyclodextrins; inclusion complexes; encapsulation of essential oil and

eucalyptol
References
Bilia A.R., Guccione C., Isacchi B., Righeschi C., Firenzuoli F., Bergonzi M.C., (2014), Essential oils loaded in
nanosystems: a developing strategy for a successful therapeutic approach. Evid Based Complement
Alternat Med, 2014:651593
British Pharmacopoeia, (2003), Appendix 9 (vol IV) A238
Chaieb K., Hajlaoui H. Zmantar T., Kahla-Nakbi A.B., Rouabhia M., Mahdouani K., Bakhrouf A., (2007), The
chemical composition and biological activity of clove essential oil, Eugenia caryophyllata (Syzigium
aromaticum L. Myrtaceae): a short review. Phytother Res. 21(6):501-6
Marques H. M. C., (2010), A review on cyclodextryn encapsulation of essential oils and volatiles. Flavour
Fragr J, 25:314-316
Piletti R., Bugiereck A. M., Pereira A. T., Gussati E., Dal Magro J., Mello J. M. M., Dalcanton F., Ternus R. Z.,
Soares C., Riella H. G., Fiori M. A. (2017), Microencapsulation of eugenol molecules by β‐
cyclodextrine as a thermal protection method of antibacterial action. Mater Sci Eng C Mater Biol
Appl, 75:259-271
228
INFLUENCE OF THE AGRICULTURAL PRACTICES ON THE COMPOSITIONAL PROFILE

OF VEGETABLES - CONVENTIONAL VERSUS ORGANIC
Raluca Popescu, Diana Stegarus, Claudia Sandru, Mihaela Iordache, Felicia

Bucura, Anca Zaharioiu, Elisabeta-Irina Geana, Corina Ciucure, Diana Costinel,
Roxana-Elena Ionete
Valcea, Uzinei Street no. 4, PO Box 7 Raureni, 240050, Râmnicu Vâlcea, Romania
Corresponding author: raluca.popescu@icsi.ro
Organic food production is a growing sector of agriculture as a consequence

of increasing customer awareness concerning food security and nutritional quality
of fresh produce. Organic agriculture has many advantages, from providing natural
and additive free food, to resources and waste recycling, environmental protection
and rural development; while it's disadvantages include lower production yields
and more laborious procedures for fertilization and pest control. The consumers,
retailers and producers are interested in correct labeling of the quality and origin of
food, especially if this results in added value to the final product being sold. The
quality of organic food is mainly related to its traceability, nutrient composition,
adequate sensorial and storage properties, security and safety related to chemical
and microbiological contamination. All these aspects require the possibility of
checking the label declarations concerning origin and quality by using analytical
techniques. Contaminants and traceability markers could be used as reliable
instruments to assess the organic quality of food, since the complexity of the
biological and technological processes that lead to obtaining the final product being
sold doesn't allow for a single parameter or analysis to be used (Citak and Sonmez,
2010; Herencia etal., 2011; Sobolev et al., 2005). As a consequence, in the present
study a series of analytical procedures were used to determine the composition of
organic and conventional vegetables: preliminary physico-chemical properties:
humidity, total solids and pH; C/H/N elemental analysis, protein content and
energy by combustion-GC (Gas Chromatography); macro-element composition by
atomic absorption; soluble vitamins by HPLC (High Performance Liquid
Chromatography); 1H/13C-NMR (Nuclear Magnetic Resonance) profile of the
soluble organic compounds; pesticides measured by GC and δ18O and δ2H of the
plant water measured by IRMS (Isotope Ratio Mass Spectrometry). These
characteristics were then used to evaluate the influence of agricultural practices on
the compositional profile of vegetables, in order to identify the best parameters to
differentiate organic produce (Fig. 1).
229
Centroids (axes F1 and F2: 100.00 Subst

1 Variables uscata(
(axes F1Zn-PP
and F2:
%) 0.75 100.00
Ca-PP%)K-PP%) Zn-SU
K-SU
0.5 Ca-SU Na-PP Mg-PP
Qs PP
F2 (0.00 %)
Mg-SU
Proteina
409.6 0.25 Na-SU
307.2 δ2H[‰] (%PP)
N(%SU)
F2 (0.00 %)
conventi 0
organic 204.8 Proteina
102.4 onal H(%SU)
-2E-12 -0.25 H(%PP) Fe-SU Qs SU Umiditat%SU)
-102.4 C(%PP) pHe(%)
fitrat
-512-409.6
-307.2
-204.8
-102.4
1E-12102.42 04.8307.2409.6 -0.5 Fe-PP
-204.8 δ18O[‰ C(%SU)
-307.2 -0.75
-409.6 ] N(%PP)
-512 -1
F1 (100.00 %) -1 -0.75 -0.5 -0.25 0 0.25 0.5 0.75 1
F1 (100.00 %)
Figure 1. Discriminant analysis (DA) of vegetables using specific chemical parameters, with 100%
correct cross-validation
Keywords: vegetables, organic vs. conventional; composition profile; tracebility

markers
Aknowledgement: This study has been financed by the Romanian Ministry of

Research and Inovation, National Authority for Scientific Research, NUCLEU
Program, under Project 18120302/2018 ‐ "Studies regarding advanced analytical
methods development for organic food investigation".
References
Citak S., Sonmez S., Influence of organic and conventional growing conditions on the nutrient
contents of white head cabbage (Brassica oleracea var. capitata) during two successive
seasons, Journal of Agricultural and Food Chemistry, 2010, 58, 1788-1793;
Herencia J.F., Garcia-Galavis P.A., Dorado J.A.R., Maqueda C., Compariosn of nutritional quality of
the crops grown in an organic and conventional fertilized soil, Scientia Horticulturae, 2011,
129, 882-888;
Sobolev A.P., Brosio E., Gianferri R., Segre A.L., Metabolic profile of lettuce leaves by high-field NMR
spectra, Magnetic Resonance in Chemistry, 2005, 43, 625-638.
230
SPECTROSCOPIC AND CHEMOMETRIC METHODS FOR WINE CLASSIFICATION
Dana-Alina Magdas1, Simona Cinta Pinzaru2, Ioana Feher1, Bogdan Ionut Cozar1
1
67‐103 Donat Str., 400293 Cluj‐Napoca, Romania
2
Babes‐Bolyai University, Biomolecular Physics Department, Kogalniceanu 1, RO‐400084
Cluj‐Napoca, Romania
Corresponding author: alina.magdas@itim‐cj.ro
In the recent years, many efforts were made in the development of accurate,
rapid analytical techniques, which require either no sample preparation process or an
easy one. This need came as an alternative approach to more labor and time-
consuming methods, such as gas chromatography or liquid chromatography coupled
with mass spectrometry (GC/MS or HPLC/MS). Thus, a special attention is focused on
vibrational techniques for food and beverages authenticity control, due to their fast,
automated, cost-effective, non-destructive and environmental-friendly character.
This work is focused on application of FT-Raman and SERS spectroscopic
methods along with chemometric methods in wine discrimination. For both techniques
a set of 30 white wine samples was used and experimental results were
chemometrically processed using linear discriminant analysis (LDA). The main criterions
used for wine classification were: geographical, vintage and variety classifications.
For variety discrimination (Feteasca vs Sauvignon), FT-Raman results and LDA,
provided a percent of 100 % initial and cross validation. Also, the characteristic bands,
from both Stokes and anti-Stokes regions, were highlighted. For SERS technique, the
obtained percent was lower, 93.3 % for both classifications. Specific markers for this
case were attributed to hydroxycinnamic acids, resveratrol and other polyphenols.
For geographical origin differentiation, three areas were compared: Banat,
Transylvania and Moldova. For FT-Raman method, for both classifications a percent of
100 % was obtained. In this case, little literature data is available in order to make
same attributions to corresponding obtained wavelengths. For SERS, initial
classification was 96.7 %, while for cross validation the values were 83.3 %. The main
predictors were assigned to caffeic acid, p-coumaric acid and sinapic acid.
For last classification, vintage discrimination (five years were compared, 2011,
2012, 2013, 2014, 2015), FT-Raman combined with chemometric, provided 100 % for
both classifications. In SERS case, the obtained percentages were 90% for initial
classification while in cross-validation a proportion of 83.3% was achieved.
Keywords: spectroscopic, LDA, wines, discrimination
Acknowledgments: This work was supported by Romanian National Authority for

Scientific Research and Innovation, CNCS/CCCDI – UEFISCDI, project number 187
PED‐2017
231
GEOCHEMICAL CHARACTERIZATION OF THE OLT RIVER (ROMANIA) USING PIPER

AND DUROV DIAGRAMS
Claudia Sandru, Mihaela Iordache, Andreea Iordache, Violeta Niculescu,

Roxana Elena Ionete
Corresponding author: claudia.sandru@icsi.ro
In this work the assesment of Olt River waters chemical behaviour and of
involved chemical processes are performed using Durov and Piper diagrams.
Therefore, water samples were collected from the Olt River basin in its middle and
lower basin, from 22 points, from which 19 accumulation lakes, 1 point from the
Olt River before flowing into the Danube River and 2 points in the Danube River,
and subject to analytical investigation and chemistry rendering. To plot the
diagrams, the Aquachem Scientific software was used.
Piper diagram is a multifaceted plot where concentrations, in milliequivalents
percentage, of major cations (Ca, Mg and Na) and anions (HCO3-, SO42-, and Cl-) are
plotted in two triangular fields, that are further projected into a central diamond
field. The central diamond-shaped field (quadrilateral field) is used to show the
overall chemical character of the water. The trilinear diagram (Piper, 1944) is an
effective tool in segregating analysis data with respect to sources of the dissolved
constituents in water, modifications in the character of water as it passes through
an area and related geochemical problems.
In contrast, Durov diagram (Durov, 1948) is a composite plot consisting of 2
ternary diagrams where the milliequivalents percentages of the cations of interest
were plotted against that of anions of interest; sides form a central rectangular,
binary plot of total cation vs. total anion concentrations.
These diagrams were created for comparing the results of water types and
applied in various studies (Ionete et al., 2015; Hoaghia et al., 2015; Senila et al.,
2017). For the area selected in this study, the graphical methods were able to
identify specific hydrogeochemical processes. The Piper diagram showed two types
of surface water quality and Durov diagram deduced important hydrogeochemical
processes (e.g., inverse ion exchange and mixing). These methods can be useful for
deduction of different hydrogeochemical processes and hydrogeochemical
evolution and variation in a hydrogeological system.
Results of the hydrochemistry suggest that all the collected water samples are
of alkaline in nature. Major process controlling the water quality is mineral
dissolution, cation exchange and inverse cation exchange processes. The relative
232
abundance of major cations and anions in water (mg/L) is Ca>Na>Mg and Cl->HCO3-
>SO42->N-NH4>N-NO2>N-NO3, respectively.
Majority of the samples were behaved more or less same way except for few
samples. Using both methods, 59% of the water samples were classified as Ca-Cl
type. Was obviously from the obtained data that the water quality of the Olt River
is influenced by the various natural and anthropogenic factors on its flow path.
Keywords: surface water quality, geochemical characterization, Piper diagram
Acknowledgments: This work is part of the project PN 18 12 03 03 "Assessing the

impact of waste water discharges on the environment through advanced analytical
investigations based on nuclear and other related techniques", financed by the
Romanian Ministry of Research and Innovation.
References
A.M. Piper, (1944), A graphic procedure in the geochemical interpretation of water‐analyses. Eos,
Transactions American Geophysical Union, 25(6):914-928
S.A. Durov (1948) Natural waters and graphic representation of their composition. In Dokl Akad
Nauk SSSR, 59(3):87-90
R. E. Ionete, R. Popescu, D. Costinel, (2015), An isotopic survey of some mineral water resources in
the Carpathian chain (Romania). Environmental Engineering & Management Journal (EEMJ),
14(10):2445-2456
M.A. Hoaghia, C. Roman, C. Tanaselia, D. Ristoiu, (2015), Groundwater chemistry rendering using
Durov, Piper and ion balance diagrams. Study case: the northern part of Sibiu county. Studia
Universitatis Babes-Bolyai Chemia, 60(2):161-168
M. Senila, D. Micu, D., A. Hoaghia, E. Levei, O. Cadar, G. Kucsicsa, D. Balteanu, (2017), Multivariate
statistical analysis of water chemistry in wells from Sub‐Carpathians of Curvature, Romania.
Advances in Environmental Sciences, 9(1)
233
DATABASE OF DRINKING WATER SOURCES MONITORING IN BABENI-VALEA MARE

AREA – PRELIMINARY RESULTS
Carmen Varlam, Nicolae Sofilca, Ionut Faurescu, Alin Chitu, Irina Vagner, Mihaela
Iordache, Diana Costinel, Denisa Faurescu
Corresponding author: irina.vagner@icsi.ro
Pollution problems caused by anthropogenic activities developed in the

monitored area, Babeni-Valcea, can be identified using a multi-stable isotopes
approach. Hydrogen, Nitrogen, Oxygen, and Carbon isotopes measurements
combined with hydrochemical data provide key information for vulnerability
assessment of potential sources of water supply for urban areas. The stability of
water resources in the study area can be evaluated by spatiotemporal distribution
of water stable isotopes. Environmental isotopes such as tritium and C-14 can be
also used to date the sources of drinking water in Babeni-Valcea, yet an important
information on circulation and renewability of water resources.
The isotopes hydrogeological study need at least one year monitoring of
drinking water sources and surface water existing in the area. There were
established 32 sampling points in the Babeni-Valea Mare area due to a wide type of
drinking water sources used by the local community. Wells, springs and drillings are
located in monitored area. Beside small streams active during heavy rain, three
rivers flow in the area. More than 20 parameters (physical, chemical, and
isotopically parameters) are recorded for each sampling points, and it is foreseen
monthly campaign during one year in order to establish protection degree of
drinking water sources.
In order to facilitate records and interpretation of monitoring data, an ACCESS
application and database was designed. Using geographical coordinates, the
database is imported as layers in a GIS application using ADO Objects. All recorded
data can be presented and update in GIS application using ActiveX connections and
database queries. Preliminary results of the sampling campaigns carried out so far
are presented.
All the mentioned parameters are analyzed at the ICSI where the necessary
equipment and knowledge already exist. The main outcome of this study will be the
integration of isotope techniques to evaluate drinking water sources for urban
areas. Moreover, the main expected output will be a guideline on integrating
environmental isotopes to assist water managers. The knowledge exchange will
234
facilitate the vulnerability assessment of drinking sources and thus will improve
management practices in Babeni-Valcea.
Keywords: environmental isotopes, drinking water sources
facility PESTD.
235
APPLICATION OF SPECTROSCOPIC TECHNIQUES COUPLED WITH MULTIVARIATE

STATISTICAL ANALYSIS FOR WINES AUTHENTICITY ASSESSMENT
Elisabeta-Irina Geană1, Corina Teodora Ciucure1, Raluca Popescu1,

Constantin Apetrei2*, Victoria Artem3
1
2
”Dunarea de Jos” University of Galati, Faculty of Science and Environment, Department of
Chemistry, Physics and Environment, 47 Domneasca Street, RO‐800008, Galati, Romania
3
Research Station for Viticulture and Oenology Murfatlar, Calea Bucuresti str., no. 2, 905100,
Murfatlar, Constanta, Romania
Corresponding author: apetreic@ugal.ro
Wine is a product widely consumed of economic importance in many

countries around the world (Azcarate, et al., 2013). From chemical point of view,
wine is a complex mixture of different compounds with water and ethanol as the
main compounds and other minority constituents like phenolic compounds, organic
acids, amino acids, minerals, sugars, glycerol which provide different characteristics
to wines (Martelo-Vidal & Vázquez, 2014). One of the most important issue in the
wine sector and prevention of adulterations in wine are discrimination of grape
varieties, geographical origin of wine, and year of vintage (Godelmann et al., 2013).
However, it is necessary to identify the best strategy, the most promising analytical
method(s) considering economic aspects (screening vs. confirmatory methods) to
address this topic. In this context, spectroscopic techniques have become one of
the most attractive and common methods of analysis providing rapid and accurate
results.
The purpose of this research is to assess the potential of spectroscopic
techniques (UV-Vis, FTIR and 1H-NMR) in conjunction with chemometrics to
discriminate between different red and white Romanian wines and years of
vintage.
There were studied 4 red wine varieties (Cabernet Sauvignon, Merlot,
Feteasca Neagra, Babeasca Neagra), 7 white wine varieties (Chardonnay Riesling
Italian, Columna, Sauvignon Blanc, Feteasca Regala, Pinot Gris amd Muscat Ottonel)
and one rose variety (Mamaia) produced at SCDVV Murfatlar during 9 year of
production (from 2009 to 2017). The UV-Vis spectra collection was done at 300–
800 nm working range, while FTIR fingerprint was acquired between 600-1800 cm-1
using a FTIR equipped with a versatile high throughput ZnSe ATR crystal and NMR
experiments were recorded at 300 K using a Bruker spectrometer operating at 9.4
T, observing 1H at 400.2 MHz and 13C at 100.6 MHz. Data matrices were
constructed with columns corresponding to the specific signals and rows
236
representing wine samples. Principal Component Analysis was performed using

different regions of the obtained spectra to examine the differences within the set
of red and white wines.
Figure 1 shows the overlap of typical 1H-NMR spectra highlighting the
differences between red wine varieties.
Figure 1. 1H-NMR spectra of red wines (Cabernet Sauvignon-green, Merlot-blue,

Feteasca Neagra-pink and Babeasca Neagra-red)
The results suggested that spectroscopic methods (UV-Vis, FTIR and NMR),
coupled with PCA represents a very powerful tools for distinguishing groups with
very similar properties and consistent overall differences. The proposed
methodologies allow the classification of wines according to grape variety and year
of vintage, better than 75%.
UV-Vis and FTIR spectroscopic techniques coupled with PCA might be used as
accessible instruments for the discrimination between different red and white wine
varieties, without the need for costly and laborious chemical analysis, which makes
them more accessible to many laboratories.
Despite presenting good capabilities to discriminate between wine categories, NMR
spectroscopic approach needs expensive instrumentation and specialized
personnel, being used only in prestigious laboratories.
Keywords: spectroscopic techniques, red and white wines, UV‐Vis, FTIR, NMR

research projects PN‐III‐P1‐1.1‐PD‐2016‐0518– “Innovative strategies based on
screening techniques coupled with multivariate statistical analysis used for wines
authenticity assessment”, SCREEN‐WINE, 45PD/2018, supported by the Romanian
National Authority for Scientific Research and Innovation, CNCS – UEFISCDI.
237
References
Azcarate, S. M., Cantarelli, M. Á., Pellerano, R. G., Marchevsky, E. J., & Camiña, J. M., (2013), Classification
of Argentinean Sauvignon Blanc Wines by UV Spectroscopy and Chemometric Methods. Journal of
Food Science, 78(3):C432-C436. http://doi.org/10.1111/1750-3841.12060
Godelmann, R., Fang, F., Humpfer, E., Schütz, B., Bansbach, M., Schäfer, H., & Spraul, M., (2013),
Targeted and nontargeted wine analysis by (1)h NMR spectroscopy combined with
multivariate statistical analysis. Differentiation of important parameters: grape variety,
geographical origin, year of vintage. Journal of Agricultural and Food Chemistry, 61(23):5610-
9, http://doi.org/10.1021/jf400800d
Martelo-Vidal, M. J., & Vázquez, M., (2014), Classification of red wines from controlled designation
of origin by ultraviolet‐visible and near‐infrared spectral analysis. Ciência e Técnica
Vitivinícola, 29(1):35-43. http://doi.org/10.1051/ctv/20142901035
238
CHARACTERIZATION AND CLASSIFICATION OF HONEYS WITH DIFFERENT

BOTANICAL SOURCES BASED ON ORGANIC ACIDS AND WATER-SOLUBLE
VITAMINS IN CONJUNCTION WITH CHEMOMETRIC ANALYSIS
Corina Teodora Ciucure, Elisabeta-Irina Geană

1
Corresponding author: irina.geana@icsi.ro
Honey is a supersaturated solution of sugars with about 18% water content

and other minor components such organic acids, vitamins, flavonoids, phenolic
acids, proteins, free amino acids, enzymes and minerals (León-Ruiz et al., 2013)
with therapeutic potential. The qualitative and quantitative characterization of the
minor constituents like organic acids and water soluble vitamins in sugar based
matrices (e.g. honey) are still scarcely explored research areas. Thus, development
of reliable analytical methods for the determination of organic acids and water
soluble vitamins in honey as powerful tools for honey botanical origin
authentication is an important (Ciulu et al., 2011; Mato et al., 2006).
The aim of this work was to develop two chromatographic methods for
separation and quantification of the main organic acids and water soluble vitamins
in different honeys types in order to create databases for honey botanical origin
discrimination.
A ultra-high-performance liquid chromatography (UHPLC) separation with diode
array (DAD) detection methods were developed and used for the characterization of
organic acids and water-soluble vitamins of 82 honey with different botanical origin
(acacia, sunflower, linden, rape, polyfloral and honeydew). Chromatographic
separation of organic acids (oxalic, formic, malic, lactic, ascorbic, maleic, succinic, citric,
propionic and fumaric acids) was performed at 15°C with a Hypersil Gold aQ reversed
phase column (250x 4 mm, 5 µm) and isocratic elution of water with 0.02% H2SO4 at
0.3 mL/min flow rate, while water soluble vitamins (B1, B2, B3, B5, B6, B7, B9, B12, C)
were separated using a Syncronis C18 reversed phase column (250x 4.6 mm, 5 µm) and
gradient elution of two solvents (A: water with 0.025% TFA and B: ACN) at 0.8 mL/min
flow rate. The organic acids were isolated and pre-concentrated from the honey matrix
by solid-phase extraction using ion-exchange cartridge Sep-Pak (500 mg) (Suárez-Luque
et al., 2002), while water soluble vitamins were analysed directly after their complete
dissolution from the honey matrix. Sample extracts were injected into analysing system
after filtering through a 0.45 µm pour size membrane filter. Identification of organic
acids and water-soluble vitamins was done using reference standards and the amounts
239
in the extracts were calculated as mg/100 g honey using external calibration curves,
which were obtained for each compound.
The proposed methods have been successfully applied for the separation and
quantification of organic acids and vitamins in honeys with different botanical origins.
The honey samples had similar, but quantitatively different, organic acids and water
soluble vitamins profiles. Relatively high amounts of citric and propionic acids were
identified in all honey extracts. Citric acid was predominant in sunflower honeys while
propionic acid in acacia and rape honeys. Formic acid was identified only in honeydew
honeys and tree rape honeys. Oxalic acid was identified in all honey samples, in some
cases in high amounts, indicating residency after the bee treatment. The overall
amount of the investigated water soluble vitamins in honey samples was quite low or
undetectable, in many cases, confirming that honey is not a vitamin-rich food. Vitamin
C seems to be not abundant in honey, due to his low stability, the highest
concentration observed in our study being for honeydew honey. Vitamin B5 seems to
be less common than vitamin C and B3, but in considerable amounts.
The samples were classified according to the botanical origin using multivariate
statistical analysis and specific markers were identified for each honey type. LDA
revealed acceptable scores for the two defined discriminant factors (F1 and F2),
providing a 89.07% percentage of predicted membership according to the honey floral
origin (62.32% F1 and 26.75% F2) (Fig.1).
acacia honeydew linden polyfloral rape sunflower
4
F2 (26.75 %)
-2
-4
-6
-10 -8 -6 -4 -2 0 2 4 6
F1 (62.32 %)
Figure 1. Scatter plot of the first two discriminant functions showing

separation between honey types
Keywords: honey, botanical origin, organic acids, vitamins, UHPLC
240
Acknowledgements
This work was performed within the framework of the research projects PN‐III‐P2‐2.1‐PED‐2016‐
1656 – “Alternative analytical approaches for detecting adulteration of honey with emphasis on its
biologically active compounds”, SAFE‐HONEY, 194PED/2017, supported by the Romanian National
References
Ciulu, M., Solinas, S., Floris, I., Panzanelli, A., Pilo, M.I., Piu, P.C., Spano, N., Sanna, G., 2011. RP-HPLC
determination of water-soluble vitamins in honey. Talanta 83, 924–929.
doi:10.1016/j.talanta.2010.10.059
León-Ruiz, V., Vera, S., González-Porto, A. V., San Andrés, M.P., 2013. Analysis of Water-Soluble
Vitamins in Honey by Isocratic RP-HPLC. Food Anal. Methods 6, 488–496.
doi:10.1007/s12161-012-9477-4
Mato, I., Huidobro, J.F., Simal-Lozano, J., Sancho, M.T., 2006. Analytical Methods for the
Determination of Organic Acids in Honey. Crit. Rev. Anal. Chem. 36, 3–11.
doi:10.1080/10408340500451957
Suárez-Luque, S., Mato, I., Huidobro, J.F., Simal-Lozano, J., Sancho, M.T., 2002. Rapid determination
of minority organic acids in honey by high-performance liquid chromatography. J.
Chromatogr. A 955, 207–14.
241
GEOGRAPHICAL, VINTAGE AND VARIETY FINGERPRINTING OF WINES BASED ON

ELEMENTAL CONTENT AND CHEMOMETRIC APPROACH
Ioana Feher1, Dana-Alina Magdas1, Adriana Dehelean1, Costel Sarbu2

1
Donath, 400293 Cluj‐Napoca, Romania
2
Babeș‐Bolyai University, Faculty of Chemistry and Chemical Engineering, 11 Arany János, 400028,
Cluj‐Napoca, Romania
Corresponding author: ioana.feher@itim‐cj.ro
Wine authentication related to vintage, variety or geographical origin, is very

important every where in the World, for both consumers and producers, in order to
maintain a healthy and fair-trade environment. Analytical techniques must develop or
improve continuously, because the methods of changing wine composition change
often. For geographical fingerprinting one method of choice for authentication if
represented by inductively coupled plasma mass spectrometry (ICP-MS). The elemental
content corresponding to the soil are reflected directly into the wine composition.
There are also external factors that might have a direct influence upon elemental
content of wine. And might be represented by agricultural practices (for instance Cu
from copper sulfate, which is widely used as fungicide, or other pesticides metal based)
or by climatic condition during the grape growing stage (precipitation in large quantities
might wash out some impurities from surrounding areas). Another influence of metal
content might arise from vinification process, more precisely from tanks or other
substances that are added for different purposes (bentonites, for example).
Due to the large experimental data that need to be taken into consideration for
a comprehensive conclusion regarding a certain matrix, chemometric approach has
become the method of choice for data processing. In food and beverages field, for
classification or discrimination purposes, such a high number of samples is mandatory in
order to provide reliable and robust conclusions. In this context, chemometric tools
became the methods of choice for reducing the data dimensions and to make available
hidden information that could lead to successful characterization and discrimination of
samples.
The main aim of this work was to employ robust chemometric methods, such
Fuzzy-Principal Component Analysis (FPCA), Fuzzy-Principal Component Analysis-Linear
Discriminant Analysis (FPCA-LDA) and fuzzy divisive hierarchical associative-clustering
(FDHAC), including also classical methods (hierarchical cluster analysis-HCA, principal
component analysis-PCA and principal component analysis-linear discriminant analysis-
PCA-LDA) were successfully applied for characterization and classification of white
wines according to the geographical origin, vintage or variety using analyzed elemental
content. The obtained results clearly demonstrated the efficiency and information
power of the robust fuzzy methods in food characterization and authentication.
HCA provided two dendrograms (one for elemental content and one for wine
samples), where the grouping of elements and sample could be observed. PCA and
242
FPCA was applied using the experimental matrix (30 samples x 24 concentrations)
indicate an insignificant reduction in the number of variables. It can also be seen that
the first three components explained less than 48.67% of the total variation, for PCA
and 64.53% for FPCA respectively.
LDA revealed that a separation of samples according to the variety (grouping
variable) of wines is 83.33%, based on Na, Ca, Nb and Al. If geographical area is the
grouping variable, Sr>Fe>P are best markers and the percent is 96.67% in this case. If
the vintage is considered the grouping variable, the elements whose concentration
changes significantly from one year to another were Sb, Pb, Zn and Co, separation of
samples according to the harvest period being complete (100 %).
The results obtained in the case of PCA/FPCA-LDA methods when area was
considered as a grouping variable, showed that sample separation reaches the percent
of 100 % in both cases, more compact groups being obtained for FPCA scores. A similar
separation of samples is also obtained in the other case, when the geographical area
and the variety are used as grouping variable. In the case of vintage, the initial
classification is again 100 %.
By analyzing the fuzzy partitions at each level in parallel with the analytical data,
the following remarks may be taken. At the first partition level the samples are
separated into two fuzzy partitions A1 and A2 respectively, the characteristic elements
(corresponding concentrations for the respective samples) are those between La and
Ce for the first partition, and for the second partition the elements between Na and Fe.
The order in the table for both samples and elements considered, corresponds to
membership degrees, i.e. the first / first has the highest membership degree, and the
last / last one has the lowest membership degree. It is also easy to note that samples
from Moldova are much better separated than those from Banat and Transylvania,
which are more similar to each other. To further illustrate the operation and
effectiveness of the fuzzy classification method, consider the partitions A111, A112,
A1111, A1112. Partition A111 contains three samples of the same variety and two
adjacent areas (Bs, Ts, Ts), and the associated elements are Nb and Mn. For the three
samples, the concentrations corresponding to the two elements are the smallest (Nb:
0.0, 0.02, 0.0, and for Mn: 434.2; 225.04; 548.12). Given differences in Mn
concentration, partition A111 is split into A1111 (Bs, Ts, associated with Nb: 0.0, 0.0
and Mn: 434.2, 548.12) and A1112 respectively (Ts, associated with Nb: 0.02 and Mn:
225.04). The split of the A212 partition (Mf, Bs, associated with As: 7.98, 1.62, Fe:
3760.5, 5096.72, the highest values) is equally relevant. The two resulting partitions
separate the two different varieties and associate the elements whose concentration is
the highest from all samples: A2121 (Mf, As: 1.62, Fe: 5096.72) and A2122 respectively
(Bs, As: 7.98, Fe: 3760.5).
Chemometric methods along with elemental determinations proved their
suitability for geographical, vintage and variety discrimination purposes.
Keywords: elemental content, chemometric, fuzzy, geographical, vintage, variety
Acknowledgments: This work was supported by Romanian National Authority for

Scientific Research and Innovation, CNCS/CCCDI – UEFISCDI, project number 187 PED‐
2017.
243
IMPACT OF ADULTERATION WITH DIFFERENT SUGAR SYRUPS ON HONEY

ORGANIC ACIDS AND WATER-SOLUBLE VITAMINS
Corina Teodora Ciucure, Elisabeta-Irina Geană
Corresponding author: irina.geana@icsi.ro
Honey is a high-value food product, which is composed mainly of sugars and

water together with many minor components with therapeutic potential such as
organic acids, vitamins, phenolic and volatile compounds, proteins, enzymes, etc
(da Silva et al., 2016). According to international standards, authentic honey is a
natural product that should not contain any added substances, such as sugar
syrups. Due to its market value which is much higher than other commonly utilized
sweeteners, honey is a temptation for adulteration with cheap industrial
sweeteners, in order to obtain additional benefits (Amiry et al., 2017). Detection of
honey adulteration is not simple and for that numerous analytical methods were
proposed (Trifković et al., 2017).
This study investigated the impact of adulteration with different sugar syrups
on honey organic acids and water-soluble vitamins. For this purpose, different
authentic honey samples and adulterated honeys produced by direct incorporation
of different percent of sugar syrups in honey (5, 10, 20, 30, 40 and 50%) or
produced by bees that had been fed supplementary with sucrose syrup were
analyzed.
UHPLC-DAD methods were used for organic acids and water soluble vitamins
fingerprinting, after the appropriate sample extraction procedures. Figure 1 shows
the overlay of 10 ppm standard solution of organic acids (black) and pure polyfloral
honey extract (blue) chromatograms.
Due to the fact that sugar syrups used for direct adulteration of honey do not
contain organic acids and vitamins, except lower quantities of oxalic and propionic
acids, direct incorporation of sugar syrups in honey or intensive bee feeding with
sugar syrups has produced a decrease of these bioactive compounds in honey, but,
in most cases, in the natural range of variation for pure honeys.
244
Figure 1. UHPLC chromatogram of organic acids in honey extract
Multicomponent analysis, which involves the analysis of numerous

parameters is necessary for quality control and authentication of honey.
Quantification of the amount of added C4 sugar syrup in honey must be done by
standardised isotopic method (SCIRA).
Keywords: honey, sugar syrups, adulteration, organic acids, vitamins, UHPLC

research projects PN‐III‐P2‐2.1‐PED‐2016‐1656 – “Alternative analytical approaches
for detecting adulteration of honey with emphasis on its biologically active
compounds”, SAFE‐HONEY, 194PED/2017, supported by the Romanian National
References
Amiry, S., Esmaiili, M., Alizadeh, M., (2017), Classification of adulterated honeys by multivariate
analysis. Food Chem. 224:390-397, doi:10.1016/J.FOODCHEM.2016.12.025
da Silva, P.M., Gauche, C., Gonzaga, L.V., Costa, A.C.O., Fett, R., (2016), Honey: Chemical composition,
stability and authenticity. Food Chem. 196:309-323, doi:10.1016/J.FOODCHEM.2015.09.051
Trifković, J., Andrić, F., Ristivojević, P., Guzelmeric, E., Yesilada, E., (2017), Analytical Methods in
Tracing Honey Authenticity. J. AOAC Int. 100:827-839, doi:10.5740/jaoacint.17-0142
245
SHIFTING RETENTION TIME IN GAS-CHROMATOGRAPHY. PRACTICAL PROBLEMS

FOR ANALYTICAL METHOD DEVELOPMENT OF URETHANE IN THE ALCOHOLIC
DISTILLATES BY GC-MS
Aurel Mircia Toderici
Corresponding author: mircia.toderici@icsi.ro
Present work describes the shifting of gas chromatographic retention time for
ethyl-carbamate (urethane) due to influence of a matrix polar compound effects.
Even if the shifting of gas chromatographic retention times due to solvent effects
was first mentioned by Edward A. Dietz Jr in an article from 1996 (Dietz, 1996), the
effects due to the influence of a matrix compound was never mentioned. This
phenomenon is suspected to appear in that situation where the target compound,
the matrix compound and the GC column stationary phase have a high affinity and
strongly influences each other. This effect was highlighted during the method
development steps required to establish the appropriate gas-chromatographic
analytical method for quantitative determination of ethyl-carbamate in distilled
drinks. This analytical method was developed based on OIV (OIV-MA-BS-25:R2009)
official method [OIV]. The goal was to separate the ethyl-carbamate peak from
other matrix compound peaks in the pre-validation step, when was tested the new
method on real alcoholic distillate samples. The resolving steps of chromatographic
coelution are presented. GC-MS ion chromatograms and related mass spectra are
presented and the physical phenomena is highlighted and tried to be explained
also.
Keywords: retention time shifting, ethyl‐carbamate, matrix effect, GC‐MS, method

development.
References
Dietz Jr Edward A., (1996), J. Sep. Sci., 19(9):485-491
OIV, Compendium of International Methods of Spirituous Beverages of Viti-vinicultural Origin,
http://www.oiv.int/en/technical-standards-and-documents/methods-of-analysis/compendium-of-
international-methods-of-spirituous-beverages-of-vitivinicultural-origin
246
ASPECTS ON ADVANCED ISOTOPIC AND MULTIPARAMETRIC INVESTIGATION OF

SURFACE WATERS AS SUPPORT IN ENVIRONMENTAL PROCESSES
Andreea-Maria Iordache1, Mihaela Iordache1, Claudia Sandru1, Cezara Voica2,

Ramona Zgavarogea1, Roxana Elena Ionete1
1
2
Donat Str., Cluj‐Napoca, Romania
Corresponding authors: andreea.iordache@icsi.ro; roxana.ionete@icsi.ro
The investigation of data regarding the translocation of pollutants (Voica et l.,

2017; UNEP GEMS) from different environmental compartments (water, sediments
and biota) was made on the main tributary of Danube in Romania, the Olt river, on its
middle and lower basin. Water and sediment samples were collected from 22 sampling
points and analyzed by inductively coupled mass spectrometry (ICP-MS) for the
selected multiparametric compounds (heavy metals, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb),
respectively isotopic composition using continuous flow-isotope ratio mass
spectrometry (CF-IRMS) (Popescu et al., 2015; Popescu et al., 2014; Ionete et al. 2015).
The measurements for were performed with a mass spectrometer ICP-MS
model Elan DRC-e, Perkin-Elmer. The accuracy and precision of the analytical
technique was evaluated by analyzing a certified standard reference material.
Precision of the instrument, the RSD values ranged from 0.4 % to 6.4 %. In addition,
the mass spectrometer with continuous flow for stable isotopes analysis CF-IRMS
Thermo Delta V Plus was used for environmental isotops such as 18O and 2H.
Characterization in terms of rare metals concentrations, comparing water
samples versus water resulting after settling sediment, revealed that the sediments
accumulates rare metals (the concentrations both in water and sediment are very
low, but there is a slight increase in sediment). Was also highlighted that sediment
accumulate a larger amount of rare earth metals than soils. Determination of rare
earths in various types of environmental samples it can serve to establish a
fingerprint sample and so the results could be used in determining the origin of the
sample in question and to identify sources of pollution.
Values of D/H and 18O/16O isotope ratios from surface water on middle and
lower basin of Olt River, present the differences due the variations the climatic and
geographical parameters (e.g. seasonal variation in temperature, altitude and
latitude), the physical setting of the drain age basin (e.g. topography). The highest
,,d” value for deuterium excess calculate for middle basin of Olt river (16,38‰)
indicates a rain fall in this geographic part.
247
Correlations with the climatic factors and the location of the sampling points
were performed in relation to the pollution sources. The most important factor in
determining the concentration values of the pollutant metal chemical species has
proved to be the location of sampling points relative to the anthropogenic sources
of pollution. The study is an effective management which requires both the
understanding of environmental processes and the ability to quantify the risk of the
transfer mechanism.
Thereby improving environmental quality will become the action against
disorder and the reaction against the inertia and of the compromises when
considering human life environment.
Keywords: heavy metals, ecological risk, ecosystem, environmental isotopes,

sediments
Acknowledgments: This work is part of the project PN 18 12 03 03 “Assessing the

impact of waste water discharges on the environment through advanced analytical
investigations based on nuclear and other related techniques” financed by the
Romanian Ministry of Research and Innovation.
References
Voica C., Iordache A., Ionete R. E., Stefanescu I., (2017), Water Quality, chapter 12
UNEP GEMS/Water Programme Water Quality Outlook, ISBN: 95039-11-4 UN GEMS/Water
Programme Office.
Popescu R., Mimmo T., Dinca O. R., Capici C., Costinel D., Sandru C., Ionete R. E., Stefanescu I., Axente
D., (2015), Science of the Total Environment, vol. 533:17-23
Popescu R., Costinel D., Ionete R. E., Axente D., (2014), Isotopes in Environmental and Health Studies,
50(4):461-474
Ionete R. E., Popescu R., Costinel D., (2015), Environmental Engineering & Management Journal,
14(10):2445-2456
248
MEASUREMENT OF Ra-226 VIA Rn-222 IN WATER SAMPLES BY LSC
Relu Dobrin, Cristian Dulama, Crina Bucur, Valentina Neculae
Institute for Nuclear Research, Piteşti, Romania

Corresponding author: relu.dobrin@nuclear.ro
Ra-226 is a naturally occurring radionuclide with a relatively long half-life (1600

yr.); it is chemically very similar to calcium, so it is incorporated in bones when
ingested. From a radioecological point of view, Ra-226 is very important because of
its long half-life, its bone-seeking characteristics, and its high-energy α emission. In
addition, Ra-226 plays an important role as a natural radiotracer of environmental
processes. Finally, it is of interest for evaluating the radioecological impact of
different human activities, such as mining or phosphate fertilizer production. For
these reasons, it is very important to develop adequate methods that can
determine this radionuclide.
The paper presents the experimental results obtained during the
implementation phase of a method developed for determination of Ra-226 content
in aqueous samples. The measurement method is based on continuous extraction
of Rn-222 in a water immiscible organic liquid scintillator. The sample aliquot and
scintillator are maintained in contact, within the scintillation vial, during the
ingrowth of Rn-222 and its decay products (Po-218 and Po-214) and are periodically
counted by liquid scintillation counting (LSC). Through a regression algorithm, the
equilibrium activity of Rn-222 and therefore Ra-226, is determined. A series of
experimental determinations have been performed to develop and optimize the
method, by using various dilutions of a standard solution containing Ra-226 and a
Tri-Carb 4910TR LSA model, from PerkinElmer.
Also, in the paper is presented our explanation referred to the value of the
detection efficiency of the method, which, theoretically, should be about 3.0 (at
equilibrium, there are 3 alpha emitters, and the efficiency of detecting alpha
particles with liquid scintillators is about 1.0). However, the experimental value of
the efficiency we recorded in a tracer study with more than one hundred samples
containing Ra-226 was only about 2.6 for all the samples. In fact, this is the most
commonly reported value in the literature for the detection efficiency of this
method. In our opinion, the lower value of the detection efficiency is due to the
hardware limitation of the liquid scintillation analyser; the upper limit of the alpha-
MCA of the LSA is set to the channel 2000, and about 13-14% of the 7.7 MeV alpha
peak of Po-214 extends outside this range being therefore not recorded in the
alpha spectrum (see Fig.1).
249
Figure 1. LSC spectrum of a Ra-226 experimental sample
Keywords: Ra‐226 determination, alpha‐LSC.
Acknowledgments: The research leading to these results has received funding from
the European Union's Horizon 2020 Research and Training Programme of the
European Atomic Energy Community (EURATOM) (H2020‐NFRP‐2014/2015) under
grant agreement n° 662147 (CEBAMA).
250
CANDU 600 FAILED FUEL LOCATION SYSTEM. ANALYSIS OF BF3 DELAYED

NEUTRON DETECTORS AGEING
Oana Iuliana Popescu, George Serbanescu, Mihaela Vitan, Simona Budan,

Alexandru Florea
Institute of Nuclear Research Pitesti, Romania

Corresponding author: oana.popescu@nuclear.ro
CANDU 600 Reactor is equipped with Failed Fuel Location System (FFLS) for
nuclear fuel localized in active Reactor area CALANDRIA. This system is designed for
an economic life – time duration of thirty years. It is important the evaluation
components ageing and attrition of delayed neutron measure lines for accuracy
evaluation and calibration or replacing operation.
This paper presents verification and calibration tests for a set of eight BF3
delayed neutron detectors having ten years operational interval time. Normal
operation plateau for every BF3 detector was traced first. After normal plateau
determination we performed ten measures for every BF3 detector at the same
level of supply voltage. The obtained results shows that measured and calculated
precision values for all BF3 detectors even if present some variations there are
within confidence interval.
Our work proved an acceptable degradation degree of detectors performances
with a 20% maximum error in calibration curve and correction possibility through
laboratory adjustment.
251

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National R-D Institute for

Ministry of Research and Cryogenics and Isotopic Technologies

NEW CRYOGENIC AND ISOTOPE TECHNOLOGIES FOR

Baile Govora, Romania

Băile Govora, Romania

The conference is organized with the financial co-support of

ENERGY STORAGE AND HYDROGEN TECHNOLOGIES

ESHT 14-O Shin Ki-Yeol, Cristian Hoarca

ISOTOPES OF HYDROGEN AND ITS APPLICATIONS

ISHA 15- P Tatiana Voronina, Daria Tugusheva

MATERIAL SCIENCE FOR ENERGY AND ENVIRONMENT

MSEE 2- O Jasmina Grbović Novaković, Sandra Kurko, Sanja Milošević

MSEE 12- O Daniela Ion-Ebrasu, Bruno G. Pollet, Adnana Spinu-Zaulet,

MSEE 33- P Michail-Liviu Craus, Vitalij Turchenko, Valerij Simkin, Tat'jana

LIFE QUALITY AND ENVIRONMENT TECHNOLOGIES

POST LI-ION BATTERIES

Norbert Wagner, Alexander Kube, Frieder Warth, Andreas Kaspar Friedrich

German Aerospace Center (DLR), Institute for Engineering Thermodynamics,

investigate how the electrolyte penetration depth influences the electrochemical

ADVANCED LITHIUM ION BATTERIES

Krum Banov1,2, IlyaPopov1, Dimka Ivanova2, Ludmi Fachikov2,

developed a complex method for improving and stabilizing the characteristics of

VALORIZATION OF A LOCAL ENERGY RESOURCE: HYDROGEN APPLICATIONS

Mathilde Bangoura*, Frédéric Thiebaud, Dominique Perreux, Benoit Delobelle,

MAHYTEC, 6 rue Léon Bel, 39100 Dole, France

When it comes to managing the final consumption of energy, local energy

Keywords: H2 technologies, hydrogen production, hydrogen storage, hydrogen

NCMS AS CATHODE MATERIALS FOR LITHIUM – ION BATTERIES

Aishui Yu, Siyang Liu, Congcong Zhang

Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials,

Keywords: LiNi1‐x‐yCoxMnyO2, at elevated temperature, at high voltage, coating,

LITHIUM SULPHUR BATTERIES: STRATEGIES TO INCREASE THE CYCLE LIFE

Electrochemistry Group – Politecnico di Torino

Finally the use of an interlayer based on C3N4 is presented and allowing to

THE ROLE OF ENERGY STORAGE IN LOW CONSUMPTION WORKING VEHICLES

Aurelio Somà, Francesco Mocera, Elena Vergori

Department of Mechanical and Aerospace Engineering (DIMEAS), Politecnico di Torino,

Table 1. Different types of energy storage systems

Each type of storage in Table 1, is characterized by different discharge

Another theoretical limitation is specific capacity and specific energy, which

Keywords: Energy transition, energy storage, lithium‐ion batteries, diagnostic,

STUDY ON GEOTHERMAL ENERGY ON ROMANIAN TERRITORY

Natalia-Silvia Asimopolos, Laurentiu Asimopolos

Geological Institute of Romania, Caransebes Street, 1, Bucharest, 012271, Romania

Geothermal energy is an unconventional renewable energy source with

Keywords: environment, geothermal, renewable energy, geophysical portal.

Acknowledgments: This work was supported by a grant of the Romanian Ministry

NUCLEAR ASSISTED HYDROGEN PRODUCTION

Damian Axente, Cristina Marcu

Li-ION BATTERY MANUFACTURING IN EUROPE: ITALIAN INITIATIVE

Mihaela Aneta Dumitrescu

Lithops s.r.l, Strada del Portone 61, 10137 Torino

The market of Li-ion batteries is continuously growing due to the progresses

Keywords: Li‐ion battery, manufacturing, competitiveness.

α-SETS SOFTWARE FOR ANALYSIS, MODELLING AND SIMULATION OF THE

Adrian Bot, Vasile Rednic, Nicolae Aldea

Keywords: Stirling engine, isothermal analysis, adiabatic analysis, scaling parameter

Acknowledgments: Financial support from the MCI, Core Programme, Project PN 18

THERMAL RECEPTOR FOR CONCENTRATED SOLAR POWER. AN EXPERIMENTAL

Keywords: Concentrated solar power, Thermal receptor, Energy conversion, Thermal

Acknowledgments: Financial support from the MCI, Core Programme, Project PN

TECHNIQUES BASED ON POSITRONS AT ELI-NP

Andreea Oprisa, Nikolay Djourelov, Victor Leca, Doru Dinescu

We present a brief description of the techniques based on positrons that we