Applied nanotechnology - Zachodniopomorski Uniwersytet

Transkrypt

POSTERS
ANGELIKA A. ADAMUS*/**/***, BEATA MIKSA**, MAREK POTRZEBOWSKI**,
ZBIGNIEW H. KUDZIN***, ELŻBIETA BUDZISZ*
*
Uniwersytet Medyczny, Wydział Farmaceutyczny, Katedra Kosmetologii,
Muszyńskiego 1, 90-151 Łódź
**
Centrum Badań Molekularnych i Makromolekularnych Polskiej Akademii Nauk,
Sienkiewicza 112, 90-363 Łódź
***
Uniwersytet Łódzki, Wydział Chemii, Katedra Chemii Organicznej,
Tamka 112, 91-403 Łódź
SYNTEZA I BADANIA STRUKTURALNE NANOLIPOPOLIMERSOMÓW
Składnikiem błon biologicznych występujących w komórkach żywych organizmów
są fosfolipidy. Związki te wyróżniają się właściwościami amfifilowymi (hydrofobowohydrofilowymi). Cechy te pozwalają w środowisku wodnym na spontaniczne tworzenie
pęcherzyków zwanych liposomami. Wewnątrz liposomów mogą być zamykane aktywne
substancje chemiczne. Dlatego też, liposomy są wykorzystywane do transportu środków
farmakologicznych (różnego rodzaju leków) w kosmetologii, dermatologii oraz jako
suplementy diety.
Celem pracy jest zastosowanie liposomów będących modelem naturalnych membran
w badaniach dotyczących transportu leków antynowotworowych. Ponieważ liposomy
cechują: biokompatybilność i łatwa przenikalność przez warstwy nabłonka (dzięki
podobieństwu strukturalnemu) lecz jednocześnie bardzo wysoka niestabilność dlatego też
poszukiwane są metody ich wzmocnienia.
Moje badania dotyczą syntezy liposomów utrwalonych polimerami tzw.
nanolipopolimersomów. Wybranym przeze mnie związkiem modelowym przeznaczonym do
enkapsulacji jest fosforylowany cholesterol. Syntezę fosfocholesterolu przeprowadziłam
samodzienie na podstawie przepisu dostępnego w literaturze (Gotoh M., Ribeiro N., Michels
B., Elhabiri M., Albrecht-Gary A-M., Hato M., Ourisson G., Nakatani Y., A novel type of
membrane based on cholesteryl phosphocholine, cholesteryl phosphate or sitosterol
phosphate and dimyristoylglycerol, Chemistry & Biodiversity, 3 (2006) 198-209.) W swoich
badaniach starałam się rozróżnić sposób i miejsce lokowania substancji enkapsulowanych
(cholesterolu i jego analogu fosforylowanego cholesterolu) w hydrofobowej dwuwarstwie
lipidowej utworzonej przez acylowe łańuchy węgla lub w hydrofilowej wewnętrznej
przestrzeni nanolipopolimersomów. Trwałe polimerowe struktury nanopęcherzyków
otrzymałam w wyniku nasycenia naturalnych liposomów styrenem, który następnie poddałam
polimeryzacji rodnikowej pod wpływem UV. Warstwa syntetyzowanego polistyrenu o
grubości kilku nm jest transparentna i umożliwia analizowanie enkapsulowanych związków
metodami spektrofotometrycznymi: UV i za pomocą fluorescencji. Dodatkową dogodną
metodą badawczą jest magnetyczny rezonans jądrowy w ciele stałym, który pozwala na
sprawdzenie dynamiki oddziaływań substancji enkapsulowanych z błonami fosfolipidowymi.
Wielkości polimerowych nanopęcherzyków zostały wyznaczone metodą dynamicznego
rozpraszania światła (DLS) oraz za pomocą mikroskopu sił atomowych (AFM).
Wyniki przeprowadzonych badań będą mogły zostać wykorzystanie w planowaniu
dalszych eksperymentów naukowych dotyczacych enkapsulacji substancji czynnych
farmakologicznie.
Projekt finansowany w ramach badań statutowych 503/3-066-02/503-01.
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silver nanostructired, building materials,
antifungal activity
MARCIN BANACH*, RENATA SZCZYGŁOWSKA**, JOLANTA PULIT*,
MIROSŁAW BRYK***
*
Politechnika Krakowska im. Tadeusza Kościuszki, Instytut Chemii i Technologii
Nieorganicznej
**
Spółka Wodna "Strzegowa", Laboratorium Badawcze
***
Firma Wdrożeniowa "Damiton"
BUILDING MATERIALS WITH ANTIFUNGAL EFFICACY ENRICHED
WITH SILVER NANOPARTICLES
Building materials used in modern construction should be microbially and
mycologically resistant due to the stability of the product prior its application and during
using of the final product in the form of a coating. The results of environmental tests indicate
increasing biodeterioration of mold and fungus, which significantly affects the health of users.
The aim of this study was to obtain a suspension of nanostructured silver on the basis
of the aqueous extract of raspberry fruit, as well as evaluation of antifungal activity of silicon
paint, parget and brick layer containing silver nanoparticles and also mycological resistance
efficacy analysis of tested samples referring to different concentrations of silver.
In the process of obtaining nanosilver particles (500 ppm) a raspberry fruit extract
was used which consists of both stabilizing and reducing agents. The extract was obtained by
aqueous extraction and silver nitrate was used as a source of silver ions.
The resulting suspensions were studied spectrophotometrically. Particles sizes were
determined by dynamic light scattering method (DLS).
Brick layer and silicone parget with nanosilver particles at a concentration of 1% and with
biocide as well as silicone paint with nanosilver particles at a concentration of 1%, 2%, 3%
and also silicone paint with biocide were subjected to assessment of antifungal activity.
Silicone paint in two different protective systems: 1% nanosilver + 0.05% MBT at a
concentration of 50% and 1% nanosilver + 0.1% SEE were also analysed. Fungus resistance
test was carried out according to PN EN 15457:2008.
It has been proved that the aqueous raspberry extract may be used as both stabilizing
and reducing agent in the synthesis of stable suspensions of nanocrystalline silver (500 ppm,
50 nm).
Studies of antifungal activity of nanostructured silver for tested products were carried
out. Obtained results match or exceed the results achieved by applying a fungicidal substances
as biocides. Attention should be paid to silver nanoparticles at a concentration of 2% and 3%
in the silicone paint, because the efficiency its activity outranks the antimicrobial activity
characterised for biocides. Nanosilver received based on prescribed method may be a
promising alternative to the commonly used biocides. The question remains whether
nanosilver would provide the required protective efficacy against fungi also for external
coatings.
This study was supported by the research grant LIDER/03/146/L-3/11/NCBR/2012
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zinc selenide, stearate, nucleation,
molar ratios, photoluminescence
MATEUSZ BAŃSKI, ARTUR PODHORODECKI, JAN MISIEWICZ
Wroclaw University of Technology, Institute of Physics,
Wybrzeże Wyspiańskiego 27, 50-370 Wroclaw, Poland
BAND GAP ENGINEERING OF ZnSe NANOCRYSTALS – INSIGHT INTO
THE ZINC STEARATE ROLE IN SYNTHESIS
The ability to engineer the band gap energy of semiconductor nanocrystals (NCs) has
led to the development of nanomaterials with many new exciting properties and applications.
Numerous approaches have been already developed to tune the energy gap of a semiconductor
NCs. Altering the crystal size is the most common way. However, changing the crystal
composition in alloying process recently grown in significance.[1]
A novel phosphine-free route for the preparation of highly quality ZnSe nanocrystals
we have successfully developed. The synthesis involve the reaction of zinc stearate with
selenium powder in non-coordinating 1-octadecene solvent. In this case, stearate ions play the
role of capping agent allowing to obtain the nanocrystals in cubic zinc blende structure and
ca. 5.5 nm in diameter. The nanocrystal size was primary controlled by the synthesis reaction
time. Moreover, influence of Zn/Se precursors ratio was investigated regarding size
distribution and agglomeration of nanocrystals as well as their optical properties. The as
prepared nanocrystals exhibit intensive excitonic blue emission which is blue shifted due to
quantum size effect.[2]
In order to extend the tunability of energy gap the proposed synthesis method was
modified and the nanocrystals with an alloyed structure was prepared as well. A set of
synthesis was performed with various S and Se precursors ratio. Every synthesis was
monitored in time and the samples were taken for investigation at various stage of NCs
growth. Based on a spectroscopic and structural investigations a gradient alloy core/shell
structure was proposed for the as-synthesized NCs. This structure has a significant impact on
the photoluminescence quantum yield and temporal stability of NCs.
Literatura
[1] J. Akhtar, M. Afzaal, M. Banski, A. Podhorodecki, et al. J. Am. Chem. Soc., 133, 5602-5609 (2011)
[2] M. Banski, A. Podhorodecki, et al., submitted (2013)
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hydrothermal synthesis, titanate nanotubes
sol-gel method
AGNIESZKA BASZCZUK*, MAREK JASIORSKI*, KATARZYNA ŁUSZCZYK*,
BEATA BORAK*, JERZY WÓDKA**
*
Wrocław University of Technology, Institute of Materials Science and Applied Mechanics,
Smoluchowskiego 25, 50-370 Wrocław, Poland
**
Wrocław University of Technology, Faculty of Chemistry,
HYDROTHERMAL SYNTHESIS AND PHYSICOCHEMICAL
PROPERTIES OF TITANATE NANOTUBES, NANORIBBONS
AND NANOWIRES
Different one-dimensional titanate nanostructures with controllable phases and
morphologies were synthesized via an alkaline hydrothermal process with titanium dioxide
(anatase) obtained by the sol-gel method as a starting material.
Phase analysis and crystal structure data of obtained materials were characterized by
X-ray powder diffraction and Raman spectroscopy. The morphology and composition of the
sample were analyzed by scanning and transmission electron microscopy.
A series of experiments indicates dependence of morphology and structure of titanate
nanopowders on parameters of hydrothermal synthesis. Furthermore, the mechanism of
transformation from nanotubes to nanoribbons and nanowires was demonstrated.
Acknowledgements:
The research was supported by the Wrocław Research Centre EIT+ within the project “The Application of
Nanotechnology in Advanced Materials” – NanoMat (POIG.01.01.02-02-002/08), co-financed from the
resources of European Fund of Regional Development (PO IG 1.1.2).
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rozkład termiczny (NH4)6Mo7O24·4H2O w argonie, metoda TG-DSC,
kinetyka procesu, metoda Kissingera, równanie Coatsa-Redferna
ANNA BIEDUNKIEWCZ*, MARTA KRAWCZYK*, URSZULA GABRIELPÓŁROLNICZAK**, PAWEŁ FIGIEL*
*
Zachodniopomorski Uniwersytet Technologiczny w Szczecinie,
Al. Piastów 17, 70-310 Szczecin
**
Akademia Morska w Szczecinie, Wały Chrobrego 1-2, 70-500 Szczecin
ANALIZA TERMICZNEGO ROZKŁADU (NH4)6 Mo7O24·4H2O W ARGONIE
W MIESZNINIE Z WĘGLEM AKTYWNYM
Badano rozkład (NH4)6Mo7O24·4H2O w mieszaninie z węglem aktywnym w argonie
metodą TG –DSC. Stosowano mieszaniny o składzie początkowym, wyrażonym proporcją
C/MoO3 równą 4 mol/mol. Proces przebiegał w pięciu etapach. Etapy I, III i IV były
przemianami endotermicznymi, a II i V egzotermicznymi. Po zakończeniu procesu otrzymano
MoO3. Podczas przemian w etapach wydzielały się: H2O, NH3, NO i N2O. Na podstawie
przeprowadzonych analiz zaproponowano sumaryczne równania stechiometryczne. Następnie
dla wyróżnionych etapów wyznaczono Tm i m odpowiadające maksymalnym szybkościom
przemian, zakresy temperatury T =0†T =1 oraz (T). Wyznaczono parametry kinetyczne: g( )
i f( ) (modele kinetyczne) oraz współczynniki równania Arrheniusa A i E. Stosowano
rekomendowaną przez ICTAC Kinetics Comitee metodę Kissingera oraz równanie Coatsa –
Redferna. Wyznaczone metodą Kissingera parametry kinetyczne g( ), A i E stosowano, w
dalszym etapie, podczas obliczeń metodą Coatsa – Redferna. Obliczono dla etapów badanego
procesu stopnie przemiany m, odpowiadające maksymalnym szybkościom przemiany i
porównano je z wartościami m, wyznaczonymi na podstawie pomiarów. Dla wszystkich
etapów otrzymano dobrą zgodność. Dla całych zakresów (T) dotyczących danego etapu nie
uzyskano dobrych wyników. Dlatego, stosując równanie Coatsa – Redferna ponownie
wyznaczono parametry kinetyczne. Wymagano, aby obliczone przebiegi (T) i wyznaczone z
pomiarów były zgodne w szerokim zakresie. Jako dodatkowe kryteria stosowano: zgodność
wykresów funkcji f( ) oraz zgodność przebiegów wykresów DTG i wykresów dotyczących
szybkości procesów. Dla etapów otrzymano stałe wartości A i E, dla stosownych szybkości
ogrzewania próbek. Wynik jest interesujący ponieważ pokazuje, że stosując metody
tradycyjnej kinetyki chemicznej, dla heterogenicznych reakcji niekatalitycznych,
prowadzonych w warunkach nieizotermicznych, można uzyskać dobre rezultaty.
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silica particles, sol-gel method,
accumulation, rats, drug carrier
PAWEŁ BIERNAT*, KATARZYNA ZABŁOCKA-SŁOWIŃSKA**, BEATA BORAK***,
ANNA PRESHA**, HALINA GRAJETA**, JANUSZ PLUTA*
*
Katedra i Zakład Technologii Postaci Leku UM we Wrocławiu,
Katedra i Zakład Bromatologi i Dietetyki UM we Wrocławiu,
***
Institute of Materials Science and Applied Mechanics, Wrocław University of Technology,
**
IN VIVO STUDY OF SILICA PARTICLES ACCUMULATION IN THE RATS
Recently, nanotechnology has been rapidly coming out in biomedical applications,
such as drug or gene delivery carriers, cancer therapy and diagnosis of diseases. A significant
advances in drug-delivery systems have enabled more effective drug administration. A range
of organic systems, such as: micelles, liposomes, dendrimers and polymeric nanoparticles
have been designed to deliver drugs to specific organs. All mentioned organic systems suffer
from limitations, including poor thermal and chemical stability and rapid elimination by the
immune system. Inorganic materials, especially silica has a fundamental advantages over the
organic materials. Amorphous SiO2, in contrast to crystalline silica, offers a biocompatible,
stable and promising alternative. The advantages of silica lie also in well developed silane
chemistry and easy preparation. Bioactive molecules (drugs) can be adsorbed on the silica
surface and encapsulated within silica materials by the sol-gel method or emulsion chemistry.
Sol-gel method enables the production of various materials with homogeneous drug
distribution and permits ambient temperature processing, necessary for handling biologically
active molecules. The silica materials employed as a matrix are chemically inert towards the
encapsulated substances.
The aim of this study was to investigate the SiO2 elimination process from rats‟
organisms and to ascertain the distribution and prospective accumulation sites of the silica
particles. Silica particles with diameter size of 40-60 nm and about 150 nm have been
obtained by the sol-gel method. A suspension of silica particles in water solution was
introduced into rats‟ circulatory system through the vein in the rats‟ tails. Rat‟s urine, blood
and organs (heart, lungs, kidneys and liver) were analyzed after 14 days. The level of Si in
samples was measured using atomic absorption spectrometry (AAS, Perkin-Elmer 3110 AAS
spectrometer).
All experiments were approved by the First Local Ethical Committee for
Experiments on Animals at the Institute of Immunology and Experimental Therapy in
Wrocław, Poland.
Acknowledgment:
This work was partially supported by Institute of Materials Science and Applied Mechanics (no. S20256/I19).
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titanium dioxide, anatase, PLD,
porous structures
ANNA BIAŁOUS*, MARIA GAZDA**, PETER ATANASOV***,
NIKOLAY NEDYALKOV***, GERARD ŚLIWIŃSKI*
*
Photophysics Dept, The Szewalski Institute, Polish Academy Of Sciences,
Fiszera 14, 80-231 Gdańsk, Poland
**
Faculty of Applied Physics And Mathematics, Gdańsk University of Technology,
Narutowicza 11/12, 80-233 Gdańsk, Poland
***
Institute of Electronics, Bulgarian Academy of Sciences,
Tzarigradsko shousse 72, Sofia 1784, Bulgaria
CHARACTERIZATION OF TIO2 NANOSTRUCTURES
PREPARED BY PULSED LASER DEPOSITION
The career of titanium dioxide spans a broad range of applications from white
pigments known since ancient times [1] up to the nanostructured photoreactive materials [2,3]
recently. It is used for photocatalysis and environmental purification, light harvesting and
production of renevable energy. In particular, meso- and nanoporous titanium dioxide
structures of large active surface are subject of concentrated research.
We report on the structural and optical properties of TiO2 thin layers grown onto
glass substrates by pulsed laser deposition (PLD) using oxygen as reactive gas. Titania films
are grown from bulk Ti and also from pressed TiO2 (rutile) pellets. It is shown that by keeping
constant the substrate temperature at 300 °C during the deposition and by modifying only the
background gas pressure in the range up to 10 Pa, it is possible to grow so the pure anatase or
rutile thin layers, as well as films composed by a mixture of both polymorphs.
The effect of the buffer O2 pressure is concluded from X-ray diffraction (XRD)
patterns and Raman spectra. The structure inspection and morphology of the surface is
observed by means of the SEM, TEM and AFM techniques. The µ-Raman and XRD spectra
confirm consistently both the anatase and rutile crystalline phases and the dependence of the
phase content ratio on target material and deposition conditions. The crystallite size obtained
from XRD reflections varies in the range between (2 – 30) nm and (6 – 14) nm for anatase
and rutile, respectively. Values of the films thickness derived from transmittance
measurements are in the range of (0.3-1.5) µm and values of the energy band gap of (3.5 –
4.1) eV are blue shifted in comparison with these reported for undoped TiO2 (anatase).
References:
[1] Edwards H.G.M., Nik Hassan N.F., Middleton P.S., Anatase-a pigment in ancient artwork or a modern
usurper?, Anal Bioanal Chem 384 (2006) 1356–1365
[2] A. Białous, M. Gazda, G. Śliwiński, Structure and optical properties of TiO2 thin films prepared by pulsed
laser deposition, Proc. of SPIE 8770 (2013) 877008 (8 pp)
[3] F. Di Fonzo, C.S. Casari, V. Russo, M.F. Brunella, A. Li Bassi, C.E. Bottani, Hierarchically organized
nanostructured TiO2 for photocatalysis applications, Nanotechnology, 20 (2009) 015604 (7 pp)
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WOJCIECH CIESIELSKI*, OSKAR MICHALSKI**, DAMIAN KULAWIK*,
JÓZEF DRABOWICZ*, DOROTA KRASOWSKA*, JERZY PESZKE***
*
Jan Dlugosz University, Institute of Chemistry and Environment Protection,
al. Armii Krajowej 13/15, 42-200 Czestochowa, Poland,
**
University of Agriculture, Department of Chemistry and Physics,
ul. Balicka 122, 31-149 Kraków, Poland,
***
University of Silesia, Faculty of Mathematics, Physics and Chemistry,
ul. Uniwersytecka 4, 40-007 Katowice
CARBON NANOTUBES FUNCTIONALIZED BY SUBSTITUENTS
CONTAINING A STEREOGENIC HETEROATOM
This poster‟s goals will concentrate on developing experimental procedures leading to
the isolation of new groups of single-walled (SWCNT) or multi-walled(MWCNT) carbon
nanotubes functionalized with substituents containing a stereogenic heteroatom bonded
covalently to the surface of a carbon nanotube and “supramolecular” complexes of SWCNTs or
MWCNTs with heteroorganic derivatives containing simultaneously a stereogenic heteroatom.
These synthetic goals will be amended by structural studies and model experiments on the
application of the prepared nanotubes in the chemistry of “ new materials” and asymmetric
synthesis. Realization of this project will lead to an enlargement of libraries of nanotubes by a
group of derivatives in which the presence of a stereogenic heteratom allows the isolation of
functionalized derivatives as optically active species and induces physico-chemical properties
useful when one considers the application of the designed derivatives.
Thermal analysis of CNTs, halogenated CNTs and salt of thioacid/CNT system were
made. The thermal behavior of investigated systems indicates the formation of inclusion
complexes. The weight loss steps (TG) and thermal effects (DSC) were measured using DSC –
TG NETZSCH STA 409C apparatus. The thermal decomposition was studied over a
temperature range of 293 – 1173 K at a heating rate of 5K/min. All samples (about 20 mg) were
heated in corundum crucible covered with no hermetic lids. Weight loss steps (TG) and thermal
effects (DSC) were determined. Recorded thermograms were analysed with the NETZSCH–
TA–ANALYSIS and NETZSCH SEPARATION OF PEAKS programmes. Also elemental
analysis and scanning electron microscope (SEM) studies was performed.
As a starting material we used brominated and iodinated multiwall nanotubes [1]. The
reactions of the MWCNT-X (X=I, Br) with the chosen thioacid salt lead to nanotubes bearing
bulky chiral grups (scheme 1).
M
W
C
N
T
X
+
Na S P
O
methanol or
acetonitrile
M
W
C
N
T
S P
O
+
NaX
X=I, Br
[1] L. Stobiński, O. Michalski, P. Tomasik, A. Borodziński, P. Kędzierzawski, Patent 395834, Biuletyn Urzędu
Patentowego, 2013, 3, 13.
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foams, silicon carbide, SiC,
pyrolysis, polycarbosilane
CEZARY CZOSNEK, MARIUSZ DRYGAŚ, BARTŁOMIEJ SZMYD, JERZY F. JANIK
AGH University of Science and Technology, Faculty of Energy and Fuels
Al. Mickiewicza 30, 30-059 Kraków, Poland
C/SiC CARBON/SILICON CARBIDE FOAMS OBTAINED FROM
POLYCARBOSILANE BY A DIRECT SELF-BLOWING PROCESS
Macrocellular foams show, generally, very interesting properties such as low density,
low thermal conductivity, and high thermal shock resistance. In this regard, silicon carbide
foams are, additionally, highly chemically resistant; they also show high temperature strength
and high thermal conductivity. Therefore, they could be appropriate for hot gas filtration,
catalysts supports, metal-ceramic composites, and many other relevant applications.
Ceramic foams can be produced by saturation of preceramic polymers with, for
instance, CO2 and nucleating large number of bubbles due to the system‟s thermodynamic
instability followed by pyrolysis of such microcellular preceramics. Another way for
processing of microcellular foams could be realized by mixing a silicone resin with polymer
microbeads as sacrificial templates with subsequent pyrolysis of such a system, or by using
mixtures of preceramic polymers with various expandable microspheres.
In this work, composite carbon/silicon carbide foams were synthesized from a
system made of the mixtures of polycarbosilanes of different molecular weights using a direct
foaming phenomenon – a self-blowing process resulting from an on-going precursor pyrolysis
with evolution of volatiles. In such a mixture of polycarbosilanes, the ones with the lower
molecular weights play the role of a blowing agent. During the thermal decomposition, the
blowing agent produces large quantities of volatiles which take part in the formation of
macropores in the, initially, liquid high molecular weight polycarbosilanes of progressively
increased viscosity with temperature and time. The selected mixtures of the precursors were
pyrolyzed with heating rate of 7 C/min up to 1200 C under an argon atmosphere.
The black foamy products were examined using SEM, XRD, and FT-IR
spectroscopy. The results showed that the prevailing crystalline phase in the foams was the
cubic polytype of silicon carbide, β-SiC, accompanied by excess of some free carbon C,
supporting the feasibility of this simple one-step process to prepare the composite C/SiC
foams. A plausible removal of free C from the system by mild oxidation/combustion in air
can, in principle, lead to foams of pure silicon carbide SiC.
Acknowledgement
This work was supported by AGH University of Science and Technology Grant No. 11.11.210.213.
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titanium dioxide, anatase,
rutile, nanoparticles
PAULINA DOBROWOLSKA, MAGDALENA GAJDA-RĄCZKA, BARTOSZ
BARTOSEWICZ, MARTA MICHALSKA-DOMAŃSKA*, BARTŁOMIEJ J. JANKIEWICZ
Military University of Technology, Institute of Optoelectronics,
*
Military University of Technology, Faculty of Advanced Technologies and Chemistry,
Kaliskiego 2, 00-908 Warsaw, Poland
INFLUENCE OF ANNEALING TEMPERATURE AND DURATION ON TITANIUM
DIOXIDE NANOPARTICLES PHASE COMPOSITION
Nowadays, technology development is inherently bound up with the miniaturization
of functional structures finding their applications in science, industry and everyday life.
Potential application of the nanoparticles is mainly dependent on their physico-chemical
properties determined by their size and morphology, and, above all, the material from which
they are made. One of the simplest and most common form of nanostructures being fabricated
are colloidal particles made of different materials, including titanium dioxide. This material is
available in different crystalline forms, of which the most stable are rutile and anatase. Rutile
is the most thermodynamically stable crystalline form of titanium dioxide. Anatase is
a metastable form, which is formed at the lower temperatures than rutile. From the point of
view of applications, the most desirable form of TiO2 is anatase due to the best photocatalytic
properties.
In this work we present the results of studies on the influence of annealing time and
temperature on the composition of resulting crystalline forms of titanium dioxide. The
amorphous TiO2 particles were prepared by the sol-gel method [1]. The resulting particles
were heated in a muffle furnace [2]. The crystalline forms composition was characterized on
the basis of Raman spectra (Figure 1) and XRD. Particle morphology was determined by
means of scanning electron microscopy (SEM).
Figure 1. The Raman spectra of TiO2 nanoparticles annealed in
900°C in various periods of time
The financial support from the National Science Centre under Grant No. 2011/03/D/ST5/06038 is greatly
appreciated.
Literatura
[1] E. Mine, M. Hirose, D. Nagao, Y. Kobayashi, M. Konno, J. Colloid Interface Sci. 2005, 291, 162-168.
[2] D. Regonini, A. Jaroenworaluck, Surf. Interface Anal. 2010, 42, 139-144
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nanomaterials, nanopowders, gallium nitride GaN,
gallium phosphide GaP
MARIUSZ DRYGAŚ*, MIROSŁAW M. BUĆKO**, JERZY F. JANIK*
AGH University of Science and Technology, *Faculty of Energy and Fuels,
**
Faculty of Materilas Science and Caramics, Al. Mickiewicza 30, 30-059 Krakow, Poland
PRELIMINARY STUDIES ON THE CONVERSION OF MICROCRYSTALLINE
GALLIUM PHOSPHIDE GaP TO NANOCRYSTALLINE GALLIUM NITRIDE GaN
A multitude of unique physical and chemical properties of the gallium nitride GaN
semiconductor makes it a material of choice in modern electronics. The compound‟s broad
bandgap of ca. 3.4 eV is very well suited for various optoelectronic applications in the visible
blue to UV range. Its ability to form solid solutions with other nitrides such as InN and AlN
as well as to be doped with various elements expands its application potential through
controlled modifications of semiconducting, optical, and magnetic properties. Such
circumstances laid the ground for numerous studies on new preparation methods for GaN.
Among those, prevailing attempts have been focused on making nitride‟s thin films and
microcrystalline powders while, recently, methods for making bulk monocrystals have gained
a significant weight. In this regard, affordable preparation and controlled properties of
nanocrystalline powders of GaN still appear to pose a challenge.
The known mastered methods of GaN preparation, ususally, in microcrystalline or
monocrystalline forms include high temperature nitridation of metallic gallium or gallium
oxide with ammonia, the former one requiring, additionally, high pressures. More advanced
methods resort to gallium organometallic compounds and strict anaerobic reaction conditions
with an advantage of nanoparticle formation.
In this study, an attempt was made to utilize metathetical nitridation with ammonia
of affordable microcrystalline gallium phosphide GaP towards powders of GaN; the
nitridation was applied to ground platelets of monocrystalline GaP.
The ground GaP substrate was placed in an alumina tube reactor inserted into a tube
furnace. Temperatures in the range 600-1100 ºC, soaking times up to several dozen hours,
and an atmosphere of flowing ammonia were applied. The products included powder solids
with color ranging from dark beige (lower temperatures) to yellowish (higher temperatures).
They were characterized at this point with powder XRD and SEM/EDX microscopy.
The XRD results were helpful in determining optimum reaction temperatures and
times of the nitriding conversion. Below 800 ºC, no GaN formation was detected and the
cubic c-GaP persisted through even the longest heating times. The reactions at 800 ºC
resulted in small quantities of the hexagonal h-GaN. Experiments at 850 ºC yielded visibly
increased quantities of h-GaN that were proportional to a soaking time. The application of
temperatures in the range 900-1100 ºC caused complete nitridation towards GaN. In all cases,
the products included nanocrystalline hexagonal h-GaN with an average crystallite sizes from
a few (lowest temperatures) to several dozen nanometers (higher temperatures). The
morphology by SEM indicated agglomerated particles of irregular shapes that in products
from higher temperatures assumed a habit of regularly shaped larger crystallites.
Study was funded by AGH University of Science and Technology Grant No. 11.11.210.213.
- 101 -
nanocatalyst, reaction kinetics,
starch degradation
MARTA FALKOWSKA, EUGENIUSZ MOLGA*
*
Warsaw University of Technology
NANOSILVER: A CATALYST IN ENZYMATIC DEGRADATION OF STARCH
Nowadays, it is very crucial to implement rules of sustainable development and to
adopt 12 fundamental principles of green chemistry in every industrial process. Catalysis is
one of the concepts of green chemistry.
The development of catalysts that have high activity and selectivity, can be easily
removed from reaction medium and recycled, is desirable. These properties are likely to occur
with the usage of nano-sized catalysts, which bond advantages of homogeneous (high surface
area, easily accessible) and heterogeneous (stability, ease of separation and recovery) catalyst
systems with the limitation of their disadvantages. The activity and selectivity of
nanocatalysts can be obtained by tailoring their chemical and physical properties, such as
morphology, size, shape.
The aim of present work is to investigate the enzyme-catalysed starch degradation in
the presence of nanocatalyst (nanosilver) and to study its kinetics. An influence of soluble
starch concentration, nanocatalyst concentration and -amylase concentration, on rate of
reaction was studied.
Nanosilver of uniform size was prepared by the reduction of silver nitrate in the
presence of soluble starch. Soluble starch acted as a reducer and as a stabilizer. Synthesis of
stable silver nanoparticles was carried out in an autoclave at 103 kPa, 121 C for 5-10 min.
The average size of nanosilver was found to be 40 nm as analyzed using Nanoparticle
Tracking Analysis.
The soluble starch hydrolysis was carried out under isothermal conditions. Tests
were performed in tubes containing starch as a control and starch as a test. Equal amounts of
-amylase were addend to each tube. Tubes were incubated at room temperature for 30 min.
Samples were taken at regular intervals and Color Reagent Solution was added to assay the
reducing sugar concentration in colorimeter at 540nm, according to Miller method.
The rate of starch digestion in the presence of nanocatalyst was compared with the
rate of reaction without nanosilver. The rate of enzymatic degradation of starch was found to
be increased in the presence of silver nanoparticles. It is considered that -amylase was
immobilized onto the surface of nanoparticles.
Our future goal is to investigate the mechanism of soluble starch enzymatic
degradation with usage of nanosilver acting as a catalyst.
- 102 -
semiconductors, molybdenum disulfide,
Raman scattering, photoluminescence
KATARZYNA GOŁASA, MAGDALENA GRZESZCZYK, KRZYSZTOF KORONA,
RAFAŁ BOŻEK, ANDRZEJ WYSMOŁEK, ADAM BABIŃSKI
Faculty of Physics, University of Warsaw, Hoża 69, 00-681 Warsaw
OPTICAL PROPERTIES OF MOLYBDENUM DISULFIDE (MOS2)
Layered transition metal dichalcogenide materials MX2, which properties
dramatically change as a result of the 3D to 2D transition, have demonstrated the unique
physical and optical properties associated with theirs 2D atomic layer structure [1]. These
materials show a weak interlayer van der Waals bonding and strong intralayer ionic-covalent
bonding. Molybdenum disulfide (MoS2) is a typical representative of the TMDs family. In its
bulk form MoS2 is an indirect-gap semiconductor with a band gap of about 1.3 eV. A single
layer of this material, which consists of one hexagonal plane of Mo atoms sandwiched
between two atomic planes of S atoms, becomes a direct-gap semiconductors with a band gap
of 1.87 eV.
In this communication, we report our research on optical properties and morphology
of monolayer and bulk MoS2 crystals. The few-layer MoS2 samples were mounted on a
SiO2/Si substrate. Optical microscopy and atomic force microscopy (AFM) were applied to
study the optical properties and morphology of the samples. The number of layers in the
investigated MoS2 samples were determined from Raman scattering measurements. It is well
known that two Raman active modes (see Fig. 1a) near 400 cm-1 are sensitive to the MoS2
layer thickness [2]. This allows us to unambiguously identify 1ML material.
Photoluminescence (PL) spectra related to band-gap of bulk (>5ML) and a 1ML of
MoS2 are shown in Fig. 1b. It can be seen that the PL intensity from the bulk is significantly
weaker in comparison to the PL from the 1ML sample. The A and B transitions are related to
the spin-orbit splitting in the valence band maximum, peak C reflects the indirect band-gap
transition in bulk material.
We relate the low-energy tail of the interband transition (A) to the defects present in
the investigated material. In our presentation we will discuss the properties of the PL spectra
from the single- and multi-layer materials.
(a)
T=300 K
25.1 cm-1
PL intensity (arb. u.)
Intensity (arb. u.)
A 1ML
(b)
T=300 K
1 ML
bulk
-1
18.4 cm
10k
B
Bulk
C
1k
100
370
380
390
400
410
420
1.4
Raman shift (cm-1)
1.6
1.8
Energy (eV)
2.0
Figure 1. Raman active modes (a) and photoluminescence spectra (b) in bulk material and 1ML of MoS 2
References:
[1] A. Splendiani et al., Nano Lett. 10, 1271-1275 (2010).
[2] C. Lee et al., ACS Nano 4, 2695 (2010).
- 103 -
semi-regular nanostructures, dephasing time,
damping mechanisms
KATARZYNA GROCHOWSKA*, PETER ATANASOV**, NIKOLAY NEDYALKOV**,
GERARD ŚLIWIŃSKI*
*
The Szewalski Institute of Fluid-Flow Machinery, Photophysics Department,
Fiszera 14, 80-231 Gdańsk, Poland
**
Bulgarian Academy of Sciences, Institute of Electronics,
Tzarigradsko Shousse 72, Sofia 1784, Bulgaria
DAMPING OF THE PLASMON RESONANCE
IN SEMI-REGULAR Au NANOARRAYS
Excitation of the coherent oscillations of conduction band electrons in metal
nanoparticles known also as surface plasmon resonance (SPR) represents an intensively
studied subject due to potential applications in many areas of nanotechnology, such as surface
enhanced spectroscopies, light harvesting, photocatalysis, etc. Recently, growing interest is
observed in the SPR damping phenomena. It follows from literature that the SPR decay
mechanisms, described by the dephasing time (T2) or equivalently by components of the
decay rate of the SPR are not sufficiently understood and their descriptions seem not to be
clear enough. The different processes responsible for the decay are widely discussed and it is
believed that the main contributions are due to: radiative damping, surface scattering, Landau
damping, chemical interface damping (CID) and direct emission of electrons [1-3]. However,
the identification and separation of the various damping components represent a serious
problem. Another obstacle in determination of the decay processes of real nanostructures is
the size and shape distributions of nanoparticle arrays that cause an increase of the
inhomogeneous line broadening and make it difficult to obtain the precise value of T2.
Contrary to the case of single particles or regular particle pattern of strict geometry,
in this work the semi-regular particle arrays characterized by distributions of the size and
interparticle distances are investigated. Samples are produced from thin (10-60 nm) Au films
sputtered on SiO2 glass and annealed by pulsed laser radiation (6 ns, 266 nm, fluence: 60-300
mJ/cm2) [4]. The surface morphology of the sample is examined by the scanning electron
microscope and the characteristic distributions of mean values up to 120 nm are obtained. The
enhancement factor of the optical far field of the nanoarrays is obtained from the microRaman spectra recorded under excitation at 514 and 785 nm. The damping parameter A and
dephasing time for the Au/SiO2 samples are estimated from the absorbance spectra. The
nonradiative damping is deduced to be approximately constant for all structures as their
resonance energies lay below 2.3 eV. Therefore, the radiation damping is believed to be the
most dominant damping mechanism.
References:
[1] F. Hubenthal, Prog. Surf. Sci. (2007) 82:378
[2] T. Ziegler et al., Chem. Phys. Lett. (2004) 386:319
[3] K. Watanabe et al., Chem. Rev. (2006) 106, 4301-4320
[4] K. Grochowska et al., Plasmonics (2013) 8(1), 105-113
- 104 -
confocal microscopy,
molibdenum disulfide
MAGDALENA GRZESZCZYK, KATARZYNA GOŁASA, ADAM BABIŃSKI,
JACEK SZCZYTKO
University of Warsaw, Nanostructure Engineering, Faculty of Physics, Institute of
Experimental Physics, ul. Hoża 69, 00-681 Warsaw, Poland
CONFOCAL MICROSCOPE STUDIES OF MOLIBDENUM DISULFIDES
LAYER THICKNESS
Molybdenum disulfide (MoS2) is a typical representative of the layered transition
metal dichalcogenide materials MX2 family. A single layer of this material consists of one
hexagonal plane of Mo atoms sandwiched between two atomic planes of S atoms. It is a
direct-gap semiconductor with a band gap of 1.87 eV, while the bulk is an indirect-gap
semiconductor with a band gap of about 1.3 eV.
Due to weak interlayer van der Waals effect single layers of MoS2 can be obtained
by simple exfoliation technique. Small amount of MoS2 was taken from crystal using tape,
then by multiple tearing up the same space, varying thickness flakes were obtained. The fewlayer MoS2 samples were embedded on a SiO2/Si substrate and examined at room temperature
in confocal microscope.
Experimental setup allowed for observation of spatial resolution up to about 300 nm
by the 542 nm green laser light. The reflectivity of MoS2 flakes (figure below) was compared
with results of Raman spectroscopy, which was used for the designation of sample thickness.
The correlation between the number of monolayers and the intensity of reflected light can be
used for preliminary determination of the thickness of exfoliated flakes.
- 105 -
titanium dioxide nanocomposite,
magnetic resonance, photoactivity
NIKO GUSKOS*/**, ALEKSANDER GUSKOS**, SPIROS GLENIS*, GRZEGORZ
ŻOŁNIERKIEWICZ**, JANUSZ TYPEK**, PAWEŁ BERCZYŃSKI**, DIANA DOLAT***,
BARBARA GRZMIL***, BUNSHO OHTANI****, ANTONI W. MORAWSKI***
*
University of Athens, Faculty of Physics, Department of Solid State, Panepistimiopolis,
Zografou 15 784, Greece
**
West Pomeranian University of Technology, Department of Physics,
Al. Piastów 48, 70-311 Szczecin, Poland
***
West Pomeranian University of Technology, Institute of Chemical and Environment
Engineering, Al. Piastów 17, 70-310 Szczecin, Poland
****
Hokkaido University, Catalysis Research Center, Sapporo 001-0021 Japan
FMR AND PHOTOCATALYTIC INVESTIGATIONS OF nFe-TiO2
(n=1%, 5% AND 10%) COMPOUNDS
The nanocomposites of nFe/N-TiO2 (n=1%, 5% and 10%) have been prepared by
co-modification of a commercial amorphous titanium dioxide via impregnation with Fe(NO3)3
followed by calcination at 800°C in ammonia atmosphere. The essential increase in the visible
light photoactivity of the co-modified samples in comparison with the single-modified ones
was observed. A very good photocatalytic properties, especially for samples with n=5%, were
determined. The temperature dependence of ferromagnetic resonance/electron paramagnetic
resonance (FMR/EPR) spectra have been carried out. The FMR spectra of iron agglomerates
have dominated the observed spectra in the whole region of temperatures and their smallest
concentration was observed in sample with n=5%. Additionally, the EPR spectra of free
radicals and trivalent titanium ions were recorded at low temperatures. The greatest
concentrations of trivalent titanium ions was observed for sample n=5% and the lowest for
sample n=10%. It is proposed that in the case of sample with n = 5% the largest number of
iron ions is involved in processes causing the appearance of the largest numbers of trivalent
titanium ions.
- 106 -
thin films,
ferromagnetic resonance
NIKO GUSKOS*/**, GRZEGORZ ŻOŁNIERKIEWICZ**, PAWEŁ BERCZYŃSKI**,
JANUSZ TYPEK**, ALEKSANDER GUSKOS**, JOLANTA BARANOWSKA***,
SEBASTIAN FRYSKA***
*
University of Athens, Faculty of Physics, Department of Solid State, Panepistimiopolis,
15 784 Zografou Athens, Greece
**
West Pomeranian University of Technology, Institute of Physics,
Al. Piastów 48, 70-311 Szczecin, Poland
***
West Pomeranian University of Technology, Institute of Materials Science and
SPIN WAVES EXCITATIONS IN THIN FILM OF EXPANDED
AUSTENITE PHASE S(γN)
Four samples of expanded austenite phase S (γN) has been prepared as thin films on
silicon plates substrate. Coatings were deposited by reactive sputter deposition in different
temperatures and total gas pressure. They were strongly textured and the grains grown in
[100] directions perpendicular to samples surface. Grains in all coatings were nanomeric in
sizes as revealed by AFM study of surfaces. Very intense ferromagnetic resonance (FMR)
spectra were obtained for all samples. Strong angle dependence of the FMR spectra were
observed. A single strong asymmetric resonance line was recorded if the applied external
magnetic field was perpendicular to sample‟s surface. For different configurations of sample
in regard to the static magnetic field many resonance lines were registered. They could be
attributed to spin waves excitations in various grains formed during the preparation of
samples.The lines were shown very strong resonance field dependence on the angle with
external magnetic field. This phenomenon could be connected with the reorientation
processes of the spin system. It was observed that the resonance fields of the FMR lines due
to spin wave excitations strongly depended on the preparation conditions.
- 107 -
bismuth selenide, topological insulator,
density functional theory, ABINIT
MICHAŁ HERMANOWICZ*, MARIAN WOJCIECH RADNY*/**
*
Poznan University of Technology, Institute of Physics,
ul. Nieszawska 13A, 60-965 Poznan, Poland
**
The University of Newcastle, School of Mathematical and Physical Sciences,
Callaghan NSW 2308, Australia
SURFACE FUNCTIONALIZATION OF A TOPOLOGICAL INSULATOR
Any strong topological insulator (TI), such as bismuth selenide, is characterized by
its topologically protected electronic surface states (massless Dirac electrons) [1,2].
Therefore, the primary goal of any modifications of TIs‟ surfaces – to manufacture functional
TI-based nanostructures – is to control their unique electronic properties. Methods of
functionalization include adsorption of atoms and/or molecules as well as mechanical
deformations of the surfaces. In this submission, the effect of the adsorption of transition
metal elements on the atomic and the electronic structures of the (111) surface of bismuth
selenide is discussed. The results were obtained based on the first principles density
functional theory calculations [3,4,5].
This work was supported by the Polish Ministry of Science and Higher Education (N N202 195840) and partially
supported by the PL-Grid Infrastructure (Polish Infrastructure for Supporting Computational Science in the
European Research Space).
References:
[1] M.Z. Hasan, C.L. Kane, Rev. Mod. Phys. 82, 3045-3067 (2010).
[2] W. Zhang et al., New J. Phys. 12, 065013 (2010) .
[3] X. Gonze et al., Computer Phys. Commun. 180, 2582-2615 (2009).
[4] X. Gonze et al., Zeit. Kristallogr. 220, 558-562 (2005).
[5] The ABINIT code is a common project of the Université Catholique de Louvain, Corning Incorporated, and
other contributors (URL http://www.abinit.org).
- 108 -
izolator topologiczny, Bi2Se3,
selenek bizmutu domieszka Ca, Bi2Se3:Ca)
ANDRZEJ HRUBAN, ANDRZEJ MATERNA, STANISŁAWA STRZELECKA,
MIROSŁAW PIERSA, ELŻBIETA JURKIEWICZ-WEGNER, WACŁAW ORŁOWSKI,
WOJCIECH DALECKI, MAGDALENA ROMANIEC, RYSZARD DIDUSZKO
Instytut Technologii Materiałów Elektronicznych, Wólczyńska 133, 01-919 Warszawa
IZOLATORY TOPOLOGICZNE - MATERIAŁY DLA PRZYSZŁOŚCI
Przedmiotem intensywnych badań i teoretycznych rozważań w ostatnich kilku latach
(2007 – 2013 r.), są materiały wykazujące efekt izolatora topologicznego. Zgodnie z
różnicami w strukturze stanów elektronowych tradycyjne materiały podzielone są na dwie
grupy: metale i izolatory. Trójwymiarowy izolator topologiczny (TI – 3D) jest nowym
stanem materii kwantowej różnym w stosunku do pozostałych metali albo izolatorów w
takim sensie, że jego powierzchnia jest metaliczna natomiast jego objętość jest izolacyjna, (z
objętościową przerwą energetyczną). Najbardziej interesującą grupą materiałów
wykazujących ten efekt są znane dotychczas jako materiały termoelektryczne związki
bizmutu o symbolu Bi2X3 (X = Se, Te,) oraz Sb2Te3.
Cechą charakterystyczną tych materiałów jest budowa
warstwowa sieci
krystalicznej. Każda warstwa składa się z 5-ciu warstw atomowych obsadzonych na przemian
atomami jednego pierwiastka związku w sekwencji (dla Bi2Se3): Se1-Bi-Se2-Bi-Se1. Ten
układ warstw atomowych nazywany jest kwintetem, którego grubość wynosi ~1nm, a
wielkość przerwy energetycznej dla Bi2Se3 wynosi Eg ~ 0,3 eV. Izolatory topologiczne są
bardzo atrakcyjne z powodu teoretycznie przewidzianych, egzotycznych własności
fizycznych i możliwości zastosowań w spintronice i komputerach kwantowych.
W 2011 r. w ITME, rozpoczęliśmy prace nad otrzymywaniem związków bizmutu:
Bi2Se3, Bi2Te3, i Bi2Te2Se o składzie stechiometrycznym. Niedomieszkowane kryształy
Bi2Se3 otrzymane z fazy ciekłej o składzie stechiometrycznym posiadają koncentrację
nośników w typie „n”= 2† 4 x 1019 cm-3, ponieważ ich przewodnictwo elektryczne,
zdefiniowane jest przez gęstość defektów sieci typu donorowych wakansów selenowych (VSe), które stanowią defekty elektrycznie czynne, lecz w tej „ zmetalizowanej postaci” - nie
spełniają kryterium izolatora topologicznego.
Zbadaliśmy możliwość uzyskania kryształów selenku bizmutu w typie
przewodnictwa „p” o koncentracji nośników p= 2†6 x 1018 cm-3 przez domieszkowanie
wapniem (Ca - o stężeniu poniżej 1% wagowego), materiału nadstechiometrycznego (przy
nadmiarze Se w stosunku do stechiometrii). w/g. danych literaturowych [1] najlepszego
materiału dla uzyskania właściwości izolatora topologicznego. Otrzymaliśmy Bi2Se3 typu „p”
wskazujący na własności izolacyjne w objętości materiału [ρ = f(T)]. Uzyskany materiał
nadstechiometryczny w typie „n” posiadał o ok. 1,5 rzędu niższą koncentrację nośników w
zakresie n = 5 † 40 x 1017 cm.-3.Otrzymano go poprzez obniżenie koncentracji donorów
(VSe). Istnieją informacje w literaturze, że również w materiale w typie „n” o tak niskiej
koncentracji nośników, otrzymywano efekt takiego izolatora. Prowadzimy badania nad
wykorzystaniem innych domieszek: Cu – dla otrzymania materiału nadprzewodzącego i Mn –
- 109 -
domieszki magnetycznej. Własności wytwarzanych kryształów oceniane były przy
zastosowaniu następujących metod:
- pomiary rezystywności i parametrów Hall‟a w 300 K i w funkcji temperatury,
- rentgenowska analiza fazowa do oceny składu,
- EDX do oceny zawartości poszczególnych pierwiastków,
- AFM i mikroskop skaningowy do oceny grubości płytek i warstw kwintetowych oraz
badań powierzchni. Wykonano również badanie metodą ARPES.
Literatura:
[1] Y.S. Hor, A. Richardella, M.Z. Hasan, at al: Physical Review B 79, 195208, (2009)
- 110 -
DDS (Drug Delivery Systems), CNT (Carbon nanotubes),
CR (Congo red), Dox (Doxorubicin), EB (Evans blue)
ANNA JAGUSIAK*, BARBARA PIEKARSKA*, TOMASZ PANCZYK**,
PIOTR LAIDLER*
*
Chair of Medical Biochemistry, Jagiellonian University Medical College, Cracow, Poland
Institute of Catalysis and Surface Chemistry, Polish Academy of Science, Cracow, Poland
**
COMPLEXES OF CARBON NANOTUBES AND SELF-ASSEMBLING
MOLECULES OF THE CONGO RED TYPE AS POTENTIAL DRUG DELIVERY
SYSTEMS - PRELIMINARY REPORT
The rapid development of the research on drug carriers, observed in recent years, is
related to the huge benefits that their use brings to the medicine. A major problem is the lack
of specificity in the delivery of drugs into cells and damage of healthy tissues. The adverse
effects are particularly considerable in anticancer therapy. Finding a therapeutically effective
carrier that could help to provide the drug directly to the site of inflammation or tumor
without damaging the healthy tissue, is a goal for many research teams. The carrier should
show the high drug-loading capacity and low toxicity, ensure the effective transport of the
carried drugs across cell membranes and be easily removed from the body. The model drug
used in this study is doxorubicin (Dox) - the commonly used chemotherapeutic agent.
Because of its serious side effects many different carrier systems for this drug are under
investigation. Carbon nanotubes (CNT) are studied as potential transporters of drugs absorbed
to their surface. The supramolecular ribbon-like assemblies created by the dyes of the Congo
red (CR) type can incorporate certain drugs (especially polycyclic, planar molecules like Dox)
and thus can also be considered as potential drug carriers. The combination of both systems
appears to be a promising solution. The aim of the study is to determine whether it is possible
to use Congo red-functionalized carbon nanotubes for drug delivery into cells, and whether
CR improves drug-loading properties of CNT.
The method of solubilization of CNT based on the exchange of the preliminary
solubilizer - sodium cholate - to CR was developed. AFM and TEM analysis of the CNT- CR
complexes showed the increase in the diameter of the CNT, as compared to the control
sample, suggesting that the dye binds the nanotube in its supramolecular form. Interactions of
CNT with structural analogs of CR, differing in their self-association tendency were also
investigated, showing that only supramolecular dyes can stabilize the solubilized form of
CNT. CNT covered with the mixed supramolecular system composed of CR and EB (Evans
blue) showed the increased rigidity - straight and shortened (broken) CNT-CR-EB complexes
were observed in TEM. This may be of practical importance, since shorter nanotubes can
better permeate the membranes and are more easily excreted. The quantitative analysis of the
amount of CR complexed to CNT was performed. The method of CNT-CR-Dox complexes
formation was developed and the release of Dox from these complexes was studied in
different pH conditions. The highest rate of the Dox release was observed in acidic solutions.
This is advantageous since the pH of the endosomes is low.
Preliminary studies concerning the cytotoxicity of the above described system were
performed using the human glioblastoma U87MG cell line (doxorubicin sensitive). The
addition of the CNT-CR-Dox led to the inhibition of cell proliferation, while cells treated with
carriers free of Dox (CR, CNT-CR) showed the proliferation at the level of the control cells.
Acknowledgements
Anna Jagusiak acknowledges the financial support from the project Interdisciplinary PhD Studies "Molecular
sciences for medicine" (co-financed by the European Social Fund within the Human Capital Operational
Programme)
- 111 -
nanoparticles, in vivo, dextran,
doxorubicin, drug delivery
MAGDALENA JANCZEWSKA*, JERZY PIECZYKOLAN**, IGA WASIAK*,
TOMASZ CIACH*
*
Warsaw University of Technology, Faculty of Chemical and Process Engineering,
Laboratory of Biomedical Engineering
**
Adamed Sp. z o. o., Pieńków 149, 05-152 Czosnów
IN VIVO STUDIES OF EFFICIENCY OF DEXTRAN-DOXORUBICIN
NANOPARTICLES AGAINST HUMAN UTERINE SARCOMA
Modern nanomedicine still seeks for a new efficient particle suitable for targeted
chemotherapy. Closure of anti-cancer drug inside a fully biodegradable particle and delivery
of the system directly to the cancerous cells provides effective and safe for the patient
therapy. Thus, it is crucial for a nanoparticle to be accurate and consistent with human body
environment. Following this approach we developed a nanoparticle from natural
polysaccharide – dextran, which is particularly attractive material for biomedical engineering
due to its biocompatibility and low toxicity. Moreover, thanks to its chemical structure
dextran is easy to modify even in water solutions and considering intravascular administration
of nanoparticles, using dextran is completely safe as it is currently used for blood substitution.
Nanoparticles are prepared in aqueous solution of oxidized dextran, doxorubicin and
dodecyloamine hydrochloride. The chemical modification of dextran chain is observed and
hydrophilic – hydrophobic effects organize dextran molecule into nanoparticle. The major
advantage of this method is complete lack of usage of organic solvents that could induce
immunological response after administration of nanoparticles and their fast clearance by
defense system. Obtained nanoparticles were purified by dialysis against pure water and the
diameter was determined by Nanoparticle Tracking Analysis (NTA) using NanoSight.
Measured parameter‟s value was about 70 nm which is perfect size for potential nanoparticle
drug carrier.
In order to examine the influence of dextran-doxorubicin NPs on cancer cells and
their biodistribution in organism, we conducted in vivo studies against MES-SA/Dx5 human
multidrug resistant uterine sarcoma implanted tumors. The impact of free doxorubicin and
nanoparticles dextran – doxorubicin conjugates was simultaneously examined. Moreover,
targeted therapy was carried out in three dosage strategies to distinguish the most efficient
therapy regime. Free doxorubicin in comparison to nanoparticle drug carrier administrated in
the same dosage system induced massive cachexia, dramatic body mass loss, whereas NPs
therapy didn‟t cause any toxicity. What is more, targeted therapy showed increase of Tumor
Growth Inhibition (TGI) and after 19 days from first application reached nearly 30%. Autopsy
showed that liver, kidney and spleen masses of group treated with NPs were comparable to
masses of organs in control group. The therapeutic effect could be grater if doxorubicin were
firmly attached to dextran molecule and could not be removed by membrane pumps before
bounding to DNA and leading to cell apoptosis.
- 112 -
pylistość, nanomateriały,
nanoobiekty
ELŻBIETA JANKOWSKA*, PIOTR SOBIECH*, OLIVIER WITSCHGER**,
SEBASTIAN BAU**, BERNARD BIANCHI**
*
Centralny Instytut Ochrony Pracy - Państwowy Instytut Badawczy (CIOP-PIB)
ul. Czerniakowska 14, 00-701 Warszawa
**
Institut National de Recherche et de Sécurité (INRS), F-54519, Vandoeuvre, France
BADANIE PYLISTOŚCI NANOMATERIAŁÓW
Wiedza na temat skłonności do uwalniania się nanoobiektów z nanomateriałów do
otaczającego powietrza jest istotna z uwagi na projektowanie i stosowanie wielu procesów
przemysłowych oraz określanie wpływu uwalniających się nanoobiektów na zdrowie ludzi i
środowisko naturalne. W opracowanym w 2012 roku dokumencie ISO/TS 12025 [1] zostały
przedstawione jedynie ogólne wytyczne dotyczące metod badania pylistości nanomateriałów.
Aktualnie w INRS, HSL, IGF, NRCWE i CIOP-PIB są prowadzone prace badawcze, których
celem jest opracowanie standardów (EN) badań pylistości z wykorzystaniem różnych
sposobów generowania nanomateriałów: metodą obrotowego bębna (RD), ciągłego opadania
materiału (CD), małego obrotowego bębna (SRD) i metodą wstrząsania (VS). Badanie
pylistości nanomateriałów metodą wstrząsania jest prowadzone w INRS i w CIOP-PIB.
Zbudowano dwie opcje stanowiska do badania frakcji respirabilnej uwalniających się
nanoobiektów (rysunek 1), co umożliwia wykonywanie badań: a) w czasie rzeczywistym z
zastosowaniem ELPI (Electrical Low Pressure Impactor), CPC (Condensation Particle
Counter) i z możliwością pobierania próbek do analizy mikroskopowej, b) metodą
grawimetryczną z zastosowaniem filtru pomiarowego.
a)
b)
Rysunek 1. Ogólne schematy stanowisk do badania pylistości nanomateriałów metodą wstrząsania
Publikacja przygotowana na podstawie prac wykonanych w ramach zadania nr 04.A.18 programu wieloletniego
"Poprawa bezpieczeństwa i warunków pracy" – II etap, w zakresie służb państwowych finansowanego przez
Ministerstwo Pracy i Polityki Społecznej. Koordynator programu: CIOP–PIB.
[1] ISO/TS 12025:2012 Nanomaterials - Quantification of nano-object release from powders by generation of
aerosols.
- 113 -
nanorurki haloizytu, mieszanie,
potencjalne narażenie
ELŻBIETA JANKOWSKA, WOJCIECH ZATORSKI, JOANNA ŁUKASZEWSKA
Centralny Instytut Ochrony Pracy - Państwowy Instytut Badawczy (CIOP-PIB)
ul. Czerniakowska 14, 00-701 Warszawa
POTENCJALNE NARAŻENIE NA NANORURKI PODCZAS MIESZANIA
NANOPROSZKU HALOIZYTU
Mieszanie nanoproszków przed ich wprowadzeniem do ciekłej matrycy polimerowej
w celu homogenizacji jest jedną z najbardziej pyłotwórczych operacji w procesie
otrzymywania pianek poliuretanowych. Celem badań było określenie potencjalnego narażenia
podczas mieszania nanoproszku haloizytu, w kontekście podejścia do oceny ryzyka
zawodowego zaproponowanego przez instytuty niemieckie [1]. Określenie potencjalnego
narażenia na nanorurki przeprowadzono w wyniku analizy parametrów cząstek, określonych
w szerokim zakresie wymiarowym (6nm-10μm), czyli cząstek, które są z reguły wdychane
przez człowieka w postaci cząstek pojedynczych oraz ich agregatów lub aglomeratów. Jako
parametry charakteryzujące emisję przyjęto: 1) stężenie liczbowe cząstek 6nm-10 m (P-Trak,
SMPS i ELPI+), 2) rozkład wymiarowy cząstek 15-661nm (SMPS), 3) stężenie
powierzchniowe cząstek 10-1000nm (Aero-Trak). Stwierdzono, że w wyniku operacji
mieszania wiertarką o obrotach 2000/min przez 20s próbki nanoproszku ok. 20g emisja
cząstek do powietrza, w porównaniu do "tła", wzrosła znacznie. Stężenie powierzchniowe
cząstek 10-1000nm (Aero-Trak) wzrosło 2-krotne, stężenie liczbowe cząstek 20-1000 nm (PTrak) 3-krotnie, natomiast stężenie liczbowe cząstek 6nm-10 m (ELPI+) 4-krotnie. Badania
rozkładu wymiarowego (SMPS - rysunek 1) potwierdziły wzrost stężeń cząstek o mniejszych
wymiarach podczas mieszania nanoproszku. W wyniku analizy zdjęć mikroskopowych oraz
jakościowego składu chemicznego określonego z zastosowaniem mikroskopu elektronowego
SEM z detektorem EDS potwierdzono obecność nanorurek haloizytu w powietrzu na
stanowisku pracy.
a)
b)
Rysunek 1. Rozkłady wymiarowe cząstek 15-661nm (SMPS): a) "tło", b) podczas mieszania nanoproszku
haloizytu.
Publikacja przygotowana na podstawie badań wykonanych w ramach projektu nr I.B.03 programu wieloletniego
Poprawa bezpieczeństwa i warunków pracy (II etap), finansowanego przez Ministerstwo Nauki i Szkolnictwa
Wyższego. Koordynator programu: CIOP–PIB.
[1] Tiered approach to an exposure measurement and assessment of nanoscale aerosols released from
engineered nanomaterials in workplace operations (2011), https://www.vci.de/Downloads/Tiered-Approach.pdf.
- 114 -
silver nanoparticles, sol-gel method,
submicron silica spheres
MAREK JASIORSKI, AGNIESZKA BASZCZUK, KATARZYNA ŁUSZCZYK
AMINE-FUNCTIONALIZED SIO2 SPHERES AS A CONVENIENT MATRIXES FOR
SILVER NANOPARTICLES DECORATION
Herein, we report a facile one-step synthesis method to obtain uniform aminefunctionalized silica spheres. We demonstrate that as-prepared SiO2 monodisperse spheres can
be easily use for Ag+ ions attachment. Silver ions located on the surface of modified silica can
be subsequently reduced to metallic silver by direct thermal reduction. Formation of the
metallic silver during the sintering at relatively low temperature (300ºC) is a result of electron
attachment to Ag+ ions from the organic substances of the sol-gel SiO2 matrixes. The prepared
silver nanoparticles are uniform and spherical with an average particles size less than 5 nm.
The synthesis method reported in this work is safe, simple as well as economical and can be
used for a large-scale production of inexpensive SiO2/Ag composite nanoparticles.
Acknowledgment
This work was financially supported by Institute of Materials Science and Applied Mechanics (no. S20256/I19)
- 115 -
C-Pd films, hydrogen sensor,
XRD, resistance changes
ANNA KAMIŃSKA*, RYSZARD DIDUSZKO*, SŁAWOMIR KRAWCZYK*,
ELŻBIETA CZERWOSZ*, KAMIL SOBCZAK**
*
Tele and Radio Research Institute, Ratuszowa 11, 03-450 Warsaw, Poland
Institute of Physics, PAS, Al. Lotników 32/46, 02-668 Warsaw, Poland
**
NANOSTRUCTURAL C-Pd FILMS FOR HYDROGEN SENSING – INTERACTION
WITH HYDROGEN
Nanostructural carbonaceous palladium films (C-Pd films) prepared by physical
vapor deposition (PVD) method and annealed in argon atmosphere at the temperature of
500°C interact with hydrogen and change their resistance with changing hydrogen
concentration. This behavior is connected to the adsorption and dissolution of hydrogen in
palladium nanograins. In this presentation we show dynamical changes of C-Pd films
structure due to hydrogen concentration changes.
The structure of prepared C-Pd films was studied by transmission electron
microscopy (TEM) and X-ray diffraction (XRD) methods. TEM results show us the size and
distribution of palladium nanograins within the film. XRD experiment was performed in a
flow of hydrogen through especially designed experimental cell and it shows the changes in
the film structure.
Resistance changes due to hydrogen concentration changes for C-Pd films were also
measured. The results of these measurements are shown in Fig. 1. These results are consistent
with XRD results and can be interpreted as an effect of formation of solid solution of
hydrogen in palladium at lower H2 concentration and creation of palladium hydride at higher
H2 concentration.
20
R/R0, %
15
Fig. 1. Sensitivity of C-Pd film in the function of
hydrogen concentration
10
5
0
1
2
3
[H2], %
4
This project is co-financed by the European Regional Development Fund within the Innovative Economy
Operational Programme 2007-2013 No. UDA-POIG.01.03.01-14-071/08-08.
- 116 -
tlenek itru, synteza solwotermalna mikrofalowa,
luminofory, pierwiastki ziem rzadkich, spektroskopia
JAROSŁAW KASZEWSKI*, SERGIY YATSUNENKO*, RAFAŁ WRÓBEL**,
IWONA PEŁECH**, ANNA JĘDRZEJEWSKA**, EWELINA KUSIAK-NEJMAN**,
KAROLINA WENELSKA**, EWA MIJOWSKA**, ANTONI W. MORAWSKI **,
URSZULA NARKIEWICZ**, MAREK GODLEWSKI*
*
Instytut Fizyki PAN, al. Lotników 32/46, 02-668 Warszawa
Instytut Technologii Chemicznej Nieorganicznej i Inżynierii Środowiska,
Zachodniopomorski Uniwersytet Technologiczny w Szczecinie, ul. Pułaskiego 10, 70-322
Szczecin
**
DWUETAPOWA KRYSTALIZACJA TLENKU ITRU (Y2O3)
Z UŻYCIEM AZOTANU(V) ITRU
Tlenek itru jest materiałem o dużym znaczeniu technologicznym, a stosowany jest
głównie w ceramice, optyce, magnesach, katalizatorach, laserach, technice podczerwieni [1].
Znalazł również zastosowanie jako host lattice dla jonów emitujących luminescencję: Eu, Tb,
Dy [2]. Zastosowanie matryc Y2O3 doprowadziło do uzyskania wydajnych luminoforów.
Najintensywniej badanym jest Y2O3:Eu - tradycyjnie stosowany w telewizji kineskopowej [3].
Przyjmowano różne strategie, aby poprawić właściwości emisyjne materiałów bazujących na
tlenku itru m.in. krystalizacja tlenkowych nanorurek oraz tworzenie struktur core-shell. Cel
ten uzyskiwano poprzez krystalizację materiału w różnych warunkach [4]. W niniejszej pracy
otrzymano tlenek itru dwuetapowo, z wykorzystaniem etapu solwotermalnego
mikrofalowego.
W pierwszym etapie strącono z roztworu wodnego azotanu(V) itru osad, który
następnie wypłukano i poddano procesowi solwotermalnemu mikrofalowemu. Strącenia
dokonano za pomocą wody amoniakalnej. Proces przeprowadzono pod ciśnieniem 6 MPa.
Uzyskany prekursor wysuszono i utarto w moździerzu w celu uzyskania jednorodnego
proszku. Drugim etapem było wygrzewanie w atmosferze powietrza. Materiał wstępny
poddano kalcynacji w różnych temperaturach i poddano analizom strukturalnym (XRD,
TEM) oraz spektroskopowym (FTIRS, spektroskopia Ramana, spektroskopia UV/Vis).
Dokonano także analizy termograwimetrycznej materiału.
Uzyskany w procesie solwotermalnym mikrofalowym prekursor jest mieszaniną faz
wodorotlenku itru: Y(OH)3 oraz YO(OH). Gdy materiał poddano wygrzewaniu nastąpiły
fundamentalne zmiany w jego strukturze. Do temperatury 400˚C istniał przejściowy produkt,
o strukturze cechującej się wysoką symetrią, a wygrzewanie w temperaturze 600˚C i wyższej
skutkowało w uzyskaniu fazy regularnego Y2O3. Także w tym zakresie temperatur
następował tylko wzrost krystalitów tlenku itru ze wzrostem temperatury kalcynacji. Analiza
termiczna wykazała dwa znaczące etapy krystalizacji produktu, w których prekursor tracił
dużą część swojej masy, a kończące się w temperaturach 377 oraz 493˚C. Ogólny ubytek
masy wynosił 25%, a zmiany masy zakończyły się w temperaturze ok. 800˚C. Termiczna
analiza różnicowa wskazała, że obu etapom utraty masy towarzyszył silny endotermiczny
efekt. Materiał krystalizuje w postaci igieł (rys. 1) oraz w postaci pakietów igieł o długościach
rzędu mikrometrów i szerokościach rzędu dziesiątek nanometrów. Analiza HRTEM
- 117 -
wykazała, że poszczególne igły stanowią aglomeraty nanocząstek o kształcie zbliżonym do
owalnego.
Rys. 1. Obraz TEM materiału uzyskanego w temperaturze 400˚C
Widma absorpcji w ultrafiolecie i świetle widzialnym ukazują skomplikowaną
strukturę elektronową prekursora. We wszystkich przypadkach absorpcja jest rzędu kilku
procent przez cały zakres widzialny, aż do 350 nm, lub w przypadku materiału wygrzewanego
w najwyższych temperaturach nawet do 250 nm. Potem następuje nagły wzrost absorpcji do
ok. 95%, co świadczy o prostej przerwie energetycznej materiału.
Literatura
[1] S. Zhong, J. Chen, S. Wang, Q. Liu, Y. Wang, S. Wang, J. Alloys Compd. 493 (2010) 322-325
[2] A.P. de Moura, L.H. de Oliveira, E.C. Paris, M. S. Li, J. Andrés, J.A. Varela, E. Longo, I.L. Viana Rosa,
J. Fluorescence 21 (2011) 1431-1438
[3] X. Bai, H. Song, G. Pan, Z. Liu, S. Lu, W. Di, X. Ren, Y. Lei, Q. Dai, L. Fan, Appl. Phys. Lett. 88 (2006)
143104
[4] Y. Zhang, J. Guo, T. White, T. Thatt, Y. Tan, R. Xu, J. Phys. Chem. C 111 (2007) 7893-7897
- 118 -
ditlenek cyrkonu, synteza hydrotermalna mikrofalowa,
powierzchnia, spektroskopia fotoelektronów, luminofory
JAROSŁAW KASZEWSKI*, SERGIY YATSUNENKO*, RAFAŁ WRÓBEL**,
PAWEŁ ŁUKASZCZUK**, KAROLINA WENELSKA**, EWELINA KUSIAK-NEJMAN**,
DARIUSZ MOSZYŃSKI**, EWA MIJOWSKA**, WALDEMAR A. MORAWSKI**,
URSZULA NARKIEWICZ**, MAREK GODLEWSKI*
*
Instytut Fizyki PAN, al. Lotników 32/46, 02-668 Warszawa
Zachodniopomorski Uniwersytet Technologiczny w Szczecinie, Instytut Technologii
Chemicznej Nieorganicznej i Inżynierii Środowiska, ul. Pułaskiego 10, 70-322 Szczecin
**
STUDIA NAD POWIERZCHNIĄ DITLENKU CYRKONU (ZrO2) OTRZYMANEGO
METODĄ HYDROTERMALNĄ MIKROFALOWĄ
Nanoproszki ditlenku cyrkonu otrzymano metodą hydrotermalną mikrofalową. Do
roztworu powstałego przez rozpuszczenie ok. 13 g azotanu (V) cyrkonylu w wodzie
destylowanej wprowadzano wodę amoniakalną do pH=10. Powstały osad koloru białego
odsączono od roztworu macierzystego pod zmniejszonym ciśnieniem i płukano wodą
destylowaną. Mokry osad wprowadzono do reaktora hydrotermalnego mikrofalowego i
prowadzono proces pod ciśnieniem 5,5 MPa przez 20 minut. Po ostudzeniu zlewano
mieszaninę reakcyjną znad osadu, a sam osad suszono. Suchy materiał był wygrzewany w
temperaturach 400, 800 oraz 1200˚C w atmosferze powietrza. Uzyskane proszki poddano
analizie XRD, spektroskopii XPS, spektroskopii FTIR, spektroskopii UV/Vis oraz
spektroskopii ramanowskiej.
Metoda rozpraszania ramanowskiego ukazała generalną zgodność składu fazowego
materiału z wynikami uzyskanymi metodą XRD. Preparaty nie poddane wygrzewaniu oraz
wygrzane w 400 i 800˚C stanowią mieszaninę faz jednoskośnej oraz tetragonalnej ditlenku
cyrkonu, natomiast preparat wygrzany w 1200˚C - czystą fazę jednoskośną. Ewolucja
strukturalna materiału przejawia się także w zmianach intensywności i poszerzeń linii
ramanowskich. Ze wzrostem temperatury wygrzewania wzrasta intensywność linii
ramanowskich odpowiedzialnych za poszczególne fazy, co świadczy o wzroście udziału fazy
o uporządkowaniu dalekiego zasięgu w materiale. Spektroskopia UV Vis ukazała
charakterystyczne dla faz jednoskośnej i tetragonalnej pasma absorpcji w zakresie UV. Pasma
charakterystyczne występują we wszystkich preparatach oprócz wygrzanego w 1200˚C, tam
występuje tylko maksimum absorpcji przy 235 nm charakterystyczne dla fazy jednoskośnej
ZrO2. Informację w zakresie ultrafioletu można traktować jako powierzchniową, wyniki
wskazują, że powierzchnia materiału jest jednolita fazowo. Spektroskopia fotoelektronów
ukazała relacje form powierzchniowych dla proszków wygrzewanych w różnych
temperaturach. Porównano te relacje z materiałem otrzymanym metodą kalcynacji i
sporządzono zależności ilościowe, aby dyskutować odstępstwa ZrO2 od stechiometrii
w każdej temperaturze. Spektroskopia w podczerwieni ukazała ewolucję powierzchniowych
struktur wodnych i wodorotlenkowych wykazujących drgania rozciągające, zginające i grupy
wodorotlenkowe nie oddziałujące na siebie wzajemnie. Analiza porównawcza z materiałem
otrzymanym metodą kalcynacji ukazała charakterystyczne wibracje grup funkcyjnych
występujące w badanych preparatach.
- 119 -
plant biomass, nanofibres,
flax, hemp
JANUSZ KAZIMIERCZAK*, ARKADIUSZ BLODA*, EWA KOPANIA*,
JUSTYNA WIETECHA*, DANUTA CIECHANSKA*, TADEUSZ ANTCZAK**
*
Institute of Biopolymers and Chemical Fibres, Lodz, Poland,
Faculty of Biotechnology and Food Sciences, Technical University of Lodz, Poland
**
EXTRACTION OF MICRO- AND NANOFIBRES FROM PLANT BIOMASS USING
BIOTECHNOLOGICAL METHODS
Plant biomass is commonly considered as an immense and renewable source of
various biopolymers such as cellulose, hemicelluloses, lignins and pectins. Among them,
cellulose is the most known raw material and cellulose fibres are characterized by a wide
range of useful properties including relatively high strength, high stiffness, low density and
biodegradability.
In this research several types of plant biomass i.e. straws of hemp, flax-fibre variety
and flax-oilseed variety were selected as starting materials. The straws were subjected to a
preliminary thermal, mechanical and chemical treatments in order to liberate cellulose fibres
from non-cellulose matrix composed of lignins, hemicelluloses and pectins. As a result of
biomass purification process, cellulose pulp in the form of fibres with high alpha-cellulose
content and only slight amount of lignin was obtained. Next, biotechnological methods were
applied using commercial cellulases or cellulolytic multi-enzyme preparation from
Aspergillus niger developed at Technical University of Lodz in order to facilitate further
fibrillation of cellulose fibres to micro- and nanofibres during high shear mechanical
treatment. After the process morphological changes in the cellulose structure were examined
by scanning electron microscope and alpha-cellulose and lignin content (Kappa number) was
determined. After subsequent enzymatic and mechanical treatment of cellulose fibres from
flax and hemp straws appearance of cellulose nanofibers with diameters ranging from tens to
several hundred nanometers was observed in the SEM images.
The research project has been supported by the European Union European Regional Development Fund,
Contract No. POIG.01.01.02-10-123/09-00.
- 120 -
Raman, graphene,
overtone
PIOTR KAŹMIERCZAK*/**, ANNA PIOTROWSKA**, ELIANA KAMIŃSKA**,
ANDRZEJ WYSMOŁEK*
*
Faculty of Physics, University of Warsaw, Hoża 69, Warsaw, Poland
Institute of Electron Technology, Al. Lotników 32/46, Warsaw, Poland
**
SECOND ORDER RAMAN MODES OBSERVED IN FEW-LAYER GRAPHENE
FORMED ON NICKEL ON SIC
Due to large variety of future applications graphene and graphene-based materials
are intensively studied both theoretically and experimentally. Raman Spectroscopy is one of
the most widely used methods to investigate graphene. It allows to evaluate strain distribution
[1], free carrier and defect concentration [2] as well as degradation in different graphene
structures [3]. Basic information can be deduced from the observation of three most intense
bands (D, G and 2D). More advanced studies revealed the existence of several bands which
arise from different second order phonon overtones [4-9]. The knowledge about these
excitations is still very limited.
In this communication we present research of overtone bands in graphene, which
include temperature and excitation dependence of the Raman spectra. The experiments were
performed using a 0.5 m confocal Raman spectrometer in the temperature range 300-500K, using
532 and 633 nm laser lines as excitation sources. High quality graphene layers were formed
during preparation of ohmic contacts to SiC. Contacts were obtained by sputtering of Ni layer on
Si face of n-type 4H-SiC substrate followed by annealing at 1100oC in Ar in atmospheric pressure.
Typically, Raman spectrum of overtone bands, which occurs in the range of
1400-2600 cm-1, is difficult to observe, since their intensities are of about 100 times smaller than
those observed for the G band. The best know peak in this region is called M band, which
occurs around1750 cm-1. The presence of this band is a fingerprint of the more than one
graphene layer [10]. Dependence of the bands of temperature was measured. Opposite, to the
2D band, majority of overtone bands do not shift upon temperature change. On the other
hand, all the observed overtones show substantial energy shifts upon excitation energy
change. The obtained results provide new information about the nature of lattice excitations
participating in the second order phonon spectrum of multilayered graphene structures.
This work was partially supported by National Centre for Research and Development project GRAFTECH/NCBR/02/19/2012.
References:
[1] A. Jorio, International Scholarly Research Network ISRN Nanotechnology Vol. 2012, 234216, 16 A.C.
Ferrari, Solid State Communications 143 (2007) 47–57
[2] L. G. Cançado, et al., Nano Lett., 2011, 11 (8), pp 3190–3196
[3] Felix Herziger, arXiv:1203.6043v2 (March 2012) Rahul Rao, ACS Nano, 2011, 5 (3)
[4] Rahul Rao, arXiv:1108.3502 (2011)
[5] A. Jorio, et al. Wiley-VCH,Weinheim, Germany 2011
[6] P. H. Tan, et al. Phys. Rev. B 64 214301
[7] T. M. G. Mohiuddin, et al., Phys. Rev. B 79, 205433,2009
[8] C. Cong,Ting Yu, et al., ASC Nano,vol. 5, No. 11, 8760-8768, 2011
- 121 -
nanosilica, nanoparticles,
nanomaterials
BLANKA KĘPSKA, REGINA JEZIÓRSKA, MARIA ZIELECKA,
MAGDALENA WENDA, ELŻBIETA BUJNOWSKA
Industrial Chemistry Research Institute, Rydygiera 8, 01-793 Warsaw, Poland
NEW COMPOSITE MATERIALS OF INCREASED RESISTANCE AGAINST
MICROORGANISMS
In recent years, engineered nanoparticles have become very popular for use in
various industrial applications. Silica nanoparticles have attracted considerable interest
because of their excellent physical and chemical properties. Nanosilica was obtained by solgel method. Reaction is carried out in the silicon alkoxide-alcohol-water-ammonia system [1].
Structures and porosity of the materials obtained are strongly influence by pH of reaction
mixture. Silica surface can be modified by incorporation of functional groups or methods due
to the presence of reactive silanol groups.
This study it was focused on modification of nanosilica surfaces with copper
nanopraticles [2,3]. The nanosilica and nanosilica containing immobilized copper
nanoparticles were tested by using the following methods e.g.: Atomic Absorption
Spectroscopy (AAS), Scanning Electron Microscopy (SEM), Energy Dispersive
Spectroscopy) EDS, Photon Correlation Spectroscopy (PCS).
Based on the experimental results it can be concluded that nanosilica modified with
copper can be applied as an effective biocides to industrial products. The biocidic activity of
the nanosilica with immobilized copper nanoparticles was tested using the following fungi:
Aspergillus, Penicillium and Pseudomonas bacteria as well as single Alcoligenes Faecalis
strains, Stapylococcus Xylosus, Aerococcus Virdans [4]. In all cases, the development of both
fungi and bacteria was inhibited as expected one to the known antibacterial properties of
copper.
Nanosilica containing copper nanoparticles has been used as nanofiller in
nanocomposites of polyolefin. These materials have obtained better physico-chemical,
mechanical and microbiological tests.
References:
[1] W. Ströber, A. Fink, E. Bohn; Journal of Colloid and Interface Science 26 (1968) 62
[2] Polish Patent Apply No: P-391169, 2010, PCT/PL2011/000047
[3] M. Zielecka; Characteristics of silica nanopowders and sol containing immobilized nanoparticles of copper
or silver; Rapid Communication; Polimery 56 (2011) 10
[4] M. Zielecka, E. Bujnowska, B. Kępska, M. Wenda, M. Piotrowska, Antimicrobial additives for
architectural paints and impregnates; Progress in Organic Coatings 72 (2011) 193
- 122 -
titanium dioxide film, Ag nanoparticles,
photocatalysis
ANETA KISIELEWSKA, IRENEUSZ PIWONSKI, KINGA KADZIOLA,
KATARZYNA SOLIWODA
University of Łódź, Faculty of Chemistry, Department of Materials Technology and
Chemistry, 90-236 Łódź, Pomorska163, Poland
INVESTIGATION ON THE ENHANCEMENT OF THE TITANIUM DIOXIDE
COATINGS PHOTOCATALYTIC PROPERTIES TOWARDS
THE PHOTODEGRADATION OF ORGANIC DYES
This work presents several methods for the improvement of the photocatalytic
properties of TiO2 coatings. The effect of such parameters as TiO2 film thickness, the
presence of silver nanoparticles (AgNPs), the initial pH and the addition of H2O2 on the
organic dye phtodegradation process were studied. TiO2 semiconductor (anatase form) was
chosen as photocatalyst, because of its high photoactivity and photostability. Titania coatings
were prepared by the sol-gel dip-coating method on silicon wafers as substrates. The TiO2
film thickness was controlled by the number of deposited layers of the liquid sol, resulting in
thin and thick coatings produced by single or multiple immersions of the substrate into the sol
respectively. In order to obtain anatase crystalline form of TiO2, coatings were annealed at
500°C. Silver nanoparticles (AgNPs) were grown in situ on the surface of titania coatings in
the AgNO3 solutions having the concentrations of C1=0,1 mM/L and C2=1,0 mM/L under UV
illumination ( =365 nm). Coatings were illuminated for 5 and 30 min. for both concentrations
of the silver ions. Atomic force microscopy (AFM) images revealed, that the diameter and
number of AgNPs strongly depend on the thickness of TiO2 coating. The AgNPs average size
(in nm) varies, depending on the Ag+ concentration and the time of illumination, from 11±4
to 31±8 and from 63±11 to 122±26 for single and ten-layered TiO2 coating respectively.
Photocatalytic efficiency of TiO2 and AgNPs/TiO2 coatings was evaluated by the
photocatalytic decomposition of Rhodamine B (RhB) and Methyl Orange (MO) in aqueous
medium using UV light. The effects of initial pH (from 3 to 12) and the addition of H2O2 on
the degradation process were observed. It was found that the photocatalytic degradation
of RhB and MO by TiO2 and Ag/TiO2 films is an effective method for their removal from
aqueous solutions. The experiment showed an increase of the organic dye photodegradation
on the TiO2 coatings with increasing the film thickness and optimum amounts of AgNPs.
The greatest improvement of the photocatalytic properties was obtained in the presence
of H2O2 (from 2 up to 5 times for RhB and 15 to 270 times for OM). It was also observed that
the highest values of the decomposition rate constants for RhB and OM can be achieved in the
pH = 3.
Acknowledgments
This work was supported by the Ministry of Science and Higher Education of Poland – grant number N
N507497538
- 123 -
graphene on SiC, CVD, STM,
Raman spectroscopy
MICHAŁ KLUZ
University of Warsaw, Faculty of Physics, Nanostructures engineering,
Hoża 69, 00-681 Warsaw, Poland
SURFACE CHARACTERIZATION OF GRAPHENE FORMED BY CVD
TECHNIQUE ON SiC
Graphene is known for its exceptional properties, both physical and chemical [1]. It has the
potential to become a revolutionary material with various possible applications. However
today, commercial applications of graphene are limited by the lack of manufacturing methods
for growing high quality layers of graphene. Strupiński et al [2] developed a method of
producing entire layers of graphene using chemical vapour deposition (CVD) on conducting
SiC substrates. The surface of multi-layered graphene grown by this technique was examined
using various methods, mainly STM and Raman Spectroscopy. We observed unique surface
defects of yet unknown cause. We named them “bark beetles”. Further examination of “bark
beetles” is important for improving our knowledge of graphene and for enabling future
applications of graphene formed by CVD technique in electronic based wafer scale.
References:
[1] Geim, A.K. & Novoselov, K.S., The rise of graphene, Nature Mater. 6, 183-191 (2007).
[2] Strupinski W. et al., Epitaxy by Chemical Vapor Deposition on SiC, Nano Lett, 11, 1786 (2011).
- 124 -
efekty zdrowotne, płuca,
nanocząstki, glinokrzemiany
DOROTA KONDEJ*, TOMASZ R. SOSNOWSKI**
*
Centralny Instytut Ochrony Pracy – Państwowy Instytut Badawczy, Warszawa
Politechnika Warszawska, Wydział Inżynierii Chemicznej i Procesowej
**
FIZYKOCHEMICZNA OCENA WPŁYWU WDYCHANYCH NANOAEROZOLI NA
FUNKCJONOWANIE SURFAKTANTU PŁUCNEGO
Surfaktant płucny będąc pierwszą barierą oddzielającą tkankę płucną od środowiska
gazowego wprowadzanego do płuc w procesie oddychania, pełni istotną rolę w fizjologii
układu oddechowego. Surfaktant jest odpowiedzialny za znaczące obniżenie wartości
napięcia powierzchniowego cieczy pokrywającej tkankę płucną, co ma istotne konsekwencje
dla mechaniki cyklu oddechowego oraz procesów przenoszenia masy w płucach (w tym:
wymiany gazowej oraz usuwania zanieczyszczeń pyłowych z powierzchni płuc). Celem
przedstawianych badań jest określenie czy wybrane nanocząstki zawarte we wdychanym
powietrzu wpływają na właściwości fizykochemiczne surfaktantu płucnego, co mogłoby
świadczyć o możliwości wystąpienia zaburzeń w funkcjonowaniu układu fizjologicznego. W
badaniach skoncentrowano się na nanocząstkach mineralnych z grupy glinokrzemianów,
których podwyższona zawartość w powietrzu może występować m.in. podczas produkcji
materiałów kompozytowych, w których nanocząstki tego typu są stosowane jako dodatki
funkcjonalne. Określono wpływ pięciu typów nanocząstek (bentonit, haloizyt oraz trzy
rodzaje montmorylonitów o zmodyfikowanej zwilżalności) na dynamiczne wartości napięcia
powierzchniowego w trakcie zmian wielkości powierzchni międzyfazowej ciecz-gaz
odpowiadających charakterowi odkształcenia powierzchni pęcherzyków płucnych podczas
oddychania. Badania wykonano z wykorzystaniem tensjometru z pulsującym pęcherzykiem
(Electronetics, USA) oraz wagi Langmuira-Wilhelmy‟ego (KSV, Finalndia). W pomiarach
zastosowano odzwierzęcy surfaktant płucny (Survanta – Abbott, Francja) oraz fosfolipid
DPPC (Sigma Aldrich), będący głównym składnikiem naturalnego surfaktantu. Zawartość
nanocząstek w stosunku do ilości cieczy i surfaktantu stosowanych w pomiarach określono w
oparciu o obliczenia procesu depozycji wdychanych aerozoli w układzie oddechowym.
Wyniki badań wykonanych dwiema komplementarnymi technikami pozwalają stwierdzić, że
wszystkie z badanych nanocząstek wykazują wpływ na aktywność powierzchniową
surfaktantu, jednak obserwowany efekt silnie zależy od stężenia nanocząstek, zaś na charakter
zmian dynamicznego napięcia powierzchniowego wpływa powierzchnia właściwa
nanocząstek oraz obecność modyfikatorów zwilżalności cząstek. Cząstki niemodyfikowane
(bentonit, haloizyt) w widoczny sposób obniżają aktywność powierzchniową surfaktantu
płucnego, podczas gdy cząstki o zmodyfikowanej zwilżalności wywołują wzmocnienie
efektów powierzchniowo czynnych w badanym układzie, co wynika najprawdopodobniej z
obecności dodatkowych tensydów wykazujących silniejszą aktywność powierzchniową niż
związki obecne w surfaktancie płucnym. Wnioski z badań sugerują możliwość zaburzenia
właściwości powierzchniowych surfaktantu płucnego w wyniku oddychania powietrzem
zawierającym nanocząstki glinokrzemianowe.
Publikacja opracowana na podstawie wyników II etapu programu wieloletniego pn. „Poprawa bezpieczeństwa i warunków
pracy” dofinansowywanego w latach 2011-2013 w zakresie badań naukowych i prac rozwojowych ze środków Ministerstwa
Nauki i Szkolnictwa Wyższego. Koordynator programu: Centralny Instytut Ochrony Pracy – Państwowy Instytut Badawczy.
- 125 -
magnetic nanocomposite, nickel(II),
adsorption, kinetics, thermodynamics
WOJCIECH KONICKI*, IWONA PEŁECH**, EWA MIJOWSKA**
*
Department of Integrated Transport Technology and Environmental Protection, Maritime
University of Szczecin, H. Pobożnego 11, 70-507 Szczecin, Poland.
**
Institute of Chemical and Environment Engineering, West Pomeranian University of
Technology, Pułaskiego 10, 70 322 Szczecin, Poland.
REMOVAL OF NICKEL(II) FROM AQUEOUS SOLUTIONS BY ADSORPTION
ONTO MAGNETIC MULTIWALLED CARBON NANOTUBE NANOCOMPOSITE
Nickel is the one of the important toxic heavy metals. It is used in a wide range of
manufacturing industries, such as metal plating, galvanizing, smelting, mining, pigment and
ceramics industries and is present in the wastewaters. Nickel is non-biodegradable metal and
may cause dermatitis and allergic sensitization. At higher concentrations it is a potent
carcinogen and causes cancer of lungs, nose and bone [1]. Therefore, it is necessary to remove
the nickel from various industrial effluents.
The investigations on the removal of Ni(II) ions from aqueous solutions by magnetic
multiwalled carbon nanotube nanocomposite MMWCNTs-C were conducted in a batch
adsorption system. MMWCNTs-C was synthesized by chemical vapor deposition proces
using ethylene as a carbon source and nanocrystalline iron as catalyst. MMWCNTs-C was
separated from the aqueous solution by an external magnetic field. The influence of different
parameters such as initial Ni(II) concentration (0.82-4.12 mg/L), pH solution (3.5-11.2) and
temperature (20-60OC) were investigated. The equilibrium data for the adsorption of Ni(II) on
MMWCNTs-C were tested using both the Freundlich and Langmuir adsorption isotherm
models. The equilibrium data were best represented by the Langmuir isotherm, with
maximum monolayer adsorption capacity of 2.11 mg/g at 30OC. Kinetic adsorption data were
analysed using the Lagergren pseudo-first-order kinetic model and the pseudo-second-order
kinetic model. Kinetic studies showed that the kinetic data were well described by the pseudosecond-order kinetic model. Thermodynamics parameters such as GO, HO and SO, were
also calculated. All GO values were negative. The HO values and SO values were 5.41
kJ/mol and 18.9 J/(mol K), respectively, indicating that the adsorption of Ni(II) onto
MMWCNTs-C was spontaneous and endothermic in nature and was a physisorption process.
References:
[1] R. Hema Krishna, Avvs Swamy, Kinetic and isotherm modeling of adsorption of Ni (II) form aqueous
solutions onto powder of papaya seeds, Int. J. Sci. Res. Publications 1(1) 2011 1-6.
- 126 -
bionanomedycyna, ferrytna, magnetyt,
właściwości magnetooptyczne
MARCELI KORALEWSKI*, MIKOŁAJ POCHYLSKI*, JAROSŁAW KŁOS*,
MIKOŁAJ BARANOWSKI*, ZUZANA MITROOVA**, PETER KOPCANSKY**,
WALTHER SCHWARZACHER***
*
Wydział Fizyki, Uniwersytet im. A. Mickiewicza, ul. Umultowska 85, 61-614 Poznań
Institute of Experimental Physics, SAS, Watsonova 47, 040-01 Kosice, Slovakia
***
H.H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Royal Fort, Bristol,
BS8 1TL, UK
**
MAGNETOOPTYCZNE METODY OKREŚLANIA RDZENIA NATURALNYCH
I SYNTETYCZNYCH FERRYTYN
Ferrytyna jest białkiem globularnym o średnicy zewnętrznej około 12 nm i wnęce o
średnicy 7- 8 nm, w której organizmy żywe magazynują żelazo w postaci oksywodorotlenku
w obecności zmiennej zawartości fosforanów. Mann i wsp. [1] pokazali, że wnęka ferrytyny
może być również znakomitym nanoreaktorem do syntezy różnego typu związków, w tym
tlenków metali innych niż żelazo. Odkrycie to spowodowało intensywny rozwój badań oraz
poszukiwań aplikacji ferrytyn o zmodyfikowanym składzie rdzenia (nośniki informacji,
elektronika, nanobaterie itp.). W tym samym okresie Kirschvink i wsp. [2] odkryli złogi
magnetyczne w ludzkim mózgu, a dalsze badania wskazały na korelacje pomiędzy
występowaniem toksycznego żelaza Fe(II) a chorobami neurodegeneracyjnymi (Alzheimer,
Parkinson). Niewłaściwe funkcjonowanie ferrytyny może przyczyniać się do zwiększonej
ilości Fe(II) z czym kojarzy się powstawanie nadmiernej liczby szkodliwych wolnych
rodników. Jednakże mimo intensywnych badań, określenie składu mineralnego kompleksów
żelaza w ludzkim mózgu nastręcza trudności i ciągle toczą się dyskusje nad tym czy są one
źródłem czy konsekwencją chorób neurodegeneracyjnych. Stąd niezwykle cenne są badania
nad ferrytynami naturalnymi i syntetycznymi zarówno in vivo jak i in vitro.
W pracy zostaną zaprezentowane magnetooptyczne badania wodnych roztworów
ferrytyny, magnetoferrytyny oraz nanocząstek tlenków żelaza (Fe3O4, Fe2O3, FeOOH)
stabilizowanych dekstranem. Dla wymienionych nanocząstek przedstawione będą pomiary
magnetycznej liniowej dwójłomności optycznej (efekt Cottona-Moutona) [3], magnetycznej
kołowej dwójłomności optycznej (efekt Faradaya) [4] oraz ich opis wykorzystujący funkcje
Langevina z dystrybucją rozmiaru ziarna obok standardowych metod charakteryzujących
nanocząstki a mianowicie XRD, TEM, VSM. Pokazane będzie, że badania wymienionymi
metodami magnetooptycznymi pozwalają scharakteryzować strukturę rdzenia ferrytyny (lub
innej nanocząstki) i odpowiedzieć na pytanie jaki minerał go tworzy. Zaproponowana w pracy
metoda jest znacznie tańsza i łatwiej dostępna od wykorzystywanych w tym celu
spektroskopii Mossbauera w silnych polach magnetycznych czy synchrotronowych pomiarów
krawędzi absorpcji promieniowania X metalu (XANES). Sądzimy, że metody
magnetooptyczne mogą znaleźć w przyszłości szerokie zastosowanie kliniczne w badaniach
substancji biologicznych.
References:
[1] F.C. Meldrum, B.R. Heywood, S. Mann, Science 257, 522 (1992).
[2] J.L. Kirschvink, A. Kobayashi-Kirschvink, B.J. Woodford, Proc. Natl. Acad. Sci. USA 89, 7683 (1992).
[3] M. Koralewski et al. J. Magn. Magn. Mater. 323, 2413 (2011)
[4] M. Koralewski et al. Nanotechnology 23, 335704 (2012)
- 127 -
fluoroalkylsilanes, titania surface, nano-microtribology,
atomic force microscopy, stability tests
KATARZYNA KOŚLA*, WOJCIECH PAWLAK**, WITOLD KOZŁOWSKI***,
WITOLD SZMAJA***, JAROSŁAW GROBELNY*, MICHAŁ CICHOMSKI*
*
University of Lodz, Faculty of Chemistry, Department of Materials Technology and
Chemistry, Pomorska 163, 90-236 Lodz
**
Technical University of Lodz, Faculty of Mechanical Engineering,
Stefanowskiego 1, 90-924 Lodz
***
University of Lodz, Faculty of Physics and Applied Informatics, Department of Solid State
Physics, Pomorska 149/153, 90-236 Lodz
STABILITY AND TRIBOLOGICAL INVESTIGATIONS OF 1H,1H,2H,2HPERFLUOROALKYLTRICHLOROSILANE ON TITANIA SURFACE
Selective surface modification techniques have been the focus of research and
technology for a variety of applications including wetting, lubricants, sensors and electronic
devices. Different compounds have been used for surface selective modification, such as
alkylphosphonic and organosilanes. Nowadays the films obtained from organosilanes have
attracted a growing interest because they show good thermal and chemical stability, low
values of the adhesive force and coefficient of friction. For the mentioned these compounds
are effective surface modifying agents for cobalt, silicon and alumina substrates. They can be
also applied via a specific interaction to modify the surface properties of the titania substrate.
Covalent surface modification of the titania is of great interest in view of its importance in
photocatalysis and medical implants because the titania has been used as a model system for
the surface of medical implant devices based upon titanium alloys.
For these reasons the present work reports the gas-phase deposition and
characterization of the film of 1H,1H,2H,2H-perfluorodecyltrichlorosilane on the titania
surface. In order to correlate the surface structure with the tribological and stability
characteristics, various surface analysis techniques, such as X-ray photoelectron spectroscopy
(XPS), ellipsometry, atomic force microscopy (AFM), microtribometry and contact angle
measurements, were used. The stability of fluoroalkylsilane was investigated in tris- and
phosphate-buffered saline at 37 °C using XPS and contact angle goniometry. The performed
measurements proved that the fluoroalkylsilane film shows long-term (minimum 14 days)
physiological stability.
The influence of relative humidity on the adhesion and friction tests in micro- and
nanoscale was also studied. Friction tests performed in the humidity range 10–90% by means
of microtribometer and AFM reveal that fluoroalkylsilane is capable to decrease the value of
the coefficient of friction by a quarter in comparison with the unmodified surface. From wear
tests it was also found that the fluoroalkylsilane film on the titania surface could not be easily
removed even under a few micro- Newton normal load.
This work was supported by the National Science Centre Research Grant No. 2011/03/N/ST8/05680.
- 128 -
silver nanoparticles,
cellular uptake, genotoxicity
MAGDALENA KOWALSKA*, ANETA WĘGIEREK-CIUK*, HALINA LISOWSKA*,
MARCIN KRUSZEWSKI**/***, SYLWESTER SOMMER**, MARIA WOJEWÓDZKA**,
ANNA LANKOFF*/**
*
Jan Kochanowski University, Institute of Biology, Deptartment of Radiobiology and
Immunology, Kielce, Poland
**
Institute of Nuclear Chemistry and Technology, Centre for Radiobiology and Biological
Dosimetry, Warsaw, Poland
***
Institute of Rural Health, Independent Laboratory of Molecular Biology, Lublin, Poland
THE UPTAKE KINETICS AND GENOTOXIC EFFECTS OF SILVER
NANOPARTICLES IN HepG2 AND A549 CELLS
In the recent years a number of applications of nanoparticles (NPs) in everyday life
has increased dramatically. Nowadays NPs are found in many different products such as
cosmetics, household items, new food packaging systems, food additives and biosensors. NPs
are also used in biological sciences and medicine, especially in drug and gene delivery, tissue
engineering, detection of protein and pathogens and cancer treatment. Despite all the benefits
of NPs, their possible toxic effects are not completely determined and characterized. Taking
this into account, our study was designed to examine the uptake kinetics of silver
nanoparticles (nominal size = 20 nm, hydrodynamic diameter in Williams medium + 10%
FCS = 78.22 nm and in F12K medium + 10% FCS = 82.66 nm) and their genotoxic effects in
HepG2 and A549 cells. The kinetics of cellular uptake/binding of silver nanoparticles was
examined by flow cytometry, whereas genotoxic effect was determined by the micronucleus
assay. HepG2 and A549 cells were incubated with 10, 50 and 100 g/ml of silver nanoparticles
for 2–72 h. Cells were washed and re-suspended in PBS for flow cytometry. Following
gating, control and particle-exposed cells were run and plotted to examine the increase in side
scatter distribution ratio which was calculated by dividing the SSC value in the particletreated cells by the SSC value in control cells. For the micronucleus assay analysis, cells were
fixed with cold methanol: glacial acetic acid and stained with Giemsa. Our results revealed
that the cellular uptake/binding of silver nanoparticles into HepG2 and A549 cells depended
on the particle concentration, time-point and cell line used. A concentration-dependent and
time-dependent cellular uptake/binding of silver nanoparticles into A549 cells was observed,
with a progressive increase from 10 to 100 g/ml. However, in the HepG2 cells a
concentration-dependent increase in cellular uptake/binding was observed which was not a
time-dependent. There frequencies of micronuclei in A549 and HepG2 cells were slightly
increased after 48 hours, however the results between the control and the treated cells were
no statistically significant. Summarizing, the obtained results showed that silver nanoparticles
were taken up by A549 and HepG2 cells, however their genotoxic effect was not evident in
these cell lines.
- 129 -
nanorurki węglowe, nanokompozyty,
kleje epoksydowe
ANDRZEJ KUBIT*, KATARZYNA OWODZIŃ**, URSZULA NARKIEWICZ**,
WŁADYSŁAW ZIELECKI*
*
Politechnika Rzeszowska, Wydział Budowy Maszyn i Lotnictwa, Katedra Technologii
Maszyn i Inżynierii Produkcji, Al. Powstańców Warszawy 8, 35 - 959 Rzeszów,
**
Chemicznej Nieorganicznej i Inżynierii Środowiska, ul. Pułaskiego 10, Szczecin,
BADANIE WPŁYWU DODATKU NANORUREK WĘGLOWYCH NA
WŁAŚCIWOŚCI KLEJÓW EPOKSYDOWYCH
Połączenia klejowe są coraz szerzej stosowaną grupą połączeń konstrukcyjnych
cechująca się jednak niską wytrzymałością przy naprężeniach normalnych do warstwy kleju
w spoinie oraz znaczącym spadkiem wytrzymałości mechanicznej przy podwyższonej
temperaturze pracy złącza [1,2,6]. Badano wpływ dodatku nanoproszków ceramicznych [3]
na właściwości klejów, a następnie w oparciu o doniesienia literaturowe dotyczące wpływu
nanorurek węglowych na poprawę właściwości tworzyw polimerowych [4,5], zastosowano je
jako napełniacz. Nanorurki węglowe syntezowano metodą CVD przy użyciu katalizatorów
Fe-Co. Materiał węglowy po procesie poddano utlenianiu, a następnie obróbce w kwasach w
celu oczyszczenia z węgla amorficznego i cząstek katalizatorów. Wysuszony materiał dodano
w ilości 5% mas. do klejów epoksydowych (ARALDITE 2013, BISON EPOXY oraz
EPIDIAN 57/PAC). Do kleju epoksydowego (bez utwardzacza) dodano w odpowiedniej
ilości nanorurki węglowe, całość podgrzano do temperatury 50oC, mieszano w środowisku
ultradźwięków.
Próbki klejów poddano różnicowej kalorymetrii skaningowej (DSC), natomiast
złącza klejowe badaniom wytrzymałości statycznej oraz zmęczeniowej na oddzieranie.
Badania wykazały poprawę własności wytrzymałościowych oraz wzrost temperatury
zeszklenia dla wariantów kompozycji klejowych z napełniaczem w postaci nanorurek
węglowych.
Literatura:
[1] Godzimirski J., Kozakiewicz J., Łunarski J., Zielecki W., Konstrukcyjne połączenia klejowe elementów
metalowych w budowie maszyn, Oficyna Wydawnicza Politechniki Rzeszowskiej, Rzeszów 1997
[2] Mirski Z., Piwowarczyk T., Podstawy klejenia, kleje i ich właściwości. Przegląd Spawalnictwa 8/2008.
[3] Zielecki W., Kubit A., Wpływ proszkowych nanonapełniaczy ceramicznych na wytrzymałość statyczną
połączeń klejowych, Technologia i Automatyzacja Montażu, 1/2014
[4] Bauera, F., Gl.asela, H.-J., Hartmanna, E., Langgutha, H., Hinterwaldner, R., Inter. J. Adhesion & Adhesives,
2004, 24, 519–522
[5] Kim, J.Y., Han, S.I., Kim, D.K., Kim, S.H., Composites: Part A, 2009, 40, 45–53
[6] Godzimirski J., Wytrzymałość doraźna konstrukcyjnych połączeń klejowych, Wydawnictwo NaukowoTechniczne, Warszawa 2002.
- 130 -
wielowarstwy Cu/Ni, wygrzewanie oporowe,
stabilność temperaturowa
EDYTA KULEJ, BARBARA KUCHARSKA, MICHAŁ OLEJNIK
Instytut Inżynierii Materiałowej, Politechnika Częstochowska,
al. Armii Krajowej 19, 42-200 Częstochowa
ZMIANY STRUKTURY I REZYSTYWNOŚCI UKŁADÓW
WIELOWARSTWOWYCH Cu/Ni PODDANYCH WYGRZEWANIU OPOROWEMU
Stabilność temperaturowa jest podstawowym terminem używanym do opisu zmian
właściwości materiału w funkcji temperatury i może być odniesiona zarówno do struktury
materiału jak i jego własności fizycznych oraz mechanicznych [1, 2]. Artykuł przedstawia
wyniki
badań
temperaturowych
wielowarstw
Cu/Ni.
Układy
typu
ferromagnetyk/paramagnetyk, w tym również wielowarstwy Cu/Ni, nie pracują w
podwyższonych temperaturach, mimo to istotne jest określenie maksymalnej temperatury, w
której wielowarstwy zachowają ciągłość, periodyczność układu i będą cechować się
własnościami magnetycznymi. W wyniku zamierzonego lub przypadkowego dostarczenia
energii cieplnej może dochodzić do dyfuzji wzajemnej atomów składników wielowarstwy, co
w konsekwencji doprowadzi do rozmycia granic międzyfazowych i obniżenia właściwości
magnetycznych.
W pracy przedstawiono wyniki badań powłok wielowarstwowych Cu/Ni
wykonanych techniką rozpylania magnetronowego na monokrystalicznym podłożu
krzemowym Si(100). Wielowarstwy złożone ze 100 biwarstw zróżnicowano grubością
podwarstwy Ni (1 † 3 nm) przy zachowaniu stałej grubości podwarstwy Cu (2nm).
Wpływ wzrostu temperatury indukowanej przepływem prądu elektrycznego
na trwałość wielowarstw zbadano poprzez ich włączenie jako elementu oporowego
do obwodu prądu stałego. Wzrostem temperatury sterowano poprzez zwiększanie mocy prądu
płynącego przez wielowarstwy. Na podstawie wartości napięcia i natężenia prądu
wyznaczono rezystancję wielowarstw w określonych temperaturach. Najwyższą rezystancją
charakteryzowała się najcieńsza wielowarstwa (Cu/Ni = 2/1 nm). Wraz ze zwiększaniem się
grubości podwarstw Ni, a tym samym całkowitej grubości wielowarstw rezystancja malała.
Wygrzewanie oporowe wielowarstw prowadzono aż do utraty przez nie ciągłości.
Po każdorazowym wygrzewaniu stan powierzchni wielowarstwy kontrolowano w pomiarach
mikroskopowych, które wykazały delamiancję wielowarstw od podłoża. Wykazano, że
badane wielowarstwy uległy zniszczeniu w zakresie temperatur 220º † 300ºC. Maksymalną
trwałość termiczną wykazała wielowarstwa o najmniejszym periodzie Cu/Ni=2/1 nm,
Literatura:
[1] A. Raveh, I. Zukerman, R. Shneck, R. Avni, I. Fried, , Surf Coat Tech 201 (2007) 6136
[2] C.B. Ene,G. Schmitz, R. Kirchheim, A. Hütten, Acta Mater 53 (2005) 3383
- 131 -
magnetic nanoparticles, coating,
targeted delivery
JOANNA KURCZEWSKA, GRZEGORZ SCHROEDER
Faculty of Chemistry, Adam Mickiewicz University in Poznań,
Umultowska 89B, 61-614 Poznań, Poland
APPLICATION OF MAGNETIC NANOPARTICLES COATED BY SILANE
AGENTS FOR TRANSFERRING OF BIOACTIVE COMPOUNDS
The research studies concerning drug carriers are of great interest for a long time.
The library of nanoparticles is impressive and it includes fullerens, liposomes, nanoshells,
dendrimers and more. It is well known that iron oxide nanoparticles demonstrate unique
properties, which can be used for drug delivery. However, due to their high chemical activity
and the tendency to aggregate, the particles are usually coated to ensure their stability while
maintaining magnetic properties. The iron oxide core can be coated by either inorganic (e.g.
silica) or organic materials (e.g. polymers), which largely depends on the intended application
of the matrix. A coating should not only protect the magnetic core but also reduce toxicity and
improve biodegradability. A conjugation of bioactive materials is another factor taken into
account when choosing a cover. Therefore, the coating shells having organic functional
groups are often desired and applied. They can function as a final form of a core-shell
structure, and many examples confirm an increase of their efficiency compared to the pure
magnetic core. On the other hand, they are used as a bridge for a loading of bioactive
compounds, like drugs. Of course it is necessary to fulfill a number of conditions, and the
essential is to preserve the pharmacological properties of the immobilized agent and release it
at a target site at a specific rate.
In this work we present the synthesis of magnetic nanoparticles based on iron oxide
having an average diameter of 10 nm. The magnetic core has been covered with different
silane compounds having active functional groups. Silanes, having high density of surface
functional groups, form cover layer of iron oxide nanoparticles but it is associated with the
increase of average diameter. During the further stage the functional groups have participated
in the reaction with compounds of biological activity. The properties of the functionalized
magnetic nanoparticles have been reported.
Acknowledgements:
The authors would like to thank The National Science Center of Poland (Grant No. 2011/03/B/ST5/01573) for
financial support.
References:
[1] A.K. Gupta, M. Gupta, “Synthesis and surface engineering of iron oxide nanopraticles for biomedical
applications”, Biomaterials, 26, 3995-4201, 2005;
[2] S. Parveen, R. Misra, S.K. Sahoo, “Nanoparticles: a boon to drug delivery, therapeutics, diagnostics and
imaging”, Nanomedicine:Nanotech. Biol. Med., 8, 147-166, 2012.
- 132 -
magnetic nanoparticles, submicron silica
spheres, sol-gel method
KATARZYNA ŁUSZCZYK, AGNIESZKA BASZCZUK, MAREK JASIORSKI
MAGNETIC METAL NANOPARTICLES ON THE SURFACE OF SILICA SPHERES
OBTAINED BY THE SOL-GEL METHOD
Synthesis and measurements of magnetic metal nanoparticles is a very popular area
of research interest nowadays. It is mainly related to huge potential for many applications of
these materials. Magnetic nanostructures can be implemented in magnetic fluids [1,2] as well
as in medicine as drug delivery or for hyperthermia treatment [3].
This study was aimed to elaborate a simple method of obtaining the stable magnetic
structures. Cobalt ions were deposited on the surface of silica matrix obtained by the sol-gel
Stöber method. The reduction process of Co2+ ions was carried out in a hydrogen atmosphere.
As a result, silica spheres doped with magnetic metal nanoparticles were obtained. Silica
matrix was used to prevent nanometals from negative process of aggregation into larger
clusters. SiO2/Co was a black powder with strong magnetic properties. Phase identification
and surface morphology characterization of obtained material were performed by x‐ray
diffraction technique (XRD), scanning electron microscopy (SEM), transmission electron
microscopy (TEM) and EDX spectroscopy. Basic magnetic measurements were carried out at
magnetic magnetometer.
Acknowledgment
Fellowship co-financed by European Union within European Social Fund (MK/SN/441/VIII/2013/U)
Literature
[1] Mayer D., Advances in Electrical and Electronic Engineering, 7, 2008, 9-14
[2] Hoinville J., Bewick A., Gleeson D. et al., J. Applied Physics, 93, 2003, 7187-7189
[3] Hofmann-Amtenbrink M., Rechenberg B., Hofmann H., Nanostructured Materials for Biomedical
Applications, 2009, 119-148
- 133 -
TiO2 , basalt fibres,
sol-gel
PATRYCJA ŁYCZKOWSKA*/**, MAŁGORZATA CIEŚLAK*,
GRZEGORZ CELICHOWSKI**
*
Scientific Department of Unconventional Technologies and Textiles, Textile Research
Institute, Brzezinska 5/15, 92-103 Lodz, Poland
**
Department of Materials Technology and Chemistry, Faculty of Chemistry, University of
Lodz, Pomorska 163, 90-236 Lodz, Poland
THE USE OF SOL-GEL TECHNIQUE TO MODIFY BASALT FIBERS WITH
TITANIUM DIOXIDE
The use of nanotechnology offers new capabilities to produce innovative materials
for targeted properties, giving them a range of new applications. The oxidising and reducing
properties of TiO2 and the ability to obtain it in the nanometric form cause development of its
use as photocatalytic modifiers [1,2]. The photocatalytic properties of TiO2 used to modify the
textile materials provide the huge potential application. This justifies the need to search
methods of modification textile materials with TiO2. The aim of this study was the
modification of basalt fibers surface with TiO2, based on the sol - gel technique.
TiO2 was prepared in the sol-gel technique both as powder and TiO2 film using as
precursor of Ti - titanium isopropoxide. The basalt fibers with high thermal resistance were
used. TiO2 sol was deposited on the basalt fibers by dip – coating technique. The same steps
for silicon wafer as a reference material were performed. The TiO2 film on wafer and fibers
surface was calcined in 500°C (for 2 hours) to obtain photocatalytically active structure anatase. The presence of anatase on fibers surface using Raman spectroscopy was confirmed.
The structure and the quantity of TiO2 deposited on silicon wafer and basalt fibers using
scanning electron microscopy equipped with an X-ray microanalyzer SEM/EDS was
examined. The value of band gap energy prepared TiO2 powder on the basis of its UV/VIS
spectra was calculated.
The sol - gel method allows to obtain sol TiO2 and modification basalt fibers by dipcoating technique. The use of fibers with high thermal resistance enables to perform
calcination process without degradation or changes in their structure. The proposed method of
calcination TiO2 film on the basalt fibers allows to obtain photocatalytically active form of
TiO2 – anatase directly on a fiber surface.
The study has been carried out within the Key Project – POIG.01.03.01-00-004/08 Functional nano- and micro
textile materials - NANOMITEX co-financed by the European Union with the financial resources of the
European Regional Development Fund and the National Centre for Research and Development within the
framework of the Innovative Economy Operational Programme, 2007-2013, Priority 1. Research and
development of modern technologies, Activity 1.3. Supporting R&D projects for enterprises undertaken by
science establishments, Subactivity 1.3.1. Development projects.
[1] Han Z., Chang V. W. C., Zhang Li, Tse M. T., Tan O. K., Hildemann L. M. Aerosol and Air Quality
Research 12, 2012, 1327–1335.
[2] Fujishima A., Zhang X., Tryk D.A. Surface Science Reports. 63, 2008, 515-582.
- 134 -
metallic nanoparticles, nanosilver,
nanogold, synthesis
DAGMARA MALINA, AGNIESZKA SOBCZAK-KUPIEC, ZBIGNIEW WZOREK
Institute of Inorganic Chemistry and Technology, Cracow University of Technology,
Warszawska 24, 31-155 Cracow, Poland
METALLIC NANOPARTICLES –
SYNTHESIS, CHARACTERIZATION AND POTENTIAL MEDICAL USES
Nanostructured particles, because of their unusual properties, have been the subject
of numerous intensive researches. One of the most important advantages of them is a high
surface to volume ratio with decreasing size of nanoparticles leading to increase chemical
activity. Highly developed surface area has a significant effect on the adsorption properties,
reactivity of nanomaterials, optical features and the other properties including antimicrobial
activity. Metallic nanoparticles are widely used in many industries due to their unusual
properties, which are dependent on the nanometric sizes. Recently, attention has been focused
around the noble nanoparticles, which beside unusual optical, electronic and chemical features
also ehibit remarkable antimicrobial properties. There are many methods of metallic
nanoparticles synthesis, however the most widespread are chemical methods which require
the use of suitably selected reducing agents and stabilizers.
In this paper we synthesized silver and gold nanoparticles. Silver nanoparticles
(AgNPs) were prepared by a chemical reduction method from the aqueous solution of silver
nitrate and polyvinylpyrrolidone (PVP) as a stabilizer in the presence of sodium borohydride
as a reducing agent. The gold nanoparticles (AuNPS) are prepared by sodium citrate reduction
method in which sodium citrate act both as a reducing and stabilizing agent. Obtained
nanoparticles were characterized by scanning electron microscopy (SEM) with BSE detector
(Back Scaterred Electrons) and EDS (Energy Dispersive X-ray Spectros-copy). The optical
properties were studied through UV-Vis spectroscopy. Dynamic light scattering (DLS)
measurement using Zetasizer Nano ZS was applied for the size estimation.
We have described the synthesis and characterization of surface-functionalized silver
and gold nanoparticles in order to develop a medical applications. All samples demonstrated
peaks due to surface plasmon resonance in the UV-Vis absorption spectra. SEM images and
DLS measurement show that particles are spherical and monodispersed, respectively. The
successful synthesis of nanoparticles with expected properties will allow to used these
nanoproducts as structure modiﬁers, as well as additives improving the properties of ceramic
biomaterials used as bone substitutes.
The research was supported by The National Centre for Science in Poland.
- 135 -
nanotechnology regulations,
nanomaterial characterization methods
IWONA MALKA, JOANNA SOBCZYK, WITOLD ŁOJKOWSKI
Institute of High Pressure Physics, Polish Academy of Sciences,
Sokołowska 29/37, Warsaw, Poland
RECOMMENDATIONS FOR NANOTECHNOLOGY REGULATIONS
In the recent years, an increasing number of applications and products containing
nanomaterials have become available. This causing concerns that some of these materials may
introduce new risks for humans or the environment. Additionally, in October 2011 the
European Commission published the „Recommendation on the definition of a nanomaterial‟,
primarily intended to provide identical criteria to identify materials for which special
regulatory provisions might apply, but also to promote consistency on the interpretation of the
term „nanomaterial‟. However, existing regulation do not take into account different
properties of nanomaterials resulting from their morphology and particle size distribution.
Nanomaterials because of these new and unique properties are also most often different from
their conventional chemical equivalents with respect to their behavior in the environment and
their kinetic and toxic abilities. This raises concerns in connection to their widespread use,
since it leads to an increase of exposure to these nanomaterials for workers and end-users as
well as the environment.
In this paper we present proposals for the nanotechnology regulations, taking into
account key factors such as nano-particle shape and size, surface chemistry and even
synthesis methods. From our experiences and literature data we know that synthesis method
influence greatly nanomaterials properties. Additionally, transfer of nanoparticles from one
medium to another can also affect nanoparticles properties and influence it‟s toxicity. We are
also considering nanomaterials fate at the environment and inside human body. There are still
open questions: Do they still remained nanomaterials after agglomeration and ionization in
the liquid medium? Do they keep their properties?
As the result of NanoForce European project we would like to present
Nanotechnology Recommendations Tree, where we show the way from current stage to
proper legal regulations concerning nanostructures, including all definitions, request for
registration all nano-products and exposure scenarios for all stages of nanoproducts
manufacturing processes. Recommended is establishment of databases/ libraries for
toxicological and characterization tests and experiments with open access for future use.
- 136 -
hierarchical surface topography, surface chemical modification,
superhydrophobicity, soft litography
JACEK MARCZAK, GRZEGORZ CELICHOWSKI, MACIEJ PSARSKI
Chemistry, Pomorska 163, 90-236 Lodz, Poland
WELL-DEFINED SUPERHYDROPHOBIC LOTUS-LIKE MATERIALS
Nature inspires many researchers in designing and preparing synthetic materials with
superhydrophobic properties, which can be used as self-cleaning surfaces. Their water and
dust repellent properties are due to hierarchical (micrometer- and nanometer-scale) surface
morphological structures, usually made of hydrophobic substances. Artificial
superhydrophobic surfaces are also considered for anti-icing coatings of airplane wings.[1-2]
A superhydrophobic hierarchical structure on epoxy resin and nanoparticles
composite surface was obtained, by replication three kind of template with micron-sized welldefined surface topography. The composite surface was modified with hydrophobic
fluoropolymer thin films, synthesized and deposited in bath modification. The influence of
surface topography on the hydrophobic properties of obtained and modified replicas was
investigated. The chemical structure of deposited fluoropolymer was examined using the
FTIR spectroscopy. The topography of modified surfaces was characterized using the
scanning electron microscopy (Fig. 1.). Water contact angles and sliding angles of obtained
materials were measured to verify their hydrophobic properties.
As a result lotus-like superhydrophobic materials were obtained, with dual surface
structure, the water contact angle of 169° and the sliding angle below 10°.
Fig. 1. SEM image of modified epoxy resin nanocomposite replica with hexagonal
oriented microstructures. Water contact angle was about 169°.
This work was supported by Polish Ministry of Science and Higher Education, Grant No: 2011/03/N/ST8/05879.
[1] K. Koch, B. Bushan, W. Barthlott Progress in Materials Science 2009, 54, 137-178;
[2] M. Ma, R. M. Hill, Roman, Current Opinion in Colloid & Interface Science 2006, 11, 193-202
- 137 -
Pt/SnO2, platinum complex,
immobilized catalyst, Karstedt catalyst
AGNIESZKA MARTYLA*, ROBERT PRZEKOP**
*
Institute of Non Ferrous Metals, Branch in Poznan, Central Laboratory of Batteries and
Cells, Forteczna Str. 12, 61-362 Poznan.
**
Advanced Technology Center AMU, A. Mickiewicz University,
Grunwaldzka Str. 6, 60-780 Poznan
PLATINUM(0)-1,3-DIVINYL-1,1,3,3-TETRAMETHYLDISILOXANE COMPLEX
AS A Pt SOURCE FOR Pt/SnO2 CATALYST
Pt/SnO2 catalysts are widely used for industrial processes, catalytic oxidation of
carbon monoxide, hydrogenation process, electrocatalysis [1,2,3]. The immobilized Karstedt
catalyst was used for hydrosilylation reaction [4]. In this study we used platinum (0) -1,3divinyl-1,1,3,3-tetramethyldisiloxane complex (Fig. 1) as a precursor of metal for Pt/SnO2
catalyst synthesis. Tin (IV) oxide was obtained by sol-gel process using tin (IV) acetate. SnO2
is an excellent precursor for the synthesis of sol-gel for the binary oxide systems [5]. We
examined the stability of this complex. After drying the gel at room temperature, heat
treatment was provided to obtain small groups of platinum metal. The resulting systems
containing a platinum complex (0) were characterized by transmission electron microscopy,
XRD studies, FT-IR spectroscopy and thermal gravimetric analysis.
Fig. 1 Platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex - Karstedt Catalyst
References:
[1] G. Incera Garrido, F.C. Patcas, G. Upper, M. Turk, S. Yilmaz, B. Kraushaar-Czarnetzki,
Applied Catalysis A: General 338 (2008) 58.
[2] K. Liberkova, R. Touroude, J. Mol. Catal. A: Chem. 180 1 (2002) 221.
[3] P. Zhang, S.-Y. Huang, B. N. Popov, J. Electrochem. Soc. 157 8 (2010) 1163.
[4] F. Faglioni, M. Blanco, W. A. Goddard, D. Saunders, J. Phys Chem. B 106 (2002) 1714.
[5] P. Kirszensztejn, A. Szymkowiak, P. Marciniak, A. Martyla, R. Przekop, Applied
Catalysis A: General 245 (2003) 159.
- 138 -
Pt/SnO2, small metal particles,
electrocatalyst, fuel cells
AGNIESZKA MARTYLA*, ROBERT PRZEKOP**
*
Institute of Non Ferrous Metals, Branch in Poznan, Central Laboratory of Batteries and
Cells, Forteczna 12, 61-362 Poznan.
**
Advanced Technology Center AMU, A. Mickiewicz University,
Grunwaldzka 6, 60-780 Poznan
TIN (IV) ACETATE AS A PRECURSOR FOR SOL-GEL SYNTHESIS OF Pt/SnO2
CATALYST FOR FUEL CELLS APPLICATIONS
SnO2 was reported as the catalyst to enhance the activity of the platinum catalyst for
methanol and ethanol electrooxidation [1,2]. Doped SnO2 is one of the most promising
materials of catalyst supports for alkaline fuel cells due to its chemical stability and the high
promoting effect [3]. In this study, tin (IV) acetate was used as a gel precursor of tin oxide
(IV). Application sol-gel technique allows to obtain mesoporous oxide structures and
consequently may affect the stabilization of small particles of metallic phase [4]. Platinum
crystallite size plays a key role in catalysis and electrochemistry [5]. It is equally important to
ensure the stability their size during the work of a catalyst. In this study we obtained Pt/SnO2
catalysts with different metal content, H2PtCl6 as a precursor of the metallic phase was used.
An aqueous solution of hexachloroplatinic acid causes a rapid crosslinking, tin (IV) and
precipitated colloidal SnO2. The aim of the study was to determine the effect of the
concentration of Pt in the media, and the effect of the heat treatment on the metal crystallite
size on the surface of catalysts. The resulting systems were characterized by textural
properties, transmission electron microscopy and XRD studies. The drying and heat treatment
of the gel technique Pt/SnO2 were characterized by ATR/FT-IR and thermal gravimetric
analysis.
Fig. 1. SnO2 gel obtained by hydrolysis of alcoholic solution of tin (IV) acetate.
References:
[1] Z. Liu, B. Guo, L. Hong, T.H. Lim Electrochem. Commun., 8 (2006) 83.
[2] E. Higuchi, K. Miyata, T.Takase, H. Inoue, J. Power Sources, 196 (2011) 1730.
[3] H.L. Pang, X.H. Zhang, X.X. Zhong, B. Liu, X.G. Wei, Y.F. Kuang, J.H. Chen J. Colloid Interface
Sci., 319 (2008) 193.
[4] P. Kirszensztejn, A.Szymkowiak, R. Przekop, E. Mackowska, Polish J. Envir. Stud., 15 6a (2006) 74.
[5] I. Alonso-Lemus, Y. Verde-Gómez, L. Álvarez-Contreras, Int. J. Electrochem. Sci., 6 (2011) 4176. URNAL
OF APPLIED ELECTROCHEMISTRY 20 (1990) 537-5
- 139 -
lithium-manganese oxide, spinel, LiMn2O4, nanocrystalline powder,
cathode material, lithium-ion batteries
MONIKA MICHALSKA*, BARTOSZ HAMANKIEWICZ**/***, DOMINIKA
ZIÓLKOWSKA****, MICHAŁ KRAJEWSKI**, MARIUSZ ANDRZEJCZUK*****,
LUDWIKA LIPIŃSKA*, RYSZARD DIDUSZKO*, ANDRZEJ CZERWIŃSKI**/***
*
Institute of Electronic Materials Technology, Wólczyńska 133, 01-919 Warsaw, Poland
Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland
***
****
Faculty of Physics, University of Warsaw, Hoża 69, 00-681 Warsaw, Poland
*****
Faculty of Materials Engineering, Warsaw University of Technology,
Wołoska 141, 02-507 Warsaw, Poland
**
NANOCRYSTALLINE LiMn2O4 POWDER OBTAINED USING MODIFIED
SOL-GEL SYNTHESIS AS A CATHODE MATERIAL FOR Li-ION BATTERIES
Lithium-ion secondary (rechargeable) batteries have been commonly used in many
portable electronic devices, such as: cell phones, notebooks, tablets, ipods, media players, as
well as in hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), owing to
its high energy density and working voltage, long lifecycle, small dimensions and weight.
Lithium manganese oxide (LiMn2O4) of spinel structure is very promising cathode material
for rechargeable lithium ion batteries. This compound has several advantages which make it
an excellent replacement for layered Ni or Co oxides. These include, among others, low cost
and easiness in preparation, non-toxicity, high discharge potential (4 V vs. lithium metal),
reasonable capacity of 120 mAh/g, high-energy density and low self-discharge. The
electrochemical properties of LiMn2O4 (LMO) spinel strongly depend on synthesis method
and as a result on structural and morphological properties of obtained materials.
There are a lot of low temperature (LT) wet chemical syntheses like i.e. Pechinni, coprecipitation, hydrothermal, microemulsion but sol-gel method is the most effective way for
preparation of homogeneous powders of high surface area, which enhance the performance of
the electrode. Sol-gel synthesis has some advantages, such as good stoichiometric control and
production of submicron-sized particles with narrow particle-size distribution, low calcination
temperature and relatively shorter processing time.
Also it is well known that physico-chemical properties of oxide powders strongly
depend on the complexing agent used in the sol-gel method. This is a very important point in
sol-gel synthesis to choose the proper complexing agent which allows to receive pure
nanocrystalline powder with desired structure and electrochemical properties.
In this work, lithium manganese oxide (LiMn2O4) powders were synthesized via modified solgel method using citric acid as a main complexing agent with i.e. acetic acid or ethylene
glycol as a second complexing agents.
The crystal structures of all powders were characterized by X-ray powder diffraction
(XRD) and Raman spectroscopy. The particle size and morphology were observed by: SEM,
HRSEM, TEM. The electrochemical properties were investigated using a three-electrode
(SWAGELOK® type) electrochemical cell with Li metal foil as a reference and counter
electrode and working electrode made of LMO. Lithium hexafluorophosphate LiPF6 dissolved
in mixture of EC:DMC = 1:1 was used as an electrolyte. The porous polymer Celgard® 2400
was applied as the separator.
Acknowledgments
This work was supported by The National Centre for Research and Development through the research grant PBS1 (contract
no. PBS1/A1/4/2012). Monika Michalska would like to thank for the scholarship awarded by the Mazovia Voivodship Office.
- 140 -
lithium-manganese oxide, spinel, LiMn2O4, ceramic oxide coatings,
cathode material, lithium-ion batteries
MONIKA MICHALSKA*, LUDWIKA LIPIŃSKA*, BARTOSZ HAMANKIEWICZ**/***,
DOMINIKA ZIÓLKOWSKA****, MICHAŁ KRAJEWSKI**,
MARIUSZ ANDRZEJCZUK*****, ANDRZEJ CZERWIŃSKI**/***
*
Institute of Electronic Materials Technology, Wólczyńska 133, 01-919 Warsaw, Poland
Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland
***
****
Faculty of Physics, University of Warsaw, Hoża 69, 00-681 Warsaw, Poland
*****
Faculty of Materials Engineering, Warsaw University of Technology,
Wołoska 141, 02-507 Warsaw, Poland
**
THE EFFECT OF CERAMIC COATINGS ON ELECTROCHEMICAL
PERFORMANCE OF LIMN2O4 NANOPOWDER
Lithium manganese oxide (LiMn2O4) of spinel structure has been considered to be
the most promising cathode material for Li-ion batteries, because of low cost and easy
preparation, high discharge potential (4V vs. Li metal) and good safety compared with the
layered lithium cobalt LiCoO2 or lithium nickel LiNiO2 oxides. It is also environmentally
friendly. However, LiMn2O4 electrodes suffer from capacity fading during charge-discharge
cycles, at the 4V potential (vs. Li/Li+) region, especially at elevated temperature (50-60°C),
which limits the application in commercial Li-ion batteries. The capacity loss has been
ascribed to three main factors: (1) dissolution of Mn2+ ions; (2) Jahn-Teller (J-T) distortion
effect; (3) decomposition of organic solvents in electrolyte. Hence, many researchers have
attempted to synthesize: (1) doped transition or non-transition metal ions on Mn-sites; (2)
surface coated with metal or ceramic oxides to minimize the surface area of LiMn2O4
contacting with the electrolyte.
In this work, we investigated and compared the electrochemical performance of
LiMn2O4 nanopowder coated by ceramic oxides (like i.e. CeO2, La2O3). The low temperature
chemical synthesis (LTCS) was used to modify the surface grains of pristine lithium
manganese oxide powder.
The effect of the ceramic coatings on LMO nanopowders were characterized by Xray powder diffraction (XRD) and Raman spectroscopy. The particle size and morphology
were observed by: SEM, HRSEM, TEM. The electrochemical properties were also
investigated of pristine and surface modified LiMn2O4 powder.
Acknowledgments
This work was supported by The National Centre for Research and Development through the research grant
PBS1 (contract no. PBS1/A1/4/2012). Monika Michalska would like to thank for the scholarship awarded by the
Mazovia Voivodship Office.
- 141 -
nanotechnology, chemical synthesis, electron microscopy,
cement mortar, testing the strength
SYLWIA MIJOWSKA*, ELŻBIETA HORSZCZARUK*, EWA MIJOWSKA**,
KRZYSZTOF CENDROWSKI**, PAWEŁ SIKORA*
*
West Pomeranian University of Technology, Department of Civil Engineering and
Architecture
**
West Pomeranian University of Technology, Institute of Chemical and Environmental
Engineering
STUDY ON THE MECHANICAL PROPERTIES OF CEMENT MORTARS
MODIFIED WITH SILICA NANOSPHERES WITH DIFFERENT MORPHOLOGY
Widespread application of nanotechnology in construction is only a matter of time.
There are many published studies on the effects of nanoparticles on the properties of cement
mortar and concrete. Research of composites modified with nanosilica are popular due to the
widespread use of microsilica, which is of inestimable importance in improving the strength
of cement composites. It was also found with the decrease of particle size, and thereby
increasing the surface area, increasing the value of the compressive strength of test samples.
The aim of the presented study is to reveal the flexural and compressive strength of
cement mortars modified with two types of silica nanostructures: silica nanospheres with
mesoporus shell (m-SiO2) and solid silica nanospheres without mesoporus shell (n-SiO2).
Both types of nanomaterials have a similar diameter, but the specific surface area of m-SiO2
was significantly. This is due to the presence of pores created in the mesoporous layer.
Applied nanosilica was administered in aqueous solution to cement and aggregate
(sand). Flexural and compressive strength studies were taken after 28 days. Silica
Nanospheres and mesoporous silica nanospheres additives in an amount of 3 wt% and 5 wt%
by weight result in an increase of compressive strength and flexural strength of cement
mortars. Based on the study the optimal content of silica nanoparticles was determined to be
3 wt%.
- 142 -
xerographic printer, nanometer particle,
occupational exposure
URSZULA MIKOŁAJCZYK, STELLA BUJAK-PIETREK, IRENA SZADKOWSKASTAŃCZYK
Department of Environmental Health Hazards, Nofer Institute of Occupational Medicine,
91-348 Lodz, Poland
XEROGRAPHIC PRINTER AND XEROGRAPHY PROCESS - DOES IT RELEASE
NANOMETER PARTICLES INTO THE ENVIRONMENT?
Aim of communication
Some of the recent studies revealed that office equipment such as xerographic printer or laser
printers can emit particles with nanometer dimensions. The particles are released from the
toner in the machine under the influence of higher temperature. It was also found that the
nanometer particles released from xerography machines or laser printers very easily absorbed
into the alveoli, which can pose a risk to human health. This study was designed to assess
potential rise the number concentration, surface area and mass of particles released during
operation of xerographic printer.
Methods
The study was carried out at the xerography service before the start of the working day, and
after turn on the device.
Condensation Particle Counter (TSI model 3007-2) was used to determine the number
of particles in a given volume of air in the 10-1000nm rage (in particles/cm3). AeroTrak 9000
(TSI) – was used to determine the surface area concentration of particles potentially deposited
in the alveolar (A) and tracheo-bronchial (TB) region of lungs in the 10-100nm (in μm2/cm3)
DustTrak (TSI model 8534) – was used to determine size segregated mass fraction (PM1,
PM2,5, RESP., PM 10 and total dust).
Air samples were collected for 16 minutes each sample at a height of 1.5 m from the ground
in the breathing zone of workers.
Results
Before the start of the working day the average concentration of particles was 11271
particles/cm3, while after the turn on xerography printers was 12662 particles/cm3. The
surface area concentration of the particles, potentially deposited in the region A was
20,97 μm2/cm3 before start the working day and 31,31 μm2/cm3 during the xerography
machines activity. In the case of TB fraction the values were 4,75 μm2/cm3 before the start of
the working day and 7,89 μm2/cm3 during the activity. Total mass concentrations of the
particles were 0.04 mg/m3 and 0.06 mg/m3 before and during activity of xerography machines
respectively.
Conclusions
 During the xerography process the number concentration of particles (<1000nm) was
slightly elevated.
 Mass concentration of emitted particles increased 1,5-fold during analysed activity.
 During xerographic printers activity the surface area concentration of the particles was 1,5fold higher in the case of particles possibly deposited in a region A, and 2 - fold higher the
TB region.
This work was supported under grant agreement nr 5052/B/P01/2010/38.
- 143 -
hydroxyapatite,
carbon nanofibers
EWA MINIACH, AGATA ŚLIWAK, GRAŻYNA GRYGLEWICZ
Wrocław University of Technology, Department of Polymer and Carbonaceous Materials,
Faculty of Chemistry, Gdańska 7/9, 50-344 Wrocław, Poland
GROWTH OF CARBON NANOFIBERS FROM DECOMPOSITION OF METHANE
OVER Ni/HYDROXYAPATITE CATALYST
W [gCNF/gcat]
The catalytic chemical vapor deposition (CCVD) is frequently employed to synthesis
of nanostructured carbon materials. Nickel is known to catalyze the growth of carbon
nanofibers of herringbone structure. In most cases, the nickel is supported on Al2O3, SiO2,
TiO2, MgO, zeolites and activated carbon. Novel and promising catalyst support seems to be
hydroxyapatite (Ca5(PO4)3OH) which is a naturally occurring mineral.
In this work, we report the synthesis of carbon nanofibers (CNFs) by CCVD over
hydroxyapatite supported nickel catalyst (Ni/HA) using methane as a carbon source. The
catalyst containing 14 wt% of Ni was characterized by SEM-EDX, XRD, TPR and sorption of
N2 at 77 K. CCVD process was carried out at 650oC in a fixed bed of catalyst. The synthesis
time ranged from 5 min to 3 h. The morphology and structure of the resultant CNFs were
determined by SEM, HRTEM, XRD and TGA.
The Ni/HA catalyst showed a high catalytic effect for the formation of CNFs at
o
650 C. After 3 h of the process, the yield of CNF synthesis is as high as 10 gCNF/gcat (Fig. 1a).
The diameter of CNF is in the range from 20 to 80 nm regardless of the synthesis time. The
CNF length increases with the reaction time, reaching about 10 μm after 3h of synthesis (Fig.
1b). HRTEM analysis revealed that the CNF growth proceeds according to the "tip" growth
mechanism. Individual graphene layers are stacking at an angle to the fiber axis as can be seen
in Fig. 1c, giving the herringbone structure. The growth rate of CNFs is the highest for the
first 20 min of synthesis (Fig. 1a). CNF-HA composites with tailored CNF contribution are
expected to show enhanced mechanical properties which is important from point of view of
clinical application of HA as a bone implant material.
10
9
8
7
6
5
4
3
2
1
0
a
0
20
c
b
40
60
80
100 120 140 160 180
t [min]
Fig. 1. Yield of CNFs versus time (a), SEM image of CNFs obtained after 3 h of synthesis (b), HRTEM image of CNFs (c)
The research was supported by the Wrocław Research Centre EIT+ within the project “The Application of
Nanotechnology in Advanced Materials” – NanoMat (POIG.01.01.02-02-002/08), co-financed from the
resources of European Fund of Regional Development (PO IG 1.1.2)
- 144 -
supercapacitor, carbon nanofibers,
structure type
ADAM MOYSEOWICZ, AGATA ŚLIWAK, GRAŻYNA GRYGLEWICZ
Wrocław University of Technology, Department of Polymer and Carbonaceous Materials,
Gdańska 7/9, 50-344 Wrocław, Poland
INFLUENCE OF GRAPHENE LAYERS ARRANGEMENT ON THE
CAPACITANCE OF CARBON NANOFIBERS
Carbon nanofibers (CNFs) are being recognized as promising type of carbon
material, which give a wide range of potential applications due to their extraordinary structure
and size. Carbon nanofibers (CNFs) consist of stacked graphene layers. The structural
diversity of CNF occurs by the anisotropic alignment of graphene layers, which results in
several different types of structures such as platelet (pCNF), herringbone (hCNF) and tubular
(tCNF). The high electrical conductivity of carbon nanofibers is the most interesting property
in point of view of electrochemical application.
This work presents the study on the electrochemical properties of homogenous and
well-defined structured carbon nanofibers. CNFs were synthesized by catalytic chemical
vapor deposition (CCVD) from different carbon sources using nickel and iron catalysts. The
morphology and structure of CNFs were characterized by SEM and HRTEM. Textural
characteristics of the CNFs were determined by N2 sorption at 77 K. Electrochemical
measurements were carried out in a voltage range from 0 to 0.8 V using 6 M KOH as an
electrolyte.
The CNFs with different type of structure were obtained, Fig. 1a-c. The diameter of
CNFs was in the range from 10 to 60 nm. An increase in the nanofiber diameter resulted in a
decrease in the porosity development. The capacitance value for the studied CNFs was
between 4 and 26 F/g at 10 mV/s, with the highest value for pCNF. hCNF2, which has a range
of nanofiber diameters and BET surface area comparable to pCNF, has shown slightly lower
capacitance. The cyclic voltammetry results were confirmed by galvanostatic measurements.
At 0.5 A/g the capacitance value was 4, 11, 18 and 21 F/g for tCNF, hCNF1, hCNF2 and
pCNF respectively (Fig. 1d). There is no correlation between CNF structure type and the
resistance value which ranges from 0.40 to 0.65 Ω.
Summarizing, the capacitance properties of CNF are related not only to the graphene
layers arrangement and the surface area but also to the nanofiber diameters.
(a)
30
(c)
(b)
tCNF
hCNF1
hCNF2
pCNF
25
C, F/g
20
(d)
15
10
5
0
0.1
1
i, A/g
10
Fig. 1. HRTEM images of tCNF (a), pCNF (b), hCNF (c) and specific capacitance vs. current load for different CNFs (d).
The research was supported by Wrocław Research Centre EIT + within the project “The Application of
Nanotechnology in Advanced Materials”-NanoMat (POIG.01.01.02-02-002/08) financed by the European
Regional Development Fund (Operational Programme Innovative Economy, 1.1.2)
- 145 -
carbon nanotubes, catalytic processes, transition metals,
chemical vapor deposition
URSZULA NARKIEWICZ, AGNIESZKA KACZMAREK, ANNA JĘDRZEJEWSKA,
IWONA PEŁECH
West Pomeranian University of Technology, Szczecin, Institute of Chemical and
Environment Engineering, Pulaskiego 10, 70-322 Szczecin, Poland
PREPARATION AND CHARACTERIZATION OF MULTI-WALLED CARBON
NANOTUBES OBTAINED ON THE TRANSITION METAL CATALYSTS
One of the most popular method to obtain carbon nanotubes is catalytic chemical
vapor deposition method, which is characterized by a simple experimental system, easy
available reagents and is very attractive for mass production. This technique is based on the
hydrocarbons decomposition on the metallic catalysts. Heterogeneous catalysts are usually
supported. It means that the catalysts are dispersed on a carrier that enhances the effectiveness
or minimizes their cost. Sometimes the support is merely a surface on which the catalyst is
spread to increase the surface area. More often the support and the catalyst interact affecting
the catalytic reaction. Supports are porous materials with a high surface area, most commonly
alumina or various kinds of carbon. Specialized supports include silicon dioxide, titanium
dioxide or calcium carbonate.
Generally, to provide the active catalyst with the desired stability, powder catalysts
used for CNTs growth are supported on hard-to-reduce oxides (i.e. alumina, silica or titanium)
to minimize the metal particles size. These supported catalysts are successfully used in largescale production of carbon nanotubes, but after synthesis require too aggressive purification
treatments that cause damages of CNTs and are not always effective. For this reason
synthesizing unsupported powder catalysts with well defined and uniform dimensions of the
particles it is a goal to be pursued.
In this work preparation of unsupported catalysts and their application to the multiwalled carbon nanotubes synthesis is presented. Iron, cobalt and bimetallic iron-cobalt
catalysts were obtained by co-precipitation of iron and cobalt ions followed by solid state
reaction. Although metal particles were not supported on hard-to-reduce oxides, this catalysts
showed nanometric dimensions. The catalysts were used for the growth of multi-walled
carbon nanotubes by chemical vapor deposition method. Synthesis was conducted under
ethylene – argon atmosphere at 700°C. The Fe-Co-based powder catalyst revealed the highest
activity, larger carbon amounts were obtained than using the pure iron or cobalt catalyst.
Obtained catalysts and carbon materials after synthesis were characterized using scanning
electron microscopy (SEM), X-ray diffraction method (XRD), Raman spectroscopy and
thermogravimetric analysis.
This work was supported by project: LIDER/25/58/l-3/11/NCBR/2012 financed by The National Centre for
Research and Development
- 146 -
carbon nanotubes, chemical vapor deposition,
microwave enhanced purification, acid digestion
URSZULA NARKIEWICZ, AGNIESZKA KACZMAREK, ANNA JĘDRZEJEWSKA,
IWONA PEŁECH
West Pomeranian University of Technology, Szczecin, Institute of Chemical and
Environment Engineering, Pulaskiego 10, 70-322 Szczecin, Poland
REMOVAL OF METAL PARTICLES FROM CARBON NANOTUBES USING
CONVENTIONAL AND MICROWAVE METHOD
A number of methods for the synthesis of carbon nanotubes (CNTs), among others:
chemical vapor deposition (CVD), electric arc discharge or laser sputtering of graphite has
been developed. One of the most commonly used method is the chemical vapor deposition,
which is simple, cheap and very attractive for mass production. The final product contain
various contaminants in the form of catalyst particles and by-products of synthesis. A sample
can be composed of amorphous carbon, carbon nanofibers or encapsulates, which have a
metal core surrounded by graphite layers. Therefore after synthesis the purification of carbon
nanotubes is usually necessary. All purification methods can be divided into two groups. First
group involves chemical methods like gas phase oxidation, gas phase reduction, liquid phase
oxidation and electrochemical oxidation. The physical methods are: filtration, solubilisation
with functional groups and high temperature annealing. The best results are obtained using
combination of two kinds of methods. In the available papers many CNTs purification
techniques are described, e.g. acid reflux, oxidation and filtration, but the majority of these
methods cannot be successfully applied to CNTs produced using CVD method because they
are unable to the remove catalyst particles and other impurities. Additionally these method are
time-consuming. An alternative route to the purification of carbon nanotubes can be a
microwave assisted acid one. It is a promising technology for large-scale purification,
avoiding long processing times or multiple stages, utilizing minimal acid volumes and
achieving high purity of carbon material.
In this work purification of multi-walled carbon nanotubes was studied. As a raw
material CNTs obtained on the iron, cobalt or iron-cobalt catalysts without support were
applied. Two methods of the purification of carbon nanotubes were employed: acid digestion
under reflux and microwave assisted acid purification. Microwave assisted acid purification
method demonstrates significant efficiency improvements over traditional acid reflux in nitric
acid. The samples before and after the treatment were characterized using different
techniques. The removal degree of metal particles was determined using a thermobalance.
The thermogravimetric analysis was performed on DTA-Q600 SDT TA Instruments
apparatus with the heating rate of 10°C/min from room temperature to 900°C in air. The
phase composition of the samples was characterized by X-ray diffraction (XRD) analysis
(X‟Pert PRO Philips diffractometer) using a CuKα radiation. Raman measurements were
obtained using excitation laser lines 785 nm (1.58 eV) with a Renishaw InVia Raman
Microscope spectrometer.
This work was supported by project: LIDER/25/58/l-3/11/NCBR/2012 financed by The National Centre for
Research and Development
- 147 -
ta-C growth mechanisms, ta-C characterizing
Nanotechnologic Application Perspectives
STÉPHANE NEUVILLE
Tetrahedral Carbon Engineering, 1 rue du Gal de Gaulle, F-77165 CUISY (France),
Tel. +33(0)1 64 36 14 07 Mob. +33(0)6 45 86 01 48,
e-mail: [email protected]
APPLICATION PERSPECTIVE FOR TETRAHEDRAL AMORPHOUS
CARBON COATINGS
Within the wide range of carbon materials and associated coatings, the denser tridimensional more stable tetrahedral amorphous carbon (ta-C) combines actually a high
number of interesting simultaneous superior material properties, in contrast to first generation
DLC hard carbon coatings and which none of presently other known coating materials has.
The ta-C materials can be produced in form of very thin films corresponding to a quasi-two
dimensional sp3 atomic multilayers and which are expected to present in some case
advantages over graphene layers especially concerning adhesion strength, homogeneity and
larger windows of optoelectronic properties. However, these can only be achieved when the
right processes parameters and right coating devices are used to produce them and for which
appropriate extended fundamentals have to be considered. Reviewing newly developed
quantum electronic fundamentals on sp3 atomic rearrangement and using a new more univocal
engineering Raman nomenclature, we describe an engineering methodology with which the
ta-C coating properties can be optimized and which concerns for instance photovoltaic and
glassfiber encapsulating and electrochemical applications.
- 148 -
rozkład amoniaku, nanorurki węglowe,
katalizatory
KATARZYNA OWODZIŃ, ZOFIA LENDZION-BIELUŃ, URSZULA NARKIEWICZ
Chemicznej Nieorganicznej i Inżynierii Środowiska, ul. Pułaskiego 10, 70-322 Szczecin
BADANIE AKTYWNOŚCI NANORUREK WĘGLOWYCH OTRZYMANYCH
NA KATALIZATORZE ŻELAZOWO-KOBALTOWYM W REAKCJI
ROZKŁADU AMONIAKU
Reakcję rozkładu amoniaku przeprowadza się w celu otrzymania czystego wodoru,
który może zostać wykorzystany jako ekologiczne paliwo [1-5]. W reakcji rozkładu amoniaku
stosuje się katalizatory metaliczne, jak na przykład żelazo czy kobalt [6]. W literaturze
opisano także możliwość zastosowania materiału węglowego w reakcji rozkładu amoniaku
[7].
Celem pracy było sprawdzenie aktywności nanorurek węglowych otrzymanych
metodą CVD, gdzie zastosowano katalizatory żelazowo-kobaltowe o różnym stosunku metali,
w reakcji rozkładu amoniaku. Katalizatory te syntezowano metodą współstrącania z
roztworów azotanów żelaza i kobaltu. Następnie poddano je procesowi nawęglania etylenem
w temperaturze 700°C. Otrzymany materiał węglowy zawierał cząstki katalizatora.
Pomiar aktywności katalizatorów w reakcji rozkładu amoniaku przeprowadzono w
reaktorze różniczkowym umożliwiającym jednoczesny pomiar zmiany masy oraz analizę fazy
gazowej. Proces rozkładu amoniaku przeprowadzono pod ciśnieniem atmosferycznym w
zakresie temperatur od 500 do 600oC. Przed pomiarem aktywności katalizator poddano
redukcji wodorem w temperaturze 500oC.
Otrzymywane w trakcie badań próbki katalizatora oraz materiał węglowy
scharakteryzowano metodami: ICP-OES, dyfrakcja promieniowania rentgenowskiego,
termograwimetria oraz skaningowa mikroskopia elektronowa.
Literatura:
[1] Lendzion-Bieluń, Z.; Pelka, R.; Arabczyk, W. Catal. Lett., 2009, 129, 119-123
[2] Lendzion-Bieluń, Z.; Pelka, R.; Kiełbasa, K.; Arabczyk, W. Polish patent application no 397426
[3] Schlogl, R. Angew. Chem., Int. Ed. 2003, 42, 2004–2008
[4] Christensen, C. H.; Johannessen, T.; Sørensen, R. Z.; Nørskov, J. K. Catal. Today 2006, 111, 140–144
[5] Zhang, J.; Comotti, M.; Schu¨th, F.; Schlo¨gl, R.; Su, D. S. Chem. Commun. 2007, 1916–1918
[6] Lendzion-Bieluń, Z. Arabczyk, W. Catal. Today DOI: 10.1016/j.cattod.2012.12.014
[7] Zhang, J.; Muller, J; Zheng, W.; Wang, D.; Su, D.; and Schlogl, R. Nano Lett. 2008, 8, 2738-2743
- 149 -
all-trans β-carotene, 15-cis β-carotene, room temperature ionic
liquids, photoacoustic spectroscopy, excited state deactivation
KRZYSZTOF PAWLAK*, JANUSZ SZURKOWSKI**, ANDRZEJ SKRZYPCZAK***,
GRAZYNA E. BIALEK-BYLKA*
*
Poznan University of Technology, Faculty of Technical Physics,
Nieszawska 13A, 60-965 Poznan, Poland
**
University of Gdansk, Institute of Experimental Physics,
Wita Stwosza 57, 80-952 Gdansk, Poland
***
Poznan University of Technology, Faculty of Chemical Technology,
Maria Skłodowska-Curie Sq. 2, 60-965 Poznan, Poland
EXCITED STATE DEACTIVATION OF ALL-TRANS AND 15-CIS- -CAROTENE IN
IONIC LIQUIDS WITH AND WITHOUT METHYLENOXY GROUP FOLLOWED
BY THE PHOTOACOUSTIC SPECTROSCOPY
β-Carotene is a very important molecule in photosynthesis, pharmacy, medicine and
cosmetology. All-trans and 15-cis-β-carotene isomers play very important functions in
photosynthesis as light harvester and photoprotector, respectively. β-Carotene in ionic liquids,
so called „green solvents‟, behaves from spectroscopic point of view very similar as in situ.
Room temperature ionic liquids with and without methylenoxy group were
synthesized and carefully purified for our experiment.
The photoacoustic spectroscopy was applied to study the non-radiative transitions of
the excited states of both all-trans and 15-cis-β-carotene isomers in ionic liquids. The
photoacoustic measurement of β-carotene in traditional solvent, for example n-hexane, is not
accurate due to the fast evaporation of the solvent, which leads to the concentration
fluctuation. Room temperature ionic liquids are good medium for photoacoustic study
because of their high thermal stability and low volatility.
The photoacoustic and absorption spectra of all-trans and 15-cis-β-carotene, at
concentration range of 25 M and 80 M, in ionic liquids with and without methylenoxy
group were recorded.
The non-radiative deactivations of both β-carotene isomers in ionic liquids occur via
1
+
1 Bu state but in a case of 15-cis-β-carotene by an additional path 11Ag+ ('cis' peak)
transition. The non-radiative deactivation of the excited states of all-trans and
15-cis-β-carotene isomers depends on the presence of the methylenoxy group in the ionic
liquid structure.
- 150 -
gallim nitride, nanowires,
photoluminescence
PAULINA S. PERKOWSKA*, ANNA RESZKA**, KRZYSZTOF P. KORONA*,
ANDRZEJ WYSMOŁEK*, ZBIGNIEW R. ZYTKIEWICZ**
*
University of Warsaw, Faculty of Physics, Institute of Experimental Physics,
Hoża 69, 00–681 Warsaw, Poland
**
Institute of Physics, Polish Academy of Sciences,
al. Lotnikow 32/46, 02–668 Warsaw, Poland
PHOTOLUMINESCENCE OF SINGLE GALLIUM NITRIDE NANOWIRES
PL Intensity (arb. u.)
Due to excellent physical and optical properties gallium nitride (GaN) is an
important semiconductor for current optoelectronic technology. Nowadays mainstream
experiments on GaN are focused on low dimensional structures, like quantum well, quantum
dots, microcavities and nanowires (NWs). In the case of nanowires, the role of surface effects,
electric fields fluctuations and defects in optical processes is still not well understood.
In this communication low
temperature photoluminescence (PL),
time-resolved
photoluminescence
(TRPL) and electron microscopy (SEM)
experiments performed on ensemble of
GaN Nws as well as on single GaN NWs
deposited on various substrates including
silicon, gallium arsenide and copper are
GaN NWs/Cu x1
presented. Emission was observed in the
GaN NWs/Si x1
GaN NWs/GaAs x20
energy for the range from 3,3eV to 3,5eV.
3,44
3,45
3,46
3,47
3,48
The GaN nanowires were grown by MBE
Energy (eV)
on Si(111) (a length of about 1-2 μm and Fig. 1: Photoluminescence spectrum at low temperature
a diameter of 30-50 nm). Then they were
(4 K) gallium nitride nanowires.
cut off from the Si substrate using
methanol ultrasonic bath and deposited on a desired substrate. SEM studies showed that main
part of NWs formed self-arranged groups on the substrate. However, also single NWs could
be observed.
The low temperature photoluminescence spectra for nanowires on different
substrates are plotted in Fig. 1. The position of the main peak compared with that in the bulk
material indicates its excitonic origin. The difference in the intensity of photoluminescence
for nanowires deposited on different substrates was clearly observed. NWs deposited on
gallium arsenide and silicon platforms gave a very weak emission. The most interesting
results were observed for nanowires deposited on a copper plate. In the energy range of 3,45
eV narrow emission lines with a width of 0,3 meV were visible. Their origin will be discussed
in terms of excitons emission related to single acceptors and defects located at different
depths from the surface of the nanowire.
3,445
3,450
3,455
3,460
This work was supported by the Foundation for Polish Science International PhD Projects Programme cofinanced by the EU European Regional Development Fund.
- 151 -
JERZY PESZKE*, WOJCIECH CIESIELSKI**
*
University of Silesia, Faculty of Mathematics, Physics and Chemistry,
**
Institute of Chemistry and Environment Protection, Jan Dlugosz University,
al. Armii Krajowej 13/15, 42-200 Częstochowa, Poland,
STARCH AND NANOTUBES
Carbon nanotubes have found numerous applications in chemistry and physics on
account of their anisotropic shapes. Nanotubes have unique physical properties, for example,
high thermal and electrical conductivities.
Amylose form many inclusion complexes with a wide range of molecules. Amylose
is composed of glucopyranose residues, and have a left-handed helical conformation in
aqueous solution.
It forms inclusion complexes as a result of hydrophobic interactions between guest
molecules and the cylindrical cavity inside the amylose helix, which typically comprises
around six glucopyranose resides per turn.
The cavity of amylose helix is a variable dimension that allows the biopolymer to
adapt itself and accommodate the variety of differently proportioned guest molecules with
which it is known to complex.
Amylose can adjust its helical dimensions according to the size of the guest, we have
carried out molecular dynamics (MD) calculations to probe the nature of the interactions
between nanotubes and an amylose fragment (eight glucopyranose residues).
These calculations inform about formation of a supramolecular complex in which the amylose
wraps itself helically around the nanotube.
SCF LCAO MO AM1 and PM3 calculations with Cache program (evaluation version)
were carried out for many systems: nanotubes linked and included into amylose helix. Bonding
energies and heats of formation were determined and the maps of spin and electron densities are
presented.
- 152 -
JERZY PESZKE*, WOJCIECH CIESIELSKI**, OSKAR MICHALSKI***,
DAMIAN KULAWIK**, JÓZEF DRABOWICZ**, DOROTA KRASOWSKA**
*University of Silesia, Faculty of Mathematics, Physics and Chemistry,
**
Institute of Chemistry and Environment Protection, Jan Dlugosz University,
al. Armii Krajowej 13/15, 42-200 Czestochowa, Poland,
***
Department of Chemistry and Physics, University of Agriculture,
ul. Balicka 122, 31-149 Kraków, Poland,
SYNTHESIS OF SULFODERIVATIVES OF CARBOXYLATED MWCNTS ON
SOLID STATE IN MICROWAVE FIELD
Selective decoration of multiwaled carbon nanotubes on the surface with active
chemical groups are one of important results of chemistry of MWCTS. We showed one of the
simple methods of synthesis of those structures on the mixture SiO2/MWCNTS-COOH. In
results was received sulfoderivatives of MWCNTS-COOH on the surface. Degree of
decorated by sulfone groups can be controlled by time, concentration of starting material and
concentration of reagents: H2SO4/Oleum.
Thermogravimetric (TG) and calorimetric (DSC) studies were carried out. The
weight loss steps (TG) and thermal effects (DSC) were measured using DSC–TG NETZSCH
STA 409C apparatus. The thermal decomposition was studied over a temperature range of
293–723K at a heating rate of 5K/min. All samples (about 20 mg) were heated in corundum
crucible covered with no hermetic lids. Weight loss steps (TG) and thermal effects (DSC)
were determined.
- 153 -
nanocząstki rutenu, fluorek magnezu, redukcja
chemiczna, hydrogenacja chloronitrobenzenu i toluenu
MARIUSZ PIETROWSKI, MICHAŁ ZIELIŃSKI, MARIA WOJCIECHOWSKA
Uniwersytet im. Adama Mickiewicza, Poznań, Wydział Chemii, Zakład Technologii
Chemicznej
KOLOIDALNE KATALIZATORY Ru/MgF2 DLA PROCESÓW UWODORNIENIA
CHLORONITROBENZENU I TOLUENU
Osadzanie nanocząstek metali szlachetnych otrzymanych metodami redukcji
chemicznej na powierzchni nośnika stanowi interesującą alternatywę dla tradycyjnych metod
preparatyki katalizatorów. Nanocząstki metaliczne otrzymywane metodami redukcji
chemicznej, charakteryzują się zazwyczaj większą monodyspersyjnością niż krystality metalu
na powierzchni katalizatorów otrzymanych metodą impregnacji, czy strącania-osadzania.
Prowadzić to może do zwiększenia nie tylko aktywności katalitycznej ale również do
zwiększenia selektywności do pożądanych produktów.
W niniejszej pracy nośnikiem koloidalnych nanocząstek rutenu jest fluorek magnezu,
stosowany wcześniej w takich reakcjach jak: hydrodesulfuryzacja [1], redukcja tlenków azotu
[2], uwodornienia toluenu do metylocykloheksanu [3], utlenianie CO [2]. Zaletą fluorku
magnezu jest łatwość jego preparatyki jak i niska cena stosowanych substratów [4, 5].
Katalizatory testowano w reakcji uwodornienia orto-chloronitrobenzenu (o-CNB) do ortochloroaniliny (o-CAN) i uwodornienia toluenu do metylocykloheksanu.
Nanocząstki rutenu osadzone na powierzchni fluorku magnezu charakteryzują się
wyższą aktywnością hydrogenacyjną niż analogiczne układy uzyskane przez impregnację
nośnika roztworem chlorku rutenu. Zabezpieczone przy pomocy poliwinylopirolidonu (PVP)
nanocząstki rutenu na MgF2 były 3-krotnie aktywniejsze w reakcji uwodornienia
o–CNB i 2-krotnie aktywniejsze w reakcji uwodornienia toluenu od analogicznych układów
otrzymanych metodą impregnacji chlorkiem rutenu. Wysoka aktywność układów
koloidalnych związana jest z małymi rozmiarami cząstek koloidalnych - znacznie mniejszymi
niż uzyskane metodą konwencjonalnej impregnacji. Zastosowanie metody redukcji
chemicznej przy pomocy metanolu pozwala na otrzymanie nanocząstek rutenu o wielkości od
1.6 do 2.6 nm i wysokiej monodyspersyjności.
Podziękowania
Badania wykonano w ramach projektów badawczych finansowanych przez NCN - N N204 181640 i N N204
141339.
Literatura:
[1] M. Wojciechowska, A. Wajnert, I. Tomska-Foralewska, M. Zieliński, B. Czajka, Catal. Lett. 128 (2009) 7782.
[2] J. Haber, M. Wojciechowska, M. Zielinski, W. Przystajko, Catal. Lett. 113 (2007) 46-53.
[3] M. Zielinski, M. Pietrowski, M. Wojciechowska, ChemCatChem, 3 (2011) 1653-1658.
[4] M. Wojciechowska, M. Zielinski, M. Pietrowski, J. Fluorine Chem. 120 (2003) 1-11.
[5] M. Wojciechowska, B. Czajka, M. Pietrowski, M. Zielinski, Catal. Lett. 66 (2000) 147-153.
- 154 -
silica nanoparticles, macrophages,
cytotoxicity
BŁAŻEJ POŹNIAK*, BEATA BORAK**, MARCIN ZAWADZKI***,
MIROSŁAW MILLER****
*
Katedra Biochemii, Farmakologii i Toksykologii, Wydział Medycyny Weterynaryjnej,
Uniwersytet Przyrodniczy we Wrocławiu,
**
Laboratorium Materiałów Zol-Żelowych i Nanotechnologii, Politechnika Wrocławska,
***
Katedra Medycyny Sądowej, Uniwersytet Medyczny we Wrocławiu,
****
Międzynarodowe Laboratorium Silnych Pól Magnetycznych i Niskich Temperatur PAN
we Wrocławiu
SILICA NANOPARTICLE CYTOTOXICITY ON MURINE
MACROPHAGES IN VITRO
Due to unique physicochemical and biological properties different nanostructures
received much attention as potential drug carriers. In recent years, silica nanoparticles emerge
as a promising platform for drug delivery. One reason for that is their natural biocompatibility
and dissolution in vivo. Moreover, unlike e.g. carbon nanotubes, silica nanoparticles‟
synthesis does not require the use of potentially toxic metals as catalysts. Enormous
possibilities for structure modification further contribute to their usefulness as drug delivery
systems. Although much effort was put into the development of a variety of silica
nanoparticles, the biological effects, including toxicity of these structures, is still not entirely
revealed. This is especially important for particles intended for pharmaceutical applications.
One of the most important factors affecting the circulation of nanoparticles in the bloodstream
(and thus the carried drug‟s kinetics) is the interaction with immune system with particular
regard to macrophages. The aim of the present study was to synthesize amorphous silica
nanoparticles, to describe their characteristics in cell culture medium (RPMI 1640
supplemented with 10% foetal calf serum) and to assess their effect on the viability of murine
macrophage-derived cell line (J774.E). The silica nanoparticles were obtained by the sol-gel
method with tetraethoxysilane used as a substrate. The single particle diameter determined by
the transmission electron microscopy (TEM) was 205 ± 20 nm. The hydrodynamic diameter
in water was 180 nm (PDI 0.031) and in culture medium was 247.7 nm (PDI 0.543), whereas
zeta potential in water was -27.4 mV and in culture medium was -10.8 mV. Apart from silica
and oxygen, the elemental analysis has identified the presence of carbon, and traces of sodium
and sulphur. The particles‟ effect on cellular viability was determined by the 3-(4,5dimethylothiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) reduction assay. Strong time
and concentration dependence in cytotoxicity was shown. The inhibitory concentration for
50% of cells (IC50) was 41.3 ± 2.4 µg/mL , 34.4 ± 0.7 µg/mL and 14.7 ± 2.4 µg/mL after 24,
48 and 72 hours of exposition, respectively. The distinct time dependence in cytotoxicity
suggests particle sedimentation as an important factor that influences the biological response
to nanoparticles in vitro. Further studies should focus on identifying features that reduce silica
nanoparticle cytotoxicity and enforce their potential for becoming a therapeutic tool in future.
- 155 -
MARTA PRZEŚNIAK, MARCIN ŁAPIŃSKI, BARBARA KOŚCIELSKA,
WOJCIECH SADOWSKI
Politechnika Gdańska, Wydział Fizyki Technicznej i Matematyki Stosowanej, Katedra Fizyki
Ciała Stałego, ul. Gabriela Narutowicza 11/12, 80-233 Gdańsk
NANOSTRUKTURA TLENKÓW VXOY OTRZYMANYCH METODĄ ZOL-ŻEL
Ze względu na swoje właściwości, tlenki metali są w ostatnich latach obiektem
intensywnych badań. Wśród tlenków metali szczególne miejsce zajmują tlenki wanadu. Ich
unikatowe właściwości fizyczne i chemiczne, które zawdzięczają różnym stopniom utlenienia
od +2 do +5 oraz zmiennej geometrii koordynacyjnej tlenu, sprawiają, że stanowią one
fascynującą klasę materiałów. Z tego względu znajdują bardzo wiele komercyjnych
zastosowań w urządzeniach optycznych, elektrycznych, elektrochemicznych i
termochromowych.
Niniejsza praca skupia się na nanostrukturach proszków wanadu. Próbki
przygotowano metodą zol-żel. W celu przygotowania zolu zmieszano ze sobą tripropanolan
wanadylu OV(OC3H7)3 z bezwodnym alkoholem etylowym jako rozpuszczalnikiem i
acetyloacetonem. Zole były suszone w atmosferze powietrza a następnie wygrzewane w
szerokim zakresie temperatur.
Strukturę krystaliczną przygotowanych próbek zbadano metodą dyfrakcji
rentgenowskiej, natomiast morfologia próbek była obserwowana skaningowym mikroskopem
elektronowym. Następujące w materiale przemiany fazowe zostały przebadane za pomocą
analizy termicznej.
Wydaje się, że proponowana w niniejszej pracy metoda zol – żel ma duży potencjał
do przygotowywania jednowymiarowych nanostruktur tlenków metali do zastosowań
komercyjnych.
- 156 -
nanosilver, Vitis vinifera,
chemical reduction,
JOLANTA PULIT, MARCIN BANACH
Politechnika Krakowska, Wydział Inżynierii i Technologii Chemicznej, Instytut Chemii
i Technologii Nieorganicznej, ul. Warszawska 24, 31-155 Kraków
OBTAINING NANOCRYSTALLINE SILVER USING AN AQUEOUS EXTRACT OF
WHITE GRAPES (VITIS VINIFERA)
Nanosilver is known to have biocidal properties which locates it among precious
antimicrobial materials. By destroying bacteria, viruses and fungi, it is used in such industry
branches where antiseptic performance is particularly desirable. Several methods leading to
the preparation of nanosilver is known. Among the most popular are: chemical reaction, laser
ablation, method in electric arc, photochemical reduction and microwave radiation. From the
industrial point of view, the chemical reduction method is the most profitable one. It involves
mixing the solution of silver ions source with the solution of stabilizing agent and after
reaching the appropriate temperature, a solution of reducing agent is added. Carrying out this
process in conventional way, it is necessary to mix tree different compounds: silver salt,
stabilizing agent and reducer.
It was decided to find such a natural source of compounds which would deliver both
stabilizing and reducing agents. Basing on pharmacognosy, it was found out that the white
grape (Vitis vinifera) is a plant which contains such substances as polyphenols (gallic and
ellagic acids), ascorbic acid, anthocyanes, tannins, phenolic acids and sugars. These
compounds are mainly known to have antioxidant properties thus they can be used to reduce
ionic form of silver to the zero oxidation state. Besides these substances white grape contains
also mucous compounds, peptides and biopolymers. They are useful to stabilize the emerging
suspension so as not to allow to agglomerate the metallic form of silver to particles whose
size would be larger than 100 nm.
Primarily, a white grapes extraction method was developed. Studies assumed
checking out the extraction test results conducted at different conditions. Processes were
conducted in the Soxhlet extractor. In obtained extracts amounts of polyphenols, ascorbic acid
and anthocyanins have been analyzed and the effectiveness of free radical deactivation was
determined. Having given which mode involves the best extraction ratio, the chemical
reduction in order to get silver nanoparticles has been carried out. In order to perform the
synthesis, an aqueous solution of silver nitrate was mixed with the chosen white grapes
extract. The concentration of silver nitrate solution was so recalculated, to get the systems at
about 50, 275 and 500 ppm of silver. The differences in the samples were generated by the
final determination of pH value (6, 9 and 11) and samples incubation at different temperatures
(20, 40 and 60oC). The resulting suspensions were studied spectrophotometrically. Particles
sizes were determined by dynamic light scattering method (DLS) and a study on Malvern
Zetasizer Nano test-CI provided information about the electrokinetic potential, which reflects
the stability of the system.
It was possible to get stable suspensions of nanosilver obtained by using aqueous
extract of white grapes. Basing on the results of UV-Vis analyzes, DLS and SEM the most
favorable parameters of the process were determined.
By the use of renewable natural materials such a way of obtaining nanosilver
suspensions adheres the green chemistry and sustainable development principles.
- 157 -
plasmon resonance, metallic nanostructure,
nanosphere lithography
JUDYTA REĆKO, BARTŁOMIEJ J. JANKIEWICZ, MAREK STEFANIAK,
JÓZEF FIRAK, PIOTR NYGA
Institute of Optoelectronics, Military University of Technology, Warsaw, Poland,
PREPARATION OF SILVER NANOTRIANGLES BY NANOSPHERE
LITHOGRAPHY
Plasmonics is a very exciting, rapidly developing field of physics. In the center of it
is the effect of electromagnetic wave interaction with noble metal nanoparticles. These
nanostructures exhibit surface plasmon resonance – collective oscillations of metal free
electrons. This leads to electromagnetic field concentration in subwavelength regions which is
of great importance for applications such as surface enhanced Raman spectroscopy,
fluorescence enhancement, optical absorption enhancement in photovoltaic devices just to
mention a few. Moreover the spectral position of plasmon resonance can be controlled by type
of metal and shape and size of nanoparticles.
In this contribution we report arrays of silver nanotriangles fabricated on planar
substrates employing nanosphere lithography (NSL) [1-3]. In this fabrication method a
hexagonal close-packed monolayer of dielectric spheres is formed on a water-air interface.
Next it is transferred onto a substrate and acts as a mask in metal deposition process. The
voids between dielectric spheres have triangular shape. After metal evaporation in physical
vapor deposition system (Fig.1a) the mask is removed and array of metallic nanotriangles is
left on the substrate (Fig.1b). We controlled the size of nanotriangles and the spectral position
of their plasmon resonance by the diameter of spheres used for mask fabrication.
(a)
(b)
Fig. 1. Scanning electron microscope images of (a) monolayer of polystyrene spheres overcoated with Ag film,
(b) Ag nanotriangles after mask removal.
References:
[1] J. C. Hulteen, R. P. Van Duyne, J. Vac. Sci. Technol. A 13, 1553 (1995)
[2] M. Giersig, P. Mulvaney, Langmuir, 9, 3408 (1993)
[3] P. Patoka, M. Giersig, J. Mater. Chem. 21, 16783 (2011)
- 158 -
nanoparticles, electrospraying,
electronic devices
MARCIN ROSOWSKI*, B. TKACZ-SZCZESNA*, K. SOLIWODA*, A. KRASKA*,
G. CELICHOWSKI*, J. NOVÁK**, F. SCHREIBER**, G. CASULA***,
P. COSSEDDU***, A. BONFIGLIO***, J. GROBELNY*
*
Chemistry, Pomorska 163, 90-236 Lodz, Poland
**
Eberhard Karls University Tübingen, Institute of Applied Physics, Auf der Morgenstelle 10,
D-72076 Tübingen, Germany
***
University of Cagliari, Dept. of Electrical and Electronic Engineering, Piazza D'Armi,
09123 Cagliari, Italy
INCORPORATION OF GOLD NANOPARTICLES INTO THE HYBRID MEMORY
ELEMENTS BY ELECTROSPRAYING TECHNIQUE
One of the novel application of gold nanoparticles (AuNP) is their use as building
blocks for hybrid memory elements. Recently, production of non-volatile memory devices
using a combination of organic/inorganic materials i.a. AuNP, has attracted a lot of attention
in various fields of science.
In order to incorporate nanoparticles it is necessary to understand their chemical and
physical properties. Therefore, gold colloids were precisely characterized by different
methods such as: dynamic light scattering, atomic force microscopy, transmission electron
microscopy and small-angle X-ray scattering.
Well characterized nanoparticles can be deposited in dry form from water colloid by
the electrospraying technique. Here, dispersion of liquid is controlled by electrical forces.
An important advantage of this method is that the evaporation of solvent is so quick that it is
possible to deposit particles in dry condition. It can be extremely important if solvents can
cause damage solid substrate structure such as surface of components of memory devices. The
coverage of the sample can be changed by controlling different parameters of electrospraying
system e.g. the flow rate, the deposition time, the acceleration voltage, the distance between
the sprayer nozzle and the substrate, the operation mode, the nanoparticles concentration or
solvent system in sprayed solution.
The successful deposition of AuNP onto memory elements via electrospraying was
demonstrated The IV characteristics performed on the prepared devices show readily the
desired memory-effect.
Scientific work supported by MNiSW, funds for science in 2011-2014 allocated for the cofounded international project
This work was supported by FP7-NMP-2010-SMALL-4 program, project number 263073
- 159 -
PVD, nanokrystality Pd,
fulleren
JOANNA RYMARCZYK*, ELŻBIETA CZERWOSZ*, MIROSŁAW KOZŁOWSKI*,
PIOTR DŁUŻEWSKI**, WOJCIECH KOWALSKI **
*
Instytut Tele- i Radiotechniczny, ul. Ratuszowa 11, 03-450 Warszawa,
Instytut Fizyki PAN, Al. Lotników 32/46, 02-668 Warszawa
**
WPŁYW PARAMETRÓW PROCESU PVD NA BUDOWĘ, STRUKTURĘ
KRYSTALICZNĄ I MOLEKULARNĄ NANOKOMPOZYTOWYCH WARSTW C-Pd
W pracy przedstawiony został wpływ parametrów procesu wytwarzania
nanokompozytowych warstw węglowo-palladowych (C-Pd) na budowę oraz strukturę
krystaliczną i molekularną składowych elementów warstwy. Warstwy te otrzymywane są
metodą fizycznego odparowywania w próżni (PVD) z fullerenu C60 i octanu palladu.
Wszystkie warstwy wybrane do badań nanoszono na podłoża z kwarcu
polerowanego przy stałej odległości obu źródeł prekursorów warstw od podłoża d = 60mm.
Temperatura źródeł była zależna od natężenia prądów płynących przez te źródła: IC60
natężenie prądu płynącego przez źródło fullerenu oraz IPd natężenie prądu płynącego przez
źródło octanu palladu. Powstała w ten sposób warstwa nanokompozytowa C-Pd składa się z
nanoziaren palladu osadzonych w matrycy węglowej zbudowanej z różnych form
alotropowych węgla (np. ziarna fullerytu, grafitu i węgla amorficznego). Wyniki wskazują,
że w trakcie procesu osadzania w niektórych warunkach technologicznych procesu PVD
octan palladu nie rozkłada się całkowicie i obserwuję się również pozostałości tego związku
w warstwie.
Warstwy badano przy pomocy mikroskopu sił atomowych, transmisyjnego
mikroskopu elektronowego, skaningowego mikroskopu elektronowego wyposażanego w
opcję mikroanalizy (EDX - Energy Dispersive X-ray Spectroscopy) oraz fourierowskiego
spektrometru absorpcji w podczerwieni. Mikroanaliza z EDX pozwoliła na zbadanie
zawartości palladu w warstwach C-Pd. Zmiany strukturalne w warstw C-Pd w zależności od
parametrów technologicznych procesu PVD badane były metodą TEM oraz FTIR. Rys.1a, b,
c to przykładowe obrazy SEM, AFM oraz TEM, pokazujące odpowiednio topografię
wytworzonych warstw oraz nanokrystality palladu obecne w takiej warstwie. Przedstawiona
warstwa zawiera 8,5% wg. palladu, średnia wielkość nanocząstek Pd wynosi 5nm.
a
b
c
Rys. 1 Obrazy a) SEM, b) AFM oraz c) TEM w jasnym polu warstwy C-Pd zawierającej 8,5 %wag. Pd
Praca jest współfinansowana z Europejskiego Funduszu Rozwoju Regionalnego w ramach Programu Operacyjnego
Innowacyjna Gospodarka 2007-2013 (projekt pt. „Opracowanie technologii nowej generacji czujnika wodoru i jego
związków dla zastosowań w warunkach ponadnormatywnych”, umowa Nr UDA-POIG.01.03.01-14-071/08-08)
- 160 -
AFM, zol-żel, TiO2,
nanomateriały
ANDRZEJ SIKORA, AGNIESZKA HRENIAK, AGNIESZKA IWAN
Instytut Elektrotechniki, Oddział Technologii i Materiałoznawstwa Elektrotechnicznego we
Wrocławiu, ul. M. Skłodowskiej-Curie 55/61, 50-369 Wrocław
BADANIA AFM PROSZKÓW TiO2 DOMIESZKOWANYCH SREBREM
W pracy przedstawiono wyniki badań mikroskopii sił atomowych (AFM) dla
proszków TiO2 domieszkowanych srebrem. W badaniach AFM wykorzystano mikroskop
Innova firmy Bruker (wcześniej Veeco). Pomiary z wykorzystaniem dynamicznej techniki
chwilowego kontaktu, oraz metod kontaktowych, przeprowadzono w atmosferze powietrza, w
temperaturze pokojowej. Uzyskane wyniki topografii oraz właściwości mechanicznych
skorelowano ze składem oraz parametrami procesu technologicznego otrzymywania
materiałów. W procesie przetwarzania wyników pomiarowych, w celu lepszej wizualizacji
rezultatów, wykonano transformatę Inclination.
Nanomateriały niedomieszkowane i domieszkowane otrzymano za pomocą metody
zol-żel. Otrzymano poprzez modyfikację warunków syntezy pięć nanoproszków TiO2
niedomieszkowanych o różnej wielkości ziaren (od 124 do 257 nm) oraz sześć proszków TiO2
domieszkowanych Ag w różnych stosunkach procentowych domieszki AgNO3 w stosunku do
prekursora (1%, 5% i 10%). Syntezy TiO2 domieszkowanego srebrem prowadzono na dwa
sposoby. W pierwszym przypadku AgNO3 dodano na pierwszym etapie syntezy i mieszano
wszystkie składniki tj. tetraizopropoksytytan (TIPO), etanol i H2O przez 4 godziny. W
drugim przypadku podstawowe składniki syntezy mieszano 2 godziny, a następnie dodano
AgNO3 i kontynuowano mieszanie przez kolejne 2h. Zbadano wpływ ilości srebra dodanego
do TiO2 na etapie syntezy na topografię powierzchni w tym parametry chropowatości.
Topografię powierzchni scharakteryzowano poprzez określenie jej chropowatości z
wykorzystaniem współczynników Sa i Sq. Ponadto wyznaczono szerokość piku rozkładu
wysokości (Ssk) i asymetrię położenia piku rozkładu wysokości (Sku).
Wykazano wpływ metody syntezy zarówno na wielkość ziaren proszków TiO2
niedomieszkowanych jak i domieszkowanych srebrem jak i na parametry chropowatości.
Wielkość ziaren dla TiO2:Ag oszacowano za pomocą metody AFM w zakresie 33-194 nm w
zależności od ilości domieszki i metody syntezy.
- 161 -
silica mesoporous nanospheres,
cement mortar, nanocomposites
PAWEŁ SIKORA*, ELŻBIETA HORSZCZARUK*, EWA MIJOWSKA**,
KRZYSZTOF CENDROWSKI**, SYLWIA MIJOWSKA*
*
West Pomeranian University of Technology, Department of Civil Engineering and
Architecture, Poland
**
West Pomeranian University of Technology, Centre of Knowledge Based Nanomaterials
and Technologies, Institute of Chemical and Environment Engineering, Poland
EFFECT OF INCORPORATION ROUTE ON DISPERSION OF SILICA
MESOPOROUS NANOSPHERES IN CEMENT MORTAR
The uniform dispersion of nanoparticles into the cement matrix is a key issue in their
application in the field. Therefore, here we present different routes of introduction of
mesoporous silica nanospheres into the cement (route A – using acetone as a dispergant, route
B - using water as a dispergant) to study its influence on the mechanical properties of the
formed composite. It was observed that in both cases the presence of small amounts of silica
nanoparticles agglomerates does not change the mechanical properties of the cement mortars.
However, the addition of mesoporous silica nanospheres to the cement in acetone solution is
more effective and results in higher compressive and flexural strength than the sample of the
composite formed from water solution of silica nanoparticles and cement. Moreover, the
analysis of electron microscopy images allowed to reveal the mechanism of the mortar
properties enhancement via reduction of the thickness of the interfacial transition zone (ITZ)
between the cement paste and aggregate.
- 162 -
carbon nanostructures, carbon nanowalls,
low temperature plasma
ARKADIUSZ T. SOBCZYK*, ANATOL JAWOREK*/**, MAREK KLEIN***
*
Instytut Maszyn Przepływowych PAN, ul. Fiszera 14, Gdańsk
Instytut Fizyki, Akademia Pomorska, ul. Arciszewskiego 22B, Słupsk
***
Department of Chemical Technology, Faculty of Chemistry, Gdansk University of
Technology, Gdansk
**
CARBON NANOSTRUCTURES FORMED IN LOW CURRENT ELECTRICAL
DISCHARGE IN HYDROCARBONS
The aim of the research was to investigate the growth of carbon nanostructures, in
particular carbon nanowalls, in low-current electrical-discharges in hydrocarbon atmosphere.
The method is based on the decomposition of a hydrocarbon in electrically generated plasma
at atmospheric pressure. In this investigation the discharge was generated between a stainless
steel needle, and a plate made of a nickel alloy. The distance between the electrodes varied
from 2 to 5 mm. The experiments were carried out in a reactor chamber of 0.1 dm 3, made of
PMMA, in argon with cyclohexane as the carbon feedstock gas. The current of the lowcurrent high-voltage discharge was in the range of 1.4 – 2.4 mA. The discharge current was
stabilized by a high resistance (5 MΩ) in series. The products of decomposition of
cyclohexane in the electrical discharge were tested by SEM (morphology analysis), Energy
Dispersive Spectroscopy (elemental composition analysis) and Raman Spectroscopy. The
main gaseous products of cyclohexane decomposition was analysed by gas chromatography.
Initially, a thin carbon fiber is formed on the tip of needle electrode during the discharge, and
next the surface of the fiber is covered by a thin layer of carbon nanowalls. The growth of
nanowalls depends on the discharge current, the distance between electrodes, and the
concentration of hydrocarbons in argon. The advantage of using electrical discharges for the
synthesis of carbon deposits at atmospheric pressure is that the process occurs for relatively
low power (the mean power delivered to the discharge is about 2 W).
- 163 -
safe nanotechnology use,
risk assessment
JOANNA SOBCZYK, IWONA MALKA, ANNA ŚWIDERSKA-ŚRODA,
WITOLD ŁOJKOWSKI
Institute of High Pressure Physics, Polish Academy of Sciences
RESPONSIBLE USE OF NANOTECHNOLOGY AND RISK ASSESSMENT
Safe implementation of nanotechnology occurs as multidisciplinary task and research
investigation on the border of chemistry, nanomaterial engineering, medicine, biology and
environmental sciences. Unique and diverse properties of first generation nanomaterials as
well as engineered nanoparticles need very deep recognition of possible dynamic
physicochemical impact in causing biological injury, for example by chemical activities,
production of free radicals or magnetic fields. Size of the nanoparticles can have major
influence on their interactions with nano/bio interfaces, very small particles can easily
penetrate through borders inside the body, while big agglomerates can have toxicological
impact because of their surface chemistry. Very interesting and intriguing are investigations
on lifecycle analyses and environmental fate of nanoparticles. Toxicological tests and ecotoxicological experiments give us a chance to elaborate rather simple screening tests which
would show similar to in vivo effects based on in vitro results. All mentioned above
experiments made possible judgment about hazard generation, risk assessment and exposure
scenarios.
Dynamic development and progress in state of the art knowledge on nanotechnology,
tailored characterization methods and toxicological risk assessment give a hope for future
benefits for society by implementation safety-by-design and green nano strategies.
OECD and European Commission support many research projects activities in the
field of nanotechnology to clarify and standardize the legal status of this rapidly growing and
prospective advance technology. Project NANOFORCE has, between others, investigated the
current stage of regulations concerning nanomaterials, risk assessment procedures and
occupational exposure as well as environmental-health hazards.
In this paper we would like to discuss from different prospective, responsible use of
nanotechnology and risk assessment tools.
- 164 -
plasma frequency,
Faraday and Cotton-Mouton effect
AGNIESZKA STAROBRAT*, JACEK SZCZYTKO*, NATASA VAUPOTIC**/***,
MIKHAIL OSIPOV****, KAROLINA MADRAK*****, EWA GÓRECKA*****
*
Faculty of Physics, Institute of Experimental Physics, University of Warsaw,
ul. Hoża 69, 00-681 Warsaw, Poland
**
Institute of Physics, Faculty of Natural Sciences and Mathematics, University of Maribor,
Maribor, Slovenia
***
Jozef Stefan Institute, Ljubljana, Slovenia
****
Department of Mathematics, University of Strathclyde, Glasgow, United Kingdom
*****
Department of Chemistry, University of Warsaw, Warsaw, Poland
MAGNETIC MOMENT AND PLASMA FREQUENCY OF SINGLE METAL
NANOPARTICLE DETERMINED FROM FARADAY AND COTTON-MOUTON
EFFECT IN FERROFLUIDS
Ferromagnetic fluids (ferrofluids) are homogeneous colloidal dispersions of
ferromagnetic nanoparticles dispersed in a liquid carrier. The large linear and circular optical
anisotropy can be induced by applying relatively small external magnetic fields [1]. They are
extensively studied for applications in optical technology as fast shutters, switches, tunable
phase retarders, etc.
Optical properties of a composite material made of ferromagnetic metal
nanoparticles embedded in a dielectric host are studied. An effective dielectric tensor of the
composite material was constructed taking into account the orientational distribution of
nanoparticle magnetic moments in external magnetic field. A nonlinear dependence of the
optical rotation on magnetic field resulting from the reorientation of nanoparticles is
demonstrated. The theoretical findings were applied to the magneto-optical experimental data
of cobalt ferromagnetic nanoparticles embedded in a dielectric liquid host. The dependence of
the Faraday rotation on Co-based ferromagnetic nanoparticles was measured as a function of
the external magnetic field and the wavelength of light.
We present a combination of experimental measurements and theoretical modeling,
which enables determination of the magnetic moment of a single nanoparticle, its plasma
frequency and the effect of particle chain formation on optical properties. Induced optical
activity (Faraday effect, [2]) and induced birefringence (Cotton-Mouton effect, [3]) in a
composite material made of cobalt nanoparticles embedded in a dielectric liquid host are
studied. The proposed approach enables quantitative determination of the magnetic moment
and the plasma frequency of a single nanoparticle, and from this the size of the nonmagnetic
shell of magnetic nanoparticles. The considerable induced birefringence determined
experimentally, has been attributed to the formation of chains of nanoparticles. Experimental
results agree well with the theoretical model based on a simple density functional approach.
References
[1] Y. Zhao, Y. Zhang, R. Lv, and Q. Wang, J. Magn. Magn. Mater. 2011, 323, 2987.
[2] J. Szczytko, N. Vaupotič, K. Madrak, P. Sznajder, and E. Gorecka, Phys. Rev. E 2013, 87, 033201.
[3] J. Szczytko, N. Vaupotič, M. Osipov, K. Madrak, P. Sznajder, and E. Gorecka, submitted
- 165 -
nanorurki węglowe, nanokrystality Pd,
PVD, CVD, sensory gazowe
IZABELA STĘPIŃSKA*, JOANNA RADOMSKA*, MIROSŁAW KOZŁOWSKI*,
ELŻBIETA CZERWOSZ*, WOJCIECH KOWALSKI**
*
Instytut Tele- i Radiotechniczny, ul. Ratuszowa 11, 03-450 Warszawa
Instytut Fizyki PAN al. Lotników 32/46, 02-668 Warszawa
**
WARSTWY NANORUREK WĘGLOWYCH POKRYTYCH
NANOKRYSTALITAMI PALLADU
Nanorurki węglowe (CNTs - Carbon Nanotubes) szeroko wykorzystywane są w
różnych dziedzinach nauki i przemysłu. Najwięcej zastosowań skupia się wokół ich
właściwości elektrycznych i mechanicznych. W ostatnich latach zaproponowano
wykorzystanie ich jako sensorów chemicznych, głównie gazowych. Detekcja w sensorach
zbudowanych z nanorurek wiąże się z obserwowalną zmianą przewodnictwa CNTs. Dla
gazów, których cząsteczki są obojętne (np. H2) zmiana ta jest niewidoczna, ponieważ
cząsteczki takie nie adsorbują do powierzchni nanorurek lub adsorbują na tyle słabo, że nie
wpływają na ich przewodnictwo. W tym przypadku rozwiązaniem okazuje się być
funkcjonalizacja nanorurek nanocząstkami odpowiedniego metalu. Aby sensor nanorurkowy
był czuły np. na wodór na powierzchni nanorurek osadza się nanocząstki palladu. Kilka
metod zostało opracowanych do dekoracji nanorurek cząstkami Pd: autokatalityczna
depozycja, rozkład termiczny, osadzanie z fazy gazowej, impregnacja czy elektrodepozycja.
W tej pracy przedstawiono nową, opracowaną w Instytucie Tele- i Radiotechnicznym, metodę
wytwarzania warstw nanorurek węglowych pokrytych nanoziarnami Pd (CNTs-Ni-Pd).
Metoda składa się z trzech kolejnych etapów: procesu PVD (Physical Vapor Deposition),
CVD (Chemical Vapor Deposition) oraz PVD. Otrzymane w ten sposób warstwy badano za
pomocą skaningowej mikroskopii elektronowej (SEM) oraz transmisyjnej mikroskopii
elektronowej (TEM).
Rys. 1. Obrazy SEM warstwy a) czystych nanorurek
węglowych zawierających Ni, b) nanorurek pokrytych
Pd
Rys. 2. Obraz TEM warstwy CNTs-Ni-Pd (a)
wraz z dyfrakcją elektronową (b)
Praca jest współfinansowana z Europejskiego Funduszu Rozwoju Regionalnego w ramach Programu Operacyjnego
Innowacyjna Gospodarka 2007-2013 (projekt pt. „Opracowanie technologii nowej generacji czujnika wodoru i jego
związków dla zastosowań w warunkach ponadnormatywnych”, umowa Nr UDA-POIG.01.03.01-14-071/08-08)
- 166 -
foam stability, foamability, surfactant,
silica nanoparticles, surface tension
JERZY STOPA*, EWA KNAPIK*, ANNA MARZEC**
*
Faculty of Drilling, Oil and Gas, AGH University of Science and Technology
Faculty of Materials Science and Ceramics, AGH University of Science and Technology
**
FOAMS STABILIZED WITH NANOPARTICLES FOR GAS WELL
DELIQUIFICATION
Foam is widely used to remove liquid loading up in mature gas well. Hydrocarbon
condensate, water salinity and high temperature in down hole have negative effect on foam
formation. Particles act as stabilizers in many foam systems and could improve the
foamability of commercially available surfactants. This study examined the interactive
behaviour of solid nanoparticles and non-ionic surfactant at an air–water interface. Aqueous
foams stabilized by silica nanoparticles in the presence or absence of liquid hydrocarbons
were studied in detail. The stability of the solid/surfactant dispersion was evaluated by
interface tension and zeta potential. Influence of the content of nanoparticles and the
concentration of surfactant on the foamability, drainage behavior and structure of wet foams
was studied. The foam performance was measured using dynamic foam stability test.
It was found that the foamability of dispersion is strongly dependent on the concentration of
surfactant and the hydrophobicity of solid particles. The adsorption of hydrophobically
modified silica particles and surfactants reduces the air/water interface tension. Foam
generation occurs more efficiently with increasing surfactant concentration, until a plateau
value was reached. The addition of solid particles increases the foamability and allows to
achieve foams with extended lifetimes. The phase behavior of the solid/surfactant dispersions
(separation, flocculation) indicates adsorption of the surfactant on the solid particles. The zeta
potential of silica particles directly reflects the adsorption mechanism. The decrease of zeta
potential of silica particles enhances their adsorption on the bubble surface. The synergistic
effect of surfactant and nanoparticles on the foam stability mainly comes from the formation
of a steric network in the coherent phase.
- 167 -
PNIPAM, SEM, DLS
TOMASZ ŚLIWA*/**, MACIEJ JARZĘBSKI*/**, MIKOŁAJ GRZESZKOWIAK**
*
Zakład Biofizyki Molekularnej, Wydział Fizyki, Uniwersytet im. Adama Mickiewicza
w Poznaniu,
**
Centrum NanoBioMedyczne UAM
WŁAŚCIWOŚCI FIZYCZNE WYBRANYCH KOPOLIMERÓW PNIPAM
Polimery oparte o łańcuch poli-N-izopropyloakryloamidowy (PNIPAM) stanowią
interesujący obiekt badawczy, ze względu na ich kontrolowaną zmianę właściwości
fizycznych w zależności od bodźców zewnętrznych takich jak: temperatura, pH,
promieniowanie elektromagnetyczne czy przepływ prądu. Możliwość kontroli rozmiaru stała
się podstawą do badań nad wykorzystaniem polimerów PNIPAM w systemach
kontrolowanego uwalniania leków. Pod wpływem zmian pH objętości pojedynczej cząstki
może się zmieniać 8-krotnie, co pozwala na umieszczenie wewnątrz struktury polimeru na
przykład substancji terapeutycznej i uwalnianie jej w kontrolowany
Badanymi substancjami były trzy kopolimery PNIPAM: PNIPAM-co-ALA,
PNIPAM-co-Vim, PNIPAM-co-MAA. Wysuszone w temperaturze 20°C i 40°C próbki
polimerów poddano analizie za pomocą skaningowego mikroskopu elektronowego (SEM).
Na podstawie zdjęć SEM obliczono średni promień cząstek. Otrzymane wartości porównano
z promieniami hydrodynamicznymi otrzymanymi uzyskanymi metodą spektroskopii korelacji
fotonów (DLS). Dodatkowo scharakteryzowano zmiany pH roztworu zawierającego
cząsteczki PNIPAM w funkcji temperatury.
Zauważono, że sposób suszenia cząstek do SEM nie wpływa na ich końcowy
rozmiar. Utrata wody skutkuje zapadaniem się cząstek do przeciętnej wartości promienia
200nm. Roztwory wodne poddane wpływom zmiany temperatury wskazują na kurczenie się
cząstek do rozmiarów promienia 300 nm. Uzyskano również wyniki wskazujące, że zmianie
ulaga pH roztworu zawierającego PNIPAM co świadczy o zjawisku protonacji i powstawania
wiązań wodorowych między łańcuchami polimeru prowadzących do skurczu cząstki przy
czym zmiana pH zależy od obecności odpowiednich grup funkcyjnych kopolimeru.
- 168 -
nanoparticles, phase-transfer,
hybrid memory devices
BEATA TKACZ-SZCZESNA*, K. SOLIWODA*, M. ROSOWSKI*, E. MACKIEWICZ*,
G. CELICHOWSKI*, S. SAX**, S. NAU**, E.J.W. LIST**/***, M. SCHMUTZ****,
M. BRINKMANN****, J. GROBELNY*
*
Department of Materials Technology and Chemistry, Faculty of Chemistry, University of Lodz, Poland
Nanotec Center Weiz Forschungsgesellschaft mbH, Franz-Pichler-Straße 32, 8160 Weiz, Austria
***
Institute of Solid State Physics, Graz University of Technology Petersgasse 16, 8010 Graz, Austria
****
Centre National de la Recherche Scientifique, Institut Charles Sadron, 23 rue du Loess, 67034
Strasbourg, France
**
SELECTION OF GOLD NANOPARTICLES SURFACE MODIFIER
AND THE SOLVENT SYSTEM FOR APPLICATIONS IN OPTOELECTRONICS
Nanoparticles (NPs) have been one of the key research areas in recent decades due to
their unique size- and shape-dependent optical and electrical properties, which significantly
differ from the behavior of the respective bulk material and results from localized surface
plasmon resonance of nanoparticles. This phenomenon allows for the use of NPs in various
fields such optics, optoelectronics, medicine and biotechnology. Nanoparticles used as
building blocks for HYBRID organic/inorganic memory devices requires the use of an
organic solvent suitable for printing or spin coated layers i.e. (e.g. toluene, chloroform,
dichlorobenzene).
The method which allows obtaining NPs in organic solvent is the phase transfer of
aqueous synthesized nanoparticles. Obtained by chemical reduction method nanoparticles can
be transferred into organic phase by using a modifier e.g, thiols, carboxy acids,
dialkylodithiophosphates etc. This method allows obtaining colloids, without stabilizers and
by-products of the synthesis.
In this presentation the main idea of the phase-transfer method and results of research
obtained for gold nanoparticles will be shown. The water colloid of AuNPs was synthesized
by chemical reduction method and characterized by DLS (Dynamic Light Scattering), AFM
(Atomic Force Microscopy), TEM (Transmission Electron Microscopy) and UV-Vis
(Ultraviolet – visible spectroscopy) techniques. Different compounds were used to modify the
surface of nanoparticles providing them hydrophobic in organic solvent. The size, size
distribution and stability of gold nanoparticles in organic media were tested by DLS
measurements. UV-Vis spectroscopy was used to determinate the efficiency of described
method. Organic colloids are stable over the long period of time and can be used as ink
component for printing electronics or spin coated layers as it will also be shown.
This work was supported by FP7-NMP-2010-SMALL-4 program, project number 263073.
Scientific work financed from funds for science in 2011-2014 allocated for the cofounded international project .
- 169 -
nanopłyn, nanocząstki, przewodnictwo cieplne,
model statystyczno-fizyczny
BOGUSŁAW USOWICZ
Instytut Agrofizyki im. Bohdana Dobrzańskiego Polskiej Akademii Nauk, Zakład Metrologii
i Modelowania Procesów Agrofizycznych, Lublin
STATYSTYCZNO-FIZYCZNY MODEL PRZEWODNICTWA CIEPLNEGO
NANOPŁYNÓW
Zdyspergowane nanocząstki metaliczne lub niemetaliczne, cząstki rzędu 1-100 nm,
w różnym stopniu wpływają na współczynnik tarcia płynu bazowego, jego lepkość, gęstość
oraz jego właściwości cieplne, jak przewodnictwo cieplne i ciepło właściwe. Nanocząstki
stosowane w nanopłynach są to cząstki metali, tlenków lub innych związków chemicznych, a
typowym płynem bazowe jest woda, glikol etylenowy i olej. Nanopłyny charakteryzują się
znacznie większymi przewodnictwami cieplnymi niż płyny bazowe. Znalazły one szerokie
zastosowanie w wymianie ciepła w różnych urządzeniach, między innymi, w
mikroelektronice, w technologiach farmaceutycznych, w silnikach, w agregatach, w ogniwach
paliwowych, w reaktorach jądrowych, w kotłach spalinowych zmniejszających ich
temperaturę oraz wielu innych obszarach. Zrozumienie procesów i wpływu poszczególnych
składników nanopłynu na wzrost przewodnictwa cieplnego, może okazać się użyteczne do
opracowania bardziej wydajnych metod chłodzenia czy podwyższenia wymiany ciepła w
urządzeniach. Celem pracy było oszacowywanie przewodnictwa cieplnego nanopłynów za
pomocą statystyczno-fizycznego modelu przewodnictwa cieplnego dla różnych nanocząstek
metalicznych i niemetalicznych ze zróżnicowaną ich zawartością w wodzie, w glikolu
etylenowy i przy różnych temperaturach.
Model statystyczno-fizyczny przewodnictwa cieplnego nanopłynów zbudowano na
bazie pojęć oporu cieplnego, dwóch praw Kirchhoffa i rozkładu wielomianowego. W modelu
tym jednostkową objętość nanopłynów, tworzą kul, warstwy, nakładające się na siebie, które
są reprezentowane przez połączenia równoległe oporników cieplnych w warstwie i połączenia
szeregowe oporników między warstwami. Kule, to cząstki cieczy, gazu i fazy stałe z
określonymi właściwościami fizycznymi i geometrycznymi. Określenie rozkładu cząstek i ich
konfiguracji w nanopłynie jest bardzo trudno i tym samym trudno jest oszacować wartość
średnią przewodnictwa cieplnego takiego nanopłynu. Dlatego też zastosowano podejście
statystyczne, które ujmuje wszystkie możliwe konfiguracje przewodzących cząstek i
uwzględnia prawdopodobieństwa ich wystąpienia w danej konfiguracji w nanopłynie.
W pracy przedstawiono model statystyczno-fizyczny, który pozwala określić
przewodnictwo cieplne nanopłynów w zależności od objętościowej zawartości nanocząstek i
temperatury. W modelowaniu uwzględniono również współczynnik przenikania ciepła z
efektem Browna nanocząstek obecnych w płynie bazowym. Wyniki otrzymane z modelu
odniesiono do wyników znanych z literatury z klasycznych wzorów określających efektywne
przewodnictwo cieplne nanopłynów. Porównano i określono również zgodność danych
otrzymanych z modeli i pomiarów. Użyte dane do modelowania przewodnictwa cieplnego jak
i zmierzone dane użyte do porównań pochodziły z literatury.
Zaproponowany w pracy model statystyczno-fizyczny pozwała oszacować
przewodnictwo cieplne nanopłynów z zadawalająca dokładnością.
- 170 -
titanium dioxide, modification with arenes,
visible light- responsive TiO2 photocatalysts
AGNIESZKA M. WANAG, EWELINA KUSIAK-NEJMAN, SYLWIA MOZIA,
ANTONI W. MORAWSKI
West Pomerania University of Technology, Szczecin, Institute of Chemical and Environment
Engineering, Pułaskiego 10, 70-322 Szczecin, Poland
PREPARATION OF VISIBLE LIGHT-RESPONSIVE TiO2 BY HYDROTHERMAL
MODIFICATION WITH ARENES
Titanium dioxide is a semiconductor, which has been testing as a photoactive
nanostructural material for water treatment since almost four decades. Considering postulates
of sustainable development different kinds of TiO2 modification were proposed. One of that
kind of modification it is modification of starting titania by carbon from different carbonic
precursors.
In this study modification of TiO2 (anatase phase) by carbon in pressure reactor at
150°C for 4 hours was used to prepare TiO2/C nanomaterials. Arenes (benzene, naphthalene
and anthracene) were used as a carbon dopants.
On basis of UV-Vis/DR analysis it was possible to find insignificant changes in band
gap energy but it was also noted that modification of pristine TiO2 with arenes, especially
with naphthalene and anthracene leads to improve absorption in visible range. It could be
explained by changes in photocatalysts colour from white for starting titania and TiO2
modified with benzene to purplish grey for TiO2 photocatalyst modified with naphthalene and
light brown for TiO2 modified with anthracene.
100
80
60
%R
Serie1
TiO
2
40
Serie2
TiO
2/benzene
TiO
Serie3
2/naphthalene
20
TiO
2/anthracene
Serie4
0
250
350
450
550
650
750
wavelenght [nm]
Figure 1. UV-Vis/DR absorption spectra of starting TiO2 and TiO2 modified with arenes
Acklowledgements:
This work was supported by grant No. 506-10-011-4524/6 (National Science Centre, Poland).
- 171 -
polysaccharide nanoparticles,
cancer treatment
IGA WASIAK, TOMASZ CIACH
Warsaw University of Technology, Faculty of Chemical an Process Engineering, Biomedical
Engineering Laboratory
POLYSACCHARIDE NANOPARTICLES FOR CONTROLLED DELIVERY OF
CANCER DRUGS
Development of the techniques of designing and production of controlled drug deliver
system is one of the most important area of contemporary medicine and science.
Conventionally drug carrier are ineffective due to numerous of limitations. This disadvantages
include nonspecific biodistribution and targeting, lack of water solubility, poor oral
bioavailability, low therapeutic indices and partial degradation as a consequence of lack of
control over concentration. It makes they uncomfortable for patients and cause side effects
due to affect both cancerous and normal cells.
The ideal drug carrier should be inert, biocompatible, biodegradable, nontoxic
efficient in loading and release of drug and simply to administer and produce. Polysaccharide
as natural biomaterials, polysaccharides are highly stable, safe, non-toxic, hydrophilic and
biodegradable. In addition, polysaccharides have abundant resources in nature and low cost in
their processing. Mentioned properties satisfy the requirements for ideal drug carrier and are
believed to be sufficient materials for biomedical applications.
Nanoparticle drug delivery systems have outstanding advantages: they can pass
through the smallest capillary vessels and avoid rapid clearance by phagocytes so that their
duration in blood stream is greatly prolonged; they can penetrate cells and tissue gap to arrive
at target organs such as liver, spleen, lung, spinal cord and lymph; they could show controlled
release properties due to the biodegradability, pH, ion and/or temperature sensibility of
materials; they can improve the utility of drugs and reduce toxic side effects; etc. As drug
delivery system, nanoparticles can entrap drugs or biomolecules into their interior structures
and/or absorb drugs or biomolecules onto their exterior surfaces. Now a days, nanoparticles
have been widely investigated to deliver drugs, polypeptides, proteins, vaccines, nucleic
acids, genes and so on. Nanoparticle drug delivery systems have shown huge potential in
biological, medical and pharmaceutical applications.
The aim of this study was to prepared polysaccharide nanoparticles in simple
procedure in water solution at room temperature. Nanoparticles are formed due to
hydrophobic – hydrophilic interactions, this process is verified by using light scattering
technique. Obtained nanoparticles are very stabile and poses narrow size distribution.
Produced nanoparticles can be lyophilized to dry powder and resuspended in water again.
Cytotoxicity of produced nanoparticles was tested with mouse fibroblast cells, particles
showed to be non toxic even at fairly high concentration. Then doxorubicine was tested as a
potential anticancer drug to be encapsulated, it was covalently attached to nanoparticles via
amine group - Schiff base bound. Obtained drug loaded NPs were stable (t½ 48h).
- 172 -
fluorescence nanocrystal,
polysaccharide nanoparticles
IGA WASIAK, TOMASZ CIACH
Warsaw University of Technology, Faculty of Chemical an Process Engineering, Biomedical
Engineering Laboratory
PREPARATION OF POLYSACCHARIDE COATED FLUORESCENCE
NANOCRYSTALS FOR CANCER DIAGNOSIS
According to the WHO, cancer is the major cause of mortality, more than 8 million deaths
annually, and this number is expected to rise. Cancer occurs over the years, from one normal cell via
multistep carcinogenesis process entailing numerous cellular physiological system. This make it
highly incomprehensible and complex disease. Despite the big international scientific effort cancer
treatment remains one of the biggest challenges of contemporary medicine. There is no single test
that can accurately diagnose cancer. The complete evaluation of a patient usually requires a
thorough history and physical examination along with diagnostic testing. Many tests are
needed to determine whether a person has cancer, or if another condition (such as an
infection) is mimicking the symptoms of cancer. Many different tests exist to detect and
measure almost any type of chemical component in blood or urine. Components may include
blood glucose, electrolytes, enzymes, hormones, lipids (fats), other metabolic substances, and
proteins.
Endoscopic Confocal Microscopy (ECM) is probably one of the most important
technological advances for the early detection of dysplastic lesions or adenocarcinoma within
gastrointestinal tract, and for identification of risky fields suitable for targeted biopsies and a
definitive histological evaluation. However, there is an urgent clinical need for increasing the
detection sensitivity, and this depends on the development of new specific fluorescent probes.
The aim of this study was to coated organic nanocrystals (NC) based on fluorescent
dyes by a polysaccharide shell. These particles could display distinct advantages. Dye
nanocrystals offer the highest dye concentration in the smallest volume, are particularly stable
and allow fine tuning of the photophysical properties. The role of the polysaccharide shell is
to limit crystal growth, protect the dye molecules from the outer medium, and avoid their
dispersion before they have reached their target. Above all, it should make the particle less
phagocyte-prone and ensure long circulation time in the blood stream. The coated
nanocrystals could then enter the cancerous cells owing to the inherent leaky vasculature that
serves cancerous tissues, and get concentrated there (EPR effect), quite selectively.
This research was financed from EuroNanoMed-FONDiag
- 173 -
engineered spider silk, biomaterial,
Atomic Force Microscopy
MAREK WEISS*, ARKADIUSZ PTAK*, HANNA DAMS-KOZŁOWSKA**/***
*
Institute of Physics, Faculty of Technical Physics, Poznan University of Technology,
Department of Biomedical Engineering, Poznan University of Medical Sciences
***
Department of Cancer Immunology, Great Poland Cancer Center, Poznan
**
DETERMINATION OF DIMENSIONS OF ENGINEERED SPIDER
SILK SPHERES BY ATOMIC FORCE MICROSCOPY
Spider silk is a natural building material formed by spiders‟ silk glands. It has
numerous unique properties such as: incredible strength and high biocompatibility, which
makes it a good material for future applications in both industry and medicine. In order to
ensure the high amount of top quality material for an industrial scale, the methods of spider
proteins (spidroins) production in form of engineered spider silk (ESS) were developed [1,
part I]. ESS is a base which is used for the production of various biomaterials as: nano- and
microspheres, microcapsules and ultra-durable fibers. One of the main applications of the
protein spheres is a usage in physical drug delivery systems. An important advantage of such
a system (in comparison with other materials) is controlled release of substances at their
destination and its biodegradability. The protein spheres can be obtained by spontaneous
aggregation of proteins during the mixing process in presence of appropriate concentration of
phosphate ions [1, part II]. Depending on the concentration of the phosphate ions and mixing
rate, various diameters of the spheres in range 250 nm to 2 µm could be obtained. Careful size
control of the obtained spheres is an important element for their application as a drug delivery
system. The aim of this work was to determine the dimensions of the protein spheres prepared
in various conditions. The study was done by means of Atomic Force Microscopy.
Measurements have been carried out by the intermittent contact mode (tapping mode) in
normal pressure and temperature conditions. Samples were prepared by slow evaporation of
the solution from a glass microscope slide at the temperature below 38oC. For the purpose of
measurements, isolated spheres were sought. Unfortunately, due to the strong intermolecular
interactions, protein spheres may aggregate and deform each other mutually. Also slightly
hydrophilic substrate of the sample causes additional flattening of the spheres. Due to the
nature of the measurement by scanning probe, the curvature and size of the tip should be also
considered in xy-plane dimension measurements. These effects were taken into account in the
determining the size of the spheres. For different samples, the spheres were found to be in
diameters from 500 nm to 2 µm. Every sample was considered individually and the dispersion
of the results for each sample was relatively small and do not exceed 100 nm.
References
[1] A. Florczak, K. Piekoś, K. Kazimierska, A. Mackiewicz, H. Dams-Kozłowska: Engineered spider silk: the
intelligent biomaterial of the future. Part I and II. Postepy Hig Med Dosw (online), 2011; 65: 377-396.
- 174 -
nanotechnology, characterization of
nanomaterials, education
ALEKSANDER WERBOWY, PIOTR FIREK
Institute of Microelectronics and Optoelectronics, Warsaw University of Technology
ACADEMIC EDUCATION IN THE FIELD OF NANOTECHNOLOGY AT THE
DIVISION OF MICROSYSTEM AND ELECTRONIC MATERIALS TECHNOLOGY
Two lectures are offered students in the field of nanotechnology: "Nanotechnologies"
and "Characterization of materials for microelectronic (and nanoelectronic) applications".
Both are intended for students pursuing M.Sc. and Ph.D. degrees and open not only for those
from the Faculty of Electronics and Information Technology but also from other faculties of
the Warsaw University of Technology.
The aim of the lecture "Nanotechnologies" is to present the current status and the
future of nanotechnologies as well as discuss problems and limitations related to their
development. Technological and physical determinants of the processes that enable
fabrication and processing of nanoscale materials, structures, devices and systems (i.e.
specificity of the clean-room, vacuum and plasma environments) are also discussed. Finally,
classical fabrication methods of low-dimensional nanostructures along with their
modifications and alternative approaches are presented.
The lecture "Characterization of materials for microelectronic (and nanoelectronic)
applications" is complementary to "Nanotechnologies". Its goal is to present contemporary
techniques that are the most commonly used in characterizing materials as well as micro- and
nanostructures. These include: microscopy, scanning, diffraction, spectroscopy and profiling
methods. Their advantages and disadvantages as well as ranges of application and operation
principles are discussed.
Laboratory of material characterization of micro- and nanostructures (MCMN Lab)
enables students to get familiar with modern observation and analytical methods allowing to
study surface morphology (e.g. topography, structure) as well as their surface and bulk
chemical composition of classic and advanced materials. These include semiconductors,
insulators and metals already applied or considered to be prospective for applications in
electronics, particularly in electronic devices like micro-, nanoelectronic and photonic
structures or hybrid microsystems as well as MEMS and MOEMS structures.
MCMN Lab instrumentation includes: surface profiler Dektak 150 (VEECO),
scanning electron microscope S-3400N (HITACHI) with energy dispersive X-ray
spectrometer, confocal laser scanning microscope LEXT OLS3100 (OLYMPUS), secondary
ion mass spectroscope MiniSIMS (MILLBROOK), high-frequency (10 MHz – 13,5 GHz)
network analyzer N4395A (AGILENT TECHNOLOGIES).
- 175 -
nanocrystalline thin films, wide bandgap materials,
electronic properties, structural properties
ALEKSANDER WERBOWY, PIOTR FIREK, JAN SZMIDT
Institute of Microelectronics and Optoelectronics, Warsaw University of Technology
ELECTROPHYSICAL PROPERTIES OF NANOCRYSTALLINE THIN FILMS OF
WIDE BANDGAP MATERIALS
Wide band gap materials in a form of thin (max. 200-300 nm thick) films are
prospective from the viewpoint of electronic, in particular high-power and high-temperature,
applications. They can play the role of dielectrics as well as semiconductors (if properly
doped). Layers of such materials (oxides (e.g. Al2O3, TiO2, BaTiO3), nitrides (e.g. BN, AlN,
GaN, CN) and nanocrystalline diamond (NCD)) obtained by means of relatively cost-efficient
plasma methods, like radio-frequency chemical vapor deposition (RF CVD) or impulse
plasma deposition (IPD) demonstrate nanocrystalline structure and interesting electronic
properties, like large resistivity (up to 1014 cm) and high critical electric field (up to 5
MV/cm) when undoped (insulators), whereas their synthesis (when in situ doped) on
semiconductor (e.g. Si) substrates may result in producing heterojunction structures showing
for instance electroluminescence and rectification of electric current (Ifor/Irev up to 104).
- 176 -
BaTiO3, TiO2,
stała dielektryczna
ALEKSANDRA WYPYCH, IZABELA BOBOWSKA, AGNIESZKA OPASIŃSKA,
MILENA PAWLUCHA, PIOTR WOJCIECHOWSKI, JACEK ULAŃSKI
Politechnika Łódzka, Wydział Chemiczny, Katedra Fizyki Molekularnej,
ul. Żeromskiego 116, 90-924 Łódź
SYNTEZA I CHARAKTERYSTYKA WŁAŚCIWOŚCI NANOMATERIAŁÓW
CERAMICZNYCH O WYSOKICH WARTOŚCIACH STAŁEJ DIELEKTRYCZNEJ
Materiały ceramiczne o wysokiej stałej dielektrycznej i nanometrycznych rozmiarach
mają duże znaczenie we współczesnej elektronice. Jednym z najbardziej popularnych
przykładów są wielowarstwowe kondensatory ceramiczne charakteryzujące się wysokimi
wartościami pojemności elektrycznej i małymi rozmiarami. Aktualna problematyka badawcza
związana z optymalizacją metod wytwarzania cienkowarstwowych tranzystorów
organicznych dotyczy wykorzystania hybrydowej warstwy dielektryka, którą stanowią
nanocząstki ceramiczne o wysokiej wartości przenikalności elektrycznej homogenicznie
zdyspergowane w polimerowej matrycy [1]. BaTiO3 oraz TiO2 w formie rutylu charakteryzują
się dużymi wartościami przenikalności elektrycznej i mogą być wykorzystane do
wytwarzania hybrydowych warstw dielektryka w tranzystorach cienkowarstwowych.
Pierwszym etapem do osiągnięcia tego celu jest opracowanie metody wytwarzania cząstek o
rozmiarach nanometrycznych i wąskim rozrzucie rozmiarów.
Do syntezy nanometrycznych proszków BaTiO3 i TiO2 wykorzystano różne metody
tzw. chemii miękkiej, które prowadzą do otrzymania prekursorów o strukturze nanoskopowej.
Taka struktura pozwala na obniżenie temperatury transformacji prekursora do pożądanej fazy
krystalicznej, tj. fazy tetragonalnej BaTiO3 oraz TiO2 w postaci rutylu. Prekursory zostały
poddane systematycznemu wygrzewaniu w zakresie temperatur od 473 K do 1573 K, a
otrzymane nanoproszki były scharakteryzowane m.in. za pomocą spektroskopii
ramanowskiej, dyfraktometrii rentgenowskiej, skaningowej mikroskopii elektronowej oraz
szerokopasmowej spektroskopii dielektrycznej. Najmniejsze rozmiary nanocząstek uzyskano
w syntezie metodą zol-żel. Zastosowana procedura wytwarzania pozwoliła na uzyskanie
nanocząstek TiO2 o średnim rozmiarze około 60 nm i stałej dielektrycznej wynoszącej 70 w
temperaturze pokojowej, natomiast wartość stałej dielektrycznej BaTiO3 w temperaturze
pokojowej wynosiła 500 przy średnim rozmiarze ziaren około 200 nm .
Podziękowania
Praca była finansowana w ramach grantu NCN, nr decyzji DEC-2011/03/D/ST5/06074
Literatura
[1] Ortiz, R.P., Facchetti, A., Marks, T.J., Chem. Rev. 110, 205–239 (2010).
- 177 -
iryd, fluorek magnezu-tlenek magnezu,
uwodornienie toluenu
MICHAŁ ZIELIŃSKI, MARIUSZ PIETROWSKI, MARIA WOJCIECHOWSKA
Uniwersytet im. Adama Mickiewicza, Poznań, Wydział Chemii, Zakład Technologii
Chemicznej
MgF2-MgO JAKO NOŚNIK KOLOIDALNYCH KATALIZATORÓW IRYDOWYCH
Procesy uwodornienia, ze względu na ich zastosowanie w wielkotonażowych
procesach przemysłowych oraz do usuwania związków azotu, siarki, tlenu a także do
obniżenia stężenia rakotwórczych związków aromatycznych stały się procesami najwyższej
wagi [1]. Znajdują one zastosowanie w tak ważnych dziedzinach jak poprawa jakości paliw
silnikowych, produkcja włókien nylonowych czy utwardzanie tłuszczów. Bardzo aktywną i
często używaną fazą metaliczną w procesach hydrogenacji jest platyna. Jednak zdecydowanie
tańszym platynowcem, stosowanym stosunkowo rzadko w katalizie jest iryd [2]. Jego niższa
cena w porównaniu z platyną oraz większa odporność na dezaktywację pod wpływem
zanieczyszczeń znajdujących się w przerabianym surowcu czyni go interesującym
zamiennikiem platyny.
Nośnikami katalitycznymi, cieszącymi się ostatnimi laty coraz większym
zainteresowaniem są układy podwójne. Są to materiały o zupełnie nowej jakości, posiadające
odmienne i zazwyczaj lepsze parametry w porównaniu z układami pojedynczymi. Otrzymuje
się je poprzez mechaniczne mieszanie komponentów nośnika lub współstrącanie. W naszych
badaniach do preparatyki układów podwójnych MgF2-MgO wykorzystano metodę zol-żel. Ta
metoda preparatyki sprawdziła się w preparatyce nośników podwójnych: Al2O3-SiO2 [3],
Al2O3-TiO2 [4], MgO-Al2O3 [5].
W ramach prowadzonych badań, przygotowano serię katalizatorów zawierających
1% wagowy irydu naniesiony metodą impregnacji stosując następujące prekursory: Ir(acac) 3,
Ir4(CO)12 oraz H2IrCl6. Spośród przebadanych katalizatorów najwyższą aktywnością
charakteryzował się katalizator otrzymany z karbonylku irydu i nośnika mieszanego o
zawartości 60% molowych MgO. Charakteryzował się on również najmniejszymi
wielkościami krystalitów irydu o wielkościach poniżej 1 nm i wysoką monodyspersyjnością.
Podziękowania
Badania wykonano w ramach projektów badawczych finansowanych przez NCN – N N204 141339 i N N204
214140
Literatura
[1] A. Stanislaus, B.H. Cooper, Aromatic Hydrogenation Catalysis: A Review, Catal. Rev. Sci. Eng. 36 (1994)
75-123.
[2] http://www.platinum.matthey.com
[3] B. Pawelec, R.M. Navarro, J.M. Campos-Martin, A. López Agudo, P.T. Vasudevan, J.L.G. Fierro, Catal.
Today 86 (2003) 73-85.
[4] G. Murali Dhar, B.N. Srinivas, M.S. Rana, M. Kumar, S.K. Maity, Catal. Today, 86 (2003) 45-60.
[5] P. Kirszensztejn, R. Przekop, A. Szymkowiak, E. Maćkowska, J. Gaca, Micropor. Mesopor. Mater. 89
(2006) 150-157.
- 178 -
nanorurki węglowe, kompozyty polimerowe,
wytrzymałość mechaniczna
PATRYCJA ZYGOŃ*, MONIKA GWOŹDZIK*, JERZY PESZKE**,
ZYGMUNT NITKIEWICZ*
*
Politechnika Częstochowska, Instytut Inżynierii Materiałowej,
Al. Armii Krajowej 19, 42-201 Częstochowa
**
Uniwersytet Śląski, Zakład Fizyki Ciała Stałego, Uniwersytecka 4, 40-007 Katowice
CHARAKTERYSTYKA WŁAŚCIWOŚCI KOMPOZYTÓW POLIMEROWYCH
WZMACNIANYCH NANORURKAMI WĘGLOWYMI
Nanorurki węglowe łączą w sobie nadzwyczajne właściwości wytrzymałościowe,
elektryczne i cieplne. Dzięki temu są obiecującą nową klasą materiałów do szczególnych
zastosowań. Charakteryzują się małą gęstością oraz wysoce rozwiniętą powierzchnią
właściwą. Przy małej średnicy (1-80 nm) i dużym współczynniku kształtu (L/D nawet
powyżej 10000) są potencjalnie atrakcyjnym materiałem wzmacniającym do polimerów,
materiałów ceramicznych i metali. Kompozyty otrzymywane z wykorzystaniem nanorurek
mają nie tylko dobrą wytrzymałość mechaniczną i przewodnictwo elektryczne ale też łatwo
poddają się obróbce mechanicznej bez powstawania pęknięć, które występują przy włóknach
węglowych.
Nanorurki węglowe dodane do polimerów znacząco wpływają na zmianę własności
fizycznych materiału, nawet ich niewielka ilość nadaje cechy polimeru przewodzącego. Aby
osiągnąć jak najbardziej pożądane cechy kompozytu ważne jest, aby siły oddziaływań między
fazą rozproszoną a osnową polimeru były jak największe, rozkład napełniacza w polimerze
był jednorodny oraz aby napełniacz miał dobrą zwilżalność polimerem. W badaniach jako
wzmocnienia użyto wielościennych nanorurek węglowych, które zostały umieszczone w
osnowie polimerowej. Osnowę stanowił alkohol poliwinylowy wraz z dodatkiem dyspersji
akrylanowo-poliuretanowej.
W pracy przedstawiono wyniki badań właściwości mechanicznych kompozytów
polimerowych wzmacnianych nanorurkami węglowymi, wyznaczone przy pomocy próby
trójpunktowego zginania. Dla każdego z otrzymanych kompozytów określono gęstość oraz
wyznaczono przewodność właściwą w temperaturze pokojowej. Przy pomocy profilometru
wyznaczono parametr chropowatości kompozytów, który został porównany z parametrem
chropowatości wyznaczonym podczas badania na mikroskopie sił atomowych (AFM).
Przeprowadzono pomiary topografii powierzchni metodą Tapping Mode zbierając dane
z wysokości i obrazowania fazowego.
- 179 -
nanocząstki tlenku cynku, bakteriofagi,
spektrometria luminescencyjna
KAMILA ŻELECHOWSKA*, PIOTR GOLEC**, ANDRZEJ M. KŁONKOWSKI***,
GRZEGORZ WĘGRZYN**
*
Politechnika Gdańska, Wydział Fizyki Technicznej i Matematyki Stosowanej
Uniwersytet Gdański, Wydział Biologii
***
Uniwersytet Gdański, Wydział Chemii
**
NANOCZĄSTKI ZnO OTRZYMYWANE METODĄ
BIONANOTECHNOLOGICZNĄ
Bakteriofagi (w skrócie fagi) to szeroko występująca w przyrodzie grupa wirusów,
które atakują bakterie. Zbudowane są z materiału genetycznego, otoczonego białkami
strukturalnymi, które tworzą tzw. kapsyd. W kapsydach fagowych istnieje możliwość
modyfikacji różnych białek, w taki sposób, aby wykazywały one powinowactwo do
określonego rodzaju materiału [1]. Otrzymano fagi eksponujące peptydy zdolne do
selektywnego wiązania kryształów ZnO, które wykorzystano do otrzymywania nanocząstek
tego materiału o różnych wymiarach. Wielkość nanocząstek była determinowana ilością par
jonowych tlenu i cynku znajdujących się w roztworze. Otrzymane nanocząstki
scharakteryzowano przy użyciu refleksyjnej spektrofotometrii absorpcyjnej, spektrometrii
luminescencyjnej, mikroskopii elektronowej oraz dyfrakcji rentgenowskiej.
Nanocząstki tlenku cynku ze względu na unikalne właściwości fotofizyczne mogą
znaleźć zastosowanie między innymi jako materiały luminezujące w nowoczesnych źródłach
światła czy jako materiały w wysokowydajnych ogniwach fotowoltaicznych [2]. Mogą być
również wykorzystywane w obrazowaniu tkanek oraz stanowią obiecujący składnik budowy
biosensorów [3].
Literatura
[1] M. Li, Nat. Biotechnol. 18 (2000) 1251.
[2] G. Pérez-Hernández et al. Solar Energy Materials and Solar Cells 100 (2012) 21.
[3] Xingyong Wu, et al., Nat. Biotechnol. 21 (2003) 41.
- 180 -
nanoparticles, magnetic properties,
semiconductors
GRZEGORZ ŻOŁNIERKIEWICZ*, JANUSZ TYPEK*, NIKO GUSKOS*/**,
ALEKSANDER GUSKOS*, URSZULA NARKIEWICZ***
*
West Pomeranian University of Technology, Faculty of Mechanical Engineering and
Mechatronics, Institute of Physics, Al. Piastów 48, 70-311 Szczecin, Poland
**
University of Athens, Faculty of Physics, Department of Solid State Physics,
Panepistimiopolis, 15 784 Zografou Athens, Greece
***
West Pomeranian University of Technology, Institute of Chemical and Environment
DC MAGNETIZATION STUDY OF NANOCRYSTALLINE
(MnO)I/(ZnO)(1-I) (I=0.2, 0.3 AND 0.4)
DC magnetization study of (MnO)I/(ZnO)1-I (I=0.2, 0.3 and 0.4) nanopowders have
been carried out in the 2–290 K temperature range using a Quantum Design Magnetic
Property Measurements System MPMS XL-7 with superconducting quantum interference
device magnetometer. Initially, samples were characterized by XRD that revealed the
presence of different concentrations of ZnO and ZnMnO3 phases. An average size of
magnetic ZnMnO3 nanocrystallites was in the range 9-10 nm. The morphology of samples
was studied by use of TEM and has revealed the presence of ZnO hexagonal and spherical
ZnMnO3 nanograins. Magnetization measurements in ZFC and FC modes have been made to
determine the values of the blocking temperature TB. The blocking temperature was measured
to be below 10 K for all samples and above that temperature the presence of the
superparamagnetic state was registered. The value of TB depended on the content of magnetic
phase and increased with ZnMnO3 concentration. It was also noticed that the value of TB
depends on the strength of the measuring magnetic field – if it is smaller than 100 Oe, TB
increased by as much as 1.5 K. This indicates on important role of magnetic dipol-dipole
interactions in this system.
- 181 -

Applied nanotechnology - Zachodniopomorski Uniwersytet

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