PhD Michał Cichomski - Urząd Miasta Łodzi · Education for “Preparation of ultrathin films of...

AUTHOR ’S REVIEW OF HIS RESEARCH

PhD Michał Cichomski

University of Lodz

Faculty of Chemistry

Department of Materials Technology and Chemistry

Lodz 2013

Michał Cichomski Author’s review of his research

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Contents I. Curriculum vitae----------------------------------------------------------------------------------------- 3

II. Description of scientific work ------------------------------------------------------------------------ 4

1. Description of scientific work before receiving of doctorate --------------------------------- 4

2. Description of scientific work after receiving of doctorate------------------------------------ 5

III. Scientific achievements submitted for the habilitation procedure ----------------------------- 8

IV. Description of series publications which are the scientific achievement submitted for the

habilitation procedure-------------------------------------------------------------------------------- 9

V. Scientific works published before receiving of doctorate---------------------------------------22

VI. Other scientific works published after receiving of doctorate ---------------------------------26

VII. Participation in national and international scientific conferences----------------------------29

VIII. Participation in conference organization -------------------------------------------------------36

IX. Patent application ------------------------------------------------------------------------------------36

X. Scientific projects -------------------------------------------------------------------------------------36

XI. Scientific reviews ------------------------------------------------------------------------------------37

XII. Didactics----------------------------------------------------------------------------------------------37

1. Leading and coordinaton of courses ----------------------------------------------------------------37

2 Substantive care of students---------------------------------------------------------------------------38

XIII. Received awards and distinctions ---------------------------------------------------------------38

XIV. Expertises or other investigations related to business or other entities performing public

functions-----------------------------------------------------------------------------------------------38

XV. Promotion of chemistry ----------------------------------------------------------------------------39

XVI. Statistic of scientific work ------------------------------------------------------------------------39


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I. Curriculum vitae

Education:

1990–1995 Technical High School in Elecrtonics–Zdunska Wola.

1995–2000 Chemistry studies − University of Lodz, Faculty of Physics and Chemistry

Master thesis, title:

“Investigation of surface topography and nanotribolgical properties of siliceaus

ceramic materials by atomic force microscopy”

Supervisor: Prof. dr hab. Stanisław Płaza.

2000–2004 Doctoral studies at the University of Lodz

Doctoral thesis, titled:

“Morphological and nanotribological studies of nanocomposite materials”

Supervisor: Prof. dr hab. Stanisław Płaza. Defense of doctoral thesis was in 2005.

Employment:

2004–2005 University of Lodz, Department of Chemical Technology and Environmental

Protection – assistant

2005–2006 Ohio State University, Nanotechnology Laboratory for Storage and

MEMS/NEMS (now Nanoprobe Laboratory for Bio- & Nanotechnology and

Biomimetics) Columbus, USA – postdoctoral researcher

2006– University of Lodz, Department of Chemical Technology and Environmental

Protection (now Department of Materials Technology and Chemistry) – adjunct


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II. Description of scientific work

1. Description of scientific work before receiving the doctor degree

In 1995 I finished the Technical High School in Electronics in Zdunska Wola and

undertook studies in chemistry at the University of Lodz. The master thesis, whose title was

“ Investigation of surface topography and nanotribolgical properties of siliceaus ceramic

materials by atomic force microscopy”, I made in the Department of Chemical Technology

and Environmental Protection and Department of Solid State Physics in the Division of

Physics and Technology of Nanometric Structures. This work had an interdisciplinary

character and was defended in 2000. The supervisor of my work was Prof. Stanisław Płaza.

The experiences obtained during the master thesis were the inspiration to continue the

scientific activity. In this case, I undertook doctoral studies in the Faculty of Physics and

Chemistry at the University of Lodz. In this time, my interest was focused on self assembled

monolayers. The first study consisted of obtaining molecular resolution and verification of

chemical resistance of thiols monolayers.

To achieve these goals I used the experience acquired during my cooperation with a

team of Prof. Wielisława Olejniczak from the Division of Physics and Technology of

Nanometric Structures associated with atomic force microscopy (AFM) and scanning

tunneling microscopy (STM). These experiences, in connection with widely understood

chemical knowledge obtained at the Department of Chemistry University of Lodz, were the

basis for the understanding and control of phenomena at the nanoscale.

The next step was studies which improved tribological properties of the thiols compared

to the substrates on which they are attached [B-11]. The aim of these studies was to create

a model, atomically flat silica, from a 3-merkaptopropylotrimethoksysilane (MPTMS)

precursor, prepared as a monolayer on polycrystalline gold Au(111). This self assembled

monolayer was hydrolyzed and condensed leading to an SiO2 layer. This layer served as

a model ceramic substrate for the addition of subsequent, chemically bounded individual

organic layers, creating nanocomposities.

The optymalization of monolayer fabrication was controlled by a topography and

tribological point of view. The main objective was to find a system which possessed the

lowest coefficient of friction. Nanocomposite systems prepared from SiO2 layer and

chemically bounded organic films were characterized in nano- and microscale. The results


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showed that in the nanotribological test, nanocomposites are characterized by the lowest

coefficient of friction when compared to the substrate. However, in miliscale, I have shown

that the layers have the same trend of the coefficient of friction compared to nanoscale [B16].

In the first phase of doctoral studies the results achieved allowed the application for and

awarding of a grant from the Polish Ministry of Science and Higher Education.

The final result of my doctoral study and grant realization was my dissertation titled

“Morphological and nanotribological studies of nanocomposite materials” Defense of this

doctoral thesis was in 2005.

In 2004-2005, I was employed as an assistant in the Department of Chemical Technology and

Environmental Protection, University of Lodz

2. Description of scientific work after receiving of doctorate

In 2005─2006 I worked as a postdoctoral researcher at the Ohio State University,

Nanotechnology Laboratory for Storage and MEMS/NEMS, Columbus, USA (now

Nanoprobe Laboratory for Bio-& Nanotechnology and Biomimetics) in the group of Prof.

Bharat Bhushan. Research subjects in the group focused on the fundamental studies in the

interdisciplinary areas of bio-/nanotribology and characterization nanomaterials

The main objectives of the research group were to carry out bio-inspired

nanostructured surfaces, superhydrophobic and self-cleaning surfaces and interfaces with

smart adhesion. Another main goal was the development of theoretical models and

measurements of electrical and mechanical properties of nanostructures. In Prof. Bharat

Bhushan’s research group, I dealt with the production of ultrathin films and control of friction

and adhesion phenomena at the nanoscale. Instrumentation used in the study was atomic force

microscopy with the registration of lateral force (FFM). Through cooperation with Prof.

Derek Hansford (Department of Biomedical Engineering, Ohio State University),

I constructed a system for the controlled deposition of ultrathin organic layers (Vapor Phase

Deposition) [A-3].

Based on the tests carried out, I proved that the obtained ultrathin layers are

hydrophobic and have low adhesion and a coefficient of friction lower than previously used

materials [A-1–A-3]. The studies also show that the test compounds can be used in systems

NEMS/MEMS (nano-/microelectromechanical systems) and biomedical applications [A-1–

A-3].


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The Postdoctoral Fellowship allowed me to directly cooperate with experts from other

scientific centers (Patrik Hoffmann, Hans Jörg Mathieu and James A. DeRose from the Ecole

Polytechnique Fédérale de Lausanne), as well as with corporations dealing with research in

the field of electronics and fabrication of digital media and digital recording data (Imation

Corporation). Through cooperation with Imation, I gained experience in working with high

and ultra-high vacuums. The results of our work improved the recording of information on

magnetic media and were presented in the publication B-20.

After returning from the USA, I continued my tribological investigations at the

University of Lodz and received a grant from the Polish Ministry of Science and Higher

Education for “Preparation of ultrathin films of organofluorine compounds for tribological

applications” (Grant number N N507 551538 – head of project).

The project was focused on chemical modification of different surfaces, such as silicon,

titanium, aluminum, cobalt and copper by various ultrathin fluoororganic films. The surfaces

were modified by using the vapor phase deposition method. The aim of the modification

process was to obtain ultrathin films of organosilanes which minimize adhesion, friction and

wear. Preparation of ultrathin films was designed to increase surface resistance in

physiological conditions and laboratory environments. The results of tribological research in

nano- and microscale allowed me to describe the conclusions that the structure of

organosilane compounds (chain length, presence of fluorine atoms and type of terminal group

( not sure what a ‘terminal group’ is) influence on coefficient of friction values.

In parallel with the work on fabrication and tribological characteristics of self-

assembled layers, I conducted research on magnetic domain structure and morphological

structure using magnetic force microscopy (MFM) and atomic force microscopy. These

studies were performed in cooperation with Prof. Witold Szmaja from the Department of

Solid State Physics, University of Lodz and focused mainly on the analysis of the study of

magnetic domain structure and morphological structure of massive single crystals of cobalt,

anisotropic sintered magnets Nd–Fe–B and SmCo5, nanocrystalline magnets Nd2Fe14B/Fe3B

and thin films of permalloy and cobalt. The use of magnetic force microscopy gave the

opportunity to increase the resolution imaging of magnetic domain structures and, thus, the

possibility of knowledge and understanding of magnetic domains and their details of structure.

These were the first studies for this type of magnetic materials.

In this cooperation twelve scientific articles [B-6, B-9, B-10, B-12−B-14, B-19, B-21,

B-27−B-29, B-31] and many presentations on conferences were published.


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Cooperation with Professor Arkadiusz Ptak from Poznan University of Technology

has resulted in investigations centered on the control of adhesion in nanometer scale. This

experimental work was based on gold and silicon surface modification by alkylthiols and

fluoroalkylsilanes, respectively. These modified surfaces were used to determine the humidity

influence on adhesion of films which possessed different wettability. The result of the

research was the development of the method of analysis which allows for quantitative

information about single atomic bonds. For this purpose Dynamic Force Spectroscopy and

mechnical-adhesive interactions models were used: the Johnson-Kendall-Roberts and the

Derjaguin-Muller-Toporov model. This cooperation resulted in the publication of the article

B-25.

Other research achievements were related to electrochemical investigations of the

modification of glassy carbon electrodes with phenanthroline complexes of manganese

Mn (II) immobilized in a nafion layer. I also participated in the studies of properties of glassy

carbon modified with Ce (III) ions immobilized in nafion film and the catalytic activity of

these ions or the catalytic activity of the modified conducting phase in electrochemical

oxidation of some hydroquinone, phenylenediamine and 4-hydroxybenzoic acid derivatives.

I was also involved in the works connected with preparation of the bioconjugantes

which include metallocarbonyl compounds, gold nanoparticles and antibodies and could be

potential tools to monitor antigen-antibody interactions by infrared spectroscopy (FT─IR).

The results were published in publications B-17, B-18, B-32.

During my research I specialized in the study of surface properties using scanning

probe microscopy, using this technique to determine the size of the nanoparticles for

biomedical and technology applications. The result of these studies was the research project

realization, “Synthesis and characterization of gold, silver and copper nanoparticles" for

which I was the main project contractor.

The above research achievements helped to enrich academic experience and provided

an opportunity to establish cooperation with other research centers – Nanoprobe Laboratory

for Bio- & Nanotechnology and Biomimetics (Columbus, USA), Institute of Chemical

Physics, Chinese Academy of Science (Lanzhou, China), Poznan University of Technology,

Institute of Physics, Departments of University of Lodz: Solid State Physics, Inorganic and

Analytical Chemistry and Organic Chemistry. These studies also provide inspiration for

further research and scientific development.


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III. Scientific achievements submitted for the habilitation procedure

As an achievement resulting from Article 16, section 2 of the Acto on Academic

Degrees and Titles and about Degrees and Titles in the Field of Fine Arts of March 14, 2003

(Dz.U. No 65/2003, item 595, with subsequent amendments) I’m designating the series of ten

of scientific publications [A-1−A-10] entitled “Preparation and characterization of ultrathin

organic layers to tribological applications”.

A-1. B. Bhushan, M. Cichomski (30%), E. Hoque, J. A. DeRose, P. Hoffmann, H. J. Mathieu

Nanotribological characterization of perfluroralkylphosphonate self-assembled monolayers

deposited on aluminum coated silicon substrates

Microsystem Technologies 12, 588–596 (2006) – IF 0,931

A-2. E. Hoque, J. A. DeRose, P. Hoffmann, H. J. Mathieu, B. Bhushan, M. Cichomski (30%)

Phosphonate self assembled monolayers (SAMs) on aluminum surfaces

Journal of Chemical Physics 124, 174710–74716 (2006) – IF 3,333

A-3. B. Bhushan, M. Cichomski (50%)

Nanotribological characterization of vapor phase deposited fluorosilane self-assembled

monolayers deposited on polydimethylsiloxane surfaces for biomedical micro-/nanodevices

Journal of Vacuum Science and Technology A: Vacuum, Surfaces and Films 25, 1285–1293

(2007) – IF 1,253

A-4. M. Cichomski (50%), K. Kośla, J. Grobelny, W. Kozłowski, P. J. Kowalczyk,

A. Busiakiewicz, W. Szmaja, J. Balcerski

Nano- and microtribological characterization of silanes deposited on cobalt

Journal of Alloys and Compounds 507, 273–278 (2010) – IF 2,289

A-5. M. Cichomski (60%), K. Kośla, J. Grobelny, W. Szmaja, J. Balcerski

Tribological and magnetic characterization of fluorosilanes on cobalt surface

Journal of Alloys and Compounds 501, 362–365 (2010) – IF 2,289


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A-6. M. Cichomski (60%), E. Tomaszewska, K. Kośla, W. Kozłowski, P. J. Kowalczyk,

J. Grobelny

Study of dithiol monolayer as the interface for controlled deposition of gold

Materials Characterization 62, 268–274 (2011) – IF 1,572

A-7. M. Cichomski (80%), W. Szmaja

MFM and AFM study of thin cobalt films modified by fluorosilane

Applied Physics A: Materials Science and Processing 102, 339–343 (2011) – IF 1,63

A-8. M. Cichomski (60%), K. Kośla, W. Kozłowski, W. Szmaja, J. Balcerski, J. Rogowski,

J. Grobelny

Investigation of the structurce of fluoroalkylsilanes deposited on alumina surface

Applied Surface Science 258, 9849–9855 (2012) – IF 2,103

A-9. M. Cichomski (100%)

Tribological investigations of perfluoroalkylsilanes monolayers deposited on titanium surface

Materials Chemistry and Physics 136, 498–504 (2012) – IF 2,234

A-10. M. Cichomski (60%), K. Kośla, J. Grobelny, W. Kozłowski, W. Szmaja

Tribological and stability investigations of alkylphosphonic acids on alumina surface

Applied Surface Science 273, 570–577 (2013) – IF 2,103

IV. Description of series publications which are the scientific achievement

submitted for the habilitation procedure

Introduction and objective of the dissertation

The development of modern technologies, such as bio-technology, electronics and

information technology, requires miniaturization of devices and systems while increasing

their efficiency, reaction time and longevity. In order to meet these requirements we are

looking for new surfaces and protective materials which reduce the wear of these devices. One

of the methods of solving problems which arise from high friction and wear is surface


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chemical modification by compounds such as alkylsilanes, alkylphosphonic acids or thiols.

This modification can be carried out by chemical adsorption of molecules on an active solid

surface (called self-organization). This process involves the formation of a thin organic layer

of the tested surfaces and is carried out in several steps. The first step is hydrolysis of the

silane molecules which, in consequence, form silanol bonds. The next step forms a hydrogen

bond between the hydroxyl groups from silane molecules and ─OH groups existing on the

modified surface. The final step is the creation of an ultrathin layer.

Due to the increasing demands and requirements of modern technology, the objective

of scientific work was defined, which was to provide development strategies that control

physicochemical properties of the surface by chemical modification with organic compounds.

Major results of publications which are the scientific achievement submitted for the

habilitation procedure

The series of scientific publications designated as achievements for habilitation

proceedings consists of 10 works listed hereunder, published in the years 2006–2013, entitled

“Preparation and characterization of ultrathin organic layers to tribological applications” in

journals listed in the Journal Citation Reports.

A-1. „Nanotribological characterization of perfluoroalkylphosphonate self-assembled

monolayers deposited on aluminum-coated silicon substrates”

In this study, I investigate contact angle, surface energy, friction, adhesion and wear

properties of a perfluoroalkylphosphonate films on aluminum and compare them with those of

alkylphosphonate. The influence of relative humidity, temperature and sliding velocity on the

friction and adhesion behavior is studied. Failure mechanisms of films obtained from

perfluoroalkyl- and alkylphosphonate molecules are investigated by wear tests.

Both fluorocarbon and hydrocarbon films showed a reduction in adhesive force,

friction force and coefficient of friction as compared to bare aluminum. Fluorinated

phosphonic acid, which has the lowest surface energy, also exhibited a lower adhesive force

than either of the hydrocarbon compounds. The films deposited on the aluminum substrate

showed a negligible dependence of adhesive force on the relative humidity. However, there

was some decrease in the coefficient of friction. This effect could be attributed to lubrication

by the adsorbed water layer. The long hydrocarbon chain molecules and the fluorocarbon


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backbone chains showed higher critical loads (20 µN) than short hydrocarbon chain molecules

(5 µN) and bare aluminum. From a tribological point of view, it is found that films with

compliant and long hydrocarbon backbone chains and those with fluorocarbon backbone

chains show a highly desirable behavior.

My contribution is related to: studies of the influence of relative humidity, temperature and sliding velocity on the friction and adhesion in the nanoscale, designation of critical loads, and the interpretation of results and manuscript preparation. I declare my contribution to be equal to 30%

A-2. „Phosphonate self-assembled monolayers on aluminum surfaces”

The work includes preparation and properties of the perfluoroalkyl- and

alkylphosphonic acids deposited on aluminum. The X-ray photoelectron spectroscopy (XPS)

analysis confirmed the presence of perfluorinated and nonperfluorinated alkylphosphonate

molecules on the aluminum surface. The static contact angle of pure water on

perfluoroalkylphosponic acids was typically more than 130° and surface free energy was 11

mJ/m2. For alkylphosphonic acids the static contact angle value was typically more than 125°,

indicating that all phosphonic acids were very hydrophobic. The surface energy was

determined to be approximately 20 mJ/m2 for alkylphoshopnic acids. The films obtained from

fluorinated compounds gave the lowest adhesion and coefficient of friction values, while bare

aluminum gave the highest.

My contribution is related to: preparation of perfluoroalkyl- and alkylphosphonic acids, determination of the wettability and nanotribological characterization of the layers. I declare my contribution to be equal to 30%.

A-3. „Nanotribological characterization of vapor phase deposited fluorosilane self-

assembled monolayers deposited on polydimethylsiloxane surfaces for biomedical micro-

/nanodevices”

The objective of this research was the preparation of self-assembled monolayers on

polydimethylsiloxane, which are desirable to control the hydrophobicity of the surface to

reduce or prevent undesired protein adsorption or cell interactions, critical for the performance

of many biomedical micro-/nanodevices. In this work, the vapor phase deposition was used to

deposit fluorosilanes on polydimethylsiloxane and deposition conditions for an optimal

process were identified. The films were characterized by means of a contact angle analyzer for

hydrophobicity and an atomic force microscope for adhesion and friction measurements. The


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influence of relative humidity, temperature and sliding velocity on the friction and adhesion

behavior was studied.

My contribution is related to: determination of optimal conditions for the deposition of layers, studies the influence of relative humidity, temperature and sliding velocity on the friction and adhesion in the nanoscale, designation of critical loads, interpretation of results, manuscript preparation. I declare my contribution to be equal to 50%.

A-4. „Nano- and microtribological characterization of silanes deposited on cobalt

substrate”

The main aim of this work was the preparation, and nano- and microtribological

investigations of organosilanes on cobalt surface. The modification was performed by

compounds with different structure. The applied organosilane compounds possessed different

chain length [1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS) and 3,3,3-

trifluorotrichlorosilane (FPTS)], different content of reactive atoms in the head group [3,3,3-

trifluorodimethylchlorosilane (FPDMS) and FPTS] and also different content of fluorine

atoms in the carbon chain [1H,1H,2H,2H-perfluorodecyldimethylchlorosilane (PFMS) and

n-decyldimethylchlorosilane (DDMS)]. The films were characterized by XPS for

identification of fluoroorganic films deposited on the surfaces. The thicknesses of the layers

determined from the ellipsometric measurements on the cobalt surface modified by different

compounds are comparable with the values obtained using the theoretical model. In this study,

the XPS spectra analysis suggests the formation of Co–O–Si linkages between silanes and the

cobalt surface and also shows the relationship between number of reactive atoms in head

group and quantity of generated bonds.

Adhesion and friction measurements were performed by AFM and compared with

those made by microtribometer operated in applied millinewton load range. Nano- and

microtribological measurements show that cobalt modified by fluoroalkylsilanes has lower

adhesion and coefficient of friction. The investigation also indicates a decrease of the friction

coefficient with increasing fluoric alkyl chain length. Covalently bonded fluoroalkylsilanes

with longer alkyl chains are found to be a prime candidate for practical use as a lubricant.

It should be noted that I was the first author who performed chemical modification of

the cobalt substrate by silanes and also who done tribological characterization in mili- and

nanonewton load range.

My contribution is related to: preparation of the organosilanes layers, nano- and microtribological investigations, analysis and interpretation of results, manuscript preparation. I declare my contribution to be equal to 50%.


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A-5. „Tribological and magnetic characterization of fluorosilanes on cobalt surface”

In this work, I present a study of tribological and magnetic properties of fluorosilane –

FDTS on cobalt surface. The effectiveness of modification of the cobalt surface by FDTS was

monitored by the measurement of the wetting contact angle and surface free energy. The

increase of surface hydrophobicity was observed upon the modification by reducing the

surface free energy and increasing the wetting contact angle. The nanotribological properties

were characterized by means of adhesion, friction and wear, using AFM. The cobalt surface

modified by FDTS exhibits lower values of adhesion and coefficient of friction in comparison

with those for the unmodified surface. It was also found that FDTS effectively reduces the

wear of the system. We also investigated the magnetic domain structure of the cobalt film

before and after modification by FDTS.

The magnetic domain structure was composed of maze stripe domains magnetized

perpendicular to the film surface, as revealed by MFM. The domain structure of the modified

cobalt film was practically the same (in character and in size) as that observed for the bare

cobalt film.

My contribution is related to: preparation of the organosilane layers, studies of the nanotribological investigations, designation of critical loads, determination of the magnetic structure of the surface investigated, analysis and interpretation of results, manuscript preparation. I declare my contribution to be equal to 60%.

A-6. „Study of dithiol monolayer as the interface for controlled deposition of gold

nanoparticles”

The paper presents the preparation of dithiol monolayers on polycrystalline Au (111).

The prepared dithiols were used as interface, which chemically bonds to the deposited gold

nanoparticles through strong covalent bonds.

The size and size distribution of the deposited nanoparticles were measured using

dynamic light scattering (DLS), scanning electron microscopy (SEM) and AFM. The average

size was in the range from (22 ± 4) nm to (27 ± 1) nm and depended on the used technique.

The size of monodisperse nanoparticles obtained from the DLS measurements is slightly

larger than that obtained from the AFM and SEM measurements. This is due to the fact that

the DLS technique measures the hydrodynamic radius, which is dependent on the protective

chemical layer on nanoparticles. The AFM results showed that nanoparticles are immobilized

and stable during scanning process and do not contaminate the AFM tip.


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The effect of the presence of the aromatic ring and alkyl chain connecting on the

efficiency of dithiols nanoparticles was also studied. The 1,6-heksadithiol (HDT) film was

found to be a better candidate for the controlled nanoparticle deposition interface. It was

determined that the best properties of the alkyl chains compounds are connected with the lack

of steric hindrance (presented in the aromatic dithiols) and associated with these lack of

hindrance defects in the formed film.

My contribution is related to: preparation of the self assembled monolyers, the determination of the gold nanoparticles size by using AFM, STM measurements, analysis and interpretation of results, manuscript preparation. I declare my contribution to be equal to 60%.

A-7. „MFM and AFM study of thin cobalt films modified by fluorosilane”

The work is related to the research presented in the publication A-5. It contains

investigations of the magnetic and morphology structure of cobalt surfaces with FDTS films

of various thicknesses, in the range of about 2 nm to 30 nm. MFM observation showed that

the magnetic domain structure of the cobalt films modified by FDTS is composed of domains

with a considerable component of magnetization perpendicular to the film surface. This in

turn indicates that the cobalt films on naturally oxidized Si(100) substrates crystallize in the

hexagonal close-packed (HCP) phase and exhibit a texture with the hexagonal axis

perpendicular to the film surface. The magnetic domains formed a maze structure. The

domain width increased from typically 80–120 nm to 400–500 nm with increasing the

thickness of FDTS films from about 2 nm to 30 nm. AFM imaging of the surfaces of FDTS

films revealed the presence of an agglomerate morphology.

I was the first person who made the magnetic study of cobalt surface modified by

fluorosilane and indicated a relationship between the width of the magnetic domains on the

thickness of the film.

My contribution is related to: preparation of the organosilane layers, determination of magnetic, morphological and tribological properties of the layers in nanoscale, analysis and interpretation of results, manuscript preparation. I declare my contribution to be equal to 80%.

A-8. „Investigation of the structure of fluoroalkylsilanes deposited on alumina surface”

This paper is devoted to studies of the structure of fluoroalkylsilanes on alumina

surface by XPS, ToF-SIMS, FT-IR spectroscopy and AFM. The fluoroalkylsilanes were

prepared on alumina surface using the vapor phase deposition method. XPS and ToF-SIMS

measurements confirmed the presence of fluoroalkylsilanes on the alumina surface.


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AFM was used to compare the frictional behavior of samples after modifying the

alumina surface by fluoroalkylsilanes. Nanotribological investigation of fluoroalkylsilanes

films with different head groups on the alumina surface include, besides frictional studies,

also adhesive forces research. It is shown that the surface modification of alumina by

fluoroalkylsilanes decreases the coefficient of friction and adhesive forces values by more

than 50% compared to the unmodified alumina. In comparison with the non-modified alumina

surface, all tested silanes, particularly compounds with three reactive atoms in the head group,

cause a decrease in the friction coefficients in nanofriction studies. The same effect was also

observed for adhesion measurements. It was found that the alumina modified by trifunctional

fluoroalkylsilanes have a higher degree of hydrophobicity, lower adhesion and lower

coefficient of friction than the monofunctional fluoroalkylsilanes covered alumina surface.

This is connected with Si–O–Si bonds formation between trifunctional compound molecules,

which in consequence leads to higher packing density. The mentioned finding was proved by

the results obtained using the XPS, ToF-SIMS and FT-IR spectroscopy techniques.

My contribution is related to: preparation of the organosilanes layers, studies of nanotribological properties in the nanoscale, determination of IR spectroscopy data, analysis and interpretation of results, manuscript preparation. I declare my contribution to be equal to 60%.

A-9. „Tribological investigations of perfluoroalkylsilanes monolayers deposited on titanium

surface”

In this work I present a systematic study of titanium modification by fluoroalkylsilanes

and surface characterization from the tribological point of view. The vapor phase deposition

method was used to modify titanium surfaces by fluoroalkylsilanes, and the influence of the

used modifier on the tribological properties is presented. The modification procedure

efficiency, surface structure and morphology were characterized by FT-IR spectroscopy, XPS,

ToF-SIMS and AFM. The effectiveness of modification of the titanium surface was

monitored by the measurements of the wetting contact angle and the surface free energy.

The tribological performance of various perfluoroalkylsilanes films on the titanium

surface was investigated in milli- and nanonewton load ranges. Dependence of the adhesive

force and coefficient of friction values obtained in nano- and microscale on fluoroalkyl chain

length was observed. Nano- and microtribological measurements show that titanium modified

by fluoroalkylsilanes has lower adhesion and coefficient of friction than the unmodified one.

The investigation also indicates a decrease of the friction coefficient with increasing fluoric


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alkyl chain length. Fluoroalkylsilanes with three carbon atoms in chain compared to ten

carbon atoms in chain compounds are more reactive and are capable of vertical polymerizing

what confirmed FT-IR spectroscopy and ToF-SIMS measurements. Shorter chain molecules

provided weaker interactions between the backbone chain groups, larger number of structure

defects, and in consequence higher values of the adhesive force and coefficient of friction in

nano- and microscale.

This work is one of the few publications that presents a broad analysis of the impact of chains

length of organosilicon compounds on the structure of the layers, and indicates that there is

a correlation between the structure of the surface free energy and its components and

tribological properties.

My contribution is related to: preparation of the organosilanes layers, determination of the morphology structure and tribological studies in micro- and nanoscale, investigation of the modified titanium surface wettability, analysis and interpretation of results, manuscript preparation. I declare my contribution to be equal to 100%.

A-10. „ Tribological and stability investigations of alkylphosphonic acids on alumina

surface”

The paper is related to the studies reported in the publications A-1 and A-2. The

alkylphosphonic acids were prepared on the alumina surface using the liquid phase deposition

method. The effectiveness of modification of the alumina surface by alkylphosphonic acids

was investigated using water contact angle measurements, ToF-SIMS, XPS and FT-IR

spectroscopy. XPS data reveal that alkylphosphonic acids form chemical bonds with the

alumina surface. Contact angle studies prove that n-octadecylphosphonic acid (ODP) and

n-decylphosphonic acid (DP) films are highly hydrophobic, yielding water contact angles

120° and 116°, and surface energies 28 mJ/m2 and 29.5 mJ/m2, respectively. The results

obtained by contact angle and FT-IR spectroscopy agree well, and indicate that ODP produces

more ordered phosphonate films on the alumina substrate than DP. This finding is evidenced

by the highest value of contact angles and the presence of the asymmetric and symmetric

stretching bonds at lower wavenumbers for ODP.

Frictional behavior in millinewton load range was also studied by microtribometry. It

is shown that surface modification of the alumina surface by alkylphosphonic acids reduces

the coefficient of friction values compared to the unmodified alumina. In comparison with

the non-modified alumina surface, all tested alkylphosphonic acids cause a decrease in the

friction coefficients in friction tests for counterparts made from different materials, such as


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steel, zirconia and silicon nitride. It is also found that the alumina surface modified by

alkylphosphonic acids with longer chain has a higher degree of hydrophobicity and lower

coefficient of friction. The best frictional properties are obtained for the system consisting of

the alumina surface modified by n-octadecylphosphonic acid and silicon nitride counterpart.

Stability tests in different environmental conditions: laboratory, acidic and alkaline

solutions were also monitored. Stability tests performed in acidic and basic environments

reveal that longer chain alkylphosphonic acids modified alumina surface shows comparatively

better stability than shorter chains compounds. Contact angle and FT-IR spectroscopy

measurements confirmed the presence of alkylphosphonic acids after six months exposure to

laboratory conditions.

So far, a few works have investigated the chemical stability of organosilanes on copper and

silicon nitride. As one of the first authors, I conducted a investigations of impact of solutions

pH on the chemical stability of alkylphosphonic acids deposited on alumina surface.

My contribution is related to: preparation of the preparation of alkylphosphonic acids layers, determination of the morphology structure and tribological studies, analysis and interpretation of results, manuscript preparation. I declare my contribution to be equal to 60%.

This series of works present the research results involving the preparation and

tribological investigations of self-assembled monolayers/surface systems. The research

objective was obtaining nanometer thickness films which could allow control of surface

properties, such as wettability, adhesion, wear and in consequence could act as a lubricant.

As fabrication methods for these types of layers I used liquid phase deposition and

vapor phase deposition methods. Research was done with compounds: silanes,

alkylphosphonic acids and thiols with different structure. Chemical modification included

surfaces of titanium, alumina, silicon, cobalt, polydimethylsiloxane and gold.

In my research I used a variety of techniques (Secondary Ion Mass Spectrometry with

time of flight mass analyzer ─ ToF─SIMS, X─ray photoelectron spectroscopy ─ XPS,

infrared spectroscopy ─ FT─IR, scanning tunneling microscopy ─ STM). These techniques

allow the verification of film preparation and bond formation between compounds and

modified surfaces. Atomic force microscopy – AFM and microtribometer, have enabled

tribological investigations in nano- and micronewton load range. Magnetic force microscopy

– MFM, observation of the magnetic structure of the cobalt films composed of domains with a

considerable component of magnetization perpendicular to the film surface.


- 18 -

In addition, I used ellipsometry in determining the thickness of the formed film. Based

on these studies, it was found that the thickness of films were below 10 nm, allowing us to

conclude that we are dealing with ultra-thin layers.

For prepared films micro- and nanotribological investigations were also performed.

They allow us to determine the influence of the compounds on adhesive force, coefficient of

friction and wearing values for systems consisting of the self-assembled monolayers/surface.

The experimental materials collected in these studies helped to determine the effect of the

compound‘s structure on the tribological properties of the systems.

Among the above-mentioned studies five dominant areas can be distinguished that mainly

focused on the:

– developing of an effective method for obtaining films with nanometer thicknesses on

substrates used in biomedical and electronics devices (publications A-1 − A-10)

– determining of the tribological properties in micro- and nanoscales (publications A-1−A-5

and A-7−A-10)

– indication of the correlation between compounds structure and adhesive force, coefficient of

friction and wear values (publications A-1−A-4, A-8, A-9)

– investigations of magnetic properties of unmodified cobalt and cobalt surface modified by

silanes (publications A-5, A-7)

– demonstration of the film’s application possibilities for the controlled deposition of gold

nanoparticles, protection of devices used in biomedical applications from wear and film

applications as a lubricant in devices where the micro- and nanonewton normal loads

dominate (publications A-3, A-4, A-6, A-8 )

Research from the first point has been taken with a view to developing an effective

method of preparation, selection of compounds which will be effective in modifying surfaces

and creating low-friction ant anti-wear ultrathin films.

In these series of publications I present methods of preparation and characterization of

ultrathin films. These films were obtained by using the following compounds:

alkylphosphonic acids, organosilanes and thiols. Films were prepared on surfaces such as

titanium, alumina, cobalt, gold and polydimethylsiloxane. Surface modification was carried


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out by compounds with different structure: chain length, type and structure of head and

terminal groups.

The investigated compounds had the following terminal groups: ─CH3, ─CF3,

and head groups: ─SH, ─PO(OH)2, ─SiCl3, ─Si(OMe)3, ─Si(OEt)3, ─Si(CH3)2Cl.

Surface modification was performed by gas and liquid chase deposition methods.

Optimum deposition parameters, such as immersion time, temperature and solution

concentration and gas pressure were performed experimentally. These conditions depend on

the type of compounds used, compound structure and surface which is being modified [A-3,

A-9, A-10].

Self-assembled monolayers were prepared from liquid and gas phase deposition

methods. The verification of the modification procedure was performed by XPS, ToF-SIMS

oraz FT-IR techniques. On the basis of XPS and FT-IR spectra it was found that compounds

form ultrathin films on studied surfaces.

Interpretation of the results obtained by using XPS and ToF-SIMS allows for the

verification of chemical modification of the titanium, alumina, cobalt and gold surfaces and

suggests the production of chemical bonds between the molecules and the substrate surface

surface–O–Si–, surface–O–P– and surface–S–.

The ellipsometry measurements allowed us to determine the thickness of the films.

Based on these studies and also on XPS measurements, it can be concluded that the obtained

film thickness is below 10 nanometers. The thicknesses of films, determined from the

ellipsometric measurements on the titanium, alumina and silicon surfaces modified by

different compounds, are comparable with the values obtained by the theoretical model

determined using HyperChem 7.5 (except FPTS film). The thickness of the FPTS layer is

much larger than the theoretical value which is probably due to vertical polymerization and

formation of multilayers and agglomerates of the FPTS compound.

Analysis of the results of the ToF-SIMS and ellipsometry measurements stems from

the compound structure’s (carbon chain length) effect on various types of polymerization that

occur on the surface. In the case of FDTS compound, horizontal polymerization occurs, while

for FPTS, vertical polymerization takes place. Horizontal polymerization provides densely

packed and ordered films while vertical polymerization gives a lot of possible surface

F F

F

FF


- 20 -

structures, including formation of gauche defects and disorder in the formed layer. This

disorder has an influence on the wettability and frictional measurements.

Investigations performed in the second and third research question allowed the

identification and explanation of the tribological properties which are the key to the

possibility of self-assembled layer usage in applications. The coefficient of friction

measurements was performed using microtribometer and AFM. These techniques allowed me

to characterize the frictional properties of the films and compare the impact of changes in the

chemical structure and topography of the measured coefficient of friction in the micro- and

nanonewton load range. Finding a correlation between the results of friction tests confirm the

thesis that the chemical structure of materials determined the friction processes (for the

described normal loads).

The result of tribological research shows that the compound’s structure affects the

coefficient of friction values. The crucial factors are: carbon chain length, the presence of

fluorine atoms in the backbone chain and the structure of the head group. Comparing the

effect of the presence of aromatic ring and alkyl chain on the coefficient of friction and

adhesive force values, it can be concluded that the higher values are obtained for aromatic

compounds. This is due to the presence of stearic hindrance and in consequence with

a packing density decrease.

In the case of silanes, compounds with a longer, perfluoroalkyl, chain (FDTS) exhibit

lower coefficient of friction values and adhesive force in mili- and nanonewton load range.

The effect of the chain length on the tribological properties results from the different degree of

order and packing density. The shorter molecules assemble into a less dense, liquid-like

structure. Increasing the chain length results in an increase of the van der Waals interaction

between the alkyl chains, and this in turn leads to a more crystalline, all-trans conformation of

the chains. The lower order for shorter molecules is supported by FT─IR spectroscopy

investigations and is also evident in the smaller contact angle and surface free energy values.

Siloxane networks between neighboring molecules also provide lower values of the

coefficient of friction and adhesive force values.

Surfaces modified by FDTS are hydrophobic, hence lower values of the surface free

energy and show insignificant changes in the coefficient of friction values in nano- and

microscale. It is connected with the limitation of the formation of water meniscus. Limitation

of the formation of water meniscus affects the decrease of capillary forces existing between

studied surface and their counterparts. In the case of phosphonic acids the lowest coefficient


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of friction, adhesive force values and the highest wear resistance in nanoscale provide

compounds with perfluoroalkyl chains. Modified surfaces show a stable value of coefficient

of friction and adhesive force in the 10–90% humidity range (for unmodified surfaces these

values increase with a relative humidity increase).

In summary, the best modifiers (compounds which provide the lowest values of

coefficient of friction, adhesion and wear in investigated, tribological systems) are compounds

which possess fluorinated, ten carbon atom chains.

Another undertaken research area was the investigation of the magnetic structure of the

cobalt film before and after modification by silanes. This issue is important because of the use

of cobalt and its alloys in magnetic sensors and magneto-optics. Cobalt and its alloys have

also been used in the military, aerospace industry and also in biomedical applications,

including the therapy of cardiovascular diseases and orthopedics. The widespread use of

cobalt alloys is associated with their high resistance to corrosion and wear, and their tolerance

in an environment of tissue and body fluids.

They exhibit different magnetic properties, such as magnetic anisotropy, magnetic

microstructure, coercivity and magnetoresistance, depending on their thickness, composition,

crystalline structure and preparation conditions.

The main aim of the A-5 and A-7 publications was imaging magnetic and morphology

structures of the silane modified cobalt by atomic and magnetic force microscopies. The

presented research showed that the magnetic domain structure exhibited a maze stripe pattern.

The domains had their magnetizations perpendicular to the film surface. The domain structure

of the cobalt film modified by fluorosilane was practically the same (in character and in size)

as that observed for the bare cobalt film. MFM observation showed that domain width

increased from typically 80–120 nm to 400–500 nm with an increasing thickness of films

from about 2 nm to 30 nm. This is connected with magnetic anisotropy decrease in the

investigated system: cobalt-silane.

In the presented series of publications I have shown the possibility of film application for

controlled deposition of gold nanoparticles [A-6], as protection layers for biomedical devices

[A-3] and as lubricants in applications where nanonewton and milinewton normal loads

dominate [A-1, A-2, A-5, A-9]. In the case of the controlled deposition of gold nanoparticles

for their characterization using by STM, I have shown that a compound’s structure affects

gold deposition efficiency. The film composed with aliphatic molecules was found to be

a better candidate for the controlled nanoparticle deposition interface than molecules with


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aromatic rings. It was determined that the best properties of the aliphatic compounds are

connected with the lack of steric hindrance (presented in the aromatic dithiols) and, associated

with this hindrance, defects in the formed film.

In the case of the self-assembled monolayer application in protection devices used in

biomedicine, I focused on studies of the polydimethylsiloxane properties. Due to its

properties: high hydrophobicity and visco-elastic properties, polydimethylsiloxane is used in

biomedical applications; for example for the production of contact lenses and microsystems

which are used in DNA analysis, enzymatic and immunology tests or stent covering. In

publication A-3 I show that silanes are an effective protection for PDMS against wear.

The main issues presented in the literature which is the basis for the habilitation procedure

application was to control the tribological properties of the surfaces used in systems where the

loads are ranges nano- and micronewtons such as microelectromechanical systems.

I proved that silanes and alkylphosphonic acids can be an effective protection for surfaces

used in MEMS/NEMS applications. The self-assembled monolayer coefficient of friction,

adhesive force and wear decrease even several times in comparison with the unmodified

surface.

Analyzing the collected results, I have shown an effective method to modify surfaces

and also prove the existence of the correlation between the structure of compounds and their

physicochemical properties.

V. Scientific works published before receiving of the doctor degree

B-1. S. Kadłubowski, J. Grobelny, W. Olejniczak, M. Cichomski, P. Ulański

„Pulses of fast electrons as a tool to synthesize poly(acrylic acid) nanogels. Intramolecular

cross-linking of linear polymer chains in additive-free aqueous solution”

Macromolecules 36, 2484–2492 (2003)

My contribution is related to: visualization and identification of the nanogels roughness obtained using an atomic force microscope. I declare my contribution to be equal to 20%.

B-2. G. Celichowski, I. Piwoński, M. Cichomski, K. Koralewski, S. Płaza, W. Olejniczak,

J. Grobelny

„The influence of methyl groups content on tribological properties of organo-silica

thin films”


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Tribology Letters 14, 181–185 (2003)

My contribution is related to: studies of the tribological properties by atomic force microscopy, analysis and interpretation of results, manuscript preparation. I declare my contribution to be equal to 20%.

B-3. J. Grobelny, G. Celichowski, M. Cichomski, K. Koralewski, I. Piwoński

„Friction force microscopy study of porous methylsilica thin films”

Tribologia 188, 19–26 (2003)

My contribution is related to: measurements of the topography, determination of the pore diameters in the methylsilica films, frictional investigations in nanoscale and also analysis and interpretation of results, manuscript preparation. I declare my contribution to be equal to 20%.

B-4. M. Cichomski, L. Margielewski, E. Barylska, I. Piwoński

„ Investigation of nanostructure ordering and nanofrictional property of O,O,S-methyl

polyethoxyglycol triester of dithiophosphoric acid layer on stainless steel and on gold”

Tribologia 188, 145–158 (2003)

My contribution is related to: performance of topography of the layers adsorbed on steel and gold substrates and tribological measurements by atomic force microscopy. I declare my contribution to be equal to 40%.

B-5. K. Chrobak, J. Grobelny, M. Cichomski, I. Piwoński

„Investigation of LB monolayers of arachidic acid with use of atomic force microscopy”

Tribologia 188, 159–165 (2003)

My contribution is related to: the determination of Langmuir (LB) monolayers of arachidic acid morphology and wear, analysis and interpretation of results, manuscript preparation. I declare my contribution to be equal to 30%.

B-6. W. Szmaja, K. Polański, M. Cichomski

„ Investigation of the physical microstructure and magnetic domain structure of sintered

SmCo5 permanent magnets”

Acta Physicae Superficierum 5, 65–78 (2003)

My contribution is related to: the determination of MFM measurements and the analysis of the study of magnetic domain structure of the anisotropic sintered magnets SmCo5, at the surface perpendicular to the alignment axis. I declare my contribution to be equal to 40%.


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B-7. M. Wiśniewski, M. Cichomski

„Identification of friction and wear anti-wear coatings”

Tribologia 191, 383–394 (2003)

My contribution is related to: preparation of the composite materials with the phenol-formaldehyde resin matrix containing solid lubricant particles and optimization of the composition of solid lubricants. I declare my contribution to be equal to 50%.

B-8. J. Grobelny, G. Celichowski, M. Cichomski, A. J. Kulik, I. Piwoński, S. Płaza

„Comparison of two methods of methyl group grafting to the silica thin film surface and its

tribological properties measured by atomic force microscopy”

Tribology Letters 16, 181–185 (2004)

My contribution is related to: the frictional studies performed by atomic force microscopy, analysis and interpretation of results, manuscript preparation. I declare my contribution to be equal to 20%.

B-9. W. Szmaja, J. Grobelny, M. Cichomski, K. Makita, W. Rodewald

„MFM study of sintered permanent magnets”

Physica Status Solidi (a) 201, 550–555 (2004)

My contribution is related to: measurements and the analysis of the study of magnetic domain structure and morphological structure of the anisotropic sintered magnets Nd–Fe–B and SmCo5 at the surface perpendicular to the alignment axis. I declare my contribution to be equal to 30%.

B-10. W. Szmaja, J. Grobelny, M. Cichomski, K. Makita

„Application of MFM for studying Nd–Fe–B magnets”

Vacuum 74, 297–300 (2004)

My contribution is related to: measurements and the analysis of the study of magnetic domain structure and morphological structure of the anisotropic sintered magnets Nd–Fe–B at the surface perpendicular to the alignment axis. I declare my contribution to be equal to 30%.

B-11. M. Cichomski, J. Grobelny, A. Ilik

„Właściwości tribologiczne warstw samoorganizujących (SAMs) osadzonych na Au”

Tribologia 197, 41–47 (2004)

My contribution is related to: preparation of the self-assembled monolayers, studies of the morphological structure using scanning tunneling microscopy and also tribological investigations in nano- and microscale. I deal with the analysis and interpretation of results and manuscript preparation. I declare my contribution to be equal to 60%.


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B-12. W. Szmaja, J. Grobelny, M. Cichomski

„Domain structure of sintered SmCo5 magnets studied by magnetic force microscopy”

Applied Physics Letters 85, 2878–2880 (2004)

My contribution is related to: analysis and discussion of results. I declare my contribution to be equal to 20%.

B-13. W. Szmaja, J. Grobelny, M. Cichomski

„MFM investigation of the domain structure of cobalt single crystals”

Czechoslovak Journal of Physics 54 Suppl. D, D245–D248 (2004)

My contribution is related to: measurements and the analysis of the results of magnetic domain structure and morphological structure on the (0001) surface cobalt single crystals. I declare my contribution to be equal to 30%.

B-14. W. Szmaja, J. Balcerski, J. Grobelny, M. Cichomski

„Imaging magnetic structures: from thin films to nanometer scale domains”

Acta Physicae Superficierum 7, 125–133 (2004)

My contribution is related to: measurements performed by MFM and AFM, the analysis and interpretation of the results of magnetic domain structure and morphological structure of the anisotropic sintered magnets Nd–Fe–B at the surface perpendicular to the alignment axis. I declare my contribution to be equal to 30%.

B-15. S. Domagała, J. Dziegieć, M. Cichomski, J. Grobelny

„The mediatory activity of iron(II) ions immobilized on glassy carbon in Nafion film”

Annals of the Polish Chemical Society 3, 825–885 (2004)

My contribution is related to: the nafion film studies by AFM and the size determination of the agglomerates present on the surface after modification, interpretation and analysis of obtained results. I declare my contribution to be equal to 30%.

B-16. I. Piwoński, J. Grobelny, M. Cichomski, G. Celichowski, J. Rogowski

„Preparation method of two dimensional silica-like surface from

3-mercaptopropyltrimethoxysilane self-assembled monolayers (SAMs) on Au(111) surface”

Applied Surface Science 242, 147–153 (2005)

My contribution is related to: preparation of MPTMS layers on gold surface, determination of monolayers properties by using STM, interpretation and analysis of obtained results and manuscript preparation. I declare my contribution to be equal to 30%.


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VI. Other scientific works published after receiving of the doctor degree

B-17. L. Nowak, G. Andrijewski, D. Tomczyk, M. Cichomski

„Modification of glassy carbon electrode with phenanthroline complexes of manganese(II)

immobilized in nafion layer”

Polish Journal of Chemistry 81, 493-503 (2007)

My contribution is related to: visualization of complexes of manganese(II) deposited on glassy carbon electrode modified by nafion layer and also interpretation and analysis of obtained results. I declare my contribution to be equal to 30%.

B-18. S. Domagała, J. Dziegieć, M. Cichomski, J. Grobelny

„The Mediatory Activity of Ce(IV)/Ce(III) Redox System Immobilized in Nafion Film on

Glassy Carbon”

Polish Journal of Chemistry 81, 1049–1061 (2007)

My contribution is related to: measurements and the analysis of the study of topographical structure of the glassy carbon electrode topography modified by nafion layer and cerium ions. Interpretation and analysis of obtained results. I declare my contribution to be equal to 30%.

B-19. W. Szmaja, J. Grobelny, M. Cichomski, K. Makita, W. Kozłowski

„Imaging domains of hard magnetic materials by SEM and MFM”

Vacuum 81, 1367–1370 (2007)

My contribution is related to: measurements performed by MFM of magnetic domain structure of the anisotropic sintered magnets Nd–Fe–B and interpretation and analysis of obtained results. I declare my contribution to be equal to 30%.

B-20. B. Bhushan, M. Cichomski, Z. Tao, N.T. Tran, T. Ethen, C. Merton, R.E. Jewett

„Nanotribological characterization and lubricant degradation studies of metal-film magnetic

tapes using novel lubricants”

Journal of Tribology 129, 621–627 (2007)

My contribution is related to: studies in nanoscale of adhesive force, friction and wear of metal-film magnetic tapes performed by AFM. Lubricant degradation studies by using mass spectrometer in high vacuum. Investigations of the durability of the tapes in ambient air and high humidity, interpretation and analysis of obtained results. I declare my contribution to be equal to 30%.

B-21. W. Szmaja, J. Balcerski, W. Kozłowski, J. Grobelny, M. Cichomski

„Investigation of the Morphological Structure of Thin Cobalt Films by AFM and TEM”

Acta Physica Polonica A 113, 171–174 (2008)


- 27 -

My contribution is related to: determining by means of AFM morphological structure of the cobalt films with the 40 nm and 100 nm thickness, analysis and interpretation of the results. I declare my contribution to be equal to 30%.

B-22. M. Cichomski, J. Grobelny, G. Celichowski

„Preparation and tribological tests of thin fluoroorganic films”


My contribution is related to: modification of the silicon as the reference surface, modification of MPTMS layers obtained on gold surface and nanotribological investigations. I also performed the analysis and interpretation of the results, manuscript edition. I declare my contribution to be equal to 40%.

B-23. G. Celichowski, M. Cichomski, M. Psarski, M. Wiśniewski

„Elastic yarn tensioner with a noncontinuous antiwear nanocomposite pattern”

Fibres and Textiles in Eastern Europe 72, 91–96 (2009)

My contribution is related to: measurements performed by using AFM, determination of the dispersion degree of nanoparticles in the polymer matrix, the analysis and interpretation of the results, manuscript edition. I declare my contribution to be equal to 30%.

B-24. P. Neska-Bakus, L. Margielewski, M. Cichomski

„Tribological properties of n-alcohols, n-alkylphenyls and glycols alkoxy dithiophosphates in

friction contacts: steel-steel, Al2O3-Al2O3 and steel-Al2O3”

Tribologia 234, 87–98 (2010)

My contribution is related to: studies of lubricating additives adsorption on steel surface, analysis and interpretation of the results, manuscript edition. I declare my contribution to be equal to 30%.

B-25. A. Ptak, M. Makowski, M. Cichomski

„Characterization of nanoscale adhesion between a fluoroalkyl silane monolayer and

a silicon AFM tip. Complex character of the interaction potential”

Chemical Physics Letters 489, 54–58 (2010)

My contribution is related to: preparation of the silane monolayer by gas phase deposition and manuscript edition. I declare my contribution to be equal to 30%.

B-26. A. Busiakiewicz, A. Huczko, T. Dudziak, M. Puchalski, W. Kozłowski, M. Cichomski,

S. Cudziło, Z. Klusek, W. Olejniczak

„Defects of SiC nanowires studied by STM and STS”



- 28 -

My contribution is related to: discussion and interpretation of results. I declare my contribution to be equal to 5%.

B-27. W. Szmaja, W. Kozłowski, J. Balcerski, P. J. Kowalczyk, J. Grobelny, M. Cichomski

„Study of obliquely deposited thin cobalt films”

Journal of Alloys and Compounds 506, 526–529 (2010)

My contribution is related to: determining by means of AFM morphological structure of the cobalt films with the 40 nm and 100 nm thickness, analysis and interpretation of the results. I declare my contribution to be equal to 20%.

B-28. W. Szmaja, W. Kozłowski, K. Polański, J. Balcerski, M. Cichomski, J. Grobelny,

M. Zieliński, E. Miękoś

„Investigation of thick cobalt films electrodeposited on gold substratem”

Chemical Physics Letters 542, 117–122 (2012)

My contribution is related to: measurements and the analysis of the results of magnetic domain structure of cobalt films with 14 µm, 28 µm and 55 µm thickness. I declare my contribution to be equal to 20%.

B-29. W. Szmaja, J. Balcerski, W. Kozłowski, M. Cichomski, J. Grobelny, M. Smolny, P. J.

Kowalczyk

„Study of thermally evaporated thin permalloy films by the Fresnel mode of TEM and AFM”

Journal of Alloys and Compounds 521, 174–177 (2012)

My contribution is related to: morphological structure measurements of thin permalloy films with 10 nm and 60 nm thickness by using AFM and analysis and interpretation of the results. I declare my contribution to be equal to 20%.

B-30. W. Szmaja, W. Kozłowski, K. Polański, J. Balcerski, M. Cichomski, J. Grobelny,

M. Zieliński, E. Miękoś

„Study of the morphological and magnetic structures of nanocrystalline cobalt films obtained

by electrodeposition”

Materials Chemistry and Physics 132, 1060–1064 (2012)

My contribution is related to: measurements and the analysis of the results of magnetic domain structure of cobalt films with 14 µm and 23 µm thickness. I declare my contribution to be equal to 20%.

B-31. W. Szmaja, J. Grobelny, M. Cichomski, S. Hirosawa, Y. Shigemoto

„Magnetic force microscopy investigation of the domain structure of nanocomposite

Nd2Fe14B/Fe3B magnets ”


- 29 -

Acta Materialia 59, 531–536 (2011)

My contribution is related to: measurements and the analysis of the results of magnetic domain structure and morphological structure of nanocomposite Nd2Fe14B/Fe3B magnets. I declare my contribution to be equal to 30%. B-32. B. Rudolf, M. Salmain, J. Grobelny, G. Celichowski, M. Cichomski

„Preparation of metallocarbonyl-gold-antibody bioconjugates for mid-IR optical

Immunosensing”

Journal of Organometallic Chemistry734, 32–37 (2013)

My contribution is related to: topographical studies of the bioconjugantes which include metallocarbonyl compounds, gold nanoparticles and antibodies, interpretation and analysis of obtained results. I declare my contribution to be equal to 20%.

VII. Participation in national and international sc ientific conferences

1) E. Barylska, A. Socha, M. Cichomski, S. Płaza, Morphology and Tribological Properties of

Self-Assembled Monolayers of Dialkyldithiophosphoric Acids on Au (111) Surfaces, IV

International Conference on Tribochemistry, 2005, Kraków, Poland

2) M. Cichomski, B. Bhushan, Nanotribological Characterization of Self-Assembled

Monolayers with Alkyl and Perfluoroalkyl Spacer Chains Deposited on Silicon and Aluminum

Substrates, Thirteenth Sponsors Meeting of Nanotribology Laboratory for Information

Storage and MEMS/NEMS, 22–23 May 2006, Columbus, USA

3) M. Cichomski, B. Bhushan, Nanotribological Characterization of Perfluorosilane Self-

Assembled Monolayers Deposited on Silicon and Polydimethylsiloxane Surfaces, Thirteenth

Sponsors Meeting of Nanotribology Laboratory for Information Storage and MEMS/NEMS,

22–23 May 2006, Columbus, USA

4) M. Cichomski, B. Bhushan, Nanotribological Characterization of Vapor Phase Deposited

Positively-Charged Self Assembled Monolayers Deposited on Polydimethylsiloxane for

Nanochannel Application, AVS 53 International Symposium & Exhibition, 12–17November,

2006, San Francisco, California, USA


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5) P. Krzyczmonik, S. Domagała, H. Scholl, J. Dziegieć, M. Cichomski, J. Grobelny,

Electrochemical activity of Ce(III) ions immobilized in nafion film on platinum, 7th

International Conference Advanced batteries and accumulators, Brno, Czech Republic, 4─6

June, 2006

6) W. Szmaja, J. Grobelny, M. Cichomski, K. Makita, W. Kozłowski, Imaging domains of

hard magnetic materials by SEM and MFM”, VI International Conference “Ion implantation

and other applications of ions and electrons”, Kazimierz Dolny, Poland, 26─29 June, 2006

7) W. Szmaja, J. Grobelny, M. Cichomski, J. Balcerski, Investigations of magnetic structures

by magnetic force microscopy and electron microscopy, IV Seminarium “Badania

prowadzone metodami skaningowej mikroskopii bliskich oddziaływan” STM/AFM,

Zakopane, 6─10 December 2006

8) W. Szmaja, J. Balcerski, W. Kozłowski, J. Grobelny, M. Cichomski, Investigation of the

morphological structure of thin cobalt films by AFM and TEM, 13th Czech and Slovak Conf.

“Magnetism”, Koszyce, Slovakia, 9–12 July 2007

9) M. Cichomski, J. Grobelny, G. Celichowski, Preparation and investigation of thin

fluoroorganic films, 3rd International Workshop “Surfaces Physics”, Polanica Zdrój, 10–15

September 2007

10) W. Szmaja, W. Kozłowski, J. Balcerski, J. Grobelny, M. Cichomski, Study of obliquely

deposited thin cobalt films, 3rd International Workshop “Surface Physics”, Polanica Zdrój,

10–15 September 2007

11) G. Celichowski, M. Cichomski, J. Grobelny, DLS and AFM in measuring of gold,

European Materials Research Society E-MRS 2007 Fall Meeting, Warsaw, 17─21 September,

2007

12) M. Cichomski, J. Grobelny, P. Kowalczyk, W. Kozłowski, J. Rogowski, Self-assembled

monolayers as surfaces to controlled deposition of gold nanoparticles

V Seminarium STM/AFM, Zakopane, 26─30 November, 2008


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13) M. Cichomski, J. Grobelny, P. Kowalczyk, W. Kozłowski, Tribological properties of self-

assembled monolayers na gold Au(111) surface, V Seminarium STM/AFM, Zakopane, 26─30

November, 2008

14) W. Szmaja, M. Cichomski, J. Grobelny, High resolution investigations of domain

structures by magnetic force microscopy, V Seminarium STM/AFM, Zakopane, 26─30

November, 2008

15) M. Cichomski, J. Grobelny, K. Kośla, P. Uznański, W. Kozłowski, A. Busiakiewicz,

W. Szmaja, J. Balcerski, Nano- and Microtribological Characterization of Fluorosilanes

Deposited on Cobalt Substrate, 4th International Workshop on Surface Physics Surfaces and

Nanostructures, Lądek Zdrój, Poland, 20─25 September 2009

16) M. Cichomski, W. Szmaja, MFM and AFM Study of Thin Cobalt Films Modified by

Fluorosilane, 4th International Workshop on Surface Physics Surfaces and Nanostructures,

Lądek Zdrój, Poland, 20─25 September 2009

17) A. Busiakiewicz, M. Puchalski, W. Kozłowski, Z. Klusek, W. Olejniczak, A. Huczko,

T. Dudziak, M. Cichomski, Defects of SiC Nanowires Studied by STM and STS, 4th

International Workshop on Surface Physics Surfaces and Nanostructures, Lądek Zdrój,

Poland, 20─25 September 2009

18) A. Ptak, M. Makowski, M. Niemier, M. Cichomski, H. Gojzewski, R. Czajka,

Characterization of Silane Nanoadhesion by means of Dynamic Force Spectroscopy,

Nanotech, Conference & Expo 2009, 3–7 May 2009, Houston

19) M. Cichomski, J. Grobelny, J. Rogowski, Nano- and Microtribological Characterization

of Fluorosilane Deposited on Titanium and Silicon Substrates, 5th International Conference

on Tribochemistry, Lanzhou, China, 14–16 September, 2009

20) M. Cichomski, J. Rogowski, K. Kośla

Characterization of fuoroalkylsilane films deposited on titanium surface

II Konferencja Nano- i Mikromechaniki, Krasiczyn 6─8 July, 2010


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21) M. Cichomski, K. Kośla

Preparation and characterization of ultrathin films obtained by polydimethylsiloxane matrix

IV Krajowa Konferencja Nanotechnologii NANO 2010, Poznań, 28 June–02 July 2010

22) M. Cichomski, K. Kośla, W. Kozłowski, J. Rogowski, W. Pawlak

Modification and tribological properties of perfluoroalkylsilanes on titanium surface

IV Krajowa Konferencja Nanotechnologii NANO 2010, Poznań, 28 June–02 July 2010

23) M. Cichomski, K. Kośla, W. Szmaja, W. Kozłowski, J. Rogowski

Investigation of the structure of fluoroalkylsilanes on alumina surface by XPS and ToF–SIMS

VIII–th International Conference, Ion Implantation and Other Applications of Ions and

Electrons, Kazimierz Dolny, 14–17 June 2010

24) W. Szmaja, M. Cichomski, K. Kośla, J. Balcerski

TEM and AFM investigation of obliquely evaporated thin cobalt films

VIII – th International Conference, Ion Implantation and Other Applications of Ions and

Electrons, Kazimierz Dolny, 14–17 June 2010

25) J. Grobelny, E. Tomaszewska, G. Celichowski, M. Cichomski, S. Różalska

Synthesis and characterization of silver nanoparticles to antibacterial applications

IV Krajowa Konferencja Nanotechnologii, NANO 2010, Poznań 28 June─2 July 2010

26) E. Tomaszewska, G. Celichowski, M. Cichomski, W. Zieliński, J. Grobelny

Synthesis and characterization of gold, silver and copper nanoparticles

IV Krajowa Konferencja Nanotechnologii, NANO 2010, Poznań, 28 June─2 July 2010

27) E. Tomaszewska, G. Celichowski, M. Cichomski, J. Grobelny

The influence of sodium citrate and tannic acid on the size and monodispersity of synthesized

silver nanoparticles

12th JCF Frühjahrssymposium, Gottingen, 17─20 March 2010, Germany


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28) W. Szmaja, M. Cichomski, J. Balcerski

Investigations of thin cobalt films on Si(100) surface by magnetic and atomic force

microscopies

VI Seminarium STM/AFM 2010 Badania prowadzone metodami skaningowej mikroskopii

bliskich oddziaływań, Zakopane, 1─5 December 2010

29) M. Cichomski, K. Kośla, J. Grobelny, W. Kozłowski

Influence of silane structures on tribological properties



30) M. Cichomski, K. Kośla, J. Rogowski

Preparation and characterization of fluoroalkylsilane



31) W. Szmaja, M. Cichomski, K. Kośla, J. Balcerski

Investigation of the domain structure of cobalt films on glass substrates

14-th Czech and Slovak Conference on Magnetism CSMAG’10, Kosice, 6─9 July 2010

32) E. Tomaszewska, G. Celichowski, M. Cichomski, K. Kądzioła, P. Neska-Bakus, B. Tkacz,

J. Grobelny

Controlled Synthesis of Copper Nanoparticles by Chemical Reduction Method

13th JCF Frühjahrssymposium, Erlangen, 23─26 March 2011, Germany

33) J. Grobelny, E. Tomaszewska, G. Celichowski, M. Cichomski, W. Zieliński

Nanoscale Metrology – Key Process in Application of Nanoobjects

V Krajowa Konferencja Nanotechnologii NANO 2011, Gdańsk 3─7 July 2011

34) K. Kośla, M. Cichomski

Preparation and frictional properties of one- and twocomponent silane layers on titanium

surface

V Krajowa Konferencja Nanotechnologii NANO 2011, Gdańsk, 3─7 July 2011


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35) M. Cichomski, K. Kośla, W. Kozłowski, J. Grobelny

Silanes and their tribological properties in nano- and microscale

V Krajowa Konferencja Nanotechnologii NANO 2011, Gdańsk, 3─7 July 2011

36) K. Kośla, M. Cichomski, J. Grobelny, W. Kozłowski, J. Rogowski

Tribological investigation of the fluoroalkylsilane film obtained by vapor phase deposition

method

5th International Workshop on Surface Physics “ Surfaces and Nanostructures” ECOSS-28,

Lądek Zdrój, 2─5 September 2011

37) M. Cichomski, K. Kośla

Nanotribological properties of the fluorosilane monolayers

5th International Workshop on Surface Physics” Surfaces and Nanostructures” ECOSS-28,

Lądek Zdrój, 2─5 September 2011

38) J. Grobelny, E. Tomaszewska, G. Celichowski, M. Cichomski, W. Zieliński

Nanoscale Metrology – Key Process in Application of Nanoobjects

WELCOME Scientific Meeting on Hybrid Nanostructures, Toruń, 28─31 August

39) B. Rudolf, M. Salmain, J. Grobelny, G. Celichowski, E. Tomaszewska, M. Cichomski

Synthesis of metalocarbonyl complexes immobilized on gold nanoparticles and trial to apply

them in biochemistry

54. Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i

Techników Przemysłu Chemicznego, Lublin, 18─22 September 2011

40) W. Szmaja, M. Cichomski, K. Kośla, J. Balcerski,

Investigation of cobalt films modified by fluoroalkylsilanes

13th European Conf. Physics of Magnetism 2011, Poznań, 27 June─1 July 2011

41) K. Kośla, M. Cichomski, W. Kozłowski

Preparation and tribological characterization of organosilanes on alumina surface

III Krajowa Konferencja Nano- i Mikromechaniki, Warsaw 4─6 July 2012


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42) J. Grobelny, E. Tomaszewska, G. Celichowski, M. Cichomski, B. Tkacz-Szczęsna,

M. Rosowski

Nanoparticles characterization for biomedical application

Workshop – New trends in toxicology: Nanoparticles and Nanomaterials, Lodz, Poland

28─30 May 2012,

43) M. Cichomski, K. Kośla, J. Grobelny, W. Szmaja

Preparation and characterization of alkylphosphonic self-assembled monolayers

VII Seminarium STM/AFM 2012 Badania prowadzone metodami skaningowej mikroskopii

bliskich oddziaływań, Zakopane, 28 November─2 December 2012

44) K. Kośla, M. Cichomski, J. Grobelny

Preparation and tribological characterization of one- and two-component organosilanes

layers on alumina surface



45) W. Kozłowski, W. Szmaja, M. Cichomski, M. Zieliński, E. Miękoś

Investigations of nonocrystalline cobalt layers sputtered on gold surface by electrochemical

method



46) J. Grobelny, G. Celichowski, M. Cichomski, A. Kisielewska, I. Piwoński, M. Psarski,

R. Stanecka-Badura

Scientific activity of the nanomaterials and tribology research group

Chemistry Workshop: Lodz─Giessen Chemistry Workshop,

Faculty of Chemistry, University of Lodz, 10─14 October 2012


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VIII. Participation in conference organization 1. 4th International Conference on Tribochemistry, 3–5 October 2005, Kraków, Poland,

Collegium Maius, Jagiellonian University

2. 6th International Conference on Tribochemistry and Nanomaterials, 4–6 September 2013

Lodz, Poland University of Lodz.

IX. Patent application

Stanisław Płaza, Andrzej Łopusiński, Stanisław Wojciech Markowicz, Renata Stanecka-

Badura, Michał Cichomski

"Application of the poly(oxyalkyl)dithiophosphates acids derivatives as multipurpose

lubricant additives with low phosphorus content"

Patent application nr P.401247 2012/10/16

X. Scientific projects

2002–2004, Research grant promotorski of KBN, number 4 T08D 038 25, „Morphological

and nanotribological studies of nanocomposite materials” – project contractor

2004–2006, Research grant of KBN, number 4 T07B 036 26, „Definition and optimization of

the tribological properties of layers obtained by sol-gel technique”– project contractor

2008–2010, Research grant of Polish Ministry of Science and Higher Education, number N

N507 350435, „Synthesis and characterization of gold, silver and copper nanoparticles” –

project contractor

2010–2012, Research grant of Polish Ministry of Science and Higher Education, number N

N507 551538, „Preparation of ultrathin films of organofluorine compounds for tribological

applications”– head of the project


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2012–2015, Research grant of National Science Centra, number 2012/05/B/ST8/02876,

„Study of the relationships between the chemical structure and topography of

superhydrophobic surfaces and their anti-icing properties” – main project contractor

XI. Scientific reviews

I reviewed 9 publications in international journals from Journal Citation Reports,

including:

1. Surface and Coatings Technology ─ 1

2. Tribology International ─ 2

3. American Chemical Society, Applied Materials & Interfaces ─ 2

4. Journal of Alloys and Compounds ─ 1

5. Journal of Physics and Chemistry of Solids ─ 1

6. Applied Surface Science ─ 2

XII. Didactics 1. Leading and coordinaton of courses

In 2006─2012 I was lecturer, both laboratory classes and lectures (including 10

different classes). I am the coordinator of items: Measurement techniques in material

properties and Nanomaterials measurements techniques.

1. Measurement techniques in material properties ─ monographic lecture

2. Measurement techniques in material properties ─ laboratory class

3. Nanomaterials measurements techniques ─ monographic lecture

4. Nanomaterials measurements techniques ─ laboratory class

5. Technology of Chemistry II ─ laboratory class

6. Technology of Chemistry II ─ laboratory class

7. Specialization subject ─ laboratory class

8. Selected Chemical Technologies ─ laboratory class

9. Petrochemistry ─ laboratory class

10 Nanotechnology ─ laboratory class


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2. Substantive care of students

With the consent of the authorities of University of Lodz, I am a supervisor of master thesis. I

supervised 15 master's theses.

XIII. Received awards and distinctions

1. Rector of the University of Lodz award - team award, the first degree for scientific

achievements in 2010

2. Rector of the University of Lodz award - team award, the second degree for teaching and

educational achievements in 2012

XIV. Expertise or other investigations realization to business or entities

performing public functions

Expertise:

The Research on concentrations on the petroleum substances by infra-red spectroscopy

in the sewages of precipitation drained from the rain sewer system of the city of Lodz to the

rivers and in the samples of sewage drained to the rain sewer system of the city of Lodz.

Water Supply and Sewage Company in Lodz 2007

The research on the petroleum hydrocarbons, determination of the mineral oil index

(the method based on the solvent extraction and gas chromatography) in the sewages of

precipitation drained from the rain sewer system of the city of Lodz to the rivers, and in the

samples of sewage drained to the rain sewer system of the city of Lodz. Water Supply and

Sewage Company in Lodz 2008

Physicochemical characterization of the modifiers having (exhibiting) photocatalytic

properties: product n°1 (TiO2) and n°2 (Ag/TiO2) supplied by Textile Research Institute in

Lodz ─ 2011


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XV. Promotion of chemistry

Workshop „Nanotribology”, in cycle of the Tribological Workshops, Lodz, 17.06.2008

Worshop „friction in microscale”, in cycle of the Tribological Workshops, Lodz, 24.05.2011

XVI. Statistic of scientific work

1. Publications:

Total number of publications from Journal Citation Reports: 33.

- number of publications before obtaining a doctoral degree: 8.

- number of publications after obtaining a doctoral degree: 25.

Total number of other publications not included in Journal Citation Reports: 9

- number of publications before obtaining a doctoral degree: 8.

- number of publications after obtaining a doctoral degree: 1.

2. Summarized impact factor (according to the data from 2012): 62,901.

3. Total points of MNiSW (according to the data from 2012): 1002.

4. Total impact factor (from years of publication of the articles): 57,887.

5. Total citations according to Web of Science: 200.

6. Citations without self-citations according to Web of Science: 167.

7. Hirsch index according to Web of Science: 8.

8. Number of publications which are scientific achievements submitted for the habilitation

procedure: 10.

9. Total impact factor of publications which are scientific achievements submitted for the

habilitation procedure according to Web of Science: 77.


habilitation procedure (according to the data from 2012 year): 19,737.


habilitation procedure (from years of publication of the articles): 19,027.

12. Total points of MNiSW for publications which are scientific achievements submitted for

the habilitation procedure (according to the 2012 year): 315.

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