TF5:
Protective and Functional Coatings
Posters
TF5.1.P
TiN/AlN BILAYERS AND MULTILAYERS
GROWN BY MAGNETRON CO-SPUTTERING
M. A. Auger1*, O. Sanchez1, J. M. Albella1, M. Jergel2,3, M. Aguilar-Frutis4, C. Falcony2
1
Instituto de Ciencia de Materiales de Madrid (CSIC), Madrid, Spain
2
Departamento de Física, CINVESTAV-IPN, México, D.F., México
3
Institute of Physics, Slovak Academy of Sciences, Bratislava, Slovakia
4
CICATA-IPN, Miguel Hidalgo 11500, México D.F., México
TiN/AlN bilayers and multilayers have been grown on Si(100) substrate by reactive
magnetron sputtering using a two cathode system and Ar + N2 as reactive atmosphere. The
total nominal 800 nm thickness of three bilayers has been divided between the top AlN and
bottom TiN layers in the ratios dAlN/dTiN = 1, 3, 19. Two periodic multilayers have been
grown by a repeated deposition of (200nm AlN/ 200nm TiN) and (5nm AlN/ 5nm TiN)
basic bilayers (multilayer periods) for 2 and 5 times, respectively. Nitrogen incorporation in
the nitrides has been correlated to the argon/nitrogen ratio in the sputtering gas in order to
get stoichiometric compounds. The chemical composition of the layers has been studied by
ESCA and Auger Electron Spectroscopies. The morphology of the coatings was observed
in cross-section by Scanning Electron Microscopy. Columnar growth was found in both
TiN and AlN layers, the column density being larger in the latter. The structural
information has been obtained by X-ray diffraction in Bragg-Brentano and grazing
incidence modes; completed by rocking curves and azimuthal scans, and by X-ray
reflectivity. The polycrystalline hexagonal and face-centered cubic structures have been
identified in AlN and TiN layers, respectively, with some tendency to texture in accord
with the columnar growth observed. The grain size and lattice perfection are affected by the
layer thicknesses. The optical properties of the layers have been obtained by spectroscopic
ellipsometry in the energy range from 1.5 to 4.75 eV. The obtained coatings have a number
of mechanical properties surpassing those of TiN, in particular the wear resistance, making
them useful for industrial applications as practical coatings in cutting tools.
*
Corresponding author: M.A. Auger, Instituto de Ciencia de Materiales de Madrid - CSIC, Departamento de
Física e Ingeniería de Superficies, Cantoblanco 28049, Madrid, Spain, Tel. +34 91 334 90 00; Fax. +34 91
372 06 23; e-mail: maauger@icmm.csic.es
TF5.2.P
DEPOSITION AND SOME PROPERTIES OF NANOCRYSTALLINE
WC AND NANOCOMPOSITE WC/a-C:H COATINGS
A. Czyzniewski
Technical University of Koszalin, Department of Materials Engineering,
Raclawicka 15-17, 75-620 Koszalin, Poland
Nanocrystalline WC and nanocomposite WC/a-C:H coatings were deposited using
reactive unbalanced magnetron sputtering of tungsten target under argon/acetylene
atmosphere on steel substrates held at the temperature below 423 K. The effect of
carbon content on microstructure and mechanical properties of coatings was
investigated. Special attention was given to the deposition of coatings with a carbon
content of 30 – 90 at. %. Chemistry of coatings was investigated with energy
dispersive X-ray analysis (EDAX) and X-ray photoelectron spectroscopy (XPS).
Beside tungsten and carbon, some coatings contain oxygen and argon and as showed
elastic recoil detection analysis (ERDA) hydrogen was also present. In the range of
carbon content of 30 – 55 at. %, formation of WC chemical bonding and
nanocrystalline cubic -WC1-x structure was observed by XPS, X-ray diffraction
(XRD) and transmission electron microscopy (TEM) respectively. Coatings
containing more than 55 at. % of carbon have two phase nanocomposite structure,
composed of nanocrystalline -WC1-x grains dispersed in amorphous carbon (a-C:H)
matrix. The presence of amorphous carbon phase was detected using XPS and Raman
spectroscopy. Mechanical properties such as hardness and Young`s modulus of
coatings were measured by nanoindentation. Nanocrystalline WC coatings show
hardness in the range of 36 - 40 GPa. The hardness of nanocomposite WC/a-C:H
coatings decreases continuously from 32 GPa to 20 GPa as the carbon content
increases from 60 at. % to 90 at. %, respectively. The results of scratch investigation
show that failure mode and cracking resistance depend strongly on carbon content
and microstructure of coatings. WC/a-C:H nanocomposites show higher fracture
toughness than nanocrystalline WC coatings of a similar hardness. The first cracks of
WC/a-C:H nanocomposites appear at load twice higher than in nanocrystalline WC
coatings with a similar hardness, as it was observed using optical microscopy and
scanning electron microscopy (SEM). Tribological properties of coatings, including
friction and wear were also investigated using ball-on-disc method. The lowest
friction coefficient (f  0,1) and high wear resistance
(k < 2  10-7 mm3N-1m-1)
show WC/a-C:H nanocomposites containing about 90 at. % of carbon.


Andrzej Czyzniewski, Tel.: +48 94 3478240; Fax: +48 94 3426753; E-mail: czyzniew@tu.koszalin.pl,
Address: Technical University of Koszalin, Department of Engineering Materials, Raclawicka 15-17,
75-620 Koszalin, Poland
TF5.3.P
Structure and properties of composite coatings from the nitride CrN and
TiN
V. Gorban
Institute for Problems of Material Science, National Academy of Sciences of
Ukraine.
The work purpose is research of the structure, phase composition, properties and
serviceability of composite coatings on the basis of nitrides CrN and TiN in conditions of
high temperatures and contact loading. The coating was obtained by the ion-plasma
spraying of Cr and Ti in nitrogen environment. The ratio of thickness of multiple coatings
was chosen as 4:1 at thickness of a layer of nitride CrN 0.4 microns. Serviceability of the
given coatings was compared with that of gas-thermal and galvanic coatings from the
chromium-based alloys. The research of structure of multiple coatings of nitrides CrN +
TiN has shown, that the technology allows to ensure the chosen ratio of thicknesses. X-ray
structure analysis of the given coatings has revealed a phase of nitrides CrN and firm
solution (TiCr) N. Chromium is distributed rather uniformly on layers, and titanium has the
precisely expressed concentration dependence. The peak minimum of titanium is on a layer
of nitride CrN, and maximum - on nitride TiN. Multiple coatings of nitrides CrN + TiN are
characterized by high stability of structure and, as a consequence, of operational properties
in the temperatures range up to 1300 Ę (Tables 1).
Tables 1. Researches of influence of annealing temperature on microhardness
of coatings from the nitride CrN and nitride TiN.
Material Nit. comp Annealing temperature, Ę1000 1100 1200 1300
CrN 15,0 15,0 15,0 14,0 14,0
CrN+TiN 24,0 24,0 24,0 23,0 22,0
The hardness of coverings is reduced from 21 up to 16 ĂĎŕ after 1 hour annealing at
temperature 1300 K. Similar dependence is characteristic and for coatings from the
chromium-base alloys. The stability of the characteristics composition coatings of nitrides
CrN + TiN is confirmed with the given dependence's of changes of force of friction on
temperature of tests of coatings from the chromium-base alloys (Tables 2).
Table 2. Dependence of force of friction (H) on temperature of tests and method of
production of coatings Method of production of coatings Temperature, K
273 473 573 673
Gas-thermal Cr 24.0 23.7 22.1 19.6
Galvanic Cr 22.0 20.0 19.3 18.5
Ion-plasma CrN+TiN 19.0 14.0 11.0 9.0
The conclusion is made, that for composition coatings of nitride CrN mechanisms of
structural changes, mass transfer and the oxidation of superficial layers bring in the
insignificant contribution in wear resistance of a material.
Gorban Viktor, 3, Krzhizhanovsky Street, 03142, Kiev, Ukraine Institute for Problems of
Materials Science, vns@materials.kiev.ua.
TF5.4.P
SYNTHESIS AND CHARACTERIZATION OF AN ANTICORROSIVE
COATING BASED ON CERAMIC AND ZrO2 NANOPARTICLES.
S. Jiménez1, G. Canizal1, H. B. Liu1, V. M. Castaño2 and J. A. Ascencio1*
1
Institito Mexicano del Petróleo, Coor. Inv. y Des. de Ductos. Eje Central Lazaro Cardenas
152, Mexico D.F. 07730, México. 2 Instituto de Física campus Juriquilla. UNAM.
Juriquilla Queretaro, Mexico
The use of nanoparticles has become really popular in the last decades, because of its
singular properties, from optical and electronic properties to mechanical properties.
Besides, the development of nanocomposites is well known as one of the most important
field in this age because of their possibility to improve the properties of a material
depending of the matrix and the nanoparticle inclusion that induce important changes over
the system.
We are reporting a new obtained film by using the synthesis of a ceramic anticorrosive
coating based on metal oxides and addition of ZrO2 nanoparticles, which helps to protect
steel pipes and to improve the properties of a common glass. Basically the mechanical
properties of the ceramic are improved by the nanoparticles inside it as a nanocomposite.
The obtained material is characterized by different techniques, from the study of its surface
by scanning electron microscopy with secondary electrons for a morphology analysis and
backscattering electron in order to have contrast from the different composition in the
sample. Atomic force microscopy was also used to study the interface by means of the
topographical and phase analysis, which allows us to study the way the nanoparticles affect
in the matrix in function of the synthesis parameters.
The analysis is also made to the local details by using a transmission electron microscopy
which allows to study the nanoparticles and to make a full structural determination. All of
these methods help to study the structure and we are also applying compositional
techniques as the use of characteristic X-ray in the scanning and transmission electron
microscopes.
Besides the analytical data, we used theoretical method to study the stability of these
systems and to identify in a better way the structures from the experimental data. To do so
we apply molecular simulation and analytical data simulation, since high resolution
electron microscopy images to crystalline morphology.


Corresponding author *: Tel 52 55 30036424; Fax. 52 55 30036414; E-mail: ascencio@imp.mx
Give full address details of the corresponding author at the bottom
TF5.5.P
TEMPERATURE DEPENDENCE OF FRICTION COEFFICIENT AND
WEAR RATE OF HARD COATINGS
T. Kubart, R. Novák, T. Polcar
Czech Technical University, Dept. of Physics, Technická 4, 166 07 Praha 6, Czech
Republic
Coating temperature rise or drop can cause changes of coating morphology, structure, phase
composition or chemical reaction on the coating surface. All these changes can affect some
macroscopic coating parameters, among them the tribological properties. Good knowledge
of the temperature dependence of tribological parameters is important especially in the
case of hard and wear resistant coatings. In operating conditions the coated machine
elements or tools are heated up due to the friction between the moving parts or between the
tool and the workpiece. The combined effect of the temperature rise and local contact stress
accelerate the coating material degradation and in this way they shorten the life-time of the
coating.
This paper resumes results of our study of the temperature dependent parameters of TiN,
CoCr, CoCrN and MoS2 coatings. All investigated coatings were sputtered by means of a
system of unbalanced magentrons with pulsed d.c. supply. The most important
deposition parameters ( e.g. total and partial pressures of Ar+N2 mixture, sample bias)
were registered. The coatings thickness, determinated by means of Calotest method, was 2
– 3 microns. The adhesion was measured with a scratch tester, for coating structure and
internal stress evaluation the XRD and for coatings hardness the Hanemann microhardness
were used.
The temperature dependence of tribological parameters was determinated by means of a
high temperature tribometer. This instruments was a conventional ball-on-disc system.
Apart from the major variables of normal load, contact area, sliding speed and testing time
also the temperature was controlled and monitored during all tests. Analysis on wear test
tracks was peformed using the ball crater method. Optical measurement and image analysis
of a ball crater produced over the wear track helped to reveal the failure mechanism, to
determine the presence of brittle interfaces or lack of adhesion. The analysis of
determinated temperature dependences could estimate the part of frictionally generated
defects and of thermally activated processes on the wear rate or on the total coating failure.
TF5.6.P
PROPERTIES OF Cr(C,N) HARD COATINGS DEPOSITED IN ArC2H2-N2 PLASMA
Marijan Maček1,2, Miha Čekada1, , Darja Kek1, Peter Panjan1
1) ”Jožef Stefan”” Institute, Jamova 39, 1000 Ljubljana, Slovenia
2) University of Ljubljana, Faculty of Electrical Engineering, Tržaška 25, 1000 Ljubljana,
Slovenia
Mechanical properties, microstructure and the average chemical composition of Cr(C,N) hard
coatings deposited in Ar-C2H2-N2 plasma strongly depends on the partial pressure of the reactive
gases (N2, C2H2) and on the type of the deposition equipment. In this study we report on the
properties of Cr(C,N) hard coatings deposited by means of the triode ion plating in the BAI 730
apparatus and those prepared by sputter deposition in Balzers Sputron in the pressure range from
0.12 Pa (pure Ar) up to 0.35 Pa with different ratios (0-100%) between C2H2 and N2.
At first mechanical properties (microhardness and adhesion) of coatings were analyzed on the
common way. Internal stress was measured by the radius of substrate curvature. Chemical
composition of coatings was analyzed by means of AES while the Raman and XPS spectroscopy
was used to determined the nature of carbon bonding in the Cr(C,N) films. Microstructure was
determined by XRD as well as by means of TEM and TED.
Results have shown that layers from pure Cr to pure CrC and CrN, as well as ternary alloy of
different Cr(C,N) have been successfully prepared in both deposition system. Typical layers
deposited at partial pressures above 0.05 Pa constitute of about 50% of Cr and the balance was C
and N in different concentrations according to the gas mixture used . XRD have revealed two
phases of chromium nitride, namely Cr2N and CrN, as well as different carbide and carbo-nitride
phases, Cr7C3, Cr(C,N), Cr2(C,N). Contrary to the XRD, TED shows in some samples also the
existence of the metastable cubic CrC phase.
Chemical state of various elements in the coating has been studied by XPS. The ratio of the
carbide bond (C-Cr) against the C-C and C-H bonds was calculated. The existence of the graphite
phase in some Cr(C,N) coatings was confirmed by Raman spectroscopy.
TF5.7.P
IMPROVEMENT OF ADHESION OF DIAMOND THIN FILMS ON
WC-Co CUTTING TOOLS
J. PAVLOV*, M. VOJS, P. KÚŠ1, A. KROMKA, V. DUBRAVCOVÁ
Department of Microelectronics, Faculty of Electrical Engineering and Information
Technology, Ilkovičova 3, 812 19 BRATISLAVA, Slovak Republic
1
Department of Solid State Physics, Faculty of Mathematics, Physics and Informatics,
Comenius University, Mlynská Dolina, 842 48 BRATISLAVA, Slovak Republic
Because of its merits, diamond is one of the most promising materials for the
tribological uses. Therefore, it is a significant interest in the diamond film growth on WCCo cutting tools. Such WC-Co based inserts are commercially used as cutting tools for nonferrous materials (wood, glass, aluminum, copper, etc.). The main problem remains of poor
adhesion of diamond over-coating to cemented carbides due to a cobalt dissolution effect of
diamond phase.
In this paper, we present the influence of pre-treatment method on adhesion of
diamond films to WC-Co. Prior to deposition, WC-Co substrates were treated in different
reactive solutions (Al2(OH)2-COOH diluted in acetic acid, Murakami, HCl:HNO3) in order
to suppress Co diffusion to WC surface. Furthermore, some treated substrates were
annealed at 600°C in vacuum conditions. After then, these substrates were once diluted in
reactive solution.
Processed substrates were over-coated by polycrystalline diamond films grown by
dual plasma HF CVD method. Raman spectra confirmed diamond phase over all samples.
Film surface morphology varied with used pre-treatment method. Adhesion strength was
evaluated using the scratch test. Combined process of etching and annealing results in
improved adhesion due to reducing of cobalt on the substrate surface.
TF5.8.P
CHARACTERIZATION OF TRANSPARENT SILICA FILMS
DEPOSITED ON POLYMERIC MATERIALS
Katsuya Teshima*1,2, Hiroyuki Sugimura1, Yasushi Inoue3, Osamu Takai4
Department of Materials Processing Engineering, Nagoya University, Nagoya 464-8603,
Japan
2
Research & Development Center, Dai Nippon Printing Co., Ltd., Kashiwa 277-0871,
Japan
3
Research Center for Nuclear Materials Recycle, Nagoya University, Nagoya 464-8603,
Japan
4
Center for Integrated Research in Science & Engineering, Nagoya University, Nagoya
464-8603, Japan
1
Silica has been applied in a wide variety of industrial fields because of its excellent
properties. Recently, silica coatings have attracted particular attention as barrier coatings
against gas and vapor permeation. Among many coating methods, plasma-enhanced
chemical vapor deposition (PECVD) is one of the preferred methods to deposit silica films
on polymeric substrates at low substrate temperature. In the present work we studied film
structures of silica deposited by PECVD under various deposition conditions and effects of
film structures on their gas barrier properties.
Silica films were synthesized by capacitively coupled RF PECVD using mixtures of
organosilane and oxygen as a source. The chemical bonding states and compositions of the
films deposited were evaluated with FTIR and XPS. Film surfaces and cross-sections were
observed by SEM. Oxygen transmission rates (OTR) of the films coated on polyethylene
terephthalate (PET) substrates were measured by an isopiestic method.
The SEM images obtained clearly demonstrated that silica domes formed on the PET
substrates only in the early stage of deposition. Silica domes did not form in the vapor
phase, but rather, directly onto the polymer surface. The growth of these silica domes
depended on the presence of activated oxygen species in the vapor phase. When no oxygen
existed in the vapor phase, the domes did not connect well with each other even after long
deposition time. In such cases, the siloxane networks in the film were terminated with many
functional groups, such as -CHx, -H and -OH. On the contrary, in the presence of active
oxygen species, many types of impurities in the film were largely eliminated, with the
result that a dense silica film in which the domes fused together well could form on the
PET substrate. The densely-packed silica film satisfied the requirements for industrial
products in the field of food packaging.
Corresponding author*: Tel. +81-52-789-4639; Fax. +81-52-789-3260; E-mail
teshima@plasma.numse.nagoya-u.ac.jp
Address: Department of Materials Processing Engineering, Graduate School of
Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
TF5.9.P
TiO2 (Fe3+) NANOSTRUCTURED THIN FILMS WITH ANTIBACTERIAL
PROPERTIES
C.C. Trapalis1, P. Keivanidis1, G. Kordas1
M. Zaharescu2, M. Crisan2, A. Szatvanyi2, M. Gartner*2
1
Instittute of Materials Science, National Center for Scientific Research “Demokritos”,
153 10 , Athens, Greece
2
Institute of Physical Chemistry “I.G.Murgulescu”, Romanian Academy,
202 Splaiul Independentei, 77208, Bucharest, Romania
TiO2 based nanostructured Fe3+ doped coatings have been prepared by sol-gel method on
glass
substrates.
The
coatings
were
characterized
by
X-ray
diffraction
and
spectroellipsometry methods. The influence of Fe3+ dopant concentration, number of
coatings, and calcination temperature on the films structure was established.
The antibacterial activity against Escherichia Coli, has been studied appling the so called
antibacterial-drop test. The bacteridicidal activity for the above bacteria cells was estimated
by relative number of bacteria survived calculated from the number of viable cells which
form colonies on the nutrient agar plates. The coatings exhibited a high antibacterial
activity, which was enhanced with the increase of the temperature of thermal treatment and
formation of anatase crystalline structure. The long time thermal treatment results to rutile
crystalline structure formation follwed by the decrease in the antibacterial activity of the
coating.
Corresponding Author: M. Gartner, Institute of Physical Chemistry “I.G.Murgulescu”,
Romanian Academy, 202 Splaiul Independentei, 77208, Bucharest, Romania Tel:+401 224
88 95, Fax: +40-1-3121147,
E-mail:mfgartner@yahoo.com
*
TF5.10.P
Titanium carbide films grown by new laser hybrid technology
Miroslav Jelínek1, Tomáš Kocourek1, Jaromír Kadlec2, Petr Boháč1, Vladimir Vorlíček
1. Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2,
182 21 Prague 8, Czech Republic (phone : 420 2 6605 2733, fax : 420 2 86890527,
e mail : jelinek@fzu.cz)
2. Military Academy, Brno, Czech Republic
Hybrid technology for thin film production, combining pulsed laser (PLD) deposition
and DC magnetron sputtering was developed. Layers are grown during one deposition
cycle from two different targets. Carbon films are grown by PLD from graphite target.
Titanium is added to grown layer by magnetron sputtering. Presence of carbon nitride was
confirmed by XRD. Results of Raman scattering, mechanical properties of grown layers
and first deposition experiences will be presented.
TF5.11.P
DLC FILMS DEPOSITED BY DC PACVD METHOD
D. Palamarchuk, F. Černy
CTU of Prague, Faculty of Mechanical Engineering,
Department of Physics, Technicka 4, 166 07 Praha 6
For engineering applications, diamond-like carbon films (DLC) are one of most suitable
coatings, when high wear-resistance is needed [1]. One problem is very poor adhesion to
steel substrates, when no intermediate layer is supplied. The most common method for
depositing DLC-films is plasma activate chemical vapor deposition process with radio
frequency discharge (RF PACVD, 13.56 MHz), which is technically difficult and expensive
to scale up to industrial dimension. In this paper the deposition of DLC coating by direct
current PACVD (DC PACVD) is presented.
DLC films were deposited on silicon (111) and steel substrates. The steel substrate consists
of 0.9 %  C, 4.14%  Cr, 6.1%  W, 5%  Mo, 2.02%  V. These samples were polished
up to a mirror finish using series of standard metallurgical polishing steps.
Prior to mounting in the process chamber the samples were cleaned with acetone and
isopropanollian ultrasonic bath.
The apparatus for plasma assisted chemical vapor deposition consisted of vacuum chamber,
diffusion pump, two parallel electrodes and generator of DC discharge plasma. We
deposited DLC films on our substrates with the same parameters, but one, which was
changed. It was bias voltage. This parameter was changed from – 400V to – 900 V.
Then we investigated the dependence of microhardness on bias voltage and the adhesion of
DLC layers to the substrate. The microhardness of the substrates and substrates with DLC
films was measured by Leica DM Inverter Research Microscope for Materials Testing.
The microhardness of the coated materials is higher than the base material about 13 GPa at
the load 50 mN and bias voltage –900 V.
These coatings can be used for example for protection of metal bioimplants [2].
REFERENCES
1. H. Dimigen, H. Hubsch, Philips Tech. Rev.41 (6) (1983) 186-197.
2. S. Konvickova, D. Valerian: Acta Mechanica Slovaca, 2 (1989) 39.
TF5.12.P
THE NANOSTRUCTURE AND MECHANICAL PROPERTIES OF
PVD CrCu (N) COATINGS
M.A.Baker1, P.J.Kench1, M.C.Joseph2, C.Tsotsos2, A.Leyland2, A.Matthews2
1
2
School of Engineering, University of Surrey, Guildford, Surrey, GU2 7XH, UK
Research Centre in Surface Engineering, University of Hull, Hull, HU6 7RX, UK
Coatings with a nanocomposite structure have been identified as offering excellent wear
resistant properties. This paper presents results on the CrCu (N) system, in which the
immiscibility of Cr (with low N concentration) and Cu offers the potential of a
predominantly metallic (and therefore tough) nanocomposite, composed of small Cr (N)
grains interdispersed in a (minority) Cu matrix. A range of CrCu (N) compositions have
been deposited using a twin-target (Cr and Cu) unbalanced magnetron sputtering system.
The stoichiometry and nanostructure have been characterised by X-ray Photoelectron
Spectroscopy (XPS), Transmission Electron Microscopy (TEM), Scanning Electron
Microscopy (SEM), X-ray Diffraction (XRD) and Electron Energy Loss Spectroscopy
(EELS). The hardness and elastic modulus have been determined by nanoindentation. The
phase composition of the coatings is generally based on Cr2N with the additional presence
of Cr and CrN depending on the elemental composition. Cu was found to be incorporated
in the Cr based phases. The formation of this metastable structure is attributed to the
relatively low deposition temperature employed (~200 ºC). The coating with the best
mechanical properties, CrCu0.07N0.48 exhibited a hardness of 20 GPa.