15. - 17. 5.

2013, Brno, Czech Republic, EU

A STUDY OF PVD MONO- AND MULTICOMPONENT THIN COATINGS FOR TOOLS
APPLICATIONS
Dagmar JAKUBCZYOV, Marek KOK, Pavol HVIZDO,
Institute of Materials Research, Slovak Academy of Sciences, Koice, Slovakia, jakubeczyova@gmail.com,
mkocik@imr.saske.sk, phvizdos@imr.saske.sk
Abstract
Two types of coatings - a mono- and a multi-component - were deposited by Arc-PVD method to steel
substrate made of machined steel (Cr-Mo-V) produced by powder metallurgy (PM). We used fractographic
analysis employing an SEM technique with EDS to evaluate morphology of fractures across mono- and
multi-component system coatings. The surface of fractures was examined macroscopically and
microscopically. Nanoindentation measurements with dynamic loading were carried out on deposited layers
of TiN and AlTiCrN type in order to verify their deformation behaviour. The nanoindentation measurements
revealed higher surface hardness of the layer AlTiCrN (47.7 GPa) resulting from the presence of Cr and Al
in its composition and the TiN layer exhibited somewhat lower hardness (26.1 GPa). With decreasing
hardness the elastic modulus decreased proportionally and it was interesting that that despite lower
hardness of the TiN layer the modulus of elasticity E of this coat was higher compared to the AlTiCrN coat.
The qualitative and quantitative analysis of metal and non-metal elements across the deposited layers was
carried out by GDOES (Glow Discharge Optical Emission Spectroscopy) technique. This allowed us to obtain
a graphical recording of in-depth concentration profile, showing concentration gradient of the selected
elements up to a depth of 4800 nm. Both types of chemical analysis (EDS and GDOES) corresponded very
well in terms of quantification in atomic percent and weight percent values. On the basis of obtained results
we evaluated structural, mechanical and chemical properties of the deposited types of coatings and
recommended their use in practice.
Keywords: PVD - coat, fractography, nanohardness, modulus of elasticity, GDOES
1. INTRODUCTION
In recent years, the surface engineering technique has been developed in order to improve the tribological
performance in industrial applications. Concepts and coatings technologies of materials and components
have a rapid development during the last years. If the first PVD TiN coatings were prepared early in 1980
and in 1988 were added only next 2 types (TiCN a CrN), so in the year 2000 it was possible to find
approximately 14 basic types of PVD coatings [1]. Hard coatings play an important role in industry for
improving tool lifetime and performance. A variety of hard coatings are widely used in the tool industry,
mainly to reduce friction and to increase wear resistance. One of the mostly used and studied coatings to
date is TiN, which has beneficial properties including high hardness, low friction, and chemical inertness [2].
The statistics based on observation of German market indicate an unmistakable trend of replacement of the
outdated TiN and TiCN layers by layers based on TiAlN. The increasing proportion of layers based on
TiAlN is a logical consequence of their basic properties and requirements of industry. The HV hardness of
the originally developed and historically oldest TiN reaches 23 GPa and their maximum working temperature
is 600C, while the TiCN layers reach a hardness of 35 GPa but their maximum working temperature is only
450C. The layers based on TiAlN exhibit high HV hardness up to 33 GPa and their maximum working
temperature may sometimes exceed even 800C, thus fulfilling the two most important requirements for
industrial applications, i.e. high abrasion resistance and chemical stability at high temperatures [3]. However,
15. - 17. 5. 2013, Brno, Czech Republic, EU


if the industrial applications require very hard coatings with increased thermal and chemical stability, then
even the common layers based on TiAlN or AlTiN do not suffice. Multicomponent coatings based on different
metallic and non-metallic elements combine the benefit of individual components leading to a further
refinement of coating properties. Metastable TiAlN materials not only exhibit superior high temperature
oxidation resistance compared to TiN and better cutting behaviour enabling the use of higher cutting speeds,
but also very interesting physical properties [4,5,6]. Some TiAlN layers are supplemented with additional
elements, such as Cr, Y, Zr, Hf and similar. These additives, when used in small quantities, affect positively
the structure of layers, namely by improving their oxidative properties, refining the structure and upgrading
the adhesive properties and thus contributing to better industrial properties [7,8]. This involves multilayers
and gradient and nanostructure layers, each of the layers having a specific function thermal, adhesive and
oxidative resistance and strength. The motivation to infiltrate into productive cutting applications, involving
high production of heat, and into dry applications, is based on promises of high ecological and economical
contributions [9]. This is related to potential increase in service life of various substrate materials based on
increased resistance to corrosion and mechanical influences of the environment.
2. EXPERIMENTAL PROGRAMME
We compared two types of coatings deposited by Arc-PVD method to steel substrate made of machined
steel (Cr-Mo-V) produced by powder metallurgy (PM). We deposited a conventional mono-component TiN
and a multi-component AlTiCrN coating. Both coatings were subjected to fractographic analysis employing
an SEM technique with EDS that was performed on the fracture surface after bending test. The surface of
fractures was examined macroscopically and microscopically. An advantage of SEM compared to SM is a
higher-order resolution and great-depth definition which allow one to observe surface unevenness even at
high magnifications. A part of evaluation of deposited coats was determination of their hardness in the
direction from the surface toward the substrate. With regard to increasing requirements on evaluation of
materials surface, namely coatings with decreasing thickness, it is necessary to abandon the evaluation of
conventional microhardness technique and instead of evaluating the size of the imprint after indentation to
focus on the indentation curve. This is the reason why we evaluated the coating hardness by a dynamic
nanoindentation technique which is used extensively to characterise the mechanical behaviour of materials
on a small scale [10]. A nanoindenter is a testing machine with high resolution that allows one to measure
properties on sub-micro and nano-scale [11,12] and serves particularly as a primary technique for
determination of mechanical properties of thin coats and small construction parts [13,14]. The attractivity of
this method is based on the fact that mechanical properties of very thin coats and materials with prevailing
elastic deformation can be ascertained directly from the indent/imprint that cannot be observed by optical
means. The loading force and position of the indenter is continuously monitored and recorded throughout the
indentation cycle. The thickness of PVD layers ranges from a few nanometres to several tens of
micrometres, therefore one must ensure that during the measurement of hardness the identer tip penetrates
to a maximum depth of 1/10 of the coating thickness. The nanoindentation testing of both coatings was
performed using an equipment TTX-NHT from CSM Instruments, Switzerland. We used a Berkovich indenter
(a three-sided pyramid) operated in a dynamic sinusoidal mode with a maximum load of 400 mN and loading
rate 800 m. min
-1
. The results were processed by the method of Olivera and Pharr [9] which allowed us to
calculate indentation hardness (H) and Young modulus of elasticity (E). The dynamic mode enabled to
measure the values continuously during loading and record them as a function of the relevant indentation
depth. This method is suitable for characterisation of coatings and thin coats as it enables to observe and,
provided that some conditions are met, to separate values corresponding to coats and to the substrate. A
minimum of 20 indentations was made on each specimen and the results were processed statistically. The
qualitative and quantitative analysis of metal and non-metal elements in the cross section of deposited
coatings was carried out by GDOES (Glow Discharge Optical Emission Spectroscopy) technique using an
optical emission spectrometer with glow discharge GDS-750. We obtained an in-depth concentration profile
15. - 17. 5. 2013, Brno, Czech Republic, EU


a graphic documentation of concentration changes of selected elements up to the depth of 100 m. The
accuracy of recalculation of the time axis to concentration profile axis is given by determination of accurate
de-dusting rate of individual calibration standards. Due to the measurement of multi-component structures
one assumes some errors in these calculations. There is no general procedure for elimination of
inaccuracies and one must proceed from one case to another [15]. The selection of individual wavelengths
for analytical purposes is subject to several steps that were discussed by the cited authors [15,16].
3. RESULTS AND DISCUSSION
The aim of the study was to use fractography to evaluate qualitatively-quantitatively the thin mono- and
multilayer coatings deposited onto a steel substrate and to verify their deformation behaviour at dynamic
loading. Figures 1 and 2 show cross-section fractures of systems coat/steel substrate and EDS analysis of
the coatings. The thickness of TiN coat was approximately 3000 nm and that of AlTiCrN coat approximately
2300 nm. The figures show continuous and compact coats with excellent adhesion properties. This is
confirmed by the coating/substrate interface which does not exhibit any failures or cracks in both cases. The
substrate has a pit-like appearance which is typical of the structure of steel prepared by powder metallurgy
while the deposited coatings have columnar morphology, consisting of the so-called columnar crystals,
considerably coat in the TiN coat.



Element
Spectrum1
Weight% Atomic%
Ti K 78.06 50.99
N K 21.94 49.01
Totals 100.00
Fig.1 Cross-sectional image of system TiN / substrate
and EDS analysis


Element
Spectrum1
Weight% Atomic%
Cr K 48.17 29.12
N K 18.49 41.48
Al K 14.81 17.24
Ti K 18.53 12.16
Totals 100.00
Fig. 2 Cross- sectional image of system AlTiCrN / substrate
and EDS analysis
15. - 17. 5. 2013, Brno, Czech Republic, EU


The EDS analysis was supplemented with in-depth concentration profile based on GDOES analysis, Figs. 3
and 4. The graphical relationship allows one to determine the concentration of selected elements in any
thickness of the coating and to read the thickness of the deposited coatings.

Both types of chemical analysis corresponded very well in terms of quantification in weight percent values. In
the monolayer, the analysis unambiguously showed presence of titanium nitride while in the multicomponent
coating chromium nitride, the compound with high hardness and resistance to wear, was found at the highest
concentration on the surface, followed by AlN/TiN with thermal-oxidative resistance and in depth of about
1900 nm, close to the coating/substrate interface, we observed increased concentration of Ti, i.e. the layer
with good adhesive properties. Its function consisted in compensation of stress and tension at the
coating/substrate interface and in acting as a barrier against development of cracks. Nanoindentation testing
determined also surface hardness which reached 26.1 GPa for TiN and 47.7 GPa for AlTiCrN coating and
13.6 GPa for the substrate. Figure 5a) shows the course of hardness in the direction from the coating
surface towards the substrate with stress on not exceeding 1/10 of the total coating thickness in order to
eliminate the influence of substrate. This was in agreement with the requirements of the international
standard for determination of the hardness of coatings [17]. The presence of Al and Cr in the AlTiCrN coat
resulted in the expected increase in hardness compared to the TiN coat by 20 - 10 GPa. With decreasing
hardness, the modulus of elasticity decreased proportionally in both cases and it was interesting that despite
lower hardness of the TiN coat the modulus of elasticity E of this coating was higher compared to the
AlTiCrN coat, Fig. 5b). With respect to the 1/10 layer thickness requirement (for TiN ~ 300 nm and for
AlTiCrN ~ 230 nm), modulus of elasticity reached only 323 GPa in the AlTiCrN and 380 GPa in the TiN coat.
The course of curves at the additional loading of the indenter was affected considerably by the substrate and
approached behaviour of the base material. On the contrary, the course of hardness and elastic modulus of
the base material was constant, which is indicative of respective steel structure, as described in the work
[18]. Many studies are available dealing with deformation mechanisms of thin coatings by means of
nanoindentation technique because many different factors may affect the coating and the substrate at
loading.


Fig. 3 GDOES analysis across TiN coat in weight % Fig. 4 GDOES analysis across AlTiCrN coat in weight %
15. - 17. 5. 2013, Brno, Czech Republic, EU



Fig. 5a) Nanohardness HV and b) modulus elasticity vs. displecement into surface.
Previous studies showed that hardness and Young modulus of coatings depended on various factors, such
as yield point, adhesion, layer thickness, internal structure and density of coating and, obviously, the
geometry of the indenter [4,19,20]. The obtained information allowed us to state that lower values of E for
AlTiCrN coating may be related to composition and internal structure of the deposited coats and morphology
of grains/crystallites. Arrangement of crystallites in coats of both types is visible in fracture cross sections of
systems, see Fig. 1 and 2. The cross section of TiN coat shows long columnar grains while cross section of
AlTiCrN contains smaller columnar grains with the lamellar arrangement in the direction from the surface
towards the substrate: coatings CrN, AlN/TiN and TiN. Lower elastic modulus E of the multilayer coating
most likely results from the arrangement of individual layers and concentration of elements across its
thickness. Both the coatings fulfilled the purpose, i.e. produced a protective coating on the surface of the
steel substrate which exhibited good adhesive and mechanical properties. Due to higher hardness and thus
also higher resistance to wear and thermal-oxidative influences, the AlTiCrN coat has a more universal use
in practical applications.
4. CONCLUSIONS
Two types of coatings - TiN and AlTiCrN deposited by PVD technology to PM steel substrate were
analysed and documented by fractographic and nanoindentation methods and by emission spectroscopy.
Examination of cross-section fractures of the systems coating/steel substrate indicated that the deposited
coats were continuous and compact and had excellent adhesive properties. The interface between the
coating and the substrate was free of any failures or cracks in both cases. Morphology of coatings was
based on columnar crystallites/grains. The grains were longer in the TiN in comparison with the AlTiCrN
coating and their size corresponded to the thickness of lamellar layers located one above another. EDS
method was used to carry out semi-quantitative analysis of the elements present.
The EDS analysis of present elements corresponded well with the in-depth concentration profile always
down to the substrate. GDOES analysis allowed us to determine the concentration of elements in any
depth of the coating and, of course, the thickness of the deposited coating with sufficient accuracy.
According to expectations, nanoindentation measurements revealed higher surface hardness of the coat
AlTiCrN (47.7 GPa) resulting from the presence of Cr and Al in its composition; the TiN layer exhibited
somewhat lower hardness (26.1 GPa) and the hardness of the PM substrate used reached 13.6 GPa.
With decreasing hardness the elastic modulus decreased proportionally and it was interesting that that
despite lower hardness of the TiN coat the modulus of elasticity E of this coating was higher compared to
the AlTiCrN coat. These results allowed us to state that lower values of E in case of the AlTiCrN coating
could be related to chemical composition, internal structure of deposited coatings and morphology of
15. - 17. 5. 2013, Brno, Czech Republic, EU


grains/crystallites. Lower elastic modulus E of the multilayer coating most likely resulted from different
arrangements of individual layers and concentration of elements across its thickness.
The deposited types of coatings ensured increased hardness and elastic modulus of the base material and
the coating/substrate interface was without failures, which confirmed excellent adhesion properties of the
system. Due to their specific properties, the coatings appear suitable for use in practical operations.
ACKNOWLEDGEMENT
The work was carried out within the framework of the project VEGA 2/0060/11.
REFERENCES
[1] http://www.mmspektrum.com/clanek/pocitacova-simulace-rustu-pvd-povlaku-a-nova-rada-trojvrstvych-
povlaku.html
[2] DING, J., MENG, Y., WEN, S., Thin Solid Films, Vol. 371, 2000, p. 178-182
[3] http://www.shm-cz.cz/cs/technicke-informace/literatura
[4] NAKONECHNA, O., CSELLE, T., MORSTEIN, M., KARIMI, A. Thin Solid Films, Vol. 447-448, 2004, p. 406-412
[5] C.H. ZHANG, Z.J. LIU, K.Y. LI et al.: Journal Appl. Phys., 2004, Vol. 95, p. 1460
[6] KAUFFMANN, F., DEHM,G., SCHIER, V. et al. Thin Solid Films, Vol. 473, 2005, p. 114
[7] HOLUB, P., JLEK, M., MA, M. Nov prmyslov technologie povlakovn, MM Prmyslov spektrum,
4/2003M
[8] HAGAROV, M., BLHOV, O., SAVKOV, J. Acta Metallurgica Slovaca, Vol. 15, No.4 , 2007, p. 221-227
[9] http://www.shm-cz.cz/files/literatura/30.pdf
[10] W. C. OLIVER, G. M. PHARR, Measurement of hardness and elastic modulus by in strumented indentation:
[11] Advances in understanding and refinements to methodology. Journal of Materials Research, Vol. 19, 2004, p.3-20
[12] FISCHER-CRIPPS, A. C., A review of analysis method for sub-micron in dentation testing, Vacuum, 58, 2000, p.
569-585
[13] NEWEY, D., WILKINS, M.A., POLLOCK, H.M., Journal. Phys. E: Sci. Instrum, Vol. 15, 1982, p. 119
[14] HAGAROV, M., Journal of Metals, Materials and Minerals. Vol.17, No.2, 2007, p. 29-35
[15] SAHA, R., NIX, W.D., Acta Materialia., Vol. 50, 2002, p. 23
[16] VNOUEK, M., Povrchov efekty pi GDOES. (Surface Effects at GDOES.) PhD study work. The University of
West Bohemia in Pilsen, 2002 (in Czech)
[17] SETTINERI, L. et al. Evaluation of wear resistance of AlSiTiN and AlSiCrN nanocomposite coatings for cutting
tools, CIRP Annals-Manufacturing Technology, Vol. 57, 2008, p. 575-578
[18] ISO 14577-4 (2007): Metallic materials - Instrumented indentation test for hardness and materials parameters --
Part 4: Test method for metallic and non-metallic coatings
[19] http://www.matnet.sav.sk/index.php?ID=160
[20] LOGOTHETIDIS, S., KASSAVETIS, S., CHARITIDIS, C., PANAYIOTATOS, Y., LASKARAKIS, A.,
Nanoindentation studies of multilayer amorphous car bon films. Carbon, Vol. 42, 2004, p. 1133-1136
[21] PICEK, R., BOH, P., Measurement of Elastic Constants of Thin Films by the Law Method, MaterialsStructure,
Vol. 13, No. 2, 2006, p. 97-101