Beruflich Dokumente
Kultur Dokumente
Tribology International
journal homepage: www.elsevier.com/locate/triboint
Laboratorio de Fsica del Plasma, Universidad Nacional de Colombia Sede Manizales, Km. 9 via al Magdalena, Manizales, Colombia
PCM-Computational Applications, Universidad Nacional de Colombia Sede Manizales, Colombia
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 20 May 2012
Received in revised form
15 December 2012
Accepted 20 January 2013
Available online 16 February 2013
This study investigates W/WCN coatings grown by means of a repetitive pulsed vacuum arc discharge
while varying the substrate temperature from room temperature (RT) to 200 1C. The coatings were
grown using a cathode with W (6N) and WC (6N) targets for the W and WCN layers, respectively, and
an anode that contains stainless-steel 304 as a substrate. The lms grown at RT and at 150 1C possessed
a lower percentage of carbon obtained from energy dispersive spectroscopy. This characteristic was
related to the hardness, the coefcient of friction and the adherence. These lms also possessed the best
mechanical and tribological properties. Several wear mechanisms were identied, such as delamination
and plowing out of abrasive and adhesive particles.
& 2013 Elsevier Ltd. All rights reserved.
Keywords:
Hardness
Wear
Coefcient of friction
Adherence
1. Introduction
The mechanical, tribological and thermal properties of several
metals can be signicantly improved by controlling the incorporation of interstitial elements, such as boron, nitrogen and
carbon [1]. The main interest for studying the properties of
binary and ternary metals containing carbides and nitrides
centers on improving their functional properties and technological applications [2].
Although both W and WC coatings have been used for a
number of applications, not much is known about coatings with
carbon concentrations in an intermediate range below that of
stoichiometric WC [3]. Only tungsten carbide coatings have
thus far been used as coatings for mechanical purposes [4]. The
primary W(N/C) coatings were deposited onto high-speed steel
due to the good wear properties of cemented M2 (AISI) and were
then heat treated (via quenching and tempering) to form carbides
in the bulk state [5]. Gouy-Pailler and Pauleau [6] determined that
the increase in hardness of coatings containing tungsten and
small amounts of carbon was due to isotropic dilatation of the
a-W structural lattice. More recently, Quesnel et al. [7] formed W
layers containing small amounts of carbon for use in W/WC
multilayers as erosion-resistant coatings.
n
Corresponding author at: Laboratorio de Fsica del Plasma,
Universidad Nacional de Colombia Sede Manizales, Km. 9 via al
Magdalena, Manizales, Colombia. Tel./fax: 57 6 887 9495.
E-mail address: erestrepopa@unal.edu.co (E. Restrepo-Parra).
0301-679X/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.triboint.2013.01.014
2. Experimental details
Both the W and WCN layers were deposited using a repetitive
pulsed vacuum arc discharge in a reaction chamber made of
stainless steel. In this chamber, there are two facing electrodes,
a cathode with W (6N) and WC (6N) targets for the W and WCN
layers, respectively. Moreover, samples of 304 stainless steel with
1.3 cm diameter and 2 mm thickness were employed. The substrates were polished and cleaned using an ultrasonic cube.
A high power source designed for generating pulses with different
active and passive times was used to produce a discharge
between the electrodes, and each coating was produced with
four pulses. The active time is limited to the minimum time
necessary for arc formation under a given set of working conditions such as the target material, working gas and pressure. The
inactive arc time can take any theoretical value; however, it is
necessary to take into account that the minimum value is
subjected to the arc extinction time under the given working
conditions (mainly the target material and the working gas).
Initially, the reaction chamber was evacuated to 10 3 Pa; then,
layers were deposited onto the substrates by varying the substrate temperature (TS) using argon as the working gas for the W
layer and a mixture of argon and nitrogen (1:1) for the WCN layer
at 300 Pa with 280 V between the electrodes and a current of
100 A. Both, the W and WCN layers were deposited on the
substrates with four pulses at 1 s and 2 s as passive and active
time respectively. The W layer was grown at RT, while the TS
varied between room temperature (RT) and 200 1C during the
deposition process for the WCN layer. The temperature was kept
constant, being monitored during the entire experiment. This
system is thoroughly described in a previous work published by
our group [14].
A Nanovea Microphotonics nanoindenter was employed for
mechanical characterization of the materials. This indenter consists of a Berkovich-type diamond tip coupled to an IBIS head
(Fischer-Cripps Lab) and a Nanovea Series displacement control
frame. The applied load was varied between 3 mN and 5 mN. IBIS
software for controlling, correcting and analyzing the results was
employed. A scratch test was performed using Micro-Test equipment. The indentation hardness is dened as the mean contact
pressure and is given by HFmax/Ap, where Fmax is the maximum
normal load and Ap is the projected contact area at that load [15].
A Rockwell C indenter was used with a 200-mm radius, a variable
load between 0 N and 90 N, a load application velocity of 1 N/s
and a distance of 5 mm. The coefcient of friction (COF) was
measured with a pin on disc (POD) CSEM instruments tribometer
with a sphere of alumina (Al2O3) that was 6 mm in diameter, a
scratch velocity of 10 cm/s, a radius of 3 mm, a distance of 100 m
and an applied load of 1 N. Energy dispersive spectroscopy (EDS)
was carried out for semi-quantitative elemental analysis. Morphological analysis was carried out with scanning electron microscopy (SEM; Philips XL-30TMP) with a standard probe at energy
of 20 kV with a magnication of 200 .
125
W2(C,O) and a-WCN (hexagonal) [13,16]. With EDS, the W coating composition was analyzed and the result is presented in
Table 1. Furthermore, the percentages of W, N and C as a function
of TS for WCN coatings were also obtained and are included in
Table 1. These values showed a competition between the percentages of C and N. Initially, an increase in carbon is observed with
increasing TS, thereby generating the formation of CC, CN, CQC
and CQN bonds that cause amorphization of the sample, in
agreement with Kukie"ka et al. [17].
3.2. Morphological characterization
Table 1 lists the values of the W/WCN bilayers thickness as a
function of TS and it also included the thickness of the W layer.
During the thin lm deposition process, there are several
growth mechanisms such as adsorption, nucleation, coalescence
and resputtering. Initially, the thickness of the lm decreases with
increasing TS, which is in agreement with a previous study by Pal
and Jacob [18]. These authors produced WO3 lms on silicon
substrates and stated that the observed behavior is caused by an
increase in the vapor pressure of the deposited material. This
behavior can also be attributed to the resputtering process, which
is important because the atoms gain enough energy at sufcient Ts
to return to the plasma; as a result, less material is deposited, as
reported by Beena et al. [19]. Additionally, the surface morphology
can be described by the average roughness (Ra), which is the most
widely used surface parameter in the industry [20]. The surface
roughness of the lms decreases with increasing TS, as shown
in Table 1. The decrease in surface roughness as a function of TS can
be attributed to the increased diffusion of surface atoms [21].
3.2.1. Nanoindentation test
The mechanical characterization of materials at small length
scales has been widely studied and reported in the literature.
There are several micro- and nano-scale testing techniques for
studying the mechanical properties of materials of interest to the
scientic and industrial communities. The most common technique for determining the hardness of thin lms is the nanoindentation method [22]. A characteristic load and unload curve for the
indentation process for a sample grown at 150 1C is shown
in Fig. 1. In this curve, a maximum load of 1 mN can be obtained
with a penetration depth of 60 nm. The hardness was determined
using the unload curve and nanotribometer software. The hardness values of the W layer and the W/WCN bilayers as a function
of TS are shown in Table 2. In all cases, the hardness of the
W/WCN coatings is greater than that shown by the substrates
with and without W interlayer. Thicker lms (grown at RT and
150 1C) possessed the greatest hardness. These samples also
showed the highest nitrogen percentage according to Table 1.
However, the lm with the least hardness was that grown at 50 1C
Table 1
Percentages of carbon, nitrogen, tungsten, thickness and roughness values for W
layers and W/WCN bilayers depending on TS.
TS (1C) C (wt%)
N (wt%)
W (wt%)
Thickness
(mm)
Roughness
(mm)
RT
W
0.057 0.02
98.67 0.4
0.32 7 0.08
0.27 0.01
RT
50
100
150
200
W/WCN
14.73 7 1.85
21.65 7 1.3
25.13 7 1.4
18.11 7 0.9
29.61 7 1.8
5.72 70.51
2.18 70.19
3.25 70.10
6.21 70.25
2.36 70.11
69.047 1.3
62.38 71.6
58.707 1.2
63.707 1.9
55.11 71.7
0.91 7 0.02
0.87 7 0.02
0.82 7 0.04
1.33 7 0.03
0.65 7 0.01
0.137 0.01
0.117 0.01
0.107 0.02
0.057 0.02
0.037 0.01
126
1.2
HSS
1.0
COF (adim.)
W
0.8
200 C
0.6
100 C
0.4
50 C
150 C
0.2
RT
0.0
0
Fig. 1. Loadunload curve of the W/WCN bilayer grown at 150 1C, obtained by
nanoindentation.
20
40
60
Distance (m)
80
100
Fig. 2. Plot of the friction coefcient vs. sliding distance for HSS substrates, HSS/W
and W/WCN coatings grown at different values of TS.
Table 2
Wear, adherence and hardness of the HSS substrates, HSS/W and the W/WCN
bilayers as a function of TS.
Material
COF
(adim.)
Maximum
depth (nm)
Wide
(nm)
Hardness
(GPa)
Lc1
(N)
Lc2
(N)
HSS
W
TS
RT
50 1C
100 1C
150 1C
200 1C
1.0 70.5
0.7 70.1
W/WCN
0.35 7 0.06
0.35 7 0.08
0.35 7 0.06
0.32 7 0.05
0.65 7 0.10
700 710
190 7 8
210 7 7
490 7 10
6.37 0.3
7.17 0.2
287 2
43 7 4
650 7 12
700 714
590 7 10
210 7 15
750 7 10
235 7 9
200 75
330 7 8
130 7 4
370 7 6
167 2
7.57 0.4
107 1
187 2
97 1
327 1
97 1
207 2
477 3
197 2
36 7 3
28 7 2
27 7 2
63 7 3
27 7 2
127
Fig. 3. SEM micrographs obtained for the W/WCN bilayers grown by varying TS, following a pin on disc test.
128
Fig. 4. (a,b) SEM micrographs of the wear track produced by a pin on disc test on samples grown at 150 1C; and (c) EDS analysis of the center of the track left by a pin on
disc test on the sample grown at 150 1C.
TS=150 C
COF (adim.)
0.3
0.2
Lc1 Cohesive
Lc1 Adhesive
0.1
0.0
0
20
40
Load (N)
60
80
Fig. 5. (a) Scratch test of the sample grown at 150 1C. Images of (b) the total scratch track, (c) region of Lc1 and (d) region of Lc2.
recurring spallation of the coating [32]. Fig. 5(b) shows a micrograph of the total scratch test track. The two zones of the critical
load and the nal behavior of the lm can be observed. Fig. 5(c)
and (d) shows the magnication of the Lc1 and Lc2 failures,
respectively.
The values obtained for the critical loads Lc1 and Lc2 are listed
in table 2. It is again observed that the W/WCN coating produced
at 150 1C presents the highest critical load (Lc1 and Lc2) values and
the best adhesion behavior. These results are caused by an
increase in resistance to deformation due to the greatest hardness
4. Conclusions
W/WCN bilayers were grown using a repetitive pulsed vacuum
arc system by varying the substrate temperature. This study
focused on analysis of the mechanical and tribological properties
of these systems. The lm grown at 150 1C exhibited the highest
degree of hardness, the lowest COF and the highest adhesive and
abrasive loads (Lc1 and Lc2). In addition, the typical wear mechanisms identied were delamination, fracture, plowing, microwelding, adhesion, abrasive particles and laminar particles. Moreover, EDS analysis of the center of the track indicated an increase
in the percentage of oxygen from 3.7% to 14.9% due to oxidation
arising from the tribochemical process.
Acknowledgments
The authors gratefully acknowledge the nancial support of La
direccion Nacional de Investigaciones de la Universidad Nacional
de Colombia Sede Manizales during the course of this research
under the Project Produccion y Caracterizacion de recubrimientos
con aplicaciones industriales y biocompatibles.
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