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Surface and Coatings Technology 167 (2003) 221–225

The effect of relative humidity on wear of a diamond-like carbon coating

Jiaren Jianga,*, Sam Zhangb, R.D. Arnellc
Integrated Manufacturing Technologies Institute, National Research Council Canada, 800 Collip Circle, London, Ont., Canada N6G 4X8
School of Mechanical and Production Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore
Centre for Advanced Materials and Surface Engineering, University of Salford, Salford M5 4WT, UK


Sliding wear behaviour of a diamond-like carbon (DLC) coating deposited using the combined closed field unbalanced
magnetron sputter ion plating and plasma assisted chemical vapour deposition technique has been investigated against tungsten
carbide balls in air with various relative humidity (RH) levels as well as in water. A smooth transfer layer was always formed
on the ball surface and wear of the ball was negligible. The wear rate of the coating decreased significantly with increase in RH,
with sliding in water showing the lowest wear rate. When sliding in dry air or in a vacuum, the coating failed very quickly,
producing a wear rate of approximately two orders that for sliding in humid air. Under the investigated conditions, sliding speed
(0.25 and 0.05 m sy1) had no significant effect on the wear behaviour of the DLC coating in the various environments. The role
of humid air in reducing wear rate of the DLC coating has been attributed to the formation of low energy surfaces by the
adsorption of water at the dangling carbon bonds on the edge-faces of the sp2 clusters in the DLC coating.
䊚 2002 Elsevier Science B.V. All rights reserved.

Keywords: Wear; Tribological behaviour; Diamond-like carbon; Relative humidity; Environmental effect

1. Introduction (;80% RH). Friction coefficients were higher in vac-

uum (10 Pa) than in dry nitrogen and in humid air.
The high hardness, high chemical stability and low Data on the wear performance of DLC coatings in
friction and wear make diamond-like carbon (DLC) different environmental conditions is relatively less
coatings good candidates for a wide range of tribological available compared with that for their frictional behav-
applications. However, studies have shown that their iour. There seems to be no direct relationship between
tribological behaviour can be very sensitive to environ- frictional and wear behaviour w2,5,6,9,14,15x.
mental factors, especially to relative humidity (RH), Various theories have been proposed to explain the
and is dependent on the deposition method and deposi- tribological behaviour of DLC coatings w16–25x and
tion conditions w1–11x. Under most of the conditions, they are subject to controversy. The role of environments
the hydrogenated DLC coatings showed low values of on friction and wear of amorphous carbon coatings is
friction coefficients in dry environment and in vacuum still not well understood. Considering that air is the
w2,3,5–8x and very low friction coefficients have been most commonly encountered environment in DLC appli-
observed in ultrahigh vacuum w5,7,8x. Friction coeffi- cations and RH is one of the main factors affecting
cients increase with increase in RH w2,3,6–11x. Oxygen tribological properties of DLC coatings, in this study,
has been found to increase the friction coefficients of the tribological behaviour of an unhydrogenated com-
such DLC coatings w3x. On the other hand, Voevodin et posite DLC coating has been investigated in air with
al. w12,13x showed an opposite effect of environment on various RH using a ball-on-disk sliding wear rig.
friction of a-C and a-C:H coatings deposited using the
pulsed laser deposition technique. The friction coeffi- 2. Experimental method
cient after a certain number of cycles of sliding against
steel or sapphire balls decreased with increase in RH DLC coatings were deposited on an M42 tool steel
*Corresponding author. Tel.: q1-519-430-7121; fax: q1-519-430- substrate using the combined closed field unbalanced
7064. magnetron sputtering and plasma assisted chemical
E-mail address: (J. Jiang). vapour deposition technique w26,27x. The coating was

0257-8972/03/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
222 J. Jiang et al. / Surface and Coatings Technology 167 (2003) 221–225

Fig. 1. Typical variation of wear volume as a function of sliding distance at various RH levels and at sliding speeds of 0.05 and 0.25 m sy1.

composed of multilayers of, from the substrate outwards, 3. Results

TiyTiNytransitional Ti(N,C)yTiCyDLC. The thickness
of the DLC coating layer, measured using a ball crater 3.1. Wear as a function of relative humidity
method, was approximately 1.2 mm. The hardness and
Fig. 1 shows some wear curves for sliding in different
elastic modulus of the DLC coating, measured using a RH at sliding speeds of 0.05 and 0.25 m sy1. The
nanoindenter, were 7 and 180 GPa, respectively. variation of wear volume as a function of sliding
Wear tests were carried out on a continuous ball-on- distance was roughly linear. Specific wear rate decreased
disk sliding wear rig with a controllable environment with increase in RH.
chamber. The RH of the environment was controlled by Fig. 2 summarises the results for the effect of RH on
mixing different proportions (flow rates) of dry com- specific wear rate of the DLC coating at sliding speeds
pressed air and air saturated with water vapour before of 0.05 and 0.25 m sy1. The normal load was 10 N
introducing the gas into the chamber. The actual RH in except that a load of 20 N was applied when sliding in
the testing chamber enclosing the specimen was meas- water because the wear measurement in this case was
ured using a hygrometer. The balls were made of very difficult at a load of 10 N. The results obtained
sintered tungsten carbide and had a diameter of 6.35 from sliding in water are plotted in Fig. 2 at a RH of
mm. Two sliding speeds were used: 0.05 and 0.25 100%. The results for the two sliding speeds essentially
m sy1. The applied normal load was 10 N. followed the same trend except at the low RH end
During sliding, wear volumes of the disk specimens where the wear rate at 0.25 m sy1 seemed to be slightly
were measured in situ after a certain sliding distance higher than at 0.05 m sy1. Under dry conditions
using a profilometre attached to a PC. The average (RH;0%), the coating failed very rapidly. The wear
cross-section area of a wear track was calculated from life of the coating was approximately 160–190 m, giving
a specific wear rate of approximately 2.0=10y15
at least 12 measurements. The reproducibility of this
m3 Ny1 my1 which is almost two orders that for sliding
technique was within 1.6%. After each wear measure-
in wet air. There was a relatively wide spread in the
ment, an optical photograph of the wear scar formed on
values of wear rate at low RH, indicating some unstable
the ball was taken. Then, the specimen chamber was situations during the sliding. However, the reasons are
closed and purged for more than 20 min and the not clear. With increase in RH from dry condition to
specimens were put back into contact again to restart approximately 20%, the wear rate decreased rapidly.
the sliding. Between RH of 20 and 60%, the variation in wear rate
Detailed examination of scars on the balls in SEM with increase in RH became insignificant. Above
showed that a significant amount of material was trans- approximately 60% RH, wear rate decreased rapidly
ferred from the coating to the ball surface and little again with further increase in RH. The wear rate for
wear from the ball had actually occurred; this was sliding in water was significantly lower than in air; but
confirmed by profilometre scanning over the surface of it seemed to fall on the same curve as the results for
the ball wear scar. sliding in high humidity air.
J. Jiang et al. / Surface and Coatings Technology 167 (2003) 221–225 223

Fig. 2. The effect of RH in air on wear rate of the DLC coating at sliding speeds of 0.05 and 0.25 m sy1 . Data for sliding in water is plotted at
a RH of 100%.

When the sliding wear test was carried out in a where k is a material-related constant and p is the yield
vacuum of 8=10y6 Torr at a speed of 0.25 m sy1, the strength of the wear material.
coating failed within a sliding distance of less than 50 Eq. (1) indicates that reducing the surface energy of
m. Large and loose wear debris particles were formed. the rubbing material will lead to the formation of wear
debris particles with reduced sizes which are prone to
3.2. Examination of wear surfaces agglomerate and get compacted onto the wear surfaces
to form wear protective layers w29x. A high RH may
According to SEM observations, the major noticeable also assist in the agglomeration and compaction of the
difference in the topography of wear surfaces formed at wear debris particles to the wear surfaces by the capillary
different RH was that wear surfaces were much smooth- effect, further reducing wear.
er in high RH than in relatively dry conditions (Fig. 3). For the unhydrogenated DLC coating as investigated
The photographs were taken on wear surfaces of the top in the present study, its structure is primarily constituted
DLC coating layer which was not won through at this of an amorphous or nanocrystallised framework of sp2-
stage. Wear surfaces produced by sliding in water (Fig. coordinated carbon atoms with a very small fraction of
3c) were very similar to those formed at high RH as sp3-bondings, as has been shown by infra-red spectros-
shown in Fig. 3b. copy w30x. In the sp2 configuration, three of the four
Wear scars formed on the ball specimens observed valence electrons of a carbon atom are assigned to the
under optical microscope were very similar under the trigonally directed sp2 hybrid orbitals to form strong
various conditions. Fig. 4 shows the variation of scars covalent bonds with nearest neighbouring atoms. The
on the ball specimen as a function of sliding distance fourth electron, also known as the p electron, lies in an
for sliding in RH of 16%. Material transfer from the orbital normal to the sp2 hybrids. This bonding config-
coating to the ball surface was apparent, while wear of uration would ideally lead to the formation of the perfect
the ball was negligible. With the progress of sliding, graphite lattice in which layers of atoms in hexagonal
wear debris particles were accumulated and compacted network are stacked in an ABAB sequence with weak
surrounding the ball wear scars. Van der Wall’s force between the adjacent layers. In the
DLC coatings, clusters of sp2 bonds with localised
4. Discussion ordering are formed. On the material surface of such
clusters is composed of cleavage-faces (with high
Rabinowicz w28x analysed the formation of wear degrees of disorder) and edge-faces. The cleavage-face
debris particles during sliding wear due to plastic defor- of the sp2 structure, which is graphite-like, is a low-
mation and obtained a relationship for the particle size, energy surface that is essentially formed by the basal
D, as a function of material properties and surface planes. The dangling covalent bonds on the edge-face
energy, g, of the sp2-bonded clusters have high energy levels and
are highly active. However, they can be readily passi-
g vated by the adsorption of water vapour or other gases
Dsk (1)
p from the environment to give a low energy surface.
224 J. Jiang et al. / Surface and Coatings Technology 167 (2003) 221–225

amorphous carbon structures into more ordered graphitic

structures which are subject to ‘dusting’ under vacuum
and dry conditions. The high surface energy dictates the
formation of large wear debris particles (Eq. (1)), which
are difficult to be incorporated into the compact transfer
layers on the rubbing surfaces but rather are easily
removed from the rubbing interface to cause wear loss.
As a result, a very high rate of wear of the DLC coating
was observed when sliding in vacuum and in very dry
On the other hand, as RH increases, the freshly formed
dangling bonds on the wear surface can be passivated
rapidly by the adsorption of water vapour to keep low
energy surfaces, leading to the formation of finer wear
debris particles than those formed under dry conditions
(Eq. (1)). Therefore, wear rate decreases with increase
in RH (Fig. 2).

Fig. 3. SEM observations on the wear surfaces formed during sliding

at different RH: (a) RH 3.1%; (b) RH 82% and (c) water.

When sliding is carried out in vacuum or in a dry

environment, the newly created wear surface areas with
the dangling carbon bonds due to wear cannot be
passivated rapidly after each cycle of sliding. Strong
adhesion can occur to cause high frictional forces
(friction coefficient of 0.5–0.6). This is different from
situations for hydrogenated DLC coatings where the
dangling bonds are passivated by hydrogen atoms within
the coating structure to give a low energy surface and
low friction coefficients. The high frictional heat gen- Fig. 4. The evolution of wear scars on the ball specimen during sliding
erated during sliding in vacuum or in dry environment in air (RH 16%, 10 N, 0.25 m sy1). (a) Sliding distance 390 m and
can lead to a fast transformation of the metastable (b) 1845 m.
J. Jiang et al. / Surface and Coatings Technology 167 (2003) 221–225 225

From the SEM observations, abrasive wear might w5x C. Donnet, M. Belin, J.C. Auge, ´ J.M. Martin, A. Grill, V.
have occurred when sliding in low RH air due to the Patel, Surf. Coat. Technol. 68y69 (1994) 626–631.
w6x T. Le Huu, H. Zaidi, D. Paulmier, P. Voumard, Thin Sold
entrapment of large hard wear debris particles within Films 290–291 (1996) 126–130.
the rubbing interface before being removed, leaving w7x K. Enke, H. Dimigen, H. Hubsch, Appl. Phys. Lett. 36 (1980)
rough grooves on the wear track (Fig. 3a). However, at 291–292.
higher RH levels, smooth wear track surfaces were w8x K. Enke, Thin Solid Films 80 (1981) 227–234.
formed due to the formation of fine wear debris particles w9x A.K. Gangopadhyay, W.C. Vassel, M.A. Tamor, P.A. Willer-
and wear protective transfer layers (Fig. 3b). These are ment, J. Tribol. ASME Trans. 116 (1994) 454–462.
w10x C. Donnet, T. Le Mongne, L. Ponsonnet, et al., Tribol. Lett. 4
consistent with the predictions of Eq. (1) and support (1998) 259–265.
the argument that low surface energy due to water w11x E.-S. Yoon, H. Kong, K.-R. Lee, Wear 217 (1998) 262–270.
adsorption in humid air reduces wear rate of the unhy- w12x A.A. Voevodin, M.S. Donley, J.S. Zabinski, J.E. Bultman, Surf.
drogenated DLC coating. Coat. Technol. 76–77 (1995) 534–539.
w13x A.A. Voevodin, A.W. Phelps, J.S. Zabinski, M.S. Donley,
5. Summary Diamond Relat. Mater. 5 (1996) 1264–1269.
w14x M. Hilden, J. Lee, G. Ouano, N. Nayak, A. Wu, IEEE Trans.
Magn. 26 (1990) 174–178.
The wear behaviour of a multi-layered unhydrogen- ¨
w15x Yilmaz Ozmen, Akihiro Tanaka, Touru Sumiya, Surf. Coat.
ated DLC coating has been investigated on a ball-on- Technol. 133–134 (2000) 455–459.
disk wear rig in air with various RH levels as well as w16x K. Miyoshi, Surf. Coat. Technol. 43y44 (1990) 799–812.
in water. Tungsten carbide balls were used as the w17x J.-P. Hirvonen, R. Lappalainen, J. Koskinen, A. Anttila, T.R.
countering rubbing surface. While the wear of the balls Jervis, M. Trakula, J. Mater. Res. 5 (1990) 2524–2530.
w18x J. Robertson, Adv. Phys. 35 (1986) 317–374.
was negligible, the wear rate of the DLC coating w19x Y. Liu, A. Erdemir, E.I. Meletis, Surf. Coat. Technol. 81
decreased significantly with increase in RH, especially (1996) 48–56.
below 20% RH. In dry air and in vacuum, the wear rate w20x Y. Liu, A. Erdemir, E.I. Meletis, Surf. Coat. Technol. 94–95
of the coating was two orders of magnitude of that for (1997) 463–468.
sliding in humid air. The decreasing wear rate with w21x Y. Liu, E.I. Meletis, J. Mater. Sci. 32 (1997) 3491–3495.
increase in RH has been attributed to the formation of w22x Y. Kokaku, M. Kitoh, J. Vac. Sci. Technol. A 7 (1989)
low energy surfaces by the adsorption of water at the 2311–2314.
w23x S.V. Pepper, J. Vac. Sci. Technol. 20 (1982) 643–646.
dangling carbon bonds on the edge-faces of the sp2 w24x M.N. Gardos, B.L. Soriano, J. Mater. Res. 5 (1990)
clusters in the DLC coating. 2599–2609.
w25x S. Jahanmir, Wear 133 (1989) 73–81.
References w26x D.P. Monaghan, D.G. Teer, P.A. Logan, I. Efeoglu, R.D. Arnell,
Surf. Coat. Technol. 60 (1993) 525–530.
w1x C. Donnet, Condensed Matter News 4 (1995) 9–10. w27x D.P. Monaghan, D.G. Teer, K.C. Laing, I. Efeoglu, R.D. Arnell,
w2x D.S. Kim, T.E. Fischer, B. Gallois, Surf. Coat. Technol. 49 Surf. Coat. Technol. 59 (1993) 21–25.
(1991) 537–542. w28x E. Rabinowicz, Wear 7 (1964) 9–22.
w3x R. Memming, H.J. Tolle, P.E. Wierenga, Thin Solid Films 143 w29x J. Jiang, F.G. Stott, M.M. Stack, Tribol. Int. 31 (1998) 245–256.
(1986) 31–41. w30x J. Jiang, R.D. Arnell, Development and application of diamond-
w4x A. Erdemir, M. Switala, T. Wei, P. Wilbur, Surf. Coat. Technol. like carbon coatings, Progress Report No. 10, DTI-EPSRC
50 (1991) 17–23. Link Project, UK, July, 1998.