Wear 254 (2003) 945949

The friction of natural and CVD diamond

S.E. Grillo a, , J.E. Field b
a

Groupe Rev etements Cramiques, IMPCNRS (UPR 8521), Rambla de la Thermodynamique, Tecnosud, 66100 Perpignan, France b Cavendish Laboratory, PCS Group, Madingley Road, Cambridge CB3 OHE, UK

Abstract We present results on the effect of the environment, load and sliding velocity on the tribological properties of natural diamond sliding upon natural and CVD diamond. Under given conditions of sliding, extremely low friction coefcients, of the order of 103 , have been measured. Our results show that adhesion plays a fundamental role in explaining diamond friction in air, and not only in vacuum as previously thought. We explain the reductions observed in the friction coefcient in terms of the decrease in the adhesive interaction between the two surfaces, following saturation of the dangling bonds by adsorbed species, and by the production of lubricating debris consisting of sp2 hybridised carbon. 2003 Elsevier Science B.V. All rights reserved.
Keywords: Tribological; CVD diamond; Adhesion

1. Introduction The friction of natural and CVD diamond is highly dependent on the environment. As is well established, the friction coefcient varies by an order of magnitude, decreasing from a value of approximately 1 under UHV conditions to between 0.05 and 0.15 in air. It is also known that the presence of organic lubricants does not reduce the coefcient of friction from its ambient value, and this has suggested that out of the two mechanisms traditionally proposed to explain diamond frictionadhesion [1] and surface roughness [2] the latter alone is responsible for friction in air. On the other hand, adhesion has traditionally been used to explain friction in vacuum: under these conditions the surfaces are not passivated by adsorbed molecules and therefore the dangling bonds on the two diamond surfaces are free to join at the interface of contact, thus causing high resistance to sliding. The surface roughness theory faces, however, the problem of explaining the mechanism of energy dissipation, since the energy required to ascend the asperities of the surface should in theory be recovered when descending them. Simple estimates show that for a material like diamond the energy loss due to inelastic processes is far lower than that needed to account for the measured friction coefcients in air (see, for example, [3]). In the present work, the tribological properties of diamond are investigated further by studying the effect of introducing a number of different liquids at
Corresponding author. E-mail address: grillo@univ-perp.fr (S.E. Grillo).

the interface of contact. These experiments can be of interest both from the fundamental and from the applied point of view. From the theoretical point of view, they can yield insight into the friction mechanism since it can be argued that if adhesion does not take place in air, then introducing any liquid whatsoeverand not only organic lubricantsshould not have the effect of reducing the friction coefcient. Conversely, if liquids can be found whose introduction at the contact interface produces a reduction in friction, than this suggests that adhesion does contribute to friction in air and not only in vacuum. From the point of view of potential tribological applications of diamond and diamond coatings, it is also important to establish which liquids, if any, have lubricating properties for this material. The liquids were chosen in such a way as to yield insight into the effect of the chemical composition and steric hindrance of the molecules they contained. For this purpose, the effect of deionised water and of water of different pH values was studied, as well as that of oxygen containing liquids (ketones and aldehydes) of different steric hindrances.

2. Experimental In the experiments reported here, a natural diamond stylus was made to perform reciprocating motion on at natural diamond and on CVD diamond surfaces, under different conditions of environment, load and sliding velocity. Our home-made friction apparatus has been described in detail elsewhere [4]. A diamond tip, mounted at the extremity of a

0043-1648/03/$ see front matter 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0043-1648(03)00297-7

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rotating balanced arm, can be lowered onto a at diamond sample performing reciprocating motion at a chosen velocity. The system supporting the arm was designed in such a way as to minimise the force exerted on it in the direction of rotation, thus allowing the effect of very small loads, down to approximately 0.005 N, to be investigated. The frictional force is computed by measuring the deection of the arm during sliding. Readings are taken at regular 10 m intervals along the length of the track in each traversal and are then averaged by the computer, discarding data corresponding to the rst and to the last 25% of the traversal, in order to obtain a corresponding mean value of the friction coefcient for the cycle. The diamond stylus used in these experiments had a hemispherical tip with a radius of 80 m for the experiments on natural diamond, and with a radius of 25 m for experiments on CVD diamond. In these experiments friction was measured under loads of 0.5, 1 and 2 N. Assuming elastic contact (Hertz theory), these conditions produced maximal contact pressures of approximately 11, 14 and 18 GPa, respectively, for natural diamond; and of 24, 30 and 38 GPa for CVD diamond. The tangent plane to the sphere at the point of contact was a {1 0 0} plane and the direction of sliding of the stylus was chosen to be a 1 1 0 direction. Diamond wear is highly anisotropic (the wear rates can vary by two orders of magnitude depending on the plane and direction of sliding) and on the {1 0 0} plane the 1 1 0 direction is the most resistant to wear. By orienting the stylus in this direction it was thus ensured that wear of the stylus during each experiment was negligible in comparison to that of the sample. This was conrmed by regularly examining the stylus under a microscope. As soon as wear became detectable, the stylus was replaced in order to avoid signicant changes in the contact pressure from the values predicted above. The natural diamond at sample was a Type Ia diamond, polished on a {1 0 0} surface. Traversals were performed along a 1 0 0 direction. The CVD diamond tested was a polycrystalline diamond lm, approximately 20 m thick, deposited on a sintered silicon nitride substrate using the hot lament CVD technique [5]. The predominant orientation of the grains was parallel to the {1 0 0} plane. After deposition, the lm was rst rough polished on a bonded diamond wheel and secondly on a cast iron scaife charged with diamond powder, thus giving a nal local surface roughness of approximately 10 nm peak to trough, measured using an Alpha step prolometer. For the experiments on the effect of the pH value of water on the friction coefcient, the solutions were prepared using pH buffering tablets. In order to check that the impurities introduced by these did not affect the results, some of the experiments were repeated using pure solutions specially prepared in the laboratory. For the liquid with pH = 2, deionised H2 O was mixed with HCl at a concentration of 102 M, and for the liquid with pH = 13 deionised H2 O was mixed with NaOH at a concentration of 101 M. These liquids gave results consistent with those obtained by using the

Fig. 1. Chemical diagrams of the ketones and aldehydes used: (a) pentanone, (b) butanone, (c) benzaldehyde and (d) butylaldehyde.

buffering tablets, and therefore all results will be presented here. Experiments were also carried out to check the effect of the Na+ and Cl ions, by using pure deionised water mixed with NaCl at a concentration of 101 M. These ions were found to have no measurable effect on the coefcient of friction. The inuence of oxygen containing liquids (ketones and aldehydes) has also been studied. It is of interest to compare the effect of these liquids to that of mineral oils, which, as has been mentioned above, do not have a lubricating effect on diamond. Ketones and aldehydes posses a higher steric hindrance than water, but, in contrast to mineral oils, contain the oxygen atom which may bond to the diamond surface and thus reduce adhesion. The liquids tested were: pentanone (molar mass = 86.13 g/mol, coefcient of viscosity = 1 103 Pa s), butanone (molar mass = 72.04 g/mol, coefcient of viscosity = 0.38 103 Pa s), benzaldehyde (molar mass = 106.12 g/mol, coefcient of viscosity = 1 103 Pa s and butylaldehyde (molar mass = 72.04 g/mol, coefcient of viscosity = 0.48 103 Pa s). These liquids were also chosen to investigate further the effect of geometric factors on the adsorption of molecules on the diamond surface. Assuming that these molecules adsorb on the diamond surface with the oxygen atom located towards it, the effect of steric hindrance on adsorption can be ranked in the following decreasing order: pentanone, butanone, benzaldehyde, butylaldehyde (Fig. 1). In order to eliminate the possibility that these liquids contained a signicant amount of water molecules which could have been responsible for any observed changes in the friction coefcient, dry solvents were prepared using molecular sieves. The experiment was conducted in an enclosed environment, by having a plastic box surrounding the friction apparatus, to reduce water vapour reaching the interface.

3. Results The effect of the environment was studied by beginning experiments in air and then introducing a given liquid at the interface of contact using a syringe. The liquid was subsequently blown off using a nitrogen ow (since nitrogen is known not to adsorb on the surface) and a second set of traversals in air was performed, before varying again the environment by introducing a different liquid. This method is illustrated in Fig. 2. By using it, and by comparing the values

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Fig. 2. Friction coefcient for natural diamond sliding upon CVD diamond (sliding velocity = 0.2 mm/s, load = 1 N).

Fig. 4. Friction coefcient for natural diamond sliding upon CVD diamond as a function of pH value (load = 0.5 N, sliding velocity = 0.05 mm/s).

of the friction coefcient at different stages of the experiment, one can ensure that the changes measured when varying the environment are real and not due to drifts or changes with the number of traversals. In order for this method to be applicable, all measurements had to be taken after the friction coefcient in air had stabilised and the initial transition period was over. In a typical experiment, the friction coefcient was initially up to twice as high as its steady-state value, and then decreased fairly smoothly before levelling off. By performing measurements only in the steady-state region it was thus possible to focus on the effect of the environment. The results show that the friction coefcient of CVD diamond is reduced by the presence of water at the interface of contact, and that it is sensitive to the pH value of the water. Results on natural diamond showed a similar trend. The effect of the load and sliding velocity was next studied and high reductions of the coefcient of friction were measured at low load (0.5 N) and low sliding velocities (0.05 mm/s). The results for CVD diamond are shown in Fig. 3. The effect of the environment was investigated further in the low friction coefcient regime for both natural

diamond and for CVD diamond, and Figs. 4 and 5 exhibit the variation of the friction coefcient with pH value for the two samples, showing that similar trends take place. A similar set of experiments was performed using the same method for oxygen containing liquids (ketones and aldehydes), and the results are summarised in Fig. 6. Results on the analysis of the wear debris using EELS performed in a STEM are shown in Fig. 7. These results were obtained when sliding occurred at high velocity between a diamond at sample and diamond powder charging a cast iron wheel, but are consistent with those obtained on the analysis of the debris produced using the friction apparatus employed in these experiments [6]. The pre-peak observed in the carbon K-edge at approximately 285 eV corresponds to the antibonding orbital, and is thus a clear indication that a transformation of diamond to sp2 hybridised carbon has occurred on the surface during sliding. Furthermore, semi-quantitative analysis of the low loss spectra based on free electron theory, producing an approximate estimate of the electron density from the plasmon frequency, reveal that

Fig. 3. Friction coefcient for natural diamond sliding upon CVD diamond in deionised water as a function of load (sliding velocity = 0.05 mm/s).

Fig. 5. Friction coefcient for natural diamond sliding upon natural diamond as a function of pH value (load = 0.5 N, sliding velocity = 0.05 mm/s).

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Fig. 6. Friction coefcient for natural diamond sliding upon natural diamond with ketones and aldehydes introduced at the contact interface (load = 0.5 N, sliding velocity = 0.05 mm/s).

Fig. 7. EELS spectrum for a typical piece of debris obtained by rapid sliding of a at diamond surface upon diamond particles.

the worn material has a density matching quite closely that of graphite.

4. Discussion The natural diamond and the CVD diamond sample tested in these experiments exhibit similar trends, and both water and oxygen containing liquids have been found to affect signicantly the friction coefcient. Furthermore, the trend followed by the friction coefcient at different loads and sliding velocities is similar in the two cases, with friction decreasing with decreasing load and velocity and reaching extremely low values under a load of 0.5 N and a velocity of 0.05 mm/s. The extent of the reduction in the friction coefcient caused by the oxygen containing liquids was not that ex-

pected from consideration of steric hindrance. Benzaldehyde was more effective than butanone, as expected from arguments based on spatial considerations, but pentanone was the most effective and also the largest molecule, while for butylaldehyde the friction coefcient was the highest of the four, despite its low steric hindrance. A possible reason for a lack of straightforward correlation between steric hindrance and reduction in friction coefcient is that the argument given above takes into account only the rst molecular layer on the surface. If instead the effect of a thin lm of liquid is considered, the steric hindrance affects the coefcient in the opposite way. This is due to the fact that the lms at the interface, which are assumed to be only a few molecular layers thick, are expected to have solid-like properties, with an effective viscosity which can be up to 106 times higher than the bulk values given in Section 2 [7]. The effect of the size of the molecules becomes then signicant as smaller molecules can pack more easily in solid-like ordered layers, and if sliding occurs through a stick-slip mechanism, in which the two surfaces remain pinned to each other until a large enough shear stress is produced to melt the lm and cause slipping to occur, then more closely packed lms will require a larger force to shear them and hence produce greater friction. In this case molecules of lower steric hindrance would produce higher friction. The friction coefcient has been found to be highly dependent on the sliding velocity and the possibility of the presence of viscous resistance thus deserves consideration. A lubricant lm, consisting of a hydrodynamic layer of liquid, may be thought to arise during sliding. The lm would form preferentially at higher sliding velocities and under lower loads, and its thickness would decrease with increasing Hertzian pressures. This would, however, suggest that the effect of the lm should be more signicant at higher sliding velocities, so that the difference in the friction coefcient in various liquids should be more marked as the speed increases. For the case of ketones and aldehydes the reverse is found instead to be the case (Fig. 6). Moreover, the extent to which friction is reduced by oxygen containing liquids cannot be related to their coefcient of viscosity, with pentanone and benzaldehyde having the highest coefcient but producing the greatest reductions in friction. Also, water has been found, under all conditions tested, to have the best lubricating effect, though its viscosity (0.9 103 Pa s) is lower than that of pentanone and benzaldehyde, but higher than that of butanone and butylaldehyde. It therefore seems that, in view of the very high Hertzian stresses arising during contact, viscous resistance can be considered negligible. The variation of friction coefcient with sliding velocity is instead consistent with the hypothesis that adhesion is reduced following adsorption of the molecules introduced at the contact interface. The effect of the sliding velocity can then be interpreted in terms of the recombination time of the molecules on the surface. If we assume that at each traversal molecules are desorbed due to the action of the stylus, simple calculations based on diffusion theory [8] indicate that the

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time taken for them to re-adsorb on the surface is between 10 s (the period for a cycle at the highest sliding velocity tested) and 40 s (the period for a cycle at the lower velocity tested), in agreement with the present ndings. In addition to the reduction of adhesion caused by the introduction of molecules at the interface of contact, we propose that an additional mechanism of lubrication takes place due to the production during sliding of sp2 hybridised carbon, as indicated by EELS analysis. The graphitic debris may then be expected to act as a lubricant, thus producing ultra-low friction coefcients. This is also in agreement with the above mentioned observation of a transition period at the beginning of the experiments, during which the friction coefcient is up to twice as high as its steady-state value. The production of sp2 hybridised carbon during wear of the friction track would thus be responsible for lowering the friction coefcient from its initial value. Our results are consistent with reports of very low friction coefcients (of the order of 103 ) for molybdenum disulphide [9]. These results were interpreted in terms of the sliding of the basal planes of the crystal structure along the sliding direction. The essential difference between MoS2 and graphite is that for the former friction is low under UHV conditions and high in air, whereas the friction of graphite, in agreement with the present results, is high in vacuum and low when its basal planes are intercalated by donors or acceptors. The lubricating effect of water, which is a weak donor (a Lewis base), can thus be explained in terms of its intercalating effect [10]. The transformation of diamond to sp2 hybridised carbon during the sliding of diamond upon diamond at high pressure is consistent with theoretical work based on pseudopotential total energy calculations [11]. Further work is presently being performed on the development of a model to explain the transformation of diamond to graphitic carbon, and its dependence on crystal direction and orientation, in terms of the strains induced at the interface during sliding. Initial predictions of this model are consistent with results on the variation of the friction coefcient with applied load [12]. 5. Conclusions We have shown that the coefcient of friction for natural diamond sliding upon natural and CVD diamond can be greatly decreased from its value in air by introducing at the interface of contact water and other oxygen containing

liquids. Under particular conditions of load and sliding velocity the measured friction coefcient is as low as 103 . We have explained these results in terms of the reduction of adhesion following adsorption on the surface of the molecules contained in the liquids. We furthermore propose that the sp2 hybridised material produced during sliding acts as a lubricant, due to the weak resistance to sliding of the graphitic basal planes.

Acknowledgements We thank De Beers Industrial Diamonds (UK) Ltd. for nancial support. Professor D. Tabor and Dr. F.M. van Bouwelen are thanked for many valuable discussions.

References
[1] D. Tabor, Adhesion and friction, in: J.E. Field (Ed.), Properties of Diamond, Academic Press, London, 1979, pp. 325350. [2] M. Casey, J. Wilks, The friction of diamond sliding on polished cube faces of diamond, J. Phys. D 6 (1973) 17721778. [3] S.E. Grillo, J.E. Field, The friction of CVD diamond at high Hertzian stresses: the effect of load, environment and sliding velocity, J. Phys. D 33 (2000) 595602. [4] S.E. Grillo, J.E. Field, Very low friction for natural diamond in water of different pH values, Eur. Phys. J. B 13 (2000) 405408. [5] T. Srivinyunon, A. Joseph, Y. Tzeng, Surface morphologies and photoluminescence of diamond lms deposited in a hot lament CVD reactor, in: Proceedings of the Second International Conference on the New Diamond Science and Technology, Materials Research Society, Pittsburgh, Pennsylvania, 1991, pp. 581586. [6] F.M. van Bouwelen, Mechanically induced degradation of diamond, Ph.D. Thesis, University of Cambridge, 1996. [7] J.N. Israelachvili, P. McGuiggan, M. Gee, A. Homola, M. Robbins, P. Thompson, Liquid dynamics in molecularly thin lms, J. Phys. 2 (1990) SA89SA98. [8] S.E. Grillo, The friction and polishing of diamond, Ph.D. Thesis, University of Cambridge, 1995. [9] J.M. Martin, C. Donnet, T. Le Mogne, T. Epicier, Superlubricity of molybdenum disulphide, Phys. Rev. B 48 (1993) 1058310586. [10] M.N. Gardos, The problem-solving role of basic science in solid lubrication, in: I.M. Hutchings (Ed.), New Directions in Tribology, Mechanical Engineering Publications Ltd., Bury St., Edmunds, 1997, pp. 229250. [11] M.R. Jarvis, R. Perez, F.M. van Bouwelen, M.C. Payne, Microscopic mechanism for mechanical polishing of diamond (1 1 0) surfaces, Phys. Rev. Lett. 80 (1998) 34283431. [12] S.E. Grillo, J.E. Field, F.M. van Bouwelen, Diamond polishing: the dependency of friction and wear on load and crystal orientation, J. Phys. D 33 (2000) 985990.