Carbon 40 (2002) 125135

Letters to the editor

Protective coatings from ultra ne diamond

T. Patrusheva*, V. Letunovsky, L. Gorjacheva, A. Gorschkov, V. Sergienko, E. Jakovleva
Institute of Chemistry and Chemical Technology of SB RAN, Technical University, Krasnoyarsk, Russia Received 6 January 2000; accepted 16 August 2001 Keywords: A. Diamond-like carbon; B. Coating; C. X-ray diffraction; D. Frictional properties; Mechanical properties

Diamond wear coatings have been studied and used throughout the world for the past 15 years [1,2]. We proposed a new material for carbon coatings UFD from detonation synthesis of explosive substances. Nanomaterials, which contain grains of a few thousand atoms, have unique physicochemical properties. The structure of the ultra ne diamond (UFD) particles consists mainly of surface atoms with open valences, which contribute to high chemical and adsorption activity. From this it was considered possible to obtain UFD-coatings through adsorption from a UFD suspension [3]. The calculations based on optical investigations showed that the dimensions of UFD-particles in organic suspensions are in the limits of 26 nm. Ultra ne diamond gives stable suspensions in organic solvents with a solid phase concentration of 0.010.03 g / l, with the suspensions remaining stable and transparent to a concentration of 0.61.0 g / l when the dispersion medium is driven off. As this takes place, the suspension viscosity and thickness of the wetting lms increase. The wetting lms were obtained by immersion in liquids and removal of the excess liquid by shaking off. The evaporation of the dispersion medium was performed at 573 K in conformity with the thermal stability of UFD. The high reaction ability of UFD nanoparticles on the surface leads to chemisorption and dense packing of layers. Wetting and evaporation were repeated as many times as needed to prepare a coating of the desired thickness. The use of diluted suspensions gives transparent layers of nanoparticles. Viscous suspensions produce white porous coatings consisting of particle aggregates. In model experiments, we used platelets of polycrystalline molybdenum (603531 mm) as a substrate, which

were coated with 150 layers of the UFD suspension. The thickness of the coating varied from 0.03 to 1.5 mm. It was earlier established [4] that there are structureforming effects in wetting lms and also an inuence of substrate alignment on the properties of the covered materials. The subsequent study of these phenomena by internal friction and performance tests allows one to obtain additional information about mechanisms of lmsubstrate interaction and interface processes under different parameters of external load, and to optimize the deposition technology and establish an area of the most effective application. For study of the surface properties of molybdenum and molybdenum with thin coatings of UFD, the method of internal friction measurement was used. There are a few methods for the measurement of internal friction on the winding vibration of the pattern [57]. The oldest and more convenient method of internal friction measurement is a method of twine pendulum [5]. The measure of internal friction is by a coefcient of absorption c and mechanical quality Q 21

c 5 DW/W,
Q 21 5 c / 2p where W is the energy of vibration. For the samples obtained, the internal friction deviation 21 (Q ), the dynamic modulus of rigidity (G9), and the tangent of mechanical loss angle (G) were measured by the method of twisting pendulum [8] in the temperature range of 293873 K. After experiments the samples were studied by X-ray diffraction. Similarly, the coatings were deposited on the working surface of hard-metal cutter plates (92% tungsten carbide, 8% cobalt) for the tool-life tests [9]. Figs. 1 and 2 show typical energy dissipation spectra of

*Corresponding author. E-mail address: pat@rtf.kgtu.runnet.ru (T. Patrusheva).

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Fig. 1. Internal-frictiontemperature curves for the samples prepared from UFD-suspensions. (A) 1, Mo-substrate; 2, Mo with 10 layers UFD (30 nm); 3, Mo with 24 layers UFD (70 nm); 4, Mo with 50 layers UFD (150 nm). (B) 1, Mo-substrate; 2, Mo with one layer of UFD concentrating suspension (30 nm); 3, Mo with 15 layers UFD concentrating suspension (450 nm).

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Fig. 2. The phone internal-frictiontemperature curves for the samples prepared from UFD-suspensions. (A) 1, Mo-substrate; 2, Mo with 10 layers of UFD (30 nm); 3, Mo with 50 layers of UFD (150 nm). (B) 1, Mo-substrate; 2, Mo with one layer of UFD concentrating suspension (50 nm); 3, Mo with 15 layers UFD concentrating suspension (450 nm).

diamond-coated molybdenum samples. It was determined that increasing the temperature from 293 to 553 K leads to some growth of the internal friction background. In the range 553 to 745 K the distinction between coated and

non-coated samples proved to be insignicant. In the temperature range of 745 to 873 K the background grows exponentially because the coating signicantly changes the activation energy of the interface processes in this tem-

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perature region. The activation energy (DH ) of high-temperature friction (Q 21 and Q 21 ) was calculated from the 0 formula: DH 5 2.3 RT log (Q 21 /Q 21 ). 0 The results obtained show that DH values increase signicantly with increased coating thickness (Fig. 3). The increased nanoparticle concentration does not break this trend, but leads to some increase of DH in the investigated range of coating thickness. The energy dissipation spectrum of polycrystalline molybdenum is very complex and is characterized by the presence of a number of internal friction peaks in the temperature ranges of 563573, 593713, and 773873 K. On the basis of the peak analysis, one can conclude that the changes in the structural environment in molybdenum in these temperature regions are caused by a number of simultaneous relaxation-type processes with activation energy DH1 5 0.50.6 eV, DH2 5 1.51.8 eV, and DH3 5 2.63.7 eV. Similar internal-friction peaks were found earlier [10,11] in single crystal molybdenum doped with oxygen, nitrogen, and carbon and in polycrystalline molybdenum exposed to neutron beams of 10 14 10 20 n / cm 2 . The authors connected the peak nature with the migration of single vacancies and carbon atoms to dislocations, redistribution of the doped atoms in the power eld of the dislocation, the reduction of the total energy of the system, and an increased degree of dislocation locking. Coatings with nanodiamond particles suppresses the processes occurring at temperatures of 573717 K and induces signicant growth of the peaks at the temperature of 773873 K. Increasing the coating thickness and the

concentration of nanodiamond particles in the suspensions causes an increase of activation energy and changes in the structural environment of surface layers. The temperature dependence of the dynamic modulus of rigidity and the tangent of mechanical loss angle correlate well with the temperature spectra of internal friction. The results of X-ray diffraction measurements of the UFD-coating on molybdenum after examination for internal friction (Fig. 4) shows that a carbide phase is formed in the sample surface. Such carbide formation usually requires high temperatures. The low temperature surface change is one of the important properties of diamond nanoparticles. Due to the presence of carbides in the surface layers there is a possible increase in wear resistance. The results of accelerated tool-life tests of hard metal tool platelets (92% tungsten carbide, 8% cobalt) with UFD-coatings are shown in Fig. 5. It was established that the tools with a higher concentration of diamond nanoparticles on the working surfaces have the lowest tool-wear rate. The increased efciency of the tools might be explained by interaction of coating particles, which have high surface energy, with the tool material. The critical pressure of dislocation displacement and the loss to the surface increases. One of the reasons for this increased tool efciency is a possible decrease in the coefcient of external friction of high temperatures on the contact of the tool with the cutting surface of the work piece. We conclude that such coatings from ultra ne diamond

Fig. 3. Activation energy of internal friction backgroundcoating thickness curves. 1, Mo with coat of 50 nm UFD; 2, Mo with coat of 450 nm UFD.

Fig. 4. X-ray diffraction patterns. a, Mo-substrate; b, Mo with UFD-coatings after examination using internal friction.

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serviceability of products and metal cutting tools with coatings at the manufacturing stage without labor-intensive serviceability tests.

Acknowledgements A grant from the Krasnoyarsk Region Fund of Science supported this research.

References
[1] Collins CB. The production and use of amorphous diamonds. Am Ceram Soc Bull 1992;71(10):153542. [2] Wilks J, Wilks E. In: Properties and application of diamond, Oxford: Butterworth-Heinemann, 1991, p. 525. [3] Adrianova TN, Zakharov AA. Colloid J 1999;61(2):2937. [4] Deriyagin BV. The wetting lms, Moskow: Nauka, 1978. [5] Ke TS, Ross M. Rev Sci Instrum 1949;20:795. [6] Ke TS, Tsien CT. Scientia Sinica 1956;4:635. [7] Zener C. Elasticity and inelasticity of metals, 1948. [8] Krishtal MA, Golovin CA. The interior friction and structure of metals, Moscow: Metallurgy, 1976. [9] Bashkov VN, Kancev PG. The testing of cutter on the resistance, Moscow: Mashinostroenie, 1985. [10] Vasilev AA, Grusin PL. The mechanisms of interior friction in metals, Moscow: Nauka, 1970. [11] Perevezencev VN, Platonov PA. In: The mechanisms of interior friction in semiconductors and metals, Moscow: Nauka, 1972, pp. 1048.

Fig. 5. Tool-wear ratecutting speed curves. 1, Mo-substrate; 2, Mo with coat of 50 nm UFD; 3, Mo with coat of 450 nm UFD.

on working surfaces improves their serviceability by 1.52 times because of the barriers formed in the thin adjacent surface layers of the tool material, which prevents dislocations from coming to the free surface and because of the change of relaxation process energy parameters. If the data about internal friction and the parameters of dislocation processes are known it is possible to predict the

Edge-state effects on the magneto-polarizability of nanographite layers

Stephane Pleutin*, Alexander Ovchinnikov
Max-Planck-Institut f ur Physik Komplexer Systeme, Nothnitzer Strae 38, D-01187 Dresden, Germany Received 22 May 2001; accepted 5 September 2001 Keywords: A. Activated carbon; Graphitic carbon; D. Dielectric properties; Magnetic properties

Only very recently a new type of magnetism similar to a spin glass state was found for activated carbon bers prepared at heating temperatures over 12008C [1]. These materials are supposed to be well described by a disordered network of nanographite layers with a characteris*Corresponding author. Albert-Ludwigs University Freiburg, Hermann-Herder Strae 3, 79104 Freiburg, Germany. Tel.: 149761-203-7685; fax: 149-761-203-5881. E-mail address: pleutin@physik.uni-freiburg.de (S. Pleutin).

tic length of some tens of angstroms [2]. In connection with recent theoretical work on graphite ribbons, it was suggested by Shibayama et al. that the spins observed in Ref. [1] are due to the edge states of the p electrons whose wave functions are mainly localized on the boundaries of the layers. Indeed, several theoretical studies of graphite ribbons [3,4] had predicted the existence of such states. These edge states are expected to affect novel electrical and magnetic properties such as a paramagnetic behaviour at low temperatures [4]. These theoretical predictions

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