Tribol Lett (2007) 28:223228 DOI 10.

1007/s11249-007-9254-5

ORIGINAL PAPER

Friction and Wear Properties of Electrodeposited NickelTitania Nanocomposite Coatings

X. J. Sun J. G. Li

Received: 26 October 2005 / Accepted: 24 July 2007 / Published online: 21 September 2007 Springer Science+Business Media, LLC 2007

Abstract A novel nanostructure metallic composite coatings consisting of nanocrystalline nickel matrix (average grain size: 10 nm) and dispersed titania nanoparticles (average grain size: 12 nm) have been electrodeposited on copper substrates from a modied Watts bath. Microstructure, friction, and wear properties of the coatings were investigated by means of X-ray diffraction, scanning electron microscopy, Vickers microhardness test, and ballon-disk friction test. The results showed that the content of titania nanoparticles in the nanocomposite coatings could be controlled by changing the concentration of the suspending titania nanoparticles in the electrolytes. The friction coefcient and wear rate of the nanocomposite coatings decreased with increasing the content of titania nanoparticles while sliding against 440C stainless steel at room temperature. Keywords Electrodeposition Nanocomposite Nickel Titania Friction Wear

Introduction Investigations on preparation, microstructure, and properties of particle reinforced metal matrix nanocomposite materials with grain size of both matrix and dispersed
X. J. Sun (&) J. G. Li Institute of Materials Science and Engineering, Lanzhou University, Lanzhou 730000, P.R. China e-mail: xjsun@lzb.ac.cn X. J. Sun State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P.R. China

particles less than 100 nm have been increased to meet the particular demands of low friction coefcient and high wear resistance for current advanced technological applications, such as aerospace, defence, automobile, and nuclear power industries. Recently, nanometer scale microstructure design by grain size renement and hard inert particle dispersion became powerful tools to obtain superior mechanical properties of conventional metallic materials [13]. Erb et al. reported that electrodeposited nanocrystalline nickel was about ve times harder than conventional microcrystalline nickel [4, 5]. Lu and his coworkers represented the Superplastic Extensibility of nanocrystalline copper at room temperature, which was never been found in microcrystalline copper [6]. The above works indicated that nanocrystalline metals generally have much improved mechanical properties as compared with their microcrystalline counterparts. Based on the principle of dispersion-strengthening, further improvement in mechanical performance of the nanocrystalline metals can be achieved by incorporating ceramic nanoparticles into metal matrix [7]. Generally, electrodeposition is a single step deposition process under relatively low temperature followed without heat treatment. The advantages of this established technique used to fabricate nanocrystalline metallic coatings include low cost and industrial applicability, easy operation, exibility, large size availability and high deposition rate, and almost full density [8]. Numerous nickel matrix nanocomposite coatings containing multifarious types of hard inert nanoparticles, such as TiO2, SiC, Al2O3, Si3N4, ZrO2 and diamond, etc., have been electrodeposited from different electrolytes in which the nanoparticles were suspended [917]. Friction and wear properties of electrodeposited nickeldiamond and nickel CeO2 nanocomposite coatings were examined [12, 18], and it was found that titania nanoparticles can be used as

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lubricant under liquid lubrication condition [19, 20]. However, little work has been concerned with the friction and wear properties of nanostructure metallic coatings containing titania nanoparticle up to now, In our previous work, anatase titania nanoparticles with average grain size in 12 nm have been obtained by solgel method and nanocrystalline nickel with average grain size in 10 nm have been successfully electrodeposited, and the titania nanoparticles as the dispersive phase were found to play a key role on the improvement of the mechanical and corrosion resistance performances of the nanocrystalline nickel coatings [21, 22]. In this article, the primary target of our work is the expanded exploration on the friction and wear properties of the electrodeposited nickeltitania nanocomposite coatings.

Experimental Procedure A polished pure copper sheet (15 10 1 mm) and a pure nickel sheet (40 20 5 mm) were used as cathode and anode, respectively. Before electrodeposition, the copper substrates were ultrasonically cleaned in acetone and ethanol, degreased in 2.0 M sulfuric acid, rinsed with distilled water, activated in 1:1 hydrochloric acid for about 3 min, and again rinsed with distilled water. The nickeltitania nanocomposite coatings were electrodeposited on copper substrates from a modied Watts bath in which the titania nanoparticles were suspended. The composition of the electrolyte for nanocrystalline nickel electrodeposition was 250 g/L six-hydrated nickel sulfate, 25 g/L boric acid, and 5 g/L saccharin. 100 or 200 g/L anatase titania nanoparticles with grain size of 12 nm were added in the electrolyte when preparing nickeltitania nanocomposite coatings. Before electrodeposition, the electrolyte was treated by intense ultrasonic irradiation combined with high-speed mechanical agitation for about 8 h to disperse the particles uniformly. During the electrodeposition, the electrolyte was slowly stirred to keep the particles well suspended. The pH value of the electrolyte was kept at a constant of 3.0 0.2, and the bath temperature was kept at 30 2 C. The electrodeposition was carried out by using a SMD-30 plating power supply (made in Dashun Co. Handan, China) at a direct current density of 10 A/dm2. The XRD analysis was performed on a Rigaku D/max-2400 X-ray diffractometer at room temperature. The as-deposited nanocomposite coatings were rst examined by X-ray diffraction (XRD) to determine average grain size and phase content. The average grain sizes were calculated from the diffraction data by Scherrer equation, and the phase content was estimated by the K-value method. The surface morphology was observed with a JSM-5600LV scanning electron microscope (SEM). The sliding friction

test was conducted on a reciprocating ball-on-disk tribometer. All of the counterparts are 440C stainless steel balls with 3.0 mm diameter and hardness of 58 2 HRC. The friction test conditions were listed as follows: the sliding speed was 0.1 m/min, the moving amplitude was 10 mm and the normal load was 3.0 N. The environmental humidity and temperature were 2030% RH and 1518 C, respectively. The friction coefcient was calculated by dividing the friction force with normal load. A Shimadzu M type microhardness tester calibrated with standard sample was used to determine the Vickers microhardness, and the reported value was an average of 10 tests carried out on different locations in the center section of the coating samples with a load of 100 g for 25 s. The wear rates were calculated from the worn volume which was measured by a prolometer. The uncertainties of the microhardness test and wear rate test were 0.2 GPa and 1.5 1015 m3, respectively.

Results and Discussion The X-ray diffraction patterns of the electrodeposited nanocrystalline nickel coatings containing various concentrations of titania nanoparticles are shown in Fig. 1. It is found that the relative intensity of the titania diffraction peaks compared to the nickel peaks increased with increasing content of the titania particles in the electrolyte, indicating that content of the incorporated particles increase with increasing concentration of the titania particles suspended in the electrolyte. The broader peaks of both nickel and titania in the X-ray diffraction pattern are indicative of small grains of both the matrix phase and the dispersive phase in the electrodeposited composite coatings. The average grain size of titania and nickel in the coatings were calculated from the diffraction data according to the Scherrer equation to be 12 and 10 nm, respectively. The deviation of the average grain size determination is less than 10%. The contents of titania particles in the coatings were calculated from the diffraction results through a K-value method to be 6 and 11 wt.% while the particle concentrations of the electrolytes were 100 and 200 g/L, respectively. To describe the friction characteristic of the coatings sliding against 440C steel, two types of friction coefcients were introduced. One is directly proportional to the applied load and the other is independent of the contact area. In the case of solidsolid sliding friction condition, the two friction coefcients are conventionally dened, respectively, as ls = Fs/P and lk = Fk/P, where Fs is the force just sufcient to prevent the relative motion between two surfaces, and Fk is the force needed to maintain relative motion between two sliding surfaces. The denition of the

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4000

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Titania (anatase)
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Nickel 1 0 g/L 2 100 g/L 3 200 g/L

Intensity

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1000 500 0 20 40 60 80 100

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Fig. 1 XRD patterns of nickeltitania nanocomposite coatings electrodeposited from the electrolytes with various concentration of titania nanoparticles

Nc

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0.30 0 0.25 0.20 6% 11%

two friction coefcients can be traced back to Amontons law of friction, and easily be distinguished: ls represents the friction opposing the beginning of relative motion, and lk represents the friction opposing the continuance of relative motion once the motion has started [23]. As shown in Fig. 2a, b, the ls and lk are dependent on the content of the nanoparticle in the coatings. It is clearly seen that both ls and lk decreased with increasing the content of titania nanoparticle. This result reveals that the friction coefcient between nanocrystalline nickel and 440C steel can be much lowered by incorporating titania nanoparticles. The similar results were found by several authors in kinds of electrodeposited nickel-based metallic composite coating systems, the reported particles including SiC, CeO2, diamond, Al2O3, WC, Si3N4, etc. [12, 18, 2428]. These results indicate that the microstructure design through the ne particles embedded into electrodeposited metal matrix is a simple and effective way to obtain metallic lubricating coatings. Figure 3 shows the dependence of wear rate and Vickers microhardness on the content of titania nanoparticles in the composite coatings. One can see that the microhardness of the nanocomposite coatings increase with increasing the content of titania nanoparticles. This result means that mechanical properties of the nanocrystalline metal coatings can be tailored by incorporating nano-sized hard inert particles. This can be attributed to particle-strengthening effect by dispersing titania nanoparticles which inhabit the grain boundaries of the nanocrystalline nickel coatings, and acts as obstacles to the grain movement and grain boundaries migration under an cyclic normal load during sliding friction test [7]. It is also observed in Fig. 3, the titania nickel nanocomposite coatings exhibit much lower wear rates than the nanocrystalline nickel, indicate that the wear resistance of nanocrystalline nickel coatings is obviously improved by incorporating titania nanoparticles.

0.15 0.10 0.05 0.00 0

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40

60

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Fig. 2 Friction coefcients of nickeltitania nanocomposite coatings containing varies contents of titania nanoparticles with the cycle number Nc. (a) static friction coefcient, (b) kinetic friction coefcient
50 8.0

Wear rate Vickers microhardness

Wear rate (10-15 m3)

40

30

20 6.0 10 5.0 12

10

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Fig. 3 Variation of microhardness and wear rate of nickeltitania nanocomposite coatings with the content of titania nanoparticles in the coatings

Figure 4 shows the SEM photographs of as-deposited and worn surfaces of the pure nanocrystalline nickel and the nanocrystalline nickel-based composite coatings containing 11 wt.% titania nanoparticles. Comparing the micrographs, an obvious difference can be found between the coatings with and without titania nanoparticles.

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Figure 4a, b are the surface morphology of the asdeposited coatings, showing the evolvement from particle free to 11 wt.% titania nanoparticles. The nickel nanocrystalline coatings exhibit a more regular surface (Fig. 4a), while the coatings incorporated with titania nanoparticles show up nodule-like surface (Fig. 4b), and the grain size of nickel in the nanocomposite coatings is smaller than that in the nanocrystalline nickel coatings, conrming that titania nanoparticles are uniformly distributed in the nanocrystalline nickel matrix. According to Orowan dispersion strengthening theory, besides intrinsic properties of the nanoparticles, the size and the distribution of the particle are the two key factors to result in the superior mechanical behaviors compared to pure metallic matrix. Figure 4c, d show the worn surface micrographs of the pure nanocrystalline nickel coatings and the nickeltitania nanocomposite coatings containing 11 wt.% titania nanoparticles under dry sliding against 440C stainless steel at room temperature. The microcracks and the tearing debris are clearly visible on the worn track of the pure nanocrystalline nickel coatings, but almost no visible cracks on the worn surface of the nanocomposite coatings containing 11 wt.% titania nanoparticles. The worn surface of nanocomposite coatings appears to be smoother than that of the pure nanocrystalline nickel coatings. Our experimental results reveal that the incorporation of titania nanoparticles in the nanocrystalline nickel can markedly reduce the wear rate of this kind of coatings, and the wear resistance can
Fig. 4 SEM photographs of nanocrystalline nickel and nickeltitania nanocomposite coatings at 5,000 magnication. (a) as-electrodeposited nanocrystalline nickel, (b) aselectrodeposited nickeltitania nanocomposite coatings containing 11 wt.% titania nanoparticles, (c) worn surface of nanocrystalline nickel, (d) Worn surface of nanocomposite coatings containing 11 wt.% titania nanoparticles

be further enhanced by increasing the content of titania nanoparticles in the nanocomposite coatings. The improvement of the friction and wear properties by the titania nanoparticles can be attributed to both dispersionstrengthening and particle-strengthening effects, which agrees with other similar works [18, 29]. The titania nanoparticles inhabit the grain boundaries and the triple junctions to obstruct the grains of the nanocrystalline nickel from moving and recrystallization, which consequently enhances the mechanical behaviors of the nanocomposite coatings and further prevents the micro crack growing along the grain boundaries. During the friction process, the well-distributed titania nanoparticles, which are located near the coatings surface, reduced the real area of metalmetal contact, which consequently reduces the adhesion between the metalmetal contacts instead metalceramicmetal contact type appears. Furthermore, nano-sized titania particles may act as a tool to reduce the friction and enhance the wear resistance of the electrodeposited nanocrystalline nickel coatings. According to the principle of particle-strengthening, we have designed a novel nanostructure by the type of particulate metal matrix composite coatings. The matrix phase of the coating is electrodeposited nanocrystalline nickel and dispersed phase is nano-sized nanocrystalline titania particles prepared by solgel method. A series of this kind of coatings varies with particle contents have been electrodeposited from a modied Watts bath by controlling the particle concentration. Comparing with nanocrystalline

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227 3. Zong, Y., Zuo, L.: Materials design of microstructure in grain boundary and second phase particles. J. Mater. Sci. Technal. 19(2), 97101 (2003) 4. Erb, U.: Electrodeposited nanocrystals: synthesis, properties and industrial applications. Nanostruct. Mater. 6, 533538 (1995) 5. Erb U., Palumbo G., Aust K.T.: Electrodeposited nanostructure materials. In: Chow, G.M., Ovidko, I.A., Tsakalalos, T. (eds.) Nanostructured Films and Coatings, p. 11. Kluwer Academic Publishers, Dordrecht (2000) 6. Lu, L., Sui, M.L., Lu, K.: Superplastic extensibility of nanocrystalline copper at room temperature. Science 287(5457), 14631466 (2000) 7. Zhang, Z., Chen, D.L.: Consideration of Orowan strengthening effect in particulate-reinforced metal matrix nanocomposites: a model for predicting their yield strength. Scripta Materialia 54, 13211326 (2006) 8. Tjong, S.C., Chen, H.: Nanocrystalline materials and coatings. Mater. Sci. Eng. R45, 188 (2004) 9. Low, C.T.J., Wills, R.G.A., Walsh, F.C.: Electrodeposition of composite coatings containing nanoparticles in a metal deposit. Surf. Coat. Technol. 201, 371383 (2006) 10. Zimmerman, A.F., Palumbo, G., Aust, K.T., Erb, U.: Mechanical properties of nickel silicon carbide nanocomposites. Mater. Sci. Eng. A328, 137146 (2002) 11. Moller, A., Hahn, H.: Synthesis and characterization of nanocrystalline Ni/ZrO2 composite coatings. Nanostruct. Mater. 12, 259262 (1999) 12. Liping, W., Yan, G., Qunji, X., Huiwen, L., Tao, X.: Effects of nano-diamond particles on the structure and tribological property of Ni-matrix nanocomposite coatings. Mater. Sci. Eng. A390, 313318 (2005) 13. Steinbach, J., Ferkel, H.: Nanostructured NiAl2O3 lms prepared by DC and pulsed DC electroplating. Scripta Materialia 44, 18131819 (2001) 14. Zhou, Y., Erb, U., Aust, K.T., Palumbo, G.: The effects of triple junctions and grain boundaries on hardness and Youngs modulus in nanostructured NiP. Scripta Materialia 48, 825830 (2003) 15. Shao, I., Vereecken, P.M., Chien, C.L., Searson, P.C., Cammarata, R.C.: Synthesis and characterization of particle-reinforced Ni/Al2O3 nanocomposites. Mater. Res. 17, 14121418 (2002) 16. Benea, L., Bonora, P.L., Borello, A., Martelli, S.: Wear corrosion properties of nano-structured SiCnickel composite coatings obtained by electroplating. Wear 249, 9951003 (2002) 17. Karimpoor, A.A., Erb, U., Aust, K.T., Palumbo, G.: High strength nanocrystalline cobalt with high tensile ductility. Scripta Materialia 49, 651656 (2003) 18. Xue, Y., Jia, X., Zhou, Y., Ma, W., Li, J.: Tribological performance of NiCeO2 composite coatings by electrodeposition. Surf. Coat. Technol. 200, 56775681 (2006) 19. Ye, W., Cheng, T., Ye, Q., Guo, X., Zhang, Z., Dang, H.: Preparation and tribological properties of tetrauorobenzoic acidmodied TiO2 nanoparticles as lubricant additives. Mater. Sci. Eng. A. 359, 8285 (2003) 20. Xue Q., Liu W., Zhang Z.: Friction and wear properties of a surface-modied TiO2 nanoparticle as an additive in liquid parafne. Wear. 213(12), 2932 (1997) 21. Li, J., Jiang, J., He, H., Sun, Y.: Synthesis, microstructure and mechanical properties of TiO2/Ni nanocomposite coatings. J. Mater. Sci. Lett. 21, 939941 (2002) 22. Li, J., Sun, Y., Sun, X., Qiao, J.: Mechanical and corrosion resistance performance of electrodeposited titanianickel nanocmoposite coatings. Surf. Coat. Technol. 192, 331335 (2005) 23. Blau, J.P.: The signicance and use of the friction coefcient. Tribol. Int. 34, 585591 (2001)

nickel electrodeposits, much higher hardness, lower friction coefcient and higher wear resistance have been reached. Namely, electrodeposition of nanostructure metalceramic composite coatings breaks a new path for properties control through microstructure design of nanostructure metallic materials. Thus, the particular demands for advanced industry applications, such as enhanced mechanical properties, lubrication and wear resistance, etc., could be reached by adjusting electrodeposition parameters of the established industrial technology.

Conclusions Friction and wear properties of the electrodeposited nickeltitania nanocomposite coatings were investigated. The coatings consist of nanocrystalline nickel matrix and titania nanoparticles. The average grain size of nickel and titania were determined by X-ray diffraction method to be 10 and 12 nm, respectively. The phase content of the titania nanoparticles in the composite coatings increased from 6 wt.% to 11 wt.% with increasing the concentration of the nanoparticles suspended in the electrolytes from 100 g/L to 200 g/L. The surface morphology, Vickers microhardness, friction coefcient, and wear rate closely depended on the content of the titania nanoparticle. Compared with the nanocrystalline nickel coatings electrodeposited under the same conditions, titanianickel nanocomposite coatings exhibited smoother surfaces, higher hardness, and lower friction and higher wear resistances.
Acknowledgments The authors sincerely thank Prof. J. Z. Zhao and Mr. D. K. Song for their kind help in scanning electromicroscope observation and X-ray diffraction analysis. Thanks to Prof. X. G. Hu, Prof. W. M. Liu, Dr. L. P. Wang, Dr. H. Yang and Dr. Z. B. Lu for their helpful discussions. Thank Prof. W. T. Tysoe, Mrs. Linda Singer and two reviewers for their kind attention and hard works on the revision and publication of this article. The nancial support by the National Science Foundation of China (Grant Nos. 50421502, 50371035, and 50272068) and the National Basic Research Program of China (Grant No. 2007CB607600), the Specialized Research Fund for the Doctoral Program of Higher Education of China and the Opening Fund of State Key Laboratory of Solid Lubrication, Chinese Academy of Sciences (Grant No. 0401) are also acknowledged.

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