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Applied Surface Science 242 (2005) 326–332

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Microstructure and tribological properties of
electrodeposited Ni–Co alloy deposits
Liping Wanga,b, Yan Gaoa,b, Qunji Xuea, Huiwen Liua, Tao Xua,*
a
State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics,
Chinese Academy of Sciences, Lanzhou 730000, PR China
b
Graduate School of the Chinese Academy of Sciences, Beijng 100039, PR China
Received in revised form 24 August 2004; accepted 30 August 2004
Available online 20 October 2004

Abstract

Ni–Co alloys with different compositions and microstructures were produced by electrodeposition. The effects of Co content
on the composition, surface morphology, phase structure, hardness and tribological properties of Ni–Co alloys were investigated
systemically. Results showed that the morphology and grain size of alloys are mainly influenced by the Co content and the phase
structure of Ni–Co alloys gradually changed from fcc into hcp structure with the increase of Co content. The hardness of Ni–Co
alloys with a maximum around 49 wt.% Co followed the Hall–Petch effect. It was found that the improvement of wear resistance
of Ni-rich alloys with hardness increase fits Archard’s law. In addition, the Co-rich alloys exhibited much lower friction
coefficient and higher wear resistance when compared with Ni-rich alloys. It has been concluded that hcp crystal structure in Co-
rich alloys contributed to the remarkable friction–reduction effect and better anti-wear performance under the dry sliding wear
conditions.
# 2004 Elsevier B.V. All rights reserved.

Keywords: Ni–Co alloy; Electrodeposition; Structure; Tribological properties

1. Introduction activity [1–5]. Additionally, the use of Ni–Co alloys
has been extended to the production of three-
Ni–Co alloys have been investigated as important dimensional, complex-shaped finished components
engineering materials for several decades because of by the electroforming technique [6,7]. The investiga-
their unique properties, such as high-strength, good tions on the electrodeposited Ni–Co alloys have
wear resistance, heat-conductive, electrocatalytic shown that their microstructure and properties were
found to depend strongly on the Co content, which can
* Corresponding author. Tel.: +86 931 496 8169;
be controlled by the experimental parameters, such as
fax: +86 931 496 8169. bath composition, temperature, pH value, and current
E-mail address: lpwang@lsl.ac.cn (T. Xu). density, etc. [1,3,8]. The effects of plating parameters

0169-4332/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2004.08.033

Results and discussion Watts-type electrolyte. pure Ni was also produced for The dependence of the composition of Ni–Co alloys comparison purpose.9]. activated for 20 s in the 20 vol. on the concentration of Co2+ ions in the electrolyte at a ited on AISI-1045 steel substrates by choosing a fixed concentration of Ni2+ ions is presented in Fig. wear rates correlate the structure and tribological properties of of all the alloy deposits were calculated using the Ni–Co alloys. the substrates Co in the alloys was always higher than in the were mechanically polished to a 0. the steel substrates were phenomena was the change of the near-electrode pH. where V is the wear volume loss in mm3. friction coefficient and sliding time were recorded ical. . A the running water to remove contamination on the generally accepted explanation for these anomalous substrate surface. USA) at room limited studies focused on the friction and wear temperature with a relative humidity of 45–55% under properties of Ni–Co alloys as a function of their dry sliding conditions.16]. (diameter 4 mm with hardness of RC 62) was used In the present paper. Composition of Ni–Co alloys l).12 mm electrolyte in agreement with [3.1 g/l) and cobalt sulfate (0– 80 g/l). In addition. indentations were made on these alloys in various magnetic devices. sodium chloride (20 g/l). diffraction (XRD). Note that the percentage of dilute sulfuric-acid. The composition. Wang et al. AISI-52100 stainless steel ball microstructure and composition. Unfortunately. there are very (Center for tribology. the hardness of a deposit was the average of 10 actuators and inductors [12.0 adjusted by ammonia water or centration in the electrolyte. alloy deposits were investigated using a JSM-5600Lv Golodnitsky et al. The crystal structure and phase hydrogen evolution reaction were also studied on composition of alloy deposits were studied by X-ray electrodeposited Ni–Co ultramicroelectrodes [10. adsorption [15. boric-acid (30 g/ 3. Namely. and tribological properties of Ni–Co alloys were automatically during the test. containing Nickel sulfate (200 g/l). The anode was a pure Ni plate. internal stress and tions of Ni–Co alloys were determined with energy high-temperature oxidation of Ni–Co alloys [3].1. The substrates. Ni–Co alloys with different Co as the counter body. / Applied Surface Science 242 (2005) 326–332 327 on the composition and morphology of Ni–Co The surface morphology and microstructure of the deposits were compared in many literatures [4. microstructure. California. magnetic properties of Ni–Co alloy are greatly The tribological behavior was tested on a influenced by the composition and phase structure reciprocating ball-on-disk UMT-2MT tribometer of Ni–Co alloy [14]. Experimental Ni–Co alloys were electrodeposited from a typical 3.13].% HCl solution.11]. Before deposition. rinsed in the less noble metal (Co) is preferentially deposited. equation of K ¼ V=SF. recently studies the effects of Co scanning electron microscopy (SEM). acetone with ultrasonic cleaning for 5 min. 1.5]. The pH of the increased gradually with the increase of Co2+ con- bath was kept at 4. mechan. especially in the 50 mm thick deposits.10–0. The Ni–Co alloys were depos. Microhardness of the deposits was Moreover. much interest is focused on the magnetic determined using a Vicker’s microhardness indenter properties of Ni–Co alloys due to the application of with a load of 50 g for 10 s. Inc. sodium lauryl sulfate (0. The wear volume loss compared systemically in order to specifically was measured using a surface profilometer. It is reported that the measurements. L. which is confirmed surface finish. and the formation of metal hydroxyl and their competitive finally rinsed with distilled water. Their dispersive X-ray spectroscopy (EDS) analysis tool activities for the oxygen evolution reaction and attached to SEM. the substrate was then degreased in by the anomalous codeposition of Ni–Co alloy.. It current density of 3 A/dm2 at a bath temperature of is clearly observed that the Co content in alloy deposits 45 8C. 2. The final value quoted for microsystem technology for manufacture of sensors. After than. The composi- content on the tensile strength. S the total sliding distance in m and F the normal load in N. all tests were performed under a content were electrodeposited on AISI-1045 steel load of 3 N with a sliding speed of 55 mm s1.5.

however.% Co.%. the in alloys.%. Sequentially increasing Co content from 7 to 49 wt. respectively. which is in agreement with previously crystallites (Fig. contents of (a) 0 wt. which has relatively large grain size (3–10 mm) and showed polyhedral crystallites. the Ni–Co solid solution was formed. (e) close observation of SEM morphology at high. have spherical cluster surface piled with a large number of equally sized grains with spherical-shape. With the codeposition of deposits. the grain size of Ni–Co largest grain size of pure Ni. (d) 49 wt. For the Ni-rich alloys with Co content lower Ni–Co alloy showed a rather regularly branched than 49 wt. 2b–f. and the FWHM of the Bragg line for the investigated using XRD shown in Fig. increased with the increase of Co Co. 1. As can be content in alloys.%. (f) 81 wt.%. SEM morphologies of Ni–Co alloy deposits with their Co grain size.% in growth orientation. (b) 7 wt. 3a. As can be (1 1 1) peak also increased correspondingly. Fig.%. Furthermore. both the crystal structure and phase 81 wt.3]. in accordance with the gradual reduction of grain size centered cubic (fcc) lattice with remarkable (2 0 0) when increasing the Co content from 0 to 49 wt. (c) 27 wt. The alloy compositions as a function of Co2+ concentrations in the baths. Wang et al. which can be attributed to the Ni–Co alloys as shown in Fig. / Applied Surface Science 242 (2005) 326–332 Fig. when . 2f). the pure Ni deposit exhibits face.%.%.328 L. 3b–f. reported results [2. 3. When increasing Co content up to seen in Fig. 2. 2b–d.2.%. 2b–d) results in a gradual decrease in the grain size of the Ni–Co alloy down to a sub-micron Fig. At above 49 wt. and with less compact structure. 2a shows a typical morphology of a Watt Ni deposit. the morphology of the Ni–Co alloys changes composition are mainly dependent on the Co contents dramatically. the (1 1 1) growth The phase composition and structure of pure Ni and orientation gradually increased with the increase of Co Ni–Co alloys with different Co contents were content. Morphology and phase structure of Ni–Co alloys Typical surface morphologies of Ni–Co alloys with different Co content are shown in Fig.% (Fig. (g) high-magnification of Ni–49 wt. 66 wt.% Co magnification (Fig. 3. the Ni–Co alloys show complete fcc structure with extended acicular 3–6 mm length phase structure. 2g) revealed that the Ni–Co alloys alloy. Moreover. which is seen from Fig.%. When the Co content reached the 49 wt.

(b) 7 wt. (d) 49 wt.3. which can be associated with the smallest grain size as mentioned in Fig. strengthening of polycrystalline materi- (f) 81 wt.%. / Applied Surface Science 242 (2005) 326–332 329 81 wt. 2e–f. L. The explanation to this gradual reduction of microhardness is the gradual increase of grain size with the increase of Co content in Co-rich alloys as shown in Fig. indicating that H ¼ H0 þ kd 0:5 (1) the crystal structure of the Ni–Co alloy changed from where H0 is hardness constant.%.% Co. which can be the Co content was increased to 66 wt. 3.%. as shown in Fig.5 (b) of the Ni–Co deposits. (c) 27 wt. (e) 66 wt.%. Microhardness as function of Co content (a) and d0.%. 4. and then gradually decreased as Co content increased further above 49 wt. XRD patterns of Ni–Co alloy deposits with their Co contents microstructure analysis sector. 3. which is commonly observed in both conventionally electrodeposited Co and nano- crystalline Co [17.%. At above grain size (d) of the Ni–Co deposits is shown in Fig.18]. The hardness change with average (minority of hcp) phase as shown in Fig. and d complete fcc lattice into a mixed (majority of fcc) + diameter of grain. the presence represented by the classical Hall–Petch effect: of (1 0 0) peak demonstrated the initial formation of a hexagonal close packed (hcp) lattice. Therefore.%. 3. Normally. 3f that a very strong hcp (0 0 2) texture with pronounced (1 0 0) and (1 1 0) peaks were observed.%. it can be concluded that the phase structure of Ni–Co alloys gradually changed from fcc into hcp with the increase of Co content as shown in Fig. of (a) 0 wt.%. .%. It is clearly that microhardness of Ni–Co alloys increased initially with Co content varying from 0 to approximately 49 wt. 3e. Microhardness of Ni–Co alloy deposits Fig. Note that the microcrystalline Ni–Co alloys show the maximum hardness at approximately 49 wt. als by grain size refinement is technologically attractive because it generally does not adversely affect ductility and toughness [19]. k constant. Wang et al. 4a presented the microhardness of Ni–Co alloys as a function of Co content in alloys. 4b Fig.

3.21].23]. rate of Ni–Co alloys slowly decreased with the the close friction coefficient for Ni and Ni-rich alloy can increase of Co content from 6 to 49 wt. . such a relationship has also been observed on pure Ni.% Co alloy. dramatic reduction of resistance with hardness increase. as from 315 to 462 HV. between Ni-rich and Co-rich alloy deposits. Hence.% Co alloy. in this study due to friction coefficient was observed due to the higher ratio the grain size reduction. 6.% exhibited the smallest friction coefficient change of crystal structure from fcc to hcp crystal phase. could be expressed using of hcp phase structure. we can conclude that the Archard’s law mostly used in adhesive wear condi- reduction in friction coefficient of Co-rich alloys with tions [22. the Co. Above improvement of wear for the Ni–81 wt.330 L. (more than two times lower than Ni and Ni-rich alloys). The comparison of friction coefficients vs. 5. 7. Wear rates as function of Co content in the Ni–Co alloy alloy deposits. since the wear mechanism of Ni and Fig. 6). the In case of Ni–66 wt. sliding time close. Furthermore. It is obvious that the Ni–Co alloy deposits exhibit a nearly constant Hall– Petch gradient. Friction coefficient as function of Co content in the Ni–Co Fig.4. / Applied Surface Science 242 (2005) 326–332 in the form of a Hall–Petch plot. It is observed that all Ni–Co alloy In addition. pure Co and pure Zn from other studies [20. Wang et al. the wear deposits (see Fig. a mixed fcc/hcp phase gradual decrease of wear rates with the increase of Co with smaller ratio of hcp phase structure led to the content was attributed to the microhardness increase gradual reduction of friction coefficient.%. Combined with the XRD analysis. that when the Co content is lower than 49 wt. It is clear be attributed to the same fcc crystal structure they have. deposits.% (Ni-rich alloys) were quite Fig. The variation of the wear rates of Ni–Co alloys as a followed by Ni–66 wt.% Co alloy (a litter lower than Ni function of Co content and microhardness of alloys are and Ni-rich alloys) under identical wear test conditions. the friction coefficients of Co-rich alloys deposits in this study have lower wear rates when were much more stable than that of Ni-rich alloy compared with pure Ni deposit. rich alloys showed excellent friction–reduction beha- vior. With the further increase of Co content. It is observed that the friction coefficient of pure Ni and Ni–Co alloys with Co content lower than 49 wt. shown in Fig. The Co-rich alloy deposit with Co content higher the increase of Co content can be associated with the than 81 wt. Friction and wear properties The effect of Co content on friction coefficient of Ni– Co alloys were shown in Fig. Moreover. 5. 7.%.

The wear rate of Co-rich alloy with alloys. Compared with pure Ni and Ni-rich alloys. LN The difference in the wear behavior of Ni–Co Q¼K (2) alloys can be further verified by the worn surface H morphologies of Ni-rich and Co-rich deposit as shown where Q is the volumetric wear loss. wear rate for microcrystalline Ni–Co alloys with Co which results in larger wear rate of pure Ni and Ni-rich content lower than 49 wt. Wang et al.% fit Archard’s law very alloys. the lower and stable friction on the worn surface (Fig. 8a–c. the wear rates of Co-rich alloys of formation of asperity junctions resulting in higher decreased rapidly in spite of the fact that the hardness and unstable friction coefficient for Ni and Ni-rich also decreased. The data of under the combined stresses of compression and shear. 8a and b) shows the larger extent of adhesion same wear conditions. That is also the reason why the friction Fig. larger tendency for plastic well. a approximately 81 wt. the wear rate is proportional to wear and severe deformation in the sliding direction the inverse microhardness of materials. K the wear coefficient with completely fcc crystal structure. (b) 27% Co. only some light grooves and scars are noted Co-rich alloys. 8. seems to take place. However. N the applied in Fig. This wear and rather smooth surface with smaller damaged agree well with the reduction in friction coefficient for regions. the Archard’s law can be important is the fact that the Co-rich alloys exhibited expressed as: excellent wear resistance and anti-friction behavior. L. while the alloys. For the pure Ni deposit and Ni-rich alloy load. 8a and b. this in turn increased the probability above 49 wt. This reverse-Archard law may be caused with hcp crystal structure revealed slight adhesion by special hcp crystal structure of Co-rich alloys. Worn surface of Ni–Co alloy deposits: (a) 0% Co. This resulted in the coefficient of Co-rich alloys caused by hcp phase better wear resistance of Co-rich alloy than Ni-rich structure resulted in the less wear loss.% Co content is more than one densification of the worn surface of Co-rich alloy order of magnitude lower than that of pure Ni and Ni. the worn surface of Co-rich alloy rich alloys. the wear track and H the hardness of the wear surface. . / Applied Surface Science 242 (2005) 326–332 331 Ni-rich deposits is mostly the adhesive wear as higher friction coefficient of Ni-rich alloys due to evidenced by SEM morphology of worn surface in fcc phase structure led to the more wear loss. Under the (Fig. (c) 81% Co. More Fig. Thus. with further increase in Co content deformation. Furthermore.%. namely. 8c). L the total sliding distance.

Acta 45 (2000) 3323. Appl. Y. law.H. and then gradually decreased as Soc. D. fcc into hcp with the increase of Co content. Acta 45 (2000) 4. E. Mater. Electrochim.T. gradually with the increase of Co2+ concentration [4] A. Avaca.S. Electrochem. Machado. F. Appl. Correia.H. [2] V.%. Vallés. [6] D. N. Van Swygenhoven. Gudin.N. . Ramirez. Burzynska. Phys. Rudnik. Singh. much lower friction coefficient and higher wear 50 (2002) 3957. 48 (1997) regularly branched structure. Acta Mater. S. E. Fedkiw. Finish.B. N. Arzt. 50271080 and 50323007). 24 (1953) 981. [21] Kh. Aust. Soc. from 7 to 49 wt.S. G. J. Koch. Electrochem. Wen. Saber. The phase Commun. resistance with hardness increase fits Archard’s [19] E. and ‘Top Hundred influences the friction and wear behavior of Ni–Co Talents Program’ of Chinese Academy of Sciences for alloys. [3] D.C. / Applied Surface Science 242 (2005) 326–332 coefficients of Co-rich alloys were much more stable Acknowledgements and more than two times lower than that of Ni and Ni-rich alloys. Singh. Lee. The [16] N. T.W. Archard.332 L. Electrochim. Golodnitsky. 1974. Palumbo. 62 (1964) 82. G. Vallés. in the electrolyte. et al. Hu. Finish. Gómes. J.A. Rosenberg. Dalla Torre.S. Eng. Sci. Electrochem. Poklaha. [15] D. J. the 863 Program crystal structure is indeed a dominant factor. J. the Co-rich alloys exhibited [20] F. Ulus.A. Volyanuk. Phys. anomalous codeposition of iron group metals. Met. Co content increased further above 49 wt. Hence.A. It is evident that the high the amount of The authors gratefully acknowledge the National hcp phase structure. Hydrometallurgy 54 (2000) 133. [18] G. Surf.%. 28 rical cluster surface when increasing Co content (1998) 71. mately 49 wt. Electrochem. A. 44 (4) For the Ni-rich alloys. (2) Surface morphology of Ni–Co alloys changed [7] H.-C. Hibbard. Mater. which of China (No.N. (2001) 493. Surf.A. Electrochem. Golodnitsky. Hu. Volyanuk. Electrochem. Plat. Dini. Jeong. 70 (1983) 47. Appl. Gómes. Acta 47 (2002) 3447. Electrochim. K. dependent on the Co content in alloys. [8] E. E. Yu. S. 32 (2002) (3) Microhardness of Ni–Co alloys increased initially 693. suggested that hcp crystal structure in Co-rich [22] J. 1 (1996) 600. the better the friction and wear Natural Science Foundation of China (Grant No behavior will be. L. Appl. alloys contributed to the remarkable friction– [23] D. structure in Ni–Co alloys contributed to the remark- able friction–reduction effect and better anti-wear performance of Co-rich alloys. [14] E. J.R. H. structure of Ni–Co alloys gradually changed from [12] E. Bai.. Armyanov. G.V. it clearly demonstrates that hcp crystal financial support of this research work.-C. Hall–Petch effect. J.A. C.F. 29 (1999) 805. Finish. 85 (1998) 65. Victoria.R.% and the morphology of the [9] W.-C. V. Finish. 2003AA305670). A 341 resistance than Ni-rich alloys. References [1] A. Gonzalez. Conclusions 1733. Scripta Mater. J. Scripta Mater.-S. Above evidence suggests that the 50172052. et al. Wang et al.V. Valles. Zech. Palumbo. structure and phase composition are mainly [11] A. Morral.% Co showed a rather Alloys. 44 reduction effect and better anti-wear performance. In addition. 7 (1976) 34. Electrochim. P. from regularly polyhedral crystallites into sphe. Chem. Correia. Golodnitsky. with Co content increasing from 0 to approxi. Surf.J. Machado. G. [10] C. Plat. Johnson. Acta 47 (1) The Co content in Ni–Co alloys increased (2002) 2707. New York London. [13] S. Safranek. Both the crystal 246. E. Properties of Electrodeposited Metals and Ni–Co alloys with 81 wt. E. 46 (1998) 5611. C. M. Gómes. J. Acta Mater. which is confirmed by the [5] L. Landolt. 146 hardness change of Ni–Co with grain size follows (1999) 2886.N. 147 (2000) 4156. It has been (2003) 174. [17] F. the improvement of wear (2001) 513. Gudin. Plat.