Wear 255 (2003) 917923

Communication

Sliding wear behaviour of electrodeposited cobalttungsten and cobalttungsteniron alloys

H. Capel, P.H. Shipway , S.J. Harris
School of Mechanical, Materials, Manufacturing Engineering and Management, Advanced Materials Group, University of Nottingham, University Park, Nottingham NG7 2RD, UK

Abstract Hard-chrome plate is traditionally employed as a wear resistant surface. However, concerns that the processing of such materials is not environmentally friendly have lead to a search for potential replacements. This work examines the behaviour of two alloy systems, namely CoW and CoWFe. Alloys from these systems were electrodeposited onto steel substrates. The CoW alloys were further heat treated to increase their hardness, although this was deemed unnecessary for the CoWFe alloys which had high as-deposited hardnesses. The sliding wear behaviour of these materials was examined, along with the behaviour of a hard chrome under similar conditions. It was found that under some conditions, the CoW alloys exhibited a wear resistance and a coefcient of friction similar to that of hard chrome. Moreover, the corrosion resistance of the CoW alloys was higher than that of the hard-chrome plate. The CoWFe alloys exhibited a high as-deposited hardness. At a critical iron level of 30 wt.%, the wear rate of these coatings decreased substantially. All the CoWFe coatings were more corrosion resistant than the hard chrome; however, even the most wear resistant exhibited a high coefcient of friction and more wear than the hard chrome. 2003 Elsevier Science B.V. All rights reserved.
Keywords: Electroplating; Chrome replacement; Amorphous; Nanocrystalline

1. Introduction Chromium electrodeposition is a well-established technique for the production of decorative and functional coatings which possess attractive properties such as high hardness, excellent wear resistance and low coefcient of friction. Chromium coatings can also provide excellent protection against corrosion. As a consequence, chromium electrodeposits have found extensive use, particularly for their resistance to wear, in a wide range of engineering industries. However, replacement of hard chromium electrodeposits is being actively pursued on environmental grounds. The primary concern with the processing of such materials is that normally a hexavalent chromium solution is employed in the electrodeposition bath, which produces large volumes of chrome contaminated toxic waste requiring special disposal methods [1]. Expensive breathing apparatus and exhaust systems must also be employed to deal with emissions during plating. Hexavalent chromium in solution is also a recognised carcinogen and causes other health problems such as skin and lung irritation [2]. A
Corresponding author. Tel.: +44-115-951-3760; fax: +44-115-951-3764. E-mail address: philip.shipway@nottingham.ac.uk (P.H. Shipway).

further technical concern is associated with the fact that chromium-plating baths are generally only 15% efcient and that operators often have difculty maintaining uniformity of coating thickness [3]. As a result, the plating industry has been forced to consider alternative materials and/or processes that do not involve hexavalent chromium [46]. The co-deposition of alloys of tungsten with one or more of the iron group metals provides a number of electrodeposit systems that may be considered as possible replacements for conventional hard chromium electrodeposits. It is well known that alloys such as CoW/B and NiW/B are characterised by high surface hardness; Vickers hardness values between 450 and 650 kgf mm2 have been reported for these coatings in the as-deposited condition [68]. It is also known that heat-treatment improves their hardness further, to values exceeding that of hard-chrome electrodeposits. Tungsten-containing alloy coatings can be produced with widely different compositions and microstructures depending on the composition of the plating bath and the deposition parameters. Amorphous, crystalline and nanocrystalline forms of CoW and NiW electrodeposits have all been reported in the literature [911]. The development of CoW and NiW alloys with amorphous or nanocrystalline structures is expected to be of particular future interest since materials with such microstructures often possess

0043-1648/03/$ see front matter 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0043-1648(03)00241-2

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better corrosion resistance and tribological properties when compared to their crystalline counterparts. The majority of the work reported in the literature for W-containing electrodeposits concerns the optimisation of the electroplating process, i.e. electroplating bath chemistry and operating controls, in order to produce high quality coatings. A number of studies have been conducted on the effect of heat-treatment on the microstructure of CoW and NiW electrodeposits [6,12,13] and the change in hardness of these coatings, with respect to ageing conditions, has been well documented. However, whilst heat treatment of other amorphous electro- and electroless plated materials to improve wear resistance has been reported [1419], there is a relative paucity of literature concerning the wear behaviour of CoW and NiW based alloys [6]. If such alloys are to be considered as replacements for hard chrome in engineering applications, a detailed understanding of their tribological performance and behaviour in corrosive environments must be gained. Whilst it is known that heat treatment can be used to improve the hardness of amorphous electrodeposited alloys, it is also known to embrittle them. The aim of the present investigation was therefore to examine the wear and corrosion resistance of amorphous/nanocrystalline electrodeposits in the CoW system in both the as-deposited and heat-treated conditions. Alloys in the CoWFe system were also examined which, with higher as-deposited hardnesses, were hoped could be competitive materials without heat treatment. The protective properties of hard-chrome electrodeposited onto mild steel were also measured for comparison.

gluconate, 30.0 g l1 sodium chloride. The bath was maintained at pH 6.0, controlled by the addition of either NaOH or H2 SO4 , and the volume of the bath was adjusted, during approximately 6 h of plating, by additions of distilled water. Boric acid was added to the bath since it has been shown that small amounts of boron co-deposited with the CoW alloy promotes an amorphous structure, and hence the excellent properties that are characteristic of such materials, such as high hardness [20]. CoWFe electrodeposits of three different alloy compositions were also produced from the same bath with additions of ferrous sulphate heptahydrate. The addition of 3.48, 6.95 and 13.9 g l1 of ferrous sulphate produced coatings with iron contents of 15, 23 and 30 wt.%, respectively. The cobalt content of the coatings decreased as the iron content increased whilst the tungsten content remained approximately constant. Electrodeposition of the CoW and CoWFe alloys was carried out at an applied current density of 5 A dm2 at a constant temperature of 80 C. The standard plating time was 1 h to produce a deposit which was approximately 20 m thick. Hard-chrome plated onto mild steel specimens prepared in the same way as described above was performed commercially, yielding a hard-chrome layer of approximately 20 m in thickness. 2.2. Heat treatment CoW alloy coatings were heat treated in an argon inert atmosphere in a tube furnace. Samples were placed in the furnace at room temperature, which was then heated to the annealing temperature at a constant rate of 20 C min1 . Once the annealing temperature of 600 C was reached the samples were aged for 2 h. Work conducted by the authors had previously shown that these conditions produced coatings of optimum hardness [21]. A titanium powder getter was placed in the furnace alongside each of the samples to remove any residual oxygen remaining in the furnace and thereby prevent oxidation of the CoW alloy. 2.3. Wear testing The wear performance of the electrodeposited coatings was examined using a BICERI universal wear tester. Ball-on-plate geometry was employed with a reciprocating sliding action in simple harmonic motion driven by a crank and wheel arrangement (see Fig. 1). The counterface was a martensitic stainless steel (AISI 440C) ball with a diameter of 25.4 mm (Dejay Distribution Ltd., Wokingham, UK) and a hardness of 739 kgf mm2 (20 kg hardness test load). All of the wear experiments were conducted under dry sliding conditions at ambient temperature (2123 C). The amplitude of the motion was 11 mm giving a sliding distance of 44 mm per cycle. The frequency was 158 cycles per minute and the duration of testing was 4000 cycles. Any point on the coating experienced the passage of the slider twice per cycle with a velocity which depended upon the position

2. Experimental details 2.1. Electrodeposition Polished mild steel sheet (BS080A15 with a hardness of 225 kgf mm2 when measured with a 200 gf indentation force) was used as the substrate material. The plating area of each specimen was approximately 30 cm2 . All specimens were subjected to a series of cleaning stages and nally rinsed in dilute 10% H2 SO4 to remove any residual alkali and to activate the surface for electrodeposition. Electrodeposition of CoW was carried out in two ways: (a) directly onto the mild steel substrate and (b) on top of a thin cobalt strike applied to the substrate prior to alloy deposition. All deposits were produced using an ACM Instruments AutoAC DSP 300W model potentiostat/galvanostat, under galvanostatic conditions. An iridium oxide coated platinised titanium mesh (70 mm 100 mm) formed the anode. The plating bath used for the deposition of the cobalt strike was simply 25 g l1 cobalt sulphate in distilled water. The temperature was maintained at 80 C and the plating time was 2 minutes The CoW alloy plating bath composition was as follows: 15.0 g l1 cobalt sulphate heptahydrate, 16.5 g l1 sodium tungstate dihydrate, 40.0 g l1 boric acid, 110.0 g l1 sodium

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Fig. 1. Schematic diagram of wear testing apparatus.

on the wear track. The normal load on the coated samples, applied by adding weights to the loading arm on the equipment, was approximately 61 N in most tests, although a small number of tests were carried out with the higher load of 162 N. Following the wear tests, the depth of the wear tracks produced was measured using a Surfcom prolometer (Advanced Metrology Systems Ltd., Leicester, UK). The average steady state coefcient of friction of each sample was also calculated from data collected during the wear tests. 2.4. Corrosion testing The breakdown in corrosion resistance of the plated samples was measured as the time until the rst spots of red rust appeared on the surface of samples placed in a neutral salt spray cabinet working to ASTM B117. In the case of the iron-containing deposits, some corrosion of the deposits themselves occurred producing a corrosion product which looked similar to that associated with substrate corrosion. These were distinguished by cross-sectional microscopy following testing. Also, it was noted that whilst corrosion product from the electrodeposits occurred in the early stages of the salt-spray tests, it did not tend to increase with further time in the cabinet. Once substrate corrosion occurred, it tended to proceed rapidly. 2.5. Characterization Coatings were examined in a Philips XL30 environmental scanning electron microscope tted with a eld emission gun (ESEM FEG) and energy dispersive X-ray (EDX) analyser. Coatings were examined before and after wear testing. Cross-sections were taken through the wear tracks, parallel to the direction of sliding. The top surfaces of some of the worn coatings were also examined. EDX analysis was conducted on the wear debris and the transfer layer to identify its composition. X-ray diffraction (XRD) was conducted on a Siemens D500 Diffractometer for structural and compositional analysis using Cu K radiation, scanning a 2 range of 10100 at a step size of 0.05 and a dwell time of 2 s. Hard-

ness measurements were made on coating cross-sections using a Leco-400 Vickers microhardness indenter, under a load of 25 g for 15 s. A small load had to be used when making these measurements in order to prevent damage to the thin coatings. Average hardness values were estimated by making 20 indents on each sample.

3. Results and discussion 3.1. Coating characteristics The CoW and CoWFe deposits were in all cases semi-bright and light grey in colour. All the deposits had an average thickness of 20 m. For the CoW alloys, EDX and XRF measurements revealed an average alloy composition of Co53 wt.% W (Co27 at.% W), which was constant throughout the thickness of all deposits, both with and without the intermediate cobalt layer. A very small amount of boron was detected in the deposits (0.05 wt.%). For the CoWFe alloys, the tungsten content remained approximately constant at 53 wt.%. As the concentration of ferrous sulphate in the bath increased, then the iron concentration in the coatings increased; coatings with iron contents of 15, 23 and 30 wt.% were produced, with the balance being cobalt. A cross-sectional micrograph of a typical as-deposited coating is shown in Fig. 2. XRD showed that all coatings were in the amorphous/nanocrystalline state on deposition. The hardnesses of the iron-containing alloys were higher of those of the plain CoW deposits. The increase is small for the two lower levels of iron; however, there is a signicant increase from 605 kgf mm2 for 23 wt.% Fe to 838 kgf mm2 for 30 wt.% Fe (Table 3). Heat treatment of CoW coated mild steel, both with and without the cobalt strike layer, was carried out in an attempt to improve the mechanical properties of the alloy deposit. A hardness increase from 540 to almost 1200 kgf mm2 was observed at the optimum heat treatment conditions of 600 C for 2 h in argon (Table 3). This increase in hardness was due to partial crystallisation of the material [21]. This increase in hardness is higher than those observed in much other

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Fig. 2. As-deposited coating of Co53 wt.% W30 wt.% Fe alloy.

work. For instance, Eskin et al. [6] reported an increase in hardness for a Co30 wt.% W deposit from around 450 to around 700 kgf mm2 following heat treatment for 1 h at 600 C in air. The differences may be explained by the much lower tungsten content in their work and the fact that heat-treatment in air results in signicant oxidation of the deposit. Whilst heat treatment improves the hardness of the alloy, the integrity of the coating is considerably reduced in that signicant through-thickness cracking is observed. The cracking does not penetrate the cobalt strike when this is present [22] and the strike remains in good contact with the steel substrate following heat treatment. 3.2. Corrosion resistance The limit of corrosion resistance was measured as the time taken until the rst spots of red rust associated with substrate corrosion appeared on the sample surface in the salt-spray test. Care was taken to distinguish between deposit corrosion and substrate corrosion as previously described. The results of these tests are given in Table 1. As-deposited CoW on mild steel has shown very promising corrosion protection. Substrate corrosion was not observed for the CoW alloy without a strike layer until over 2560 h in the neutral salt-spray test. As-deposited CoW with an underlying Co strike has shown even greater corTable 1 Corrosion and wear properties (under 61 N load) of electrodeposited coatings Deposit Co53 wt.% W as-deposited Co53 wt.% W as-deposited Co53 wt.% W heat treated Co53 wt.% W heat treated Co53 wt.% W15 wt.% Fe as-deposited Co53 wt.% W23 wt.% Fe as-deposited Co53 wt.% W30 wt.% Fe as-deposited Hard-chrome as-deposited Strike layer thickness ( m) 0 2 0 2 2 2 2 0

rosion protection with no sign of substrate corrosion after over 3300 h of testing. A yellow/gold surface layer formed on top of all the as-deposited CoW samples after approximately 20 h, but this layer was too thin to be identied by XRD. Some as-deposited samples, both with and without the strike layer, have also displayed evidence of surface pitting after 100 h. These small pits were lled with a black corrosion product again in quantities too small to be analysed by XRD or EDX. The benets of using a Co strike were more evident when the corrosion resistance of heat-treated CoW alloy was investigated. Samples heat treated at 600 C for 2 h with no underlying Co strike provided substrate protection for only around 20 h. After this time the whole sample was completely covered with red rust. Heat-treated CoW with an underlying 2 m thick Co strike showed no sign of substrate corrosion for 100 h. No surface pitting was observed on any of the heat-treated samples as seen with the as-deposited samples, but the as yet unidentied gold/yellow surface layer was observed on some samples, typically after 100 h of testing. The substrate corrosion protection offered by the CoWFe electrodeposits with varying Fe contents was also examined. It can be seen that as the iron content increases the protection against substrate corrosion markedly decreases. Deposits containing 30 wt.% Fe prevented substrate attack for only 35 h. However, considerable corrosive attack to the coating itself occurred almost instantaneously with exposure to the salt spray environment. The surface of these coatings became completely covered in a red corrosion product after only 2 h. XRD conrmed that this product was iron oxide. Substrate corrosion for samples coated with CoWFe alloy, with an Fe content of 23 wt.%, was observed after 120 h. Corrosion of the coating itself initiated after 4 h exposure to the salt spray but the corrosion product covered only approximately 20% of the coated surface. The coating only reached a similar level of attack as observed for the 30 wt.% Fe deposits in 2 h after 55 h in the salt spray. Deposits containing only 15 wt.% Fe showed even greater resistance to both attack of the alloy deposit itself and substrate corrosion. No change to the surface of the coatings was observed in this case for over 35 h of exposure. After 80 h of exposure, the thin yellow/gold layer, also seen in

Onset of substrate corrosion (h) 2563 3334 21 100 289 120 35 8

Wear track depth ( m) 20.9 17.5 1.4 2.1 23.4 23.9 4.5 1.2

Coefcient of friction 0.41 0.40 0.47 0.50 0.91 0.95 0.75 0.4

H. Capel et al. / Wear 255 (2003) 917923 Table 2 Wear properties of selected electrodeposited coatings following sliding under 162 N load Deposit Co53 wt.% W heat treated Hard-chrome as-deposited Strike layer thickness ( m) 0 0 Wear track depth ( m) 4.2 4.1

921

the case of the CoW deposits, was observed. Attack of the CoWFe coating occurred after 120 h in the salt spray and substrate corrosion was prevented for almost 300 h. SEM observation of some of the corroded CoWFe samples revealed that as deposit attack took place a thick oxide layer formed across the top surface of the coatings, covering any pits and cracks that were present. This layer aided prevention of corrosion of the substrate at weak points in the coatings, by blocking the pathway where corrosive media could travel directly to the substrate, which would otherwise have caused immediate substrate attack. This layer however did not prevent further attack to the coating itself and hence the relatively poor protection properties of the CoWFe deposits in comparison to the CoW coatings. Electrodeposited chromium, 20 m thick, consistently failed to provide substrate protection after less than 10 h in the salt-spray test. This is even less than the time for corrosion seen for the heat-treated CoW without the presence of a cobalt strike and was a result of the cracked nature of the deposits. 3.3. Wear resistance The resistance to reciprocating wear of the as-deposited and heat-treated CoW alloy, as well as the chromium electrodeposit, was measured by the depth of the wear track after a given number of testing cycles, under the specied load. The results of these tests are shown in Table 1. It can be seen that after 4000 cycles, substantial wear of the as-deposited CoW with no underlying cobalt strike layer has occurred, the track depth equal to the thickness of the deposit itself in-

dicating complete coating removal. A slight improvement in the wear resistance was seen for this material when a strike layer was present between the substrate material and the alloy. However, the wear resistance of the as-deposited CoW alloy still does not approach that of the chromium electrodeposit, which produced a wear scar depth of only 1.2 m after 4000 cycles. It should be noted that when these deposits begin to break down during sliding, debris is produced which is hard and abrasive. As such, once such debris has been produced, further wear is rapid and often catastrophic. An example of the result of catastrophic wear can be observed in Fig. 6b where nely comminuted debris has been folded into the sample surface during the wear process. Accordingly, this wear test tends to measure primarily the ability of the coating to survive severe breakdown under the conditions applied. If the coating survives such catastrophic failure, discrimination can be made on the basis of depth of wear. A signicant improvement in the wear resistance of the CoW alloy was observed when samples were heat treated prior to wear testing. For heat-treated CoW deposited directly onto the steel substrate the wear scar after 4000 cycles was now consistently only 1.4 m, a value that approaches that of the chromium sample. The resistance to wear of CoW electrodeposits with an underlying cobalt strike layer was also greatly improved when compared to their as-deposited counterparts. However, a difference in the wear depth of the samples with and without the cobalt strike was observed in both the as-received and heat-treated conditions. This is attributed to differences in the stress state and lm morphology, both of which will be affected by the cobalt strike layer. However, the details of this interaction are not, as yet, well understood. Also, the coefcient of friction increased from around 0.4 prior to heat-treatment to around 0.48 after heat-treatment. Amorphous alloys are well known to exhibit low coefcients of friction and the increase following heat-treatment is due to partial crystallisation. Fig. 3 shows a cross-section and plan view of a wear scar in the heat-treated deposit. Comparing this with Fig. 2, some cracking can be seen to result from the wear testing. The plan view image (Fig. 3b) shows that the cracking gener-

Fig. 3. (a) Cross-section and (b) plan view of wear scar in a heat-treated Co53 wt.% W coating (with cobalt strike) following 4000 cycles of wear under a 61 N load.

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Fig. 4. (a) Cross-section and (b) plan view of wear scar in as-deposited hard chrome following 4000 cycles of wear under a 61 N load.

ally occurred within nodules and was stopped at the nodule boundaries, thus preventing catastrophic failure. Much of the worn surface was covered with a lm (the light grey areas towards the edges of the image in Fig. 3b) which is thought to be oxide. The increase in wear resistance was due to the signicant increase in hardness upon heat treatment which made it harder than the counterface ball. EDX provided some evidence of iron oxide present on the surface of the deposits which had resulted from wear of the ball. Fig. 4 shows the wear behaviour of the chromium deposits under the same conditions. Again, the deposit was seen to be severely cracked and more signicant cracking of the deposit was observed on the plan view (Fig. 4b) than in the heat-treated CoW coating. In the chromium, the cracking was observed to be more extensive and not limited by any nodular microstructural features. Cracking was primarily perpendicular to the sliding direction. Some evidence of delamination was also seen. However, it is notable that although the damage appears worse in the chromium (Fig. 4) than in the heat-treated CoW (Fig. 3), the wear of the chromium was slightly less (Table 1). The friction coefcient in the heat-treated CoW (around 0.48) was higher than that in the chromium (0.4) and this may have resulted in the higher rates of wear in the former materials.

Table 2 illustrates that the heat-treated CoW alloy has a high load bearing capacity. Both this deposit and the chromium were able to withstand wear under a signicantly higher load of 162 N. Neither coating failed catastrophically, although the depth of wear was now much higher than under the lower load, indicating that the deposits were wearing attritively. The CoW and the hard chromium deposits wore to a very similar depth in this test. Fig. 5 shows a cross-section through the heat-treated CoW coating tested under these conditions. The deposit exhibits more cracking than under the lower load (Fig. 3). The nodular structure can be discerned with the major cracks running between nodules. Where material has been removed from the surface, pores have been lled with an oxide which (as indicated by EDX analysis) had iron as the primary metal. The CoWFe deposits were examined in the as-deposited state. Table 3 shows that the hardness of the two deposits with the lower iron contents were higher than that of the plain CoW alloy by a small amount. Table 1 indicates that they showed no advantage in wear over the plain CoW alloys, exhibiting catastrophic failure of the coating. Fig. 6b shows a cross-section through such a catastrophic failure. Increasing the iron content in the deposit to 30 wt.% resulted in an as-deposited hardness of 838 kgf mm2 , very close to that of chromium. However, Table 1 indicates that the wear resistance of this material was signicantly worse than that of chromium, even though it wore attritively and not catastrophically. Fig. 6a shows that the degree of cracking in the

Table 3 Hardness of electrodeposited coatings and wear counterface Deposit Co53 wt.% W as-deposited Co53 wt.% W heat treated Co53 wt.% W-15wt.% Fe as-deposited Co53 wt.% W23wt.% Fe as-deposited Co53 wt.% W30wt.% Fe as-deposited Hard-chrome as-deposited Wear counterface (440C ball) Hardness (kgf mm2 ) 538 1185 551 605 838 848 739

Fig. 5. Cross-section of wear scar in a heat-treated Co53 wt.% W coating (without cobalt strike) following 4000 cycles of wear under a 162 N.

Coatings tested with a 25 gf load; counterface tested with 20 kgf load.

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Fig. 6. Cross-section through wear scar in as-deposited iron-containing deposits following 4000 cycles of wear under a 61 N load: (a) Co53 wt.% W30 wt.% Fe alloy; (b) Co53 wt.% W23 wt.% Fe alloy.

iron-containing deposit was far more extensive than that observed in the chromium or the plain CoW deposit following heat-treatment. This high level of cracking may have resulted from the comparatively high coefcients of friction (>0.75) observed for the iron-containing alloys compared to those of the non-iron-containing deposits (<0.4). Cobalt oxides are known to result in low friction coefcients, and the higher friction coefcients of the iron-containing alloys may be associated with differences in the oxide structure on the surface.

chromium and its corrosion resistance much better. However, its wear resistance was lower than chromium (although no catastrophic wear was observed). References
[1] [2] [3] [4] [5] [6] [7] J.D. Schell, M. Rechtsteiner, Plating Surf. Finishing 87 (2000) 1723. P.C. Wynn, C.V. Bishop, Trans. IMF 79 (2001) B27B30. M. El-Sharif, Trans. IMF 75 (1997) B143B146. S.K. Ibrahim, D.T. Gawne, A. Watson, Trans. IMF 76 (1998) 161 165. P.L. Ko, M.F. Robertson, Wear 252 (2002) 880893. S. Eskin, O. Berkh, G. Rogalsky, J. Zahavi, Plating Surf. Finishing 85 (1998) 7984. B.N. Maruthi, L. Ramesh, S.M. Mayanna, D. Landolt, Plating Surf. Finishing 86 (1999) 8589. C. Gangmin, Y. Fangzu, H. Ling, N. Zhenjiang, X. Shukai, Z. Shaomin, Trans. IMF 79 (2) (2001) 8184. T. Wantanabe, New Mater. New Proces. 3 (1985) 307312. U. Admon, M.P. Dariel, J. Appl. Phys. 59 (6) (1986) 20022009. P. Schlomacher, T. Yamsaki, Mikrochim. Acta 132 (2000) 309313. V.M. Fedosyuk, J.M. Riveiro, J. Non-Cryst. Solids 143 (1992) 153 156. T. Yamasaki, Scripta Mater. 44 (2001) 14971502. Y.C. Wu, G.H. Li, L. Zhang, Surf. Eng. 16 (2000) 506510. C. Yong, J. Mater. Sci. Lett. 15 (1996) 629631. Y.Z. Zhang, K. Zhang, J.Z. Fan, S.M. Zhang, M. Yao, Trans. Non-Ferrous Met. Soc. China 8 (1998) 642647. Y. Choi, J. Mater. Sci. 32 (1997) 15811586. M.H. Staia, E.J. Castillo, E.S. Puchi, B. Lewis, H.E. Hintermann, Surf. Coatings Tech. 8687 (1996) 598602. M.H. Staia, C. Enriquez, E.S. Puchi, Surf. Coatings Tech. 9495 (1997) 543548. W. Wikiel, J. Osteryoung, J. Appl. Electrochem. 22 (1992) 506511. H. Capel, P.H. Shipway, S.J. Harris, in press. H Capel, P.H. Shipway, S.J. Harris, in: Proceedings of the AESF SUR/FIN 2002, American Electroplaters and Surface Finishers Society, Orlando, FL, 2002, pp. 123132.

4. Conclusions It has been shown that electrodeposits based on the CoW system with high tungsten levels can be successfully electrodeposited from a near-neutral bath. The deposit showed exceptional corrosion resistance but poor wear resistance. The as-deposited hardness of the CoW deposit can be signicantly increased by heat treatment which leads to wear resistance close to that of electroplated chromium, but a signicant reduction in corrosion resistance. The corrosion resistance is slightly better than that of chromium, but this can be signicantly improved by the use of a cobalt strike layer. Thus, plain CoW electrodeposits can be made competitive with electroplated chromium in terms of both wear resistance and corrosion resistance whilst being able to be processed under less stringent environmental controls. Deposits containing CoWFe were made by the addition of ferrous sulphate to the bath. The iron content of the coating could be controlled simply by altering the iron content in the bath. The as-deposited hardness of the alloy containing 30 wt.% Fe was close to that of electrodeposited

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