Journal of Alloys and Compounds 437 (2007) 289297

The heat treatment effects on the structure and wear behavior of pulse electroforming NiP alloy coatings
Kung-Hsu Hou a , Ming-Chang Jeng a , Ming-Der Ger b,
b

Department of Mechanical Engineering, National Central University, Chung-Li, Taiwan, 320, ROC Department of Applied Chemistry, Chung Cheng Institute of Technology, National Defense University, Tahsi, Taiwan, 335, ROC Received 4 June 2006; received in revised form 22 July 2006; accepted 24 July 2006 Available online 18 September 2006

Abstract The NiP alloy coatings with phosphorous content from 8.7 to 13.9 wt.% were prepared in this study by pulse current electroforming. The effects of operating conditions of electroformed NiP coatings on the phosphorous contents and micro-hardness of the deposits were investigated. The heat treatment effects on the morphology and grain size was evaluated by X-ray diffraction. The effects of heat treatment on the hardness and wear resistance were also investigated. Our results show that the internal stress within the pc NiP deposited coating is much lower than that of dc NiP deposited coating and the phosphorus content prole is also more stable than that of dc NiP deposited coating. The grain size of as-plated NiP deposited coating is smaller than 1.5 nm, but as the phosphorus content increased, both the grain size and microhardness decrease. After heat-treated at 400 C, the hard Ni3 P phase precipitates and the grain size become gross, however, the grain size is still smaller than 5 nm. The hardness of heat-treated coating can be enhanced efciently and is well above 1000 HV. It leads to a lower wear rate for heat-treated coating. The wear resistance of heat-treated coating can be as high as 2.5 times that of as-plated coating. In addition, the wear resistance and hardness increases with the increasing of grain size for both as-plated and heat-treated coatings. It suggests that the strength and grain size of the NiP coating with high phosphorus content obeys the inverse HallPetch relationship. 2006 Elsevier B.V. All rights reserved.
Keywords: Pulse current electroforming; NiP coatings; Wear resistance

1. Introduction In recent years, due to the development and progress in scientic technology that the mechanism structures and components are in favor of small size such as in micron, sub-micron and even nano-meter. In view of nano- or micro-structural technology, the requirement in the system regulation of lithography electroforming micro-molding (LIGA) and micro-electro mechanical system (MEMS) is that the Ni-based micro-electroforming methods be given utmost importance, say for instance in Ni-based microgrinding tool [1,2], mini-motor revolving shaft and bearing [3], micro-gear train, piston-cylinder burner or mini-turbine [4]. The contact and friction characteristics of micro-tools, power device and transmission element are generally subjected to severely high temperatures, high-pressured environment and strict con-

Corresponding author. Fax: +886 3 3900714. E-mail address: mdger@ccit.edu.tw (M.-D. Ger).

tact friction mechanism [4]. However, to this day there has not been obtained a major breakthrough that will resolve difcult tribological issues. Based on the micro-component with host and passive contact, it is imperative to have a suitable tribological properties, good anti-oxidize and anti-corrosion ability, as well as high thermal stability in nickel electroforming coatings with binary development, such as NiP, NiCo and NiFe coatings [2,5,6]. Although NiFe and NiCo alloys have good hardness at room temperature, their softening phenomenon are evident when the temperature is rising, the hardness of NiP alloy, however, can be enhanced by precipitate strengthened effect which is a result of heat treatment and it promotes the hardness signicantly [7]. Among these, NiP alloy possesses high hardness, high strength and other superior mechanical properties; so that, electroless NiP alloy or composites have been approved that they are suitable used in automobiles, aviation, food, printing, chemical, and other instruments [812]. Unfortunately, the operating conditions of electroless technique are difcult to alter

0925-8388/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.jallcom.2006.07.120

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K.-H. Hou et al. / Journal of Alloys and Compounds 437 (2007) 289297 value was recorded at 1.5, with the magnetic stirrer circulated at a speed of 250 rpm. Rectangle wave was adopted for the pulse current electroform in this experiment primarily because of its provide more ner grain in plating [17]. The pulse current was provided with a model of HC-113, HOKUTO DENKO power generator, and the current regulates the onoff period that yielding symmetrical or asymmetrical electric cycle rectangle waves, in plating. Most pulse current parameters include: peak current density ip , charging time (Ton ), rest time (Toff ), duty cycle (Ton /(Ton + Toff )), and pulse frequency (1/(Ton + Toff )). The electrodeposition conditions were scope with peak current density of 520 A/dm2 , duty cycle of 0.10.5 and pulse frequency of 101000 Hz. The internal stress of coating was measured using the dual bent copper strip stress testing method by a 683 EC deposit stress analyzer. The NiP deposits was coated on one side of copper strips bands with a non-conductive varnish and plate the exposed surface to the desired thickness (approximately 3 m) in a particular plating bath. After plating, the test strip is supported in the testing stand, which measures the distance that the test strips bands have spread. The internal stress was calculated based on the distance of the test strip bands, lm thickness, density of deposit lm and calibrated constant of copper strip. The above-mentioned information are then inserted into a calculated formula that was provided by manufacturer. In this research, the reported internal stress was an average stress that represented with three measurements. The analytical used NiP coatings were deposited approximately 200 m thickness on FC25 gray cast iron disk (same as for wear test substrate) with a 32 mm diameter and 5 mm thickness. The iron disk deposited surface were rst rubbed in the polish machine causing the supercial roughing of the surface before using the chemical oil eliminator, followed by the use of de-ionized water rinse to clean it and placed as the cathodes. Each deposition condition has have been carry out three replicate tests. As the same time, all samples were sorted, selected and using the electrical wire machine cut into small area with 1 cm2 , each one condition has prepared four samples. Half of samples take and than work with heat treatment at 400 C and hold 1 h. Before and after heat-treated samples followed by hot compression mounting, mechanical grinding, polishing, and the measurement of the phosphorus content and hardness were detected with coatings cross-section layer. The electron probe X-ray micro-analyzer (EPMA) determines the phosphorus content as well as the desired mean values using three points. On the other hand, the mean value for the hardness is calculated after 10 tests, loading with 100 g and 15 s. X-ray diffraction (XRD) measurements were carried out by a MAC Science, MXP 18 diffractometer using Cu K radiation. Diffraction patterns were used to investigate the structural evolution of NiP coatings before and after heat treatment.

and are unsuitable for thick lm coating deposition. However, these characteristics of NiP alloy as well as its wear and corrosion resistances are attractive that making it has potential to become a more valuable material in the development of nano-meter sized frictional components. Nevertheless, known as having strong internal stress of direct current (dc) electrodeposited NiP alloys, there is no way of satisfying most of the electroforming requirement. The internal stress, perhaps caused by the hydrogen-permeated in coatings [13,14], shows a close correlation with electroforming conditions. Thus, before electrodeposited NiP alloy can be used, the problem of its internal stress must be solved rstly. Generally, when nickel coating is subjected to same peak current density conditions, the internal stress of its pulse current deposition (pc) is much lower than the internal stress of its direct current deposition (dc) [15]. Based on literatures, pc as compared to dc electroforming mode is more capable of reducing coating porosity and intensifying toughness [16]. The pc system is perhaps comparatively better than dc system in terms of suitability with MEMS particularly in the precise electroforming of NiP coating. Nonetheless, it seems that systematic researches on the direct correlation of the tribological or wear qualities of pc NiP coatings have seldom been published in literatures. In this research, we focused on develop a new material of NiP alloy with nano-grain size structure that produced by pc electroforming. The pc electroforming procedures were conducted with xed electrolyte chemical composition while the operating parameters of pulsed power supply were adjusted. Furthermore, optima conditions for the NiP coatings that with characteristics such as low internal stress, high phosphorus content and a specic structure would be selected in this study. The main objectives of this paper are to discuss how the coatings structure and properties are inuenced by the pulse conditions and heat treatment at 400 C, and related wear characteristics would be also presented.
2. Experimental details 2.1. Electrodeposition experiments and analysis
This research uses nickel sulfamate (320 g/L), added nickel chloride hexahydrate (10 g/L), boric acid (40 g/L), phosphorous acid (10 g/L) to make up 1 L of electrolyte. The composition of the electrolytes can be seen in Table 1. The electrolytes were placed inside a glass chamber and were stirred until thoroughly mixed. The electrolyte temperature was adjusted to 60 C and its pH Table 1 Chemical composition of NiP electrolyte and pulse current electroforming operating conditions Ni (NH3 SO3 )2 NiCl2 H3 BO3 H3 PO3 pH Peak current density Duty cycle Frequency Stirring rate Temperature 320 g/L 10 g/L 40 g/L 10 g/L 1.5 520 A/dm2 0.10.5 101000 Hz 250 rpm 60 C

2.2. Wear test of NiP alloy coatings

The friction and wear tests were carried out on a rotational wear test machine [18] using a ring on disk pair (same as thrust washer adapter). The steel ring was made by JIS SKD-11 steel and thermal treated to achieve average hardness HRC 62 1. The stationary iron disk was coated with NiP deposit with thickness about 240 m on the counter surface. Before wear test, machined contact surfaces of friction pairs were through rubbed with #600, #800, #1200 SiC abrasive sheets, and than polished with 0.25 m alumina powder using a low speed polish machine. The resulting average surface roughness values (Ra ) of the NiP coatings was 0.1 m approximately. For each deposition conditions, ve as-plated and ve heat treated (heat treatment at 400 C, 1 h) samples were prepared and then stand by for wear test. Each friction pair was cleaned by ultrasonically washed in acetone before and after each test. The weight loss of the NiP coatings was obtained by measuring the disk weight before and after each wear test, which were using an electrical balance with 0.01 mg weight scale accuracy. During the tests, the steel ring rotating at a constant velocity was pressed against the stationary NiP coating disk. All the experiments were carried out in ambient condition of temperature 25 3 C and 55 5% relative humidity. No lubrication was used during wear tests. The tests were carried out at a speed of 0.27 m/s and under a contact pressure of 0.7 MPa, and the sliding distances was 1000 m. Three replicate friction and wear tests were carried out so as to minimize data scattering, and the average of the three replicate test results are reported in this work. Wear rate was dened as

K.-H. Hou et al. / Journal of Alloys and Compounds 437 (2007) 289297 the weight loss of NiP coatings divide by the test length and the wear resistance was dened as the reciprocal of wear rate. The morphologies of the wear traces were observed using a scanning electron microscope (SEM), with energy-dispersive X-ray analysis (EDX) attached to the SEM.

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3. Results and discussion The internal stress, phosphorus content as well as hardness are compared rstly between pc and dc NiP deposited coatings in this study. The optima operation parameters for pc electroforming to form the NiP deposited coating with high phosphorus content and low internal stress are identied and used for electroforming later on to study the effects of heat treatment on hardness, structure and wear rate. Our results and discussion are presented as follows. 3.1. The effects of operation parameters of electroforming on the NiP deposited coating Fig. 1 presents various peak current densities and compares the internal stresses associated with pc and dc electroforming NiP alloy coatings. This illustration shows that the internal stresses value of dc electroforming coatings increases with the current density, at internal stresses from 115 to 325 MPa. However, pc electroforming has duty cycle = 0.1, frequency = 1000 Hz, and the internal stress of the coating increased very slightly with the current density. The range of internal stresses was 5360 MPa. Evidently, the internal stress of pc electroforming coatings is much lower than that of dc electroforming coatings. The surface morphology of newly plated coatings is such that an internal stress of over 250 MPa makes the dc electroforming coatings layer extremely brittle such that it fractures and is likely to separate from the base material. In this research, the internal stress values of the pc NiP coatings are all lower than those of the dc NiP coatings, primarily causing by the electric current has regulated on and off periods, in the pc electroforming processing. During the on periods, the reduction rates of Ni2+ and H+ ions in the surface of the cathode greatly exceeded those during the off periods. Therefore, during the off period, the hydrogen gas bubbles generated on the cathode surface experi-

Fig. 2. The phosphorus contents and hardness of NiP coatings related with pulse current deposition conditions. (a) Corresponding to different current density at duty cycle: 0.2, and frequency: 1000 Hz. (b) Corresponding to different duty cycle at current density: 5 A/dm2 , and frequency: 1000 Hz. (c) Corresponding to different frequency at current density: 10 A/dm2 , and duty cycle: 0.2.

Fig. 1. The internal stress of NiP coatings varies with the current density for direct current deposition and pulse current deposition, respectively.

ence the uid dynamic shear force, facilitating their departure from the deposition surface, without their being entrapped in the coating layer. This fact may explain why the pc of the NiP coatings had lower internal stress than dc NiP coatings. Moreover, that the excess of hydrogen was co-deposited in the coating surface is the primary cause of hydrogen embrittlement. Fig. 2 displays the relationship between the content of phosphorus as well as hardness of NiP deposit coating and the operating parameters of pc electroforming. With the duty cycle

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of 0.2 and the frequency of 1000 Hz, Fig. 2(a) illustrates that the phosphorus content of deposited coating tends to decrease as the current density of pc increased, but the micro-hardness shows a gentle enhancement. This result implies that the reductions of nickel ions are much easier with the raising current density, it inhibits the deposition of phosphorus and, consequently, the micro-hardness of deposited coating is enhanced. On the other hand, the effect of phosphorus element on the grain renement is lower since the alloying elements act as the nucleation sites to rene the grain size [19]. Meanwhile, Fig. 2(b) shows the duty cycle effects on the phosphorus content and micro-hardness of deposited coating at the pc of 5 A/dm2 and the frequency of 1000 Hz. As the duty cycle increased (reduction of off time), the phosphorus content is decreased signicantly while the micro-hardness of deposited coating increases. Concentration of the reacting species at the interface of cathode and electroplating bath is increased as the duty cycle is decreased due to an increase of rest time during the electroforming process leading to a sufcient time to the occurrence of the mass transfer. Hence, the concentrations of the reacting species at the interface, thus, are maintained, and it increases the phosphorus content of the deposited coating. As a matter of fact, a pc electroforming with a higher duty cycle behaviors like dc electroforming, it is not surprised that the phosphorus content of deposit is less than that of a lower duty cycle 1. With the current density of 10 A/dm2 and the duty cycle of 0.2, Fig. 2(c) shows that the phosphorus content increased from about 9.312.6 wt.% as the frequency increased from 100 to 1000 Hz.

The micro-hardness of the deposit decreased slightly as the frequency increased, however, the micro-hardness is still higher than 700 HV. It seems that the phosphorus content is increased due to the increase of the number of disturbance (1000 Hz) on the diffusion layer leading to an effective enhancement of transport of ions to the interface. Meanwhile, it inhibits the growth of grain and leads to the decrease of hardness. Fig. 3 shows the photographs of as-plated NiP coatings on the FC25 gray iron disk. As shown in Fig. 3(a) and (b), the surfaces of pc coatings are smooth, but Fig. 3(c) and (d) presents that the dc coatings are brittle and fractures layers are formed leading to the separation of coatings from the substrate along the circular edge. Therefore, it is regarded that the dc NiP coatings are completely unsuitable for using as the wear-resisting materials, as their internal stresses are too high. The phosphorus content varies with the thickness of NiP deposit coatings. As shown in Fig. 4, the phosphorus contents decrease as the thickness of coating increased up to about 200 m for both pc and dc NiP deposited coatings, but the phosphorus content of pc NiP deposited coating is less affected by the thickness than that of dc NiP deposited coating does. This gure reveals that the phosphorus content prole for pc deposited coating is more stable than that of dc deposited coating. It is evident that NiP deposited coating formed by pc electroforming is a promising method for producing the MEMS parts with high aspect ratio. The above results indicate that the amorphous NiP deposited coating with low internal stress can be produced by a pulsed

Fig. 3. The macro-surface morphologies of NiP coatings in which produced using different deposition conditions: (a) pc, 10 A/dm2 ; (b) pc, 20 A/dm2 ; (c) dc, 10 A/dm2 ; (d) dc, 20 A/dm2 .

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Fig. 4. Phosphorous contents of NiP coatings were distributed along the lm thickness direction: (a) pc 5 A/dm3 , 0.1, 1000 Hz; P-13.9 wt.%; (b) pc 10 A/dm3 , 0.2, 10 Hz; P-8.7 wt.%; (c) dc 5 A/dm3 ; P-5.8 wt.%; (b) dc 10 A/dm3 ; P-4.6 wt.%.

power electroforming operation. The phosphorus content and hardness of NiP deposited coatings can be varied by this electroforming process without adjustment of H3 PO3 concentration within the electroplating bath. The properties of the deposited coatings are inuenced directly by the operating parameters of the pulsed electroforming process, the hardness of the deposited coatings decreases as the phosphorus content increased which is related to the structure of the coating (crystallite size). On the other hand, it is reasonable to assume the strength of the pc NiP deposited coating is only determined by its property and structure, such as phosphorus content and crystallite size, based on the observation that the pc NiP deposited coatings in our study all have low internal stress and stable phosphorus distribution. The XRD diffraction diagram shown in Fig. 5(a) indicated that the microstructures of NiP deposit coating depend on the phosphorus content, the relative strength of Ni(1 1 1) peak becomes weak and broad as the phosphorus content is increasing. In addition, the half width ratio of diffraction peak is larger at the higher phosphorus content. It implies that the nickel crystallite lattice sizes decrease with increasing phosphorus content. These results might be ascribed to the increasing of the numbers of phosphorus atoms within the fcc Ni lattice, it causes the increase of lattice strain which will further reduce the growth rate of crystallite. Consequently, it leads to a smaller crystallite size [20]. Fig. 5(b) presents the X-ray diffraction patterns of heattreated deposit coatings. Compared with Fig. 5(a), it is obvious that the Ni(1 1 1) peak in X-ray diffraction pattern for the heat-treated deposit coating is sharper than that of as-deposited sample. The diffraction peak corresponding to Ni3 P was also been found. This could be an indication that the morphology transits from a single Ni phase to a mixture which is combined of bct Ni3 P and fcc Ni phase after heat-treated at a temperature of 400 C. The Ni3 P precipitates are preferentially located at the grain boundaries and triple junctions [21]. Since the hardness of Ni3 P precipitate is higher than that of Ni phase, the Ni3 P

Fig. 5. X-ray diffraction pattern of pc NiP coatings: (a) as-plate and (b) heattreated coatings.

precipitates provide an additional barrier to the movement of dislocation. The crystallite sizes of NiP deposit coatings with different phosphorus contents are calculated by Scherrer equation [22]: d= 0.89 cos (1)

where is the radiation wavelength, the half-maximum width, and is the diffraction angle of the main peak. The calculated crystallite sizes, listed in Table 2, showed that the crystallite
Table 2 Phosphorous content, and average grain size for both as-plated amorphous NiP coatings and coatings that treated at 400 C for 1 h P (wt.%) Grain size (nm) As-plated 8.7 10.3 11.4 12.6 13.9 1.57 1.21 0.63 0.56 0.49 Heat-treated 4.35 4.23 3.93 3.64 3.12

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sizes of as-deposited coatings all are less than 1.6 nm and their grain sizes are ner at the higher phosphorus contents. This is in agreement with observation of Lewis [20] who stated that the crystallite size is less than 1.5 nm when the phosphorus content exceeds 10 wt.% and the higher the phosphorus content is, the ner the crystallite. However, they did not investigate the hardness and wear behavior of the NiP deposited coating in that paper. 3.2. The effect of crystallite size of deposit coating on the micro-hardness and the wear rate Fig. 6 presents the phosphorus content effect on the crystallite size and hardness of the deposited coating. As shown in Fig. 6(a) for as-received deposited coatings, there is a sudden drop in crystallite size from 1.57 to 0.49 nm as the phosphorus content increases from 8.7 to 13.9 wt.%. After annealed at 400 C, their crystallite sizes are coarsened to 4.35 and 3.12 nm, respectively. Fig. 6(b) indicates that the hardness decreases as the phosphorus content increased for as-received deposited coatings. However, the hardness for all samples with different phosphorus content are promoted to over 945 HV. This hardness enhancement has mainly been attributed to the precipitation of Ni3 P phase, which

Fig. 7. The effects of phosphorous content vs. micro-hardness and wear rate for (a) as-plated and (b) heat-treated NiP coatings.

Fig. 6. The effects of phosphorous content that inuence of (a) grain size and (b) micro-hardness, for both as-plated and heat-treated NiP coatings.

strengthens the structure of deposited coating. However, the larger crystallite size after annealing might have some effects on it. Both the crystallite size and hardness of the amorphous NiP deposited coating are decreased with the increasing of the phosphorus content. Fig. 7 displays the relationship between hardness and wear rate with reciprocal square-root grain size (d1/2 ). As shown in Fig. 7, the hardness always decreases as d1/2 increased (grain size decreased), while the wear shows an opposite trend. The wear rate increases with the increasing of d1/2 . It is evident from Fig. 7(a) and (b) that the heat treatment is an efcient method to reduce the wear rate. The wear rates for heat-treated coatings, as shown in Fig. 7(b), are from about 3.6 to 7.1 103 mg/m, which are much lower than those for asplated coating (8.515.7 103 mg/m shown in Fig. 7(a)). Our results show that the NiP coating with phosphorus content of 8.7 wt.% has best hardness and lowest wear rate and the wear rate increased as the phosphorus content decreased. As a whole, the strength of amorphous NiP deposited coating with high phosphorus content increases with the increasing of crystallite size, which shows the opposite trend to the HallPetch relationship. This result is known as inverse HallPetch relationship (or breakdown), which can be ascribed to the absence of the dislocation accumulation, the occurrence of the creep diffusion, rapid

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the surface. At the commencement of the sliding, the microroughen peak of the counter-part presses onto as well as contact adhesively with the relevant deposited coating. Under these acting, deposited coating undergoes plastic deformation and shear cut as a result of the adhesive and plowing effects. It results in the development of grooves and trace of indent on the surface of deposited coating. Since the grain size and hardness increase as the phosphorus content decreased, it is believed that the wear resistance will be improved when the phosphorus content of deposited coating is lower. As shown in Fig. 8(b), it appears that the worn surface of the as-plate deposited coat-

Fig. 8. Worn surface morphology of pc NiP as-plated coatings with different phosphorous contents: (a) 13.9 wt.% P, (b) 11.4 wt.% P, and (c) 8.7 wt.% P.

dislocation annihilation at grain boundaries and softening caused by the presence of a signicant amount of grain triple junctions [21,23]. However, a complete theory is not fully developed to satisfactorily explain the experimental results. 3.3. Wear characteristics and wear resistance The worn surface morphologies for as-plated NiP deposited coating are shown in Fig. 8. For NiP coating with phosphorus content of 13.9 wt.%, Fig. 8(a) conrms the presence of abrasion trace and the occurrence of coatings delaminated from

Fig. 9. Worn surface morphology of pc NiP heat-treated coatings with different phosphorous contents: (a) 13.9 wt.% P, (b) 11.4 wt.% P, and (c) 8.7 wt.% P.

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ing with phosphorus content of 11.4 wt.% displaying only some smooth and shallow sliding abrasion traces. As the phosphorus content is further down to 8.7 wt.%, there is no plowing and plastic deformation appeared on the surface as shown in Fig. 8(c). Meanwhile, the red debris, which is identied as ferrous oxide by EDX, are distributed unirmly on the worn surface of coating. It is reasonable to consider that the iron is fragmented and transmitted to the rubbing surface from the SKD steel counterpart during the sliding period. It is, then, oxidized and adhered on the rubbing surface. The change in the wear behavior as a result of heat treatment can be noticed with the examination of the worn surface. The micrographs shown in Fig. 9 indicate that after heat treatment, the sliding abrasion trace and delaminating phenomenon do not formed any more. This is related to the precipitation of Ni3 P phase on the Ni grain boundary. The disperse strengthen effect as a result of pin force generated by the Ni3 P phase provides a resistance to the pressure and shear cut caused by the micro-roughen peak of the counter-part. The presence of red ferrous oxide debris also been observed on these heat-treated samples. This has been related to the high hardness of heat-treated deposited coating. After heat-treated at 400 C, the hardness of heat-treated deposited coating is well above 900 HV, which is higher than that of the relevant SKD11 counter-part. This means that the steel counter-surface has also been worn by the deposited coating during the sliding stage. Since the hardness increases with the heat treatment, it leads to the increase of the amount of debris on the NiP coating surface owing to the increasing of wear loss of the counter-surface as indicated in Fig. 9(a)(c). It is obvious that the wear rate of heat-treated coating is less than its relevant asplated one and the abrasion wear phenomenon for heat-treated coating is also lower. It shows in Fig. 8(c) that the debris uniformly distributed on the worn surface of the deposited coating when the hardness of the as-plated coating is above 700 HV. However, Fig. 9 indicates the coagulation of the debris. This result might be ascribed to the presence of ferromagnetic property for the heat-treated NiP coating [24] and, hence induces the coagulation of the debris.

The hardness of material represents its capability to resist the occurrence of local plastic deformation under load. It is considered that the wear resistance is related to the hardness of the material. Our results do show the existence of such relationship. From Fig. 10, it is clear that the wear resistance increases almost linearly as hardness increased. It means the wear resistance will be enhanced if the material has a bigger grain size. However, the hardness effect on wear resistance is more signicant for heattreated coatings than that for as-plated coating. This behavior can be attributed to the precipitation of hard Ni3 P phase after annealing which strengthens the structure of NiP matrix. Heat treatment increases the wear resistance of the coatings to about 2.12.5 times that of as-plated coatings. 4. Conclusion With comparison of their properties, structures as well as wear behaviors between as-plated and heat-treated coatings, our conclusion can be summarized as follow: 1. The pc NiP deposited coatings in this study display they have low internal stress. It also shows that the phosphorus content distribution along the depth direction that for pc NiP deposited coatings are more stable than those of dc NiP deposited coatings. In addition, the grain sizes of pc NiP deposited coatings are within to the nano-scale, and as the phosphorus content increases from 8.7 to 13.9 wt.%, the grain size decreases from about 1.570.49 nm and the micro-hardness also decreases from 765 to 573 HV. 2. The precipitation of Ni3 P compound within the NiP coating with heat treatment temperature at 400 C enhances the hardness of deposited coating well above 1000 HV as the gross grain is smaller than 5 nm. It results in decreasing of the wear rate. The wear resistance of heat-treated coating can be increased up to about 2.5 times that of as-plated coatings. 3. The wear resistances and hardness for both as-plated and heat-treated coating increase with the increasing of grain size, it represents that the strength and grain size for the pc NiP with high phosphorus content follows the inverse HallPetch relationship. References
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Fig. 10. The relationships of wear resistance vs. micro-hardness for both asplated and heat-treated pc NiP coatings.

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