Materials Chemistry and Physics 76 (2002) 3845

Effect of surfactants on codeposition of PTFE particles with electroless Ni-P coating

Ming-Der Ger, Bing Joe Hwang
Microelectrochemistry Laboratory, Department of Chemical Engineering, National Taiwan University of Science and Technology, 43, Keelung Road, Section 4, Taipei 106, Taiwan, ROC Received 10 May 2001; received in revised form 7 June 2001; accepted 21 July 2001

Abstract Effects of surfactants on codeposition of PTFE particles with electroless Ni-P coating were investigated in this study. Dependence of the deposition rate of Ni-P matrix and PTFE particles on the surfactant concentration and the PTFE loading were reported. It indicates that the deposition behaviors of the Ni-P matrix and PTFE particles depends strongly on the weak adsorption of PTFE particles on the substrate, the reactivity of the surfactants (strong adsorption) and the surface coverage of the surfactant on the substrate. A theoretical model was proposed to provide a more deep insight into the codeposition behaviors. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Surfactants; Codeposition behaviors; PTFE; Electroless Ni-P coating

1. Introduction It is well known that the electroless Ni-P coating has a highly even plating capability, high bonding strength, excellent weldability, electrical conductivity, good antiwear properties, and controllable magnetic properties through suitable heat treatment. Furthermore, the mechanical and tribological properties of the electroless Ni-P coatings can be improved by the incorporation of solid particles of lubricants such as graphite, PTFE, MoS2 , etc. Due to its non-stick nature, non-galling, excellent dry-lubricity, low friction, good corrosion and wear resistance [13], the electroless Ni-P/PTFE composite coating becomes of great interest. Although the implementation of such electroless deposits has been considerably developed, very few mechanisms have been proposed to elucidate the phenomena of the codeposition of PTFE with electroless Ni-P coating and the related paper is negligible. It is noted that the role of surfactant is not negligible, particularly in Ni-P/PTFE system. Surfactants can not only improve the stability of a suspension by increasing the wettability and the surface charge of suspended particles but also enhance the electrostatic adsorption of suspended particles on a cathode surface by increasing their net positive charge
Corresponding author. Tel.: +886-227376624; fax: +886-227376644. E-mail address: bjh@ch.ntust.edu.tw (B.J. Hwang).

[4]. In addition, this positive charge (known as the zeta potential) of PTFE particle would be affected by the amount of surfactant absorbed on the surface of PTFE particle. Matsuda et al. [5] and Hu et al. [6] have proposed that the zeta potential is the dominant factor for the codeposition of PTFE with electroless nickel. In other words, it implies that as long as the zeta potential of PTFE can be changed to a positive level, the codeposition would, therefore, be carried out without any difculty. However, in our previous study [7], it appears that the amount of inert particle embedded in the codeposition layer correlates signicantly not only to the zeta potential of the inert particles, but also to the reduction reaction of the surfactants. It was suggested that the cationic surfactants on the PTFE surface has replaced the role of the hydrogen or metal ions on the SiC surface in the electro-codeposition of Co/SiC [8]. When surfactant adsorbed on the inert particle providing itself strong reduction reaction on the cathode would therefore increase the possibility for the inert particle being embedded in the codeposition layer [7]. It was reported that the reactivity of the surfactants plays an important role in the electroless Ni-P/PTFE composite coating in our previous paper [7]. The effect of the surfactant concentration and the PTFE loading on the deposition rate of Ni-P matrix and PTFE particles will be investigated in this paper. A model is also proposed to illustrate the phenomena of the codeposition of PTFE with electroless Ni-P coating.

0254-0584/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 2 5 4 - 0 5 8 4 ( 0 1 ) 0 0 5 1 3 - 2

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Nomenclature B B Cp Cs CR k k K1 K2 K Vm Vp constant in the Tafel equation relating to the particle deposition constant in the Tafel equation relating to the metal deposition particle concentration in solution (g dm3 ) the concentration of adsorbed surfactants on the particle surface reductant concentration in solution (mol dm3 ) constant of particle deposition rate expression constant in the Tafel equation relating to metal deposition adsorption constant of reductant equilibrium constant of loose adsorption constant of metal deposition rate expression deposition rate of metal ions (g h1 ) deposition rate of particles (g h1 )

used. Surfactant (FC) uorinated alkyl quaternary ammonium iodides was obtained from 3M Co. The substrate employed was low carbon steel with dimension of 10 cm 6.5 cm. The electroless plating was carried out at the conditions of pH = 5, T = 89 C, stirring rate of 300 rpm and deposition time 1 h. The weight percentage of PTFE particles in the lm was determined as follow. The lms were dissolved in nitric acid (50/50) at 100 C. After centrifuging, multiple washing in distilled water and separation of the supernatant solution by pipette, the PTFE sediment was dried at 120 C and weighed. The volume percentage of embedded particles in the deposits was determined with the technique of image analysis. Adsorption experiments of the surfactant were performed at 25 C and pH of 5. The surfactant (FC) exhibits a signicant UV absorption at 224 nm. After equilibrium, the suspension was centrifuged. Surfactant concentrations were analyzed using UVVis spectrophotometer. 3. Theoretical model 3.1. Model description A model for the CoSiC system has been proposed in our previous paper [8]. On its way from the bulk solution to deposit the inert particle must proceed through three stages: (1) the particles are transferred primarily by forced convection; (2) the particles with their adsorbed ionic cloud are adsorbed loosely at the cathode surface; (3) the particles are incorporated irreversibly into the metal matrix by the reduction of some of the adsorbed ions. For a Ni-P/PTFE system, as shown in Fig. 1, the H2 PO2 ions would reach the substrate surface and therefore release the electrons to reduce other ions. The Ni2+ ions in the bulk solution diffuse through

Greek symbols volume fraction of particle in the deposits weight percent of the embedded particle overpotential (V) 1 reductant adsorption coverage 2 surfactant adsorption coverage 3 strong adsorption coverage

2. Experimental work The electroless bath contains NiSO4 6H2 O (29.3 g l1 ), NaH2 PO2 H2 O (30 g l1 ), glycine (10 g l1 ), Sodium lactate (41.3 g l1 ), KIO3 (15 mg l1 ) and PbNO3 (0.38 mg l1 ). PTFE powders (Du Pont, 30J) of average size 0.2 m were

Fig. 1. Reaction sequence of electroless codeposition in present proposed model.

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the diffusion layer and are deposited on the surface to meet the demands of the reduction process. The partial current is consumed to reduce surfactants and H+ ions in which they diffuse through the diffusion layer from the bulk solution. The adsorbed ions proposed are surfactants and the reactivity of the adsorbed surfactants plays an important role in the deposition of the PTFE particles [7]. 3.2. Model development The weight percent of the embedded particles is determined by the deposition rate of the metal ions and particles. These two processes are discussed as follows. 3.2.1. Particle deposition In our previous study, the deposition rate of the PTFE in an electroless plating system can be established as [7] Vp = k exp(B)Cs K 1 CR 1 + K 1 CR K2 Cp (1 )2 1 + K 2 Cp (1) where Cs is the concentration of adsorbed surfactants on the particle surface, B the constant in the Tafel equation, which depends on the surfactant, the overpotential of the electroless system, K1 the adsorption constant of reductant, CR the concentration of reductant, K2 the equilibrium constant of loose adsorption, which depends on the zeta potential of the surfactant-modied PTFE particles, Cp the particle content in suspension and the strong adsorption coverage. In the present study, Ni-PPTFE composite deposits were carried out by chemical way, that is to say, without external current. If we x the operation parameter of the composition of electroless bath, temperature and pH, then

in Eq. (1) would be considered as constant. In addition, due to surfactant would be absorbed on the cathode surface, therefore, would occupy the site of the reaction area on the cathode and should not be neglected; therefore it is necessary to modify Eq. (1). It can be modied as Vp = ACs K 1 CR 1 + K 1 CR K2 Cp (1 1 2 3 )2 1 + K 2 Cp (2)

where A = k exp(B), 1 is the reductant coverage, 2 the surfactant coverage, 3 the strong adsorption coverage. 3.2.2. Metal deposition The deposition rate of metal ions can be expressed as Vm = k exp(B ) K 1 CR (1 1 2 3 ) 1 + K 1 CR (3)

where Vm is the deposition rate of metal ion and k as well as B represent the constants in the Tafel equation relating to metal deposition. The weight percent of the embedded particle in the deposits can be expressed as = Vp Vp + V m (4)

4. Results and discussion 4.1. Background In order to reasonably and efciently analyze the studied system, it is carried out by xing the concentration of the

Fig. 2. The weight percentage of codeposited dispersed PTFE particles in various concentrations of surfactant (FC) in the plating bath.

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Fig. 3. The deposition rate of Ni-P (Vm ) and PTFE particles (Vp ) is individually in various concentrations of surfactant (FC) in the plating bath.

PTFE in the plating bath, changing the concentration of the surfactant would make it possible to analyze the effect of surfactant on the weak or strong adsorption in the system (Section 4.1). Furthermore, xing the concentration ratio of surfactant and PTFE would provide the effect on PTFE loading in this system (Section 4.2). 4.2. Concentration of PTFE at 4.5 g l1 , changing the concentration of surfactant (FC) (i.e. Cp = Constant) In this section, it is attempted to study the deposition rate of Ni-P and PTFE particles under the xed concentration PTFE at 4.5 g l1 .

Fig. 2 shows the amount of codeposited dispersed PTFE particles in various concentrations of surfactant (FC) in the plating bath. It appears that the amount of PTFE would reach maximum at the concentration of 200 mol l1 and continuously increasing the surfactant concentration would result in the PTFE particles decreasing in the codeposition layer. The deposition rate of Ni-P and PTFE particles is individually shown in Fig. 3. It shows that the deposition rate of metal (Ni-P), Vm , is decreased linearly with the increased surfactant concentration; the deposition rate of PTFE particle (Vp ) thus reach the maximum deposition rate at the concentration of FC 140 mol l1 then decreased with the increased FC concentration.

Fig. 4. The volume percentage ( 3 ) of codeposited dispersed PTFE particles in various concentrations of surfactant (FC) in the plating bath.

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does the zeta potential of the PTFE particle (Fig. 7). Once the zeta potential increases, it would result in the increase of the K2 , therefore, Vp would increase. If, however, the concentration of surfactant is continuously increased, the zeta potential would reach a saturation value. Therefore, the weak adsorption effect would reach its limit and this would cause K2 to no longer increase; in the mean time, (11 2 3 ) would be continuously decreased resulting in the weak adsorption and the adsorption of reductant decrease, therefore Vp value is decreased. 4.3. Concentration ratio of FC (mol l 1 )/PTFE (g l 1 ) = 45, changing the loading of PTFE In this section, it is attempted to study the deposition rate of Ni-P and PTFE particle under the xed concentration ratio of surfactant (FC) and PTFE particles. Fig. 8 shows the amount of codeposited PTFE particles in various loading of PTFE in the plating bath under the xed concentration ratio (FC/PTFE = constant). Again, the amount of PTFE increased abruptly up to the concentration of PTFE reaches 6.3 g l1 then slightly decreased with the increased PTFE concentration. Fig. 9 shows the deposition rate of Ni-P and PTFE particles separately in various loading of PTFE in the plating bath. It clearly shows that deposition rate of Ni-P (Vm ) decreased with increasing PTFE loading; the PTFE particle deposition rate (Vp ) increased with increasing PTFE loading up to 4.5 g l1 in the plating bath then decreased again. It is noted that, Vm decreases with the increased PTFE loading. Again, when the concentration of surfactant is increased, the particle coverage ( 3 ) would abruptly increase to 27% then slightly decreased (Fig. 10). When the PTFE loading is increased, the FC concentration would be correspondingly increased, therefore the 2 (surface coverage on

Fig. 5. SEM photomicrograph of composite surface morphology showing the PTFE particles (black spots) in the matrix. The volume fraction of PTFE particle is about 25% (Cp = 4.5 g l1 , FC = 200 mol l1 ).

It is noted that Vm decreases with the increased FC concentration. When the concentration of surfactant is increased, the particle coverage ( 3 ) would abruptly increase to 25% then slowly decreased to 18% (Fig. 4). Fig. 5 shows the morphology of PTFE particle in the Ni-P matrix with the volume fraction about 25%. The adsorption isotherm (Fig. 6) shows that when surfactants (FC) were added into the solution, the remaining FC concentration would signicantly increase resulting in the enhanced possibility of surfactant coverage on the cathode. As surface coverage on the cathode (1 + 2 + 3 ) increased with increased FC concentration, it would therefore produce signicant barriers for the Ni-P codeposition, i.e. the deposition rate is decreased. Vp may be explained as: in the earlier stage, when surfactant concentration is increased, Cs would increase, and so

Fig. 6. Adsorption isotherm of surfactant (FC) on the PTFE surface.

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Fig. 7. Zeta potential of the dispersed PTFE particles in various concentrations of surfactant (FC) [7].

the cathode) would increase as mentioned above. The result of Vm decreasing would again be explained as discussed above. For the Vp curve, due to the concentration ratio of FC/PTFE is constant, then A, K and Cs in Eq. (2) would remain constant; Vp would be affected by Cp and (1 1 2 3 ) separately; when PTFE loading starts to increase, Cp would be increased. In addition, the concentration of FC in the solution is very limited in the earlier stage therefore, not surprisingly, the Vp increased with increased PTFE loading. Thus, once PTFE loading reach a critical value (4.5 g l1 ), 3 would reach 25% together

with the 2 increasing and this would result in the item (1 1 2 3 ) signicantly decreased. Therefore, this effect would be more dominantly affected than the loading of PTFE (Cp ) and this would result in the Vp decreasing. It is again demonstrated in Eq. (2) that the 2 starts with very limited value without affecting the codeposition rate of Vp . However, once the 2 reach a signicant value it would affect the (1 1 2 3 ) term in Eq. (2), therefore would lower the codeposition rate of Vp . It is noted that, as shown in Fig. 3, when deposition rate Vm is decreased, Vp is increased (FC concentration <200 mol l1 ) and this suggests that the deposition rate

Fig. 8. The weight percentage of codeposited PTFE particles in various loading of PTFE in the plating bath.

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Fig. 9. The deposition rate of Ni-P and PTFE particles individually in various loading of PTFE in the plating bath.

of PTFE particles is not dominated by the deposition rate of Vm . The increased amount of surfactants adsorbed on the surface of the PTFE particles would enhance the possibility of the weak and strong adsorption effect. This is very different to the general composite codeposition system in which Vm increased together with the Vp increasing [8]. It is also possible that increasing the amount of the surfactant would enhance the amount of the surfactants adsorbed on the cathode therefore hinder both the codeposition rate of Vm and Vp . As the particle size of PTFE (0.2 m) is much

bigger than that of Ni2+ , when the cathode surface is signicantly hindered by the presence of surfactant, the relative resistance for being deposited on the cathode surface would therefore be increased. Thus, Vp would lower down more abruptly than Vm resulting in decreasing the amount of the PTFE particle in the codeposition layer. Therefore, the optimum amount of PTFE in the codeposition layer is expected. The optimum weight percent of PTFE in codeposition layer is about 9%. This is in agreement with the earlier work, which the maximum content of PTFE in Ni-P/PTFE was reported [3,9,10].

Fig. 10. The volume percentage ( 3 ) of codeposited dispersed PTFE particles in various loading of PTFE in the plating bath.

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5. Conclusions 1. It was found that the surface coverage of the surfactant on the substrate would provide signicant barriers for the Ni-P codeposition (Vm ). 2. The increased amount of surfactants adsorbed on the surface of the PTFE particles would enhance the possibility of the weak (K2 Cp /(1 + K2 Cp )) and strong adsorption (Cs ) effect. However, surfactant would also lower down the deposition rate of PTFE particles in the codeposition layer as the surface coverage ( 2 ) is increased. The competition of the above three factors would dominate the deposition rate of PTFE particles (Vp ). 3. At the state of surfactant signicantly present in the solution, as Vp lowers down more abruptly than Vm and this would result in the limited amount of the PTFE particles in the codeposition layer. The optimum amount of PTFE in the codeposition layer is about 9%. 4. The proposed model provides a more deep insight into the codeposition behaviors of PTFE particles with electroless Ni-P coating.

Acknowledgements This work was nancially supported by the National Science Council of the Republic of China (Grant NSC-87-2212-E-014-005) and National Taiwan University of Science and Technology. References
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