Surface and Coatings Technology 157 (2002) 282289

Electrolytic composite NiPTFE coatings: an adaptation of Guglielmis model for the phenomena of incorporation
b, J. Pagettia P. Bercot a,*, E. Pena-Munoz
a

Corrosion, Traitements de Surface et Systemes ` Laboratoire de Chimie des Materiaux et interfaces, Pole Electrochimiques, 16 route de Gray 25000 Besancon, France b Universidad de Monterry, Morones Priesto 4500 Pte., Garza Garcia, NL, Mexico Received 20 February 2002; accepted in revised form 18 April 2002

Abstract Co-deposition of inert particles in a metallic matrix enables the production of a large range of composite materials with unique properties. Previous work on examination of the effects of the variation of experimental conditions has produced some understanding of the mechanism. When stirring is carried out using a rotating disk electrode, the hydrodynamic conditions are well defined and can be taken into account. In this paper the model proposed by Guglielmi, which does not take into account agitation of the bath, has been used and modified to explain results for NiPTFE deposition incorporating a correction based on the speed of magnetic rotation. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Plating; Nickel; Polytetrafluoroethene (PTFE); Composite

1. Introduction The possibility of incorporating particles finely dispersed in a metallic matrix by plating has led to a new generation of composites that present interesting chemical and physical properties w149x. These properties depend on several variables, such as the shape and size of the particles in the plating bath and their distribution inside the composite, which is influenced by the coating structure and morphology. First of all, mathematical modelling of nickelpolytetrafluoroethene (PTFE) co-deposition is complex because the PTFE particles do not take part in any reduction reaction during the electrochemical process. The PTFE particles are non-conducting. Moreover, there is a need to introduce a dispersion of PTFE particles to avoid the problems related to difficult wettability. In this case, the magnetic stirring bar must keep the dispersion stable for the success of the operation. In order to study the co-deposition process, a magnetic stirring bar has often been used for others kind of particles w112x.
*Corresponding author. Tel.: q33-303-81-66-20-30; fax: q33303-81-66-20-33. ). E-mail address: patrice.bercot@univ-fcomte.fr (P. Bercot

Other factors also influence the composite properties, such as the nature of the bath, the type of particle w13 16x, the particle size w17x and concentration in the bath w2,7,10,14,15,18,19x, the surface charge of the particles w7,2022x, the current density w2,8,1315,23,24x, the temperature w25,26x, the pH w25,27,28x, and mainly the degree of stirring, which has to be analysed w7,20,25,29 31x. Contrary to inorganic particles, such as alumina, zircon oxide, silicon carbide and barium sulfate, PTFE particles cannot have a small negative or positive charge in an electrolytic bath w29,3139x. Among all the existing models, Guglielmis model w40x was adopted because it has been checked with different co-deposition systems (e.g. NiSiC and Ni TiO2 w40x, NiAl2O3 w41x, CuAl2O3 w42,43x, Cu TiO2 w43x, AgAl2O3 w44x, CrC w45x, CuSiC w46x, CuP w47x, ZnNi particles w35x, CoSiC w48x, Ni SiC w23x and NiMoS2 w49x). In order to develop the mathematical model, experiments were performed in solutions containing PTFE particles at different concentrations. The validation of this model for nickelPTFE coatings was carried out in direct current using mechanical stirring solutions.

0257-8972/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 2 5 7 - 8 9 7 2 0 2 . 0 0 1 8 0 - 9

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Fig. 2. Co-deposition of NiPTFE at various cathodic current density values Jc with vs500 rev. miny1.

Fig. 1. Electrochemical device.

Hydrodynamic conditions depend on the stirring bar speed v, which leads to results not validated by the predicting Guglielmi model. Taking into account the influence of hydrodynamic conditions, a correction factor was added to the Guglielmi model to adapt the mathematical model in order to predict the incorporation of PTFE particles in nickel deposits under magnetic stirring. 2. Experimental Electrolytic coatings were performed in a classical nickel sulfamate bath without brightener w50x:
Ni(NH2SO3)2 NiCl2 H3BO3 PTFE Operating conditions: pH J T v 45 17 A dmy2 55"1 8C 4001000 rev. miny1 300 g l
y1

mine the PTFE incorporation rate under different hydrodynamic conditions, the rotating speed v of the stirring bar was varied from 400 to 1000 rev. miny1. First, the copper cathode was degreased in a classical alkaline bath at 55 8C, then rinsed in deionized water and finally etched in a classical acidic bath. It was then covered with a 10-mm layer of nickel using the bath previously described. 3. Results and discussion 3.1. Description of Guglielmis model The model of Guglielmi w40x has two major objectives that aim to: Establish the influence of particle concentration in the bath over the incorporation rate in nickel electrodeposits; and Quantify the rate of particle incorporation as a function of current density. The knowledge of the curves a vs. C, in which a is the volume fraction of particles in the deposit and C the concentration of particles in the bath, has experimental and theoretical importance. The hypothesis of a Langmuir adsorption isotherm was put forward from the a vs. C curve shapes, for which a particle saturation effect is noted when the concentration increases w51x. Guglielmi based his model on the similarity between the experimental co-deposition and Langmuir isotherm curves. We reproduced this result in experiments with nickelPTFE (Fig. 2). Guglielmi deduced a connection between a and the concentration C of particles in the bath w40x:
B E C MJo 1 s exphAyB..C qCF a nFdVo Dk G

10 g ly1 30 g ly1 550 g ly1

A suspension of PTFE particles was added to the electrolytic bath. The particles had an average size smaller than 0.5 mm. Dispersion was stabilised using a non-ionic wetting agent. In order to make a comparative study, nickel deposits were also realised under the same operating conditions. The experimental set-up used to make up the electrolytic coatings included a cell (Fig. 1) into which two electrodes were placed: the anode was made up of nickel rounds and the cathode was formed by a 12-cm2 copper sheet. A stirring bar placed at the bottom of the cell was used for varying the hydrodynamic conditions. To deter-

(1)

where: a: volume % of particles in suspension in the deposit (vol.%)

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Fig. 3. Ratio Cya according to the PTFE concentration in the bath at various current density values.

h: A: B: C: d: F: J o: k: M: n: Vo:

overpotential (V) constant in Tafel equation for metal deposition (Vy1) constant in Tafel equation for particle deposition (Vy1) volume % of particles in suspension in the bath (g ly1 or vol.%) density of the electrodeposited metal (g dmy3) Faradays constant (Fs96500 C) (C moly1) exchange current density (A dmy2) coefficient of adsorption (l gy1 or vol.%y1) molecular weight of the electrodeposited metal (g moly1) valence of the electrodeposited metal constant for particle deposition (dm sy1)

3.2. Calculation of constants B and Vo If we agree with the assumption according to which the particles are fixed at the cathode by electrochemical discharge of the adsorbed cations, the electrochemical parameters B and Vo can be related to the PTFE particles. Then an approximation of the current density JcfJoeAh can be made, and the ratio B y A is calculated using the following substitution:
(B yA) (1yB yA) Joe(AyB)hsJoe(1yByA)AhsJo Jc

(2)

Substituting the last expression into Eq. (1), we obtain: as nFdVo C ByAy1) J( c ByA MJo 1ykqC. (3)

and taking logarithms, we obtain a linear relationship between log(a) and log(Jc): logasxlogC
y w
B

For coatings carried out with various current density values, the plot of C y a against C gives a series of straight lines, which converge towards the same point on the C-axis. According to Eq. (1), when C y as0, this point represents the value y1 y k, which makes it possible to obtain the adsorption coefficient value k. Fig. 3 shows the lines obtained for our nickelPTFE system. Current density was in the range of 17 A dmy2 with mechanical stirring at a rotating speed v of the stirring bar of 500 rev. miny1. C and a are expressed as a volume percentage (for C, 1%s30 g ly1). From extrapolation of the experimental linear curves, it is then possible to calculate the value of the y1 y k point of intersection with the C-axis. In our case y1 y ksy0.53 and ks1.9, which is of the same order of magnitude obtained by Guglielmi w40x for NiTiO2.

nFdVo E F ByA D MJo G

Ez C F|qByAy1.logJc. D 1ykqC. G~ B

qlogC

(4)

From the experimental results, the curves log(a) vs. log(Jc) were plotted and are shown in Fig. 4. Calculation of the slopes of the linear regression lines enables the deduction of B y A. Since all the curves are parallel, the ratio B y A remains constant whatever the PTFE concentration in the bath. The value computed for the ratio B y A is 0.66, which is close to that obtained by Guglielmi w40x for Ni TiO2, where B y As0.65. In our system, the B y A ratio is lower than 1. This means that the Ni cations adsorbed on the particles are reduced more slowly than the solvated Ni cations. The

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Fig. 4. Curves of log (a) vs. log (Jc) for the NiPTFE system at various current density values.

fact that B is lower than A can be noted and involves a decrease in a when the current density increases wEq. (3)x. For Jcs1 A dmy2, the straight regression line of the curves log(a) vs. log(Jc) cross the a-axis at the point Ko, which value makes it possible to calculate Vo. Then KoslogawJcs1xsxlogC
y w
B

Vos

yA 1ykqC MJB o F10Ko C nFd D C G

(6)

The value found for Vo was 0.072 mm sy1. 3.3. Validation and comments After we determined all the electrochemical constants of the various systems, the theoretical curves of codeposition of a vs. C were plotted using the Guglielmi expression wEq. (1)x and were compared with the experimental results. In accordance with Guglielmis theory, the co-deposition curves have the same shape and a increases with

nFdVo E F ByA D MJo G

Ez C F| D 1ykqC. G~ B

qlogC and

(5)

Fig. 5. Theoretical (dotted lines) and experimental curves (full lines) of a vs. C for each current density value, with vs500 rev. miny1.

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Fig. 6. Incorporation rate according to the stirring of the solution, at various PTFE concentrations and a current density of Jcs3 A dmy2.

the concentration of particles up to 30 g ly1. This increase is fast from 0 to 10 g ly1, slow from 10 to 30 g ly1 and finally weakly decreases from 30 to 50 g ly1. Fig. 5 gives an outline of the results. It clearly appears that all the curves have the same shape, whatever the current density value. Moreover, the connection between a and Jc is also highlighted. The rate of particle incorporation decreases when the current density increases. The Guglielmi prediction (dotted lines) remains always higher than the experimental results (full lines). 3.4. Hydrodynamic effect To study the influence of the hydrodynamic effect on the incorporation rate, we carried out tests at various speeds of the stirring bar used in the electrolytic bath. The angular velocity of the stirring bar varied from 400 to 1000 rev. miny1 and the current density was fixed at Jcs3 A dmy2 (Fig. 6). From the shape of these curves several comments can be made: There is an optimum incorporation rate, which is a function of both the particle concentration in the bath and the stirring bar speed. This optimum incorporation rate increases with both C and v. At high rotating speed, which corresponds to strong stirring of the bath, the incorporation rate decreases, whatever the PTFE concentration. The problems linked with the maintenance of particles in suspension seem to be at the origin of this behaviour. Indeed, the most significant incorporation rate for a PTFE concentration of 10 g ly1 is obtained with vs 500 rev. miny1, whereas for a concentration of 30 g

ly1, the optimum is obtained with vs700 rev. miny1. Thus, we can distinguish different hydrodynamic flows in connection with the stirring bar speed. For a fixed particle concentration C in the bath, when the angular velocity v is slow (for instance 400 rev. miny1), the incorporation rate remains low. This corresponds to a laminar flow. When v increases to values from 500 to 800 rev. miny1, the optimum of the a v curve is reached. This indicates a maximum incorporation rate (marked with a vertical arrow), which corresponds to a transient laminarturbulent flow. Finally, when v reaches values higher than 800 rev. miny1, this corresponds to a pure turbulent flow and the incorporation rate decreases. These results are in accordance with the analysis by Fransaer et al. w29x concerning the influence of fluid flow velocity, particle concentration and current density on the particle deposition rate. 3.5. Discussion Comparing experimental and theoretical curves (Fig. 5), Guglielmis model has predicted higher values than those obtained experimentally. Since the differences are always of the same nature, this means that the theoretical results depend on other parameters that are not taken into account in the model. In particular, significant parameters, such as the hydrodynamic conditions, pre-treatment of PTFE particles and components included in the sulfamate bath, are not included in Guglielmis model. Celis and Roos w42x and Buelens w52x, in their model based on a statistical approach, included the effects of several parameters of the process that Guglielmi neglected, such as the adsorption of ionic species on the particle surface, the particle nature, the ions to be reduced, the bath components and the hydrodynamic conditions.

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Fig. 7. Curve used for the calculation of parameters h and m. Results obtained with vs500 rev. miny1 and Jcs3 A dmy2.

Fig. 9. Comparison between theoretical, experimental and corrected curves for NiPTFE deposits carried out with Jc s3 A dmy2 and vs 500 rev. miny1.

They proposed a model suitable for many experimental systems that include solid particles and fine metal particles. Their model has the advantage of being validated with particles of 0.05-mm diameter, which corresponds to the average size of the PTFE particles in our system. However, they used a rotating disk electrode to control the hydrodynamic conditions in order to set up their model. In our case, which is a practical case, this model is not available since magnetic stirring does not perfectly control the hydrodynamic flow. Fransaer et al. w29x have advanced a new approach to the fundamental study of the influence of hydrodynamic conditions. Their study was based on the calculation of the forces that act on the particle and which are at the origin of their migration towards the cathode. Knowledge of the particle trajectories inside the solution makes it possible to determine the fluid velocity in the vicinity of the cathode. The fluid velocity field allows the establishment of a more complete statistical analysis, which leads to an estimate of the probability of particle capture in the coating. As our work is related to the influence of mechanical stirring, we can analyse the hydrodynamic conditions

by varying the angular velocity v in order to insert a corrective factor into the expression for a. 3.6. Corrective factor applicable to the Guglielmi model To try to evaluate the corrective factor, we have simultaneously analysed a vs. C (Fig. 2) and a vs. v (Fig. 6) curves, as the other parameters previously quoted from Celis and Roos w42x and Buelens w52x are constant. Then Eq. (3) can be written this way: as nFdVo C ByAy1) J( hfv,C. c ByA MJo 1ykqC. (7)

where f (v,C) is a function that can be determined from experimental curves and h is a constant that is available in the range of transient laminarturbulent flow. To determine f (v,C), software (MATLAB) was used for an approximation of the differences between theoretical and experimental a values to obtain a model that reproduces satisfactory experimental results. This procedure leads to a polynomial, which describes the system correctly. This polynomial has the following general form: fv.sav3qbv2qcvqd (8)

where a, b, c and d are constants computed by the software: as5.87=10y9 bsy1.31=10y5 cs8.76=10y3 dsy1.51 Since the function obtained only depends on v in the range from 400 to 1000 rev. miny1, it is possible to separate this function f (v,C) into a product of two independent functions, so that f (v,C)sf(v) f (C).

Fig. 8. Comparisons between the experimental (full lines) and the corrected model (dotted lines); Jcs3 A dmy2.

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Then asatheohfv.fC. where atheos nFdVo C (ByAy1) Jc ByA MJo 1ykqC. (3a) (9)

For calculation of the function f (C), we consider that it has the form f (C)sC m, where m is a parameter to be determined. The final formulation of a becomes: ashatheoCmfv. (10) According to the experimental results, we can plot, on a logarithmic scale, the ratio a y watheo f (v)xshC m . The parameters h and m are directly calculated by this method. For a stirring bar speed of 500 rev. miny1 and a current density of 3 A dmy2 (Fig. 7), the values for h and m are: hs0.8 and ms0.08. Inserting these values in w10x, we finally obtain: asatheo0.8Cm.fv. (11) The dotted lines in Fig. 8 show the h f (C) f (v) corrected curves obtained with this function optimised for three different concentrations of PTFE and for a current density of 3 A dmy2. When we compare the experimental results (full lines) and the corrected model results (dotted lines), we note that they are close. Thus Eq. (11) is valid when v varies, but this function has to be applied to a vs. C to validate it. Results obtained using Eq. (11) with a constant stirring bar speed of 500 rev. miny1 and a current density of 3 A dmy2 are shown in Fig. 9. Experimental curves, and theoretical curves calculated from Guglielmis model and from our corrected mathematical model are plotted. Once more the experimental and corrected curves are very close. Therefore, Eq. (11) remains valid when C varies. We finally note that the function f (v,C) is valid in the two systems, namely a vs. v and a vs. C. However, the way in which the given function is determined does not make it possible to advance assumptions on its origin. Results obtained for other current density values are shown in Fig. 10. We also note that the model remains valid independently of the current density value. Finally, the model corrected with the function f (v,C) remains valid whatever the operating conditions are, namely stirring (in the range of 500800 rev. miny1), the PTFE concentration in the bath (up to 30 g ly1) and the current density (varying from 1 to 7 A dmy2). 4. Conclusions The analysis and calculation presented in this paper indicate that the corrective factor h f (v,C) added to the

Fig. 10. Comparison between the experimental results (full lines) and the corrected model (dotted lines) at various current density values with vs500 rev. miny1.

Guglielmi model is an adequate basis for studying the incorporation rate of PTFE particles into nickel electrolytic coatings performed under magnetic stirring. The comparison between experimental results and theoretical predictions proves the predominance of the fluid flow. Magnetic stirring is not an adequate method for carrying out a fundamental study compared to the use of a rotating disk electrode for electrolytic codeposition w53x. However, the reproducibility of the experiments and the good agreement between theoretical and experimental results indicate that it is possible in the future to approach industrial problems using a mathematical model that takes into account the real hydrodynamic conditions. For instance, such a model could be applicable in the connector industry, in which products are manufactured using a reel-to-reel technique. 5. List of symbols a: atheo: h: u: s: v: A: B: C: d: F: volume of particles in suspension in deposit (vol.%) theoretical volume of particles in suspension in deposit (vol.%) overpotential (V) fraction of area occupied by particles partially incorporated in the metal layer fraction of area occupied by weakly adsorbed particles angular velocity (rev. miny1) constant in Tafel equation for metal deposition (Vy1) constant in Tafel equation for particle deposition (Vy1) volume of particles in suspension in the bath (g ly1 or vol.%) density of the electrodeposited metal (g dmy3) Faradays constant (Fs96 500 C moly1)

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h: Jc: J o: k: K o: m: M: n: S: Sl: Ss: V: Vm: Vo: Vp:

constant current density (A dmy2) exchange current density (A dmy2) coefficient of adsorption (l gy1 or vol.%y1) constant (vol.%) constant molecular weight of the electrodeposited metal (g moly1) valence of the electrodeposited metal total area of the electrode (dm2) area occupied by the weakly adsorbed particles (dm2) area occupied by the particles already fixed in the deposit (dm2) total volume (metalqparticles) deposited (dm3) volume of metal electrodeposited (dm3) constant for particle deposition (dm sy1) volume of particles strongly adsorbed (dm3)

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