Surface and Coatings Technology 107 (1998) 85–93

Electrolytic and electroless coatings of Ni–PTFE composites Study of some characteristics
E. Pena-Munoz a, P. Berc ¸ ot b,*, A. Grosjean b, M. Rezrazi b, J. Pagetti b
a Universidad de Monterry, Morones Prieto 4500 Pte., Garza Garcia, N.L., Mexico ´ de Franche-Comte ´ , 32 rue Me ´ gevand, 25000 Besanc b Laboratoire de Corrosion et Traitements de Surface, Universite ¸ on, France Received 14 April 1998; accepted 12 June 1998

Abstract This work consists of the realization and characterization of composite coatings of Ni–PTFE carried out by electroless deposition on the one hand and electrolytic deposition on the other hand, obtained by pulsed current (CPS) and d.c. current (DC ). The evolution of some properties of these coatings generated by various procedures, properties such as morphology, hardness, ductility and wear resistance, are highlighted. © 1998 Elsevier Science S.A. All rights reserved. Keywords: D.c. current; Electrolytic and electroless coatings of composites Ni–PTFE; Physical characteristics; Pulsed current

1. Introduction The deposition of particles finely dispersed in a metal matrix by the process of electrocodeposition led to a new generation of composites, which present particular chemical and physical properties. These properties depend not only on the concentration, size, distribution inside deposited material, nature and morphology of the particles, but also on the type of solution used and physicochemical parameters (pH, temperature, density of current, etc.). One recalls that a composite is a polyphase solid in which two or several components are associated in order to obtain, on a macroscopic scale and at least in certain directions, an original whole of properties which the components taken separately do not make it possible to reach [1]. Among the shapes of current most employed for the implementation of the electrolytic coatings, we used d.c. current and pulsed currents. One of the most important differences between these shapes of current is the maximum value which the density of current can reach. Indeed, the reaction of deposition consumes metal ions and therefore tends to impoverish the solution in the immediate vicinity of the cathode. This impoverishment is naturally compensated by the diffusion of metal ions

* Corresponding author.

of comparable nature which move from the centre of the solution towards the impoverished area near the electrode and which, in this way, feed the reaction. However, the speed with which the ions can diffuse in the electrolyte is limited, which restricts the acceptable intensity of current in DC. The technique of electrodeposition, called ‘‘pulsed currents’’, consists in the use of discontinuous currents, the most used according to the literature have the shape of rectangular pulses, as shown in Fig. 1. The use of pulsed currents enables very high current densities by the application of impulses of current following a rest period. The duration of the impulses must be limited in order not to drastically impoverish the cathode/solution interface in metal cations, which makes it possible to avoid the problems involved in diffusion. The rest period must be long enough to allow a sufficient restocking of this zone. The amplitude of current thus reached involves an important modification of the deposit microstructure and thus properties. A plot of transitory curves V=f (t ) makes it possible to follow the evolution of the various electrochemical processes which are established on the surface of the work electrode [2]. From these curves, it is possible to define the lower limits and higher Faradaic ranges to locate the Faradaic reaction where only the transfer of loads corresponding to the deposit occurs. Fig. 2 shows the Faradaic range obtained from the nickel sulphamate bath. This makes

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Electrolytic coating A bath containing some nickel sulphamate [8]. Coatings are obtained in an electroless way and an electrolytic way. The PTFE particles are added in the form of emulsion. Dispersion is in pseudo-equilibrium. 2. Concerning electrolytic coatings. / Surface and Coatings Technology 107 (1998) 85–93 Fig. without either brightener or antipitting agent. – the electric device made up of conductors supplying the electrodes connected to a generator of current: the whole device is controlled by a computer. 3. the form of current. Helle and Opschoor [7] were pioneers in showing that incorporation of PTFE particles by electroplating deposition depends upon two vital factors: the mode of agitation to keep the particles buoyant and the use of surfactants to keep the particles from agglomeration. Concerning electroless coatings. it possible to fix the parameters related to the shapes of current. For a better comparison of the results obtained with DC and CPS. Electrochemical device. 3): – a cell containing the electrolysis bath with a magnetic stirrer. Pena-Munoz et al. . In this latter case. 1.86 E. e. is allowed to vary. pure nickel deposits are also carried out under the same operating conditions of work.5 mm. Form of the pulsed currents. – an oscilloscope to visualize the transitory curves V=f (t ) corresponding to the current impulses. coefficient of friction and distribution of thickness). Faradaic range. – electrodes immersed in the bath: an anode made up of nickel ‘‘rounds’’ and a 12 cm2 plate of copper placed as a cathode (substrate). Fig. they are studied but still remain today a curiosity of the laboratory. stabilized using a non-ionic dampening agent. They have an average size lower than 0. In order to make a comparative study. they are well mastered and used: commercial processes exist. is used in the pH range from 4 to 5 and at a temperature of 55 °C. Niflor A [3]. hardness. ductility. namely DC and CPS. 2.g. Experimental conditions 2. The experimental device is constituted of the following elements ( Fig. The aim of this study is a better knowledge of the influence of PTFE on some characteristics of coatings (morphology.1. Many articles cover the performance of this kind of deposition [4–6 ]. we allow the parameters J and T to c c Fig.

in order to always keep the same average density of current. This value is equal m to the current density of the DC experiment. A cell with agitation induced by fluid circulation with a centrifugal pump is used.E. Micrography on the surface of a composite coating Ni–PTFE with 10 g l −1 PTFE. / Surface and Coatings Technology 107 (1998) 85–93 87 Fig. with upward circulation. has the advantage of keeping the particles suspended in the solution and of ensuring the speed of particles in the solution. 5. Electroless coatings The bath used contains nickel sulphate and sodium hypophosphite and works within the pH range from 4 to 5. Fig. Micrography on the surface of a pure nickel coating.1. . carried out in DC with J=3 A dm−2. providing the agitation. Morphology Traditional optical microscopy and electronic scanning microscopy are used to realize the various stereotypes. 2. The %P was measured by means of quantitative X-ray microanalysis. namely J =3 A dm−2.2. 3. It enables us to obtain a coating of nickel–phosphorus containing phosphorus at 10% level. A ‘‘circulation overflowing’’ cell with two compartments. one regulating the temper- ature and the other doing the plating. at a temperature of 85 °C. carried out in DC with J=3 A dm−2. Experimental results 3. Pena-Munoz et al. vary. This kind of cell. 4. was chosen.

Conversely. whereas the electrolytic coating develops in a nodular way as PTFE is introduced into the solution. the second in polishing it with various granulometries. one of the most reliable methods to observe the distribution of the PTFE particles in the nickel matrix consists of taking photographs of out-of-cut deposits. A nitric . but it is appropriate to observe the morphology and brightness changes. one electrolytic (Fig. The pure nickel deposit has a rather regular surface. 3. 6). Study of morphological cuts The observation requires three successive stages: the first consists in coating a part of the covered copper plate in a chemically inert resin. Micrography on the surface of a composite coating Ni–PTFE with 10 g l −1 PTFE. Study of the surface morphology Micrographies presented allow comparison between a pure nickel coating (Fig. 5) and the other electroless ( Fig. 6.3. Micrography out-of-cut of a composite coating Ni–PTFE with 10 g l −1 PTFE.2. 4) and nickel–PTFE coatings carried out with 10 g l −1 of PTFE in the bath. and finally a chemical attack of the surface is necessary to reveal the presence of PTFE particles incorporated in the coating. The morphology of the electroless coating nickel–PTFE is uniform and the PTFE particles are clearly visible on the surface with a homogeneous distribution. we noticed that the size of the nodules increases with PTFE concentration. Pena-Munoz et al. Fig.88 E. The surface analysis of the Ni–PTFE coatings is not the most suitable method to determine the presence of PTFE in the nickel matrix. 7. 3. Moreover. carried out in electroless plating. carried out in DC with J=3 A dm−2. / Surface and Coatings Technology 107 (1998) 85–93 Fig.

7) and the other CPS (Fig. carried out in pulsed currents with J =30 A dm−2 and c J =3 A dm−2. Comparison between electroless coatings and electrolytic ones for DC and CPS with J=J =3 A dm−2. Micrography out-of-cut of a composite coating Ni–PTFE with 10 g l −1 PTFE. 9. m Fig. They appear as black points. and an electroless coating. one DC ( Fig. 8. The micrographies presented allow comparison between nickel–PTFE coatings carried out with 10 g l −1 PTFE in the bath: two electrolytic coatings. m Fig. . Hardness measurement according to the PTFE concentration in the bath. m acid 12 N solution was used during 5 s for our experiments. Comparison between electroless coatings and electrolytic ones for DC and CPS with J=J =3 A dm−2. of size at least regular. 10.E. / Surface and Coatings Technology 107 (1998) 85–93 89 Fig. Pena-Munoz et al. Inclusion rate according to the PTFE concentration in the bath. 8). The micrographies performed show the presence and distribution of the PTFE particles in the metal matrix.

We noticed that for a level of 30 g l −1.C. 11. we noted that the hardness measurement is not influenced by the thickness. Statistical processing of several images is carried out.5. The image is then memorized under 64 nuances of grey. PTFE concentration in the bath. In addition. (2) Storage of the image in a 256×64 matrix by acquisition on computer. calibrated with a load of 300 g to obtain a print of sufficient size in order to improve the measuring accuracy. the presence of PTFE in the nickel matrix is most important. Fig. like the density of current. . we used the Jo ¨ nsson and Hogmark method [12]. described as follows. while it is relatively weaker at 50 g l −1. A percentage of black points is then estimated. Concerning the electrolytic coatings. The particles then have a tendency to agglomerate during their incorporation. / Surface and Coatings Technology 107 (1998) 85–93 From the coatings obtained. The results. able to reach 30% for a concentration of 30 g l −1 PTFE in the solution. Since the measurement Fig. which shows that the result of measurement is not influenced by the substrate and that the selected method is thus valid. Fig. (1) Acquisition and digitalization of the image using a miniature camera of type C. indicate that the rate of inclusion has a maximum in the vicinity of 30 g l −1 PTFE in the bath. this corresponds in fact to the rate of built-in particles. able to dissociate the contributions of the substrate and coating on measured hardness. Formation of the cracks in the composite coatings. (3) A thresholding operation which consists in bringing back the image from 64 to two nuances of grey: one corresponding to the ‘‘black’’ points. 3. the values show that the hardness of the coating is slightly influenced by Fig. and the other at the ‘‘white’’ bottom. the use of pulsed currents makes it possible to reach rates of inclusion up to 1.90 E. The results presented depend on the conditions of development of the deposit. etc. CPS and electroless). electroless coatings have the most important rates. with a maximum close to 12% under the best conditions. the PTFE particles seem to be irregularly distributed in the layer of nickel. Pena-Munoz et al. Measurements of Vickers’ hardness These measurements are taken on samples from approximately 10 mm thickness by using a microhardness instrument of Vickers’ type. Nevertheless. In the case of electrolytic coatings. of hardness is always influenced by the substrate. in agreement with the literature [9–11]. 3. Ductility test in accordance with the standard ISO 4524/5.7 times higher than those obtained in DC. MICAM provided with an objective of 16 mm. Consequently. 10 presents hardness measurements corrected with this method for coatings carried out with the three techniques of deposition.V. the pixel being a measurement representing an elementary point of the image. 9 reproduces the rate of incorporation (according to the PTFE concentration in the bath) and allows comparison of the three techniques of development (DC.4. 12. The technique used proceeds in three quite distinct stages. shape of current employed. Inclusion rate The processing of preceding images allows us to carry out measurements of the rate of PTFE inclusion in the layer of nickel. a counting of the inclusion forms is carried out right before calculations of surface for various levels of pixels.

concentration of PTFE particles in the bath. This test does not allow us to give a quantitative measurement. the presence of PTFE involves a significant reduction in hardness. etc. this test remains qualitative and does not allow us to know the influence of the other influential parameters. 13) reveal that. which cause rather irregular thicknesses. varies with the PTFE concentration in the bath (Fig. / Surface and Coatings Technology 107 (1998) 85–93 91 Fig. the presence of PTFE. Then. On the other hand. increasing when PTFE is added to the bath and then incorporated in the coating. tests carried out in CPS show that the coatings generally have a good ductility. The distribution thickness is directly related to the problems of edge effects. the same behaviour as in DC can be observed.E. an observation under microscope (50×) enables us to detect the formation of some cracks on the sample surface. on DC. In all cases. 13. These effects do not exist in the case of electroless coatings.84 in DC. indeed the nickel–phosphorus coating without PTFE has a hardness higher than that obtained with electrolytic coatings. 11. but only a qualitative estimate of the coating behaviour with respect to this property. Distribution thickness Here only electrolytic coatings (DC and CPS) are compared. we carried out a test in accordance with the standard ISO 4524/5. shape of current employed. a more planar surface tends to be obtained. Measurements of ductility In order to study the ductility of coatings. A series of 100 measurements (10×10) is carried out on each sample to allow a more complete statistical analysis. 10). However.8. 3. The use of pulsed currents greatly reduces edge effects. Indeed. These results are obtained in CPS when cathodic currents T are imposed c for short times. which consists in folding the samples as indicated in Fig. thus leading to more regular thicknesses and close to the awaited thickness. For the samples carried out in CPS. Moreover. and the folding angle h is 30°. The 3D representation of thickness distribution shows a significant difference when one compares pulsed current and DC. Hardness is generally larger for a given PTFE concentration in the bath. 3. This is checked by the fact that the standard deviation calculated on the whole of the measurement thicknesses reaches a minimal value of 1. The results obtained with this technique allow us to carry out a 3D representation of the measured thicknesses. as the difficulty in quantifying this characteristic is concerned. and decreases strongly to become very much lower than those in the presence of PTFE. ductility is improved by the presence of PTFE in the coating. like the density of current. The number and size of created cracks depend on the operating conditions. Coefficients of friction A standard tribometer ball/plan is used to test the tribological properties of the composite coatings . Hardness varies with the rate of incorporation of particles in the metal matrix which.11 in CPS. 3. The thicknesses of the coatings are measured with an X-ray fluorescence apparatus Fisher 1600.6. and hence the general form of the surface. usually the application of CPS appears to improve ductility. with the use of CPS. whereas it reaches 3. Thickness distribution of the composite coatings. conversely to the use of DC. as we showed previously. 12 shows some micrographies of the surface quality of the samples after the standardized tests have been performed. the observations carried out ( Fig. In this form the edge effects are clearly revealed according to the various parameters of electrolysis. The bar on which the samples are folded has a diameter of 4 mm.7. Fig. the surfaces present valleys. Only the PTFE influence is strong enough to be highlighted. Pena-Munoz et al. The operation is carried out three consecutive times. In the case of electroless plating. In conclusion.

The normal load applied to the ball is obtained by fixing weights above the wiper. and has a maximum in the vicinity of 30 g l −1 PTFE in the bath. with PTFE introduction into the solution. 14. / Surface and Coatings Technology 107 (1998) 85–93 system. The measurement is always done at the same place with each passage of the wiper (detected by a position encoder). the surface of the electrolytic coatings presents some nodules whose size increases with PTFE concentration. On the other hand. Indeed. 20 and 30 g l −1. for the coatings carried out in DC. The wiper resting against the surface is a steel ball 100 C6 having a diameter of 10 mm. The friction coefficient m decreases considerably with PTFE in the bath. The rate of inclusion increases with concentration of particles in the bath. 4. according to the number of cycles. They are distributed in a homogeneous way. The force sensor is a stainless steel beam embedded in a bracket and carrying the wiper on the other end. and N then varies from 320 to 550 cycles. at least until a limit of saturation which is in the vicinity of 30 g l −1. Fig.2% for concentrations of 10. The pure nickel deposit has a regular surface. The first test realized on the coatings without PTFE shows an important difference between the electroless coatings and the electrolytic coatings. Ni–PTFE.5 for a number of cycles higher than N. The elasticity of the . makes it possible to increase the phenomenon of stick–slip. Besides.2 and 7. wear is much faster and appears even for the first cycles. 14 shows the evolution of the coefficient of friction according to the number of cycles of wear for various samples. the morphology of the electroless nickel–PTFE coatings is uniform and the PTFE particles are definitely visible on the surface. Conclusion The type of coating (electroless or electrolytic). CPS and electroless plating were compared. Deposits in DC. The difference between DC and CPS for the conditions of pulsation used is not significant. the friction coefficient becomes stable in the vicinity of 0. This behaviour is explained by the fact that the inclusion rate in selflubricating particles in the coating is higher for strong PTFE concentrations in the bath. and the number of cycles N is higher when the PTFE concentration increases. Pena-Munoz et al. This system has the advantage of guaranteeing a constant load during the test.1. which is proportional to the effort of friction generated in the contact. Coefficients of friction. the shape of the current employed as well as the effect of the incorporation of PTFE particles appears to have an influence on certain characteristics of the deposits. Gauges of deformation stuck on the blade measure the inflection of the blade. Fig. In the case of pure nickel. relatively important with respect to the traditional tests of pawn-plan. 6. which indicates the modifications of tribological conditions. The studied surface is moved with a rotary movement at a controlled angular velocity lower than 300 tr min−1. This is probably due to the presence of phosphorus in the electroless coating. The signal delivered by the gauges is digitized and stored in the form of a file by microcomputer. It is also noted that. in all cases. the rates of inclusion are respectively 4. The evolution of the average friction coefficient is then measured. The most important rate is reached with the electroless coatings and the pulsed currents allow an increase compared to the DC.92 E.

61 (1983) 147.H. Besantels reve ˆ tements. [8] R. [6 ] S. it is higher in CPS.S. Guglielmi.T. the hardness decreases with concentration of particles. Quang. Soc. A. Finish. Duncan. Chicot. September (1989) 33. In the case of the electroless coatings. References [1] M. 119 (8) (1972) 1009.R. September (1988) 65. For ductility measurements. [3] P. Thesis. Lesage. Bain au nickel sulfamate. Surf.R. ` l’e ´ tude du me ´ canisme d’incorporation de [10] F. Interfinish 80 (1980) 234. Pena-Munoz et al. Helle. Eba. Mate ´ riaux et Techniques 1011 (1994) 19. ˆ tements composites e ´ nieur M1626 (10) (1990) 2. Proc. [11] W. Techniques de l’Inge ´ tude des reve [2] P. Contribution a particules de PTFE dans un de ´ po ´ lectrolytique de nickel: influˆt e ence d’une agitation ultrasonore. Metal Finish. ductility is improved by the presence of PTFE.S. J. [5] R. Metal Finish. Opschoor. Mater. 1998. [4] P. T. Reve ´ lectrode ´ pose ´ s. Universite c ¸ on. Tournier. with a much greater effect in the case of electroless coatings. Besanc ¸ on. . J. Plat. Universite ´ de FrancheComte ´ . Bercot. Ruimi. [9] M. E ´ s: ˆ tements d’or obtenus par courants pulse corre ´ lation entre plage faradique et certaines caracte ´ ristiques de ´ de Franche-Comte ´ . Finally. Florian. 1988.N.O.E. / Surface and Coatings Technology 107 (1998) 85–93 93 With regard to the hardness of the coatings. Ebdon. Product Technol. Trans. But these properties improve with the application of pulsed currents. the samples carried out in DC show poor characteristics. 1 (2) (1986) 290. Thesis. Inst. Metalloberfla ¨ che 34 (7) (1980) 67. Electrochem. Les Fiches Techniques G. The same holds for wear resistance. Ebdon. K. [7] K. Tulsi. Metzger. [12] D. Durete ´ de mate ´ riaux de ´ pose ´ s en couches minces.V. In all cases. the use of pulsed currents allows us to obtain coatings with more homogeneous thickness distribution. J.