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Wear 259 (2005) 828834

Friction and wear of electroless NiP and NiP + PTFE coatings

A. Ramalho a , J.C. Miranda b,

Universidade de CoimbraFCTUC-Dep. Eng. Mec anica, P olo II, Pinhal de Marrocos, P-3030-201 Coimbra, Portugal b Esc. Sup. de Tecnologia e Gest ao, Inst. Politec. da Guarda, 6300-559 Guarda, Portugal Received 27 July 2004; received in revised form 24 January 2005; accepted 5 February 2005 Available online 10 May 2005

Abstract In the past 30 years, electroless nickel (EN) plating has grown to such proportions that these coatings are now found underground, in outer space, and in a myriad of areas in between. The rst criteria to use electroless nickel generally falls within the following categories: corrosion and wear resistance, hardness, lubricity, uniformity of deposit regardless of geometries, solderability and bondability and nonmagnetic properties. An important property is the amorphous structure in the as-plated condition and the ability to heat treat the deposit by precipitation hardening. Moreover, in order to improve the mechanical and tribological properties of the EN coatings (NiP) further, a EN-polytetrauoroethylene (NiP + PTFE) composite coating can be obtained that provides even greater lubricity than that which naturally occurs in the nickelphosphorous alloy deposit. The aim of the present work was an investigation of the friction and wear characteristics of NiP and NiP + PTFE coatings in sliding contacts against hard chromium steel. The role of heat treatment of the coating is discussed. 2005 Elsevier B.V. All rights reserved.
Keywords: Wear; Friction; Dissipated energy; Electroless coatings

1. Introduction It is well known that the electroless nickel (EN) coating is the autocatalytic deposition of a NiP alloy from an aqueous solution into a substrate without the application of an electric current. EN coatings provide material properties that expand the physical properties beyond those of pure nickel coating systems. These coatings are widely used in the mechanical, chemical and electronic industries because of their corrosion and wear resistance, hardness, lubricity, uniformity of deposit regardless of geometries, solderability and bondability and nonmagnetic properties [1]. The mechanical and tribological properties of these deposits can be further improved by the incorporation of hard particles (SiC, B4 C, Al2 O3 and diamond) [2,3] and dry lubricants (PTFE, MoS2 and graphite) [1,35], resulting in this case in a lm with self-lubricating and excellent anti-sticking characteristics.

Corresponding author. Tel.: +351 939306676; fax: +351 271220150. E-mail address: (J.C. Miranda).

The properties and microstructure of EN coatings depend on the post-deposition heat treatment, which is frequently used to improve adhesion or to modify properties in order to satisfy the needs of a particular application. In this case, and with an appropriate temperature used in the heat treatment, there is an increase in the hardness reaching even that of commercial hard chromium coatings [2,6]. Therefore, for some applications, EN can be a good alternative to the chromium coatings without the negative environmental impact due to the chromium deposition [68]. As a result of heat treatment, the characteristics of the deposit can be changed, namely: wear, corrosion and fatigue resistance, hardness, ductility, magnetic properties and other. Maximum hardness can be achieved after a 1-h heat treatment above 360 C, depending on the phosphorous content [1,2,9]. This has been attributed to ne Ni crystallites and hard intermetallic Ni3 P particles precipitated during the crystallization of the amorphous phase [9,10]. Depending on the conditions of the heat treatment, the structure of the EN coatings has been reported to be either crystalline, amorphous or a mixture of both.

0043-1648/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.wear.2005.02.052

A. Ramalho, J.C. Miranda / Wear 259 (2005) 828834


The present work aims to investigate the friction and wear characteristics of NiP and NiP + PTFE coatings in sliding contacts against hard chromium steel. The role of heat treatment of the coating is discussed.

2. Experimental details Friction and wear were experimentally studied using a sliding tribometer with crossed cylinder contact (Fig. 1). The equipment included a rotating specimen with cylindrical shape (3) and a smaller cylindrical stationary specimen (5). The normal load was applied by a spindle/spring system (4) and was measured by a load cell (1). The stationary specimen, a hard steel AISI 52100 with 750HV30, with a diameter of 10 mm, was supported by a free rotating system, which was equilibrated by a second load cell (2) used to measure the friction force. The diameter of the rotating disc was 60 mm and the rotation speed 159 rpm, thus, the sliding speed was 0.5 m/s. This disk, of a hard high-speed steel AISI M2 quenched and tempered with 880HV30, was used as a substrate to deposit the EN coatings. The normal load was in the range from 2 to 35 N and the test duration from 4 min to 30 h, which correspond to a sliding distance from 120 to 54,000 m. The coatings were produced in an industrial plant by Tecnocrom Industrial S.A. (Barcelona, Spain) using commercial electroless nickel solutions. Five materials were tested against AISI 52100, namely, NiP as-plated, NiP heat treated (HT NiP), NiP + PTFE asplated, NiP + PTFE heat treated (HT NiP + PTFE), and uncoated AISI M2 steel.

Before testing, the specimens were cleaned with ethylic alcohol. During the test, the friction force value was periodically acquired, with time intervals of t. In each acquisition, a set of several thousand values was collected, corresponding to an acquisition time larger than the rotation period. Therefore, a calculated from the average values of the friction force, F each set of acquired data, correspond to the average value of the friction. The friction that exists in the crossed cylinder contact is responsible for an energy dissipation [11,12]. This fact leads to the occurrence of wear in the materials. Considering that the friction is the most important process related to the changes in the system energy, it would inevitably play an important role in the wear losses. In this way, the energy dissipated in the contact can be calculated as the work of the friction force. For each time interval t, to which corresponds a displacement x, the dissipated energy E can be achieved by Eq. (1). Considering the average value of the friction force and assuming a constant sliding speed Vt , Eq. (2) can be used. E=
0 l

Fa dx =

Fa Vt dt

(1) (2)

a Vt E=F

The total energy dissipated during the test can be calculated by adding all the E calculated throughout the test. At the end of the test the stationary specimen shows an elliptical-shaped wear scar (Fig. 2). On the rotating specimen, the wear produces a circumferential track. For the stationary specimen, the volume of the wear scar can be calculated assuming an imposed wear shape using the approximate expression (3) derived by Ramalho [13]. This simple equation is very accurate with errors smaller than 0.2% [13]. V = 2 h d1 d2 2 (3)

where d1 is the diameter of the stationary specimen, d2 is the diameter of the rotating specimen, and h is the depth of the scar. Each scar is measured by taking the dimensions of the larger, a, and the smaller, b, dimensions of the wear surface

Fig. 1. Sliding tribometer with crossed cylinder contact.

Fig. 2. Typical wear scar of the stationary specimen.


A. Ramalho, J.C. Miranda / Wear 259 (2005) 828834

Fig. 3. The scanning electron micrographs of as-deposited coatings: (a) NiP and (b) NiP + PTFE.

(Fig. 2). This calculation method is well explained in an early publication [12]. The chemical composition, structure and morphology of the coatings were characterized with electron probe microanalyses (EPMA), X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The XRD was performed in a Philips X-Pert with a Co K radiation. Some of the EN specimens used for friction and wear tests were heat treated at 290 C for 10 h. The coatings microhardness was measured using a Struers Duramin equipment with Vickers indenter and a load of 50 g applied for 15 s.

Table 1 Coatings microhardness Material Hardness (MPa) As-plated NiP NiP + PTFE 5660 4880 Heat treated 9560 7250

3. Results and discussion All the coatings studied had a thickness of approximately 8 m, which was measured by the crater grinding method [14]. SEM was used to examine the coating surfaces in order to observe the morphology details (Fig. 3). In this picture, the surface of the NiP coating appears very dense and the composite coatings display large PTFE particles embedded in the nickelphosphorous matrix. The average surface roughness of the coatings was similar for both NiP and NiP + PTFE with the value of 1.12 m (Ra ). XRD was used to analyse the effect of the heat treatment on the coating structure. The X-ray spectra reveal that in the

as-deposited state, lms are amorphous either with or without PTFE (Fig. 4). In both cases, the heat treatment leads to the coatings crystallization and the phases -Ni, NiP and Ni3 P were identied. The effect of the crystallization was rst analysed by measuring the surface microhardness before and after the heat treatment. Table 1 represents the average microhardness, revealing that the heat treatment signicantly improves the coating hardness. The formation and ne dispersion of the hard phases NiP and Ni3 P justify the rise in microhardness resulting from the heat treatment. Similar results were obtained by Shoufu et al. [10]. In general, the wear of the moving specimens could not be measured because of two reasons: the EN coatings were very hard with a very small wear track; in the cases where the track was more in depth, the value of the roughness of the substrate made it impossible to accurately evaluate the corresponding wear volume. Only the wear of the stationary specimen has been evaluated applying Eq. (3). For each test

Fig. 4. X-ray diffraction pattern of EN coatings: (a) NiP and (b) NiP + PTFE.

A. Ramalho, J.C. Miranda / Wear 259 (2005) 828834 Table 2 Wear results of all the performed tests Materials NiPAISI 52100 Case 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 Normal load (N) 2 2 5 5 5 5 2 5 2 3 2 2 5 5 5 10 5 5 2 Sliding distance (m) 300 450 450 120 600 3600 10800 8100 27000 54000 9000 14400 12150 9000 18000 9000 900 1800 900 Wear volume (mm3 ) 0.0037 0.0070 0.0307 0.0386 0.0395 0.0019 0.0008 0.0030 0.0058 0.0216 0.00057 0.0008 0.0018 0.00071 0.0043 0.0034 0.0777 0.2815 0.0189


Dissipated energy (J) 269.05 606.00 1108.12 1841.16 406.00 9005.99 11064.96 19397.33 29438.14 95970.11 9648.66 16585.17 47196.87 27193.52 61256.37 62266.79 2510.69 6925.81 480.27

HT NiPAISI 52100

NiP + PTFEAISI 52100



the dissipated energy has been calculated using Eq. (2) and the procedure was outlined. Table 2 shows the results of all performed tests. The procedure based on the dissipated energy, previously described, was applied to all the tested cases. The results presented in Fig. 5 have good linear correlation between the volume removed by wear and the dissipated energy. However, the NiP coating shows a lower correlation, because in some of the tests the substrate was locally reached. Besides the energetic approach, a specic wear rate was also calculated. The wear coefcient or specic wear rate, k, was generally calculated based on the Archard [15] equation, dividing the wear volume by the sliding distance and the normal load: k= V XL (4)

This classical approach is based on the linear evolution of the wear volume, V, with both the sliding distance X and the normal load L. In the present work, the wear tests were done for several normal loads and sliding distances. Therefore, according to Eq. (4) the specic wear rate k can be calculated as the slope of the linear evolution of the wear volume against XL (sliding distance times normal load). Fig. 6 displays the obtained results. The slope of the linear equations is the specic wear rate values. The tested materials t linear laws with a minimum correlation of 0.93 expressing adequate accuracy of the experimental results. Table 3 summarises the wear results, also including the average value of the friction coefcient. If we compare the results obtained by both approaches, the ranking of the different materials is similar. Fig. 7(a) shows that the NiP coating lifted up close to the edge of the wear track. This reveals that these lms have poor

Fig. 5. Wear volume against dissipated energy on the tested materials. (NiP + PTFE data integrates the NiP + PTFE and the HT NiP + PTFE points.)


A. Ramalho, J.C. Miranda / Wear 259 (2005) 828834

Fig. 6. Wear volume against XN for the tested materials. (NiP + PTFE integrates the NiP + PTFE and the HT NiP + PTFE points.) Table 3 Average values of the friction coefcient and wear rates Materials NiP HT NiP NiP + PTFE HT NiP + PTFE AISI M2 Specic wear rate (mm3 /N m) 1.52 105 1.44 107 4.76 108 4.76 108 3.74 105 Energy wear rate (mm3 /J) 1.52 105 2.37 107 6.45 108 6.45 108 3.11 105 Friction coefcient 0.62 0.53 0.83 0.7 0.53

adhesion. When tested after heat treatment, the lm did not lift up and we can see a mild evolution of the wear track (Fig. 7(b)). Thus, the heat treatment, beyond the increase in hardness, leads to higher adhesion of the lm to the substrate, improving markedly the wear behaviour. The results of the wear study can be summarized as following: Adherent NiP coatings, with or without PTFE, have signicantly superior properties to the hard high-speed steel AISI M2, leading to lower specic wear rates k, up to approximately 3 orders of magnitude. Heat treatment noticeably improves the tribological behaviour of the NiP coatings.

Concerning the NiP + PTFE coatings, the heat treatment was not effective on the improvement of the wear resistance. Comparing the results obtained for the as-deposited coatings, the coating with PTFE displays a wear coefcient 2 orders of magnitude lower than the NiP. However, contrary to previously expected view, the addition of PTFE seems not to be effective on the friction reduction. The explanation to the highest behaviour of NiP + PTFE, in spite of their lower hardness (Table 1) could be dependent on the effect of the mild PTFE particles (Fig. 3(b)) on the stress dissipation. The NiP coatings display a signicant spalling (Fig. 7(a)), probably due to their high level of internal stress,

Fig. 7. The scanning electron micrographs of wear tracks: (a) NiP as-deposited and (b) HT NiP.

A. Ramalho, J.C. Miranda / Wear 259 (2005) 828834


Fig. 8. Worn surface morphology: (a) HT NiP and (b) NiP + PTFE.

while the NiP + PTFE coatings were always gradually removed. The test results show that the addition of PTFE seems to be not effective in the friction reduction. This can be explained by the fact that the phosphorus content by itself leads to low friction and the PTFE lubrication effect is not enough to balance the effect of increasing the surface roughness induced by the PTFE particles. A detailed view of the wear tracks reveals that the NiP coating is worn by a ne abrasion, whereas the NiP + PTFE shows local fractures in the neighbourhoods of the PTFE particles identied by the arrows in Fig. 8(b). These pits clearly increased the roughness values, and so the friction coefcient was also increased. However, it was not possible to measure the roughness directly on the wear track because it was too short, approximately between 100 and 200 m. In Figs. 5 and 6 the experimental points corresponding to the NiP + PTFE with and without heat treatment are represented by the same line because the results obtained revealed that the experimental points t the same linear relationship. Therefore, in spite of the hardness rise, the heat treatment does not increase the wear resistance. Certainly, this could be related to the same local fractures, which could be deeper in the HT NiP + PTFE, because of the lowest plasticity of the coating.

(1) All the coatings improve the wear behaviour of the hard high-speed steel AISI M2 substrate. (2) In the EN deposits, and due to the weak adherence of the lm, the worst results were obtained for the NiP lm as-deposited. (3) The heat treatment produces lms with higher hardness. Concerning the wear resistance, the heat treatment was very effective on the NiP coatings, while the NiP + PTFE coating reveals the same wear resistance in both cases: as-deposited and heat treated. (4) The introduction of PTFE particles in the electroless NiP coatings produces a signicant rise in the wear resistance.

Acknowledgements This work was carried out under a project funded by the Portuguese Foundation for Science and Technology (POCTI/33710/EME/2000). The authors acknowledge the help of Tecnocrom, S.A., Barcelona, Spain, in providing EN coatings.

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4. Conclusions In this study, the friction and wear behaviour of several electroless NiP and NiP composite coatings with PTFE particles was investigated. The hard high-speed steel used as a substrate was also tested, as a reference. Some of the EN coatings were heat treated. Dry sliding tests against a hard steel AISI 52100 counterface with a crossed cylinder contact geometry were carried out. The results showed that:


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