Surface and Coatings Technology 86-87 (1996) 598-602

Wear performance and mechanism of electroless Ni-P coating

M.H. Staia av*, E.J. Castillo a, E.S. Puchi a, B. Lewis b, H.E. Hintermann ’
a School of Metallurgical Engineering and Materials Science, Central University of Venezuela, Apartado 49141,
Caracas 1042-A, Venezuela
b Materials Research Institute, Shefield Hallam University, Shefield, UK
’ University of Neuchatel, Neuchatel, Switzerland

Abstract

An electroless Ni-P coating has been deposited onto an AISI 1020 plain carbon steel by using an acid bath based on NiCl,, as
source of nickel cations. The tribological behavior under dry non-lubricated conditions has been evaluated by employing the pin-
on-disc test, where the pin was made of AISI 52100 steel. The effects of the heat treatment carried out at 400 and 260°C for 1
and 25 h, respectively on the hardness, friction and wear behavior of the coatings were investigated and compared against the
properties of the unplated and as-deposited samples. Both optical and electron microscopic techniques were used to study the
wear surface. It was shown that the wear resistance was greatly increased with both heat treatments, the treatment performed at
400°C being a little more effective, although no influence was observed on the frictional coefficient.

Keywords: Wear mechanism; Wear-resistant coatings; Surface modification

1. Introduction microstructure, adhesion, corrosion resistance, wear and

fatigue. This complete study will allow the tailoring of
Autocatalytic chemical Ni-P deposits have been used the optimum conditions for an excellent tribological
extensively in many industries due to their wear and and/or corrosion performance. The present work reports
corrosion resistance [ 11. Most of the studies to determine the results regarding wear and friction behavior of
the wear resistance of electroless nickel coatings were electroless nickel obtained from an acid solution (pH =
devoted to coatings produced from solutions based on 5.2) with NiClz as cation source and sodium hypophos-
NiSO, as cation source [2,3]. The wear behavior of phite as reducing agent. A microscopic analysis of the
electroless nickel has been evaluated mostly under dry wear process is also presented.
non-lubricated conditions and two mechanisms :
adhesion and abrasion were quoted as mechanisms
involved in the failure of these coatings [4]. Accord-
ing to Ma and Gawne [ 51 the wear behavior of electroless
nickel is very much a function of the test method 2. Experimental details
and almost all wear mechanisms involve more than a
single process, although it is common for one type to The bath was prepared with analytical grade reagents
dominate. dissolved in distilled and de-ionized water. The sub-
In our laboratory, a systematic study was undertaken strates were plain carbon steel AISI 1020. The samples,
with the aim of identifying the influence of the nature discs of 22 mm diameter and 10 mm height, were metal-
of the plating process (composition, pH, %P) and the lographically prepared with 800 grade Sic papers and
characteristics of the post heat treatment (temperature cleaned ultrasonically in acetone. All samples presented
a rugosity of 0.05 mm. The pretreatment procedure used
and time) on the properties of electroless nickel, such as
prior to plating consisted of: ( 1) distilled water rinse,
(2) cleaning with soap, (3) distilled water rinse, (4)
*Corresponding author. Tel.: 582 7529017; fax: 582 7529017; soaking in acetone in an ultrasonic bath for 15 min, (5)
e-mail: mstaia@dino.conicit.ve. distilled water rinse, (6) cleaning by using an alkaline

0257-8972/96/$15.00 0 1996 Published by Elsevier Science S.A.

PZZSO257-8972(96)03086-l
 M. H. Staia et al./Surface and Coatings Technology 86-87 (1996) 598-602
solution of NaOH ( 10%) at 60°C for 15 min, (7) distilled
water rinse, (8) pickling in a 1: 1 HCl, and (9) distilled
water rinse.
Using a series of selection tests the bath formula and
the plating conditions were the following: 32 g 1-i
NiCl, .6H,O; 25g1-’ NaH,PO, . H20; 14gl-’
Na2C4H404. 6Hz0; temperature, 88 k 2°C; pH = 5.2;
volume/area = 60 ml cm-‘; time = 1 h.
The circular discs were suspended in the plating
reactor by steel wires which were passed through a small
hole drilled on the outer edge of the each disc. After
plating, the average thickness was determined after five
measurements using the ball cratering method. Despite
the differences in opinion concerning the structure of
the as-deposited electroless nickel, most investigators
agree that it becomes crystalline when heated, with the
precipitation of N&P. The mechanical properties are
sensitive to phosphorous content and to the heating
temperature, reaching a maximum hardness to about
400°C [6], and one tenth of the wear rate of untreated
plating [7]. It has been shown [3,8] that heat treatment
in the region around 200°C will not bring any improve-
ment to coating properties, such as hardness and
adhesion, for Ni-P alloys with medium and high
percentage of phosphorous deposited on a steel sub-
strate. Taking into account these findings, the heat treat-
ment in the present work was performed in a tube
furnace in argon, with 1 h heating at 400°C and
25 h at 260°C respectively. It was reported [9] that
no change in hardness occurs until the temperature
exceeds 260°C and temperatures below this value are
normally used to produce the hydrogen embrittlement
relief. Hardness measurements were performed using a
Knoop indenter and a load of 100 g (0.98 N) for a
loading time of 10 s. The average value of 10 measure-
ments on three different samples, produced under the
same conditions, was taken as the reported hardness
value.
Pin-on-disc tests were carried out to examine the
friction and wear properties. The tests were operated
under non-lubricated conditions in air with a relative
humidity of 40+ 5% and an ambient temperature of
22k 1°C. The pin of 6 mm diameter, made of AISI
52100 (63-66 HRC), was loaded with a normal force
of 2 N against the disc specimens and rotated with a
sliding velocity of 0.1 m s-l. The contact radius was of
8 mm and the duration of the test of 130, 520 and
1040 m sliding distance. Ten tests were carried out for
each pin-disc combination.
The depth profiles of the wear track were evaluated
by using a Mitutoyo Surftest 301 profilometer.
The morphologies of the wear tracks were examined
by using optical and scanning electron microscope. The
phosphorous content of the nickel electroless coatings
produced was determined using glow discharge optical
emission spectroscopy.
599
3. Results and discussion
3.1. Hardness of coatings
The average thickness of the samples was determined
to be 10.2 mm with an average phosphorous content of
6.7%. Fig. 1 presents the results obtained from the
hardness measurements performed on the samples under
study. As observed, due to the thermally induced micro-
structural changes, in both cases heat treatment had a
pronounced influence on the hardness value compared
with the value corresponding to the as-deposited state.
The maximum hardness value of 916 HKloo (0.63 GPa),
obtained when the samples were annealed at 400°C for
1 h, is due mainly to the precipitation of the intermetallic
N&P structure [lo], which is a very hard phase embed-
ded in the ductile nickel matrix, which corresponds to
Ni-P alloys with 7%P according to the phase diagram.
When the heat treatment temperature was 260°C for
25 h, the hardness increased to 795 HK 10,,(0.55 GPa).
It has to be mentioned that the high microhardness
value of 279 HKloo (0.19 GPa) obtained for the AISI
1020 steel is due to its previous mechanical history. The
hardness value of the as-deposited condition agrees with
the value between 500 and 700 HV or HKroo for Ni-P
deposits with around 6-7%P [ 11.
3.2. The friction and wear characteristics of the coatings
Fig. 2 presents the dependence of the average friction
coefficients with the sliding distance for all four samples
tested. By analyzing these results it has to be stressed
that, for small sliding distances, there are appreciable
differences between the friction coefficients correspond-
ing to the samples in the as-deposited condition and
those which have been treated, the former being higher.
However, for higher sliding distances this difference
tends to be decreased. In this later case, the friction
116.61
Fig. 1. Bar diagram showing the hardness values for the samples
under study.
600 M.H. Staia et al.ISurface and Coatings Technology 86-87 (1996) 598-602

1
0.9
%
0.8 ?’
3 0,7
g 0,6
k 0.5
0
g 0,4
0
z 0,3
e
5 032
IL 0.1

0
0 100 200 300 400 500 600 700 600 900 1.000
SLIDING DISTANCE (m)

Fig. 2. The relationship between friction coefficients and the sliding

distances used in the pin-on-disc test.

coefficient increased from about 0.28 to about 0.7 after

about 200 m of sliding distance (Fig. 3). The increase
in the p value is very sharp for the as-received coatings,
which contrasts with the gradual increase of this value
for the treated samples. This increase, which depends
on the sliding distance (for values higher than 180 m),
may be attributed to the difference in changes in the Fig. 4. The typical track depth profiles for all the samples after slid-
true contact area and the shear stresses in each tested ing 1040 m.
condition (as-deposited and heat treated). It has been
shown [ 111, that the higher ductility, which is character-
istic of the coatings in the as-deposited condition, allows
the formation of debris which, when added to the fact
that these coatings present smaller hardness, contribute
to an increase in the contact area between the tribologi-
cal pair. The steel discs presented an intermediate beha-
vior with a smaller variation of ~1. In general, it was
quoted [ l] that there exists a very large range of reported
p values and the high friction coefficients values mea-
sured here agree well only with the values of ~=0.6-0.7
reported elsewhere [ 12-141. The wear produced during 0 200 400 600 800 1.000 1.200
the pin-on-disc test was reported as the wear depth. SLIDING DISTANCE (m)

Fig. 4 represents a comparison between all wear profiles

Fig. 5. Wear of the samples investigated in pin-on-disc tests.
measured for a sliding distance of 1040 m, meanwhile
Fig. 5 represents a comparison between the wear depth
obtained. As can be seen, severe damage occurred for the as-deposited conditions, reaching a scar depth of
15 mm for 1040 m sliding distance, due to its inherent
properties, such as ductility, low hardness and an appar-
’ I
ent poor adhesion. The wear depth for steel discs was
03 j
I smaller, presenting a value of 10.5 mm. Both heat treated
; 0.7
samples had shown a better resistance to wear, although
5u 0.6 samples which have been treated at 400°C for 1 h were
E 0,5 slightly superior showing a wear depth of 3.5 mm for
8 the same sliding distance.
d” 0,4 I
0,6
Optical and electron micrographs for the samples
are presented in Fig. 6 and Fig. 7, respectively.
Microstructural examinations by both techniques have
shown that for the as-deposited condition, adhesive
0 10 20 30 40 50 60 70 80 90 100 110 120 130 transfer occurred and the coating morphology presented
SLIDING DISTANCE (m)
torn patches and some detachment of the coating. For
Fig. 3. Details of the relationship between friction coefficients and the the steel discs, the wear track illustrated a terrace
sliding distance at the beginning of the pin-on-disc tests. morphology due to the relatively higher ductility of the
 M. H. Staia et al.lSurface and Coatings Technology 86-87 (1996) 598402 601

Fig. 6. Optical micrographs showing wear of: (a) unplated steel sample; (b) as-deposited electroless nickel sample; (c) heat-treated electroless nickel
sample at 260°C for 25 h; (d) heat-treated sample at 400°C for 1 h.

Fig. 7. Scanning electron micrographs (tilting 30”) of the wear tracks for 130 m sliding distance of: (a) unplated steel sample; (b) as-deposited
electroless nickel sample; (c) heat-treated electroless nickel sample at 260°C for 25 h; (d) heat-treated sample at 400°C for 1 h.

steel. When heat treatments were applied to the samples, grooves along the wear track. The broadening of the
less adhesive wear occurred and abrasive wear occurred. wear tracks could also be noticed from the optical
Due to the fracture of these brittle coatings, loose debris micrographs shown in Fig. 6; the sample in the
is generated which, in contact with the surface of the as-deposited condition presented the highest. It has to
coating, displaces the material to the side forming be pointed out that the same procedure for microstuct-
602 M.H. Staia et al./Surface and Coatings Technology 86-87 (1996) 598-602
ural characterization was performed for the pins
employed in each test. The results obtained have shown
the presence of grooves only for the heat treated samples,
a fact which confirmed the type of predominant mecha-
nism indicated for each tribological pair under study.
4. Conclusions
The electroless nickel coating in the as-deposited state
exhibits high rates of wear. The severe wear of the
as-deposited coatings against AISI 52100 steel pins may
be related to adhesive wear, and the susceptibility to
abrasive wear is much less than that observed for heat
treated samples. The wear resistance of both electroless
nickel coatings which have been heat treated increased
considerably, although small differences were obtained
for the friction coefficient corresponding to both treat-
ments. The present investigation has shown that the
highest wear resistance and hardness were obtained for
samples heat treated at 400°C for 1 h.
Acknowledgement
The authors wish to acknowledge the financial support
of National Council for Scientific and Technological
Research of Venezuela (CONICIT) through the project
Sl-2612, to the Council for Scientific and Humanistic
Development (CDCH) of the Central University of
Venezuela, and to the Organization of the American
States (OAS) through the Multinational Project on
Materials.
References
[l] W. Riedel, Electroless Nickel Plating, Finishing Publications Ltd.,
1991, p. 2.
[2] G. Mallory, J. Hajdu (eds.), Electrolessplatbtg: Fundamentals and
Applications, American Electroplaters and Surface Finishers Soci-
ety, AESF, 1990, p. 123.
[3] K. Parker, Plating Surf Finishing, 68(12) (1981) 71.
[4] C.M. Li and K.N. Tandon, J. Mater. Sci., 29 (1994) 1462.
[5] U. Ma and D.T. Gawne, Galuanotechnik, 76 (1985) 1650.
[6] A.H. Graham, R.W. Lindsay and H.J. Read, J. Electrochem. Sot.,
112 (4) (1965) 401.
[7] K. Matsukawa, A. Ichikawa and M. Kobayashi, Proc. of the
Japan Inter. Trib. Conf. Ser. 1 (1990) 10.
[S] E. Broszeit, Galuanotechnik, 75, (1984) 2.
[9] R.N. Duncan, Metal Finishing, March (1990) 11.
[lo] D.T. Gawne and U. Ma, Mater. Sci. Technot., 3 (1987) 228.
[ 111 F.P. Bowden and D. Tabor, Friction and Lubrication of Solids,
Oxford Press, Vol. 1, 1964.
[12] S.S. Tulsi, Finishing, 11 (1983) 10.
[ 131 E. Schmelling and G. Schmitt, Uberfache Surf, 2.5 (1984) 140.
[14] J.P. Randin and H.E. Hintermann, J. Suisse Horlogerie, 5/6
(1967) 1.