ELSEVIER Surface and Coatings Technology 91-95 (1997) 513-548

Influence of the heat treatment on the abrasive wear resistance

of electroless Ni-P

Abstract

Electroless Ni-P coatings on plain carbon steel werr prepared by using an acid bath based on NiClz as source of nickel cations.
__-_ -___ Hear-_---
treatments were performed at 260’ and 300°C for 25 h and 1 h, respectively. The abrasive resistances of the coatings which suffered
different heat treatments were determined by using the modified ball cratering method, recently proposed by Staia et al. The abrasive media
employed was a mixture of 100 ml ethylene glycol and I g of 3 pm diamond paste. A RB3S.UGlOOP3 ball-bearing was used as tribological
pair. The individual wear constants for the substrate and coatings were determined from the recorded plots of the crater depth vs. sliding
distances with the aid of theory of the imposed shape wear scar reported in the literature by Kassman et al. Electron microscopy was used to
study the morphology of the worn surfaces. As a result, it was found that the heat treatment decreases the abrasive wear resistance of the
coatings. A comparison between the methods proposed by Rutherford and Hutchings and ours for assessing the wear constants is carried
out, particularly in relation to the relevance of including in the computation the value of the friction force. 0 1997 Elsevier Science S.A.

Keytrvrds: Heat treatment; Electroless Ni-P coatings; Wear resistance

1. Introduction parameters characteristic to each test. Moreover, combined

In the last two decades a variety of surface engineering
processes have been developed with the aim of enhancing
the performance of materials mainly from the wear, fatigue,
corrosion and biocompatibility point of view. Parallel with
the development of these coatings technologies, there has
been an increase in the number of methods employed to
determine the main properties and characteristics of the
produced coatings and, at the same time, an increase of
accelerated (laboratory tests) and in situ techniques able
to evaluate their tribological performance and/or corrosion
behavior. Without doubt, the accelerated laboratory tests
used to assess the tribological behavior of the coatings, in
most of the cases, are far away from describing the tribo-
logical performance of the system coating/substrate in ser-
vice conditions. Nevertheless, they have permitted the
screening of the quality of these surface engineered pro-
ducts, thus being able to accomplish the assessment of
their performance related to the intrinsic and extrinsic
* Corresponding author. Tel.: +58 582 7529017; fax: ~58 582 7529017;
e-mail: msraia@mailserver.reacciun.ve
with the information regarding fundamental properties, they
were able to contribute to optimization of the coating pro-
cessing.
Previous work conducted by us [I] has allowed us to
develop a novel test by modifying the cratering ball techni-
que, which is a standard method employed in measuring the
coatings thickness, in order to quantify the individual abra-
sion wear coefficient of coatings and substrates with the aid
of the theory of the imposed shape wear scar proposed for
the first time by Kassman et al. [2]. The materials under
study were silicon wafers, to test the data reproducibility
of the method, and Ni-P coatings as-deposited and heat-
treated. Wear test5 were conducted by using as abrasive
medium a mixture of 3 pm diamond paste and ethylene
glycol. Kassman et al.‘s [2] theory has proved to be a simple
and reproducible method for checking the mechanical qual-
ity of a thin coating by using the dimple grinder normally
employed for electron microscopygple preparation. By
applying it they have achieved a major improvement in
relation to all the existing laboratory methods for determin-
ing wear resistance [3], which until then were unable to
assess the separate influence of the substrate and the coating
on the overall tribological performance of the system.

0257~8972/97/$17.00 Q 1997 Elsevier Science S.A. Ail rights reserved

PZZ SO257-8972(97)00463-5
544 hl.H, Shin et a/. / Surjcrrce and Coatings Terhnoiog)~ 94-95 (1997) 543-548

Some other improvements, accordingly explained [ 1, 2.2. Mnterinls

51, were obtained when using the ball cratering method
instead of the dimple grinder. These are regarding two
main features: firstly, the fact that the modified ball
cratering equipment permits the delivery of the a fresh
abrasive mixture during the experiments, impeding its
degradation; and secondly, the possibility of collecting
the results for different values of sliding distances with-
out errors which can arise from the removal of the
sample.
At the same time, Rutherford and Hutchings [4], have
proposed the use of the ball cratering method to determine
the individual abrasion wear coefficients for a variety of thin
hard films and different bulk materials by using the theory
of the imposed wear scar shape proposed by Kassman et al.
[2]. There are many differences between their method and
that proposed by us. These differences can be divided into
two groups: those regarding the theoretical basis (mainly
calculation of the forces) and those regarding the test
method per se as sliding velocity, nature of the abrasive
mixture and its delivery, and the way of data collecting,
among others.
In the calculation of the forces in this test, Rutherford and
Hutchings [4] have pointed out the influence of the friction
force between the sphere and the sample in determining the
normal load for a water-based slurry. Also, they have
assumed that the friction force is equal to zero for a more
viscous liquid (glycerol) when it was used as carrier of the
abrasive particles, due to formation of a fully lubricating
hydrodynamic film.
Therefore, the present study has been conducted with the
aim of determining whether the frictional force between the
sample and the ball could be neglected for our experimental
abrasive mixture and, if not, to determine the extent of the
variation of the independent wear coefficients for electroless
Ni-P coatings on plain carbon steel, taking into account this
influence. At the same time, it will be very interesting to
discuss if this modification, not taken into consideration by
the authors in previous publications, is indeed necessary in
performing this test as a screening method in assessing the
The abrasive tests were performed on plain carbon AISI
1020 steel uncoated and coated with electroless Ni-P. All
samples were coated in an acid electroless deposition bath
by employing the procedure described elsewhere [6]. All
coated samples are practically identical, with an average
phosphorus content of 6.67% determined by using glow
discharge optical spectroscopy (GDEOS) and an average
coating thickness of 9.3 Frn determined by using the ball
cratering method. Table I presents some of the character-
istic features of the sample under study. Values of Knoop
microhardness determined by using a load of 0.98 N for 10 s
and of roughness determined by using a Mitutoyo Surftest
301 profilometer are also included.
2.3. Main test parameters
As was stated previously [l], there are three main para-
meters that should to be taken into consideration: load, test
velocity and abrasive medium. In the following treatment
only changes in load calculations will be addressed, keeping
the same sliding velocity (1.11 m s-‘) and the same abrasive
mixture.
2.4. Load cdcrhtion
When friction forces are not considered, the load exerted
on the sample, N,, has been reported [I] to be equal to:
Air bed
--WI Abrasive + Lubricant

three body abrasion wear resistance parameters of metallur-

gical coatings.

2. Experimental details

2.1. Test equipnerzr

A general view of the instrument and its attachments is

presented in Fig. 1.
The abrasive mixture of 100 ml of ethylene glycol and 1 g
of 3 pm diamond paste, magnetically stirred, was delivered
by using a glass syringe in such a manner as to ensure roll-
ing of the ball in contact with the shaft without slip, and at
the same time to provide the mixture continuously at a
constant flow value of 2.5 ml/h. Fig. 1. The test equipment and its attachments.
Table 1
Sample characteristics and heat treatments
Sample Heat treatment Roughness, KnoopIoo
R, k-d) micro-
hardness
(kg mm-‘)
Ni-P, as-deposited - 0.40 497
Ni-P 260°C for 25 h, air-cooled 0.41 795
Ni-P 400°C for 1 h, air-cooled 0.41
916
Nt = =~n~cosw -.-
case + 7
sinwcos8
where 0 = the angle between the direction of the normal
force N, and the weight of the ball, IV; w = the angle
between the weight of the ball, IV, and the distance, K,
between the two points of contact on the axis with the
ball; 0 = the angle between the reaction force on the axis,
N2, and the x direction.
This load depends on the size of the ball-bearing, the
angle between the sample and the horizontal plane, the fric-
tion force between the ball-bearing and the sample in the
presence of the slurry, and the distance from the sample to
the rotational axis.
When friction forces are taken into account, some addi-
tional geometrical parameters have to be determined
together with the value of the dynamic friction coefficient
for the tribological system under study. These measure-
ments are related to the angle between the direction of the
friction forcefi and the x axis, which is equal to the angle
between the direction of the normal force N1 and the weight
of the ball (0) and the angle between the friction forcefz and
the x axis (w). As the ball achieves a constant velocity, in a
few seconds from the start, it can be assumed that the net
torque acting on the ball is equal to zero, which implies that
fi and f2 are approximately equal.
The normal force exerted on the sample (Ni ), obtained by
combining the summation of forces in the z and x directions
represented in Fig. 2, is expressed as:
N1 = (WsinQcosa)/ ( cosQ[sinO~i (2cosw - cos@]
2.5. Determinatiorz of the cl~namic friction coeficient
The pin-on-disk method was employed for evaluating the
dynamic friction coefficient. The mandrel-holding rod was
substituted by a container which allows the positioning of
the coated sample and the addition of the abrasive mixture.
The maximum sliding velocity of 0.1 m s-’ was used in
order to avoid the abrasive mixture ejection. The experiment
was performed in air at 22°C and 35 F 5% humidity. The
pin, a ball-bearing of 6 mm diameter, was loaded with a
normal load of 1 N. The contact radius was of 4 mm and
five tests were carried out.
(1)
2.6. Collection of the results fi-orn the nbrnsive w’ear test
In a tested sample there are three sets of five craters each.
A wear test is made of three single tests and a single test is
made of five different runs, one for each sliding distance.
After each single run, the sample is rotated counter-clock-
wise and another identically but longer single run is per-
formed.
When the test is finished, the diameters of the craters are
measured in-an image analyzer. Subsequently, the worn-off
volume (V, and the crater depth (h) are easily calculated
from the measured crater diameters (D) for a determined
sliding-distance (S) and the ball radius (R).
3. Results and discussion
3. I. Deteeation ~~OJ the dynamic friction coeficient
The average value of the dynamic friction coefficient, p,
was found to be approximately 0.26 and no changes of it
with time were observed. With this value of ,LLI,the normal
load N, calculated by using eqn (2) gives a value of 0.12 N,
which is nearly 30% smaller than the value of the normal
load evaluated when the friction force between the ball and

+ sinwcosa[cos0 +p, (sin0 + 2sino)j)

(2)
Since the S and K distances are measured on the equipment,
the radius I’ is known, the angle 8 is set, the angles Q, 0 and
w can be readily found. From trigonometric considerations
and the measured values for K = 16.25 mm and S =23.92
mm, the angles Q = 25.48”, u = 80.56” and w = 3.46”have
been determined. Knowing that 0 = 80”, r = 19.05 mm and
W = 0.225 Kgf, a value of the normal load of 0.17 N was
obtained on this specific setup, when using eqn (1).
If eqn (2) is employed to calculate the normal load N1 the
dynamic friction coefficient, p, has to be determined. Fig. 2. Schematic diagram for load calculation.
546 M. H. Stain et al. / Srtrjke rind Coarings Techdog): 94-95 (1997) 543-548

the sample is not considered and therefore, a variation in

both individual wear coefficients of coating and substrate is 5 (hi-t)3
i= 1
expected. KS= (6)

where N represents the number of experimental data.

As reported by Kassman et al. [2] by using the special
case of a spherical cap shaped wear scar produced on a
coated material with a coating thickness, t, the approximate
sliding distance, SapPr.,is given by:
(3)
When dealing with only one homogeneous material as
steel, eqn (5) can be applied for the case corresponding to
h 2 t. For the heat-treated nickel electroless samples at 260”
and 4OO”C, the equation corresponding to h > t was used.
In all cases, as indicated previously [l], a high degree of
correlation was obtained between the experimental and the-
oretical points and, as an example, Fig. 3 presents the var-
iation of the crater depth vs. sliding distance for the Ni-P

( >
whereas:
coating heat-treated at 400°C for 1 h, irrespective of the
value of the normal load.

[ 1
IIhr h-i
SVPT. +h-t ifh>r The calculated values of the wear constants for every
14)
=-r 2t- Kc Ks material under study with and without considering the fric-
tion force N1 are presented in Table 2.
where h represents the depth of the crater. From the values As can be noticed, there is an increase of 30% in the
experimentally determined of S, h and t the constants Kc values of the wear constants for each material under study
and K, can be readily determined by means of the least- when the normal load is calculated by taking into account
square method. the friction force. This increase, without doubt, cannot be
Thus: considered insignificant. However, as was mentioned
above, the proposed experiment is a good accelerated
laboratory test which ensures reliability, as demonstrated
rb !gl 11:
by the experimental results. This method can be used for
I&=----- (5)
optimizing the deposition conditions, and to quantify the
L ‘5 Si relative wear constant of different coatings and substrates
i=l
produced by the same process under different conditions.
and
Nevertheless, this test is unable to simulate the real operat-

M-P
Heat treated (400°C x 1h)

300 400 500 600 700 800 900

Sliding Distance Im]

Fig. 3. Crater depth vs. sliding distance for the Ni-P coating heat-treated at 3OOT for 1 h. Velocity I. 1I m s-’ for both normal load values of0.17 N and 0.12
N.

Table 2
Calculated values for the wear constant of the samples under study for different values of the normal load A’, depending whether (with f.f.) or not (no f.f.) the
friction force was considered in its calculation
Sample Load (N)
Ni-P as-deposited No f.f. 0.17
With f.f. 0.12
Ni-P heat-treated (260°C x 26 h) No f.f. 0.17
With f.f. 0.12
Ni-P heat-treated (400°C x 1 h) No f.f. 0.17
With f.f. 0.12
ing conditions and cannot ensure that the coating will have
the same behavior. From the above discussion it is possible
to conclude three important facts: (a) the inclusion of the
friction force in the computation of the wear constants give
rise to a significant increase in the values; (b) however, in
order to take into account such a force it is required to
evaluate two additional geometrical parameters as well as
to determine the dynamic friction coefficient, which renders
the method much more complicated that the simpler and
easier method earlier proposed by us; (c) since for the
screening of the wear properties of different materials
only relative values of the wear constants are required, the
inclusion of the friction force in the calculation is irrelevant.
However, it must be specified wether or not such a force was
taken into account into the calculation if a comparison
between results of different laboratories is to be made.
Thus, this specification will become an intrinsic parameter
of the test in the same manner as is, for example, the abra-
sive mixture employed or the diamond tip radius used in the
scratch test to determine adhesion [6]. The inclusion of the
friction force implies additional experiments in order to
evaluate the dynamic friction coefficient for the system
under study, which makes the use of this simple technique
dependent on other equipments with their inherent experi-
mental errors.
The relative values of the wear constants obtained for
different conditions of electroless Ni-P indicate that there
is not a direct relationship between the coating hardness and
abrasion wear resistance, since other factors are injluencing
this behavior, underlying the fact that hardness could not be
considered as a key guide to the coating abrasive wear.
As can be observed, the abrasive wear constant, Kc, for
the Ni-P coating heat-treated at 400°C (a microhardness of
916 HKrm) is higher than the wear constant obtained when
the heat treatment was conducted at 260°C (microhardness
of 795 HKr,), results which contradict the explanation pre-
sented by Duncan [7] which attributed the improvement of
abrasive resistance of Ni-P coatings to the Ni3P particle
coarsening, as the heat treatment temperatures increase.
Also, it has to be mentioned that due to the difference
between the thermal coefficients of the coating and the
steel substrate, the coating heat-treated at 400°C presented
cracking at the surface which could negatively influence its
abrasive resistance behavior.
517
K, (m’&I) K,~$& R_’
3.57 x 10-11 - 0.97
5.06 x 10-l” -- 0.97
8.00 x IO“’ 1.85 x IO-” 0.95
11.39 x 10-14 ~ 2.62 x lo-” 4.95
1.00 x lo“:’ 5.17 x 10-I” 0.91
1.42 x 10-13 7.74 x 10-I” 0.91
As was indicated by Rutherford and Hutchings [A-], the
action of the abrasive particles within the contact will
depend on the ratio between the film thickness of a lubricant
between the sample and the ball and the abrasive mean
particle diameter, d. They proposed the following equation
in order to evaluate the lubricant film thickness, h,. This
equation represents the solution to Reynolds equation in
two dimensions for a sphere of radius R, sliding against a
plane in the presence of a viscous fluid and is expressed as:
where IVY is the normal load, ~1is the sliding speed and r
represents the fluid viscosity.
In the present investigation for values of V = 1.11 ms-.!,
R = 0.01905 m, qEthY]e,,e slycOl= 4.3 x IO-’ N m-?-S and
N, = 0.12, the film thickness has been determined to be
about 0.3 1 pm, that is to say smaller than the mean abrasive
particle diameter. In these conditions, the ratio hJd is equal
to 0.1, indicating that the abrasive particle has a major con-
tribution to the wear process. This can be corroborated by
analyzing the scanning electron micrographs of the worn
surfaces of the Ni-P coating, heat-treated at 4OO”C, which
are presented in Fig. 4a and b. Well-defined wear scars of
nearly the same width as the me-anva1u.e of the abrasi-ve
particle diameter are-observed, indicat%lg- a pure abrasion
wear mechanism, which results in the material removal due
to the cutting performed by the abrasive particles. Similar
morphologies of the worn surfaces were obtained for all the
samples under study.
It was considered [8] that when the tribosystem is com-
posed of a two triboelements and lubricant,it~qossible to
obtain an indication of the dominating lubrication or wear
mechanism by monitoring suitable test parameters such as
friction, lubricant film thickness, temperature, wear and sur-
face roughness. In these conditions, three main lubrication
regimes have been identified [9] as a function of the varia-
tion of the friction coefficient, ,LL,and the film thickness-to-
roughness ratio, A. In the present work a value of film thick-
ness-to-roughness ratio, X, equal to 0.77 has been deter-
mined, which together with a friction coefficient of 0.26
calculated previously possibly could place our system in a
boundary lubrication mode, were the tribological behavior
is governed by solid-solid friction and wear processes.
548 MH. Slain er al. / Surfiire cd
Fig. 3. (a and bj Scanning electron micrographs of the worn surface of the
heat-treated Ni-P coating [at 300°C ~for 1 h) at different magnifications.
4. Conclusions
The analysis carried out in the present work has shown
that our initially proposed method is able to quantify the
relative abrasive wear resistance of electroless Ni-P coat-
ings which have undergone different post-deposition treat-
ment conditions. Although a significant increase in the
values of the individual abrasive wear constants of the coat-
ings were obtained when the friction force was taken into
account, in our opinion, this approach will make this simple
test troublesome. The inclusion of the friction force implies
additional experiments in order to evaluate the dynamic
friction coefficient for the system under study, which
makes this test costly and dependent on other equipment
Coatings Technology 94-95 11997) 543-548
without ensuring the reproducibility of the real operating
conditions. A simple indication of the fact that the friction
force was not taken into account when reporting the wear
constants, as an intrinsic parameter, will be enough to allow
comparisons to be made with the work performed in other
laboratories.
Also, it has to be pointed out the simplicity of the test
proposed by us in reference to: {a) use of a mnch simpler
expression to calculate the load which involves parameters
that can be easily determined, (b) easy measurement of the
craters diameters for different sliding distances without the
misfit produced when moving the sample or the complicated
setup to measure crater in situ, and (c) practical and low-
cost setup for the slurry delivery attachment.
Acknowledgements
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 through
the project O&17-2789/95, and to the Organization of the
American States (OAS) through the Multinational Project
on Materials. The financial support of the Postgraduate Stu-
dies Council of Central University of Venezuela is also
acknowledged.
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