Wear 266 (2009) 873–877

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Short communication

Friction behavior of lubricated zinc phosphate coatings

M.C.M. Farias a,∗ , C.A.L. Santos b , Z. Panossian b , A. Sinatora a
a
Surface Phenomena Laboratory, Department of Mechanical Engineering, School of Engineering, University of São Paulo, CEP 05508-900, São Paulo - SP, Brazil
b
Corrosion and Protection Laboratory, Institute for Technological Research, Cidade Universitária, CEP 05508-901, São Paulo - SP, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The aim of the present work is to elucidate the influence of lubricants on the friction behavior of zinc
Received 19 October 2006 phosphated coatings and provide an explanation for the results in terms of physical–chemical interactions
Received in revised form 18 August 2008 between lubricant and phosphate. The friction behavior was studied through a sliding wear test, with a
Accepted 9 October 2008
conventional ball-on-disc configuration. Discs, made of AISI 1006 low carbon steel, uncoated and coated
Available online 30 October 2008
with zinc phosphate, were tested against bearing steel balls. A stearate sodium soap, paraffinic oil and
both soap and oil were used as lubricants. The sodium stearate soap was found to have the best seizure
Keywords:
resistance. The nature of the interfacial forces between the lubricant and surface has an important role in
Zinc phosphate coating
Friction
determining the friction behavior.
Lubricants © 2008 Elsevier B.V. All rights reserved.
Corrosion resistance

1. Introduction formance of phosphated and lubricated layers. The equipment

Zinc phosphate is a chemical conversion coating exten-
sively used in sheet metal forming (bending, stretching and
deep-drawing) and cold forging processes in which high level defor-
mation is produced [1–5]. Even though the coatings can prevent
metal-to-metal contact between the tool and the sheet surfaces in
the early stage of deformation, they do not have efficient intrinsic
low-friction properties due to their friability [2]. Thus, a lubricant
is applied on the zinc phosphate layer before forming operations
(post-treatment). The addition of a low-friction soap (i.e. sodium
stearate) has been established as a technological procedure. A
second option is the addition of a mineral oil film [1,6], which,
additionally, offers protection against corrosion to the sheet during
storage and transportation before the forming process. When cor-
rosion protection is necessary, the use of soap as a lubricant requires
an additional way of protecting the sheet. Either adequate packag-
ing or an extra layer of protective oil may be used for this purpose.
Despite being widely applied in sheet metal forming and forging
processes, the soap-plus-oil procedure appears to be only based on
practical experiences and no information has been found about its
theoretical fundamentals or even about systematic experimental
results that support this practice.
Studies have been developed concerning the relationship
between the phosphating process parameters and the friction per-
∗ Corresponding author. Tel.: +55 11 3091 9855; fax: +55 11 3814 2424.
E-mail address: crffer@usp.br (M.C.M. Farias).
development for the evaluation of contact conditions similar to
those corresponding to cold forming processes [7–10] has shown
that parameters as temperature, concentration, immersion time
and phosphate bath aging, as well as substrate type and its
pre-treatment [11–13] can significantly affect the useful life of
phosphated and lubricated layers.
However, little information on zinc phosphate stearate coating
behavior has been found, probably due to confidential problems
[8]. For this reason, this work was conducted to study the friction
behavior of lubricated zinc phosphate coatings produced in lab-
oratory, for the same zinc phosphated conditions (zinc phosphate
coating weight, sodium stearate and zinc stearate film weight; coat-
ing roughness; phosphate crystal size and porosity), in order to
evaluate the effect of zinc phosphate coatings and lubricant films
on the friction force behavior and also to suggest an explanation
for the results in terms of physical–chemical interactions between
lubricants and the zinc phosphate layer.
2. Experimental procedures
A conventional ball-on-disc configuration using a standard
Plint&Partners machine (Fig. 1) was used for the sliding wear tests.
In all experiments, a normal load of 150 N was applied on the
bearing steel ball and a rotational speed of 30 rpm was applied on
the carbon steel disc, which corresponded to a 0.06 m s−1 tangential
velocity. During the tests, the tangential (friction) and normal forces
were continuously measured with load cells and were acquired
at a 10 Hz rate. With these contact conditions, it was possible to

0043-1648/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.wear.2008.10.002
874 M.C.M. Farias et al. / Wear 266 (2009) 873–877

Fig. 1. Schematic representation of the ball-on-disc configuration used in sliding

wear tests.

qualitatively determine the surface treatments quality, which is

related to the number of revolutions for the occurrence of the lubri-
cant film’s breaking down. This parameter may be considered an
indicator of the seizure resistance or of the lubricant film’s lifetime.
The sliding wear tests were carried out in both controlled room
temperature (23 ◦ C) and relative humidity (35–40%). At least three
tests were performed for each experimental condition in order to
evaluate the occurrence of lubricant films’ breaking down. The sam-
ples without lubricants were cleaned ultrasonically with acetone Fig. 2. Zinc phosphate coating (SEM).
and dried with a hot air stream before and after the tests.
Discs with a diameter of 63 mm and a thickness of 1.15 mm,
3. Results
made of AISI 1006 low carbon steel, were used in the sliding
wear tests. The steel had ferritic microstructure and hardness of
3.1. Analysis of general friction behavior
101 HV30 . Balls with a diameter of 6.35 mm, made of AISI 52100
bearing steel, were used as counter bodies. This bearing steel had a
The evolution of the friction coefficient is presented as a function
martensitic matrix with carbide particles and hardness of 886 HV30 .
of the number of cycles for the different tests conditions, consider-
The carbon steel discs were phosphated in a laboratory plant,
ing steel surfaces without phosphated coating: Fig. 3(a) bare steel
according to the following steps: alkaline degreasing; water rins-
and bare steel with oil; Fig. 3(b) bare steel with soap and bare steel
ing; acid pickling (H2 SO4 1.0 mol L−1 ); water rinsing; refining
with soap and oil.
(Gardolene V-6513); phosphating (Gardobonde 210 for 53 s of
In Fig. 3(a), it was observed that the bare steel presented an
immersion); water rinsing; neutralizing (alkaline solution) and hot
abrupt increase in the friction coefficient during the first disc
air drying. For all these steps, similar process conditions were used,
revolution up to a 0.98 maximum value. Afterwards, the friction
mainly the ageing of phosphate baths and the phosphating time.
coefficient decreased and stabilized at a lower value of 0.5. This
After phosphating, lubricant films (i) sodium stearate soap, (ii)
value was associated to metal-to-metal contact.
paraffinic oil and (iii) both soap and oil (soap–oil) were applied
The friction coefficient of the oiled steel was characterized by
on the discs. These lubricants were applied on the zinc phosphate
the occurrence of several peaks in the initial period of sliding con-
coated surfaces and on the bare carbon steel surfaces, in order to
tact and a subsequent sudden increase up to 0.75, a lower value
strengthen the role of the zinc phosphate layer as an important
when compared to the bare steel, Fig. 3(a). The initial peaks, with a
lubricant carrier. The oil was of an aliphatic base, which has corro-
maximum value of 0.35, suggest the occurrence of an early breaking
sion protection characteristics and was used for comparison with
down of the oil film and a consequent seizure.
the soap lubricant. The nonlubricated and lubricated bare steel,
In the case of the soaped steel, the seizure also took place almost
as well as the nonlubricated zinc phosphate coating were used as
instantaneously, and the application of paraffinic oil on the soaped
three reference tests, which were compared with the lubricated
steel did not modify this trend, as observed in Fig. 3(b). The occur-
zinc phosphate coatings, representative of the cold forming condi-
rence of several peaks in the friction coefficient of the soaped–oiled
tions.
steel reflects the influence of the oil lubricant. The last three curves
previously explained showed a period of stabilization similar to
2.1. Characterization that of the uncoated steel.
The friction behavior of the zinc phosphated steel with and with-
The following tests for zinc phosphate coatings characteriza- out lubricants is shown in Fig. 4. When the steel was phosphated,
tion were performed: sodium stearate film and zinc stearate film the behavior of the friction coefficient was almost similar to that of
weight measurements (gravimetric method) [2]; coating roughness the non-phosphated steel described above, with the exception of
(Ra) measurement; phosphate crystal size determination (scan- the initial values, which showed a maximum of 0.63 against 0.98
ning electronic microscopy—SEM) and porosity evaluation (cyclic for the uncoated steel, as shown in Figs. 3(a) and 4(a). This fact can
voltammetry) [14–16]. be related to the friability of the zinc phosphate coating [2].
The weight measurements obtained under the aforemen- A better behavior was obtained in the case of the phosphated-
tioned laboratory conditions for the zinc phosphate coating, oiled steel, Fig. 4(a), in which a low and steady-state friction
sodium stearate and zinc stearate were 2.65 g m−2 , 0.74 g m−2 and coefficient was observed for a higher number of revolutions.
0.37 g m−2 , respectively. The zinc phosphate coating had roughness After this steady-state, an increase in the friction coefficient was
of 0.47 ␮m Ra, crystal size of 24.3 ␮m and porosity of 4 (num- observed at a critical number of revolutions. This fact was also
ber of cycles). The SEM of the zinc phosphate coating revealed a associated to the oil film breaking down. In the last step of the slid-
scaled-like crystal structure (Fig. 2). ing contact, the friction coefficient increased continuously until it
 M.C.M. Farias et al. / Wear 266 (2009) 873–877 875

Fig. 3. Ball-on-disc test results corresponding to the evolution of the friction coeffi-
cient versus the number of revolutions for the bare steel: (a) unlubricated steel and
oiled steel; (b) soaped steel and soaped–oiled steel. Fig. 4. Ball-on-disc test results corresponding to the evolution of the friction
coefficient versus the number of revolutions for the zinc phosphate coating: (a)
unlubricated phosphate coating and oiled phosphate; (b) soaped phosphate coating
reached a higher and constant value of 0.45, which represents the
and with oiled–soaped phosphate coating.
metal-to-metal contact for this study (see Fig. 3).
A much more satisfactory friction behavior was observed when
the zinc phosphate coating was lubricated with soap or with both
soap and oil, as can be seen in Fig. 4(b). In both cases, the lubricated
coatings were able to resist without any seizure until the sliding test
was completed, showing a low and steady-state friction coefficient
of 0.12, which was confirmed by SEM analysis of the worn surface
(Fig. 5).
In a general way, it was observed a change in contact condi-
tions during the test for the non-phosphated steel, as well as for
the phosphated steel without lubricant (reference tests). The fric-
tion coefficient presented high fluctuations at the beginning of the
test and, later, stabilized around a high value. In contrast, for the
lubricated zinc phosphated surfaces, at the beginning of the test
the friction coefficient remained steady around a low value, which
is typical of the industrial lubrication conditions of conformation
processes.
In order to compare the behavior of non-phosphated and phos-
phated steel, the number of revolutions for the occurrence of
lubricant films breaking down was plotted on a bar graph form
(Fig. 6). This parameter may be considered as an indicator of the
seizure resistance or the lifetime of lubricant films. From Fig. 6(a)
it can be noticed that only the soap lubricated steel exhibited a sig-
nificant high seizure resistance. In addition, the soap lubrication
was the only effective post-treatment for steel surface that limited
friction rising. However, the oil controlled the lubrication perfor-
mance and, therefore, it diminished the low-friction property of the Fig. 5. Worn zinc phosphate stearate coating (SEM).
876 M.C.M. Farias et al. / Wear 266 (2009) 873–877
Fig. 6. Ball-on-disc test results corresponding to the seizure resistance: (a) non-
phosphated steel; (b) phosphated steel.
soap lubricant when applied on the soap film, considering the lower
value of seizure resistance under the soap–oil lubrication condition.
In the case of the phosphated steel, the soap and soap–oil
post-treatments showed the highest seizure resistance, as can be
observed in Fig. 6(b). However, the soap controlled the lubricant
performance, since the seizure resistance did not decrease when
the oil was subsequently applied. The controlling effect of the soap
lubricant applied on the phosphated steel contrasted that of the
uncoated steel, in which, as explained above, the oil controlled the
lubricant performance.
Comparing the non-phosphated steel samples with the zinc
phosphated ones, Fig. 6(a and b), it is possible to verify that all the
seizure resistance values of the phosphated steel were greater than
those of the non-phosphated steel. The oil post-treatment on the
phosphated steel resulted in a three-time increase in the seizure
resistance, in relation to the non-phosphated steel. The application
of the soap on the phosphated steel resulted in an increase in the
seizure resistance by a factor of ten. The application of the soap–oil
post-treatment produced an unfavorable effect on the seizure resis-
tance of the non-phosphated steel, whereas for the phosphated
steel the seizure resistance did not change.
3.2. Physical–chemical analysis of friction behavior
In order to understand the results shown above, the adsorption
theory of solid films was used and the type of adsorption occurring
within a few nanometers of the surfaces was considered as a crit-
ical factor in determining the frictional behavior of the lubricants.
Fig. 7. Schematic representation of the lubricant layers adsorbed on the zinc phos-
phate surface: (a) adsorbed paraffinic oil layer; (b) adsorbed sodium stearate layer.
Looking at the friction evolution in Figs. 3 and 4, it is not surprising
that the lubricated zinc phosphate coated steel exhibited a dramat-
ically better friction behavior than the lubricated uncoated steel.
Probably, molecules of the lubricants attached themselves to the
uncoated steel surface by weak van der Waals forces. In this case,
both paraffinic oil and sodium stearate films were readily removed
by rubbing action and offered no real protection against metal-
to-metal contact [1,17]. On the other hand, the phosphate coating
strongly bounded by chemical reactions to the surface of the metal
served as an effective carrier for the lubricants.
Despite the clear improvement obtained with the phosphate
coating, there are differences between the lubricants performance.
In fact, Fig. 7(a and b) show that the evolution of the zinc phos-
phate coating friction coefficient was distinctly different from the
oiled, soaped and soaped–oiled conditions. Such differences could
be associated to the lubricant chemistry and adsorption mech-
anisms. Since paraffinic oils have nonpolar characteristics, their
attachment to the substrate occurs in a parallel alignment to the
surface, Fig. 7(a). This kind of attachment provides a weakly bonded
adsorbed layer with high shear strength, which suffered a conse-
quent early breaking down [17]. The low value of friction coefficient
observed during the first hundred revolutions could be attributed to
the effect of the initial roughness of the coating surface that could
act as a lubricant carrier. The breaking of the thin oil film occurs
when asperity peaks are worn out.
In the case of the sodium stearate, a portion of the soap lubri-
cant molecules reacts with zinc phosphate forming zinc stearate,
while the other part is adsorbed (probably by chemisorption) with
the end-groups (carboxylic groups) adhered strongly to the zinc
stearate coating [2,3]. The molecule chains tend to align perpendic-
ularly to the surface, Fig. 7(b), stabilized by their mutual repulsion,
and form dense monolayers. Therefore, the adsorbed film exhibits
a reasonably low shear strength, resists to removal, limits junction
growth and protects against metal-to-metal contact, leading to a
longer period of a low friction coefficient [1,17], i.e. a lubricant film
with more durability, as shown in Fig. 6(b). In Fig. 7 it is possible to
observe that molecular properties of lubricant films, i.e. chemical
identity of the end-group, the structure and the orientation of the
organic compounds are important in determining lubricant perfor-
mance for friction reduction. It is important to add that a single
monolayer of few nanometers of an adsorbed lubricant was able to
 M.C.M. Farias et al. / Wear 266 (2009) 873–877
prevent metal-to-metal contact, as well as to reduce friction. Our
results are similar to Zisman’s pioneering work on the friction, dura-
bility and wettability properties of monomolecular films on solids
[18]. Zisman has carefully demonstrated the ability of monomolec-
ular films in decreasing the friction coefficient of rubbing solids.
The satisfactory friction behavior of the phosphated steel simul-
taneously lubricated with soap and oil may be explained by the fact
that the steel ball sunk through the outer oil film and then made
contact with the disc over the chemisorbed soap layer. Thus, the
friction reduction ability of the oil film placed on the previously
soaped coating was essentially the same as the adsorbed layer of
a polar material (i.e. sodium stearate) on the zinc phosphate coat-
ing. This result also confirms the work of Zisman that compares the
frictional behavior of monolayer of a polar compound adsorbed on
the solid/air and solid/liquid interfaces [17,18].
4. Summary
A study was conducted to evaluate the friction behavior of
lubricated zinc phosphate coatings under laboratory conditions. A
sodium stearate soap was found to be more effective in increasing
seizure resistance than a paraffinic oil. This effect was more pro-
nounced in the case of the zinc phosphated surface when compared
to bare steel. The worst results observed for the oil are related to the
fact that paraffinic oil molecules are attached to bare steel and to
phosphated surfaces by weak van der Waals forces. Such physical
adsorption means that this oil film is readily wiped off and offered
no real protection against asperity contact. The best behavior of the
soap lubricant is attributed to the fact that stearate molecules react
with zinc phosphate and are adsorbed by chemisorption with the
polar end-groups strongly adhered to the zinc stearate layer, lead-
ing to a longer period of a low-friction coefficient, i.e. a lubricant
film with more durability. The nature of the interfacial forces has an
important role in determining the lubricant performance, as well
as the properties of the adsorbed lubricant film.
Acknowledgements
The authors greatly acknowledge the financial support offered
by FAPESP and Brasmetal Waelzholz S.A.
877
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