Tribol Lett (2013) 51:469–478
DOI 10.1007/s11249-013-0185-z
ORIGINAL PAPER
Durability of ZDDP Tribofilms Formed in DLC/DLC Contacts
Balasubramaniam Vengudusamy • Jonathan H. Green
Gordon D. Lamb • Hugh A. Spikes
Received: 5 June 2013 / Accepted: 3 July 2013 / Published online: 17 July 2013
Ó Springer Science+Business Media New York 2013
Abstract The tribological properties of diamond-like
carbon (DLC) coatings have drawn much attention of
OEMs and lubricant manufacturers in recent years. It is
important to know whether conventional friction modifier
and antiwear additives can form durable films and work as
effectively with DLCs as they normally do on steel sur-
faces. In this study, the film-forming and friction properties
of the antiwear additive ZDDP and the strength of tribo-
films formed by this additive on five widely used DLC
types, namely a-C:H, a-C:H:W, a-C:H:WC, Si-DLC and ta-
C, have been investigated. It is found that ZDDP-derived
tribofilms form on all the DLCs but exhibit different fric-
tion characteristics based on DLC type. With all DLCs, the
amount of tribofilm elements measured after durability
tests was less than that measured initially. Over 90 % of
thiophosphate and 70 % of sulphide/sulphate were lost
during durability tests. ZDDP tribofilms were found to be
strongly adhered on Si-DLC and a-C:H compared with the
other DLCs. The ZDDP tribofilms formed in DLC/DLC
contact appear to be similar in structure to those formed in
steel/steel contact but not to exhibit the antiwear perfor-
mance seen in steel/steel contacts.
Keywords DLC coatings
ZDDP tribofilm durability

Lubrication mechanism
Boundary lubrication
Friction

ToF–SIMS
B. Vengudusamy (&)
H. A. Spikes
Tribology Group, Department of Mechanical Engineering,
Imperial College London, London SW7 2AZ, UK
e-mail: b.vengudusamy07@gmail.com;
b.vengudusamy07@imperial.ac.uk
J. H. Green
G. D. Lamb
Castrol Ltd, Pangbourne, Reading RG8 7QR, UK
•
1 Introduction
In recent years, diamond-like carbon (DLC) coatings have
begun to appear attractive for automotive parts because of
their excellent friction and wear resistance properties.
However, establishing general rules for DLC’s behaviour
with existing engine oil additives has been a challenge as,
in practice, there are many different types of DLC coating
available for use, varying in terms of hydrogen content,
nature of carbon–carbon bonding, presence or absence of
metallic or non-metallic doping elements and their con-
centration. It cannot be assumed that these different types
of DLC will all interact in the same manner with a par-
ticular additive. Since lubricant additives rarely have con-
trol over the type of DLC used in machine components,
lubricant manufacturers need to produce oils that are
effective with many types of DLC coating.
Although there have been some studies on DLCs with
ZDDP or AW/EP additives in recent years [1–14], the
findings are quite contradictory. Some studies have repor-
ted that ZDDPs form tribofilms on DLC coatings [1–4, 6,
11–14] while some have reported they do not and/or that no
tribochemical reaction occurs between DLC and additive
[5, 7–10]. In a previous publication, the authors have
explored the possible reasons for such contradictory results
and have reported that concentration of elements present in
DLC coatings (e.g. H, W) can greatly affect the film-
forming, adhesion and wear properties of ZDDP [15].
It should be noted that most of the DLCs available today
were initially developed for applications other than auto-
motive industry and, indeed, often for non-lubricated
applications. Despite this, these DLCs have generally been
found to be suitable for lubricated automotive parts.
However, there is still a lack of understanding of how
different DLCs respond to various engine oil additives,
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470 Tribol Lett (2013) 51:469–478

especially to ZDDP. In particular, little is known about the
durability of ZDDP tribofilms formed on DLC surfaces
compared to those on steel surfaces. It has been suggested
that ZDDP tribofilms formed on DLC surfaces are easily
removable, either when washed ultrasonically [2] or when
the tribofilms are externally scratch-tested [3], both
apparently indicating that tribofilms are weakly adhered to
the DLC surface, which might explain some contradictory
results in the literature. However, these studies were lim-
ited to only one DLC type, a-C:H.
It is of great interest to know how strongly or weakly
ZDDP tribofilms are adhered to DLCs since this is likely to
control their effectiveness as antiwear additives and is also
quite likely to depend on the composition of the DLC
surface. In the current study, examples of all the main types
of DLC have been obtained from various suppliers and
their behaviour in terms of ZDDP film formation and
durability has been studied when lubricated by ZDDP
solution in base oil.
2 Materials and Test Methods
Diamond-like carbon (DLC) coatings were deposited on
the test specimens normally used in the mini-traction
machine (MTM), i.e. AISI 52100 steel balls and discs, of
hardness 760 HV and roughness Rq of 10 nm. Hardness
and elastic modulus, chemical composition and hydrogen
content, and sp3 % of all the DLC coatings were measured
using Fischerscope HM2000, SEM/EDX and ERD, and
Raman spectroscopy, respectively. Details of these mea-
surements are described elsewhere [16].
Five different types of DLC coating, namely hydrogenated
amorphous carbon (a-C:H), tungsten-containing hydrogenated
amorphous carbon (a-C:H:W), tungsten carbide-containing
hydrogenated amorphous carbon (a-C:H:WC), Si-containing
DLC (Si-DLC) and tetrahedral amorphous carbon (ta-C), were
studied, and their properties are listed in Table 1. All DLC
coatings had thickness in the range 3–4 lm. Contact mode
AFM topography images of all the DLCs before testing were
obtained and are shown in Fig. 1. Tests were conducted on
DLC/DLC tribopairs, i.e. with DLC-coated ball and DLC-
coated disc. Although DLC/steel tribopairs are more com-
monly used in practice, the use of DLC/DLC tribopairs high-
lights any interactions between the ZDDP additive and DLC.
The base fluid used in this study was an API Group III oil
having density of 0.78 g/cm3, viscosity of 3.32 cP and effective
pressure viscosity coefficient of 16.3 GPa-1 at the test tem-
perature of 100°C. The ZDDP additive had a primary alkyl
structure and was used at a concentration that gave 0.08 wt% P
in the base oil solution.
Friction tests were carried out using a ball-on-disc MTM,
where a 19 mm diameter DLC-coated ball was loaded and
rubbed against a DLC-coated disc immersed in lubricant
solution. The friction test conditions used in this study were as
follows: applied load = 31 N, corresponding to an initial
Hertzian contact pressure of ca. 1 GPa; entrainment
speed = 0.1 m/s; slide–roll ratio = 0.5; tempera-
ture = 100°C; test duration = 2 h. The entrainment speed
was defined as (ub ? ud)/2, where ub and ud are, respectively,
the speed of the ball and disc with respect to the contact, while
the slide–roll ratio SRR was defined as the ratio of sliding
speed |ub - ud| to entrainment speed. The calculated lambda
ratio (ratio of calculated elastohydrodynamic lubricant film
thickness to composite surface roughness) ranged from 0.3 to
0.5, so the operating lubrication regime was mixed-boundary
lubrication. The testing method adopted to assess the dura-
bility of ZDDP tribofilms had seven steps as follows.
1. A reference 2 h MTM test as per the conditions
mentioned above was carried out in base oil (BO)
using a fresh set of DLC-coated samples.
2. A normal 2 h MTM test was carried out in ZDDP
solution using a fresh set of DLC-coated samples.
3. The specimens from step 2 were ultrasonically washed
in cyclohexane.
4. ToF–SIMS chemical mapping was performed on the
DLC disc after testing in ZDDP solution and washing.
5. A 2 h MTM test was carried out in base oil solution
using the same specimens that were tested in step 2,
i.e. in ZDDP solution.
6. The specimens from step 5 were ultrasonically washed
in cyclohexane.

Table 1 List and details of DLC coatings investigated

No. Materials H W Si sp3 No. of Interlayer/ Rq Hardness Elastic modulus Deposition
(at.%) (at.%) (at.%) (at.%) layers inclusionsa (nm) (HV) (GPa) technique

1 a-C:H 20 – – 25 1 – 12 2460 ± 145 175 ± 7 PECVD

2 a-C:H:W 15 18 – 15 4 Graphitea 14 1318 ± 35 165 ± 3 PVD/PECVD
3 a-C:H:WC 15 14 – 25 3 Cr 35 1250 ± 80 140 ± 7 PVD
4 Si-DLC 20 – 3 30 1 Ti 32 1315 ± 130 90 ± 3 PVD/PECVD
5 ta-C 1 – – 75 1 – 40 6793 ± 350 473 ± 25 PVD
a
Inclusions

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Tribol Lett (2013) 51:469–478
a-C:H a-C:H:W a-C:H:WC
Fig. 1 AFM topography of DLC coatings before testing (scan size = 2 9 2 lm)
7. ToF–SIMS chemical mapping was performed on
washed DLC disc.
Each MTM test lasted for 2 h. An initial Stribeck friction
curve was taken prior to beginning of the test, by measuring
friction while varying entrainment speed in stages from 0.007
up to 3.5 m/s at a fixed slide–roll ratio of 0.5. Then prolonged,
slow speed rubbing was carried out in the mixed/boundary
lubrication condition mentioned above. Periodically, after 5,
15, 30, 60 and 120 min, the slow speed test was halted and a
Stribeck curve was taken. However, in this paper, only the
Stribeck curves taken initially and after 2 h rubbing are pre-
sented. After testing, the discs were ultrasonically washed in
cyclohexane before the wear tracks were examined by ToF–
SIMS IV instrument (ION-TOF GmbH, Münster, Germany)
using Ga? ion beam. The test method was designed mainly to
understand the strength of tribofilms and to determine whether
ultrasonic washing of samples and/or rubbing can remove the
films. The former is assessed by ToF–SIMS results obtained in
step 4 while the latter is assessed by comparing Stribeck
curves obtained in steps 2 (contact supplied with ZDDP) and 5
(contact not supplied with ZDDP, i.e. base oil test of tribofilm-
generated DLC surface) and by comparing ToF–SIMS results
obtained in steps 4 and 7.
3 Results
In order to understand the film-forming properties of ZDDP
and strength of tribofilms, DLCs were tested initially in
base oil for 2 h, followed, in order, by ZDDP solution and
base oil as per the procedure described in the previous
section. Friction coefficient versus entrainment speed
(Stribeck) curves were obtained for DLC/DLC tribopairs.
471
60.00 nm
Si-DLC ta-C
0.00 nm
Five Stribeck curves, namely Stribeck curves obtained
initially and after 2 h rubbing in base oil (step 1, described
in previous section), a Stribeck curve obtained after 2 h
rubbing in ZDDP solution (step 2), initial and final Stribeck
curves in base oil (step 5), were compared for all DLCs and
are shown in Fig. 2. It can be seen from Fig. 2 that ta-C
gives consistently lower boundary friction than the other
types regardless of lubricant solution (ZDDP or base oil).
This indicates that the typical low-friction property of this
DLC coating is not influenced by the lubricant, unlike other
DLCs. In general, boundary friction depends on the type of
DLC coating, and in most cases, both with and without
ZDDP, boundary friction was found to be in the following
ascending order, ta-C, a-C:H, a-C:H:W, a-C:H:WC and
Si-DLC [1]. One interesting observation, in contrast to
steel/steel lubricated by ZDDP, is that these DLCs do not
show increased friction in the intermediate speed region
after rubbing with ZDDP. This is probably because ZDDP
does not form thick pad-like structures on DLCs as they
typically do on steel surfaces. A detailed friction analysis
can be found elsewhere [1, 16].
In the current study, the Stribeck curves shown in Fig. 2
were used to understand the formation (when ZDDP is
supplied to the contact, step 2) and removal/non-removal
(when no ZDDP is supplied to the contact, step 5) of ZDDP
tribofilms. If the shape of the Stribeck curve obtained at the
end of step 5 (after 2 h rubbing in BO) is similar to that of
Stribeck curve obtained at the end of step 2 (after 2 h
rubbing in ZDDP), then it is inferred that ZDDP tribofilms
were not removed during step 5, meaning that tribofilms
are strongly adhered to DLC surfaces. However, if the
shape of the Stribeck curve obtained at the end of step 5 is
similar to that of Stribeck curve obtained at the end of step 1,
this suggests that ZDDP tribofilms were removed during
step 5, meaning that they were only weakly adhered to
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472 Tribol Lett (2013) 51:469–478

a-C:H/a-C:H b Fig. 2 Stribeck curves for DLC/DLC tribopairs obtained a initially in

0.16
(a) BO - initial
base oil b after 2 h rubbing in base oil, c after 2 h rubbing in ZDDP
solution, d initially in base oil (followed after ZDDP test) and e after
Friction Coefficient
(b) BO - 2 h
0.12 (c) ZDDP - 2 h
(d) BO - initial
2 h rubbing in base oil (followed after ZDDP test)
(e) BO - 2 h
0.08

DLC surfaces. In practice, both types of behaviour were

0.04 seen depending on the DLC type. The results and the
possible reasons are discussed later.
0
0.001 0.01 0.1 1 10
Positive and negative ion ToF–SIMS spectra were taken
Mean Speed (m/s) on DLC surfaces from steps 4 and 7. Peaks relevant to
a-C:H:W/a-C:H:W
ZDDP products were indexed and attributed to sulphide/
0.16 sulphates (S, SH, SO), phosphates (PO2, PO3) and thio-
(a) BO - initial
(b) BO - 2 h phosphates (PS2O, PS4O). These species were mapped and
Friction Coefficient

0.12 (c) ZDDP - 2 h

(d) BO - initial are shown in Figs. 3 and 4, and with quantitative results in
(e) BO - 2 h
Table 2. Brighter regions in ToF–SIMS images indicate an
0.08
abundant presence of triboelements, and darker regions
0.04
indicate their absence. It can be seen from Fig. 3 that these
species are only detected on the wear track. Any reduction
0 in tribofilm elements in step 7 (after testing in BO) was
0.001 0.01 0.1 1 10
considered to indicate film removal and thus weak adhe-
Mean Speed (m/s)
sion of tribofilms to DLC surface. Comparison of Figs. 3
0.16
a-C:H:WC/a-C:H:WC and 4 shows that ZDDP tribofilm elements are still present
(a) BO - initial on wear track when tested in base oil (step 5), indicating
(b) BO - 2 h
Friction Coefficient

0.12 (c) ZDDP - 2 h that they are not weakly adhered to DLC surfaces. How-
(d) BO - initial
(e) BO - 2 h ever, in most cases, tribofilms were found to be partially
0.08 removed, shown in Fig. 4 by darker regions on wear track.
It should be noted that Figs. 3 and 4 cannot be directly
0.04 compared by their brightness as they are not normalized.
This is resolved by normalizing the ToF–SIMS spectra
0
0.001 0.01 0.1 1 10 (negative) taken at steps 4 and 7, and the normalized
Mean Speed (m/s) concentration of tribofilm elements is shown in Fig. 5a, b.
Si-DLC/Si-DLC
It should be noted that depth of analysis in ToF–SIMS is
0.16
(a) BO - initial
generally about 3 nm, so only the top 3 nm of ZDDP films
(b) BO - 2 h
was analysed. It should be noted that ToF–SIMS does not
Friction Coefficient

(c) ZDDP - 2 h
0.12 (d) BO - initial
(e) BO - 2 h provide a quantitative measurement, so only a relative
0.08
comparison was made.

0.04
4 Discussion
0
0.001 0.01 0.1 1 10
Mean Speed (m/s)
In this study, the boundary film-forming ability of five
different types of DLC coating with ZDDP and the dura-
ta-C/ta-C
0.16 bility of the ZDDP tribofilms formed on these DLCs have
(a) BO - initial
(b) BO - 2 h
been investigated. It is clear from ToF–SIMS results that
Friction Coefficient

0.12 (c) ZDDP - 2 h

(d) BO - initial
ZDDP tribofilms form on all DLC surfaces and are mainly
(e) BO - 2 h P- and S-rich species, including thiophosphates, as can be
0.08
seen in Fig. 5a. This is in consistent with previous studies
by the authors [1, 15]. The formation of some form of
0.04
boundary film is also evident from the fall in boundary
0
friction with ZDDP seen in Fig. 2 [cp. Stribeck curves
0.001 0.01 0.1 1 10 (b) and (c)]. One exception is a-C:H:W, which shows
Mean Speed (m/s) increase in boundary friction with ZDDP and this was

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Tribol Lett (2013) 51:469–478
attributed to the blockage of low-friction graphitic inclu-
sions in the coating by ZDDP molecules [1, 16]. Here, it is
suggested that either an increase or decrease in boundary
friction means that there has been interaction of ZDDP
with DLC surfaces and the formation of tribofilms. In
general, the tribofilm thicknesses measured were in the
range of 10–30 nm on DLC discs [1]. The friction and the
ToF–SIMS results clearly demonstrate the ability of
ZDDPs to form tribofilms on DLCs regardless of DLC
type. This is in agreement with some reports in the litera-
ture [2–4, 6, 11, 13, 14], but contrary to others [5, 7, 9, 12],
and the possible reasons for this were analysed by the
authors and can be found elsewhere [15].
4.1 Durability Analysis of ZDDP Tribofilms Using
Stribeck Curves
The strength of ZDDP tribofilms was evaluated by testing
ZDDP tribofilm-generated DLC surfaces in base oil (step 5,
curve (d) in Fig. 2). An initial Stribeck curve, curve
(d) shown in Fig. 2 before any prolonged rubbing, and a
final Stribeck curve, curve (e) after 2 h rubbing in base oil,
were obtained. Since Stribeck curve (d) was obtained in
base oil immediately after testing in ZDDP solution, if
ZDDP tribofilms were strongly adhered, then Stribeck
Fig. 3 ToF–SIMS chemical S PO2
mapping taken on DLC discs
after 2 h rubbing in ZDDP
solution (step 4). Field of view
is 500 9 500 lm2 a-C:H
a-C:H:W
a-C:H:WC
Si-DLC
ta-C
473
curves (c) and (d) should be similar. As can be seen from
Fig. 2, at intermediate and high speeds, Stribeck curves
(c) and (d) were similar for all DLCs except Si-DLC. At
low speeds (\0.1 m/s, boundary lubrication), all DLCs
except a-C:H:W showed increase in boundary friction with
curve (d) compared to curve (c), and in most cases, curve
(d) was approaching curve (b). This indicates that although
the contacts have ZDDP tribofilms, their friction properties
appear to be affected when tested in base oil, even
immediately. One exception is a-C:H:W, the only type that
was able to retain the friction properties of ZDDP tribo-
films in base oil, and in fact showed lower boundary fric-
tion than that observed in curve (c). This indicates that the
tribofilm formed on a-C:H:W is strongly adhered compared
with other DLCs, probably because of the strong interac-
tion between tungsten and ZDDP. It should be noted that
Stribeck curves (d) and (c) of a-C:H:WC are quite similar;
only the last three data points in boundary lubrication
regime show slightly higher friction with curve (d), so it is
reasonable to consider that ZDDP tribofilms formed on this
DLC are strongly adhered. So, in general, ZDDP tribofilms
appear to be strongly adhered onto W-containing DLCs. It
is generally known that ZDDPs react with rubbing metals
and metal oxides to form metal-rich layer, on top of
which zinc-based phosphates develop [17, 18]. A similar
PO3 PS2O PS4O
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474 Tribol Lett (2013) 51:469–478

Fig. 4 ToF–SIMS chemical S PO2 PO3 PS2O PS4O

mapping taken on DLC discs
after 2 h rubbing in base oil
followed a 2 h ZDDP test
(step 7). Field of view is a-C:H
500 9 500 lm2

a-C:H:W

a-C:H:WC

Si-DLC

ta-C

Table 2 Chemical composition

DLC Thiophosphates Sulphides/sulphates Phosphates
of ZDDP tribofilm formed on
(PS2O ? PS4O) 9 105 (S ? SH ? SO) 9 105 (PO2 ? PO3) 9 105
DLC surfaces measured by
ToF–SIMS a-C:H
ZDDP (step 4) 4.52 9.10 18.09
BO (step 7) 0.22 2.45 16.21
a-C:H:W
ZDDP (step 4) 3.52 6.37 17.94
BO (step 7) 0.24 1.44 11.96
a-C:H:WC
ZDDP (step 4) 2.19 5.26 16.81
BO (step 7) 0.32 1.38 13.68
Si-DLC
ZDDP (step 4) 5.48 8.38 18.54
BO (step 7) 0.64 4.01 18.39
ta-C
ZDDP (step 4) 7.31 9.41 17.76
BO (step 7) 0.75 2.18 8.47

film-forming mechanism is believed to have occurred with
W-containing DLCs, so stronger adhesion of tribofilms on
them is not surprising.
As mentioned earlier, if curve (e) obtained at the end of
2 h base oil test is similar to that of curve (c) obtained in
ZDDP solution, then ZDDP tribofilms are considered to be
more durable than those that do not show similar (c) and
(e) curves. It can be seen from Fig. 2 that Stribeck curves
(c) and (e) are similar only for a-C:H:W and ta-C coatings
and are moderately similar for a-C:H:WC, while the others

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Tribol Lett (2013) 51:469–478 475

ZDDP (step 4) 100

(a) 20

% decrease in tribofilm elements

a-C:H

(comparison of steps 4 and 7)

a-C:H 90
18 a-C:H:W
a-C:H:W 80
16 a-C:H:WC
a-C:H:WC
70 Si-DLC
14 Si-DLC
Counts (10 5 )

ta-C 60 ta-C
12
50
10
40
8
30
6
20
4
10
2
0 0
Thiophosphates Sulphides/Sulphates Phosphates Thiophosphates Sulphides/Sulphates Phosphates
(PS2O+PS4O) (S+SH+SO) (PO2+PO3)
(PS2O+PS4O) (S+SH+SO) (PO2+PO3)

BO (after ZDDP test, step 7)

Fig. 6 Percentage decrease in tribofilm elements during step 5
(b) 20
a-C:H
18 a-C:H:W DLC surfaces. Rubbing for 2 h in base oil greatly reduces
16 a-C:H:WC
Si-DLC
this friction [curve (b)], indicating effective smoothing of
14
Counts (10 5 )

ta-C the surfaces due to running-in. Rubbing with ZDDP solu-

12
10
8
6
4
2
0
Thiophosphates Sulphides/Sulphates Phosphates
(PS2O+PS4O) (S+SH+SO) (PO2+PO3)
Fig. 5 Comparison of concentration of tribofilm elements from
a step 4 and b step 7
(a-C:H and Si-DLC) show dissimilar curves. This suggests
that W-containing DLCs and ta-C exhibit friction proper-
ties similar to that of ZDDP solution, suggesting that these
contacts still have ZDDP tribofilms even when there was
no supply of ZDDP molecules (i.e. when tested in base oil,
step 5). This means that ZDDP tribofilms are strongly
adhered to these DLCs (W-containing and ta-C DLCs) and
are considerably durable compared to those formed on
a-C:H and Si-DLC.
For a-C:H, Stribeck curves (e) and (b) are similar. This
suggests that this contact exhibits friction properties similar
to that of base oil (step 1), meaning that ZDDP tribofilm on
this DLC, which give low friction after 2 h rubbing, was
weakly adhered. The friction results of Si-DLC on Si-DLC
are very interesting. The low-speed boundary friction
behaviour is straightforward, with rubbing in ZDDP solu-
tion giving lower friction [curve (c)] that is largely main-
tained when the ZDDP is replaced by base oil [curves
(d) and (e)]. This suggests a durable ZDDP film. However,
the intermediate/high-speed friction results are anomalous.
Initial rubbing in base oil gives high intermediate friction,
suggestive of mixed lubrication curve (a). This probably
reflects the presence of quite high asperities on the fresh
tion (curve (c)) then increases intermediate speed friction.
This is a well-known phenomenon with ZDDP in steel/steel
contacts and is believed to represent the formation of a
relatively thick, rough ZDDP film [19]. Replacement by
base oil [curve (d)] initially has the effect of increasing
boundary friction to that of fresh base oil but not further
reducing intermediate speed friction, i.e. it does not
immediately reduce the roughness of the ZDDP film.
However, rubbing in base oil for 2 h [curve (e)] results in a
curve very similar to (b), i.e. with partially reduced
boundary friction and low intermediate friction. It is not
possible from friction measurements alone to know whe-
ther the reduction in intermediate speed friction is due to
removal of the rough ZDDP film or just its smoothing.
It is important to note that changes in friction curves
between (c), (d) and (e) do not necessarily indicate the
complete removal of any surface films formed by ZDDP,
only of the immediate, outermost part that controls
boundary friction. To determine removal of the bulk film
requires surface analysis.
4.2 Durability Analysis of ZDDP Tribofilms Using
ToF–SIMS
It can be seen from Fig. 5a that tribofilms formed from
ZDDP solution (step 2) consist of relatively high amounts
of phosphates followed, in order by, sulphides/sulphates
and thiophosphates, and these amounts were reduced when
the tribofilm-generated surfaces were rubbed in base oil
(Fig. 5b). The percentage decrease in tribofilm elements in
step 5 is shown in Fig. 6, which shows that 90 % of thio-
phosphates were removed in step 5 followed, in order by,
sulphides/sulphates (50–75 %) and phosphates (1–50 %).
Ninety percentage removal of thiophosphates is possible
only if they were present on top surface of the tribofilm.

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476
Fig. 7 Schematic diagram of (a)
ZDDP tribofilm formed on
a DLC and b steel [20] surfaces
Depth of analysis in
ToF-SIMS ~ 3 nm
(b)
This layer is followed, in order through to the DLC surface,
by sulphides/sulphates and phosphates. This suggests a
ZDDP tribofilm structure on DLC surface like the one
shown schematically in Fig. 7a, in comparison with the
structure normally reported for steel surfaces [20] shown
schematically in Fig. 7b. The possibility of thiophosphate
as a thermal film on top surface of ZDDP tribofilm has
been reported on steel surfaces [21–23].
It should be noted that ToF–SIMS can detect a change in
chemistry but, since it looks at only to top 3 nm or so, not
always a change in film thickness. Thus, if material is
removed but the composition of the film not changed, then
step 7 should only show a change in ToF–SIMS data if the
film thickness falls below ca 3 nm after steps 5 and 6. In
practice, changes in the TOF–SIMS data were seen
between steps 4 and 7, as indicated in Fig. 5, suggesting
either that the ZDDP film was layered or that rubbing in
base oil and washing caused compositional changes to the
film, or both. ToF–SIMS results shown in Fig. 5a, b indi-
cate that P–S was lost, so it is likely that this part of the film
must have removed and/or changed to phosphate, with the
sulphur being lost (indicated by reduced counts after step 7).
In general, phosphorus count also decreased after steps 5
and 6, especially for ta-C, which suggests that for all except
Si-DLC, the phosphate film thickness falls to less than ca
3 nm due to film removal during rubbing in base oil and
final washing.
Using ToF–SIMS, Minfray et al. [21] reported that ZDDP
tribofilms formed on steel surfaces were found to have
sulphides/sulphates (S, SH, SO), phosphates (PO2, PO3,
P2O2H, P2O6H) and/or thiophosphates (PS2O, PS4O, P2S4H).
Similar chemical species were found to be present on DLC
surfaces investigated in this study. This indicates that ZDDP
is able to form similar products regardless of the substrate
123
Tribol Lett (2013) 51:469–478
Thiophosphates
Sulphides ZDDP film thickness
10–30 nm
Phosphates
DLC Surface
ZDDP film
thickness
80–150 nm
Steel Surface
material (DLC or steel). However, as reported in the authors’
earlier work, the thickness, strength and antiwear properties
of ZDDP tribofilms formed on steel surfaces were found to be
superior to those formed on DLC surfaces [1].
Also, it is evident from the ToF–SIMS results shown in
Fig. 5a that ultrasonic cleaning of specimens does not
remove ZDDP tribofilms formed on DLCs, as the surfaces
showed the presence of ZDDP tribofilm products. It is
possible, of course, that DLCs had higher amounts of
tribofilm elements before ultrasonic cleaning but this was
not verified in this study. In general, it can be said that
ZDDP tribofilms formed on DLCs were able to largely
withstand ultrasonification but their durability in long-term
rubbing conditions is questionable.
4.3 Strength and Wear Properties of ZDDP Tribofilms
In terms of strength of ZDDP tribofilms, ZDDP films
formed on Si-DLC and a-C:H were found to be more
strongly adhered (as per the phosphate ToF–SIMS results
shown in Figs. 5 and 6) than those formed on other DLCs.
Interestingly, these two DLCs exhibit superior wear resis-
tance properties to the other types with ZDDP, when tested
in pure-sliding conditions [1]. This may originate from the
relatively strong adhesion of ZDDP tribofilms on these
DLCs. However, these two DLCs were also found to
exhibit superior wear resistance properties in ZDDP-free
base oil [1]. This suggests that ZDDP tribofilms do not
contribute to the superior wear resistance properties of
these two DLCs, which are primarily provided by the ori-
ginal DLC surface itself. However, for some DLC types,
such as W-containing DLCs, ZDDP tribofilms do play a
significant antiwear role [1]. In general, ZDDP appears to
play a good antiwear role (although not to the extent as it
Tribol Lett (2013) 51:469–478
(a)
Composite Wear (10 -17 m3/Nm),
Hardness (GPa), sp3 (%)
(b) 12
Composite Wear (10 -17 m3/Nm)
10
8 Thiophosphates (PS2O+PS4O)
6 10
4
2
0 0
Fig. 8 Comparison of a hardness, hardness/elastic modulus (H/E)
and sp3 content of DLC coatings and b concentration of ZDDP
tribofilm elements with wear. Wear data from [1]. Lines are drawn to
guide the eyes
does on steel surfaces) with DLCs that originally had poor
wear resistance properties (W-DLC), while not for the ones
that originally had superior wear resistance property
(a-C:H, Si-DLC). These results suggest that ZDDPs do not
affect the original superior wear resistance properties of
DLCs, but their antiwear performance can vary based on
the type of DLCs [1] and doping elements present in it
[15]. So, careful selection of DLC is important when
intended to use with ZDDP.
To understand what parameters control the durability of
ZDDP tribofilms and thus their wear resistance properties,
mechanical properties of DLCs [e.g. hardness (H), elastic
modulus (E)], coating parameters (e.g. sp3 content) and
tribofilm composition were compared with wear coefficients
of DLC/DLC tribopairs tested in ZDDP solution, as shown in
Fig. 8. The wear coefficients used for this comparison were
taken from the authors’ earlier work [1]. Despite having
similar hardness values, a-C:H:W, a-C:H:WC and Si-DLC
showed different wear properties; W-containing DLCs show
higher wear than Si-DLC, as shown in Fig. 8a. Similarly,
a-C:H:WC has higher sp3 content than a-C:H:W, so
a-C:H:WC is expected to show better wear resistance
than a-C:H:W but this was not the case. Also, although a-C:H
and a-C:H:WC have similar sp3 content, their wear resis-
tance properties were very different. One parameter that does
appear to show a good relationship with wear is the ratio of
477
80 0.16 hardness to elastic modulus, H/E [24, 25]; DLCs with high
ZDDP Wear H/E ratio (i.e. a-C:H, Si-DLC and ta-C) showed better wear
70 Hardness 0.14
sp3
resistance properties than those with low ones. When com-
60 0.12
H/E paring the tribofilm elements with wear as shown in Fig. 8b,
50 0.10
it can be seen that lesser the amount of tribofilm elements
H/E
40 0.08 greater was the wear. These results suggest that wear resis-
30 0.06 tance properties of DLCs appear not to be mainly controlled
20 0.04 by hardness or sp3 content but instead primarily by tribofilm
10 0.02 elements and to some extent by H/E ratio.
0 0.00
a-C:H a-C:H:W a-C:H:WC Si-DLC ta-C
5 Conclusions
ZDDP Tribofilm Species Counts (10 5)
20
18
16
The results demonstrate that ZDDP tribofilms formed in
ZDDP Wear
14 DLC/DLC contacts appear to be chemically similar to those
Sulphides/Sulphates (S+SH+SO) 12 formed in steel/steel contacts, but their thickness, strength
Phosphates (PO2+PO3)
and wear properties are different. ZDDP films were found to
8 be more strongly adhered onto Si-DLC and a-C:H DLCs
6 compared with the others. Also, their wear resistance prop-
4 erties were superior than those of other DLCs. However, this
2 is attributed to the original superior wear resistance properties
of a-C:H and Si-DLC as they show similar superior wear
a-C:H a-C:H:W a-C:H:WC Si-DLC ta-C
resistance even with ZDDP-free base oil. Unlike steel/steel
contacts, wear resistance in DLC/DLC contacts is mainly
provided by the original DLC itself, and the role of ZDDP as
antiwear agent is negligible although all DLCs investigated in
this study showed tribofilm products on their surfaces.
Despite the varied friction and wear behaviour, the results
clearly demonstrate that DLC coatings are potential candi-
dates in terms of friction and wear even in the absence of
widely used antiwear additives such as ZDDP.
The use of ToF–SIMS to study pre-formed ZDDP
tribofilms before and after rubbing in base oil indicates that
rubbing in base oil results in almost complete loss of sul-
phur species, both sulphide and thiophosphate, from the
film. This suggests both that these materials are normally
present in the outermost part of ZDDP films and that they
are relatively weakly bound and lost during rubbing.
Acknowledgments The authors wish to thank Castrol Limited, for
funding this project and permitting to publish this work. The authors
are extremely grateful to Dr. David Scurr and Prof. Peter Milligan of
The University of Nottingham, UK for use of their ToF–SIMS facility
and for their assistance. Also, the authors would like to thank Mr. Paul
Cave of Fischer Instrumentation (GB) Ltd, Lymington, UK for
assisting with the hardness and elastic modulus measurements of
DLCs. The authors would also like to thank Nippon ITF, Sulzer and
Oerlikon Balzers for supplying the DLC samples.
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