Professional Documents
Culture Documents
Durability of ZDDP Tribofilms Formed in DLC/DLC Contacts
Durability of ZDDP Tribofilms Formed in DLC/DLC Contacts
Durability of ZDDP Tribofilms Formed in DLC/DLC Contacts
DOI 10.1007/s11249-013-0185-z
ORIGINAL PAPER
Received: 5 June 2013 / Accepted: 3 July 2013 / Published online: 17 July 2013
Ó Springer Science+Business Media New York 2013
123
470 Tribol Lett (2013) 51:469–478
especially to ZDDP. In particular, little is known about the DLC/DLC tribopairs, i.e. with DLC-coated ball and DLC-
durability of ZDDP tribofilms formed on DLC surfaces coated disc. Although DLC/steel tribopairs are more com-
compared to those on steel surfaces. It has been suggested monly used in practice, the use of DLC/DLC tribopairs high-
that ZDDP tribofilms formed on DLC surfaces are easily lights any interactions between the ZDDP additive and DLC.
removable, either when washed ultrasonically [2] or when The base fluid used in this study was an API Group III oil
the tribofilms are externally scratch-tested [3], both having density of 0.78 g/cm3, viscosity of 3.32 cP and effective
apparently indicating that tribofilms are weakly adhered to pressure viscosity coefficient of 16.3 GPa-1 at the test tem-
the DLC surface, which might explain some contradictory perature of 100°C. The ZDDP additive had a primary alkyl
results in the literature. However, these studies were lim- structure and was used at a concentration that gave 0.08 wt% P
ited to only one DLC type, a-C:H. in the base oil solution.
It is of great interest to know how strongly or weakly Friction tests were carried out using a ball-on-disc MTM,
ZDDP tribofilms are adhered to DLCs since this is likely to where a 19 mm diameter DLC-coated ball was loaded and
control their effectiveness as antiwear additives and is also rubbed against a DLC-coated disc immersed in lubricant
quite likely to depend on the composition of the DLC solution. The friction test conditions used in this study were as
surface. In the current study, examples of all the main types follows: applied load = 31 N, corresponding to an initial
of DLC have been obtained from various suppliers and Hertzian contact pressure of ca. 1 GPa; entrainment
their behaviour in terms of ZDDP film formation and speed = 0.1 m/s; slide–roll ratio = 0.5; tempera-
durability has been studied when lubricated by ZDDP ture = 100°C; test duration = 2 h. The entrainment speed
solution in base oil. 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
2 Materials and Test Methods
ratio (ratio of calculated elastohydrodynamic lubricant film
thickness to composite surface roughness) ranged from 0.3 to
Diamond-like carbon (DLC) coatings were deposited on
0.5, so the operating lubrication regime was mixed-boundary
the test specimens normally used in the mini-traction
lubrication. The testing method adopted to assess the dura-
machine (MTM), i.e. AISI 52100 steel balls and discs, of
bility of ZDDP tribofilms had seven steps as follows.
hardness 760 HV and roughness Rq of 10 nm. Hardness
and elastic modulus, chemical composition and hydrogen 1. A reference 2 h MTM test as per the conditions
content, and sp3 % of all the DLC coatings were measured mentioned above was carried out in base oil (BO)
using Fischerscope HM2000, SEM/EDX and ERD, and using a fresh set of DLC-coated samples.
Raman spectroscopy, respectively. Details of these mea- 2. A normal 2 h MTM test was carried out in ZDDP
surements are described elsewhere [16]. solution using a fresh set of DLC-coated samples.
Five different types of DLC coating, namely hydrogenated 3. The specimens from step 2 were ultrasonically washed
amorphous carbon (a-C:H), tungsten-containing hydrogenated in cyclohexane.
amorphous carbon (a-C:H:W), tungsten carbide-containing 4. ToF–SIMS chemical mapping was performed on the
hydrogenated amorphous carbon (a-C:H:WC), Si-containing DLC disc after testing in ZDDP solution and washing.
DLC (Si-DLC) and tetrahedral amorphous carbon (ta-C), were 5. A 2 h MTM test was carried out in base oil solution
studied, and their properties are listed in Table 1. All DLC using the same specimens that were tested in step 2,
coatings had thickness in the range 3–4 lm. Contact mode i.e. in ZDDP solution.
AFM topography images of all the DLCs before testing were 6. The specimens from step 5 were ultrasonically washed
obtained and are shown in Fig. 1. Tests were conducted on in cyclohexane.
123
Tribol Lett (2013) 51:469–478 471
60.00 nm
0.00 nm
Fig. 1 AFM topography of DLC coatings before testing (scan size = 2 9 2 lm)
7. ToF–SIMS chemical mapping was performed on Five Stribeck curves, namely Stribeck curves obtained
washed DLC disc. initially and after 2 h rubbing in base oil (step 1, described
in previous section), a Stribeck curve obtained after 2 h
Each MTM test lasted for 2 h. An initial Stribeck friction rubbing in ZDDP solution (step 2), initial and final Stribeck
curve was taken prior to beginning of the test, by measuring curves in base oil (step 5), were compared for all DLCs and
friction while varying entrainment speed in stages from 0.007 are shown in Fig. 2. It can be seen from Fig. 2 that ta-C
up to 3.5 m/s at a fixed slide–roll ratio of 0.5. Then prolonged, gives consistently lower boundary friction than the other
slow speed rubbing was carried out in the mixed/boundary types regardless of lubricant solution (ZDDP or base oil).
lubrication condition mentioned above. Periodically, after 5, This indicates that the typical low-friction property of this
15, 30, 60 and 120 min, the slow speed test was halted and a DLC coating is not influenced by the lubricant, unlike other
Stribeck curve was taken. However, in this paper, only the DLCs. In general, boundary friction depends on the type of
Stribeck curves taken initially and after 2 h rubbing are pre- DLC coating, and in most cases, both with and without
sented. After testing, the discs were ultrasonically washed in ZDDP, boundary friction was found to be in the following
cyclohexane before the wear tracks were examined by ToF– ascending order, ta-C, a-C:H, a-C:H:W, a-C:H:WC and
SIMS IV instrument (ION-TOF GmbH, Münster, Germany) Si-DLC [1]. One interesting observation, in contrast to
using Ga? ion beam. The test method was designed mainly to steel/steel lubricated by ZDDP, is that these DLCs do not
understand the strength of tribofilms and to determine whether show increased friction in the intermediate speed region
ultrasonic washing of samples and/or rubbing can remove the after rubbing with ZDDP. This is probably because ZDDP
films. The former is assessed by ToF–SIMS results obtained in does not form thick pad-like structures on DLCs as they
step 4 while the latter is assessed by comparing Stribeck typically do on steel surfaces. A detailed friction analysis
curves obtained in steps 2 (contact supplied with ZDDP) and 5 can be found elsewhere [1, 16].
(contact not supplied with ZDDP, i.e. base oil test of tribofilm- In the current study, the Stribeck curves shown in Fig. 2
generated DLC surface) and by comparing ToF–SIMS results were used to understand the formation (when ZDDP is
obtained in steps 4 and 7. 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
3 Results Stribeck curve obtained at the end of step 2 (after 2 h
rubbing in ZDDP), then it is inferred that ZDDP tribofilms
In order to understand the film-forming properties of ZDDP were not removed during step 5, meaning that tribofilms
and strength of tribofilms, DLCs were tested initially in are strongly adhered to DLC surfaces. However, if the
base oil for 2 h, followed, in order, by ZDDP solution and shape of the Stribeck curve obtained at the end of step 5 is
base oil as per the procedure described in the previous similar to that of Stribeck curve obtained at the end of step 1,
section. Friction coefficient versus entrainment speed this suggests that ZDDP tribofilms were removed during
(Stribeck) curves were obtained for DLC/DLC tribopairs. step 5, meaning that they were only weakly adhered to
123
472 Tribol Lett (2013) 51:469–478
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
123
Tribol Lett (2013) 51:469–478 473
attributed to the blockage of low-friction graphitic inclu- curves (c) and (d) should be similar. As can be seen from
sions in the coating by ZDDP molecules [1, 16]. Here, it is Fig. 2, at intermediate and high speeds, Stribeck curves
suggested that either an increase or decrease in boundary (c) and (d) were similar for all DLCs except Si-DLC. At
friction means that there has been interaction of ZDDP low speeds (\0.1 m/s, boundary lubrication), all DLCs
with DLC surfaces and the formation of tribofilms. In except a-C:H:W showed increase in boundary friction with
general, the tribofilm thicknesses measured were in the curve (d) compared to curve (c), and in most cases, curve
range of 10–30 nm on DLC discs [1]. The friction and the (d) was approaching curve (b). This indicates that although
ToF–SIMS results clearly demonstrate the ability of the contacts have ZDDP tribofilms, their friction properties
ZDDPs to form tribofilms on DLCs regardless of DLC appear to be affected when tested in base oil, even
type. This is in agreement with some reports in the litera- immediately. One exception is a-C:H:W, the only type that
ture [2–4, 6, 11, 13, 14], but contrary to others [5, 7, 9, 12], was able to retain the friction properties of ZDDP tribo-
and the possible reasons for this were analysed by the films in base oil, and in fact showed lower boundary fric-
authors and can be found elsewhere [15]. tion than that observed in curve (c). This indicates that the
tribofilm formed on a-C:H:W is strongly adhered compared
4.1 Durability Analysis of ZDDP Tribofilms Using with other DLCs, probably because of the strong interac-
Stribeck Curves tion between tungsten and ZDDP. It should be noted that
Stribeck curves (d) and (c) of a-C:H:WC are quite similar;
The strength of ZDDP tribofilms was evaluated by testing only the last three data points in boundary lubrication
ZDDP tribofilm-generated DLC surfaces in base oil (step 5, regime show slightly higher friction with curve (d), so it is
curve (d) in Fig. 2). An initial Stribeck curve, curve reasonable to consider that ZDDP tribofilms formed on this
(d) shown in Fig. 2 before any prolonged rubbing, and a DLC are strongly adhered. So, in general, ZDDP tribofilms
final Stribeck curve, curve (e) after 2 h rubbing in base oil, appear to be strongly adhered onto W-containing DLCs. It
were obtained. Since Stribeck curve (d) was obtained in is generally known that ZDDPs react with rubbing metals
base oil immediately after testing in ZDDP solution, if and metal oxides to form metal-rich layer, on top of
ZDDP tribofilms were strongly adhered, then Stribeck which zinc-based phosphates develop [17, 18]. A similar
a-C:H:W
a-C:H:WC
Si-DLC
ta-C
123
474 Tribol Lett (2013) 51:469–478
a-C:H:W
a-C:H:WC
Si-DLC
ta-C
film-forming mechanism is believed to have occurred with ZDDP solution, then ZDDP tribofilms are considered to be
W-containing DLCs, so stronger adhesion of tribofilms on more durable than those that do not show similar (c) and
them is not surprising. (e) curves. It can be seen from Fig. 2 that Stribeck curves
As mentioned earlier, if curve (e) obtained at the end of (c) and (e) are similar only for a-C:H:W and ta-C coatings
2 h base oil test is similar to that of curve (c) obtained in and are moderately similar for a-C:H:WC, while the others
123
Tribol Lett (2013) 51:469–478 475
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)
123
476 Tribol Lett (2013) 51:469–478
DLC Surface
(b)
ZDDP film
thickness
80–150 nm
Steel Surface
This layer is followed, in order through to the DLC surface, material (DLC or steel). However, as reported in the authors’
by sulphides/sulphates and phosphates. This suggests a earlier work, the thickness, strength and antiwear properties
ZDDP tribofilm structure on DLC surface like the one of ZDDP tribofilms formed on steel surfaces were found to be
shown schematically in Fig. 7a, in comparison with the superior to those formed on DLC surfaces [1].
structure normally reported for steel surfaces [20] shown Also, it is evident from the ToF–SIMS results shown in
schematically in Fig. 7b. The possibility of thiophosphate Fig. 5a that ultrasonic cleaning of specimens does not
as a thermal film on top surface of ZDDP tribofilm has remove ZDDP tribofilms formed on DLCs, as the surfaces
been reported on steel surfaces [21–23]. showed the presence of ZDDP tribofilm products. It is
It should be noted that ToF–SIMS can detect a change in possible, of course, that DLCs had higher amounts of
chemistry but, since it looks at only to top 3 nm or so, not tribofilm elements before ultrasonic cleaning but this was
always a change in film thickness. Thus, if material is not verified in this study. In general, it can be said that
removed but the composition of the film not changed, then ZDDP tribofilms formed on DLCs were able to largely
step 7 should only show a change in ToF–SIMS data if the withstand ultrasonification but their durability in long-term
film thickness falls below ca 3 nm after steps 5 and 6. In rubbing conditions is questionable.
practice, changes in the TOF–SIMS data were seen
between steps 4 and 7, as indicated in Fig. 5, suggesting 4.3 Strength and Wear Properties of ZDDP Tribofilms
either that the ZDDP film was layered or that rubbing in
base oil and washing caused compositional changes to the In terms of strength of ZDDP tribofilms, ZDDP films
film, or both. ToF–SIMS results shown in Fig. 5a, b indi- formed on Si-DLC and a-C:H were found to be more
cate that P–S was lost, so it is likely that this part of the film strongly adhered (as per the phosphate ToF–SIMS results
must have removed and/or changed to phosphate, with the shown in Figs. 5 and 6) than those formed on other DLCs.
sulphur being lost (indicated by reduced counts after step 7). Interestingly, these two DLCs exhibit superior wear resis-
In general, phosphorus count also decreased after steps 5 tance properties to the other types with ZDDP, when tested
and 6, especially for ta-C, which suggests that for all except in pure-sliding conditions [1]. This may originate from the
Si-DLC, the phosphate film thickness falls to less than ca relatively strong adhesion of ZDDP tribofilms on these
3 nm due to film removal during rubbing in base oil and DLCs. However, these two DLCs were also found to
final washing. exhibit superior wear resistance properties in ZDDP-free
Using ToF–SIMS, Minfray et al. [21] reported that ZDDP base oil [1]. This suggests that ZDDP tribofilms do not
tribofilms formed on steel surfaces were found to have contribute to the superior wear resistance properties of
sulphides/sulphates (S, SH, SO), phosphates (PO2, PO3, these two DLCs, which are primarily provided by the ori-
P2O2H, P2O6H) and/or thiophosphates (PS2O, PS4O, P2S4H). ginal DLC surface itself. However, for some DLC types,
Similar chemical species were found to be present on DLC such as W-containing DLCs, ZDDP tribofilms do play a
surfaces investigated in this study. This indicates that ZDDP significant antiwear role [1]. In general, ZDDP appears to
is able to form similar products regardless of the substrate play a good antiwear role (although not to the extent as it
123
Tribol Lett (2013) 51:469–478 477
(a) 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
Composite Wear (10 -17 m3/Nm),
sp3
resistance properties than those with low ones. When com-
Hardness (GPa), sp3 (%)
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
(b) 12 5 Conclusions
18
Composite Wear (10 -17 m3/Nm)
10
16
The results demonstrate that ZDDP tribofilms formed in
ZDDP Wear
14 DLC/DLC contacts appear to be chemically similar to those
8 Thiophosphates (PS2O+PS4O)
Sulphides/Sulphates (S+SH+SO) 12 formed in steel/steel contacts, but their thickness, strength
Phosphates (PO2+PO3)
6 10 and wear properties are different. ZDDP films were found to
8 be more strongly adhered onto Si-DLC and a-C:H DLCs
4
6 compared with the others. Also, their wear resistance prop-
2
4 erties were superior than those of other DLCs. However, this
2 is attributed to the original superior wear resistance properties
0 0 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
Fig. 8 Comparison of a hardness, hardness/elastic modulus (H/E) contacts, wear resistance in DLC/DLC contacts is mainly
and sp3 content of DLC coatings and b concentration of ZDDP provided by the original DLC itself, and the role of ZDDP as
tribofilm elements with wear. Wear data from [1]. Lines are drawn to
guide the eyes
antiwear agent is negligible although all DLCs investigated in
this study showed tribofilm products on their surfaces.
does on steel surfaces) with DLCs that originally had poor Despite the varied friction and wear behaviour, the results
wear resistance properties (W-DLC), while not for the ones clearly demonstrate that DLC coatings are potential candi-
that originally had superior wear resistance property dates in terms of friction and wear even in the absence of
(a-C:H, Si-DLC). These results suggest that ZDDPs do not widely used antiwear additives such as ZDDP.
affect the original superior wear resistance properties of The use of ToF–SIMS to study pre-formed ZDDP
DLCs, but their antiwear performance can vary based on tribofilms before and after rubbing in base oil indicates that
the type of DLCs [1] and doping elements present in it rubbing in base oil results in almost complete loss of sul-
[15]. So, careful selection of DLC is important when phur species, both sulphide and thiophosphate, from the
intended to use with ZDDP. film. This suggests both that these materials are normally
To understand what parameters control the durability of present in the outermost part of ZDDP films and that they
ZDDP tribofilms and thus their wear resistance properties, are relatively weakly bound and lost during rubbing.
mechanical properties of DLCs [e.g. hardness (H), elastic
modulus (E)], coating parameters (e.g. sp3 content) and Acknowledgments The authors wish to thank Castrol Limited, for
funding this project and permitting to publish this work. The authors
tribofilm composition were compared with wear coefficients
are extremely grateful to Dr. David Scurr and Prof. Peter Milligan of
of DLC/DLC tribopairs tested in ZDDP solution, as shown in The University of Nottingham, UK for use of their ToF–SIMS facility
Fig. 8. The wear coefficients used for this comparison were and for their assistance. Also, the authors would like to thank Mr. Paul
taken from the authors’ earlier work [1]. Despite having Cave of Fischer Instrumentation (GB) Ltd, Lymington, UK for
assisting with the hardness and elastic modulus measurements of
similar hardness values, a-C:H:W, a-C:H:WC and Si-DLC
DLCs. The authors would also like to thank Nippon ITF, Sulzer and
showed different wear properties; W-containing DLCs show Oerlikon Balzers for supplying the DLC samples.
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
References
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- 1. Vengudusamy, B., Green, J.H., Lamb, G.D., Spikes, H.A.: Tri-
tance properties were very different. One parameter that does bological properties of tribofilms formed from ZDDP in DLC/
appear to show a good relationship with wear is the ratio of DLC and DLC/steel contacts. Tribol. Int. 44, 165–174 (2011)
123
478 Tribol Lett (2013) 51:469–478
2. Equey, S., Roos, S., Mueller, U., Hauert, R., Spencer, N.D., 14. Kalin, M., Roman, E., Ozbolt, L., Vizintin, J.: Metal-doped (Ti,
Crockett, R.: Tribofilm formation from ZnDTP on diamond-like WC) diamond-like carbon coatings: reactions with extreme
carbon. Wear 264, 316–321 (2008) pressure oil additives under tribological and static conditions.
3. Equey, S., Roos, S., Mueller, U., Hauert, R., Spencer, N.D., Thin Solid Films 518, 4336–4344 (2010)
Crockett, R.: Reactions of zinc-free anti-wear additives in DLC/ 15. Vengudusamy, B., Green, J.H., Lamb, G.D., Spikes, H.A.:
DLC and steel/steel contacts. Tribol. Int. 41, 1090–1096 (2008) Influence of hydrogen and tungsten concentration on the tribo-
4. Topolovec-Miklozic, K., Lockwood, F., Spikes, H.A.: Behaviour logical properties of DLC/DLC contacts with ZDDP. Wear
of boundary lubricating additives on DLC coatings. Wear 265, 298–299, 109–119 (2013)
1893–1901 (2007) 16. Vengudusamy, B., Mufti, R.A., Lamb, G.D., Green, J.H., Spikes,
5. Haque, T., Morina, A., Neville, A., Kapadia, R., Arrowsmith, S.: H.A.: Friction properties of DLC/DLC contacts in base oil. Tri-
Non-ferrous coating/lubricant interactions in tribological con- bol. Int. 44, 922–932 (2011)
tacts: assessment of tribofilms. Tribol. Int. 40, 1603–1612 (2007) 17. Taylor, L., Dratva, A., Spikes, H.A.: Friction and wear behaviour
6. Haque, T., Morina, A., Neville, A., Kapadia, R., Arrowsmith, S.: of zinc dialkyldithiophosphate additive. Tribol. Trans. 43(3),
Study of the ZDDP antiwear tribofilm formed on the DLC coating 469–479 (2000)
using AFM and XPS techniques. J. ASTM Int. 4(7), 1–7 (2007) 18. Ito, K., Martin, J.M., Minfray, C., Kato, K.: Low-friction tribo-
7. Podgornik, B., Jacobson, S., Hogmark, S.: DLC coating of film formed by the reaction of ZDDP on iron oxide. Tribol. Int.
boundary lubricated components-advantages of coating one of the 39, 1538–1544 (2006)
contact surfaces rather than both or none. Tribol. Int. 36, 843–849 19. Taylor, L.J., Spikes, H.A.: Friction-enhancing properties of
(2003) ZDDP antiwear additive: part I-Friction and morphology of
8. Podgornik, B., Vizintin, J.: Tribological reactions between oil ZDDP reaction films. Tribol. Trans. 46, 303–309 (2003)
additives & DLC coatings for automotive applications. Surf. 20. Spikes, H.A.: The history and mechanisms of ZDDP. Tribol. Lett.
Coat. Technol. 200, 1982–1989 (2005) 17, 469–489 (2004)
9. Podgornik, B., Jacobson, S., Hogmark, S.: Influence of EP 21. Minfray, C., Martin, J.M., De Barros, M.I., Le-Mogne, T., Ker-
additive concentration on the tribological behaviour of DLC- sting, R., Hagenhoff, B.: Chemistry of ZDDP tribofilms by ToF-
coated steel surfaces. Surf. Coat. Technol. 191, 357–366 (2005) SIMS. Tribol. Lett. 17, 351–357 (2004)
10. Kalin, M., Vizintin, J.: Differences in the tribological mecha- 22. Yin, Z., Kasrai, M., Fuller, M., Bancroft, G.M., Fyfe, K., Tan,
nisms when using non-doped, metal-doped (Ti, WC), and non- K.H.: Application of soft X-ray absorption spectroscopy in
metal doped (Si) diamond-like carbon against steel under chemical characterization of antiwear films generated by ZDDP
boundary lubrication, with and without oil additives. Thin Solid Part I: the effects of physical parameters. Wear 202, 172–191
Films 515, 2734–2747 (2006) (1997)
11. De Barros Bouchet, M.I., Martin, J.M., Le-Mogne, T., Vacher, 23. Minfray, C., Martin, J.M., Esnouf, C., Le-Mogne, T., Kersting,
B.: Boundary lubrication mechanisms of carbon coatings by R., Hagenhoff, B.: A multi-technique approach of tribofilm
MoDTC and ZDDP additives. Tribol. Int. 38, 257–264 (2005) characterisation. Thin Solid Films 447–448, 272–277 (2004)
12. Kalin, M., Vizintin, J., Barriga, J., Vercammen, K., van Acker, 24. Leyland, A., Matthews, A.: On the significance of the H/E ratio in
K., Arnsek, A.: The effect of doping elements and oil additives on wear control: a nanocomposite approach to optimised tribological
the tribological performance of boundary-lubricated DLC/DLC behaviour. Wear 246, 1–11 (2000)
contacts. Tribol. Lett. 17, 679–688 (2004) 25. Neuville, S., Matthews, A.: A perspective on the optimisation of
13. Kalin, M., Roman, E., Vizintin, J.: The effect of temperature on hard carbon and related coatings for engineering application.
the tribological mechanisms and reactivity of hydrogenated, Thin Solid Films 515, 6619–6653 (2007)
amorphous diamond-like carbon coatings under oil-lubricated
conditions. Thin Solid Films 515, 3644–3652 (2007)
123