SCT-21581; No of Pages 10

Surface & Coatings Technology xxx (2016) xxx–xxx

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Surface & Coatings Technology

journal homepage: www.elsevier.com/locate/surfcoat

Topography evolution and friction coefficient of gray and nodular cast

irons with duplex plasma nitrided + DLC coating
Renan Oss Giacomelli ⁎, Diego Berti Salvaro, Tatiana Bendo, Cristiano Binder,
Aloisio Nelmo Klein, Jose Daniel Biasoli de Mello
Materials Laboratory (LabMat), Federal University of Santa Catarina, Florianópolis, SC, Brazil

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

Article history: In the present study, the main critical factors affecting the production of high tribological performance coatings
Received 25 May 2016 on substrates containing near surface graphite were evaluated. Plasma nitriding followed by deposition of a hy-
Revised 15 September 2016 drogenated diamond like carbon film (a-C:H) on gray cast iron (GCI) and nodular cast iron (NCI) substrates were
Accepted in revised form 16 September 2016
carried out using a single thermal cycle. The surface topography evolution was evaluated via Scanning Electron
Available online xxxx
Microscopy (SEM) and White Light Interferometry (WLI). As expected, there is a huge variation in surface topog-
Keywords:
raphy and morphology according to graphite shape. An intense modification on the topography of GCI was ob-
PACVD served, in particular wedges formation after nitriding. In order to enable a more in-depth understanding, the
Nitriding surface evolution after plasma nitriding of cast irons was carefully investigated and discussed in light of EDS
Diamond-like carbon linescans and XRD. Micro Raman spectroscopy and TEM analysis indicated that the DLC has an average amount
Roughness of clustered sp2 bonding in the structure. Additionally, the tribological performance of multifunctional coatings
Cast iron was evaluated via durability tests in ambient air, which revealed friction coefficients as low as 0.06 during
Tribology steady-state lubrication regime for gray cast iron substrates, whereas the values were of 0.14 for nodular cast
iron substrates. Crucial differences were found between friction coefficient behaviours: the GCI presented lubri-
cious tribolayers covering most part of wear track whereas NCI presented topographic factors inhibiting
tribolayers formation, a key factor that might explain the friction coefficient variation.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Amorphous carbon thin films called diamond-like carbon (DLC)
have attracted the attention of scientific and industrial communities
due its exceptional mechanical and tribological properties: DLC films
can provide low friction coefficients in dry sliding systems and high
wear resistance simultaneously [1–3]. Among this family of coatings,
hydrogenated DLC films (a-C:H) are notorious for its excellent tribolog-
ical performance, providing friction coefficients as low as 0.05 in some
cases [4].
DLC films are usually applied on hard substrates such as tool steels or
directly in silicon wafers for characterization purposes [1,2,5–7]. For
those reasons there is still little information available regarding DLC
films deposited in comparably soft substrates, such as gray and nodular
cast irons [8,9], despite their wide use in industry for their combination
of good mechanical properties associated with lower cost. The main
challenges in applying these specific cast irons as substrates are related
⁎ Corresponding author.
E-mail address: renan.og@posgrad.ufsc.br (R.O. Giacomelli).
to their comparably low mechanical support, which reduces the adhe-
sion of hard thin films, and to surface heterogeneities due the presence
of graphite flakes and nodules.
Highly hydrogenated DLC films (a-C:H) are usually obtained by Plas-
ma Enhanced Chemical Vapor Deposition (PECVD) with the decomposi-
tion of a hydrocarbon gas in an RF capacitively coupled discharge,
however, this technique has drawbacks that limit the industrial scale
suitability, such as low parts volume per batch and low electrical
stability with larger sizes [10,11]. As alternative, a Medium Frequency
(1–500 kHz) pulsed-DC PECVD process can be used to obtain a-C:H in
industrial scale, as pointed out by several other authors [5,6,10,12,13].
The nitriding prior to DLC coating is also an attractive alternative for
large scale treatment of parts with comparably soft substrates, provid-
ing mechanical support and increasing adhesion of DLC films by me-
chanical interlocking of coatings with proper substrate roughness
increase [9,13,14].
A key factor is that gray and nodular cast irons microstructures are
composed of a metallic matrix and graphite, and these graphite flakes
or nodules located near the surface become critical regions for applica-
tions that demand high surface hardness or wear resistance [9,15,16]. In
fact, this is so crucial for some applications that motivated the

http://dx.doi.org/10.1016/j.surfcoat.2016.09.035
0257-8972/© 2016 Elsevier B.V. All rights reserved.

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2 R.O. Giacomelli et al. / Surface & Coatings Technology xxx (2016) xxx–xxx
development of a treatment for complete removal of near-surface
graphite prior to nitriding of cast irons [17].
For nodular cast irons (NCI), plasma nitriding causes small rough-
ness increase and generates only a thin nitride layer over exposed
graphite nodules, without surface cracking and ejection of these nod-
ules as observed in gaseous nitriding [18].
The nitriding of gray cast irons (GCI), however, deserves special at-
tention since it causes an intense modification of the topography, gener-
ating wedge-like features that increase the roughness of the surface.
Baranowska [19] studied the effect of different graphite flakes orienta-
tion on the gaseous nitriding of gray cast irons. In this context, a phe-
nomenological model was presented stating that different graphite
flakes orientation in relation to the surface (parallel, perpendicular or
askew) determine whether these graphite flakes will act as a nitrogen
diffusion barrier. Furthermore, the author states that this diffusion
blocking effect causes intense local nitriding, and the wedges form
due a volumetric expansion related with the structures of the nitride
layer (ε phase) and weak adhesion between matrix and graphite. Nev-
ertheless, no experimental evidence was presented quantifying these
effects, and it is not clear if the same happens in the case of plasma ni-
triding. Roliński [18,20] compared the roughness increase due wedge
formations after gaseous and plasma nitriding using the same GCI
type. In these studies, the roughness increase after gaseous nitriding
was much larger than in plasma nitriding, due a more pronounced
wedge formation. This difference was attributed mainly to the fact
that the incoming active species penetrate deep in the void between
the graphite flake and metallic matrix in the case of gaseous nitriding.
The same effect was not observed in the case of plasma nitriding since
the plasma cannot penetrate these voids near graphite flakes [18,20], al-
though a significant amount of neutral nitrogen atoms is also present in
the pulsed DC plasma and not only nitrogen ions [21]. Moreover, the au-
thor does not mention any effect regarding graphite flakes orientation,
attributing the formation of wedges mainly to differences between the
nitrided phases, graphite and metallic matrices thermal expansion coef-
ficients and densities. Thus, it is clear that, for gaseous nitriding, there
are two concurrent phenomena happening simultaneously: a diffusion
Fig. 1. Microstructures of (a) gray cast iron and (b) nodular cast iron. Aspect of polished surfaces of (c) GCI and (d) NCI.
Please cite this article as: R.O. Giacomelli, et al., Surf. Coat. Technol. (2016), http://dx.doi.org/10.1016/j.surfcoat.2016.09.035
shortcut provided by the voids between graphite flakes and matrix
and the diffusion barrier effect already mentioned. Therefore, due this
key difference in the nitriding mechanism of both processing tech-
niques, it is not clear if the orientation of graphite flakes in the case of
plasma nitriding has the same effect as observed for gaseous nitriding.
This phenomenon is of great relevance considering that this layer will
be employed as mechanical support for a DLC coating aiming tribologi-
cal applications.
The present work evaluates the surfaces of gray and nodular cast
irons before and after the plasma nitriding followed by coating with a-
C:H, providing information on how near-surface graphite morphology
(flakes or nodules) affect the topography evolution and tribological be-
haviour of such systems. Scanning Electron Microscopy (SEM) and
White Light Interferometry (WLI) were used to investigate the topogra-
phy evolution, EDS linescans were used to investigate the near-surface
graphite flakes effect on gray cast iron after plasma nitriding (wedges
formation). Additionally, durability tests were performed in order to
compare the tribological performance of the film with different sub-
strate materials. Important differences were found between tribological
behaviour of materials: the GCI presented lubricious tribolayers cover-
ing most part of wear track whereas NCI presented topographic factors
inhibiting these tribolayers formation, a key factor that might explain
the friction coefficient variation.
2. Materials and method
2.1. Substrate materials
Gray cast iron and nodular cast iron discs with 28 mm of diameter
and 15 mm height were used, their microstructures are showed in
Fig. 1(a) and (b) respectively. Both materials presented totally pearlitic
matrices, except for the ferritic regions around graphite nodules in the
NCI. The surface of samples was ground with SiC #1200 paper and
polished with 1 μm alumina suspension, exposing both graphite flakes
and nodules (Fig. 1(c) and (d)).
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Fig. 2. Industrial scale PECVD reactor used (a) and setup during processing (b).
2.2. PECVD nitriding and coating with a-C:H
Both nitriding and a-C:H coating treatments were carried out in the
same industrial scale PECVD reactor with an internal volume of 1 m3
(Fig. 2(a)). The chamber pressure and gas mixtures control was fully au-
tomated with integration of mass flow controllers and the vacuum
pump gauges. The DC plasma source used was an MKS RPDG-100
10 kW, with a constant 50 kHz pulse frequency with 75% of on time
per pulse, and a +50 V bias on the remaining time for increased process
stability. The plasma processing parameters are showed in Table 1,
where the total gas flux was kept at a constant 1000 sccm during all
steps. A small amount of methane was added to stabilize the ε phase
(Fe2–3N) during nitriding. In order to enhance chemical adhesion be-
tween substrate and the a-C:H film, a Si rich interlayer was used with
Hexamethyldisiloxane (HMDS) as precursor mixed with hydrogen
and methane, the final step contains only methane as carbon source
and hydrogen to produce a-C:H films. The process was conducted in a
single thermal cycle, with only one heating step.
One sample of each material was only nitrided and five samples
were nitrided and coated with DLC in one single thermal cycle. The
setup used to treat the samples is shown in Fig. 2(b).
2.3. Samples characterization
2.3.1. Thin films properties
In order to obtain the DLC and nitrided layers thicknesses and cross-
section morphology, the samples were sectioned with a diamond wa-
fering blade. Surfaces of interest were covered with a copper sheet be-
fore mounting with glass filled epoxy resin for excellent edge
retention during metallographic preparation grinding and polishing
steps.
In addition, XRD analysis (Philips X'Pert MPD) with Cu Kα radiation
(λ = 1.5418 Å) was used to determine which nitride phases were pres-
ent. DLC films were investigated with Raman spectroscopy, in a
Renishaw 2000 Spectrometer with a 514.5 nm Argon laser.
The structural information of the DLC films was obtained by conven-
tional TEM and electron diffraction (ED) patterns analysis using a JEOL
JEM-1011 microscope operating at 100 kV. Transparent samples,
Table 1
Processing parameters of nitriding, interlayer and DLC steps.
Step T (°C) P (Torr) Bias (V) Gas mixture
Nitriding 550 2 370 90% N2 + 9% H2 + 1% CH4
Interlayer 260 1 500–550 HMDS + H2 + CH4
a-C:H 260 1 500–550 H2 + CH4
Please cite this article as: R.O. Giacomelli, et al., Surf. Coat. Technol. (2016), http://dx.doi.org/10.1016/j.surfcoat.2016.09.035
3
suitable for cross-section Transmission Electron Microscopy were
achieved by mechanical polishing followed by argon ion beam milling,
giving priority to the DLC layer.
2.3.2. Surface evolution
Evolution of surface was evaluated in three stages: polished (alumi-
na suspension with 1 μm of particle size), after nitriding, and after DLC
deposition. White Light Interferometry (Zygo NewView7000) and
data analysis (Mountains Map Universal® 7.1) were conducted in
order to quantify the changes in topography. In addition, SEM images
and EDS analysis were performed in a JEOL JSM-6390LV to provide in-
formation on surface morphology and correlate surface features and
chemical composition.
2.3.3. Durability tests
Tribological performance was evaluated in a UMT-2 (CETR) equip-
ment with reciprocating sphere-on-plane configuration, the pair was
composed of Si3N4 spheres vs. DLC in ambient air (~60% relative humid-
ity), six tests were made for each substrate material.
The track was 10 mm long with 2 Hz of frequency (speed of 40 mm/
s), with initial normal load of 7 N and an increase of 7 N every 10 min.
The durability tests ran until the friction coefficient was above 0.2,
above this critical friction coefficient value the system cannot be consid-
ered self-lubricated and the film probably worn out or failed [22]. This
method can be used to test the resistance of self-lubricating coatings
and materials [23].
3. Results and discussion
3.1. DLC and nitrided layers properties
After careful metallographic preparation, it was possible to observe
the cross section of the nitrided and DLC layers in optical micrographs,
as shown in Fig. 3. The thickness of DLC layers is very homogeneous in
both materials, with values of 2.34 ± 0.14 μm for GCI and 2.39 ±
0.13 μm for NCI. Thin compact compound layers formed on both mate-
rials, with a regular thickness varying around 5 μm for NCI whereas a
compound layer ranging from approximately 3 until 7 μm of thickness
was observed in GCI. The surface regions located near graphite flakes
presented higher compact compound layer thicknesses, as can be ob-
served in Fig. 3(c), there are also regions with a coarsening of pearlite-
like nitride layers underneath the compound layer.
The coarsening happens where nitrogen was detected by EDS, which
can be related to the smaller density of iron nitride (7.12 to 7.24 g/cm3)
Time (min)
in comparison to an iron matrix (7.88 g/cm3) [20].
90 Fig. 4(a) presents a bright-field transmission electron micrograph
35 from representative thin section from as-deposited DLC film and the
40
Fig. 4(b) and (c) are corresponding selected area electron diffraction
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Fig. 3. SEM micrographs of (a) gray and (b) nodular cast irons showing the DLC and compound layers. On (c), a detail of coarse pearlite-like nitride in GCI with two EDS analysis regions and
their respective nitrogen wt.%.

(SAED) patterns of DLC film. The SAED patterns give information on the
degree of ordering that can be derived from the brightness and width of
the diffraction pattern. Fig. 4(b) shows three diffuse rings, indicative of
the amorphous nature of DLC film. The d-spacing of the rings for both
patterns (Fig. 4(b) and (c)) were indexed to be approximately 2.50,
2.13 and 1.50 Å, corresponding to (111)DLC (innermost ring) and the
others to sp2-graphite reflections. Fig. 4(c) shows a few dotted features
or streaks within the halos, which signify the presence of short-range
order of crystalline graphite. DLC films are composed mainly of carbon
atoms in a non-crystalline arrangement without any long range order
such that their structure contains regions that are locally diamond-like
and also certain regions that are locally graphite-like [24–27].
In the DRX analysis it was possible to identify the γ′ (Fe4N) and ε
phases (Fe2–3N) in both GCI and NCI substrates after nitriding process
(Fig. 5(a)), denoting the formation of a mixed phase compound layer
[28]. The area under the peaks can be related to the amount of phases
present in the case of nitrided layers, although for higher precision of
the method the samples must be in the powder form randomly oriented
[29]. All peaks of the γ′ phase presented a higher area in the case of GCI
compared to NCI (Fig. 5(a)), this indicates a higher amount of this phase
in the case of GCI.
Fig. 5(b) shows Raman spectra of DLC films after baseline removal
for GCI and NCI substrates, where no significant differences can be
pointed out between them. The “D” and “G” bands were quantified

Fig. 4. (a) Bright-field transmission electron micrograph of as-deposited DLC film; (b) corresponding SAED pattern obtained near the surface and (c) corresponding SAED pattern obtained
near the substrate.

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Fig. 5. DRX for nitrided GCI and NCI samples and Raman spectra of DLC coated GCI and NCI samples.
with a fit of spectra using two Gaussian curves commonly used in the
case of hydrogenated DLC [4,30]. Little dispersion was found between
different samples as shown in Table 2.
Based on the position and intensity of D and G bands, the film can be
classified as an a-C:H, where the hydrogen content lies between 20 and
40 at.% with an average amount of carbon sp2 sites clustering in the
structure, as indicated in the TEM analysis [31]. The hydrogen content
was estimated based on the visible Raman photoluminescence back-
ground slope present for a-C:H films using a method proposed by
Casiraghi in [30,32].
3.2. Topography evolution after nitriding and DLC deposition
Plasma processes involving metallic substrates almost invariably
induce changes on the topography, with different intensity depend-
ing on the imposed conditions [33,34]. In order to evaluate and quan-
tify these changes in the topography, the samples were analyzed
during three different stages of processing: (1) after polishing, (2)
after nitriding and (3) after DLC deposition.
For both NCI and GCI there is a significant evolution in surface to-
pography as illustrated in Fig. 6 and Fig. 7. In Table 3, the main topo-
graphic parameters are summarized for all conditions. For both NCI
and GCI there is a significant increase in the overall roughness after
nitriding. A major increase on the root mean square roughness (Sq)
and reduced peak height (Spk) can be pointed out for GCI after nitrid-
ing, while after DLC deposition these values remained equivalent.
This drastic change observed in GCI is related to the formation of
wedges in regions near graphite flakes in the surface, as shown in Fig.
7. Extra samples were heat-treated in protective atmosphere (95% Ar
and 5% H) with the same thermal cycle used during nitriding, 550 °C
and 1 h 30 min of dwelling time, in order to evaluate if any of the previ-
ous machining and polishing steps introduced stresses on the surface
that could be contributing in some way to this phenomenon. In the
present study, no modification was observed in the topography of
heat-treated samples.
3.2.1. Topography evolution - nodular cast iron
In Fig. 6, axonometric projections and related SEM images are
displayed. There is an intense change in the topography after nitriding,
Table 2
Raman spectra analysis.
Substrate material Pos. D (cm−1) Pos. G (cm−1) I(D)/I(G)
GCI 1386 ± 3,3 1563 ± 2,1 0,60 ± 0,03
NCI 1385 ± 1,0 1560 ± 1,0 0,58 ± 0,02
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5
whereas small modifications are observed after DLC deposition (see
Table 3). Comparing the SEM image from Fig. 6(d) to (e), there is forma-
tion of nitrides completely covering the previously exposed graphite on
the surface, however, this effect is not sufficient to fill up the depres-
sions present on the initial polished surface.
This generalized increase in roughness after nitriding can be re-
lated to the ion bombardment during plasma treatment and the for-
mation mechanism of the nitrided layer [28]. Nevertheless, when
properly controlled, this roughness increase is beneficial for the ad-
hesion of DLC films due an increase in the mechanical anchoring
[13,35]. Still related to the ion bombardment, it was observed that
the depth of the depressions where the graphite nodules were ex-
posed increases significantly after nitriding. After DLC deposition,
the depth of the depressions diminishes with the presence of the
film. A possible explanation can be attributed to the growth mecha-
nism of DLC following a ballistic model [13].
3.2.2. Topography evolution - gray cast iron
An intense modification on the topography of GCI was observed
during treatments (Fig. 7), with special importance for the wedges
formation after nitriding. These wedges form in regions where the
graphite flakes were located near the surface, in most cases
completely covering the graphite that was previously exposed
(Fig. 7(d) and (e)). After DLC deposition, little modification was ob-
served in comparison with the nitrided surface (Fig. 7(b) and (c)),
as shown in the similar topographic parameters (Table 3).
3.2.3. Wedge formation in plasma nitriding of GCI
In order to investigate this phenomenon, cross sections of GCI were
analyzed by EDS linescans in regions with three different graphite flake
orientations (Fig. 8): (a) askew, (b) vertical, (c) parallel.
The EDS linescans clearly show that the graphite flake orientation
is crucial to determine whether a graphite flake blocks the nitrogen
diffusion. For askew and parallel orientations shown in Fig. 8(a)
and (c), no nitrogen was detected under the graphite flakes, while
in the vertical orientation (Fig. 8(b)) nitrogen content gradually
decreased.
It is also important to point out that the incoming nitrogen
charged species are attracted to the biased metallic surface, charac-
teristic of PECVD processes, hindering the penetration of active
species in the voids between graphite flakes and the metallic matrix
[18,20]. Furthermore, still observing Fig. 8, it becomes clear that the
diffusion is highly oriented perpendicularly to the surface, enhanc-
ing the effect of graphite orientation as a diffusion barrier: the flakes
at.% H
act almost like an “umbrella” for the incoming nitrogen. In gaseous
40,5 ± 0,6 nitriding the exact opposite occurs: nitrogen reactive species have
39,3 ± 2,9
a shortcut to diffuse along the near-surface graphite flake, regardless
6 R.O. Giacomelli et al. / Surface & Coatings Technology xxx (2016) xxx–xxx

Fig. 6. Topography evolution details with WLI and SEM for nodular cast iron (NCI), in polished (a) and (d), nitrided (b) and (e) and with DLC (c) and (f).

Fig. 7. Topography evolution with WLI and SEM for gray cast iron (GCI), polished (a) and (d), nitrided (b) and (e) and with DLC (c) and (f).

of these voids being above or underneath the flake. This also helps
explaining why this effect does not happen for the nitriding of nod-
ular cast iron, where the area occupied by the nodules is smaller
than the area occupied by graphite flakes.
Fig. 9 summarizes the main effect of graphite flake orientation.
The most critical case happens when the graphite flake is askew to
the surface, since weak graphite-matrix interaction, interruption of
nitride layer together with an intense local volumetric expansion
happen simultaneously, creating wedges systematically in this con-
figuration (Fig. 9(b)). In the case where the graphite flake is vertical,
although there is an interruption of the nitride layer, no intense ni-
triding occurs since there is no barrier for the diffusion of nitrogen
and, thus, less volumetric expansion takes place and no wedge for-
mation was observed (Fig. 9(c)). When the graphite flake is parallel

Table 3
Topography parameters evolution.

Material Sq (μm) Sdq (μm/μm) Sk (μm) Spk (μm) Svk (μm)

NCI-polished 0.09 ± 0.02 0.07 ± 0.01 0.03 ± 0.01 0.04 ± 0.01 0.21 ± 0.06
NCI-nitrided 0.31 ± 0.10 0.26 ± 0.02 0.48 ± 0.07 0.30 ± 0.04 0.66 ± 0.40
NCI-DLC 0.27 ± 0.04 0.37 ± 0.05 0.51 ± 0.06 0.31 ± 0.02 0.46 ± 0.17
GCI-polished 0.13 ± 0.05 0.11 ± 0.02 0.07 ± 0.02 0.08 ± 0.05 0.27 ± 0.10
GCI-nitrided 0.57 ± 0.10 0.37 ± 0.04 0.89 ± 0.07 1.01 ± 0.21 0.71 ± 0.22
GCI-DLC 0.54 ± 0.12 0.46 ± 0.05 0.88 ± 0.08 0.94 ± 0.27 0.65 ± 0.22
GCI-heat-treated 0.13 ± 0.04 0.11 ± 0.01 0.09 ± 0.01 0.11 ± 0.05 0.27 ± 0.09

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Fig. 8. EDS Linescans for nitrogen and carbon (wt.%), with three graphite flakes orientations: (a) askew, (b) vertical and (c) parallel to the surface. The exact analysis locations are marked
with dotted arrows downwards.

to the surface there is no interruption of the nitride layer, inhibiting
the formation of wedges (Fig. 9(d)).
3.3. Tribological investigation
Fig. 10(a) shows the evolution of friction coefficient (COF) and nor-
mal load with sliding distance. The COF evolution is clearly different for
NCI and GCI as the normal load increases: a significant drop in the fric-
tion coefficient happens for GCI in relation to NCI (Fig. 10(c)). In addi-
tion, the average friction coefficient was determined for lubricious
steady-state regime (75–175 m) (Fig. 10(a)). Some authors reported
similar friction coefficient levels (0.05) for a-C:H against ceramic coun-
terparts in air [36]. On the other hand, the durability values are statisti-
cally equivalent for each group (Fig. 10(b)).
These results show that, only by changing the substrate material, it is
possible to achieve radically different tribological performances. Al-
though the GCI topography presents features such as the wedges,
which generates many critical points for the detachment and failure of
DLC coating, the material presented extremely low friction coefficient
during the lubricity regime.

Fig. 9. Scheme showing different situations for the wedges formation in plasma nitriding (a). Particular cases of graphite flakes orientation to the surface: (b) askew, (c) vertical and
(d) parallel.

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Fig. 10. (a) Friction coefficient vs. sliding distance curves for NCI and GCI, with corresponding normal load vs. sliding distance curve. (b) Durability and (c) friction coefficient during
lubricity regime for gray and nodular cast irons.

In order to further understand this point, additional durability tests
were interrupted in the beginning of the lubricity regime (approximate-
ly 75 m of sliding distance). In Fig. 11, typical BSE images of the wear
tracks are displayed, together with the corresponding optical microsco-
py images of the counterbodies.
By comparing Fig. 11(a) and (c) one can notice that prominent
tribolayers were found in GCI covering a significant area of the wear
track surface, while very few tribolayers islands were found in NCI wear
track. In fact, the amount of debris found on the GCI counterbody after
tests was much larger than the amount found for NCI (Fig. 11(b) and
(d)). Actually, on the NCI wear track, most wear debris were “trapped”
on the depressions present on the topography hence not participating
in the formation of the lubricious tribolayer. The higher amount of debris
found in GCI can be associated to spalled areas caused by the wedges
present on the topography acting as stress concentrators. The same
wedges also act as anchoring points for debris, nucleating tribolayers pref-
erentially on these regions. Also, all tribolayers presented a brighter color
than the DLC in BSE images, indicating the presence of elements with
higher atomic number, such as iron from wear debris of the substrate.
Fig. 12 presents higher magnification images of wear tracks for NCI
and GCI. On Fig. 12(a) it is possible to observe debris piled-up and
trapped by a graphite nodule depression on the wear track, Raman anal-
ysis in these regions showed similar results as the ones observed for
tribolayers observed for GCI in Fig. 12(b).

Fig. 11. Wear tracks of interrupted durability tests (between white dashed lines) and corresponding images of Si3N4 counterbody for NCI in (a) and (b); and for GCI in (c) and (d).

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 R.O. Giacomelli et al. / Surface & Coatings Technology xxx (2016) xxx–xxx
Fig. 12. Wear track regions of Raman analysis in detail for NCI (a) and GCI (b). Typical Raman spectra for worn DLC areas (1) and for tribolayer areas (2) for both materials (c).
Additionally, the Raman spectra of Fig. 12(c) show that tribolayers are
composed mainly by disordered graphitic structures, since the D band is
dislocated to lower Raman shift values whereas the G band position is
dislocated to higher Raman shift values, together with a higher Id/Ig
ratio (~0.72) when compared to the original DLC Raman spectra from
Fig. 5 [4]. Such structures are known to induce low friction coefficient
for hydrogenated amorphous carbon [1,4]. It is reasonable to suppose
that the presence of such tribolayer is at the origin of the low friction co-
efficient presented by GCI tribo pairs.
Summarizing, for GCI there are more debris available at the contact
areas, generating lubricious tribolayers covering a significant part of the
wear track, reducing, thus, the friction coefficient. However, for NCI, the
few debris available accumulate on the depressions present on the mate-
rial topography, inhibiting the formation of a lubricious tribolayer.
4. Conclusions
After careful comparison of the changes induced by the PECVD treat-
ments of the gray and nodular cast irons substrates, it is possible to con-
clude that:
• The morphology of graphite present on the substrates strongly influ-
ences the topography evolution after nitriding, with an increase of the
Sq from 0.13 to 0.53 μm in the case of gray cast iron, and from 0.09 to
0.31 μm in the case of nodular cast iron.
• The graphite of the gray cast iron acts as a very effective diffusion barrier
for nitrogen in plasma nitriding depending on its orientation relative to
the surface.
• The formation of wedges after plasma nitriding in the case of GCI was
attributed to a combination of: graphite flake orientation to the surface
(askew), interruption of the nitride layer, strong local nitriding causing
local volumetric expansion and weak graphite-matrix interaction.
• Durability tests showed similar performance regarding the capacity of
films maintain the system in self-lubricating regime until a critical nor-
mal load. However, the friction coefficient during lubricity regime was
2.3 times lower in the case of GCI (0.06) in relation to NCI (0.14).
• The reduction in the friction coefficient observed for the GCI can be at-
tributed to the formation of lubricious tribolayers that cover most part
of the wear track due the high amount of debris, which, in turn, are orig-
inated mainly from spalling of the coating near the wedges caused by
nitriding.
• For NCI, there is less debris formation and trapping of them in the de-
pressions present on the topography of NCI, inhibiting the formation
of the lubricious tribolayer observed for the GCI.
Acknowledgements
The authors would like to thank the following Brazilian agencies for
funding this research: CNPq, Capes, BNDES, as well as Whirpool/Embraco
and the LCME-UFSC for technical support.
Please cite this article as: R.O. Giacomelli, et al., Surf. Coat. Technol. (2016), http://dx.doi.org/10.1016/j.surfcoat.2016.09.035
9
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