Surface and Coatings Technology 177 178 (2004) 284288

Scratch test analysis of coated and uncoated nitrided steel

J.-D. Kammingaa,*, P.F.A. Alkemadeb, G.C.A.M. Janssenb
a
Netherlands Institute for Metals Research, Rotterdamseweg 137, Delft, AL 2628, Netherlands
b
Department of Materials Science and Technology, Delft University of Technology, Rotterdamseweg 137, Delft, AL 2628, Netherlands

Abstract

The mechanical properties of duplex-coated steel, nitrided steel and untreated steel were characterised by means of scratch
testing. It was obtained that upon nitriding, the yield stress of steel increases from 2.7 to 7 GPa and the ductility decreases. For
the duplex-coated steel, which consists of a 1 mm Cr2 N layer on nitrided steel, the adhesion of the Cr2 N layer was very good,
despite the presence of some iron nitride at the coatingsubstrate interface. The influence of the Cr2 N layer on the mechanical
properties of the nitrided steel is discussed. The Cr2 N coating slightly affects the hardness of the specimen and the friction of the
sliding indenter. However, the crack patterns in the scratch tracks are influenced considerably.
2003 Elsevier B.V. All rights reserved.

Keywords: Duplex treatment; Nitriding; PAPVD; Scratch test; Chromium nitride

1. Introduction of scratch testing for duplex-coated steels. Results from

Duplex coatings, consisting of a nitrided steel sub-
strate covered with a hard ceramic coating combine high
load carrying capacity and fatigue resistance of the
hardened substrate with low friction and good abrasive
wear resistance of the coating. Therefore, they are useful
for many practical applications. Earlier work revealed
superior scratch resistance and impact wear resistance
for duplex-coated steel as compared to uncoated unni-
trided steel w1x.
In this paper, scratch testing of duplex-coated steel is
elaborated. In the scratch test, usually a diamond Rock-
well indenter with a spherical tip is scratched over the
surface of the specimen under investigation, applying a
certain load and speed. Often, the load is progressively
increased during the test. The different types of failure
occurring are subsequently connected to critical loads
obtained by visual inspection of the specimen after
scratching (e.g. Refs. w24x). However, also the track
dimensions and the frictional force necessary to move
the indenter can be useful to characterise the specimen.
Until now papers concerning the characterisation of
duplex coatings by means of scratch testing are relatively
scarce w58x. The present paper explores the possibilities
*Corresponding author. Tel.: q31-1527-82234; fax: q31-1527-
86730.
E-mail address: J.D.Kamminga@tnw.tudelft.nl (J.-D. Kamminga).
duplex-coated specimens will be compared to results
from nitrided and untreated steel in order to extract the
separate contributions of the nitriding and the hard
ceramic coating.
2. Experimental
Mechanically polished cylinders of X38CrMoV5-1
steel (diameter 30 mm, height 6 mm, final polishing
step 1 mm diamond paste) were used as substrate.
Plasma nitriding and Cr2N layer deposition were per-
formed in a Hauzer HC 750 PVD apparatus. Plasma
nitriding was performed for 1 h in ArN2 plasma at a
temperature of 540 8C. A comprehensive description of
the nitriding treatment is given in Ref. w1x. Nitriding
conditions optimised for nitriding rate were employed,
resulting in a nitrided case depth of approximately 40
mm (somewhat larger than the depths obtained in Refs.
w1,9x). Under these conditions some iron nitride is
formed at the surface of the steel, accompanied by a
slight roughening of the surface. The Cr2N layer was
deposited directly after the nitriding treatment (without
first removing the iron nitride), by activating a Cr
sputter target in the ArN2 plasma. The deposition time
for Cr2N was 1 h, leading to a layer thickness of
approximately 1 mm. X-Ray diffraction measurements

0257-8972/04/$ - see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2003.09.006
 J.-D. Kamminga et al. / Surface and Coatings Technology 177 178 (2004) 284288
Fig. 1. CLSM micrographs of scratch tracks on (a) nitrided steel and (b) duplex-coated steel. For both tracks a load of 40 N was employed.
Scratch direction is from top to bottom.
showed that the layers were under a compressive stress
(approx. y1 GPa). Three specimens are considered in
the present paper: an untreated, a nitrided and a duplex-
coated substrate. Identical nitriding conditions were used
for the nitrided and the duplex-coated specimen.
Scratch tests were performed using a scratch tester
with a load range of 1200 N. Scratches (length 5 mm)
were made using a diamond Rockwell indenter with a
spherical tip (radius 200 mm) sliding at a constant speed
of 5 mmymin. During the scratch tests, the friction force
was measured. Scratches were made employing a con-
stant load between 2 and 100 N. The scratch tester is
equipped with an optical microscope, which was used
for the measurement of the track width.
Detailed microstructural investigations were per-
formed with a confocal laser scanning microscope
(CLSM). The CLSM is particularly suited for the
microstructural investigations of the scratches. By recon-
struction of many micrographs (20100) obtained at
different focal depths, an optical micrograph is obtained
that is in focus over the entire depth of the scratch.
With this procedure, also depth profiles of the tracks
can be obtained. Furthermore, a scanning electron micro-
scope (SEM) equipped with a focused ion beam (FIB)
was used for in depth investigations.
3. Results
Fig. 1a,b show CLSM micrographs (planar views) of
scratch tracks (load 40 N) on nitrided steel and a
duplex-coated steel, respectively. Tensile cracking occurs
for both specimens. In this failure mode, cohesive cracks
form in the tensile stress field in the wake of the moving
indenter. Neither in the nitrided steel nor in the duplex-
coated steel cracking is observed for loads below 40 N.
285
Cracks in the duplex-coated steel are fine as compared
to cracks in the nitrided steel. For both specimens the
tensile cracking becomes more pronounced at increased
load. In Fig. 2a,b the scratch tracks obtained with a load
of 90 N are shown. Independent on the load the crack
spacing is smaller and more regular for duplex-coated
steel than for nitrided steel. For nitrided steel, the crack
spacing decreases with increasing load from roughly 50
mm at 40 N (cf. Fig. 1a), to a value of approximately
30 mm at 100 N. For the duplex-coated specimen, a
crack spacing of approximately 6 mm was observed for
a load of 40 N (Fig. 1b). For higher loads the crack
spacing was approximately 15 mm, independent on the
load (Fig. 2b). Delamination was never observed for
the duplex-coated specimen, which shows that some
iron nitride at the nitrided substratecoating interface
does not considerably deteriorate adhesion. In scratch
tracks on the untreated specimen cracking was never
observed and at all loads significant pile-up occurred
near the edges of the scratch track.
Fig. 3 shows the load divided by 1y4pd2y4 (d is the
width of the scratch track), referred to as apparent
scratch hardness, vs. the load for the three specimens
investigated. The designation apparent scratch hardness
is used here, because the real scratch hardness (defined
as the ratio of the load and the projected load bearing
area w1012x) is in practice unknown due to uncertainty
in the projected load bearing area. In general, only the
front half of the indenter is fully supported by the
specimen while because of plastic deformation, the rear
half of the indenter may only be supported in part. The
apparent scratch hardness equals the real scratch hard-
ness if the material fully supports the rear half of the
indenter and piling-up in front of the indenter does not
occur.
286 J.-D. Kamminga et al. / Surface and Coatings Technology 177 178 (2004) 284288

Fig. 2. CLSM micrographs of a scratch tracks on (a) nitrided steel and (b) duplex-coated steel. For both tracks a load of 90 N was employed.
Scratch direction is from top to bottom.

Fig. 3 shows that nitriding considerably increases the indenter, plastic yielding occurs at lower loads due to
hardness. The Cr2N coating causes a (small) hardness shear stress. For the present experiments this effect can
increase. Fig. 3 also shows the Hertzian solution for a be neglected because the overall friction coefficient is
purely elastic contact w13x. For low loads (-10 N), the sufficiently low w13x. Therefore, the results in Fig. 3 can
data obtained for the nitrided and the duplex-coated be used to estimate the yield stress Y. From Fig. 3 it is
specimen equal the Hertzian solution for the elastic estimated that plastic deformation sets in at 3 GPa for
contact within experimental precision. The apparent the steel and 7.8 GPa for the nitrided steel and the
elastic response of the nitrided and the duplex-coated duplex-coated specimen, corresponding to yield stresses
steel at loads lower than 10 N, is confirmed in Fig. 4, of 2.7 and 7 GPa. For nitrided and duplex-coated steel
which shows depth profiles of 10 N scratches in the it was verified w15x that the maximum von Mises stress
untreated, nitrided and duplex-coated specimen. For the at the onset of plastic deformation is positioned at
nitrided steel and the duplex-coated steel, virtually no approximately 10 mm below the surface, well within the
plastic deformation is observable, except for some nitrided zone. Upon increasing the load on an ideal
smoothening inside the track. This smoothening without
considerable plastic deformation is known as ironing
w11x. For the untreated steel a clear depressed track is
formed with significant pile-up at the edges. Indeed at
this load the apparent scratch hardness is much lower
than the Hertzian solution (Fig. 3).
The total friction force divided by the load, referred
to as the overall friction coefficient, is plotted vs. load
in Fig. 5. The friction coefficient increases with increas-
ing load for all specimens. Independent on the load, the
friction coefficient is largest for the untreated steel and
smallest for the nitrided steel. For the nitrided steel and
the duplex-coated specimen, the friction coefficient is
more or less constant for loads below 10 N.

4. Discussion

Upon loading an ideal plastic material with a static

spherical indenter, in the absence of a shear stress,
plastic deformation starts to occur at a mean contact
pressure (the ratio of the load and the projected area)
of 1.1 times the yield stress w14x. In the case of a sliding
Fig. 3. Apparent scratch hardness vs. load for the specimens investi-
gated. Also, the purely elastic solution due to Hertz is shown. For the
Hertzian solution, the Youngs modulus and Poissons ratio employed
were 1100 GPa and 0.1 for the diamond indenter, and 200 GPa and
0.3 for the steel sample, respectively.
 J.-D. Kamminga et al. / Surface and Coatings Technology 177 178 (2004) 284288
Fig. 4. Depth profiles of scratch tracks (load 10 N) normal to the
scratch direction for the specimens investigated.
plastic material with a static spherical indenter, the mean
contact pressure rises until the flow under a static
indenter is fully plastic. From that point on the mean
contact pressure is independent of the load and its value
is known as the hardness H. Then the relation Hf3Y is
expected to hold w14x. Fig. 3 shows that from the present
sliding indenter experiments H cannot be determined.
Instead of increasing, the apparent scratch hardness
slightly decreases with increasing load. This is probably
due to the decreasing load bearing area below the sliding
indenter. In Ref. w1x, with micro-Vickers hardness meas-
urements, hardnesses of approximately 7 and 12 GPa
were obtained for untreated and nitrided steel, respec-
tively. The plastic properties of the untreated steel
resemble that of the ideal plastic material because the
relation Hf3Y approximately holds. For the nitrided
steel the relation is not fulfilled. In view of the micro-
Fig. 5. Overall friction coefficient vs. load for the specimens
investigated.
287
Fig. 6. Oblique-view SEM micrograph of holes milled with a focussed
ion beam. The specimen has been tilted such that a sidewall of the
holes is observed. The interface of the Cr2N layer with the nitrided
substrate is clearly visible. Cracks proceed through the coating into
the nitrided substrate.
structure of the nitrided steel (an iron matrix with very
small nitride precipitates, e.g. Refs. w1,9x) the un-ideal
plastic behaviour is not unexpected.
Two contributions to the overall friction coefficient
are often considered: an adhesion term and a ploughing
term w16,17x. The adhesion term is related to the
interfacial friction coefficient and the ploughing term
reflects the resistance as the indenter ploughs into the
material. If the deformation is purely elastic, the plough-
ing term can be neglected, because increased friction of
the front half of the indenter that has to slide up-hill
is compensated by to the down-hill sliding of the fully
supported rear half of the indenter. Indeed, a constant
overall friction coefficient is observed as long as the
deformation is purely elastic, i.e. for the nitrided steel
and the duplex-coated specimen at loads -10 N (Fig.
5). If a residual scratch track depth remains due to
plastic deformation, the rear half of the indenter is not
fully supported and the overall friction coefficient
increases. This effect becomes more pronounced if
piling-up of material in front of the indenter occurs.
This explains the higher friction coefficient observed for
the untreated steel (cf. Fig. 4). Of course, also the ease
at which the material in front of the indenter deforms,
the geometry of the indenter and the depth of the scratch
track affect the friction coefficient w16x. The overall
friction coefficient for the nitrided steel is slightly, but
significantly, smaller than the overall friction coefficient
for the duplex-coated steel. This is probably connected
to the smoother surface of the track for the nitrided
specimen (see Fig. 1a,b and Fig. 2a,b).
Nitrided and duplex-coated specimens both fail due
to tensile cracking, in agreement with Refs. w57x. An
288 J.-D. Kamminga et al. / Surface and Coatings Technology 177 178 (2004) 284288
interesting result is the smaller and more regular crack
spacing for the duplex-coated specimen as compared to
the nitrided specimen. Similar results can be observed
in the micrographs shown in Ref. w5x. The irregular
crack spacing for the nitrided steel suggests that for
these specimens the initiation of cracks is difficult,
whereas the regular crack spacing for the duplex speci-
mens indicates easy crack initiation. The oblique view
SEM image of Fig. 6 shows the FIB result on one of
the cracks in the duplex-coated specimen shown in Fig.
2b. With the ion beam two holes have been milled at
one of the cracks. In the micrograph the Cr2N layer is
clearly visible. The crack propagates without deflection
through the Cr2N layer into the nitrided substrate.
Optical microscopy on a polished cross section of the
track showed that cracks propagate to a depth as large
as 3040 mm. In view of this crack depth and the
identical nitriding treatment for nitrided steel and
duplex-coated steel, crack propagation should be similar
for both specimens and the thin Cr2N layer influences
crack initiation only.
The loading under the indenter in the majority of our
experiments is such that the steel deforms plastically.
The brittle coating cannot follow this deformation and
cracking occurs. The cracks in the coating then initiate
crack growth in the nitrided steel. According to the
Griffith criterion w18x cracks form at a critical stress and
critical flaw size. For nitrided only samples, the critical
flaw size is the roughness of the substrate. For duplex-
coated samples, once the coating has cracked, the
thickness of the coating is the flaw size initiating crack
growth in the nitrided steel. Since the Cr2N coating
thickness is larger than the roughness of the nitrided
substrate a larger stress is needed to initiate crack growth
in the nitrided only samples, leading to a wider spaced
crack pattern. For applications in the loading regime
leading to plastic deformation of the steel a Cr2N coating
may be disadvantageous. The duplex process, however,
was designed to extend the range of loading conditions
beyond that of coated not nitrided steel by preventing
plastic deformation in the steel.
Of course, the above explanation holds only if the
adhesion between the nitrided steel and the coating is
sufficient and no interfacial cracking occurs. Fig. 6
shows that in the present case the adhesion of the
coating is very good. The conclusion of a previous paper
w1x that deposition of a Cr2N coating directly after
nitriding without the formation of iron nitrides yields
duplex coatings with good adhesion between the nitrided
steel and the PVD layer, therefore, also holds if some
iron nitride is present on the interface.
The hardness of the duplex coating is slightly higher
than that of the nitrided only sample. The friction
between the diamond indenter and the Cr2N layer is
slightly larger than the friction between the indenter and
the nitrided steel.
5. Conclusions
It is demonstrated that from scratch test measurements
the yield stress of steel and nitrided steel can be
determined. A comparison of scratch test results on
untreated and nitrided steel showed that nitriding makes
the steel harder and more brittle. Due to the absence of
pile-up, the friction of a sliding indenter on nitrided
steel is smaller. It is shown that duplex coatings with
good adhesion between the nitrided substrate and Cr2N
layer can be obtained even if some iron nitride is present
at the interface. Under scratch testing, a finer crack
pattern develops in duplex coatings than in nitrided only
samples.
Acknowledgments
E.R. Peekstok and R. van der Meij are kindly
acknowledged for their assistance with the confocal
laser scanning microscope investigations. This research
was carried out under project number MC7.01087 in the
framework of the Strategic Research programme of the
Netherlands Institute for Metals Research in the Neth-
erlands (www.nimr.nl).
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