Surface & Coatings Technology 206 (2012) 3764–3771

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Surface & Coatings Technology

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Influence of Al on the microstructure and mechanical properties of Cr–Zr–(Al–)N

coatings with low and high Zr content
W.Z. Li a, b,⁎, M. Evaristo a, A. Cavaleiro a,⁎⁎
a
SEG-CEMUC - Department of Mechanical Engineering, University of Coimbra, Rua Luís Reis Santos, P-3030 788 Coimbra, Portugal
b
School of Materials Science and Engineering, Guangxi University, Nanning 530004, PR China

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

Article history: Low Zr (S1) and high Zr (S2) quaternary Cr–Zr–(Al–)N coatings with increasing Al content were deposited by
Received 15 December 2011 d.c. reactive magnetron sputtering. The structure, fracture cross-section morphology and mechanical proper-
Accepted in revised form 10 March 2012 ties of the coatings were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM),
Available online 17 March 2012
nanoindentation, scratch testing and Vickers micro-indentation testing. All the coatings present an fcc
NaCl-type B1 structure; in the low Zr content coatings, the diffraction peaks shift towards higher angles as
Keywords:
Cr–Zr–(Al–)N coatings
the Al content increases. The grain size is approximately constant in a range from 6 to 8 nm, except for
Microstructure high Zr content films where a significant decrease in crystalline order is observed (grain size ~ 2.5 nm). In
Hardness both series, the microstructure changed from equiaxed to columnar with increasing Al content. The highest
Adhesion hardness and strongest adhesion values were achieved in coatings with lower Zr and Al content. Conversely,
Toughness the coatings with high Zr and the highest Al content exhibited an abrupt decrease in hardness, adhesion
strength and toughness.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
CrN has been widely studied and used as hard, protective and
wear-resistant coatings in recent decades due to its high thermal
stability, high toughness and hardness as well as strong corrosion-
resistance [1]. However, the hardness, stability and oxidation-
resistance at high temperatures of binary CrN coating were still
inadequate for some applications, such as high speed machining
and hot forming dies. The introduction of alloying elements such
as Zr, Si or Al into the CrN coatings has been used to solve such
problems [2–5].
Among these Cr-based ternary nitride coatings, Cr–Zr–N was
regarded as a promising candidate for high temperature applications
[6]. However, Kim et al. [7] found that Cr–Zr–N coatings did not show
any marked improvement in high temperature wear resistance com-
pared to CrN due to the rapid formation of ZrO2 on the coating surface
during high temperature exposure. Many researchers have since
focused attention on the investigation of Cr–Zr-based quaternary ni-
tride coatings, introducing Si, Al or Y to improve the high temperature
⁎ Correspondence to: W.Z. Li, SEG-CEMUC - Department of Mechanical Engineering,
University of Coimbra, Rua Luís Reis Santos, P-3030 788 Coimbra, Portugal. Tel.: + 351
239 790 745; fax: + 351 239 790 701.
⁎⁎ Corresponding author. Tel.: + 351 239 790 745; fax: + 351 239 790 701.
E-mail addresses: wz-li@hotmail.com (W.Z. Li), albano.cavaleiro@dem.uc.pt
(A. Cavaleiro).
properties [8–11]. Lee et al. [8] found that a significant increase in the
hardness and toughness could be reached by adding Si. Moreover,
high-temperature annealed Cr–Zr–Si–N coatings exhibited a far
smaller decrease in the hardness than the similar ternary Cr–Zr–N
coating. Importantly, the high temperature wear resistance of the
Cr–Zr–Si–N coating was also improved markedly [9]. Kim et al. [10]
studied the mechanical properties of Cr–Zr–(Al–)N quaternary coat-
ings and found they could achieve very high hardness values in the
range [30–45 GPa]. The experimental results from Rojas et al. [11]
showed that Cr–Al–Zr–N coatings exhibited high hardness and good
oxidation-resistance due to the formation of an Al-rich outer layer
during high temperature exposure. Therefore, undoubtedly Cr–Zr-
based quaternary nitride coatings exhibited better mechanical prop-
erties and high temperature oxidation-resistance than Cr–Zr–N coat-
ings. Our previous research experience also showed that, generally, Al
alloying would also strongly influence the oxidation-resistance and
mechanical properties of nitride coatings [12]. However, to our
knowledge, none of the existing studies involved a systematic inves-
tigation of the effects of Al content in Cr–Zr-based nitride coatings on
their microstructure and mechanical properties.
In this investigation, two series (low Zr and high Zr) of Cr–
Zr–(Al–)N coatings with increasing Al content were deposited by
d.c. reactive magnetron sputtering. The influence of Al on the coat-
ing structure, microstructure and mechanic properties was investigat-
ed, and a comparison was carried out between the low Zr and
high Zr coatings with respect to phase structure, morphology,
hardness, adhesion and toughness.

0257-8972/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2012.03.035
 W.Z. Li et al. / Surface & Coatings Technology 206 (2012) 3764–3771 3765

2. Experimental The toughness, KIC, of the coatings was calculated by measuring

the length of the cracks formed during Vickers micro-indentation
Cr–Zr–(Al–)N coatings were deposited in a d.c. reactive magne- tests according to the following Eq. (1) [17]:
tron sputtering system equipped with four rectangular magnetrons    
(380 mm × 175 mm) working in unbalanced mode. All the four mag- E P
K IC ¼ δ 1=2 3=2 ð1Þ
netrons were placed at an angle of 90° in the chamber wall with the H c
Al target facing the Zr target. The configuration can be found in refer-
ence [13]. Polished M2 (AISI) steel coupons (20 mm in diameter) and where P is the applied indentation load, and δ is an indenter geometry
(111) silicon wafers were used as substrates. These were ultrasonical- constant. Values of 1 N and 0.016 were used in this study. E and H are
ly cleaned in acetone for 15 min and alcohol for 15 min. The sub- the Young's modulus and hardness from the nanoindentation test. c is
strates were mounted on substrate holders, which revolved around the maximum length of radial cracks from the SEM observation.
the center axis during deposition. Before deposition, the chamber
was evacuated to less than 2 × 10 − 4 Pa and then Ar+ ion sputter- 3. Results and discussion
etching was carried out at a bias voltage of −400 V for 20 min to re-
move any surface contaminants. Prior to the Cr–Zr–(Al–)N coating's 3.1. Chemical composition, deposition rate and microstructures
deposition, a Cr adhesion interlayer was first deposited in Ar atmo-
sphere for 10 min. Subsequently, two series of Cr–Zr–(Al–)N coatings, The chemical composition of the coatings determined by EDX
with low and high Zr content, were deposited on the Cr target in analysis is shown in Fig. 1. From now on and throughout the text,
35% Ar + 20% N2 mixtures for 180 min with a fixed power density , the coatings will be identified as CrxZryAlwNz where x, y, w, and z
2.3 W/cm 2, and with power densities of 1.5 W/cm 2 and 6.0 W/cm 2 stand for the at.% content of Cr, Zr, Al, and N, respectively. For low
at the Zr target. For both series, the Al target's power density was Zr coatings, the Al content increases linearly from 0 at.% to 15.3 at.%
changed from 0 to 3.0 W/cm 2. The detailed deposition parameters when the Al target's power density is increased from 0 W/cm 2 to
are shown in Table 1. 3.0 W/cm 2. Simultaneously, proportional decreases in the Cr and Zr
The thickness of the coatings was measured by profilometry. content were detected: Cr from 40.1 at.% to 31.1 at.% and Zr from
Fracture cross-section morphology and Vickers indentations were in- 5.6 at.% to 4.8 at.%. The highest Zr content was found in the
vestigated by scanning electron microscopy (SEM). The elemental Cr40Zr7Al4N49 coating deposited at 0.8 W/cm 2 Al target power den-
content of the coating was detected by energy dispersive X-ray sity. The N content was kept almost the same at ~ 50 at.% in the Al-
(EDX) analysis using the SEM apparatus. The crystal structure, containing coatings (Fig. 1(a)). For the high Zr coatings series, a sim-
grain size and lattice parameter of the coatings were determined ilar trend was observed for low Al target power densities (Fig. 2(b)).
by X-ray diffraction (XRD) with Co Kα radiation (λ = 0.178897 nm) However, when the Al target power density is above 1.5 W/cm 2, the
in a grazing mode (2°). The XRD patterns were fitted by using a
Voigt function to obtain both peak position information (2θ) and
full width at half maximum (FWHM) [14]. Grain size was deter-
mined using Scherrer's equation. The lattice parameter was obtained
by calculating Bragg's equation first and then the geometrical rela-
tionship equation of lattice parameter with interplanar distance
and Miller indices [15].
The hardness (H) and Young's modulus (E) of the coatings were
measured by the Oliver and Pharr method [16]. The measurements
were performed using a nanoindenter (Micro Materials NanoTest)
with a diamond Berkovich tip under 10 mN applied load. For each
sample, 12 measurements were performed.
The adhesion of the coatings to the M2 steel substrate was evalu-
ated by scratch testing. The load was increased linearly from 0 N to
60–70 N using a Rockwell C indenter with a 200 μm tip radius, a load-
ing speed of 100 N/min and a scratch speed of 10 mm/min. The Lc
values, averaged from 3 different tests, corresponding to the different
failure modes were evaluated by analyzing the scratch track under an
optical microscope.

Table 1
Sample designation and typical deposition conditions.

Sample Target power Gas Substrate Deposition Thickness

no. density (W/cm2) flow (%) bias (V) time (min) (μm)

Cr Zr Al Ar N2

Interlayer 2.3 2.3 2.3 35 0 − 70 10 0.2

S1-0 2.2 1.5 0 35 20 − 70 180 1.6
S1-1 2.3 1.5 0.8 35 20 − 70 180 1.9
S1-2 2.3 1.5 1.5 35 20 − 70 180 2.0
S1-3 2.3 1.5 2.3 35 20 − 70 180 2.1
S1-4 2.3 1.5 3.0 35 20 − 70 180 2.3
S2-0 2.3 6.0 0 35 20 − 70 180 2.2
S2-1 2.3 6.0 0.8 35 20 − 70 180 2.4
S2-2 2.3 6.0 1.5 35 20 − 70 180 4.2
S2-3 2.3 6.0 2.3 35 20 − 70 180 8.2
Fig. 1. Chemical compositions in S1 (a) and S2 (b) coatings deposited with increasing
S2-4 2.3 6.0 3.0 35 20 − 70 180 8.8
Al target power density.
3766 W.Z. Li et al. / Surface & Coatings Technology 206 (2012) 3764–3771
Fig. 2. Deposition rate vs. Al target power density in S1 and S2 coatings.
Al content suddenly jumps from 6.1 to 22.4 at.% and 27.1 at.% (Al tar-
get power of 2.3 and 3.0 W/cm 2) whereas a significant drop in the N
content was measured. Cr and Zr content also showed different
trends in these films, i.e. the Cr first registered a progressive decrease,
whereas, strangely, Zr behaved in the opposite way and its content
increased (see Fig. 1(b)). These trends suggest a change in the dis-
charge regime close to some of the targets used. In low Zr content
coatings, the N2 flow rate is high enough to keep Zr and Al targets
working in “compound mode”, i.e. the target surface is poisoned
(nitrided), whatever the Al target power was. This is typically the
regime in reactive sputtering deposition of compounds (nitrides,
oxides, …). The Cr target was probably not poisoned since Cr has a
much lower affinity for N when compared with Al and Zr (the heat
Fig. 3. XRD patterns of S1 (a) and S2 (b) coatings deposited with increasing Al target
power.
of formation of CrN is −69.1 kJ/mol compared to −255.1 kJ/mol
and −308.2 kJ/mol for AlN and ZrN respectively [18]). For high Zr
content films, similar discharge regimes should exist for low Al target
powers. However, with the increase in Al target power, associated
with higher Zr target power, the total power in these two targets
is enough to change the discharge regime, from the “compound
mode” to “transition” or even “metallic mode”. The fixed N2 flow
rate is not enough to poison the targets' surfaces. The change in dis-
charge regime can be confirmed by analysis of the discharge voltages
close to the Zr and Cr targets. In S1 depositions no changes in voltage
values are registered when Al power densities increase from 0.8 to
3 W/cm 2 (VZr ~ 293–291 V; Cr ~ 363–361 V) whereas a decrease was
detected in S2 deposition runs, particularly at the Zr target when
the Al power increases from 1.5 to 2.3 W/cm 2 (VZr ~ 326 → 310 V;
Cr ~ 336 → 327 V). The drop in voltage is due to a higher secondary
electron emission coefficient from the Zr target when its surface is
metallic in comparison to nitrided, which gives rise to higher ioniza-
tion in the discharge with a consequent increase in current and drop
in voltage [19]. Therefore, due to the much higher sputtering yield of
metals in comparison to compounds [20], the amount of Zr and Al
sputtered atoms increases significantly, promoting the observed in-
crease in their respective content in the films. As the Cr target was al-
ready in this discharge regime, its content normally decreased in
comparison to the other elements. The quantity of N in the deposition
chamber is not enough for it to combine with the sputtered elements
and it is not fully nitriding the other elements, leading to its overall
decrease in the coatings.
The deposition rate can be calculated from the coating thickness
and the deposition time. Fig. 2 shows the dependence of deposition
rate on the Al target's power density for the Cr–Zr–(Al–)N coatings.
As would be expected, in the case of low Zr content films, it is clear
that an almost linear increase exists in the deposition rate with
Fig. 4. Grain size and lattice parameter calculated from (111) diffraction peaks in Fig. 3
for S1 (a) and S2 (b) coatings.
 W.Z. Li et al. / Surface & Coatings Technology 206 (2012) 3764–3771
respect to Al target power density, due to the increasing number of
atoms being sputtered. Furthermore, for similar reasons, the deposi-
tion rate also increased for high Zr content films, in comparison to
low Zr content ones, when deposited with the same Cr and Al target
power densities. The most notable feature of the deposition rate re-
sults is the marked increase in the deposition rate of high Zr content
films when those deposited with low and high Al target powers are
compared. This large increase confirms the chemical composition
results and, as explained above, this is due to the change in discharge
regime from the “compound” to the “metallic” mode. The much
higher sputtering rates in the metallic modes produce higher amount
of ejected atoms and, consequently, thicker films.
Fig. 3 presents the XRD patterns of both series of coatings with in-
creasing Al content. In low Zr coatings (Fig. 3(a)), the fcc B1 (NaCl
type) phase is the only one detected with diffraction peaks at posi-
tions close to those of a pure CrN phase (JCPDS 11-0065). The ob-
served shifts for lower angles can be explained by the presence of
Zr in solid solution which, due to its higher atomic radius [21], pro-
motes a dilatation in the CrN lattice, as observed for the Cr–Zr–N sys-
tem [22]. As the Al content increased, the peak positions of (111),
(200) and (220) reflections are shifted towards higher diffraction
Fig. 5. SEM fracture cross-sectional micrographs of Cr–Zr–Al–N coatings: (a) Cr35Zr5Al10N50; (b) Cr31Zr5Al15N49; (c) Cr25Zr24Al3N48; (d) Cr23Zr23Al6N48;
(e) Cr19Zr27Al22N32; (f) Cr18Zr25Al27N30.
3767
angles. The peak shift is, similarly, a result of Cr or/and Zr atoms in
the fcc solid solution being substituted by Al atoms, which have a
smaller atomic radius (1.18 Å) than the Cr (1.66 Å) and Zr (2.06 Å)
atoms [21]. For small amounts of Al added to the Cr–N system, the
hexagonal AlN phase is not detected, as Al is inserted in solid solution
in the fcc CrN phase [23]. The atomic substitution can be confirmed
from the composition change in Fig. 1(a); In Al-containing coatings,
Cr and Zr content decrease with increasing Al content.
High Zr coatings appear similar to low Zr coatings; the first three
high Zr coatings exhibit the NaCl type fcc structure (Fig. 3(b)). For
similar reasons the shifts in the peak positions can be explained by
the differences in the atomic radius between Cr, Zr and Al. The
peaks are placed at lower angles in relation to low Zr content films,
very close to the fcc ZrN phase (JCPDS 35-0753). This is due to the
higher amount of Zr content, which promotes the dilatation of the lat-
tice, as Zr has the highest atomic radius,. When the Al content is in-
creased to 22.4 at.% and 27.1 at.%, a strong loss of crystallinity was
observed with an important broadening of the diffraction peaks. The
positions of the broad peaks are close to the B1 fcc phase but, consid-
ering the low N content in these coatings (Fig. 1(b)), it is not impos-
sible that some metallic or intermetallic phases could be formed
3768 W.Z. Li et al. / Surface & Coatings Technology 206 (2012) 3764–3771

during deposition. Such metallic phases should preferentially contain

Cr and Al which have lower affinities for N than Zr. The metallic or
intermetallic phases are either amorphous or of low structural
order in such a way that their low intensity diffraction peaks will
be masked by the experimental broad peaks.
The grain size and lattice parameter of the coatings calculated
from the (111) diffraction peak in Fig. 3 are summarized in Fig. 4.
Generally, no significant grain size changes can be registered in any
coatings, the only detected phase being the fcc B1, which only ranges
from 6 to 8 nm. However, a strong grain refinement to 2.2– 2.5 nm
was observed in the Cr19Zr27Al22N32 and Cr18Zr25Al27N30 coat-
ings. From Fig. 4(a), it is observed that in low Zr content coatings
with fcc B1 phase, the lattice parameter first slightly increases and,
then, drops progressively for higher Al content. If the decrease in
the lattice parameter values is expected, in agreement with the
above suggestion of the lower atomic radius Al atoms replacing Cr/
Zr in the fcc structure, the first observed increase seems to be contra-
dictory to this interpretation. However, a closer analysis of the XRD
patterns shows that the (200) peak of the Al-free Cr–Zr–N coating is
clearly shifted to lower angles, indicating that the insertion of Al
atoms in the fcc phase gives rise to a cubic lattice distortion, with het-
erogeneous contraction/dilatation of the lattice plans. Similar behav-
ior can be observed for the high Zr content coatings deposited with
low Al content. In this case, the lattice parameter calculated from
the (111) peak is kept approximately constant whereas a significant
shift for higher diffraction angles of the (220) peak is detected,
confirming again the lattice distortion promoted by Al insertion.
Higher lattice parameters are found in the Cr19Zr27Al22N32 and
Cr18Zr25Al27N30 coatings. This is evidence of the possible presence
of non-XRD detected metallic/intermetallic phases formed mainly
with Cr and Al, elements with a lower affinity for N in comparison
to Zr. Therefore, the nitride phase, resulting from the low N content Fig. 6. Effect of the Al content on hardness, Young's modulus and H3/E*2 values of S1
in these films, should preferentially have Zr in its structure, and dif- (a) and S2 (b) coatings.
fract at angles close to the standard values of ZrN.
Fig. 5 represents the typical fracture cross section micrographs
of low and high Zr coatings with various Al contents. In the these parameters slightly decrease for the highest Al content. It should
Cr35Zr5Al10N50 coating, a dense and compact morphology is ob- be noted that the observed variations are very small and are inside the
served (Fig. 5(a)). As the Al content is increased to 15.3 at.%, the coat- error bars of the hardness values. Except for the small changes in the
ing takes on a typical columnar structure (Fig. 5(b)). The difference in grain size, which are in good agreement with hardness values (higher
thickness can hardly be observed between these coatings. In high Zr grain sizes, lower hardness) there are no apparent changes in the
coatings, the microstructural evolution and thickness changes are structural parameters that could explain those small changes. Com-
very clear with the increase in Al content. A mixed morphology of pared to these coatings, those with high Zr content exhibit similar be-
equiaxed and columnar types is exhibited in the coatings with low havior to low Al content, i.e. Al free coatings have the highest E values
Al content (Fig. 5(c)). When the Al content increased to more than and the lowest hardness. The introduction of Al, distorting the nitride
6.1 at.%, a columnar structure was predominant in the coatings al- lattice due to its lower radius, improved resistance to plastic deforma-
though a featureless zone between the coating and the substrate tion (solid solution hardening). However, for higher Al content, a no-
could also be detected (Fig. 5(d)–(f)). Punctual EDX analysis indicat- table softening of the coatings was observed, probably due to the loss
ed that a ~5 at.% higher N content was detected in the featureless of crystallinity associated with a lower degree of phase nitriding. It is
zone than in the top coating (points B and A in Fig. 5(f), respectively). well known that in B1 transition nitrides the shift from MeN stoichi-
ometry gives rise to a decrease in hardness. Furthermore, the sug-
3.2. Mechanical properties gested presence of metallic phases could also contribute to this
decrease in hardness [25,26]. This trend in H values corresponds to a
3.2.1. Hardness, Young's modulus and H 3/E* 2 similar one in relation to the H 3/E* 2 ratio. The marked decrease in
The hardness and Young's modulus of the coatings were deter- the H 3/E* 2 ratio predicts a rapid decline in the resistance of the coating
mined by depth-sensing indentation tests. In order to avoid the effect to cracking. In conclusion, the mechanical property differences in the
of the substrate, the indentation depth was controlled to be less than Cr–Zr–(Al–)N coatings result from the combined effect of solid solu-
10% of the coating's thickness [24]. Fig. 6 shows the relationship of tion hardening, grain size refinement and structural and microstruc-
hardness, Young's modulus and H 3/E* 2 to the Al content in the coat- tural evolution. In S1 coatings, the grain size refining effect was
ings, where E* = E / (1 − ν 2) is the effective Young's modulus and ν responsible for the higher hardness whereas in S2 coatings the loss
is the Poisson's rate (ν = 0.25). It is suggested that the H 3/E* 2 ratio of crystallinity associated with the presence of metallic phases in the
be used to evaluate the ability of the coating to resist cracking [25]. coatings' structure can explain the significant softening observed for
From Fig. 6(a), it can be seen that the hardness and H 3/E* 2 ratio fol- the coatings with the highest Al content.
low a similar trend to the Al content in low Zr content coatings. The
highest Young's modulus is measured in the Al-free coating. As the 3.2.2. Scratch track analysis
Al content increases, both the hardness and H 3/E* 2 ratio are enhanced The scratch test is a simple method to evaluate the cohesion/
up to the maximum values of 25.2 GPa and 0.125, respectively. Then, adhesion of the coating to the substrate. After post-observation by
 W.Z. Li et al. / Surface & Coatings Technology 206 (2012) 3764–3771 3769

optical microscopy, the information for the critical load can be collect- Table 2
ed with respect to the first coating cracking (Lc1), first edge chipping Critical loads for the Cr–Zr–(Al–)N coatings during the scratch test.

(Lc2), coating delamination within the track or large area coating Sample Critical loads (N)
chipping (Lc3) [27]. Fig. 7 shows typical scratch track morphologies
First First edge Delamination or large
of low and high Zr content coatings. The corresponding Lc1, Lc2 and cracking Lc1 chipping Lc2 area chipping Lc3
Lc3 are summarized in Table 2.
Cr40Zr6N54 N/A N/A 53.3 ± 3.1
From Fig. 7 and Table 2, it is found that globally low Zr content Cr40Zr7Al4N49 N/A N/A 64 ± 1
films exhibit better behavior in relation to scratch testing than high Cr35Zr5Al10N50 N/A 62.6 ± 1.2 N/A
Zr content ones. In the same way, except for in Al-free coatings, the Cr34Zr5Al12N49 43.3 ± 2.1 43.3 ± 2.1 65.6 ± 1.5
progressive addition of Al to each coating series leads to a degrada- Cr31Zr5Al15N49 38.3 ± 2.5 38.3 ± 2.5 58.3 ± 2.9
Zr25Cr25N50 35.6 ± 1.5 35.6 ± 1.5 58.3 ± 1.5
tion of both the cohesive and adhesive failures values. Cr25Zr24Al3N48 42.3 ± 1.1 42.3 ± 1.1 53.3 ± 1.5
Cr23Zr23Al6N48 41.2 ± 1.6 41.2 ± 1.6 41.2 ± 1.6
3.2.2. Toughness evaluation from Vickers indentation Cr19Zr27Al22N32 29.3 ± 1.5 50.6 ± 1.5 50.6 ± 1.5
Toughness is the ability of a material to absorb energy during de- Cr18Zr25Al27N30 21 ± 2 48.3 ± 4.5 48.3 ± 4.5
formation up to fracture. It is an open problem to correctly evaluate
the toughness of thin coatings due to the limitation in thickness and
the disagreement of the results obtained from the different analysis main difficulties in evaluating the toughness lie in the selection of
methods. In addition to the KIC calculated from the crack length, the the crack formation threshold and the precise measurement of crack
H 3/E* 2 ratios and the scratch critical loads are often used to analyze length [28]. In the current investigation, no cracks were detected for
the toughness quantitatively or qualitatively [17,25,28]. less than 500 mN Vickers indentation; however, at a 5 N load, most
The Indentation test is often used to assess material toughness due coatings were de-bonded from the substrates. Thus 1 N was selected
to its straightforward and easy operation [17,25]. For thin films, the as the load for Vickers indentation tests. Otherwise, as the cracks do

Fig. 7. Typical scratch track morphologies of Cr–Zr–(Al–)N coatings: (a) Cr40Zr6N54; (b) Cr40Zr7Al4N49; (c) Cr35Zr5Al10N50; (d) Cr34Zr5Al12N49; (e) Cr25Zr25N50;
(f) Cr25Zr24Al3N48; (g) Cr23Zr23Al6N48; (h) Cr18Zr25Al27N30.
3770 W.Z. Li et al. / Surface & Coatings Technology 206 (2012) 3764–3771
not always propagate symmetrically on the material surface (see
Fig. 8(c)), even in bulk materials [17], the maximum crack length
was used to calculate the KIC by Eq. (1).
Fig. 8 shows SEM images of Vickers indentations with the typical
cracks that can be observed on the Cr–Zr–(Al–)N coatings after inden-
tation tests. In Fig. 8(d) the KIC–Al content curves are shown for both
series. In none of the coatings were circular cracks detected on the
coating's surface, confirming that the 1 N load did not lead to coating
delamination. Vickers indentations are different for S1 and S2 coat-
ings. In S1 coatings besides radial cracks, only vestiges of longitudinal
cracks in the indentation faces could be observed whereas, for S2
coatings, additional picture-frame cracks are clearly identified. In re-
lation to the KIC values, both series also present different trends; in
S1 coatings, after a first increase the value reaches a maximum and
then decreases, whereas only a decrease in KIC is shown for S2 coat-
ings. Globally, KIC values are higher in S2 than in S1 coatings, a
trend which seems in contradiction to both H 3/E* 2 and scratch-test
results. In fact, if any general conclusion could be extracted from
Fig. 7 and Table 2, it would be the opposite. However, this is in accor-
dance with the differences in the indentation morphologies of both
series of coatings. The greater lateral cracking (picture-frame and lon-
gitudinal) in S2 coatings is a clear indication of much higher energy
dissipation in these coatings, which would lead to a misleading low
value related to the radial cracks and superior fracture resistance.
Generally, the agreement between Vickers indentation test tough-
ness values and the other two methods is good, although some dis-
crepancies are detected. The matching is perfect between Vickers
and H 3/E* 2 methods in relation to S1 coatings. Moreover, it is found
that the calculated KIC in these coatings is very close to the results
for other thin coating materials [8,29]. Thus, considering the material
properties, KIC can be used to characterize the toughness of low Zr Cr-
Zr-(Al-)N coatings. For S2 coatings, it is obvious that the very low KIC
values in the Cr19Zr27Al22N32 and Cr18Zr25Al27N30 coatings are in
Fig. 8. Typical Vickers indentations and cracks formed on Cr–Zr–(Al–)N coatings and corresponding KIC–Al content curves (d): (a) Cr40Zr6N54; (b) Cr25Zr25N50;
(c) Cr19Zr27Al22N32.(trend lines are only for guidance).
good accordance with both H 3/E* 2 and Lc1 scratch test values. What-
ever the considered evaluation technique, these coatings show the
lowest values for fracture toughness, which can be attributed to the
synergy between the formation of low crystalline order phases in
the coatings [17] and an open columnar cross section morphology,
as observed in Figs. 5(e, f) and 8(c). For the other coatings, close
agreement can also be found with KIC using the other techniques,
with the exception of the Al-free coating. In this case, scratch testing
Lc1 and H 3/E* 2 show congruent values but much lower than that
inferred from KIC. It should be remarked that in the S1 series, the
Al-free coating also showed a lower value than the samples when
Al is added, suggesting that Lc1 and H 3/E* 2 could better represent
the toughness for these cases.
Thus, in order to correctly evaluate thin coating toughness a com-
bination of KIC calculation with microstructural characterization of
cracks and the help of depth-sensing indentation or scratch track
analysis should be used.
4. Conclusions
Low Zr S1 and high Zr S2 quaternary nitride coatings with various
Al contents were deposited by d.c. reactive magnetron sputtering for
a range of Al target power densities. The deposition rate as well as the
Al content in the low Zr S1 coatings linearly increased from 7.8 to
11.4 nm/min and 0 to 15.3 at.% respectively with increasing Al target
power density from 0 to 3.0 W/cm 2. For high Zr S2 coatings a similar
trend was registered for low Al content but a rather high deposition
rate (max. 47.5 nm/min) and a rapid increase in Al content was
detected for Al power density above 1.5 W/cm 2. An fcc B1 phase
was indexed in S1 and low Al content S2 coatings, whereas a low
order crystalline phase was formed in high Al S2 coatings. The grain
size was in the range of 6 to 8 nm in the well crystallized coatings;
 W.Z. Li et al. / Surface & Coatings Technology 206 (2012) 3764–3771
a significant decrease down to ~ 2.5 nm was found in the high Al S2
coatings.
The maximum values of hardness and H 3/E* 2 ratio were 25.2 GPa
and 0.125, respectively, in the Cr35Zr5Al10N50 coating. The adhesion
of the coatings onto the substrate decreased with the increase in
Al content; apparent large area chipping was observed in S2 coatings
for Al content above 6.1 at.%. The KIC value, calculated from Vickers
indentation, firstly increased from 1.5 to 2.0 MPa m 1/2 and then
decreased to 1.6 MPa m 1/2 in S1 coatings with increasing Al content,
whereas it steadily decreased from 3.4 to 1.5 MPa m 1/2 in S2 coat-
ings. The correlation of KIC value with the microstructural features
as well as with H 3/E* 2 ratios and scratch track analysis showed
that all these parameters should be considered to correctly evaluate
thin coating toughness.
Acknowledgements
This work was supported by EU project INTERFACE 2020 (FP7-
234324), the Portuguese Foundation for Science and Technology (FCT,
SFRH/BPD/76925/2011), the National Natural Science Foundation
of China (Grant No. 51001032) and Guangxi Science Foundation
(Grant No. 0731013), which are gratefully acknowledged. The authors
are grateful to Nelson Santos Duarte from IPN at Coimbra for the XRD
measurement.
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