Int.

Journal of Refractory Metals and Hard Materials 59 (2016) 114–120

Contents lists available at ScienceDirect

Int. Journal of Refractory Metals and Hard Materials

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

Effect of Ti content on the microstructure and mechanical properties of

TiAlSiN nanocomposite coatings
Quansheng Ma, Liuhe Li ⁎, Ye Xu, Xuan Ma, Yi Xu, Hongtao Liu
Department of 702, School of Mechanical Engineering and Automation, Beihang University, Beijing, PR China

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

Article history: TiAlSiN coatings has been proposed and studied because of their desirable properties in hardness and coating-
Received 28 January 2016 substrate adhesion. Further improvement of their performance can be achieved by better understanding the ef-
Received in revised form 31 May 2016 fect of the concentration of each element on the microstructure and mechanical properties of the coatings. In this
Accepted 5 June 2016
paper, the TiAlSiN coatings with different Ti content were deposited by reactive DC magnetron sputtering
Available online 7 June 2016
method. The microstructure and mechanical properties of the coatings were analyzed by energy dispersive spec-
Keywords:
troscopy, X-ray diffraction, transmission electron microscope, scanning electron microscope, nano-indentor and
TiAlSiN Rockwell indentation tester. The results reveal that TiAlSiN coatings consisted of amorphous phase and crystal-
Nanocomposite coating line phase. With a Ti content of 63 at.%, as well as a Si content of 7 at.%, a super-hard TiAlSiN coating with a nano-
Ti content indentation hardness of 66 GPa was achieved. What is more, in contrast to the well-described super-hard
Hardness nanocomposite TiAlSiN coatings, another “nanocomposite” microstructure coating with a Ti content of 29 at.%
Adhesion strength in which the amorphous phase is wrapped in a crystalline phase was identified, with a comparatively low hard-
ness value of 20 GPa. The highest adhesion strengths with a Rockwell indentation classes HF2 was achieved for a
coating with a Ti content of 63 or 65 at.%.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction TiN/nc-TiAlN/a-Si3N4 and reported that TiAlSiN coatings consisted of a

High-speed dry cutting technology is constantly demanding for cut-
ting tool coatings with higher hardness, better high-temperature oxida-
tion resistance, and lower friction. Since traditional nitride coatings are
no longer able to satisfy those requirements, nanocomposite coatings
such as MoN/CrN, TiSiN, and TiAlSiN have been proposed as promising
alternatives thanks to their remarkable physical and mechanical prop-
erties. Among these coatings, Ti/Al/Si/N based nanocomposite coatings
have attracted many researchers' interests because they show not
only the aforementioned excellent properties but also low thermal con-
ductivity and other excellent characteristics [1–6].
In order to predict and further improve the performance of TiAlSiN
coatings, it is crucial to understand their microstructures. Thus, much
work has been done to understand the relationship between the me-
chanical properties and their microstructures. According to Carvalho
[7], nanocomposite TiAlSiN films consist of a mixture of two phases:
TiN bulk and Ti-Si-Al-N where Si and Al atoms substitute the Ti atoms
in the TiN lattice. Vepřek [6,8–11] continuously researched on the nc-
⁎ Corresponding author.
E-mail address: liliuhe@buaa.edu.cn (L. Li).
nano-scale mixture of crystalline TiAlN phase and amorphous Si3N4
phase. It is now widely accepted that crystalline TiAlN phase is likely
to be wrapped in amorphous Si3N4 phase.
The microstructure of TiAlSiN films is determined by the concentra-
tion of each element. Some researchers [12,13] reported that when they
added Si to TiAlN, the grain size was refined, and concomitantly the
hardness increased. Silicon was present as a nitride incorporated into
TiAlN or forming a separate amorphous nitride phase, which affects
the structural evolution of TiAlN crystallites. Other researchers [14,15]
reported that an increased Al content results in a decrease of the grain
size and an increase in the thermal stability and oxidation resistance.
In addition, the replacement of more Ti atoms in TiN lattice by Al
atoms created more lattice distortion and more residual stress in the
coatings. In comparison, little was done to understand the effect of Ti
content in TiAlSiN films. The present work aims to elucidate the effect
of Ti content on microstructure and mechanical properties of TiAlSiN
nanocomposite coatings by changing the content of Ti while fixing the
ratio of Al and Si.
In this work, nanocomposite TiAlSiN coatings with a range of Ti con-
tents were deposited using magnetron sputtering. The microstructure,
morphology, and nanoindentation hardness of these coatings as well
as their adhesion strength were studied as a function of Ti content.

http://dx.doi.org/10.1016/j.ijrmhm.2016.06.005
0263-4368/© 2016 Elsevier Ltd. All rights reserved.
 Q. Ma et al. / Int. Journal of Refractory Metals and Hard Materials 59 (2016) 114–120
Fig. 1. Deposition apparatus for TiAlSiN.
The mechanism of how the Ti content affects the coatings' microstruc-
ture and mechanical properties was discussed.
2. Experimental details
2.1. Coating deposition
TiAlSiN coatings with different Ti contents were deposited onto
cemented carbide (WC-10 wt.% Co) substrates (shown as Fig. 1) by re-
active DC magnetron sputtering. Prior to deposition, all substrates
were firstly mechanically polished, then ultrasonically cleaned and
sputter-etched to remove surface contaminants and the surface oxida-
tion layer. After loading the samples, the vacuum chamber was evacu-
ated to a base pressure of 5 × 10–3 Pa and the deposition was carried
out in a mixture of high purity argon (99.999%) and nitrogen
(99.999%) gases within a hybrid ion implantation and deposition appa-
ratus equipped with six targets including Cr, TiAl and TiAlSi sputtering
targets which are rectangular plates mounted vertically, shown as
Fig. 1. The TiAlSi mosaic targets were made by mosaicking rectangular
Ti (99.999%) chips of various numbers into a Ti0.4Al0.5Si0.1 plate.
Fig. 2a–d shows schematic diagrams of TiAlSi mosaic targets with four
different Ti contents of TiAlSi, in which the dark strips are the Ti inserts
within the Ti0.4Al0.5Si0.1 target. An image of a TiAlSi mosaic target with 3
Ti chips is shown in Fig. 2e. The area of Ti in the four mosaic targets
amount to 46, 58, 64 and 70 at.%, respectively. These four targets are re-
ferred to hereafter as Ti0.46Al0.45Si0.09, Ti0.58Al0.35Si0.07, Ti0.64Al0.3Si0.06
and Ti0.7Al0.25Si0.05. In the following, Sample1, Sample2, Sample3,
Fig. 2. Tix(Al5/6Si1/6)1 − x mosaic targets.
115
Sample4 and Sample5 are designated corresponding to their prepara-
tion using the targets Ti0.4Al0.5Si0.1, Ti0.46Al0.45Si0.09, Ti0.58Al0.35Si0.07,
Ti0.64Al0.3Si0.06 and Ti0.7Al0.25Si0.05, respectively.
To improve the adhesion strength between coating and substrate,
gradient interlayers Cr + CrN + TiAlN were used. When the deposition
process began, the substrate was faced with the Cr target firstly, for the
interlayers of Cr and CrN deposition. Then, rotated the substrate to the
front of TiAl target for the TiAlN interlayer deposition. Finally, rotated
to the TiAlSi target for TiAlSiN coating deposition. In each process
above, the substrate was fixed, not rotated. The thicknesses of Cr/CrN/
TiAlN and TiAlSiN in five samples are listed in Table 1. The sputtering pa-
rameters for TiAlSiN coatings are listed in Table 2.
2.2. Coating characterization
The chemical compositions of coatings were analyzed by energy dis-
persive spectroscopy (EDS) using a scanning electron microscope (SEM:
JSM 6010LA). The phases and texture were characterized by X-ray dif-
fraction (XRD: D/Max 2500) with CuKα radiation. In order to reduce
the influence of substrate on the coating, grazing incidence mode (Graz-
ing incidence angle: 2°) in XRD was used. Morphology and thickness of
coatings were measured by examining fractured cross-sections using
SEM (JSM 6010LA). To maintain the original fracture morphology of
the cross-section, the samples were snapped after preprocessing includ-
ing wire-electrode cutting and liquid nitrogen soaking. Further micro-
structure characterization was performed by transmission electron
microscope (TEM JEM-2100). The hardness of the coatings was
116 Q. Ma et al. / Int. Journal of Refractory Metals and Hard Materials 59 (2016) 114–120
Fig. 3. Chemical compositions of Ti, Al, Si and N in the coatings as a function of the Ti content in Tix(Al5/6Si1/6)1 − x target.
obtained by nanoindentation with a load precision of 50 nN (Nano-In-
dentor G200, Agilent). The average hardness was calculated with
hardness-displacement curves collected at the indentation depth of
100–200 nm (the depth was within 1/10 thickness of the TiAlSiN coat-
ing and the data were stable) [16] at three random sites (1st, 2nd, 3rd).
The continuous stiffness method (CSM) [17] was used to obtain
displacement-hardness values from initial to final indentation depth.
The adhesion strength was evaluated qualitatively by Rockwell indenta-
tion test [18,19] with a C tip (200 μm radius) under a load of 150 kg for
15 s.
Fig. 4. X-ray diffraction pattern of TiAlSiN coatings with various Ti contents.
3. Results and discussion
To insure the uniformity of coatings deposited using mosaic targets,
five sampling points (1#, 2#, 3#, 4#, 5#) were chosen on each sample
(shown in Fig. 1) for chemical composition analyses. The average con-
centration and standard deviations of Ti, Al, Si and N in Samples 1 to 5
are presented in Table 3. The standard deviations in the content of
each element are less than 2.5%, indicating good uniformity within the
coatings. Hence, the chemical formulae of Samples 1 to 5 can be written
as Ti0.29Al0.59Si0.12N, Ti0.42Al0.48Si0.1N, Ti0.57Al0.35Si0.08N, Ti0.63Al0.3Si0.07N
and Ti0.65Al0.29Si0.06N, respectively. Fig. 3 shows the chemical composi-
tions of Ti, Al, Si and N in TiAlSiN coatings deposited as a function of
the Ti content in the targets. With increasing Ti content in the target,
the Ti content in the coatings increases from 15.24 at.% to 35.63 at.%,
while the Al and Si contents decrease concomitantly from 30.73 at.%
to 15.68 at.% and from 6.10 at.% to 3.34 at.%, respectively. The N content
in Samples 1 to 5 decreases only slightly, from about 48 at.% to 45 at.%.
Fig. 4 shows the results from XRD analysis on the TiAlSiN coatings
with different Ti contents. All peaks in the XRD spectra correspond to
the cubic B1 (NaCl) structure, as observed in TiN, (Ti,Al)N and AlN.
This result suggests that the Si atoms are incorporated in the fcc lattice
or exist as amorphous nitride phase, or both. The XRD peak positions
shift to lower angles with the increased Ti content, which may be caused
by the replacement of c-TiAlN by c-TiN accompanied by a decrease of Al
content. And the (200) peak of c-AlN phase disappeared gradually
which may also be attributed to the decrease of Al content. Furthermore,
an increased (200) peak broadening with increasing Ti content, in gen-
eral, originates from a reduction of grain size or an increase of residual
stress [20].
The relationship between hardness of nanocomposite TiAlSiN coat-
ings and displacement into the surface, tested by CSM method, is
shown in Fig. 5. The values of average hardness of each coating are
shown in Fig. 5a–e above the double arrows. The average hardness as
a function of Ti content is shown in Fig. 6. It can be seen that the hard-
ness increases from 20 GPa at a Ti content of 29 at.% with increasing Ti
 Q. Ma et al. / Int. Journal of Refractory Metals and Hard Materials 59 (2016) 114–120
Fig. 5. Hardness of TiAlSiN coatings as a function of the displacement into surface with increased Ti content: (a) 29 at.% (b) 42 at.% (c) 57 at.% (d) 63 at.% (e) 65 at.%.
Fig. 6. Grain size and hardness of TiAlSiN coatings with various Ti contents.
117
content and peaks at 66 GPa with 63 at.% of Ti. Beyond that the hardness
decreases to 56 GPa at 65 at.% of Ti. On the same figure, the average grain
size calculated from the Scherrer formula using FWHM is plotted as a
function of Ti content, which shows the opposite dependence on Ti con-
tent. The differences between Samples 4 and 5 are well within experi-
mental error, thus the two samples can be combined. Therefore, it can
be concluded that, when the grain size drops to the minimum, the hard-
ness reaches the maximum. Thus, in agreement with literature [20], the
increase in hardness may be attributed in part at least to the refinement
of grain size. The enhanced hardness of Samples 4 and 5 might in part
also be attributed to its more pronounced (111) orientation compared
to the other three samples, with the lower Schmid factor of the TiN
(111) plane compared to (200) planes for the face-centered cubic ni-
tride coatings [21] (see Fig. 4). This is also consistent with the geomet-
rical strengthening mechanism described in Qi et al. [22].
Coincidentally, when the hardness reaches a maximum, the Si con-
tent is just 7 at.% in TiAlSiN coating, which coincides with the result re-
ported by Vepřek et al. [23]. In that paper, when Si content was 7 at.% in
a TiSiN coating, the hardness reached a maximum. Vepřek et al. claimed
this super-hardness to be a consequence of the nanostructure and of the
118 Q. Ma et al. / Int. Journal of Refractory Metals and Hard Materials 59 (2016) 114–120

Fig. 7. TEM images and electron diffraction pattern of Ti0.29Al0.59Si0.12N: (a) TEM image (b) HRTEM image and SAED pattern (The light-colored parts pointed by black arrows are
amorphous phase and the dark-colored parts pointed by arrows are crystalline phase.)

large cohesive energy (stability) of the nano-crystalline MnN/a-Si3N4
(M = metal) interface. In the absence of Al, this agreement of the Si con-
tent appears as a coincidental one, but it is really interesting and de-
serves for further research.
The TEM images and selected area diffraction pattern (SADP) of
Sample1 with the lowest Ti content (29 at.%) and the highest Si content
(12 at.%) are shown in Fig. 7. It presents a particular microstructure in
that the amorphous phase (light-colored part) is wrapped in the crys-
talline phase (dark-colored part) which is in contrast to the traditional
microstructure with the lower Si content of 7 at.% and 8 at.% for TiSiN
and TiAlSiN coatings, respectively reported by some researchers [1,24].
The reason for the low hardness of Sample1 could be explained in part
by this microstructure. When the content of the Si-containing
amorphous phase increases, the increased grain boundary sliding
caused by the more amorphous phase in this microstructure could
give rise to the decrease of strength and hardness. This deduction in
hardness of TiAlSiN coatings is consistent with the result reported in
Kim et al. [25].
The fracture cross-section SEM images of TiAlSiN coatings are shown
in Fig. 8. The start of the TiAlSiN coating was marked by a yellow line in
each figure. As shown in Fig. 8a, when Ti content was 29 at.%, the coating
shows some blocky-shaped particles and no obvious columnar struc-
ture in the cross-section, which may be caused in part by the overmuch
Si-containing amorphous phase compared with other samples. In
Fig. 8b, the coating with Ti content of 42 at.%, shows some features of co-
lumnar structure. The brittle fracture is evident from the separation of

Fig. 8. Cross-section SEM images (×3000) of TiAlSiN coatings with different Ti contents: (a) 29 at.% (b) 42 at.% (c) 57 at.% (d) 63 at.% (e) 65 at.% (The start of the TiAlSiN coating was marked
by a yellow line in each figure.)
 Q. Ma et al. / Int. Journal of Refractory Metals and Hard Materials 59 (2016) 114–120 119

Fig. 9. Rockwell indentation images (×100) made with 150 kg load for 15 s in TiAlSiN coatings with increased Ti content: (a) 29 at.% (b) 42 at.% (c) 57 at.% (d) 63 at.% (e) 65 at.%.

some blocky forms from the fracture surface and the stratification be- maximum value of 65 at.%, as shown in Fig. 8e, there are more coarse
tween TiAlSiN coating and the gradient interlayers. For Fig. 8c, the grains particles seen in the cross-section but the coating is still the dense mor-
inside the TiAlSiN coating with 57 at.% Ti appear to grow first along a di- phology which implied that this coating is still nanocrystalline.
rection inclined by about 30–40° relative to the grains of the underlying The Rockwell indentation images observed by optics microscope are
TiAlN layer. This signature of the grain growth direction gradually disap- shown in Fig. 9. There are six classes (HF1-HF6) classified in the inden-
pears and halfway through the TiAlSiN layer changes to a smooth and tations to qualitatively evaluate the adhesion of coatings to substrates,
dense structure. There, the brittle fracture traces are less visible, with according to the adhesion measurement techniques reported by Gerth
only some sharp fracture lines remain. The coating with a Ti content et al. [26]. Some other researchers [21,27] also measured adhesion by
of 63 at.% (Fig. 8d) exhibits a lamellar and dense structure instead of co- this standard. In TiAlSiN coatings with 29, 42 or 57 at.% content of Ti,
lumnar structure in the cross-section. The fracture plane is smooth and there are some cracks and a little detachment around the indentations
no obvious fracture traces can be seen, which is consistent with the pre- in the coatings shown as Fig. 9a–c. The adhesion strength can thus be
vious finding that TiAlSiN coating was a nanocomposite (nc-TiAlN/a- classified as HF3. When Ti content increases to 63 or 65 at.%, there are
Si3N4) structure, which was composed of amorphous Si3N4 and nano- only a few cracks and detachments of the coating, even no detachments
crystalline TiAlN grains [13]. When the Ti content increases to the in Sample4, as shown in Fig. 9d–e, indicating very good adhesion
strength. Thus, that coating can be classified as HF2. The changing of ad-
hesion strength of TiAlSiN coatings with Ti content might be explained
Table 1
The thickness of Cr/CrN/TiAlN and TiAlSiN.
Table 2
Thickness (μm) Details of sputtering parameters.
Coatings
Sample1 Sample2 Sample3 Sample4 Sample5
Target-substrate DC Operating Target
Temperature
TiAlSiN 2.0 2.2 2.1 2.0 2.3 distance bias PN2/PAr pressure current
TiAlN 0.8 0.6 0.5 0.8 0.5
(cm) (V) (°C) (Pa) (A)
CrN 0.8 0.8 0.7 0.7 0.5
Cr 0.3 0.3 0.3 0.2 0.2 8 −100 150 1/3 0.8 2
120 Q. Ma et al. / Int. Journal of Refractory Metals and Hard Materials 59 (2016) 114–120
Table 3
Average concentration and standard deviation of each element.
Average concentration and standard deviation (at.%)
Element
Sample1 Sample2
Ti 15.24 ± 0.15 21.83 ± 0.49
Al 30.73 ± 0.30 24.61 ± 0.46
Si 6.10 ± 0.06 5.24 ± 0.08
N 47.93 ± 0.26 48.32 ± 0.99
in the framework of lattice distortion in part. With the decreasing of Ti
content, the replacement of more Ti atoms in the TiN lattice by Al
atoms created more lattice distortion and more residual stress in the
coatings. This increased residual stress makes coatings prone to crack-
ing and detaching from the substrate. There are also many potential hid-
den differences in other parameters such as in the sample pretreatment
(cleaning, surface roughness), in the deposition runs etc. that exclude
such a single cause interpretation.
4. Conclusions
The TiAlSiN coatings with different Ti contents were prepared by
magnetron sputtering with mosaic Tix(Al5/6Si1/6)1 − x targets in which
the content of Ti was varied by changing the number of Ti chips. The mi-
crostructure, hardness and adhesion of deposited TiAlSiN coatings with
different Ti content were investigated. The main conclusions are as
follows.
Ti is also a key element, which can determine the coatings' nanoin-
dentation hardness. With increasing Ti content, the hardness increases.
When Ti content is low to 29 at.%, the coatings' hardness is as low as
20 GPa and its microstructure is the amorphous phase wrapped in crys-
talline phase which was just reverse to the high hardness coating. When
Ti content is 63 at.%, as well as 7 at.% of Si, the coatings' hardness reaches
the super-hard level of 66 GPa. The TiAlSiN coatings with dense fine
globular structure were attained. TiAlSiN coatings are consisted of a
mixture of amorphous phase and crystal phase. In TiAlSiN coatings
with relative lower Ti content (29, 42 and 57 at.%), some slight columnar
structure feature or brittle fracture traces were found. When Ti content
increased to 63 at.% or 65 at.% the cross-section morphology became
more dense and smooth. With increasing Ti content, the adhesion
strength of Rockwell indentation class reaches to HF2 class when Ti con-
tent was 63 or 65 at.%.
Acknowledgements
The works were jointly supported by National Nature Science Foun-
dation of China (NSFC 11275020), National Science and Technology
Major Project (04: 2014ZX04012012), and AVIC Technological Innova-
tion Project (2012E01138).
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