Thin Solid Films 371 2000.

178182

Mechanical properties and fracture toughness of multilayer hard

coatings using nanoindentation

Jianning DingU , Yonggang Meng, Shizhu Wen

The National Tribology Laboratory, Tsinghua Uni ersity, Beijing 100084, PR China

Received 26 July 1999; received in revised form 19 April 2000; accepted 19 April 2000

Abstract

The nanoindentation fracture of multilayer hard coatings of TiNrTiC,N .rTiC, Al2 O 3rTiCrTiC,N .rTiC,
TiNrTiC,N.rTiCrTiC,N.rTiC and TiNrTiC,N.rTiCrTiC,N.rTiCrTiC,N.rTiC, deposited on cemented carbide using a
CVD technique was studied. Based on an analysis of the energy released in cracking, the calculated fracture toughness values of
these coatings were 2.18, 1.74, 3.40 and 3.90 MPa m1r2 , respectively. Both loadpenetration depth and loadpenetration depth
squared plots have been demonstrated to be necessary if a more complete understanding of the coating system behaviour is to be
gained. The interfacial failure and the critical load of interfacial failure of these coatings were also discussed. A step was found in
the forcedisplacement curves at the onset of coating fracture. A straight line segment in the loadpenetration depth squared
curves was discussed. The hardness, fracture toughness and anti-wearability of these coatings were compared. The results show
that the fracture toughness and anti-wearability are getting higher with the layers increasing. 2000 Elsevier Science S.A. All
rights reserved.

Keywords: Coatings; Elastic properties; Hardness; Multilayers

1. Introduction component nitrides like Ti,Al.N, TiB,N., TiB,C,N.,

Hard coatings play an important role in industry for
improving tool lifetime and performance. A variety of
hard coatings are widely used in the tool industry,
mainly to reduce friction and to increase wear resis-
tance. One of the mostly used and studied coatings to
date is TiN, which has beneficial properties including
high hardness, low friction, and chemical inertness w1x.
In recent years, a new generation of coating, titanium
carbon nitride TiCN., has been gaining focus. In addi-
tion to titanium carbon nitride, other nitrides such as
boron nitride BN., chromium nitride CrN., hafnium
nitride HfN., zirconium nitride ZrN., as well as multi-
U upon which coating is deposited and by the interfaces
Corresponding author. Tel.: q86-10-6277-3867; fax: q86-10-
6278-4691.
E-mail address: dingjn@post.pim.tsinghua.edu.cn J. Ding..
Ti,Zr.N and Ti,V.N have been studied w2x. The per-
formance and reliability of these hard coatings is often
limited by their mechanical properties. Interest in the
adhesion, mechanical properties and fracture tough-
ness of hard coatingrsubstrate systems is increasing
rapidly. Indentation tests and scratch tests are exten-
sively used to study mechanical properties and adhe-
sion of thin films w35x.
Despite progressive improvements in both indenta-
tion and scratch tests, some basic questions have not
been fully answered concerning the resultant deforma-
tion and fracture behaviour. Contact-induced fracture
in thin hard-film coated systems is complex and con-
trolled by the coating material itself, by the substrate
which bond the system together. Understanding the
fracture mechanisms and the sequence of fracture

0040-6090r00r$ - see front matter 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 4 0 - 6 0 9 0 0 0 . 0 1 0 0 4 - X
 J. Ding et al. r Thin Solid Films 371 (2000) 178182 179

events during loading and unloading. is critical for

understanding how the coated systems will perform in
service w6x. In recent years the term nanoindentation
has been applied to depth-sensing indentation testing
methods where the size of the residual imprint is of a
nanometer scale and where it is too small to be accu-
rately resolved by optical microscopy. With the instru-
ments having micro Newton and nanometer depth reso-
lutions it is possible to produce loadpenetration depth
curves and mechanical properties of material can be
obtained w7x. In this paper, the deformation and frac-
ture behaviour and anti-wearability of some multilayer
hard coatings, such as, TiNrTiC,N.rTiC, Al2 O3r
TiCrTi C,N . rTiC, TiNrTi C,N . rTiCrTi C,N . r
TiC and TiNrTiC,N.rTiCrTiC,N.rTiCrTiC,N.r
TiC films are investigated.

2. Experiment

2.1. Nanoindentation system

All forcepenetration depth measurements were

made with a nanohardness tester NHT. and a com-
bined opticalrscanning force microscope SFM. sys-
tem, both developed by CSEM Instruments Switzer-
land.. The NHT comprises two distinct components, a
measuring head for performing indentations and an
optical microscope for selecting a specific sample site
prior to indentation and for checking the location of
the imprint after indentation. Both components are
directly linked by an electro-mechanical positioning
system which allows movement along two perpendicu-
lar horizontal axes with a lateral displacement resolu-
tion of 1 m. The load is directly applied by an
electromagnet assembly to a vertical rod, the end of
which houses a standard Vickers diamond indenter.
Displacement of the rod is supported with a capacitor
detector and the rod is supported by two guide springs.
The system has load and displacement resolutions of 10
N and - 1 nm, respectively.
2.2. Sample materials
In this experiment, the hard coating layers were
deposited on cemented carbide WC. bulk disks. The
construction and sequence for the studied multilayer
coatings from top to substrate are TiNrTiC,N.rTiC,
Al 2 O 3 rTiCrTi C,N . rTiC, TiNrTi C,N . rTiCr
TiC,N.rTiC and TiNrTiC,N.rTiCrTiC,N.rTiCr
TiC,N.rTiC, which were all deposited using a CVD
technique. The layer thickness of these coatings are 1.5
mr1 mr1.5 m, 1 mr1 mr1 mr1 m, 1
mr1 mr1 mr1 mr1 m and 1 mr1 mr1
mr1 mr1.5 mr1 mr1.5 m, respectively.
Fig. 1. Typical forcepenetration depth observations for indentations
using the standard Vickers diamond indenter of coatings.
3. Results and discussion
Typical loadpenetration depth curves of indenta-
tions of the multilayer coatings using the standard
Vickers diamond indenter and the calculated Youngs
modulus E . and hardness H . are shown in Fig. 1.
The values of E and H were obtained using Oliver and
Pharrs approach w8x. In addition to accounting for the
curvature in the unloading data, the method also pro-
vides a physically justifiable procedure for determining
the depth that should be used in conjunction with the
indenter shape function to estimate the contact area at
peak load. The hardness H . is defined as the mean
pressure the material will support under load. Thus,
from the data obtained from the nanoindentation,
hardness of these coatings was found to be higher than
that of the TiN monolayer coating 21 GPa.. As a
wear-resistant coating, an additional important
parameter is the films fracture toughness. Understand-
ing the fracture mechanisms is critical for understand-
ing how the coated systems will perform in service.
Previous papers on continuously recorded indentation
testing have reported on ring-like cracks around
nanoindentations in coated systems w9x. The possible
effect of this kind of cracking on the appearance of
loadpenetration depth curves was also discussed in
the same paper. As established by Li et al. w10x in their
previous work, fracture process progressed in three
stages. Firstly, a ring-like through-thickness cracking
180 J. Ding et al. r Thin Solid Films 371 (2000) 178182
Fig. 2. Steps during the forcepenetration depth curves.
formed around the indenter by high stresses in the
contact area. Secondly, delamination and buckling oc-
curred around the contact area at the filmrsubstrate
interface by high lateral pressure. Lastly, another ring-
like through-thickness cracking and spalling were gen-
erated by high bending stresses at the edges of the
buckled film. In the first stage, if the film cracks via the
first ring-like through-thickness cracking, a correspond-
ing step will be present in the loading curve. If discont-
inuous cracks from the film under the indenter are not
separated from the remaining film, no step appears in
the loading curve because the film still supports the
indenter and the indenter cannot suddenly advance
into the material. Examples of such coating fracture
can be seen in Fig. 2. The loadpenetration depth
curve of these coatings exhibited a step in the loading
curve. This means that partial ring-like through-thick-
ness cracking occurs. One step in the loading curve
corresponds to one ring-like through-thickness crack-
ing. The peak indentation load Pf is defined as the
critical load of the coating fracture. The critical load Pf
of TiNrTiC,N .rTiC, Al2 O 3 rTiCrTiC,N .rTiC,
T i N r T i C ,N . r T i C r T i C ,N . r T i C and
TiNrTiC,N.rTiCrTiC,N.rTiCrTiC,N.rTiC was
16.4, 18.5, 35.5, 56.3 mN, respectively.
As shown in Fig. 2, with the number of layers in-
creasing, the critical load is getting larger. This means
the multilayer coating system can give a good solution
for improving the strength of brittle monolayer coat-
ings. Ductile coating layers in the multilayer coatings
can be used to make the coating system more resistant
to crack formation and propagation, but the thickness
and the number of ductile layers affect coating crack-
ing. The ductile layers prevent the coating from crack-
ing. According to Li and Bhushans theoretical analysis
w9x, the fracture toughness of thin films, KIC can be
defined as:
E U 1r2
KIC s
2
1 y 2 CR . / t / 1.
where E is the elastic modulus, is the Poissons ratio,
2 CR is the crack length in the film plane, U is the
strain energy difference before and after cracking, and
t is the layer film thickness. It is well known that the
area under the loaddisplacement curve is the work
performed by the indenter during elasticplastic defor-
mation of the filmrsubstrate system. The strain energy
release in the ring-like cracking can be calculated from
the corresponding steps in the loading curve. U is
assessed from the steps in Fig. 2 at the peak loads of
Pf . Based on Eq. 1., the first layer fracture toughness
of these coatings can be calculated. The calculated first
layer fracture toughness value of our coatings was 2.18,
1.74, 3.40, and 3.90 MPa m1r2 , respectively.
As analyzed above, the layer fracture toughness of
coatings can be obtained from the loadpenetration
depth curves, but the variation of the interfacial
properties of coatingrsubstrate systems, especially the
interfacial properties of the multilayer coatings can
hardly be obtained from the loadpenetration depth
curves. The changes in slope of plots of load vs. pene-
tration depth squared can reveal the changes of coat-
ingrsubstrate systems w11x. According to Loubets anal-
ysis of nanoindentation loadpenetration depth curves
w12x, if the material being indented the plastic depth of
indentation and the instantaneous elastic contribution
can be calculated. Summing the elastic and plastic
contributions to give the total depth of indentation h
results in the equation:
P P H
hs ( H
q
E ( P
2.
where is a constant which is dependent on the
cross-section and angle of the particular indenter used
and relates contact radius to real indenter geometries,
is another empirical constant, P is the applied force.
Manipulation of this gives the relationship:
P E H
h2 s
E
( H
q ( / E
2
3.
This can be written in the form Ps Km h2 , where Km
is the Loubets equivalent elasticplastic parameter.
For a range of materials, the relationship PA h2 was
found to describe the penetration depth, h, in terms of
 J. Ding et al. r Thin Solid Films 371 (2000) 178182
Fig. 3. Straight line segments during the forcepenetration depth
squared curves: a. TiNrTiC,N.rTiC; b. Al2 O3 rTiCrTiC,N.rTiC;
c . TiNrTiC,N .rTiC; d. TiNrTiC,N .rTiCrTiC,N .rTiCr
TiC,N.rTiC.
the applied force P. But, for a coatingrsubstrate sys-
tem, the relationship between P and h2 will change.
Fig. 3 shows the loadpenetration depth squared data
of our coatings. In Fig. 3, the dashed lines represent
the relationship PA h2 and the solid lines are the
relationship between P and h2 varying during the
whole process of penetration. The loadpenetration
depth squared plots of Fig. 3a,b show an initial straight
line segment from the origin to the turning point on
both the solid lines and the dashed lines. which we
identify as coating only behaviour. As the coating
deforms in response to the maximum Hertz-like shear
stress lying within the coating depth, it is apparent that
the maximum shear stress at the initial linear portion
of the loadpenetration depth squared plots experi-
enced by the subsurface is not enough to make subs-
trate yield. It should be noted that the turning point is
lower than the load at which fracture occurred step on
Figs. 2 and 3.. SEM observation of the indentations
above and below the step has established that this is
Table 1
Mechanical properties and anti-wearability of coatings
Coatings
TiNrTiC,N.rTiC
Al 2 O 3 rTiCrTiC,N.rTiC
TiNrTiC,N.rTiCrTiC,N.rTiC
TiNrTiC,N.rTiCrTiC,N.rTiCrTiC,N.rTiC
181
the load at which cracking occurred. Beyond the turn-
ing point on the loadpenetration depth squared curve,
sufficiently high shear stresses are experienced in the
subsurface for plastic yielding which in turn, requires
the coating to flex and bend to conform to this subsur-
face deformation. However, the shear stresses in the
coating are only large enough to cause plastic flow in
an area immediately around the axis of the contact and
along the indenter edges. At the same time, significant
tensile stresses are being generated in an approxi-
mately circular pattern around the outer periphery of
the contact zone as the coating is forced to bend to
conform to the subsurface deformation and pile-up.
This corresponds to the region from the turning point
to the step on the loadpenetration depth squared
plot. Increased loading causes nested cracks to occur as
the coating island is bent into the substrate. As the
load is released, an interfacial crack will occur. Thus,
we can use the load at the turning point, Pi , as the
critical load of the first layer coating interfacial failure.
The interfacial failure critical load of TiNrTiC,N.rTiC
and Al2 O3rTiCrTiC,N.rTiC is 7.50 and 13.0 mN,
respectively. However, Fig. 3c,d shows straight lines
from the origin to the step without any turning point
before the step, which means they have not experi-
enced interfacial failure until cracking occurred. Both
TiNrTiC,N.rTiCrTiC,N.rTiC and TiNrTiC,N.r
TiCrTiC,N.rTiCrTiC,N.rTiC coatings have high in-
terfacial strength and fracture toughness.
The anti-wearability of brittle materials is mainly
determined by its fracture toughness, when cracks oc-
cur on the worn surface. With the strength and fracture
toughness of materials increasing, the anti-wearability
is getting high w13x. According to the quality of material
not considering the temperature of friction area and
chemical wear., Evans w14x has established the relation-
ship between anti-wearability and mechanical proper-
ties of hard coatings as follows:
0.5 y0.8 1.43
WR s KIC E H 4.
where WR is the anti-wearability, KIC is the fracture
toughness of thin films. Based on Eq. 4., the anti-
wearability of the coatings can be calculated. The cal-
culated values of the fracture toughness and the anti-
wearability of the coatings are shown in Table 1. It
shows that multilayer coatings have high fracture
PI Pf KIC WR
mN. mN. MPa m1r2 .
7.50 16.4 2.18 1.42
13.0 18.5 1.74 1.77
35.5 3.40 1.61
56.3 3.90 1.84
182 J. Ding et al. r Thin Solid Films 371 (2000) 178182
toughness and anti-wearability than single layer TiN
coating KIC s 1.51 MPa m1r2 .. In the four coatings
s tu d ie d , T iN r T i C ,N . r T iC r T i C ,N . r T iC r
TiC,N.rTiC coating is best of all.
4. Conclusions
The nanoindentation fracture of four multilayer
coatings was studied. Good correspondence between a
step in the loadpenetration depth curve and ring-like
cracking was described. Both loadpenetration depth
and loadpenetration depth squared plots have been
demonstrated to be necessary if a more complete un-
derstanding of coating system behaviour is to be gained.
The interfacial failure and the critical load of interfa-
cial failure of these coatings were also discussed. It was
found that a step occurs in the forcedisplacement
curves at the onset of coating fracture and a straight
line segment occurs in the loadpenetration depth
squared curves. The hardness, fracture toughness, criti-
cal load of interfacial failure and anti-wearability of
four multilayer coatings were compared. The results
show that the fracture toughness and anti-wearability
are getting larger with the layers increasing. In these
four coatings, TiNrTiC,N .rTiCrTiC,N .rTiCr
TiC,N.rTiC coating is best of all.
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