Thin-film fracture during nanoindentation of a titanium

oxide film–titanium system

M. Pang and D.F. Bahr
Mechanical and Materials Engineering, Washington State University,
Pullman, Washington 99164-2920

(Received 26 April 2001; accepted 29 June 2001)

Nanoindentation testing of the titanium oxide/titanium system with electrochemically

grown oxide films exhibits permanent deformation prior to a yield excusion, indicating
that the occurrence of this suddent discontinuity is predominantly controlled by oxide
film cracking rather than dislocaton nucleation and multiplication. Observations of
circumferential cracking also lend support to this explanation. A model has been
developed to predict the mechanical response prior to oxide fracture for the case of a
hard coating on a soft substrate. During loading contact, the hard coating undergoes
elastic deflection which may include both bending and membrane stretching effects,
while the substrate is elastoplastically deformed. The model works well for surface
films thicker than 20 nm. Additionally, the maximum radial tensile stress in anodically
grown titanium oxide, which is responsible for film cracking at the critical load, is
approximately 15 GPa.

I. INTRODUCTION model which simulated the contact response of the coated

While the strengthening effect of surface thin films has
already been observed and tentatively discussed,1,2 quan-
titative evaluations of the role of surface films did not
flourish until the extensive application of ultralow-load
indentation systems, i.e., nanoindentation. Nanoindenta-
tion can be used to probe the mechanical response of a
surface layer at the scale of real asperity contact by sens-
ing penetration and displacements as low as 0.2 nm.
Many studies have focused on hard thin-film systems due
to their excellent wear resistance. In general, most coated
systems show a mixture of deformation comprising both
film and substrate effects.3 Some coated systems, such as
Al2O3/Al and TiO2/Ti, exhibit a yield phenomenon,4,5
characterized by a sudden discontinuity during loading.
Subsequently, the coating fails by means of through-
thickness fracture, nested cracks, or interfacial delami-
nation depending on the combined effect of the loading
and coating bonding condition.
Both experimental and theoretical approaches have
been developed in an attempt to explain the contact-
induced deformation and failure of hard coating/soft
substrate systems. The observation of crack initiation
and propagation around indents by scanning electron and
atomic force microscopy (AFM) and other techniques
demonstrated that most of the plastic deformation around
the indentation was dominated by the soft substrate and the
deformation of the thin film resembled a membrane be-
ing deflected by a localized pressure gradient across the
membrane.6–8 Page et al. developed a plate-bending
system as an elastically bending and flexing plate on a
plastically yielding foundation.9,10 They also predicted
that film through-thickness cracks were most likely pro-
duced in the regions where bending produced tensile
stresses, in particular immediately beneath the indenter
tip and just outside the periphery of the indentation.11,12
Gerberich et al. modeled the mechanical contact of a
hard coating/soft substrate system as a stretched thin
elastic membrane under bending while the substrate un-
derwent viscoelastic–plastic deformation and developed
a drumhead solution by the simple superposition of the
membrane effect of the hard coating and the Hertzian
elastic solution in the substrate.13 Chechenin et al. con-
structed a model that addresses the load-induced ex-
pansion of the plastic zone and set criterion for the
film cracking as the onset of plastic deformation at film/
substrate interface.4 To better understand the stress dis-
tribution of coated systems under contact pressure, many
studies have also been carried out using numerical simu-
lations.14–16 Weppelman and Swain characterized the de-
formation and fracture behavior of a hard coating on a
soft substrate after determining, by a finite element
analysis, that the maximum radial tensile stress on the
contact edge is responsible for the first fracture event of
the film.17
In this study, a new analytical approach is developed
to predict the mechanical behavior of the amorphous ti-
tanium oxide/titanium system prior to oxide film crack-
ing (manifested by a sudden discontinuity during loading
in a nanoindentation test) on the basis of the assumption

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 M. Pang et al.: Thin-film fracture during nanoindentation of a titanium oxide film–titanium system

that the system behaves as an elastically deformed hard

coating on a plastically yielding substrate under contact.
Compared with a previous approach,13 this model incor-
porates the plastic deformation of the substrate by ana-
lyzing the experimental load–depth results instead of a
direct utilization of the Hertzian elastic solution. Further-
more, the plate solution was also refined by including
both plate-bending and membrane-stretching effects.

II. EXPERIMENTAL PROCEDURE

Grade II polycrystalline titanium was vacuum an-
nealed to achieve a primarily ␣ hexagonal-close-packed
phase grain structure. The sample was then sectioned,
ground to 600 grit, and electropolished in a mixture of
60% H2SO4, 25% HF, and 15% glycerin at approxi-
mately 30 V with a titanium cathode to remove the me-
chanically deformed layer. A Teflon electrochemical cell
coupled with a scanning probe microscope (Park Auto-
probe CP) (Thermomicroscopes, Sunnyvale, CA), and
nanoindentation system (a Hysitron triboscope, Minne- FIG. 1. Typical load–depth curve for in situ indentation of a titanium
apolis, MN) enables the in situ mechanical testing of oxide/titanium system with the titanium oxide thickness 30 nm
anodically grown oxides on titanium by step polarization (formed at 5.4 V versus Ag/AgCl reference electrode in 0.1 M H2SO4).
Note the discontinuity, referred to as pop-in or an excursion.
with a Berkovich diamond tip which has a tip radius of
approximately 1.5 ␮m.18 Testing was carried out in
0.1 M H2SO4. In addition, ex situ tests were also per-
(versus an Ag/AgCl reference electrode). The disconti-
formed to study the effect of the load-bearing capability
nuity in the loading curve is commonly referred to as a
of the film.
“pop-in” or “excursion”. While it is well accepted that
The oxide film thickness was determined by x-ray
the threshold type of dislocation nucleation and multipli-
photoelectron spectroscopy (XPS) depth profiling after
cation is the controlling effect of “pop-in” in the case of
the samples were removed from solution. The XPS
nearly pure elastic deformation prior to yield point for
equipment was a Physical Electronics Quantum 2000
some materials,19–23 the titanium oxide/titanium exhibits
Scanning ESCA (Physical Electronics, Inc., Eden Prairie,
permanent deformation before the onset of the yield dis-
MN) microprobe, using focused monochromatic Al K␣
continuity as shown in Fig. 2. As discussed previously,7
x-rays (1486.7 eV) for excitation and a spherical section
this type of yield phenomenon is most probably con-
analyzer. Calibration of the sputter rate was performed
trolled by the oxide film fracture event for relatively
by measuring a known thickness of SiO2/Si. The thick-
thick (more than 20 nm) oxide films on the sample sur-
ness of each oxide film was measured by identifying the
face for a thermally oxidized tungsten single crystal. A
depth at which the oxygen is 50% of the maximum oxy-
similar explanation may be developed regarding the role
gen concentration.
of the oxide film in titanium oxide/titanium. Further-
Nanoindentation on anodically grown oxides was also
more, it is likely that the mechanically stiffer and most
carried out in ambient conditions after removing the
likely harder titanium oxide (Eoxide /ETi ≈ 3) responds to
sample from the growth cell. These indentations were
contact pressure by elastic deformation and eventually
carried out using a Nanoinstruments Nanoindenter II
brittle fracture. Images of the surface surrounding the
(MTS System, Eden Prairie, MN), with a conical tip
indentation by AFM further support this explanation. As
which had an tip radius of approximately 1 ␮m to loads
shown in Fig. 3, concentric cracks appear at the periph-
of 2 and 10 mN. After indentation, the samples were
ery of the contact, in a manner consistent with the largest
imaged using a Digital Instruments Nanoscope IIIA
applied tensile stresses in an elastic contact.24 These in-
(Veeco Metrology Group, Santa Barbara, CA), via AFM
dents did pass the excursion load, and therefore, the sec-
to identify deformation and fracture in the oxide film.
ond set of cracks is probably continued tensile cracking
of the film past the initial failure. No evidence of inter-
III. RESULTS facial delamination at the film/substrate interface is ob-
Figure 1 shows a typical load–depth curve for an in- served, which is likely due to the chemical bonding
dentation into titanium oxide/titanium in the electro- between the oxide and metal as well as the ductile char-
chemical cell while under an applied potential of 5.4 V acter of the substrate.

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 M. Pang et al.: Thin-film fracture during nanoindentation of a titanium oxide film–titanium system
FIG. 2. Load–depth curves showing permanent deformation prior to
pop in. The titanium oxide thickness is approximately 90 nm and was
formed by anodizing at 8.4 V (versus Ag/AgCl) in the sulfuric acid
solution.
FIG. 3. AFM deflection image of an indentation of 2-mN load into
anodized Ti. The arrow denotes cracks in the oxide.
Figure 4 explicitly demonstrates the considerable role
of the surface film in supporting the contact pressure
prior to its fracture. The load carried by the 120-nm-thick
surface film accounts for up to 1⁄3 of the total applied load
at the depth at which film fracture occurs. The effect of
the surface film diminishes at relatively low loads and
becomes negligible at the initial loading, as the separa-
tion of the two curves is indistinguishable. Furthermore,
the examination of the loading segments after the yield
discontinuity reveals that the loading curves of both with
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FIG. 4. Load–depth curves for a titanium with a 128-nm-thick oxide
film and pure titanium without an oxide film, respectively.
and without surface oxides follow the same geometri-
cally necessary curves, indicating that the function of the
fractured oxide is very limited in determining the plastic
properties of the deforming system. It should be noted
that these indentation were carried out in two separate
grains, which accounts for any small differences in be-
havior after film fracture.
IV. MODEL
The titanium oxide/titanium system can be modeled as
a hard elastic plate on a soft yielding substrate under
contact as it is characterized by a thin stiffer ceramic
coating (Eoxide ⳱ 300 GPa25) on a more compliant and
ductile metal substrate (ETi ⳱ 110 GPa). The plate is
assumed to undergo elastic deformation until brittle frac-
ture. The substrate is displaced elastically, elasto-
plastically, and finally fully plastically depending on the
compression pressure. In particular, the substrate is as-
sumed to be elastoplastically deformed prior to the yield
discontinuity due to the constraints of surface film.
As shown in Fig. 5, the critical depth prior to the yield
point, i.e., the maximum elastic deflection of the film, is
on the order of its thickness despite data scatter due to
effects of grain orientation and microstructural inhomo-
geneities. The error bars in this figure are the actual data
range, with the symbols denoting the average value of at
least 10 indentations in each condition. In such a condi-
tion, the midplane stretching effect must be considered
owing to the change in plate geometry.26 The plate un-
dergoes nonlinear deformation comprising of both bend-
ing and membrane stretching solutions. Consequently,
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 M. Pang et al.: Thin-film fracture during nanoindentation of a titanium oxide film–titanium system

and substrate composite. The characteristic yield or flow

stress of the substrate, as measured by indentation, is ␴f.
The value of ␴f of titanium is approximately 1.2 GPa by
estimating ␴f as H/3 (hardness, H, was measured by a
larger scale Vickers microindentation to eliminate pos-
sible indentation size effects).
Figure 6 schematically illustrates the deformation ge-
ometry of the coated system. The oxide film is modeled
as an axisymmetric circular plate with a clamped edge.
The clamped edge is defined as the outer boundary of the
plastic zone, c, in the substrate. The load concentrates on
a contact area, a, with a Hertzian pressure distribution.
Under the contact pressure, the film is depressed down-
ward in the region larger than the contact area due to the
effect of the indentation “sink-in”.6,29 Such a bending
moment in the film results in a high tensile stress region
surrounding the indentation, which can cause through
thickness fracture of the film. Although the exact loca-
tion of the first crack event is difficult to determine ana-
FIG. 5. Indenter displacement at the excursion as a function of the
lytically, some previous studies suggest that it lies
film thickness. outside, but not far from, the contact area in the case of
the hard coating and soft substrate composite. For in-
stance, the maximum tensile stress occurs at r/a ⳱ 1.24
the load actually carried by the plate can be approximated
(r is the radial distance from the contact center, and a is
as the sum of the partial loads resisted by the bending and
the contact radius) for thinner films (when the ratio of the
the membrane stretching actions.
tip radius and the film thickness is about 20) in Wepple-
The mechanical reaction of the substrate is assumed to be
mann and Swain’s study.17 In the current model, for
a Hertzian-like contact, which is defensible on the basis
the sake of simplicity, it is assumed that the onset of the
of a previous study which found the actual pressure distri-
fracture initiation and propagation occurs at the outer
bution for a bilayered sytem is quite similar to the Hertzian
boundary of the plastic zone of the underlying substrate,
distribution for modulus ratios between the film and sub-
i.e., the clamped edge of the film that is illustrated in
strate of less than 427 (Eoxide /ETi is about 3). Imaging using
Fig. 6. Furthermore, it is also proposed that the remain-
the Hysitron system shows pile up is minimal and will
ing broken film outside the circular fracture has no func-
therefore be neglected in this study. The Hertz contact as-
tional support for the indenter as the film crack happens
sumption will not contradict the fact of plastic deformation
at a location far from the actual contact region. In addi-
of substrate if a characteristic term for plastic deformation is
tion, unlike a sharp indentation, the assumed spherical
used instead of the elastic power law of 3/2. The highlight
contact will not induce a high tensile stress at the center
of the model construction is that the plastic response of the
of the contact. As the numerical calculation for the exact
substrate is realistically represented by altering the charac-
plate deflection solution of the elliptical stress profile is
teristic coefficient of the load–depth relationship. The fea-
sibility of the model is discussed in details later.
To simplify the model, the following assumptions are
also proposed: (i) Due to the bluntness of the Berkovich
tip used in the current study (the tip radius is approxi-
mately 1.5 ␮m), a spherical tip is assumed in the contact
regime. (ii) The oxide/metal interface is perfectly
bonded. No frictional stresses are involved. (iii) To first
order of approximation, the size of the plastic zone de-
veloped within the substrate is given by28

c= 冑3Ps
2␲␴f
, (1)

where c is the plastic zone radius. Ps is the load carried

by the deformed materials; in particular, Ps is the load FIG. 6. Schematic diagram of deformation profile for indenting a hard
carried by the substrate in the current study of the film film/soft substrate system.

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 M. Pang et al.: Thin-film fracture during nanoindentation of a titanium oxide film–titanium system

formidable, a loading configuration with an analytical
solution available needs to be employed to simplify the
situation. The appropriate selection depends on the rela-
tive size of the plastic zone and the contact area, repre-
sented by c/a. The value of c/a is approximately
estimated as 2.7, which is neither close to the ideal cen-
tral nor uniform loading conditions. (The details are
elaborated in Appendix A). Bearing in mind that the
central loading gives an upper bound and the uniform
loading the lower bound in the plate deflection, a better
estimation of the plate bending in the current model is
expected to give an intermediate plate deflection.
The load versus center deflection for an elastic film
prior to its fracture can be simplified as30
the elastoplastic deformation prior the yield point, the
plastic deformation after the yield point, and that of
the typical elastic deformation in the condition of unload-
ing. Similar to the power law approach of load versus
depth dealt with by Oliver and Pharr,20 Hainsworth,
Chandler, and Page,31 defined the unit of Ke to be Pa m2−n
to maintain the dimensionality. It is also worth noting that
the choice of allowing n to vary is an artifact made solely
for the convenience of the curve-fitting process. Such an
approach is rather robust in its ability to describe these
experimental data as discussed in detail later.
By superposition of film deflection solution and sub-
strate yielding solution, the resultant relationship of load
and depth for the coated system is

P= 再 冋
2␲2␴f 16E f hf3
␦+
191
E h ␦3
648 f f 册冎 1Ⲑ2

, (2) P = Ke␦n + 再 冋
2␲2␴y
3
16E f h f3
12共1 − ␯f2)
␦

册冎
3 12共1 − ␯f 兲
2
1Ⲑ2
191
where P is again the applied load, ␴f is the characteristic + E h ␦3 . (6)
flow stress of the substrate, ␦ is the deflection depth, hf is 648 f f
the film thickness, Ef is the elastic modulus of the film By curve fitting of the upper loading part prior to the
(Ef ⳱ 300 GPa in the literature25), and ␯f is the Poisson yield discontinuity using Eq. (6), a value of n can be
ratio of the film (␯f is taken as 0.3). The detailed develop- obtained. Figure 7 presents a typical curve-fitting proce-
ment of the plate deflection solution which incorporates dure to determine the value of n for loading prior to film
both the corrected plastic zone size and the compromised fracture in which plate bending dominates (nplate).
loading condition is discussed in Appendix B.
The load and depth relationship of the pure substrate V. DISCUSSION
metal can be described by the Hertzian elastic contact
A. Model analysis
mechanics when a spherical tip is loaded onto a flat
surface:24 Additional fits of the other regions of the indentation
include an offset in the load or depth to account for the
4 loading support of the film or the shape of the surface
P ⳱ √REs␦3/2 ,
3 (3)
where R is the tip radius, the value of which is 1.5 ␮m for
this Berkvoich tip. Es is the reduced elastic modulus of
the substrate that is taken to be 110 GPa.
Furthermore, Eq. (3) can be rewritten as
P ⳱ Ke␦3/2 , (4)
where Ke is defined as a characteristic constant repre-
senting the elastic deformation behavior of the substrate,
the value of which equals to 4/3 √REs.
The elastoplastic deformation behavior of the substrate
while the oxide film is still intact is proposed to be de-
scribed by a similar equation, where the 3/2 power for the
elastic contact is replaced by a variable n which repre-
sents the characteristics of the elasto-plastically deforma-
tion of the substrate:31
P ⳱ Ke␦n . (5)
In the above equation, the same elastic Hertzian con-
FIG. 7. Representative curve-fitting procedure showing various re-
stant Ke is intentionally kept in an attempt to reveal gions of the indentation and the model fits to the plate-bending com-
the change in the deformation mechanism by sensing the ponent, the plastic deformation component, and the elastic unloading.
subtle alternation of the slope of the loading curve among The raw data are slightly offset for clarity.

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 M. Pang et al.: Thin-film fracture during nanoindentation of a titanium oxide film–titanium system
after yield, respectively, for the region in which plastic
deformation of the substrate is the primary deformation
mechanism (nplastic) and the elastic unloading of the tip
(nelastic). Equation (5) is utilized for the curve fitting. At
first glance, the results may seem unreasonable since the
values of nplastic and nelastic are higher than that of a
purely elastic contact (n ⳱ 1.5) which is not logical since
conventionally a power-law relationship for the load–
depth coefficient of plastic flow should have a lower
coefficient than that of elastic deformation (i.e., n prior to
the excursion is greater than the 1.5 value expected in a
purely elastic contact). However, in further examination
of Eq. (5), the magnitude of the constant for elastic con-
tact, i.e., Ke, was employed regardless of elastic or plastic
loading; in reality the constant should be decreased to
account for plastic deformation. Therefore, it should be
emphasized that Eq. (5) is used as a convenient repre-
sentation of the real load–depth behavior and that the
choice of fitting the coefficient was bound to lead to
increased values of n since the constant was not changed.
Figure 8 summarizes the curve-fitting results of n as a
function of film thickness, showing the average values
(solid symbols) as well as the entire range of values ob-
served (open symbols). Obviously, when the film is rela-
tively thick, i.e., hf > 40 nm, the value of nplate is closer to
that of nplastic than that of nelastic, indicating that the plas-
tic deformation occurs in the substrate prior to the film
fracture. The slightly lower nplate may be the result of
the elastoplastic-like deformation which is caused by the
surface constraint of the film prior to its fracture. In
FIG. 8. Comparison of nplate, nplastic, and nelastic in the range of film
thickness used in this study. Total range of measurements is shown;
solid symbols represent averages, and the open symbols are the maxi-
mum and minimum of each sample set.
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addition, the value of nelastic is slightly greater than would
be expected for a Hertzian spherical contact. This is as
would be expected from the work of Goodman and
Keer32 for the elastic contact of spheres in cavities
(where in this case the cavity is the result of plastic
deformation). In thinner films, i.e., hf < 40 nm, the value
of nplate falls into the range of nelastic instead of that of
nplastic, which may indicate that the initial deformation is
more elastically characteristic that is in good agreement
with the experimental results shown in Fig. 4. In such
cases, the model to quantify loading using plate deflec-
tion becomes inappropriate.
B. Effect of plate bending and stretching
As described in the model, the applied load is balanced
by two independent factors, the resistance of plate de-
flection and that of the substrate. The effect of the plate
bending and stretching is illustrated in Fig. 9. The pure
plate solution locates below that of load–depth curve and
reaches almost zero in the case of very thin films, indi-
cating that the plate-bending effect diminishes as the film
gets thinner. Consequently, it is stated that the present
model works in the conditions of relatively thicker film
that can be reasonably simulated as an integrated plate
with a certain mechanical property. It would be inappro-
priate to discuss the strengthening effect of the surface
film if the film is less than 40 nm for this tip.
C. Estimation of film strength prior to fracture
The stress distribution for a film/substrate layered
system can be predicted numerically by finite element
simulations. Weppelman and Swain have already demon-
strated that radial tensile stress around the contact edge is
responsible for the film through-thickness cracking in
vapor deposited films.17 Accordingly, the strength of
the film prior to fracture can be roughly estimated by
taking into account the radial stress of both the plate
bending and membrane solution for an oxide film.
The radial stress for the condition of plate bending is
given by30
␦ hf
␴rB = ␤r E f . (7)
c2
Similarly, the radial stress in the case of pure membrane
flexure is30
␦2
␴rM = ␣ r E f , (8)
c2
where ␣r and ␤r are constants taken from Timoshenko
et al.,30 the value of ␣r is 0.357, and that of ␤r is 2.198.
Therefore, the stresses and strains in the film can be
calculated as a function of indenter displacement, and the
stress at which a “pop in” occurs can be calculated. For
2639
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 M. Pang et al.: Thin-film fracture during nanoindentation of a titanium oxide film–titanium system

a first-order estimate, the total radial stress is the super-
position of the above two effects as the strains, and sub-
sequent stresses would be additive. Table I lists the
results in the conditions for relatively thick films. Note
that the load carried by the substrate instead of the total
applied load was used to calculate c, which is accom-
plished by incorporating an empirical constant discussed
in Appendix B.
As a rule of thumb, the brittle fracture strength can
be estimated as E/10, which would be about 30 GPa
for the film. In practice, the film strength can deviate
from this estimation on the basis of specific film
properties. This titanium oxide film is microporous with
a pore size about 100 nm, as shown in Fig. 10, and the
strength is therefore expected to be lower. Futhermore,
stresses that develop during film growth could lead to
either an increase or decrease of film strength depending
on the particular stress state. Therefore, the calculated
film fracture strength based on Eqs. (7) and (8), the av-
erage value of which is about 15 GPa, appears to be a
reasonable estimation.
VI. SUMMARY
(1) On the basis of experimental nanoindentation re-
sults, which demonstrate permanent deformation prior to
a yield point and circumferential cracking on the contact
perimeter for electrochemically anodized titanium, the
mechanism of oxide film fracture rather than a threshold
for dislocation motion is presented to explain the pop-in
phenomenon observed during indentation of an anodized
titanium alloy.
(2) Assuming that the titanium oxide/titanium system
acts as a hard coating/soft substrate under contact, a
model is developed to predict the mechanical response of
the titanium oxide/titanium coated system. The compos-
ite load–depth solution is the superposition of both the

TABLE I. Calculated average values of radial tensile stress at film

fracture for films thicker than 40 nm.

Film thickness ␴r for plate ␴r for membrane Total radial stress

(nm) bending (GPa) stretching (GPa) (GPa)
40 10.14 1.15 11.29
64 15.68 1.78 17.46
90 17.20 2.59 19.79
124 19.10 2.78 21.88

FIG. 9. Selected plate deflection solutions with comparisons to the

experimental load–depth curves for film thickness of (a) 63 nm and FIG. 10. TEM bright-field image of film morphology showing the
(b) 17 nm. porosity on the order of 100 nm in a 124-nm-thick oxide film.

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 M. Pang et al.: Thin-film fracture during nanoindentation of a titanium oxide film–titanium system
large deflection of a hard coating and the plastic flow of
the underlying substrate. The highlight of the model is
that the Hertzian-like solution is employed to present the
deformation behavior of substrate by incorporating a co-
efficient obtained by curve fitting experimental load–
depth curves prior to film fracture.
(3) The model works well in the condition of rela-
tively thick oxide films (greater than 20 nm). The film
bending action gradually vanishes as the film gets
thinner.
(4) To a first-order approximation, the film fracture
strength is estimated as 15 GPa, which is in good agree-
ment with theoretical estimation (E/10) when also con-
sidering the effects of microscopic defects and stresses
in the film.
ACKNOWLEDGMENTS
The XPS characterization described in this paper was
performed by M.H. Engelhard in the Environmental Mo-
lecular Sciences Laboratory, a national scientific user
facility sponsored by the Department of Energy’s Office
of Biological and Environmental Research and located at
Pacific Northwest National Laboratory. The financial
support through a grant from the donors of the Petroleum
Research Foundation, administered through the Ameri-
can Chemical Society, is gratefully acknowledged. Ad-
ditional support was provided through Sandia National
Laboratories, under a contract from the United States
Department of Energy (No. DE-AC04-94AL85000). The
experimental assistance of C.L. Woodcock, D.E. Eakins,
and M.G. Norton of Washington State University and Dr.
N.R. Moody of Sandia National Laboratory is greatly
appreciated.
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APPENDIX
A. Evaluation of the actual loading conditions
under contact by estimating the ratio of the
plastic radius and the contact radius (c/a)
A series of ex situ indentations were made on a pas-
sivated titanium with a 128-nm-thick surface oxide film.
According to the occurrence of loads at excursion, sev-
eral indentations were made by intentionally controlling
the peak loads to be slightly lower than the average ex-
cursion load. The resultant continuous load–depth curves
prior to the film fracture provide a better estimation of
the contact depth and thus the contact radius a at the film
fracture. Refer to Fig. 2 in the text for a typical load–
depth curve.
For instance, by curve fitting the upper part of the
unloading load–depth segment prior to film fracture in
Fig. 2, the contact depth h is estimated around 60 nm.
Accordingly, the contact area, A, calculated on the basis
of the tip area function,20 is around 296,800 nm2.
The contact radius a can be roughly calculated as
a ⳱ √A/␲ ⳱ 307 nm, assuming a circular contact.
Theoretically, the plastic zone radius c can be evalu-
ated by Eq. (1) in the text. As mentioned in the text,
Ps represents the load solely carried by the substrate.
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 M. Pang et al.: Thin-film fracture during nanoindentation of a titanium oxide film–titanium system

However, the experimentally recorded load is the overall where Df is the flexural rigidity of the film which is
load distributed over both the surface film and the un- given by30
derlying substrate. A better estimation of the plastic zone
can be achieved if the partial load carried by the surface E f hf3
film can be excluded from the total applied load. A series Df = . (B3)
12共1 − ␯f2兲
of nanoindentation curves were compared among the ma-
terials with and without the surface oxide film, as shown Pf is defined as the partial load carried by the film, and
in Fig. 4. By examination of the loading section prior to c is the radius of the clamped plate which is identical to
the yield discontinuity in Fig. 4, it is obvious that the the plastic zone radius within the substrate in practice and
total load carried by the film and substrate composite is given by Eq. (B4):
higher than that without the film at a given displacement.
The actual load carried by the substrate Ps at film fracture 3Ps
c2 = . (B4)
can be estimated as the applied load for the pure substrate 2␲␴f
deformation corresponding to the penetration depth at the
For the convenience of term collection, it is assumed that
film fracture for the film/substrate system if assuming
Ps ⳱ fPf , where f is a constant, given that Ptotal ⳱ Ps + Pf.
only elastic deformation occurs in the film. Data taken
Upon the application of the empirical constant f, the
from indents of which Fig. 4 is representative give an
above equations can be further simplified as
average value of Ps at the yield point for the titanium
with a 128-nm oxide film of 1847 ␮N. Therefore, the
radius of the plastic zone can be calculated as Pf = f − 0.5冋 2␲␴f
3 冉 ␦3
64␲Df ␦ + 0.488 2
hf
冊册 0.5
, (B5)

c= 冑 3Ps
= 857 nm . (A1) for the uniform loading condition, and

冋 冉 冊册
2␲␴y
2␲␴f 191 0.5

The value of c/a is approximately 2.8. Pf = f − 0.5 16␲Df ␦ + ␲ E f hf ␦3 ,

Compared to the two extremities, uniform and central
loading conditions, the current c/a is neither infinitely
small nor close to unity. Therefore, it is qualitatively
concluded that the actual loading condition lies between
the ideal uniform loading and central loading conditions
in the manner that may be closer to the uniform loading
conditions.
B. Construction of the plate deflection solution:
Eq. (2)
The analytical solution for the actual loading condition
is challenging due to its complicated elliptical stress dis-
tribution. Therefore, an approximation of the loading so-
lution based on analytical models and the deformation of
the substrate will be presented. As the current c/a is a
finite value greater than 1, an estimation of the plate
bending deflection may be achieved if it is assumed that
the resulting solution lies between the uniform and cen-
tral loading solutions.
Timoshenko’s plate deflection solution of the uniform
loading condition is given by30
3 648
(B6)
for the central loading solution.
The further simplification of the above equations de-
pends on the quantitative evaluation of the constant f.
While it is expected that f is material-dependent, and
possibly alters with the change in the combination of the
film and substrate system, especially film thickness, a
rough estimation of f can still be achieved by comparing
the relative load contribution from the film and the sub-
strate experimentally. More than 20 sets of nanoindenta-
tion data were collected at different film thickness
conditons. Once again, the principle of such decomposi-
tion is illustrated in Fig. 4. An example of such data
processing is plotted in Fig. B1. Surprisingly, the propor-
tional constant f is relatively constant in the condition of
relatively thicker films and large displacements. The av-
eraged value of f approaches 2.5 for indents to greater
than 50% of the film thickness. The initial loading
mechanism is primarily film dominant, which is not con-
sidered for the current model construction as discussed in
the text.

冉 冊
With substitution of the value of f into above equa-
␦3 tions, the solution for both ideal uniform and central
Pf c2 = 64␲Df ␦ + 0.488 . (B1)
h f2 loading conditions can be given by

And that of the central loading condition is

191
Pf = 0.632 冋 2␲␴f
3 冉 ␦3
64␲Df ␦ + 0.488 2
hf
冊册 0.5
, (B7)

Pf c2 = 16␲Df ␦ + ␲E f h f ␦3 , (B2)
648 for the ideal uniform loading. And

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 M. Pang et al.: Thin-film fracture during nanoindentation of a titanium oxide film–titanium system
FIG. B1. Representative approach for determining the empirical con-
stant f for a titanium with a 124-nm-thick oxide film.
Pf = 0.632 冋 冉
2␲␴f
3
16␲Df ␦ +
191
648
␲E f hf ␦3 冊册 0.5
, (B8)
for the ideal central loading.
Figure B2 illustrates the theoretical plate bending
solutions represented by Eqs. (B6) and (B7). To first or-
der, it will be assumed that the actual loading solution
lies midway between the ideal uniform (upper bound)
and central (lower bound) solutions. Coincidentally, the
central loading solution without the 0.632 coefficient
[Eq. (2)] is midway between the solutions of Eqs. (B6)
and (B7). Since Pf ⳱ Ptotal − Psubstrate, the experimental
data from Fig. 4 are plotted with Eqs. (B6) and (B7).
At depths between half the film thickness and the film
fracture event, the data are within a factor of 2 of
Eqs. (B6) and (B7). At the actual film fracture event, the
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FIG. B2. Plate deflection solutions for uniform loading [Eq. (B6)],
central point loading [Eq. (B7)], and Eq. (2) compared to experimental
data.
experimental data are approximately 1⁄2 the difference
between Eqs. (B6) and (B7). Therefore, Eq. (2) in the
text appears appropriate for estimating Pf.
It should be emphasized that Eq. (2) is not the direct
employment of the central loading solution as discussed
previously13 but is a simplification of the actual condi-
tion that incorporates both the corrected plastic zone size
for deformation in the substrate and a plate-bending ap-
proximation. Such an approach is materials-dependent,
and the empirical constant f may differ for other coated
materials. However, the overall idea of achieving the
plate deflection solution is universal; current work is un-
der way to examine the range of the constant f for a
variety of materials characterized by hard films and soft
substrates.
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