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Contents lists available at ScienceDirect

Applied Surface Science

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

Effect of annealing upon the structure and adhesion properties of sputtered

bio-glass/titanium coatings
G.E. Stan a,*, C.O. Morosanu a,1, D.A. Marcov a, I. Pasuk a, F. Miculescu b, G. Reumont c
a
National Institute of Materials Physics, P.O. Box MG-7, Bucharest-Magurele, Ilfov 077125, Romania
b
Politehnica University of Bucharest, Faculty of Materials Science and Engineering, Bucharest, Romania
c
University of Lille, Laboratory of Metallurgy, Villeneuve d’Ascq, France

A R T I C L E I N F O A B S T R A C T

Article history: Bio-glass films were deposited by radio-frequency magnetron sputtering technique onto medical grade
Received 4 March 2009 Ti6Al7Nb alloy substrates from prepared silica based bio-glass target. A low deposition temperature was
Received in revised form 15 June 2009 used (150 8C) and three different working pressures, followed by annealing in air at 550 and 750 8C. A
Accepted 26 June 2009
quasi-stoichiometric target to substrate atomic transfer was found for Si, Ca and P, along with strong
Available online xxx
enrichment in Na and depletion in K and Mg, as evidenced by the energy dispersive microanalysis. The
best results, taking into account stoichiometry and surface roughness, were obtained for the BG layers
Keywords:
deposited at 0.3 Pa argon working pressure. The infrared spectroscopy of the as-sputtered and of the
Bio-glass coatings
annealed films evidenced the characteristic molecular vibrations of silicate, phosphate and carbonate
Magnetron sputtering
Adherence functional groups. The as-deposited films are amorphous and became partly crystalline after annealing
Pull-out test at 750 8C, as evidenced by X-ray diffraction. The pull-out measurements, performed with a certified pull-
Annealing test machine, gave very strong film–substrate adhesion strength values. For the non-crystalline layers,
Composition the pull-out strength is higher than 85 MPa, and decreases after annealing at 750 8C to 72.9  7.1 MPa.
Structure The main objective of this work was to establish the influence of the working pressure upon the composition
and morphology of the as-deposited films, and of the annealing temperature upon structure and film–
substrate adhesion.
ß 2009 Elsevier B.V. All rights reserved.

1. Introduction metallic substrates seems to be more difficult to accomplish in case

The first bio-glass (BG), known as 45S5 Bioglass1, was reported
in 1969 [1–5]. After this, various kinds of bioactive glasses and
glass-ceramics with different characteristics have been developed
by melting and glazing methods. Some of them are already
commercialized as valuable bone-repairing materials. The pre-
requisite for glasses and glass-ceramics to bond to living bone is
the formation of bone-like apatite layer on their surfaces in the
body. This takes place for a SiO2 content smaller than 60 wt%,
high Na2O and CaO content and a high Ca/P ratio (between 1 and 5)
[1]. Unfortunately the coating of titanium substrates with thick BG
films by enameling and plasma spray techniques, usually fail due
to a weak glass/metal interface and rapid dissolution in body fluids
when implanted [6–8]. That is why in recent years, chemical [9–
14] and laser [15–22] methods were also investigated in order to
prepare adherent micrometric thin films. In comparison with
hydroxyapatite films the control of composition and adhesion to
* Corresponding author. Tel.: +40 724131131; fax: +40 213690177.
E-mail address: george_stan@infim.ro (G.E. Stan).
1
Deceased.
of the BG ones. There are very few papers referring to BG coating
deposited by magnetron sputtering [23]. It is widely accepted that
both mechanical properties and chemical composition are
important factors in the preliminary physiological bond of such
implants. Low mechanical properties are the major problem that
prevented the use of BG/Ti structures for load-bearing applications.
The purpose of the present work is to prepare adherent magnetron
sputtered (MS) bio-glass films having a structure as much as
similar with that of the bio-glass target.
2. Materials and methods
2.1. Materials
The magnetron sputtering target was prepared from a bioactive
glass ceramic [1,2] powder with micrometric granular size. The glass
ceramic powder had the following composition (wt%): SiO2—55,
CaO—15, P2O5—10, K2O—10, MgO—5, Na2O—5. The starting reagents
were: SiO2, CaCO3, (NH4)2HPO4, K2CO3, MgO and NaHCO3. The
mixture of the desired composition was mechanically homogenized
and heat treated at 400 8C for 10 min. The heat-treated mixture was
reground and then melted at 1300 8C for 30 min and under-cooled at

0169-4332/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2009.06.117

Please cite this article in press as: G.E. Stan, et al., Effect of annealing upon the structure and adhesion properties of sputtered bio-glass/
titanium coatings, Appl. Surf. Sci. (2009), doi:10.1016/j.apsusc.2009.06.117
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room temperature, and the resulted powder was cold-pressed in
order to obtain a 100-mm diameter MS target. Pieces of 100 mm2,
cut from a commercial 4 mm thick Ti6Al7Nb sheet, were used as
substrates. In order to estimate the films thickness by a method
based on optical transmittance measurement, parallel depositions
were done on both titanium and Corning glass substrates. Prior to
deposition the substrates were ultrasonically cleaned successively
in acetone and ethanol for 10 min.
Post deposition, annealing in environmental air at 550 and
750 8C for 2 h with a low cooling rate (3 8C/min) was done, in order
to promote the crystallization of the films and hereby decrease
their dissolution rate in physiological fluids. A Nabertherm
furnace—model L3/12/P320 was used.
2.2. Deposition procedure
The films were deposited by radio-frequency magnetron
sputtering (1.78 MHz), in argon atmosphere. The target to
substrate distance was set to 30 mm. The working chamber was
evacuated to a base pressure of 10 3 Pa, and then back-filled with
high purity (99.9995%) argon at a 40-sccm flow rate. The target
pre-sputtering was done for more than 30 min, under the same
conditions as the deposition. Prior to deposition, the substrates
were etched for 10 min at a 0.4-kV DC bias voltage in argon plasma
produced by a wolfram plasmatron, in order to remove the thin
oxide layers and other impurities which might persist after the
ultrasonic cleaning. The deposition pressure was varied by
modifying the diffusion pumping speed, and the influence upon
the films structure was studied. Three deposition pressures were
used: 0.16 Pa (sample indicative—BG-a), 0.22 Pa (sample indica-
tive—BG-b), and 0.3 Pa (sample indicative—BG-c). The depositions
were carried out for 1 h, using a 1.78-MHz generator at a constant
and low RF power (DCbias target value of 44 V) in order to avoid the
overheating of the target surface. The substrates were not heated
during deposition and their temperature (around 150 8C) was only
dependent on plasma self-heating.
2.3. Characterizations
The layer thicknesses were estimated from optical spectroscopy
transmittance in the non-absorbance and low absorption region,
by the Swanepoel procedure [24], using the films deposited on
glass substrates. The transmittance measurements were per-
formed using a PerkinElmer UV-VIS-NIR Lambda 90 spectro-
photometer in the wavelength range from 300 to 800 nm.
The influence of the deposition pressure upon the surface
morphology was investigated by scanning electron microscopy
(SEM) using a FEI Quanta-FEG 400 microscope.
In order to test the stoichiometry of the target to substrate
transfer during the sputtering, chemical composition analysis was
performed by energy dispersive microanalysis (EDS), with a
Princeton Gamma-Tech, Inc., attachment. The heat-treated BG
films were examined for their surface morphology by environ-
mental scanning electron microscopy (ESEM), using a Philips XL30
unit, equipped with a Sapphire-UTW EDAX detector.
Fourier transform infrared spectroscopy (FTIR) was used for
analyzing the functional groups present in the bio-glass film. The
Table 2
Chemical composition in oxides and Ca/P molar ratios of the BG target powder and of the as-deposited films.
Sample Working pressure [Pa] SiO2 [wt%] CaO [wt%] P2O5 [wt%]
Target – 55 15 10
BG-a 0.16 58.9 8.4 9.6
BG-b 0.22 58.3 10.5 11.6
BG-c 0.30 55.5 17.0 12.6
Please cite this article in press as: G.E. Stan, et al., Effect of annealing upon the structure and adhesion properties of sputtered bio-glass/
titanium coatings, Appl. Surf. Sci. (2009), doi:10.1016/j.apsusc.2009.06.117
Table 1
Deposition pressure and film thickness.
Sample Ar pressure [Pa] Thickness [nm]
BG-a 0.16 980
BG-b 0.22 810
BG-c 0.30 750
analyses were performed with a PerkinElmer BX Spectrum
spectrometer, in attenuated total reflection mode (ATR) using a
Pike-MIRacle diamond head of 1.8 mm diameter. The spectra were
recorded in the range 4000–400 cm 1, with a resolution of 4 cm 1.
The structure was investigated by X-ray diffraction (XRD) using
a BRUKER D8 ADVANCE diffractometer, in parallel beam setting,
with monochromatised Cu Ka1 incident radiation. In order to
enhance the signal coming from the film, the patterns were
recorded in grazing incidence geometry at 28 incidence angle.
The adhesion strength at the substrate–film interface was
measured by pull-test method, using a certified adhesion tester—
PAThandy model (maximum pull force = 6.3 kN), equipped with a
2.8-mm diameter stainless steel test elements (stubs). The test
elements were glued onto the film’s surface by a cyanoacrylate
one-component Epoxy adhesive, E1100S. The stub surface was first
polished, ultrasonically degreased in acetone and ethanol and then
dried in nitrogen flow. After gluing, the samples were placed in an
oven for thermal curing (130 8C/h). The pull force was smoothly
increased until fracture occurred.
3. Results and discussions
The film’s thicknesses decrease as the working pressure
increases (Table 1). The decrease of the deposition rate with the
Ar pressure is due to the shortening of the mean free path of the
sputtered particles. Increasing the sputtering pressure, the
sputtered particles suffer more collisions while traveling from
the target to substrate, and some of the sputtered particles are
back-scattered towards the target. This resulted in a decrease of
the deposition rate due to scattering.
The EDS results reveal a quasi-stoichiometric transfer for Si, Ca
and P, while the concentration strongly increases for Na, and
decreases for K and Mg. One can notice a monotonous enrichment
in Ca and P, and depletion in K, Na and Mg by increasing the
working pressure (Table 2). The elemental percentages obtained by
EDS were converted in oxides in order to be compared with the
target composition.
It is well known that the Ca/P molar ratio is of great interest for
the biological reactivity of such structures. As proved by Hench’s
studies [1–5], the bioactivity of a glass-ceramic is favored by a SiO2
content lower than 60 wt% and a Ca/P molar ratio lying between 1
and 5. Thus, taking into account the overall composition of the
films versus the working pressure (Table 2) we can conclude that
the most promising layer was obtained at the highest working
pressure (0.3 Pa). This is the main reason why we have investigated
in the followings the effect of various annealings only upon the BG-
c type films.
An additional reason in favor of the BG-c structure was the
observation that the surface morphology becomes rougher with
K2O [wt%] Na2O [wt%] MgO [wt%] Ca/P molar ratio
10 5 5 1.89
4.5 15.8 2.8 1.11
2.6 14.4 2.6 1.13
2.0 11.0 1.9 1.70
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the increase of pressure, as it can be seen in Fig. 1. A rough surface

is preferred to a smooth one in implantology, in order to realize
primary stability. Moreover, the microcavities present on such a
surface could be rapidly colonized by sanguine cells that will
generate the growth of the new osseous tissue [25–27].
The BG-c film was analyzed by ESEM-EDAX, FTIR and XRD. In
Fig. 2, one can observe that the surface morphology of the film
annealed at 550 8C is similar to that of the as-deposited films,
showing a quite homogenous and defect free surface. This strongly
modifies after heat treatment at 750 8C, becoming smoother and
sprinkled with small prominent aggregates of 10–20 mm diameter,
which look in detailed view like agglomerates of small, needle-
shaped crystallites. EDAX investigations showed that these
particles are strongly enriched in titanium compared to the matrix
composition (Fig. 3), and the XRD analysis, presented later herein,
leads to the conclusion that these are rutile crystals. The oxidation
by annealing of the titanium substrate is probably due to the
microcracks and pores which presumably appear during heating
because of the mismatch of the thermal expansion coefficients of
the glass-ceramic layer and titanium substrate. Presumably, the
rutile crystals germinate in micropores and at 750 8C rapidly grow
up towards the more oxygenated layer surface. In Fig. 2, at 750 8C
one can see that besides these aggregates there are also many small
(micron sized), single or agglomerated, smooth-edged, light-
colored particles, which could be associated with the sodium
magnesium phosphate phase identified by XRD.
The FTIR spectra show a very similar absorption envelope for
the target and the BG-c film, as-deposited and annealed at 550 8C,
exhibiting the same broad bands at 912, 1000 and 1100 cm 1
(Fig. 4A). For the BG target, the maximum absorption peak is
shifted to 1026 cm 1. According to previous infrared studies on
silicate glasses the absorption peak at 1075 cm 1 has been
attributed to asymmetric stretch vibrations of Si–O in Q3
tetrahedral units, and the absorption at 950 and 900 cm 1 are
assigned to analogous vibrations of Q2 and Q1 units, respectively.
The peak at 1383 cm 1 might be assigned to a shifted (CO3)2
stretching band. Those from 560, 692 and 792 cm 1, could be
assigned to bending mode of PØP Q3, Q2, Q1 and Q0 units (550–
600 cm 1) and to symmetric stretching bands of PØP Q3, Q2 and Q1
units (650–800 cm 1), respectively. The spectra of the 750 8C
annealed film display also a clear 1100 cm 1 asymmetric stretch-
ing band characteristic to (PO3) present in Q1 units [28–33]. By
increasing the annealing temperature a sharp band at 670 cm 1
was evidenced, very weak at 550 8C and strong at 750 8C. This
might be assigned to TiO2, which has a strong vibration band in
700–660 cm 1 region [33]. At the same time, one can notice a
strong decrease of the overall intensity of the investigated
wavelength region of the IR spectrum reflected by the layer
annealed at 750 8C, compared to the spectra of the samples
annealed at lower temperatures. This can be correlated with the
presence of numerous surface inhomogeneities (crystallites,
possible peeling-off) evidenced by SEM and XRD investigations.
The uniformity of the films surface was tested by a point-to-
point FTIR measurement using a Pike-MIRacle diamond head of
1.8 mm diameter, starting from the central region of the sample. In
Fig. 4B–D one can notice the very good structural homogeneity of
the surface of the as-deposited and of the 550 8C annealed films. In
case of the 750 8C annealed films important differences of FTIR
intensity were obtained between point-to-point measurements,
showing that the particles evidenced by ESEM have a different
composition compared to the matrix.
Besides composition and molecular structure, the crystal Fig. 1. Evolution of surface morphology versus deposition pressure.
structure of the coating might also influence the behavior in
biological environment. A partial crystallization of the BG films is
preferred in order to reduce the dissolution rate in body fluids. A
total crystallization of the BG suppresses its bioactivity [34]. Fig. 5

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displays the XRD patterns of the BG-c films obtained in grazing

Fig. 2. Evolution of surface morphology (ESEM-secondary electrons) versus
annealing temperature.
incidence geometry at 28 incidence angle, with the scattered
intensity measured between 208 and 658 (2u). This geometry
provides an incident X-ray path length in the layer about 5–15
times greater than that obtained in conventional (Bragg-Brentano)
measurement performed in the same scattering range.
As stated above, the actual thickness of the BG-c layer is about
750 nm. A simple attenuation calculus gives that in a layer of this
thickness having the chemical composition presented in Table 2,
and a hypothetical density of 3.5 g/cm3, the X-ray beam scattered
at 2u = 208 attenuates around 15%. This means that around 15% of
the total scattered intensity at this angle originates from the layer,
and 85% comes from the substrate. Therefore, despite the grazing
incidence, the most intensive peaks of the patterns presented in
Fig. 5 are the titanium peaks of the substrate. The intensity scales of
the graphical representations are chosen so that to emphasis the
lower intensity lines that arise without any doubt from the layer
structure.
The structure of the as-deposited film is amorphous at the
sensitivity limit of the measurement. The amorphous component
is probably based on amorphous silica, as it can be deduced from
the main hump centered on 2u  228. After heat treatment at
550 8C, several weak TiO2-rutile lines appear, whose intensity
increases by annealing at 750 8C. During heat treatment at 750 8C,
crystallization occurs in the layer, but the amorphous component
only slightly diminishes. The few rather intensive peaks which
appear, were assigned to: Na2Mg(PO3)4—ICDD: 22-477 [35] and
TiO2-rutile. There are also several weak lines that might be
associated with small percents of perovskite (CaTiO3) and oxygen
deficient titanium oxides (Ti2O and TiO).
The formation of calcium titanate and, at least partly, of
titanium oxides in the heat-treated samples, is due to the inter-
diffusion at the film–substrate interface. The presence of
perovskite in heat-treated hydroxyapatite films deposited onto
titanium had already been observed by many authors [36–41].
The integrity of the substrate/coating interface is always
concerned in determining the performance and the reliability of
any implant-type coating. The mechanical quality of the interface
can be evaluated by pull-out strength measurements.
The pull test was performed on the BG-c film with the test
elements fixed on different places of the film surface. A statistical
estimation was performed based on the average of ten adhesion
values on every surface. There were investigated the as-deposited
structures as well as the annealed ones. In case of the as-deposited
and 550 8C annealed structures the failure always occurred in
glue’s volume without damaging the film integrity at an average
value of 85 MPa. This represents the bonding limit of the resin, as
confirmed by the manufacturer. For the structures annealed at
750 8C the adherence was estimated at 72.9  7.1 MPa, the film
being ruined each time. However, the measured film–substrate

Fig. 3. Detailed view of a crystalline aggregate on the sample heat treated at 750 8C, and EDS results obtained on the particle and on the film matrix.

Please cite this article in press as: G.E. Stan, et al., Effect of annealing upon the structure and adhesion properties of sputtered bio-glass/
titanium coatings, Appl. Surf. Sci. (2009), doi:10.1016/j.apsusc.2009.06.117
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Fig. 4. (A) Comparative spectra for the powder and studied films; (B–D) uniformity of FTIR results in the central region of the BG films (B—as-deposited, C—annealed at 550 8C,
and D—annealed at 750 8C).

adhesion values are much higher than those reported in literature

Fig. 5. XRD patterns of the BG-c film; & = Ti, ^ = Na2Mg(PO3)4, ~ = TiO2-rutile,
* = CaTiO3.
[6,23,42].
These high values of pull-out strength for the as-deposited
coatings, and those annealed at 550 8C, could be attributed to the
sputter cleaning and ion bombarding processes of the substrate,
done before deposition [43]. As it is known, the poor adhesion of
the coatings could be ascribed to the natural oxide layers present
on the titanium alloy surface prior deposition. Previous works
[44,45] suggested that an optimal solution for removing these
contaminants in order to increase the adherence is an argon
plasma etching pre-treatment of the titanium substrates. The
sputter cleaning process largely removes not only the native oxide
layers, but also the adsorbed gas molecules, to produce a clean,
highly active surface [46]. The argon ion bombarding process
during sputtering might enhance the atomic diffusion and mixing
in the near-interface region. The etching process has been
optimized by tuning plasma power (200 W), surface DC bias
(0.4 kV) and etching time (10 min), based on own experience and
literature [47]. The sputtering time offers a maximum of the
adhesion properties after 10 min, as a result of the removal of
surface oxides and contaminants, which leads to good bonding at

Please cite this article in press as: G.E. Stan, et al., Effect of annealing upon the structure and adhesion properties of sputtered bio-glass/
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the coating–substrate interface. On the other hand, the formation
of chemical bonding between the coating and the substrate after
heat treatment, improves the film adherence to the substrate, as it
has been reported in previous works [37,39].
The decrease of the adherence after heat treatment at 750 8C, is
probably due to the hypothetical microcracks which appear at high
temperatures because of the dilatation coefficients misfit of the
layer and of the substrate. The diminution of the adhesion strength
could also be related to the needle-shaped rutile crystals
agglomerates which penetrate through the film.
4. Conclusions
Bio-glass films with biomedical destination were deposited by
magnetron sputtering onto medical grade titanium alloy sub-
strates. The work evidenced the influence of sputtering pressure on
the film stoichiometry, thickness and surface morphology. The best
results were obtained for the BG layers deposited at the higher
argon working pressure (0.3 Pa). For this optimized BG film the
layer-substrate pull-out strength, measured with a certified pull-
test machine, exceeded the glue limit (85 MPa) for the as-
deposited films and for those heat treated at 550 8C, and dropped
down to 72.9  7.1 after the annealing at 750 8C. This very high
adherence values are due partly to the pre-deposition etching of the
substrate surface. After annealing at 750 8C, perovskite and titanium
oxides were identified, so that the chemical bounding between the
coating and substrate might be predominant in determining the
adhesion in this case. The magnetron sputtered bio-glass film
composition within the bioactivity range, and the high values of
adhesion, are promising for further researches with in vitro tests in
simulated body fluid.
Acknowledgments
The authors wish to thank Professor Simion Simon for preparing
the bio-glass powder and Professor Sorin Ciuca for the helpful
advices during the UNIL stage. This work was supported by the
Romanian Ministry of Research and Technology through R&D
framework programs: CEEX 307/2006 and PN II 71-110/2007.
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Please cite this article in press as: G.E. Stan, et al., Effect of annealing upon the structure and adhesion properties of sputtered bio-glass/
titanium coatings, Appl. Surf. Sci. (2009), doi:10.1016/j.apsusc.2009.06.117