Thin Solid Films 574 (2015) 189195

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Thin Solid Films

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

Synthesis of Ti-based metallic glass thin lm in high vacuum pressure on

316 L stainless steel
M. Sarafbidabad
University of Isfahan, Faculty of Engineering, Department of Biomedical Engineering, Isfahan, Iran

a r t i c l e

i n f o

Article history:
Received 13 January 2014
Received in revised form 25 November 2014
Accepted 25 November 2014
Available online 4 December 2014
Keywords:
Metallic glass
High vacuum pulse laser ablation deposition
Amorphicity
Thin lm

a b s t r a c t
Surface modication of ordinary alloys by advanced coating provides a means to maintain the bulk properties of
the alloy and thereby its utility in sensitive applications. In this paper, we describe the deposition of a Ti-based
metallic glass thin lm on 316 L stainless steel using a high vacuum pulse laser deposition (HVPLD) process
without a bulk metallic glass (MG) source as target. A predominant amorphous single phase lm was obtained
in the proper chemical composition (Ti57Cu28{Zr0.95Hf0.05}5Si10) by controlling several process parameters, including the target rotation speed and vacuum pressure. Our HPLD conguration entailed high vacuum pressure
(less than 13.3 106 Pa), a target rotation speed in the range of 15002000 rotation per minute (rpm) and a
substrate temperature between 450 and 600 C. These parameters provide excellent control over the amorphicity
of the lm matrix. Our work opens up interesting opportunities to improve the poor surface properties of metallic
alloys specially biometallic alloys by depositing a thin lm of Ti-based MG on their surface, which can also
overcome the problem of MG bulk form production as we just deposited a thin lm of MG.
2014 Elsevier B.V. All rights reserved.

1. Introduction
The deposition of metallic glass (MG) matrix thin lms could be a
signicant advancement in surface modication metallic biomaterials,
micro-electro mechanical systems (MEMS) applications [1,2], and
other technological areas requiring special surface properties. MGs can
be replaced with bulk crystalline materials due to their excellent chemical and physical properties. However, as the thickness limitation during
MG manufacturing is the main barrier in their applicability [38], using
them in the form of thin lms is potentially a solution to this problem [9].
Nowadays, many physical high energy deposition techniques exist for
depositing thin lms on metallic substrates usually using a lm and a
bulk source target [10]. This is not suitable for MG deposition because
the absorption of high level energy by bulk metallic glass (BMG) causes
reversible crystal transformation and consequently creates a nondenitive thin lm structure [11].
The high production cost and complexity of MG target fabrication
are the main drawbacks of conventional deposition techniques that
are used to deposit amorphous lms onto metallic substrates. One of
the most well-known deposition techniques is pulse laser deposition
(PLD). PLD is a versatile method that permits the stoichiometric deposition of materials onto a surface and may present a possible solution
for the aforementioned problems in surface deposition [12]. The
high cooling rate after that each laser pulse absorbed on the target
permits the melted zone to re-solidify into an amorphous form which
Tel.: +98 3137934034; fax: +98 3132347940.
E-mail address: m.saraf@eng.ui.ac.ir.

http://dx.doi.org/10.1016/j.tsf.2014.11.080
0040-6090/ 2014 Elsevier B.V. All rights reserved.

consequently will be ablated from the target. Thermal behaviour studies

show that the cooling rate could reach up to 107109 K/s on the laser
targeted zone under ordinary PLD conditions [13]. This could provide
the essential dynamic force required to generate conventional amorphous alloys. Under these conditions, the nucleation of crystal embryos
or growth of clusters would be suppressed and atoms would be captured randomly in the structure [14,15]. Certainly, for most of these
states, a short range order or limited crystalline structure is visible in
the matrix due to inhomogeneous heat distribution on the target
surface [16]. However, fabrication that utilizes MG lms is limited
to electromagnetic based alloys such as Fe-based MG lms in MEMS applications [17]. In contrast, other MG alloys such as Ti [18], Mg [19,20],
and Zr-based [21] alloys have excellent potential to be used as thin
lms or coatings in biomedical applications and as part of surface modication techniques due to their superior chemical and mechanical
properties [22,23].
Recently, many reports on the generation of Ti-based BMGs with
excellent surface properties were published [2426]. The deposition of
Ti-based MG lms onto bulk materials with weak surface properties
such as Fe-based alloys is a good idea for solving the thickness limitation
problem of Ti-based BMG production and related costs, and it also increases their utility in industrial and biomedical applications. However,
the precise control of structure, thickness, roughness, wear resistance,
hardness, Young's modulus, corrosion, biocompatibility, and adherence
to substrates is an important issue that must be tackled. The choice of
constituents and of the composition of the MGs play an important role
in amorphization. For example, nickel in Zr- and Ti-based MGs increases
the glass forming ability but adversely affects its biocompatibility and

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M. Sarafbidabad / Thin Solid Films 574 (2015) 189195

Furthermore, the effects of PLAD process on deposited Ti-based MG

lms were investigated.
2. Experimental details
2.1. Materials

Fig. 1. XRD pattern of milled target material with 5 at.% Zr after 32 h milling.

therefore should not be used for biological applications [18,25]. Accordingly, our research is aimed at developing a Ni-free thin lm in a TiCu
SiZrHf system by using PLD with a BMG-decient target and variable
high vacuum pressure. Cu in this composition is a known toxic element
but relevant studies on Ti-based MG alloys including copper in their
composition, proved to have acceptable biocompatibity [18,22,27]. It is
important to understand that the complete vitrication of deposited
lm structures in a TiCuSiZr system depends on the control of the
heat distribution during the PLD process that involves the laser-target
interaction area, the targetsubstrate spacing, and the substrate surface
temperature, all of which affect the thin lm nucleation and growth
mechanisms. On the other hand, if a metallic system can satisfy triple
Inoue's empirical rules then amorphization will occur at low cooling
rate during solidication and even condensation [11]. In the present
study, a proper Ti-based chemical composition for target is introduced
that together with selecting and controlling pulsed laser ablation
deposition (PLAD) processing parameters, a Ti-based metallic glass
thin lm can be generated and deposited on the 316 L stainless steel.

A Ni-free Ti-based MG lm was deposited in situ on a heated 316 L

stainless steel substrate at 550 C using a pure metallic elemental
mixture with the Ti57Cu28(Zr0.95Hf0.05)xSi15 x stoichiometric formula
as the composite target. For creating targets, Ti, Cu, and Si (Alfa Acear Co.
USA) with purities of 99.97%, 99.98%, and 99.95% respectively, were
mixed together with milled ZrHf sponge (AEO, Iran) for 1 h using a
high energy milling machine (SPEX-8000). The mixture was sieved to
obtain particle size of less than 32 m to make target pellets (10 mm
diameter and 3 mm thickness) and then compressed by using a 15 ton
hydraulic press at room temperature. The surface of each target was
then polished by using a 2000 grade SiC grinding paper to minimize
the formation of particulate matter. Structural analysis of target powder
after milling and before deposition was performed by Philips, X'pertMPD diffractometer with monochromatic CuK radiation at 40 kV.
Fig. 1 shows XRD pattern of milled target with 5 at.% Zr after 32 h. It
clearly indicates that crystalline structure still remains in milled target
precursors after 32 h without any change to amorphous state. It implies
that target pellet is not glassy and its strength is enhanced resulting in
easier pellet making. Additionally, milling of target precursors reduces
pellet splashing during ablation.
2.2. High pulsed laser deposition (HPLD) setup
The HPLD system and related apparatus used in this study are shown
in Fig. 2.
The HPLD specications were adjusted to obtain a lm with a predominantly amorphous structure. A cross shaped vacuum chamber
was evacuated before carrying out lm deposition by using a vacuum

Fig. 2. HPLD setup plan for MG composite lm deposition.

M. Sarafbidabad / Thin Solid Films 574 (2015) 189195

191

Fig. 3. XRD patterns of as-deposited lms with different composition.

system including a vacuum gauge, a pressure controller, and a rotary

and turbo molecular pump (Edwards, UK).
Before switching on the laser, the vacuum pressure was maintained
at both high (b 133.32 107 Pa) and low (N133.32 103 Pa) pressure. A second harmonic Nd:YAG laser with a wavelength of 532 nm
was used as the laser source in the PLAD experiments together with a
Q-switched driver model GSQ-2780 with 140 ns pulse width and
1.9 kHz frequency. The angle of the laser beam and the target was
aligned to 45 while the distance of the target and the substrate
plume was at least 4 cm. The pulsed green laser beam was impinged
on the target surface through a quartz window. The target rotation
speed was controlled by using a stepper motor over the range 500
3000 rpm to prevent splashing and drilling. The laser spot size on each
target was set by adjusting the focus lens-target distance to achieve
maximum conuence during the ablation process, which led to a
combined irradiance of about 0.9 107 W/cm2. Deposition and plume
formation were monitored through a quartz aperture on the vacuum
chamber. Each deposition process experiment which lasted for
15 min, resulted in the deposited lms with a thickness of about
300 nm on heated and polished 316 L SS. Substrate samples were
austenitized at 1100 C for 1 h and then their surfaces were polished
by 1002000 SiC grinding papers and a disc grinder. After PLAD, the
samples were discharged from the chamber and the deposited lms
were peeled off from the substrates surfaces using a diamond blade
for further characterization. They were divided into three groups for
structural analysis, which included an examination of morphology and
phase transformation behaviour by XRD (Philips, X'pert-MPD, CuK at
40 kV and BregBrentano geometry), eld emission scanning electron
microscopy (FESEM; Nov, NanoSEM 230-FEI, 230 kV), and transmission
electron microscopy (TEM; LEO-912AB, 120 kV) tted with an energy
lter. Thermal analysis of deposited lm is performed by deferential
scanning calorimetery technique (DSC; Mettler Tolledo/PerkinElmer,
DSC 822) at a heating rate of 0.67 K/s.

other metallic and non-metallic substrates such as polymers and ceramic materials. The lms were deposited at different target rotation speeds
and vacuum pressures. Plume formation was visible clearly with an unaided eye. By increasing the target repetition rate up to 3000 rpm the
plume became uniform while splashing and sparkling were decreased
signicantly. At 3000 rpm and above the absorbed laser energy on the
target surface was reduced and the plume was diminished. We used

3. Result and discussion

By implementing HPLD, various Ti-based composite thin lms were
deposited on the surfaces of 316 L SS substrates to be developed for

Fig. 4. Morphology of lm with 5 at.% Zr in high vacuum pressure (133.32 107 Pa).

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M. Sarafbidabad / Thin Solid Films 574 (2015) 189195

Table 1
Optimized PLAD parameters for Ti57Cu28(Zr0.95Hf0.05)5Si10 MG lm.
Target rotation speed
(rpm)

Substrate
temperature C

Vacuum pressure
(Pa)

Laser intensity
(W/Cm2)

Pulse repetition rate

(kHz)

Chamber
temperature C

Target-substrate
distance (Cm)

Deposition time
(min)

2000

500

133.32 107

107

1.9

19

2.4

15

2000 rpm to form a conical plasma plume with uniform distribution in

the targetsubstrate space.
3.1. Film structure
Fig. 3 shows XRD patterns of the Ti-based lms from which it is
evident that the lm structure is strongly inuenced by the zirconium
content of the target. The four spectra that are shown in this gure
relate to lms with 0, 5, 10, and 15 atomic percentage (at.%) of ZrHf
in their composition. Two main groups of peaks are distinguished for
the XRD results, sharp peaks and broad peaks.
The rst group of peaks concerns the deposited lms without any
ZrHf content or those that included 15 at.% of this content which exhibited different crystalline phases. These phases are basically derived from
Ti and Cu-based solid solutions such as Ti2Cu or CuSi binary systems
and related (TiCuZr) icosahedra phases [28]. In addition, for this
group, peaks pertaining to pure metallic elements (Ti, Cu and Si) are
visible and this conrms that elements are ablated from the target
individually.
The second group of spectra obtained from the Ti57Cu28(Zr0.95
Hf0.05)5Si10lm are completely different. After ltering the substrate
peaks (austenite phase), the rest of the diffraction patterns mainly is a
set of broad peaks of the TiCu phase that could be identied as the
Ti-based MG phase. The main amorphous peak of these lms is obtained
only at a Bragg diffraction angle of 43.8 and no crystalline structure and
corresponding Bragg peak is observed.
The XRD peak of 15 at.% (ZrHf) is roughly similar to the lm with
5 at.% (ZrHf) but is thinner and higher in intensity. It includes some
sharp peaks that revealed a rare solid-solution of TiCu(ZrHf)Si
and Icosahedra-phase (I-phase) system that was created by PLAD in a
super saturated plasma state. In this state, the upper limit of the extended solubility of ZrHf in Cu and Ti is increased. This means that we have
a TiCuZrHfSi solid solution system in the plasma-vapour state
where the soluble elements are insoluble under normal conditions
due to their nature and the high discrepancy in their lattice parameters
and atomic ratio (N15 at.%). By increasing atomic ratio of ZrHf to
15 at.% and removing the silicon from the target, the related broad
peak for the deposited lm with a notable intensity disappears. In fact,
the related lm peak for the TiCu(ZrHf) system shows a weak crystalline structure that involves an amorphous and/or nano-crystallized
phase. It seems that the absence of Si helped to decrease the short

range order in the lm structure by increasing enthalpy of mixing

among the constituent elements. In this state, the composite structure
shifted to an asymmetrical distribution of icosahedra phase in an amorphous matrix as the intensive broad peak for lms with (ZrHf) =
15 at.% is converted to sharper peaks with less intensity in lower diffraction angles.
The abovementioned features illustrate that the amount of ZrHf in
a TiCuSi target composition system plays an important role in
the amorphicity of deposited lms. Our results indicate that adding
515 at.% ZrHf to the target composition eases the formation of
amorphous structure in the deposited lms. Actually, this amount of
ZrHf affects directly on randomised scattering and ablation of atoms
in the target and also satises the triple Inoue's empirical rules. Additionally the high atomic radii of Zr and Hf are a barrier to the formation
of crystalline structures during lm deposition on the substrates, so that
accelerates amorphization by increasing the residual stress among the
accumulated atoms on the substrate.
3.2. Morphology and lm microstructure
Properties and performance of the deposited lms are related to
their morphology and microstructure which are controlled by the applied method and its conditions. As in this research PLAD is selected,
the inuence of PLAD conditions on the lm morphology is described.
The results that we mentioned in the previous section revealed that
the deposited lm with a nominal formula of Ti57Cu28(Zr0.95Hf0.05)
5Si10 was a MG lm with a predominantly amorphous structure. We
found that two groups of ablated species were deposited on the
substrate during PLAD. The rst were molten droplets that were ejected
directly from the target surface and the second were plasma state
atoms, which were created by explosive transformation at a thin layer
under the target surface. Both groups make the conditions ready for
amorphization if the target chemical composition and process parameters are selected carefully. Fig. 4 shows the microstructure of the deposited Ti-based MG lm including 5 at.% Zr in its composition, on the
substrate surface. The mean deposited lm thickness was 260 nm
after 180,000 pulses over 15 min of PLAD process. This conrms the
concept of amorphization that was made apparent by the XRD results
described in the previous section. The cross section of Ti-based lm
with 5 at.% Zr was quite uniform with no grain boundaries, as
amorphous structures. Therefore, deposited lms are not formed by

Fig. 5. SEM of irradiated target (a) and related lm in 133.32 107 Pa pressure (b).

M. Sarafbidabad / Thin Solid Films 574 (2015) 189195

193

Fig. 6. SEM of irradiated target (a) and related lm (b) in 133.32 103 Pa pressure.

nucleation and growth mechanism as is commonly the case for crystalline materials or else a preferable orientation in the cross section prole
of the deposited lm would be visible.
The lm topography had cloudy or scorched appearance and was
coated on the substrate with a high degree of compaction and continuity. The related and optimized PLAD process parameters for this lm are
given in Table 1. To achieve perfect and uniform deposited lm, the
manner in which the particles were ablated from the target surface is
very important that is determinatively affected by target-laser interaction. The target rotation speed plays an effective role in this interaction
and nal results like the lm quality, surface deposited lm morphology, and related target topographies that are investigated and compared
in this study.
Fig. 5 shows the surface structure of a target (a) and its related
lm (b) with 5 at.% ZrHf at high vacuum pressure less than
133.32 10 7 Pa. The lm surface is smooth and uniform, and
the thickness was greater than that of the low vacuum pressure
(N133.32 10 3 Pa). It's because of decreasing air atoms' resistance
versus ablated atoms, resulting in increasing of deposition rate so that
surface is covered homogeneously. These results give us good insight
into a surface modication method with high efciency for depositing
uniform Ti-based MG lms without any crystal structure. This modication method is developed by controlling the PLAD process parameters
that lead to formulation of two different techniques. The rst is minimizing particulate matter by selecting the proper target rotation
speed and optimizing the laser-target interaction via optic instruments
and polishing the target surface. This technique permits a smooth
deposited lm to be created. The second technique is that particulate
matter can be reduced by utilizing a very low vacuum pressure during
PLAD, which accelerates heat explosion at the target surface, so that
particulate formation is suppressed. In this case, mass transformation
is related to atomic size of species and particulate formation does
not occur when the high-velocity energetic ux passes through the
target-substrate distance.
The related SEM analysis shows that the PLAD lm surface is smooth
and uniform when the vacuum pressure is 133.32 107 Pa (Fig. 5-b).
In this state, the rate of deposition and ablation are increased and the
plume is composed of atoms and smaller species without clusters and
particulates, which is conrmed by the presence of very small holes
on the irradiated target surface (Fig. 5-a). On the other hand, the SEM
results for the low vacuum pressure indicate that the deposited lms
contain more debris compared to previous state that could decrease
the wear resistivity of the lms and the local melting effect was observable on the surface of the corresponding target (Fig. 6-a). In this case,
the vacuum required for sublimation of the irradiated target is not provided. The formation of a stable and continuous plume is difcult and
the deposited lm is composed of crystals and amorphous structures.

These melted particles with irregular shapes are ablated and deposited
on the substrate, resulting in a rough lm on the substrate surface
(Fig. 6-b).
3.3. Film thermal analysis
Table 2 shows the achieved DSC results of starting powders used to
deposit Ti-based lm. The pureTi57Cu28(Zr0.95Hf0.05)xSi15 x powder
after different milling times has exothermic peak that exhibits this
starting powder is glassy. Tg is glass transition temperature, Tx, Tm and
Tl are their crystal transition temperature, melting point and liquid
temperature respectively.
The lm on substrate is deposited in two separated concentric circular areas due to rotating target. The rst is central region with approximate radius about half of the targetsubstrate distance. In this area the
lm adhesion is strong, due to the strike angle of ablated atoms
(70 b b 90) so that diffusion depth is high and atoms can penetrate
into the substrate surface easily. Here, as coherency in lm-substrate
interface is high and adhesion strength is near to substrate strength,
we are unable to detach central area without machining methods. The
second part is outer area where strike angles are less than the rst
area and atoms should pass a further path, so that diffusion energy is
reduced and atoms are unable to penetrate into the substrate surface.
Hence, lm adhesion is so low that it can be peeled off and gathered
easily by razor blade for required characterization.
The DSC scans of the deposited lms are shown in Fig. 7 to nd glass
transition temperature and optimum amount of ZrHf in target composition for obtaining maximum amorphicity in lms.
Samples with different ZrHf at.% (015) were tested. Relevant scan
of Ti57Cu28Si15 indicates no exothermic peak and no amorphous phase
formed by this type of target in PLAD. The XRD results in the previous
section match with this result. The lms with ZrHf = 5, 10, 15 at.%
have exothermic peak that reveals an obvious super-cooled liquid
region in them. But while deposited lm with ZrHf and Si equal to 15
and 0 at.% respectively, glass transition temperature is absent and
seems to be fully crystalline after passing through targetsubstrate
distance and sustaining PLAD thermal history.
Table 2
Critical temperature of amorphous milled Ti57Cu28(Zr0.95Hf0.05)5Si10 alloys.
ZrHf content (x) at.%

Critical temperature points (C)

Tg

Tx1

Tx2

Tm

Tl

Trg

0
5
10
15

565
603
597
587

579
641
629
601

668

655
627

1015
956
1032
1013

1046
1094
1163
1141

0.55
0.63
0.58
0.57

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M. Sarafbidabad / Thin Solid Films 574 (2015) 189195

Fig. 7. DSC scans of deposited Ti-based MG lms on 316 L SS.

3.4. TEM observations

A TEM analysis of the deposited Ti-based composite material is
carried out to verify the size and particulate forms and structures.
Copper grids are attached to the substrate holder at various distances
from the target (413 cm) and then particulate matter is deposited
directly onto it. Grids are then dispersed homogeneously in an ethanol solution using an ultra-sonicator for 10 min and then dried using
a tissue paper, and observed by TEM. Particle size measuring is made
by direct scale measurement using TEM micrograph image and a
high precision ruler.
Fig. 8 shows the TEM image of a developed Ti-based composite
material with nominal composition Ti57Cu28(Zr0.95Hf0.05)5Si10 that is
ablated and then deposited onto the TEM grid copper. The ablated
particulate species is uniformly embedded in thin lm layers on the

copper grid without any obvious aggregation. The spot images that are
produced by the selected area diffraction patterns (SADP) method are
featureless without any appreciable contrast corresponding to a crystalline phase within the structure. This indicates that the spots are in a
single amorphous phase, which conrms our nding presented in the
previous sections.
The mean particle size (clusters and droplets), their size distribution, and their related morphology are determined directly from
the TEM images. Fig. 8 is a typical TEM image of an ablated
Ti57Cu 28 (Zr 0.95Hf 0.05) 5 Si10 target that is fabricated at a vacuum
pressure of 133.32 10 7 Pa and temperature of 19 C inside the
vacuum chamber. The laser power is adjusted to 10 W at 1.98 kHz
and the target is kept at 2000 rpm. Here the target-substrate distance
was xed at 7 cm.
These cohesively deposited particles are small and spherical. The formation of the amorphous structures is attributed to the size of some of
the nano-structure particles in the local region below the critical crystal
size. The nano-spherical particles in Fig. 8 had a mean grain size of about
13 nm and are distributed uniformly on the copper collector. The SADP
halo pattern has an amorphous structure in the thin lm and this
nding coincides with achieved XRD results.
The amorphous phase and small size of deposited species are two
results of the rapid solidication of the ablated particles, which are
melted after laser irradiation and then re-solidied or condensed from
the liquid or gas phase inside the plume. TEM result illustrates that
amorphization occurred in ablated clusters and thus the deposited
lm, and conrms that the deposited lm created under the aforementioned process conditions is MG with an amorphous structure, and that
its constituents are crystalline.

4. Conclusions
A none BMG target is utilized for PLAD at high vacuum pressure for
the in situ deposition of a specic class of Ti-based MG thin lms with
amorphous structure. The inuences of some process parameters such
as the vacuum pressure, target composition, and target rotation speed
on the amorphization of deposited Ti-based lms are examined. We
found that deposited lms in a TiCuSi system at high vacuum pressure (b 133.32 10 7 Pa) are amorphous with a continuous short
range ordered structure if the target precursor includes 510 at.% of
ZrHf. In the case of more ZrHf content, lm with predominant amorphous Ti-based phase is transferred to a lm with composite phases,
which is a mixture of crystalline Ti2Cu, an icosahedra Ti-based phase,
and a MG phase. The surface morphology of the Ti-based MG lm at
2000 rpm and high vacuum pressure is uniform and covers the
substrate completely. A cross-section image of the deposited lm is
dense and compact in this state. From these results, it can be concluded
that the HPLD process with our conguration is effective for ablating of
non-amorphous targets for the situ deposition of an amorphous form on
a 316 L SS substrate.
According to these ndings, we believe that this technique is an
effective method for depositing other MG alloys to overcome the thickness limitation of BMG fabrication. However, further studies need to be
carried out on the amorphization mechanism to optimize this technique
for other MG alloys.

Acknowledgements

Fig. 8. TEM image and corresponding SADP of particulate matter ablated from target with
Zr = 5 at.%.

The author would like to acknowledge the ITMA Institute of Advanced Technology for the signicant support and special thanks to
Prof. Barkawi, Director of ITMA Institute and Prof. Azmi, Head of
Advance Materials and Nanostructural Laboratory (ANML) of ITMA,
University Putra Malaysia, and their staff members and technicians for
scientic consultation and their assistance.

M. Sarafbidabad / Thin Solid Films 574 (2015) 189195

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