Home

Search

Collections

Journals

About

Contact us

My IOPscience

General nanomoulding with bulk metallic glasses

This content has been downloaded from IOPscience. Please scroll down to see the full text.
2015 Nanotechnology 26 145301
(http://iopscience.iop.org/0957-4484/26/14/145301)
View the table of contents for this issue, or go to the journal homepage for more

Download details:
IP Address: 128.122.253.228
This content was downloaded on 21/04/2015 at 20:38

Please note that terms and conditions apply.

Nanotechnology
Nanotechnology 26 (2015) 145301 (9pp)

doi:10.1088/0957-4484/26/14/145301

General nanomoulding with bulk metallic

glasses
Ze Liu1,2 and Jan Schroers1,2
1

Department of Mechanical Engineering and Materials Science, Yale University, New Haven, CT
06520, USA
2
Center for Research on Interface Structures and Phenomena, Yale University, New Haven, CT 06511,
USA
E-mail: ze.liu@yale.edu and jan.schroers@yale.edu
Received 24 November 2014, revised 30 January 2015
Accepted for publication 19 February 2015
Published 18 March 2015
Abstract

Bulk metallic glasses (BMGs) are ideal for nanomoulding as they possess desirable strength for
molds as well as for moldable materials and furthermore lack intrinsic size limitations. Despite
their attractiveness, only recently Pt-based BMGs have been successfully molded into pores
ranging 10100 nm (Kumar et al 2009 Nature 457 86872). Here, we introduce a quantitative
theory, which reveals previous challenges in lling nanosized pores. This theory considers, in
addition to a viscous and a capillary term, also oxidation, which becomes increasingly more
important on smaller length scales. Based on this theory we construct a nanomoulding
processing map for BMG, which reveals the limiting factors for BMG nanomoulding. Based on
the quantitative prediction of the processing map, we introduce a strategy to reduce the capillary
effect through a wetting layer, which allows us to mold non-noble BMGs below 1 m in air. An
additional benet of this strategy is that it drastically facilitates demoulding, one of the main
challenges of nanomoulding in general.
Keywords: bulk metallic glasses, nanomoulding, nanoimprinting, wetting/dewetting, surface
oxide
(Some gures may appear in colour only in the online journal)
1. Introduction

aspect ratio of over 20. The ability to mold BMGs in a

controllable manner has triggered broad research in exploring
applications, such as electrochemical catalysts [69], micro
fuel cell [10], MEMS/NEMS [5, 11, 12], programmable
biomaterials [1315] and wastewater treatment materials
[16, 17]. Besides these applications, molded BMG nanostructures have also enabled the scientic community to study
size and connement effects on mechanical properties [18
25], deformation modes [2629], crystallization [30, 31] and
ow behaviors [23]. However, Kumars ndings and all following BMG nanomoulding has been limited to very few,
noble-metals-based alloys such as Pt57.5Cu14.7Ni5.3P22.5 [1]
and Pd43Ni10Cu27P20 [3234] with a high resistance to oxide
formation. Enabling the broad potential applications of BMG
nanomoulding requires the development of nanomoulding
strategies for more economic BMGs. Most BMGs, however,
readily oxidize, particularly when heated into the supercooled
liquid region (SCLR) like during thermoplastic forming

A critical requirement for any moldable material is that its

intrinsic length scale is small compared to the size of the
molds features. Polymers are ultimately limited by their
chain lengths and crystalline materials are limited by their
grain sizes. Bulk metallic glasses (BMGs) lack intrinsic size
limitation on the nanoscale [15]. In addition to this crucial
attribute, BMGs are hard and tough compared to other
materials used for nanomoulding, yet they can be softened
into a state in which they can be readily molded [2]. These
properties are often combined with favorable chemistry for
biocompatibility, electrochemical activity, antibacterial
behavior, and biodegradability.
Despite their attractiveness, until recently, BMGs could
not be molded into features below 100 nm. Kumar et al [1]
was rst to mold Pt57.5Cu14.7Ni5.3P22.5 into pores of
10100 nm in diameter and lengths that correspond to an
0957-4484/15/145301+09$33.00

2015 IOP Publishing Ltd Printed in the UK

Nanotechnology 26 (2015) 145301

Z Liu and J Schroers

(TPF) [35]. Such oxidizing results in the formation of a rigid

oxide layer which dramatically affects and ultimately prohibits the TPF lling of nanosized pores for the vast majority of
BMGs. We show here a general description for quantitative
prediction of molding of BMGs into nanoscale features,
which accounts for possible oxide formation. Our model
includes a threshold pressure and a capillary contribution,
which are required to break the oxide lm and overcome the
capillary force to enter into a nanopore, respectively. In
addition, a viscous term, which when compared to the
strength of the mold, denes the possible moldable aspect
ratios. Based on this quantitative model which we use to
construct
a
nanomoulding
processing
map
for
Zr35Ti30Cu8.25Be26.75, we introduce a strategy to reduce the
capillary effect, which allows us to fabricate nanorods in air
from highly reactive, non-noble based BMGs such as
Zr35Ti30Cu8.25Be26.75,
Zr44Ti11Cu10Ni10Be25
and
Mg65Cu25Y10.

pore with diameter, d, the required pressure to drive a liquid

into a pore, p, can be calculated from HagenPoiseuille law
L
p = 4max
,

(1)

where is the liquids viscosity and max is the maximum

shear strain rate. max is located at the liquid-mold interface
when assuming a parabolic velocity distribution. This ow
resistance linearly scales with the viscosity of the liquid
(gure 1(a)). Typically for creep ow of BMGs in their
SCLRs, max ~ 1 s1, and their minimum accessible viscosity
can vary signicantly among BMG formers ranging 105
109 Pa s [46]. For > 109 Pa s, the molding pressure of 10 GPa
is prohibitively high to ll an aspect ratio of three. Figure 1(a)
and equation (1) also suggest that the viscous resistance of
BMG liquids is size independent, which has been experimentally conrmed for molds larger than approximately one
micron [47]. However, for nanosized molds, <100 nm,
experiments revealed a size dependent forming pressure [1].
Kumar et al introduced a capillary effect to the viscous term
into equation (1) to account for the size dependence [1]. The
total pressure is then

2. Materials and methods

The nanomoulding experiments are operated in air with a
heating-cell equipped Instron 5569 machine (50 kN maximum
load
capacity).
The
processing
temperature
for
Zr35Ti30Cu8.25Be26.75,
Zr44Ti11Cu10Ni10Be25
and
Mg65Cu25Y10 with/without oils is 435 C and 175 C, respectively. The total processing time for all of the samples is
2 min and the maximum loading force is 50 KN. Demoulding
of Zr35Ti30Cu8.25Be26.75 and Zr44Ti11Cu10Ni10Be25 nanorods is
achieved through etching Al2O3 templates with KOH solution
(3 mol L1, temperature of 85 C). For Mg65Cu25Y10, we use
H3PO4 solution (concentration of 85%, temperature of 85 C)
due to the high reactivity of the alloy with both alkaline and
acidic solutions.
To demonstrate the use of BMGs as molds and moldable
materials, we choose as an example Pt57.5Cu14.7Ni5.3P22.5 as a
moldable material and Pd43Ni10Cu27P20 as a mold material.
Firstly, a Pd43Ni10Cu27P20 BMG disc is thermoplastically
formed into a nanoporous Al2O3 template at 360 C. The
maximum loading force and processing time are 5 KN and
2 min, respectively. Pd43Ni10Cu27P20 nanorods arrays to be
used subsequently as a mold are exposed by etching the
Al2O3 template. We then place a Pt57.5Cu14.7Ni5.3P22.5 disc
which is covered by a thin layer of high temperature oil on the
Pd43Ni10Cu27P20 nanorods array mold and thermoplastically
form the mold-replicate combination at 270 C. Demoulding
is realized by a small mechanical force applied at room
temperature.

p = 4max

4 cos
L

.
d
d

(2)

Here is the contact angle between BMG liquid and mold,

and is the surface energy of BMG liquids. The capillary
term (second term in equation (2)) is independent of L and
inversely proportional to the diameter (gure 1(b)). Hence,
the capillary term is independent of the aspect ratio and
therefore sets the lower boundary for hydrophobic molds. For
an applied pressure below p = 4*cos /d, nanorods cannot
be molded.
However, equation (2) does not consider that most BMG
surfaces, in their supercooled state, are covered with an oxide
layer, especially when molded in air [35]. The formation and
thickness of such a rigid oxide layer increases with the
reactivity of the BMG alloys. In order to mold the BMG into
nanosized pores, this rigid oxide layer must break to allow
BMG liquid to ow into the pores. Up to now, reactive BMGs
like Zr-based BMGs have never been molded into pores
below 1 m, suggesting that the molding barrier from the
oxide layer may be dominant on the nanoscale. In order to
quantify this effect we modeled the surface oxide lm by the
Karmans nonlinear equations (in cylindrical coordinate system)
r

d 1 d 2 Eh dw 2

= 0,
r Nr +

dr r dr
2 dr

(3)

d 1 d dw
dw
pr
r
= Nr
+
,

dr r dr dr
dr
2

(4)

3. Processing map for BMG nanomoulding

where E is the elastic modulus, D =

Thermoplastic compression molding, a process in which

moldable material is heated to ow into micro/nanopore
under an applied pressure, has been widely used in surface
patterning for polymers [3639] and BMGs [3, 12, 4045]
due to its simplicity and scalability. Typically for a cylindrical

Eh3

12 1 v 2

is exural

rigidity and v is Poisson ratio, w is the normal displacement,

Nr is the total membrane stress, and p is the uniform pressure
exerted by the supercooled BMG liquid. Based on a
dimensionless analysis, the pressure (p0) to break this surface
2

Nanotechnology 26 (2015) 145301

Z Liu and J Schroers

Figure 1. Thermoplastic based nanomoulding of bulk metallic glasses. (a) Contribution of the viscosity term to the forming pressure for BMG
liquids owing into a nanopore (equation (1)) for an aspect ratio of three, and a maximum shear strain rate of max 1 s1. (b) For nanosized
molds, the capillary effect should be included in the pressure (second term in equation (2)) which inversely linearly scales with the diameter
of a pore. (c) When nanomoulding supercooled BMGs in air, the BMG surface is typically covered with an oxide layer, which deforms as a
rigid lm under normal pressure exerted by the BMG liquid. The pressure needed to break the oxide layer scales with the square of the
diameter of a nanopore. (d) Processing map for Zr35Ti30Cu8.25Be26.75 which is constructed based on (a)(c), with max 1 s1, = 107 Pa s,
= 150, = 1 J m2, and h = 10 nm. The molding pressure is limited by the strength of the mold, approximately 300 MPa [49] for Al2O3
template assuming a 0.2% elastic limit. Formation of nanorods is initially limited by the pressure requirement to break the oxide layer (black
line) and/or overcome capillary force (red line), which are the onset boundaries of nanomoulding.
1

oxide layer should be of the form of

p0
E

c
h
= f , v, ,
E
d

where = 360 (1 + v )(17373v ). By substituting the

mechanical properties of the oxide layer (E 200 GPa,
c 1 GPa, and v 0.3) and the oxide thickness (1 and
10 nm) into equation (7), the maximum deection value (wm/
h) at yielding is calculated. Then substituting this value into
equation (8), the critic pressure p0 to rupture the oxide layer is
nally obtained (gure 1(c)). It is obvious that when molding
into small pores, the surface oxide layer becomes increasingly
important. However, this is only the case for reactive alloys
such as Zr-BMGs. For alloys with high corrosion resistance
such as Pt-BMGs, the contribution of an oxide layer can be
neglected.
The maximum aspect ratio that can be achieved in
molding nanorods is ultimately limited by the strength of the
mold (0), which denes the upper bound for the applied
pressure. As a consequence, the maximum aspect ratio that
can be realized is given by

(5)

where c is the strength of the oxide layer, and h the thickness

of the oxide layer. From linear theory of small deection and
von-Mises yielding criterion, equation (5) can be written as
p0 =

16
3

h 2
,
1 v + v2 d
c

(6)

which denes the pressure to break the oxide layer. This

pressure barrier scales with (1/d)2 and is more dramatic than
the linear-scaling entering barrier from surface dewetting
(second term in equation (2)). This scaling behavior reveals
that the oxide layer barrier is indeed dominating the lling
requirements of small pores. Considering the nonlinear effect,
the more accurate pressure to break the oxide layer (p0/E) is
related to the maximum deection value (wm/h) when rst
yielding at clamped edges [48]

L
1
4 cos

0 +
.
=
d max

4max
d

c a 2
wm
1

=
4 +
(1 + v)(11313v)

2 E h
90
h
1v+v
wm 2
wm 3
1
+
,
(1 + v)2 (4026v)
(7)

h
h
1890
1 v2

p0
E

wm 3
16 1 h 4 wm

,

+

h
3 1 v2 a h

(9)

Equations (2), (7), (8) and (9) describe the general

nanomoulding of supercooled BMGs (gures 1(a)(c)). This
description can be used to construct a BMGs processing
map, which reveals the dominating effect of nanomoulding
at different pore diameters. Taking Zr35Ti30Cu8.25Be26.75 for
example, parameters are max ~ 1 s1, = 107 Pa s, = 150,
= 1 J m2. Furthermore, we assume a maximum strength of
0 = 300 MPa for Al2O3 template (with 200 nm diameter

(8)

Nanotechnology 26 (2015) 145301

Z Liu and J Schroers

Figure 2. (a) Molding reactive BMGs by reducing capillary force through the use of an interlayer wetting layer. Al2O3 templates are coated
with high temperature oil (DuPont Kryto) prior to the molding operation. (b) After thermoplastic forming Zr35Ti30Cu8.25Be26.75 into a
200 nm Al2O3 template at 435 C for 2 min. Left: without the use of a wetting layer, right: with the use of high temperature oil as a wetting
layer. (c) Nanorods do not form without oil. (d) Formation of nanorods under the same conditions as (c) but with oil.

4. Results and discussions

pores) from a 0.2% elastic limit [49]. Combining

equations (2), (3), and (5), the processing map can be constructed (gure 1(d)), where the oxide thickness is set as
h = 10 nm, the upper bound in our experiments. We measure
such a thickness of the oxide layer by oxidizing
Zr35Ti30Cu8.25Be26.75 thin plate at 435 C for 4 min in air.
Subsequently, the plate is stretched to break the surface
oxide layer and the thickness is determined using SEM
(gure 5).

4.1. Nanomoulding non-noble BMGs by adding a wetting layer

The processing map (gure 1(d)) reveals the dominating

effects controlling molding into different size pores. Prior to
this work, Zr-BMGs have not been molded into features
smaller than 1 m. For this size region, the processing map
reveals that the dominating barrier originates from either the
4

Nanotechnology 26 (2015) 145301

Z Liu and J Schroers

Figure 3. Nanomoulding Zr44Ti11Cu10Ni10Be25 and Mg65Cu25Y10 by using oil-wetted Al2O3 templates. Zr44Ti11Cu10Ni10Be25 and
Mg65Cu25Y10 are molded at 435 C and 175 C, respectively. The total processing time is 2 min and the maximum loading force is 50 KN.
(a) and (d) show the as-thermoplastic formed samples. The dark color in both of the BMGs suggests that nanorods formed. (b)(c) SEM
images of Zr44Ti11Cu10Ni10Be25 nanorods after removing the Al2O3 template through KOH etching. (e)(f) Mg65Cu25Y10 nanorods with
Al2O3 template partially etched by using H3PO4. The reactivity of Mg65Cu25Y10 with both alkaline and acidic solutions which are required to
etch the Al2O3 template causes degradation of the nanorods.

capillary effect or surface oxide. To reduce these barriers, and

hence enable nanomoulding with non-noble BMGs, we propose a simple strategy through introducing a wetting layer to
the Al2O3 template surface (gure 2(a)). Specically, we
immerse Al2O3 templates and/or BMGs into high temperature
oil prior to the molding operation. Oils typically wet ceramics
and metals. We choose DuPont Kryto oil which wets Al2O3
template and Zr35Ti30Cu8.25Be26.75 well (contact angle
< 45, gure 6). By reducing the surface energy through
the surface wetting oil, we successfully mold
Zr35Ti30Cu8.25Be26.75 and Zr44Ti11Cu10Ni10Be25 into 100 nm
nanopores. One of the results for 200 nm nanorods with
aspect ratio over ve is shown in gure 2(d). In contrast,

molding under the same processing conditions but without oil

does not result in any lling of the 200 nm pores (gure 2(c)).
We attribute the successful nanomoulding of Zr-BMG
when using an oil layer to the reduced surface energy of
BMG liquids which decreases the capillary (second term in
equation (2)). When forming supercooled Zr35Ti30Cu8.25Be26.75
into a nanopore wetted with oil, the capillary term in
equation (2) changes to 4( oil BMG oil )/d , and the interfacial
tension between oil and supercooled BMG can be estimated by
oil BMG = oil + BMG oil BMG [50]. The capillary term

thus becomes 4BMG 1 oil /BMG /d , which suggests that

the capillary effect can be reduced by using oil. In addition, the
5

Nanotechnology 26 (2015) 145301

Z Liu and J Schroers

Figure 4. BMGs used as mold or moldable materials. (a) Requirements for a BMG mold/moldable material combination are that one BMG

has sufciently softened, which is achieved by processing in its supercooled liquid region close to its crystallization temperature. The other
BMG to be used as a mold should have a 20% higher Tg than that of the moldable BMG. Such a difference guarantees several orders of
magnitude difference in strength (ow stress). (b) Schematics of nanomoulding Pt-BMG using Pd-BMG nanorods as a mold. (c)(d)
Pd43Ni10Cu27P20 nanorods after demoulding from Pt57.5Cu14.7Ni5.3P22.5. (e)(f) Replicated nanoholes in Pt57.5Cu14.7Ni5.3P22.5.

Figure 5. Surface oxide layer on Zr35Ti30Cu8.25Be26.75, formed during processing in air at 435 C. Subsequently the sample is deformed to
rupture the surface oxide, resulting in a total processing time of 4 min. (a) Optical microscopy image reveals the rupture of the surface oxide
layer. (b)(c) By using SEM (the sample stage is tilted 30 degrees), the oxide thickness is measured to about 156 nm, which corresponds to
an oxidation rate of 0.65 nm s1 by assuming a linear oxidation process. Within our processing protocol, it takes 15 s to heat the sample,
which gives the upper bound thickness of the oxide layer to 0.65*15 nm 10 nm.

Nanotechnology 26 (2015) 145301

Z Liu and J Schroers

Figure 6. Wetting of high temperature oil (DuPont Kryto) on Al2O3 template and polished Zr35Ti30Cu8.25Be26.75.

5. Conclusions

changing of sticky boundary to lubrication boundary may help

to reduce the owing resistance and thus enable the fabrication
of nanorods with larger aspect ratio, which is still under
investigation.
To demonstrate the general applicability of this strategy,
we also mold Zr44Ti11Cu10Ni10Be25 and Mg65Cu25Y10 into
pores of 200 nm in diameter (gure 3). When applying an oil
lm, both alloys can be nanomolded. The appearance of the
Mg65Cu25Y10 nanorods is affected by the subsequent H3PO4
etching to remove the Al2O3 template.

We identied the governing contributions for most general

BMG nanomoulding. These are viscous, capillary, and surface oxide layer fracture. The viscous contribution dominates
for supercooled BMGs with large viscosity, when lled into
high aspect ratios. The capillary term scales with the characteristic dimension of the nanopore and is determined by
interface wetting properties (surface energy/contact angle).
The surface oxide layer controls the lling barrier at smaller
scales since it scales with the square of the diameter of the
nanopore. Our general description allows for quantitative
predictions, which can be used to create a processing map for
BMG nanomoulding.
The processing map reveals the limiting factors, which
have prevented nanomoulding for the majority of BMG alloys
in the past. We used this knowledge to develop a molding
strategy using a wetting layer to reduce the entering barriers.
Using this method, reactive BMGs based on Zr and Mg can
be nanomolded under practical conditions. Furthermore, the
wetting layer also dramatically reduces interfacial forces,
which suggest the possibility for a non-disposable mold
method for BMG nanomoulding.

4.2. BMGs used as molds and moldable materials

Besides using BMGs as ideal moldable materials, BMGs

drastic temperature dependent strength can also be utilized as
a means to use them as molds. For example the softening
temperatures of thermoplastics are usually below 200 C,
which is lower than the glass transition temperatures (Tg) for
most BMGs. Hence, BMGs are high strength at these temperatures, hence can be used as molds for thermoplastic
polymers. Due to the large range of glass transition temperatures among BMGs, nanomoulding one BMG with
another BMG mold is also possible. The selection of the
appropriate BMGs depends on their relative glass transition
temperatures. This attribute and requirement are schematically shown in gure 4(a), where the viscosity (or ow stress)
of BMGs can decrease by several orders of magnitude when
the temperature approaches Tg. Compared with other mold
materials such as silicon and Al2O3 molds, BMG nanomolds
are advantageous due to their high elasticity, strength, and
toughness. These attributes warrant long mold life, ability to
demould, and precise and inexpensive fabrication of the mold.
To demonstrate this concept, Pd43Ni10Cu27P20 nanorod
arrays of 200 nm in diameter are fabricated by replicating
Al2O3 mold at 360 C. Subsequently, these nanorod arrays act
as a mold and are replicated at 270 C with oil-wetted
Pt57.5Cu14.7Ni5.3P22.5. Demoulding at room temperature can
be readily achieved by small mechanical forces. This method,
in contrast to all previous BMG nanomoulding methods,
allows the reuse of the mold. As such it represents a step
towards commercial usage of BMG nanostructures since it
drastically reduces fabrication costs which in the past included the disposable Al2O3 template.

Acknowledgment
This work was primarily supported by the National Science
Foundation under MRSEC DMR-1119826. Facilities use was
supported by YINQE. We thank Dr Sungwoo for help casting
Mg-BMG.

Appendix
A.1. Oxidation rates

We oxidized Zr35Ti30Cu8.25Be26.75 in air at 435 C and subsequently stretched the BMG to break its surface oxide layer.
The total processing time is 4 min. The ruptured surface
oxide layer is clearly revealed under an optical microscope
(gure 5(a)). Using SEM (gures 5(b)(c), the sample stage is
tilted 30), the oxide thickness is measured to 156 nm,
which corresponds to a 0.65 nm s1 oxidation rate if assuming
7

Nanotechnology 26 (2015) 145301

Z Liu and J Schroers

a linear oxidation. During the TPF-based molding, we usually

consume 15 s to reach the processing temperature, which
denes the upper bound thickness of the oxide layer to
10 nm (0.65*15 nm).

[18] Guo H et al 2007 Tensile ductility and necking of metallic

glass Nat. Mater. 6 7359
[19] Lee C J, Huang J C and Nieh T G 2007 Sample size effect and
microcompression of Mg65Cu25Gd10 metallic glass Appl.
Phys. Lett. 91 081601
[20] Jang D C and Greer J R 2010 Transition from a strong-yetbrittle to a stronger-and-ductile state by size reduction of
metallic glasses Nat. Mater. 9 2159
[21] Magagnosc D J et al 2013 Tunable tensile ductility in metallic
glasses Sci. Rep. 3 1096
[22] Tnnies D, Maa R and Volkert C A 2014 Room temperature
homogeneous ductility of micrometer-sized metallic glass
Adv. Mater. 26 571521
[23] Shao Z et al 2013 Size-dependent viscosity in the super-cooled
liquid state of a bulk metallic glass Appl. Phys. Lett. 102
221901
[24] Chen D Z et al 2013 Nanometallic glasses: size reduction
brings ductility, surface state drives its extent Nano Lett. 13
44628
[25] Gu X W et al 2014 Mechanisms of failure in nanoscale
metallic glass Nano Lett. 14 585864
[26] Volkert C A, Donohue A and Spaepen F 2008 Effect of sample
size on deformation in amorphous metals J. Appl. Phys. 103
083539
[27] Chen C Q, Pei Y T and De H J T M 2010 Effects of size on the
mechanical response of metallic glasses investigated through
in situ TEM bending and compression experiments Acta
Mater. 58 189200
[28] Greer J R and De H J T M 2011 Plasticity in small-sized
metallic systems: intrinsic versus extrinsic size effect Prog.
Mater. Sci. 56 654724
[29] Wang Y B et al 2014 Ultrahigh-strength submicron-sized
metallic glass wires Scr. Mater. 84-85 2730
[30] Gopinadhan M et al 2013 Finite size effects in the
crystallization of a bulk metallic glass Appl. Phys. Lett. 103
111912
[31] Sun Y T et al 2014 Understanding glass-forming ability
through sluggish crystallization of atomically thin metallic
glassy lms Appl. Phys. Lett. 105 14
[32] Mukherjee S et al 2012 Palladium nanostructures from multicomponent metallic glass Electrochim. Acta 74 14550
[33] Liu X, Shao Y, Li J F, Chen N and Yao K F 2014 Large-area
and uniform amorphous metallic nanowire arrays prepared
by die nanoimprinting J. Alloys Compd. 605 711
[34] Mukherjee S et al 2013 Tunable hierarchical metallic-glass
nanostructures Adv. Funct. Mater. 23 270813
[35] Schroers J 2008 On the formability of bulk metallic glass in its
supercooled liquid state Acta Mater. 56 4718
[36] Chou S Y, Krauss P R and Renstrom P J 1996 Imprint
lithography with 25-nanometer resolution Science 272 857
[37] Rohr T, Ogletree D F, Svec F and Frechet J M J 2003 Surface
functionalization of thermoplastic polymers for the
fabrication of microuidic devices by photoinitiated grafting
Adv. Funct. Mater. 13 26470
[38] Lendlein A, Jiang H Y, Junger O and Langer R 2005 Lightinduced shape-memory polymers Nature 434 87982
[39] Nie Z H and Kumacheva E 2008 Patterning surfaces with
functional polymers Nat. Mater. 7 27790
[40] Chu J P et al 2007 Nanoimprint of gratings on a bulk metallic
glass Appl. Phys. Lett. 90 034101
[41] Li N, Xu X N, Zheng Z Z and Liu L 2014 Enhanced
formability of a Zr-based bulk metallic glass in a
supercooled liquid state by vibrational loading Acta Mater.
65 40011
[42] Li N et al 2013 A thermoplastic forming map of a Zr-based
bulk metallic glass Acta Mater. 61 192131
[43] Xia T, Li N, Wu Y and Liu L 2012 Patterned
superhydrophobic surface based on Pd-based metallic glass
Appl. Phys. Lett. 101 081601

A.2. Wetting properties of high temperature oil with templates

and BMGs

The contact angles of oil drops on surfaces of Al2O3 and

polished Zr35Ti30Cu8.25Be26.75 are smaller than 45 (gure 6),
which suggests the high temperature oil (DuPont Kryto) used
in our experiments wet both of them well.

References
[1] Kumar G, Tang H X and Schroers J 2009 Nanomoulding with
amorphous metals Nature 457 86872
[2] Schroers J 2010 Processing of bulk metallic glass Adv. Mater.
22 156697
[3] Saotome Y, Itoh K, Zhang T and Inoue A 2001 Superplastic
nanoforming of Pd-based amorphous alloy Scr. Mater. 44
15415
[4] Kumar G, Desai A and Schroers J 2011 Bulk metallic glass: the
smaller the better Adv. Mater. 23 46176
[5] Sharma P, Kaushik N, Kimura H, Saotome Y and Inoue A
2007 Nano-fabrication with metallic glassan exotic
material for nano-electromechanical systems
Nanotechnology 18 035302
[6] Brower W E, Matyjaszczyk M S, Pettit T L and Smith G V
1983 Metallic glasses as novel catalysts Nature 301 4979
[7] Sekol R C et al 2013 PdNiCuP metallic glass nanowires for
methanol and ethanol oxidation in alkaline media Int. J.
Hydrog. Energy 38 1124855
[8] Carmo M et al 2011 Bulk metallic glass nanowire architecture
for electrochemical applications ACS Nano 5 297983
[9] Zhao M, Abe K, Yamaura S, Yamamoto Y and Asao N 2014
Fabrication of PdNiP metallic glass nanoparticles and
their application as highly durable catalysts in methanol
electro-oxidation Chem. Mater. 26 105661
[10] Sekol R C et al 2013 Bulk metallic glass micro fuel cell Small
9 20815
[11] Nakayama K S et al 2010 Controlled formation and
mechanical characterization of metallic glassy nanowires
Adv. Mater. 22 872
[12] Schroers J, Pham Q and Desai A 2007 Thermoplastic forming
of bulk metallic glassa technology for MEMS and
microstructure fabrication J. Microelectromech. Syst. 16
2407
[13] Schroers J, Kumar G, Hodges T M, Chan S and Kyriakides T R
2009 Bulk metallic glasses for biomedical applications Jom
61 219
[14] Padmanabhan J et al 2014 Engineering cellular response using
nanopatterned bulk metallic glass ACS Nano 8 436675
[15] Zberg B, Uggowitzer P J and Lofer J F 2009 MgZnCa glasses
without clinically observable hydrogen evolution for
biodegradable implants Nat. Mater. 8 88791
[16] Lin B, Bian X F, Wang P and Luo G P 2012 Application of Febased metallic glasses in wastewater treatment Mater. Sci.
Eng. B 177 925
[17] Wang J Q et al 2012 Rapid degradation of Azo dye by Febased metallic glass powder Adv. Funct. Mater. 22
256770
8

Nanotechnology 26 (2015) 145301

Z Liu and J Schroers

[47] Chiu H M, Kumar G, Blawzdziewicz J and Schroers J 2009

Thermoplastic extrusion of bulk metallic glass Scr. Mater.
61 2831
[48] Chien W Z 1947 Large deection of a circular clamped plate
under uniform pressure Acta Phys. Sin. 7 6
[49] Ko S et al 2006 Mechanical properties and residual stress in
porous anodic alumina structures Thin Solid Films 515 19327
[50] Fowkes F M 1964 Attractive forces at interfaces Ind. Eng.
Chem. 56 40

[44] Li N, Xia T, Heng L P and Liu L 2013 Superhydrophobic Zrbased metallic glass surface with high adhesive force Appl.
Phys. Lett. 102 251603
[45] Chen W, Liu Z, Robinson H M and Schroers J 2014 Flaw
tolerance versus performance: a tradeoff in metallic glass
cellular structures Acta Mater. 73 25974
[46] Kato H et al 2006 Fragility and thermal stability of Pt-and Pdbased bulk glass forming liquids and their correlation with
deformability Scr. Mater. 54 20237