Laser based synthesis of intermetallic CuZn nanoparticles

and laments
Y.B. Pithawalla
a,b
, M.S. El-Shall
a,
*
, S. Deevi
b
a
Department of Chemistry, Virginia Commonwealth University, Richmond, VA 23284-2006, USA
b
Research, Development and Engineering Center, Philip Morris USA, Richmond, VA 23261, USA
Received 27 June 2002; received in revised form 7 November 2002; accepted 14 November 2002
Abstract
Nanocrystalline (1015 nm) intermetallic compounds c-Cu
5
Zn
8
and e-CuZn
5
are prepared by the laser vaporization
controlled condensation technique. The nanoparticles can be assembled into laments and bers by applying an elec-
tric eld during the synthesis. The properties and possible applications of the nanoparticle assemblies are presented and
discussed.
2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.
Keywords: Nanocrystalline; CuZn intermetallics; Nanoparticle laments; Laser vaporization; Fibers
1. Introduction
The past few years have witnessed an intensely
growing interest in the eld of nanoparticles due to
their uses and applications in areas as diverse as
materials science, catalysis, biomedical, environ-
mental and aerospace research. Nanoparticles with
novel optical, magnetic and electronic properties
have been made from a variety of materials includ-
ing semiconductors, metals and rare earths [14].
Nanoparticles of intermetallic alloys are of
special interest because of the important advan-
tages oered by the low density and high strength
of the bulk materials. The control of the com-
position, crystalline phase and morphology of
intermetallic nanoparticles is essential for the
development of new nanophase materials with
unique properties.
Conventional gas condensation and carbon arc-
synthesis methods have not been successful for
preparing intermetallics from metals with high
melting points due to the limitation set by the
melting temperature of crucible material used in
these methods [5,6]. Mechanical alloying (MA) is
the most commonly used technique for synthe-
sizing intermetallic nanoparticles [79]. Mechani-
cal alloying involves solid-state reactions; hence if
two metals were immiscible in the solid state, ef-
cient alloy formation by MA would not take
place [10]. Other problems commonly associated
with MA are contamination from either external
or milling sources and extensively long periods of
milling time.
Scripta Materialia 48 (2003) 671676
www.actamat-journals.com
*
Corresponding author. Tel.: +1-804-828-3518; fax: +1-804-
828-8599.
E-mail address: selshall@hsc.vcu.edu (M.S. El-Shall).
1359-6462/03/$ - see front matter 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.
PII: S1359- 6462( 02) 00564- X
We recently reported the successful synthesis of
intermetallic FeAl nanoparticles from bulk targets
using the laser vaporization controlled conden-
sation technique (LVCC) [1113]. Several experi-
mental and theoretical reports have been published
on the applications of pulsed laser vaporization to
synthesize nanoparticles [1416]. Laser vapori-
zation does not require containers as the material
of interest can be directly ablated from the surface
of the bulk target of interest. The LVCC technique
relies on the principles of nucleation from a vapor
phase containing a mixture of the metal atoms of
interest in the presence of an inert carrier gas. This
eliminates the problem of solid-state immiscibility
and allows for a better control of composition of
the nanoparticles by controlling the relative con-
centrations of the metal atoms in the vapor phase.
CuZn (brass) alloys have been used for coins
and ornamental purposes since the beginning of
metallurgy [17,18]. CuZn based catalysts are well
known to enhance both catalytic activity and se-
lectivity in the synthesis of alcohols by hydro-
genolysis of fatty acids [19]. A recent study showed
that the formation of CuZn alloys is a signicant
step in the methanol synthesis over Cu/ZnO cata-
lysts [20]. CuZn alloying has been well investi-
gated in the bulk and several reports on the
chemical reactions and phase transformations in
this system have been published [2123]. Few at-
tempts to control the evolution of dierent phases
during the synthesis of nanocrystalline CuZn al-
loys by MA have been reported [24,25]. Nano-
composites of CuZn particles have been prepared
by condensing Zn vapor onto pre-formed Cu
nanoparticles, which were prepared by the gas
condensation technique [26,27]. The formation of
the Zn layer was assumed to occur via a hetero-
geneous nucleation mechanism where the Cu
nanoparticles acted as nuclei for the condensation
of the Zn vapor [26]. The nal nanoparticle com-
position revealed that Zn is present as ZnO as a
result of the slow oxidation treatment to stabilize
the double-layer nanoparticles [26].
In this work, we report the synthesis of in-
termetallic c-Cu
5
Zn
8
and e-CuZn
5
nanoparticles
using laser vaporizations of selected bulk targets.
This work demonstrates, for the rst time, that the
preferential phase formed in the nanocrystalline
CuZn system can be controlled by adjusting the
ratio of the Cu to Zn atoms in the nucleation zone
of the LVCC synthesis chamber. We also report
the formation of long chain laments of CuZn
intermetallic nanoparticles under the inuence of
an electric eld which is applied across the LVCC
chamber. The laments display stretch and con-
traction properties depending on the strength of
the applied eld. These laments are expected to
signicantly enhance the plastic behavior, ductility
and strength of CuZn consolidated nanoparticles.
This may open the door for new applications of
these materials in the areas of sensors and elec-
tronic devices.
2. Experimental
The LVCC process involves pulsed laser va-
porization of single or multiple targets into a se-
lected gas mixture in a convective atmosphere in a
diusion cloud chamber [1113]. The chamber
consists of two parallel plates separated by a
quartz ring of 5 cm height. The top plate is set at a
lower temperature than the metal target and the
bottom plate (temperatures are controlled by cir-
culating uids). The large temperature gradient
between the bottom and top plates results in a
steady convection current, which can be enhanced
under high-pressure (10
3
Torr) and large tempe-
rature gradient (DT 200) conditions. The metal
vapor is generated by pulsed laser vaporization
using the second harmonic (532 nm) of a Nd
YAG laser (2040 mJ/pulse, 10
8
s pulse). For the
assembly of the nanoparticles into laments, an
electric eld (50200 V/cm) is applied between the
parallel chamber plates.
X-ray diraction (XRD) patterns are obtained
using the Philips XPert Materials Research Dif-
fractometer, which uses Cu K
a1
radiation. The size
and shape of the individual particles are investi-
gated using a Jeol JEM-200FXII transmission
electron microscope (TEM) operated at 200 kV.
3. Results and discussion
Fig. 1a displays the XRD pattern of the black
nanoparticles obtained following the laser vapor-
672 Y.B. Pithawalla et al. / Scripta Materialia 48 (2003) 671676
ization of a commercially available brass [Cu/Zn
(63/37 wt%)] target that is golden in color. Pro-
minent peaks are observed at angles [2h] of 43.33,
50.47 and 74.11. These can be indexed to dirac-
tions from the (1 1 1), (2 0 0) and (2 2 0) planes of
Cu. It is also clear that each of these peaks con-
tains a shoulder due to the presence of an adjacent
peak. These adjacent peaks overlap each other and
could not be resolved into separate peaks due to
the peak broadening caused by the nanocrystalline
size of the particles. These shoulders are not pre-
sent in the XRD pattern of the Cu nanoparticles
prepared by vaporization of a pure Cu [99.999%]
target as can be seen in Fig. 2a. Inspection of the
XRD database [28] reveals that the shoulder peaks
can be attributed to the presence of brass [Cu,Zn]
nanoparticles within the sample. Low intensity
peaks indicating the presence of a trace amount of
ZnO are also observed as shown in Fig. 1a.
The observed phases are in accordance with
what one would expect fromthe binary equilibrium
diagram of the CuZn system. Laser vaporization
typically delivers sucient energy to the target to
eciently and non-selectively vaporize all the
components of the target. The average temperature
attained within the laser pulse (10
8
s) can reach
several thousand degrees. Such high temperatures
ensure the complete vaporization of all the ele-
ments in an alloy target. Since the laser beam is
moved several times across the target during the
experiment (or alternatively, the target is rotating),
the composition of the vapor produced is expected
to be similar to the composition of the bulk target
used. Inspection of the CuZn phase diagramin the
Cu/Zn 63/37 wt% range shows that this region lies
between the boundaries of the a (Cu) and the in-
termetallic b (Cu,Zn) phases [29]. Hence the two
stable phases expected in this region would be Cu
and brass [Cu,Zn] as conrmed by the XRD pat-
tern of the product nanoparticles.
Further assessment of the equilibrium diagram
indicates that all the intermetallic phases: b, c, d
and e are formed only at higher weight percent of
Zn as compared to the 63:37 composition. In order
to form these phases, one must increase the con-
centration of Zn atoms in the vapor phase. The
laser vaporization technique conveniently allows
the simultaneous evaporation of two or more
targets. Utilizing this feature, the Cu/Zn (63/37
wt%) sample was entrapped inside a cavity drilled
within a 99+% Zn target. The laser vaporization
spot was then split between the two targets such
that it was approximately 50% on the brass target
and 50% on the Zn target. In this case, the Cu and
Zn atoms produced from the brass sample mix
Fig. 1. XRD pattern of nanoparticles prepared by vaporization
of (a) brass [Cu/Zn 63/37] target. In (b) and (c) the Zn vapor in
the reaction chamber was enriched by simultaneously evapo-
rating from brass and Zn targets. In (b) laser beam was split
one-half on the brass target and one-half on the Zn target and
in (c) laser beam was split one-third on the brass target and
two-thirds on the Zn target.
Fig. 2. XRD patterns of nanoparticles formed by vaporization
of (a) 99.999% Cu pellet (b) 99% Zn pellet and (c) pellet made
by pressing 50/50 wt% of Cu and Zn powders used to prepare
pellets for (a) and (b).
Y.B. Pithawalla et al. / Scripta Materialia 48 (2003) 671676 673
with the additional Zn atoms produced from the
Zn target thus creating an excess of Zn atoms in
the vapor phase. The XRD pattern of the nano-
particles formed using this vapor enrichment
method is shown in Fig. 1b. As denoted in the
gure all the peaks observed can be indexed to
diractions from the intermetallic c phase of Cu
Zn which is known to have the composition
Cu
5
Zn
8
[29]. Fig. 1c displays the XRD pattern of
the nanoparticles formed after moving the laser
spot such that it was approximately one-third on
the brass target and two-thirds on the Zn target.
As expected, further increase in the concentration
of the Zn atoms in the vapor occurred, and XRD
peaks corresponding to the more Zn-rich inter-
metallic e phase were observed (denoted by j). As
shown in Fig. 1c, CuZn
5
was the preferential Zn-
rich intermetallic phase formed in this case. In
both samples (Fig. 1b and c) trace quantities of
ZnO were also detected.
These preliminary results indicate that control-
ling the relative concentrations of the metallic
components can be achieved by adjusting the po-
sition of the laser spot used in the evaporation of
binary metal targets. This process leads to enrich-
ing the binary metal vapor with the component
needed for the preferential formation of nano-
particles of one specic phase over the other stable
phases.
A more exible approach to synthesize selected
phases of intermetallic CuZn nanoparticles was
also considered. In this approach, target pellets
were made by pressing mixtures of pure elemental
Cu and Zn powders of )100 + 325 mesh size (44
lm\particle size >149 lm). The XRD patterns
of nanopowders obtained by the laser vaporization
of individual pellets made by pressing pure Cu and
pure Zn powders are presented in Fig. 2a and b
respectively. The XRD pattern of the Cu nano-
particles exhibits peaks at 2h values of 43.31, 74.09
and 89.95, which are assigned to the crystalline Cu
lines (1 1 1), (2 0 0) and (2 2 0), respectively. The
presence of Cu
2
O was also noted in this sample
and is probably due to the rapid oxidation of the
Cu nanoparticles upon exposure to air. The XRD
pattern of the Zn nanoparticles showed peaks at
2h values of 36.31, 39.02, 43.24, 54.33 and 82.09,
which can be assigned to diractions from the
crystalline Zn (0 0 2), (1 0 0), (1 0 1), (1 0 2) and
(1 1 2) planes, respectively. Fig. 2c displays the
XRD pattern of the nanoparticles formed by the
vaporization of a binary pellet formed by pressing
50/50 wt% of the Cu and Zn powders. It is clear
from the change in the XRD pattern as compared
to those displayed in Fig. 2a and b that the
nanoparticles formed are not just a mixture of
individual Cu and Zn particles, but they exhibit
the composition of the intermetallic CuZn nano-
particles. The sample shows peaks, which can be
assigned to diractions from the (3 3 0), (4 2 2),
(6 0 0) and (7 2 1) planes, respectively, of the c-
Cu
5
Zn
8
crystal lattice. A systematic study of the
XRD patterns of nanoparticles prepared by va-
porization of pellets made by pressing several dif-
ferent compositions (wt%) of Cu and Zn powders
[Cu
x
Zn
1x
] has been performed. The results ob-
tained are in accord with what would be expected
based on the equilibrium phase diagram. The re-
sults show good agreement with the trends ob-
served in the two-target experiments described
above. A detailed report on this work will be
published elsewhere [30].
The nanocrystalline nature of the c-Cu
5
Zn
8
is
conrmed by the bright eld TEM image shown in
Fig. 3. The average particle diameter is 1015 nm
Fig. 3. TEM of the c-Cu
5
Zn
8
nanoparticles.
674 Y.B. Pithawalla et al. / Scripta Materialia 48 (2003) 671676
with a few larger particles, approximately 30 nm in
diameter. Since laser vaporization produces a sig-
nicant portion of charged (by electrons and ions)
nanoparticles, the assembly of these nanoparti-
cles into laments and long chain bers can be
achieved by applying an electric eld during
the LVCC synthesis. We investigated the inuence
of the electric eld during the formation of Cu,
Zn and c-Cu
5
Zn
8
nanoparticles. Because of di-
pole forces, c-Cu
5
Zn
8
intermetallic nanoparticles
showed much higher tendency in forming laments
as compared to pure Cu and Zn nanoparticles.
Filament growth is caused by particle aggregation
at one of the chamber plates, thereby extending
them toward the opposite plate. When the metal
target is placed in contact with the bottom plate of
the chamber, it creates a gradient in the electric
eld and causes the laments to grow toward the
target as shown in the photographs of the CuZn
nanoparticle bers displayed in Fig. 4.
The nanoparticles aggregate as little chains and
stack end to end. Generally the chains grow per-
pendicular on the top and bottom plates of the
LVCC chamber. Eventually, the chains bridge the
top and bottom metal plates (electrodes), indi-
cating that both negatively and positively charged
particles are involved. The XRD and ED of the
nanoparticles of the chain aggregates are similar to
those obtained from the nanoparticles prepared in
the absence of the eld, thus indicating that the
eld has no eect on the composition of the par-
ticles. Consolidated materials based on the nano-
particle laments may show enhanced plasticity,
i.e. they may exhibit signicantly better elon-
gations as compared to cast and powder processed
components. This may lead to new applications as
additives and reinforcing agents for low viscosity
polymers and oils.
4. Summary and conclusions
A mixture of Cu and brass [Cu,Zn] nanoparti-
cles is formed following the LVCC of a commer-
cially available brass [Cu/Zn (63/37 wt%)] target.
Phase transformations resulting in the formation
of nanocrystalline intermetallic compounds c-
Cu
5
Zn
8
and e-CuZn
5
are achieved by enhancing
the concentration of the Zn vapor in the reaction
chamber through the simultaneous binary evapo-
rations of brass and Zn targets. The nanocrystal-
line intermetallic c-Cu
5
Zn
8
can be synthesized by
the vaporization of a pellet prepared by com-
pressing 50/50 wt% of pure elemental Cu and Zn
powders. TEM bright eld images conrm that the
average particle diameter of the intermetallic c-
Cu
5
Zn
8
is 1015 nm. The nanoparticles can be
assembled into long chain laments and bers by
applying an electric eld during the LVCC syn-
thesis. The lament morphology is expected to
enhance the plasticity of the intermetallic nano-
particles and this may lead to new applications as
additives and reinforcing agents.
In conclusion, laser vaporization of compo-
sition-selected bulk targets in the LVCC method
can produce intermetallic nanoparticles of dier-
ent controlled compositions. Using conventional
methods, such materials are normally dicult to
produce especially for intermetallics composed of
metals with large dierence in vapor pressures.
Acknowledgements
The authors gratefully acknowledge nancial
support from Philip Morris USA.
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