Z. Phys.
D Atoms, Molecules and Clusters 20, 293-296 (1991)
Spontaneous coalescence in ultrafine metal particle aggregates
Y.K. Huang, A.A. Menovsky, and F.R. de Boer
Natuurkundig Laboratorium, University of Amsterdam, Valckenierstraat 65, 1018 XE Amsterdam, The Netherlands
Received 10 September 1990
Abstract. In the preparation of ultrafine metal particles
(Cu, Ti, Ni or A1) by opposed-targets dc sputtering, a
substrate cooled by liquid helium flow was used, on which
the metal clusters and argon atoms were condensed simul-
taneously, forming a solid layer of the mixture. By raising
the temperature of the substrate and the argon pressure in
the chamber, the solid argon melts and evaporates, re-
maining the metal-particle aggregates. After complete
evaporation of the argon, a phenomenon was observed in
which the metal-particle aggregates shrank and suddenly
changed their colour from black to bulk-metal colour,
followed by an explosion-like noise. We offer an explana-
tion for this phenomenon by the mechanism of spontane-
ous coalescence due to the large surface energy of the
ultrafine particles. From our observation and analysis, we
conclude that a certain particle size exists, below which
the spontaneous coalescence may occur in a very fast way,
leading to melting of the particles. The fast process of
coalescence, melting and cooling introduces large internal
stress which splits the sintered particle, giving the ex-
plosion-like noise. This phenomenon may imply a size
limitation in forming nanocrystalline solid materials of
pure metals.
PACS: 75.60.J
1. Introduction
The fundamental types of solids can be distinguished
according to their characteristic ranges of structural or-
der: crystals with long-range order and non-equilibrium
systems (glasses or other amorphous solids) with short-
range order only. However, there is evidence for the
existence of a third solid-state structure in nanocrystalline
solid [1], characterized by the absence of both long- and
short-range order.
Nanocrystalline solids can be formed by compacting
pre-generated randomly oriented crystallites with size
Atoms.Molecules
zo,.=.,
~JrPhy~k D and Clusters
© Springer-Verlag 1991
below 10 nm. These materials consist of two components:
A crystalline component formed by all atoms located on
the lattice of the crystallites and an interfaciat component
comprising all atoms situated at the grain boundaries
between the crystallites. The atomic structure of an inter-
face is known to depend on the relative orientation of the
adjacent crystals and on the grain-boundary inclination. If
the crystatlites are oriented at random, the atomic struc-
tures (e.g. the interatomic spacings) of different grain
boundaries are different from each other. A nanocrystal-
line solid with a crystallite size of 5 nm contains typically
about 1019 interfaces per cm 3. The interracial component
is then the sum of the 1019 interfacial structures. If the
interatomic spacings in all grain boundaries are different,
the average of 1019 different boundaries results in no
preferred interatomic spacings except for the one pre-
vented by interatomic penetration. Hence, the interfacial
component is proposed to represent a solid-state structure
without long- or short-range order [2, 3]. Due to these
features different physical and chemical properties are
expected, which open the way for applications. Theretore
these materials have caught increasing attention in recent
years.
Owing to the intensive research in the last few decades
in the fields of microclusters, catalysis and magnetic fluids
a lot of information is available on preparation methods,
physical and chemical properties and structure stabilities
of individual small particles, free or supported on a sub-
strate. New problems arise when the small particles come
into direct contact with each other during generation and
compaction. In this paper we will describe and discuss an
observation concerning this problem.
2. Experimental
We have constructed an opposed-targets dc sputtering
equipment with a small copper block as a substrate, which
can be cooled to 30-40 K by liquid-helium flow (Fig. 1).
The target materials used are copper, titanium, nickel or
aluminum. The sputtering conditions are: background
294

I " TARGETS
j ~
COPPERBLOCK
ASSUBSTRATE K
#
>o 84K ~ / ~ aroundt70
GLASSCOLLECTOR

0 PUM Time[sec]
Fig, 1. Sketch of the experimental c o n f i g u r a t i o n Fig. 2. The temperature change during the process. At point "a",
the liquid argon was evaporated completely. The particle aggreg-
ates began to shrink, change colour and split. The thermocouple
attached to a copper foil on the bottom of the glass collector
vacuum 2 x 10 - 7 mbar, sputtering argon pressure 2 to detected some of the processes, showing several vertical steps. The
8 x 10-3 mbar, voltage 500-1000 V, current 300-600 mA. most pronounced one, appearing around 170K, is probably due to
the process of a particle aggregate situated on the copper foil
During the sputtering process, metal clusters and argon
atoms condens simultaneously on the substrate, forming a
layer of the solid-argon matrix in which the metal clusters
are embedded. When the solid layer is about 3-5 mm
thick, the sputtering is terminated. Both, the temperature temperature, at which the temperature increase is most
of the substrate and the Ar pressure in the chamber are clearly observed is around 170 K (for the copper sample).
increased to the triple point of argon (T=83.8K, Attempts to measure the temperature dependence of
p=688 mbar). The solid Ar melts and falls into a collector the resistance of the floc have failed because of the disturb-
together with the metal clusters. At the same time, the ing evaporation of the liquid argon and the quickness of
metal clusters begin to settle as black floc and the liquid the process.
argon becomes clear and transparent.
Upon reduction of the Ar pressure in the chamber
and/or by thermal conduction through the collector, the
3. Discussion
liquid Ar evaporates continuously. The temperature of the
collector remains in the range 84-87 K. No change in
In previous experiments in which we have sputtered cop-
color or morphology of the floc can be seen by the naked
per onto the liquid-nitrogen cooled substrate, the phe-
eye.
nomenon described above was not observed. Under argon
After all liquid argon is evaporated, the temperature of
atmosphere, these Cu particles were stable even at room
the collector begins to rise and the floc begins to shrink.
temperature. By x-ray diffraction it was determined that
Suddenly, some floc, beginning at the edges, turns from
the average particle size was around 70 A. In view of this,
the black color into the bulk-metal color, followed by a
we believe that the coalescence phenomenon described in
tiny stream of light white smoke and a soft explosion-like
Sect. 2 is closely connected to the size of metal particles.
noise. This phenomenon occurs discontinuously until all
Below a critical size the phenomenon can occur. Unfortu-
floc has vanished. Some material with bulk-metal color
nately, due to the instability we are not able to determine
and irregular shape remains in the collector. By x-ray
the size of the black floc at this moment.
diffraction analysis, this material turns out to beoPUre
From thermodynamic point of view, the high surface
metal with an average grain size of a few hundred Angs-
fraction in the small particles can provide an explanation
trom. Sometimes droplet (in the case of Cu) and networks
of the phenomenon of spontaneous coalescence. Consider
shape (in the case of Ti) can be found under optical
n spherical particles with initial radius ro and initial
microscope. The titanium sample is still very reactive,
temperature To which coalesce to form one spherical
which could burn spontaneously in air at room temper-
particle with radius r. If the total volume change in this
ature.
process is zero, the relation between ro, r and n is given by
In order to follow the temperature change during the
transition from the black to the bulk-metal color, we have r = nl/3ro . (1)
attached a copper-constantan thermocouple to a copper
The energy change is only due to the change in surface
foil on the bottom of a glass collector. The recorded
energy:
temperature curve is shown in Fig. 2. The result clearly
indicates that the process is an exothermal one. The A H ~urf = ( 4 n r o e n - 4 n r 2) ~' = 4 n o ~ n ( 1 - n - 1/3)roe (2)

where ?Jis the specific surface energy of the material of the
particle. If all the energy released is absorbed by the final
particle because of the poor heat contact with the sur-
rounding and the fastness of the process, the temperature
of the final particle will increase to T. The enthalpy change
is equal to
AH T°-*T = m i cpdT = 4n
- f r3onpcp(T_ To) (3)
To
if the system does not undergo any phase transition. Here,
m is the total mass, p is the density and cp is the specific
heat, in this energy consideration assumed to be temper-
ature independent. By equalizing the released energy
AH surf and the enthalpy change AH T°~r, we obtain a
relationship between the temperature change
AT = T - - To and the initial particle size ro:
A T = 3~'(1 - n-1/3)/p%ro (4)
Taking Cu as an example, using the bulk parameters
7 = 1.56Jm -2, cp=27.98Jmol 1K-1, p = 0 . 1 4 1 x 106
m o l m 3, we get
AT ~ 12000(1 -- n- 1/3)/ro, (5)
where r o is expressed in the unit A. Apparently, when n
is sufficiently large, the particles are readily small enough
to reach high temperature (e.g. if r o < 10A then
A T > 1200 K).
The enthalpy AH ruse needed to melt the particle if it
reaches the melting temperature is given by
AH fuse = mL = 4~zr3npL/3, (6)
where L is the heat of fusion per unit mass. The energy
requirement for the particle to melt is AH surf > AH ~r° ~Tm
+ AH fu~¢. From (2), (3) and (6) it follows
r o _< 3~(1 -- n-~/3)/p[L + cp(Tm-- To)J, (7)
where Tm represents the melting temperature. Again tak-
ing Cu with Tm = 1358K and L = 0.205 x 103 kJkg -~ as
an example, we find that for Too= 87 K an initial particle
size r o < 6.8 A (diameter _< 14 A) is required in order to
reach the melting temperature. Ozin and Huber [4] have
shown that, when silver is dispersed to a very low concen-
tration in argon, very small Ag, clusters (with n < 10) are
formed which could be identified by spectroscopic tech-
niques. On the other hand, for a high concentration of Ag
in the argon matrix, colloidal particles with a diameter of
the order of 10 A are formed, showing the broad absorp-
tion band typical for small metallic particles. In our
experimental configuration, the condition are similar to
the later situation. Therefore it is very likely that we may
obtain the particles with the initial size required to reach
the melting temperature.
From literature, there appears to be some evidence
that for small particles the melting temperature, T~,, may
depend on the size, ro, of the particle. Several models (e.g.
[5 7]) have been put forward to describe this dependence.
In general, the expressions proposed to describe this
phenomenon have the form
T~ = T,,(1 -- B/ro) , (8)
295
where T~ is the melting point of the bulk material, B is a
constant depending on the surface and/or the interfacial
(solid-liquid) energy, the density of the material and the
heat of fnsion. Substituting relation (8) into (7), we find
r o <_ [3y(1 - - n -1/3) + pcpTmB]/p[L + cp(T~ - To)]
(9)
This implies that the melting process folloveing the coales-
cence of the small particles can occur even for particles
with larger initial size.
From the dynamic point of view, the mechanism of
this process may be explained by Smotuchowski's model
[8] in which surface diffusion by random motion of the
entire particles is followed by collisions and coalescence.
Nichols and Mullins [9] have considered the coalescence
of two equal spherical particles and have calculated the
relaxation times for three distinct stages of the process: the
formation of a "neck" between particles, the disappear-
ance of the "neck" with the formation of single elongated
particles and the transformation of the new particle to a
spherical one. The total time for all three stages is:
z = 0.890 r~/A. (10)
Here, r0 is the radius of the spherical particle before
coalescence and A is given by the expression
A =D~NoYof~2/kT, (11)
in which Ds is the diffusion coefficient for atomic migra-
tion at the surface of the particle, No is the average density
of adsorption sites at the surface, 7o is the average surface
energy and f~ is the atomic volume. From (10), we can see
that the relaxation time strongly depends on the particle
size. If the particle size is large, the process will take very
long time, which means that, in practice, the process does
not happen. For very small particles, however, the process
will take place unmeasurably fast.
In our observation, the explosion-like process seems to
be the splitting of the particles formed by the coalescence
into smaller ones, which is similar to the observation by
Ruckenstein and Malhotra [10] in platinum crystallites
supported on alumina films. One of the possible explana-
tions for the occurrence of the process, may be that it is
due to the high internal stresses introduced by the fast
cooling, tt might also be due to the expansion of trapped
argon.
4. C o n c l u s i o n
From our observation and analysis, we conclude that
small particles below a certain size may coalesce spontan-
eously. The enthalpy necessary for the melting of the
particles is provided by the large surface energy release in
the coalescence process. This process may imply a size
limitation in the formation of nanocrystatfine solids from
pure metal particles. On the other hand, the phenomenon
of spontaneous coalescence may be used in the pre-
paration of some novel alloys which require additional
energy in the formation.
296
For a full understanding of the observed phenomenon
additional experiments are needed. Although the model of
spontaneous coalescence explains the main features, other
explanations cannot be excluded. At present, we are con-
structing a low-temperature (T ~ 77 K) pressurizing unit,
in order to press the particles which are kept at liquid
nitrogen temperature into pitlets of which the physical
properties will be investigated.
This work is part of the research program of the "Stichting voor
Fundamenteel Onderzoek der Materie (FOM)', which is financially
supported by the "Nederlandse organisatie voor Wetenschappelijk
Onderzoek (NWO)". Mr. H. Gelders is kindly acknowledged for his
technical assistance.
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