reducible metals (such as precious
metals and copper) or less reducible
Preparing
Monodisperse
Métal Powders
in Micrometer and
Submicrometer
Sizes by the
Polyol Process
F. Fievet, J.P. Lagier, and M. Figlarz
Introduction
One of the newer tendencies in mate-
rials science has been to tailor-make
classical products (long associated with
old applications) with controlled prop-
erties for spécial uses, especially in high
technology. Preparing dispersed Sys-
tems in which ail particles hâve nearly
uniform size (monodisperse solids) is a
typical example. This goal can be
achieved in some cases through cleverly
controlled particle growth from a liquid
médium. Examples of such prépara-
tions include gold colloids prepared by
Zsigmondy1"2 and later by Turkevich et
al.,3 sulfur sols obtained by LaMer,4
métal oxides and hydrous oxides pre-
pared by Matijevié et al.,5"8 silica,9 etc.
Thèse dispersions hâve been used either
to check théories of colloid science, or to
a lesser extent, for industrial purposes.10
In the case of fine métal particles, a uni-
form size distribution associated with a
low degree of agglomération, and some-
times the spherical shape, appear as par-
ticularly convenient characteristics for
certain applications. The production of
conductive inks or pastes for electronic
materials11'13 and for the préparation of
conductive paints are particularly good
examples.
MRS BULLETIN/DECEMBER1989
In so-called thick film technology,
conductive inks and pastes are screen
printed on a ceramic substrate in order
to form, after firing, a conductive film
with a thickness less than 10 /um. This
technique is, for instance, used to form
the network in hybrid integrated cir-
cuits or the internai électrodes of multi-
layer ceramic capacitors.11"16
Metallic powders in thick film compo-
sitions are usually precious metals (Au,
Ag, Pt, Pd), their mixtures, or alloys.
Cheaper metals such as copper or nickel
are tested and may be potential substi-
tutes for precious metals in différent
spécifie applications. Powders for thick
film composition are mainly obtained
through chemical précipitation from
aqueous or organic solutions,11"13 which
yield high purity powders. Modifica-
tion of précipitation parameters (such as
the nature and the concentration of the
starting metallic compound and of the
reducing agent, reaction température,
viscosity of the médium) and the addi-
tion of additives and surfactants, can
often be used to control particle size and
agglomération.
Over the past few years, we hâve de-
veloped a new process for preparing
finely divided métal powders of easily
metals (such as cobalt, nickel, cadmium,
or lead) by précipitation in liquid poly-
ols.17 This reaction will be used as an ex-
ample in order to discuss the mechanism
of formation of uniform micrometer and
submicrometer size métal particles by
précipitation reactions.
Description of the Polyol Process
Expérimental Conditions
In the polyol process a powdered
inorganic metallic compound is sus-
pended in a liquid polyol (ethylenegly-
col, diethyleneglycol, or mixture of both
hâve been mainly used). The suspen-
sion is stirred and heated to a given
température, which can reach boiling
point of the polyol for less reducible
metals, e.g., cobalt or nickel. The start-
ing compound may be rather soluble in
the polyol (e.g., silver nitrate or cobalt,
nickel and copper acétate hydrate) or it
may be only slightly soluble (e.g., cobalt
and nickel hydroxides, or copper oxides,
CuO, and Cu 2 0). A complète réduction
of thèse compounds can be achieved
within a few hours, the métal being re-
covered as a finely divided powder. In
some cases the water and the volatile
products evolved during the reaction
must be distilled off, while the polyol
is refluxed in order to shorten the reac-
tion time.
General Mechanism of the Reaction
The gênerai mechanism of the reac-
tion involved in this process has been
investigated mainly for the réduction
into métal of Co(OH)2 and Ni(OH)2 in
ethyleneglycol. Itappears, fromdetailed
results published elsewhere,18"20 that the
reaction proceeds via dissolution rather
than solid phase transformation.
In this reaction the polyol at first acts
as a solvent for the starting compound
due to its rather high dielectric constant.
Subsequently, ethyleneglycol reduces
the cobalt(II) and nickel(II) species in
the liquid phase, in which nucleation
and growth of the metallic phase occur.
Thus, ethyleneglycol also acts as a
crystal growth médium for the métal
particles.
In the réduction of Co(OH) 2 and
Ni(OH)2, the reaction mechanism is
more intricate due to the formation of
an intermediate solid phase between
the starting hydroxide and the métal
powder. From x-ray diffraction and
infrared spectroscopy it can be inferred
that both cobalt and nickel intermediate
phases show a lamellar, incompletely
29
 Preparing Monodisperse Métal Powders by the Polyol Process

ordered structure with intercalation of

ethyleneglycol molécules or the corre- Table I: General Mechanism of Réduction of Ni (OH) 2
sponding alkoxy radicals. 18 " 20 Conse- or Co (OH) 2 into Métal in Ethyleneglycol.
quently, one may consider the reaction
First stage: Crystallized Hydroxide -» Intermediate Phase
to proceed in two steps as described in
Table I.
Although the starting Co(OH) 2 and Progressive dissolution of the starting hydroxide
Ni(OH) 2 are only slightly soluble, this Précipitation of the intermediate phase
solubility is high enough to allow the Evolution of water by distillation
reaction mechanism described in Table
I. The reaction occurs because différent Second stage: Intermediate Phase -» Métal
equilibria shift as the metallic phase
grows until the réduction is completed.
Dissolution of the intermediate phase
This reducing action of ethyleneglycol Réduction in solution
has been investigated by analyzing the
Evolution of the volatile products of reaction
volatile compounds resulting from its
oxidation, among which diacetyl appears Homogeneous nucleation and growth of métal particles
as the main product. 1822 Its formation
can be explained by a duplicative oxida-
tion of acetaldehyde, previously pro-
duced by dehydration of ethyleneglycol, Table II: Chemical Analysis of Two Cobalt Powders Obtained from the Same
as follows: Parent Hydroxide by Solid-Gas Réduction and by the Polyol Process
(main impurities/cobalt ratios in ppm by weight).
2CH 2 OH—CH 2 OH ' 2 " 2 °>
Cobalt Cobalt (solid- Cobalt (polyol
2 C H 3 C H O ^ CH 3 — C — C — C H 3 Hydroxide gas réduction) process)
O O Ca 150 150 <5
+ H20 + M Fe 80 80 20
Ni 250 250 250
The reducing action of ethyleneglycol Si 150 150 130
is certainly différent for metals other Cl 2000 500 60
than cobalt and nickel. The occurrence S 150 150 <50
of an intermediate solid phase is not a
Na 250 250 <10
gênerai feature of ail métal reactions.
However, it must be emphasized that
the mechanism of métal particle forma-
tion through nucleation and growth
from the solution is quite gênerai for ail
metals obtained by the polyol process.

Characteristics of Métal Powders

Metals obtained by the polyol process
are recovered as finely divided crystal-
line powders, as determined by x-ray
diffraction. T h e y are c o m p o s e d of
equiaxed particles with a mean size of
1-10 /iim, depending on the métal con-
sidered and the reaction conditions. The
exceptions are precious metals, whose
mean particle size is usually smaller
than 1 ixm. It should be stressed that the
particle size distribution is usually nar-
row, as exemplified with a cobalt pow-
der obtained in a boiling mixture of
1 2 3 d iim
ethyleneglycol and diethyleneglycol
(20-80% by volume). Figure 1 illustrâtes Figure 1. Cobalt powder obtained from Co(OH)2 in a mixture of diethyleneglycol and
such particles of the mean diameter of ethyleneglycol and particle size distribution of the particles (d = 1.75 fim, a = 0.24 \xm).
1.75 ixm with the standard déviation of
—15%. In this case, the particles are
nearly spherical and show a very low
degree of agglomération. hydroxide, the intermediate poorly crys- the intermediate phase as thin crumpled
It is noteworthy that in the réduction tallized phase, and the final métal pow- films, and the metallic phase as equiaxed
of Co(OH)2 and Ni(OH) 2 , there is no simi- der. For instance Ni(OH) 2 appears as particles (d = 0.78 fim). Thèse very dif-
larity in the morphologies of the parent hexagonal platelets (0.1 jum x 0.02 ju.m), férent morphological characteristics are

30 MRS BULLETIN/DECEMBER1989
 Preparing Monodisperse Métal Powders by the Polyol Process
Figure 2. (a) Copper, (b) silver, and (c)
platinum powders obtained by the polyol
process.
consistent with the fact that each of the
two stages of the méchanism described
in Table I proceeds via dissolution. 21
The high degree of purity of métal
powders obtained by the polyol process
(except for the carbon content which
can reach 1 wt%) can also be related to
the solution reaction méchanism. Impu-
MRS BULLETIN/DECEMBER1989
rities in the starting hydroxide, such as
Ca, Fe, or Na, are considerably lower in
the cobalt p o w d e r o b t a i n e d by the
polyol process as c o m p a r e d w i t h a
cobalt powder prepared by solid-gas
réduction (Table II). This is caused by
the inability of the polyol to reduce
thèse contaminants into pure metals.
Homodisperse System and
Homogeneous Nucleation
Cobalt powder obtained by the polyol
process in an ethyleneglycol-diethyl-
eneglycol mixture is of very narrow size
distribution (Figure 1), which is also
observed with other metals obtained by
the polyol process, such as nickel (Fig-
ure 4a), copper (Figure 2a), and pre-
cious metals (Figure 2b-c). This expéri-
mental feature must be accounted for by
a reasonable reaction méchanism.
LaMer's Model
It is well known that the précipitation
of a solid from a solution proceeds in
two steps: nucleation and growth. Dur-
ing nucleation, solid tiny particles form
from the supersaturated solution. If
thèse nuclei a p p e a r s p o n t a n e o u s l y ,
without the promoting effect of impuri-
ties, the nucleation is called homoge-
neous. During the second step, the
original nuclei grow into larger parti-
cles. In order to obtain monodisperse
particles, a gênerai condition must be
fulfilled: nucleation and growth must be
two completely sépara te steps.10-23 This
condition has been expressed by LaMer
in his study of sulfur sols prepared from
acidified thiosulfate solutions. 24,25
The LaMer diagram (Figure 3) can be
u s e d to d e s c r i b e t h e f o r m a t i o n of
monodisperse cobalt and nickel parti-
cles in polyol as follows. The métal is
slowly generated in the solution by pro-
gressive dissolution of the intermediate
phase and by subséquent réduction of
cobalt(II) and nickel(II) species in the
liquid p h a s e . The c o n c e n t r a t i o n of
metallic species in solution increases
and reaches the saturation concentra-
tion, which is unknown but probably
very small. As the réduction reaction
proceeds, the soluté content further
increases until critical supersaturation is
reached, leading to rapid, spontaneous
nucleation. Many nuclei are formed
during a short time and, therefore, the
métal concentration is quickly lowered
below critical. Particle growth occurs on
the original nuclei, as long as the métal
is slowly provided by the réduction,
eventually yielding solids of equal size.
In order to actually obtain such uniform
CONCENTRATION OF METAL
IN SOLUTION
/ _ \ NUCLEATION
A " rVCONCENTRATION
/ ! ! ^^SATURATION
/ S \ ~ CONCENTRATION
1
! D
! ID
TIME
l 1 1 -»
Figure 3. LaMer's model for the
formation of a monodispersed System: u
I — prenucleation period; Il—nucleation
step; Ul—growth step.
particles, it is also necessary to prevent
their coagulation during the growth
stage. In the polyol process, the grow-
ing médium, i.e., the polyol itself, can
act to some extent as an inhibitor for
c o a g u l a t i o n . An a n a l o g o u s g ê n e r a i
méchanism was proposed by Turkevich
to a c c o u n t for t h e p r é p a r a t i o n of
monodisperse gold colloid by réduction
of chlorauric acid solution by sodium
citrate. 3
Modification of Particle Size
The mean size of the métal particles
obtained by the polyol process can be
varied by modifying the parameters that
govern the reaction méchanism.
Température. In the polyol process, the
mean size of the particles usually de-
creases as the reaction température in-
creases. For instance, micrometer-size
nickel particles (Figure 4a) are obtained
from Ni(OH) 2 in boiling ethyleneglycol
under atmospheric pressure (195°C),
whereas submicrometer-size particles
(d = 0.3 /xm; cr = 0.05 /am) are gener-
ated at 210°C under higher pressure
(Figure 4b). The same trend is observed
with cobalt or copper. This température
effect can be explained in terms of the
previous model. As the température
rises, the number of nuclei formed dur-
ing the short nucleation stage increases
due to faster dissolution of the interme-
diate phase and faster réduction in solu-
tion. Consequently, the mean particle
size decreases for a given amount of
precipitated métal.
Starting C o m p o u n d Polyol Ratio.
When the starting compound/polyol
ratio is increased, the particle size sig-
nificantly increases. For instance, when
31
 Preparing Monodisperse Métal Powders by the Polyol Process
the molar ratio Ni(OH)2/ethyleneglycol
is changed from 0.01 to 0.15, the mean
particle size in the micrometèr range
almost doubles. The same trend is ob-
served during the réduction of Co(OH)2
into cobalt. This trend can be related
to the previous model if one considers
that, at a given température, the num-
ber of nuclei formed during the short
nucleation step remains independent
of the amount of starting material
brought into the System. When this
amount is increased, the number of par-
ticles remains constant and their mean
size increases.
In conclusion, the size uniformity of
the particles and the influence of différ-
ent expérimental factors on the main
size are consistent with the formation of
métal particles through a spontaneous
nucleation step followed by a well-
separated growth step.
Modification of Particle Shape
For ferromagnètic metals like cobalt
and nickel, particle shapè can be drasti-
cally modified when the précipitation of
thèse metals occurs under the influence
of a magnetic field. For nickel, the appli-
cation of an external magnetic field
leads to metallic filaments rather than
spherical particles (Figure 4c). The
field's rôle is to line up small ferromag-
nètic particles, which resulted from the
homogeneous nucleation step, during
the early stages of their growth. Thèse
tiny particles join together and lead to
metallic filaments as subséquent growth
proceeds.
Modification of Particle Surface
Chemical redox cycling can modify
the surface of the original metallic parti-
cles. For example, if standard cobalt
particles are submitted to a superficial
oxidation followed by hydrogen réduc-
tion, important surface modifications
occur. The particle surface which was
initially smooth becomes spiky.
Heterogeneous Nucleation
In order to separate the nucleation
step from the growth step more effi-
ciently, and to better control the num-
ber of nuclei, one can add preformed
particles as seeds. Zsigmondy1"2 intro-
duced this substitution of the homoge-
neous by heterogeneous nucleation in
the préparation of gold sols. In the
polyol process two attempts hâve been
rnade to seed the solution with hetero-
geneous nuclei by: (1) adding external
foreign particles and (2) forming hetero-
geneous nuclei in situ.
32
Seeding by External Foreign Nuclei
This method has been used for the ré-
duction of Co(OH)2 in an ethyleneglycol-
diethyleneglycol mixture. The System
has been seeded with ~3 nm palladium
particles suspended in ethyleneglycol.
The Pd particles are introduced before
the spontaneous nucleation occurs with
a molar ratio Pd/Co of -4.10-4.
Formation of Foreign Nuclei in situ
In this alternative method, the hetero-
geneous nuclei are formed in situ. This
can be obtained by admixing a small
amount of silver nitrate solution in
ethyleneglycol to the original reactant
solution. Due to the easy réduction of
AgN0 3 into Ag by polyols, tiny parti-
cles of metallic silver form more rapidly,
i.e., before the métal of interest nucle-
ates. Thus, silver particles act as nuclei
for the subséquent growth of the métal
particles. This method has been suc-
cessfully used in the réduction of
Co(OH)2 in an ethyleneglycol-diethyl-
eneglycol mixture and in the réduction
of Ni(OH)2 in ethyleneglycol.
Métal Particles in the Submicrometer
Range
In both the above cases, seeding of
the reactive médium is followed rapidly
by the beginning of the précipitation of
cobalt or nickel. When the growth step
is completed the métal particles recov-
ered show a mean size significantly
smaller than that obtained under stan-
dard conditions, as shown in Table III
and Figure 6 for nickel and cobalt. Con-
sequently, seeding allows obtaining
cobalt or nickel particles in the sub-
micrometer range. Thèse ultrafine parti-
cles remain uniform in size, which
implies a complète substitution of
homogeneous by heterogeneous nucle-
ation. In the latter case, the significant
decrease of particle size can be explained
if one considers that the number of for-
eign nuclei introduced into the System
is higher than the number of nuclei
Figure 4. Ni powders obtained from
which would spontaneously form Ni(OH)2 in boiling ethyleneglycol: (a) at
through homogeneous nucleation. 195°C, micrometèr size; (b) at 2W°C,
The number of nuclei formed in situ submicrometer size; (c) at 205°C in a
can easily be altered by varying the magnetic field, nickel filaments (10 fxm
amount of silver nitrate added in order x 0.5 pm).
to seed the reactant médium. The mean
size and the standard déviation of métal
particles obtained for différent amounts
of AgN0 3 are given in Table III for
Ni(OH)2. For molar Ag/metal ratio <10-*,
the métal is recovered as a polydisperse
powder because the number of silver
nuclei is too small to completely replace
homogeneous by heterogeneous nucle-
MRS BULLETIN/DECEMBER1989
 Preparing Monodisperse Métal Powders by the Polyol Process

Table III: Size of Nickel Particles

Obtained in the Polyol Process by
Heterogeneous Nucleation with
AgN0 3 .
Ag/Ni (mole) dm (fim) a(fim)

5.5 10-" 0.20 0.058

5.5 1(T3 0.10 0.027
2.7 1CT2 0.07 0.015

.( Pm)
0.3

ONi
0.2
• Co

0.1
-1/3
m Ag

0.5

Figure 6. Corrélation betiveen the mean

diameter, d, of submicrometer-size cobalt
and nickel particles luith the number of
silver nuclei (mAg in mg for préparation
ivith 250 cm3 of polyol ivith molar ratio
Ag/Co and Ag/Ni in the range of
Figure 5. Cobalt powders obtained from Co(OH)2 in diethyleneglycol ethyleneglycol boiling 10-4-10-2).
mixture by homogeneous or heterogeneous nucleation: (a) homogeneous nucleation,
micrometer-size particles; (b and c) heterogeneous nucleation, seeding by AgN03 ivith an
increasing amount of nuclei, submicrometer-size particles; (d) heterogeneous nucleation,
seeding with submicron-size cobalt particles, occurrence of coagulated particles.
ter range. In principle, this goal could
be achieved by seeding the reactive
médium with submicrometer métal par-
ticles (such as those obtained above).
ation. Therefore, both processes occur tional to mAg. If the amount of precipi- Numerous experiments with cobalt
simultaneously. On the contrary, when tated métal remains constant as mAg is hâve been conducted without being able
the number of nuclei is high enough varied, the relationship d = k m~Àg is to overcome a major difficulty. The cobalt
(Ag/Co ratio in the ÎO^-IO"2 range) the theoretically expected. This relationship powders obtained were made up of a
cobalt particles are uniform with a mean is indeed expèrimentally observed with mixture of homodisperse micrometer-
d i a m e t e r varying from about 0.3 to Co particles obtained from Co(OH) 2 in size spherical particles and of larger
0.1/um (Figures 5b-c), which may be an ethyleneglycol-diethyleneglycol mix- particles, as illustrated in Figure 5d. The
explained by a purely heterogeneous ture and with Ni particles obtained from latter coagulated solids are probably due
nucleation. Ni(OH) 2 in ethyleneglycol (Figure 6), as to a strong tendency of the submicron
It is possible to correlate the mean long as mAg is neither too small nor too cobalt nuclei to form agglomérâtes at
size of cobalt and nickel particles to the large. If the amount of A g N 0 3 intro- the very beginning of the growth stage.
amount of silver nitrate introduced into duced is too low, homogeneous nucle-
the System if two simple hypothèses are ation competes with the heterogeneous Conclusion
assumed. The first is that the size of the nucleation, whereas if the amount is too There is a growing demand for uni-
silver nuclei formed at a given tempéra- high silver nuclei coagulate. form métal powders, especially for pre-
ture is independent of the amount of sil- paring conductive inks and pastes for
ver introduced; therefore, the number Variation of Mean Particle Size in the various applications, including elec-
of nuclei is directly proportional to the Micrometer Range by Heterogeneous tronic thick film technology. One suc-
mass of silver (mAg) The second hypothe- Nucleation cessful method to obtain uniform métal
sis is that each silver nuclei yields to one We tried to use heterogeneous instead powders is the réduction of metallic
métal particle; therefore, the number of of homogeneous nucleation in order to compounds and précipitation of metals
métal particles is âlso directly propor- control the particle size in the microme- from aqueous or organic média, pro-

MRS BULLETIN/DECEMBER1989 33
 Preparing Monodisperse Métal Powders by the Polyol Process

vided a clear séparation of nucleation
and growth stages is achieved and
coagulation between particles during
their growth is avoided. The first condi-
tion is sometimes fulfilled by seeding
the System with foreign nuclei, and the
second by using protective agents such
as surfactants or complexing species.
The polyol process which applies to
cobalt, nickel, copper, and precious
metals (this article focuses on cobalt and
nickel) is an interesting and unexpected
example of such a method for preparing
uniform métal powders. The reaction
proceeds via dissolution, the polyol
acting simultaneously as a solvent, a
reducing agent, and to some extent a
protective agent. For metals such as
cobalt and nickel, micrometer-sized
uniform particles can be obtained under
standard conditions through a ho-
mogeneous nucleation step and a sub-
séquent growth step. Submicrometer
uniform cobalt and nickel particles can
be obtained by seeding the reactive
médium with heterogeneous métal
nuclei to achieve a complète substitu-
tion of homogeneous by heterogeneous
nucleation. By varying the number of
nuclei it is possible to control to some
extent the average particle size in the
submicrometer range.
For cobalt, a feasibility study to scale
up this process to an industrial level is
now in progress. This process can also
be used to obtain other uniform métal
powders, namely copper and precious
metals. In the latter cases the coagula-
tion of the particles during their growth
appears to hâve a more important effect,
which has to be avoided as far as pos-
sible. Finally, the possibility of extend-
ing this process to prépare uniform
composite métal powders should be
emphasized; the corresponding studies
are now in progress.
Acknowledgments
The authors are indebted to Ministère
de la Recherche, the DGA/DRET and
Eurotungstene Poudres, who supported
this study.
Références
1. R. Zsigmondy, Z. Physik. Chem. 56 (1906)
p. 65.
2. R. Zsigmondy and P. A. Thiessen, Das Kol-
loide Gold, (Akad. Verlagsges, Leipzig, 1925).
3. J. Turkevich, Gold Bull. 18 (3) (1985) p. 86.
4. V.K. LaMer and M.D. Bames, /. Colloid
Sci. 1 (1946) p. 71.
5. R. Demchak and E. Matijevic, /. Colloid
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6. R. Brace and E. Matijevic, /. Inorg. Nucl.
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7. T. Sugimoto and E. Matijevic, /. Colloid
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8. E. Matijevic, Langmir 2 (1986) p. 12.
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20. K. Tekaia-Ehlsissen, A. Delahaye-Vidal,
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34 MRS BULLETIN/DECEMBER1989