Journal of Colloid and Interface Science 260 (2003) 75–81

www.elsevier.com/locate/jcis

Preparation of highly concentrated stable dispersions of uniform

silver nanoparticles ✩
Ivan Sondi, Dan V. Goia, and Egon Matijević ∗
Center for Advanced Material Processing, Clarkson University, Potsdam, NY 13699-5814, USA
Received 16 April 2002; accepted 16 December 2002

Abstract
Stable concentrated aqueous dispersions of silver nanoparticles of narrow size distribution were prepared by reducing silver nitrate
solutions with ascorbic acid in the presence of Daxad 19 (sodium salt of a high-molecular-weight naphthalene sulfonate formaldehyde
condensate) as stabilizing agent. The latter has excellent ability to prevent the aggregation of nanosize silver at high ionic strength and
high concentration of metal (up to 0.3 mol dm−3 ). The presence of the dispersing agent on the surface of silver particles was confirmed by
ATR-FTIR spectroscopy and electrokinetic measurements, explaining both the negative charge over the entire pH range and the electrosteric
effect responsible for their long-term stability. The other experimental conditions, i.e., the pH of the reacting solutions, the concentration of
the stabilizing agent, and the metal/dispersant ratio, also have a significant impact on the size and stability of these dispersions. The final
nanosize silver can be obtained as dried powder, and can be fully redispersed in deionized water by sonication.
 2003 Elsevier Science (USA). All rights reserved.

Keywords: Dispersions of silver; Monodispersed silver; Nanosized silver; Silver, nanosized

1. Introduction and photoreduction in reverse micelles [5–11], and radiation

Metallic silver, either in bulk form or finely dispersed,
is an increasingly important material in many technologies.
It displays unique properties normally associated with the
noble metals (chemical stability, excellent electrical conduc-
tivity, catalytic activity), along with other more specific ones
(antibacteriostatic effects, nonlinear optical behavior, etc.),
while still being reasonably priced. Consequently, highly
dispersed silver nanoparticles are used as catalysts, as stain-
ing pigments for glasses and ceramics, as antimicrobial ma-
terials, in surface-enhanced Raman spectroscopy, as trans-
parent conductive coatings, in electronics, etc. Since many
of these applications have reached a mature stage, there is a
lot of interest in finding ways to produce dispersions of sil-
ver nanoparticles in large quantities.
Several methods were used in the past to prepare silver
nanoparticles, including chemical reduction of silver ions in
aqueous solutions with or without stabilizing agents [1–3],
thermal decomposition in organic solvents [4], chemical
chemical reduction [12–14]. However, most—if not all—
procedures described so far yield stable silver dispersions
only at relatively low concentrations of metal and, therefore,
are not suitable for large-scale manufacturing.
The precipitation process, described here, yields highly
concentrated and stable dispersions of monodispersed silver
nanoparticles in a simple and cost-effective manner, by
reduction of concentrated aqueous solutions of silver nitrate
with ascorbic acid in aqueous medium. Daxad 19 was
selected as the most suitable dispersant for this purpose,
based on preliminary evaluations of the protective ability
of several classes of dispersing agents. Obtaining such a
desired system is a subject of many limitations, including
the mentioned choice of the stabilizing agent, and of other
experimental parameters (i.e., concentration of reactants,
pH, and method of mixing).
2. Experimental

✩
2.1. Materials
Supported in part by a grant from Ferro Electronic Materials, and by
NSF Contract DMR-0102644.
* Corresponding author. Silver nitrate and ascorbic acid were of high purity grade.
E-mail address: metcalf@clarkson.edu (E. Matijević). Various surfactants were tested to produce stable nanosized
0021-9797/03/$ – see front matter  2003 Elsevier Science (USA). All rights reserved.
doi:10.1016/S0021-9797(02)00205-9
76 I. Sondi et al. / Journal of Colloid and Interface Science 260 (2003) 75–81

Table 1
Conditions for the preparation of silver hydrosols using Daxad 19 as the stabilizing agent
Sample Daxad 19 AgNO3 Ascorbic acid HClO4 Observationa
(wt%) (mol dm−3 ) (mol dm−3 ) (1 mol dm−3 )
1 0.5 0.3 0.25 No −
2 1 0.3 0.25 No −
3 2 0.3 0.25 No −
4 5 0.3 0.25 No +
5 10 0.3 0.25 No +
6 5 0.03 0.25 No −
7 5 0.3 0.25 No −
8b 5 0.3 0.25 No −
9 5 0.3 0.25 7 cm3 +
The pH of dispersions with addition of perchloric acid was 1.6 at the beginning and 1.2 at the end of the reaction. The corresponding values for systems
without acid were 5.5 and 1.2, respectively.
a +, stable; −, unstable.
b Daxad 11.

silver hydrosols, including the nonionic [polyoxyethylene
sorbitan monolaurate (Tween 20), polyoxyethylene nonyl-
phenyl ether (Igepal CO-630)], cationic [cetyltrimethylam-
monium bromide (CTBA)], and anionic [sodium dodecyl
sulfate (SDS)], alkyl ether sulfonate (Avanel S-70), sodium
salts of naphthalene sulfonate formaldehyde condensate
(Daxad 11, mol wt ∼4000, and Daxad 19, mol wt 8000).
2.2. Preparation of silver particles
To obtain highly concentrated stable dispersions of nano-
sized silver particles, the chemical reduction in aqueous so-
lutions of the most common silver compound, silver nitrate,
was used. Ascorbic acid was selected as the reductant of
choice, because of its ability to precipitate metallic silver in
acidic solutions according to
2Ag+ + C6 H8 O6 ⇔ 2Ag0 + C6 H6 O6 + 2H+ .
The important aspect of this process is the increase in the
acidity of the reaction mixture during the reduction, due to
the release of protons. Most other common reducing agents,
such as hydrazine and formaldehyde, are effective only in
solutions of neutral or basic pH and, therefore, require a base
to complete the reaction. Various surfactants and different
concentrations of Daxad 19 and of silver nitrate were used
to establish their effect on the size and the stability of the
resulting dispersions of silver particles.
In principle, well-defined silver hydrosols could be ob-
tained by adding under vigorous mixing an ascorbic acid so-
lution at a constant flow rate into the solution containing sil-
ver nitrate and a stabilizing agent, all at room temperature.
In all experiments ascorbic acid was maintained in excess of
66 mol% over the required stoichiometric amount relative to
silver.
Experiments using different surfactants listed above
showed that, regardless of the experimental conditions, un-
stable silver dispersions were obtained, except with Dax-
ad 19. Thus, only the latter was used in this study. Indeed
the same compound was found earlier to yield nanosize sil-
ver particles for a different purpose [15].
The following optimal experimental conditions were
established to produce well-defined silver hydrosols. To
83.3 cm3 of an aqueous silver nitrate solution, containing
5 wt% Daxad 19 was added 16.7 cm3 of a 1.5 mol dm−3
ascorbic acid solution at a controlled flow rate of 2.5
cm3 min−1 . In the evaluation of different parameters, the
concentrations of reactants were changed, while maintain-
ing the final volume of 100 cm3 . In some experiments the
initial pH was lowered by perchloric acid, which was added
into the silver nitrate solution. To find out if the method of
mixing affected the resulting silver particles, the reactant so-
lutions were rapidly combined, while keeping all other con-
ditions the same.
After completion of the precipitation process, the sil-
ver precipitates were washed with deionized water to near-
neutral pH, and redispersed in water. Alternatively, the
(1) nanoparticles could be obtained as dry powder after the
solids were separated by centrifugation, washed with ace-
tone, and subsequently dried in vacuo at low temperature.
The dry silver particles could be redispersed in deionized
water in an ultrasonic bath to obtain concentrated disper-
sions.
A number of studied systems are described in Table 1,
which illustrates the effects of different conditions on the
resulting products.
2.3. Characterization
The optical properties of silver hydrosols were moni-
tored as a function of time in 10-mm-optical-path-length
quartz cuvettes with a Perkin–Elmer UV–Vis Lambda 6
spectrophotometer. To measure absorbances during the re-
action, known small volumes of samples were taken at dif-
ferent times and immediately diluted with water in a quartz
cell to a final volume of 2 cm3 .
The size and the morphology of the particles were exam-
ined by transmission electron microscopy (TEM). The sizing
of samples was carried out from transmission electron mi-
crographs using the Image Tool for Windows (Version 2.0)
 I. Sondi et al. / Journal of Colloid and Interface Science 260 (2003) 75–81 77

software, while data were analyzed by means of the Micro-

cal Origin 6.0 software.
The presence of the Daxad 19 surfactant at silver surfaces
was assessed by attenuated total reflection infrared spec-
troscopy (FTIR-ATR) over 4000–500 cm−1 at a resolution
of 4 cm−1 .
Electrokinetic measurements of silver nanoparticles as a
function of the pH in 1 × 10−3 mol dm−3 aqueous solutions
were evaluated with a ZetaPals instrument at 25 ◦ C.

3. Results

The formation of silver particles was followed by ab-

sorbance measurements. Figure 1 shows the evolution of the
absorption spectra of the silver hydrosols during the very
early stages (15, 30, and 60-s reaction time) of the reduc-
tion process, carried out under the conditions of sample 4 in
Table 1. The precipitation of nanosize silver particles starts
almost immediately on addition of the reducing agent, and
continues throughout the investigated period, as indicated by
the emergence and the progressive increase in the intensity
of the well-defined plasmon band at 413 nm.
Figure 2 displays analogous plots during the later stages
of the precipitation, which indicate that the concentration
of silver particles had increased, and that some growth
took place. After 3 min, the spectrum is characterized by
a shoulder at 550 nm (spectrum d) and some background
absorbance at longer wavelengths. After completion of the
process (∼7 min) a decrease in the main plasmon band,
a shift to 425 nm, and high absorbance toward the longer
wavelengths are observed.
Sample 4 is described in Table 1 as “stable,” which
requires some explanation. The stability of a dispersion
can be viewed in terms of the propensity for aggregation
Fig. 1. Absorption spectra of silver hydrosols (sample 4, Table 1) recorded
at different reaction times at early stages of precipitation: (a) 15 s, (b) 30 s,
(c) 1 min.
Fig. 2. Absorption spectra of silver hydrosols (sample 4, Table 1) recorded
during the later stages of precipitation: (c) 1 min, (d) 3 min, (e) 7 min (end
of reaction).
and in the redispersibility of the final particles. Figure 2
shows that limited aggregation occurred before completion
of the process, which is not unexpected at such high particle
concentration. Indeed, analogous effects were previously
reported by several authors [5,6,12] with metal hydrosols
of orders of magnitude lower concentrations. In addition,
the sample described here was fully redispersible after long-
term storage, by simple agitation in an ultrasonic bath.
Transmission electron micrographs in Figs. 3a and 3b
display silver particles obtained under conditions of sam-
ple 4 (Table 1) after 1 min and after completion of the
process (7 min). Higher-magnification images of the latter
indicate internal structures, such as strain effects and stack-
ing faults (Fig. 3c), and a slight degree of particle aggre-
gation (Fig. 3d). The corresponding particle size distribu-
tion histograms of the obtained nanoparticles are given in
Figs. 4a and 4b. The solid lines are the Gaussian fits of data,
which yield modal diameters of 15 and 26 nm, respectively.
Increasing the concentration of Daxad 19 produced dis-
persion of the same particles as sample 4; however, lower-
ing the amount of this stabilizer resulted, as expected, in ag-
gregated dispersions (samples 1–3, Table 1). Surprisingly, a
smaller initial concentration of AgNO3 , under otherwise the
same experimental conditions, produced an unstable silver
hydrosol (sample 6, Table 1).
The method of mixing also affected the nature of the
product; thus, rapid introduction of the reducing agent
yielded aggregated particles (sample 7, Table 1). Finally,
Daxad 11, which has the same chemical composition as
Daxad 19, but is of lower molecular weight, resulted in
unstable dispersions (sample 8, Table 1).
According to Eq. (1), acidification of the reactants should,
in principle, shift the equilibrium, and as such affect the nu-
cleation and growth stages in the precipitation of silver. For
this reason, perchloric acid was added into the solution con-
taining silver nitrate and Daxad 19 under experimental con-
78 I. Sondi et al. / Journal of Colloid and Interface Science 260 (2003) 75–81

Fig. 3. Transmission electron micrographs of silver nanoparticles (sample 4, Table 1): (a) after 1 min of reaction time, (b–d) after 7 min (end of reaction).

Fig. 4. Particle size distribution histograms of silver nanoparticles shown in Figs. 3a and 3b evaluated from the corresponding electron micrographs. The solid
lines are Gaussian fits of the data.

ditions that were shown to yield the dispersion of optimal
properties (sample 9, Table 1). The spectra of this system at
early and later stages are given in Figs. 5 and 6. Considerably
weaker plasmon bands and somewhat higher background ab-
sorbances at longer wavelengths are already apparent during
the first minute of the reaction (Fig. 5), as compared with
the same system in the absence of HClO4 (Fig. 1). With the
progress of the reduction process the plasmon band essen-
tially disappears, indicating polydisperse hydrosols of large
particles (Fig. 6), as corroborated by the electron micro-
graphs displayed in Fig. 7. A comparison with Fig. 3 shows
that silver particles initially precipitated are larger, and that
 I. Sondi et al. / Journal of Colloid and Interface Science 260 (2003) 75–81 79

Fig. 5. Absorption spectra of silver hydrosols (sample 9, Table 1) recorded Fig. 6. Absorption spectra of silver hydrosols (sample 9, Table 1) recorded
at different reaction times at early stages of precipitation: (a) 15 s, (b) 30 s, during the later stages of precipitation: (c) 1 min, (d) 3 min, (e) 7 min (end
(c) 1 min. of reaction).

Fig. 7. Transmission electron micrographs of silver nanoparticles (sample 9, Table 1) obtained after 1 min of reaction time (a) and at the end of the reaction
(b–d).
80 I. Sondi et al. / Journal of Colloid and Interface Science 260 (2003) 75–81
Fig. 8. ATR-FTIR spectra of (a) Daxad 19 dispersant agent and (b) nano-
sized silver particles (sample 4, Table 1).
Fig. 9. ζ potential of nanosized silver particles (sample 4, Table 1) in
10−3 mol dm−3 KCl solution as a function of pH.
with the progress of the reaction a high degree of aggregation
occurs (Fig. 7d). In addition, the presence of some idiomor-
phic silver nanocrystals is evident in Fig. 7c.
The ATR-FTIR spectra of Daxad 19 (Fig. 8a) and of sil-
ver nanoparticles (Fig. 8b) clearly indicate that the disper-
sant adsorbs on the surface of silver particles. Both spectra
are characterized by the aromatic C=C stretching vibrations
between 1300 and 1600 cm−1 and symmetric and asymmet-
ric stretching of the sodium sulfonate groups between 1030
and 1100 cm−1 .
Finally, the zeta potentials of silver nanoparticles (sam-
ple 4, Table 1), plotted at a constant ionic strength (10−3
mol dm−3 KCl) (Fig. 9), show them to be negatively charged
over the studied pH range, supporting the spectroscopic evi-
dence for the adsorption of Daxad 19.
4. Discussion
This study has demonstrated that stable dispersions of
nanosized silver particles can be rapidly prepared in high
concentration by reduction of silver ions with ascorbic acid
in the presence of the stabilizer Daxad 19. However, the
conditions under which such hydrosols are obtained are
rather restrictive in terms of the surfactant used and other
experimental parameters.
Several general observations are in order. The absorbance
spectra clearly indicate that during the very early stages
(
1 min) the number of silver particles increases (Fig. 1),
followed by some growth and limited aggregation until the
process is terminated (Fig. 2), all of which can be visualized
in transmission electron micrographs (Fig. 3). The slight
aggregation of primary particles, which can also be observed
in the TEM image (Fig. 3d), may be in part caused by the
lowering of the magnitude of the zeta potential, since the pH
during the reaction drops from the initial value of 5.5 to the
final value of 1.2 (Fig. 9).
It was also observed that the majority of the particles in
this case exhibit internal structure, characterized by strain
effects and/or stacking faults that, according to previous
investigations [16–18], can be related to “multiple-twinned
particle” (MTP) formation.
Some other effects, such as the impact of the concentra-
tion of the stabilizer or its molecular weight, are as antici-
pated. However, a rather unexpected finding, that the low-
ering of the initial concentration of AgNO3 leads to larger
particles and less stable silver hydrosols, needs some com-
ments. While the formation of larger particles could be ex-
plained by the generation of a smaller number of nuclei at
lower reactant concentrations, the extent of aggregation of
the final silver particles (as indicated by the lack of a well-
defined plasmon band and the SEM image in Fig. 10) is sur-
prising, since the presence of the large excess of the disper-
sant should increase the dispersant/Ag ratio and favor the
formation of more stable colloids. One aspect that could ac-
count for the observed behavior is the interaction between
the Ag+ ions and the sulfonic group of the Daxad 19 to form
a silver/dispersant complex, which may act as a more effec-
tive protective species in this system. The decrease in the
Fig. 10. Scanning electron micrograph of a silver hydrosol prepared under
the experimental conditions for sample 6 (Table 1).
 I. Sondi et al. / Journal of Colloid and Interface Science 260 (2003) 75–81
initial concentration of Ag+ would result in a lower concen-
tration of this “active” dispersant and, therefore, weaken the
particle protection. This stabilization mechanism could also
explain the agglomeration of the silver hydrosol, prepared
by the standard procedure at the later stages of the precip-
itation (sample 4, Table 1), when the concentration of the
Ag–Daxad complex decreases due to the reduction of sil-
ver ions to metallic atoms. This phenomenon will be further
studied in more detail.
It is known that E 0 , the standard redox potential of
reactions that involve H+ and OH− ions, is highly dependent
on the pH. The changes in the redox potential of the reducing
species affect the E 0 of the overall redox reaction, causing
changes in the supersaturation concentration of metal atoms
and, consequently, the nucleation rate which control the final
particle size. In the case of the ascorbic/dihydroascorbic
system, an increase in the concentration of protons reduces
the ability of the oxidized species to supply electrons,
causing a significant slowdown of the reduction reaction.
To verify these assumptions, the pH of the silver nitrate
solutions was lowered by the addition of HClO4 , an acid that
does not form any complexes or compounds with the Ag+
ions; thus, it affects the redox potential of only the ascorbic
acid, but not of the Ag+ /Ag0 system. As predicted, starting
from a silver nitrate solution acidified with perchloric acid
(sample 9, Table 1) the reduction reaction was slower
and the size of the final individual silver particles was
significantly larger (Fig. 7 b). However, stable hydrosols of
81
nanosize silver particles were not obtained even at the early
stages of precipitation (Fig. 5), since at the low pH of the
reaction medium the particle charge was weaker, lowering
the stability of the dispersions.
References
[1] L.M. Liz Marzan, I. Lado-Tourino, Langmuir 12 (1996) 3585.
[2] D.G. Duff, G. Baiker, Langmuir 9 (1993) 2301.
[3] D.N. Glavee, K.J. Klabunde, C.M. Sorensen, G.C. Hadjipanayis,
Langmuir 9 (1993) 162.
[4] K. Esumi, T. Tano, K. Torigoe, K. Meguro, Chem. Mater. 2 (1990)
564.
[5] C. Petit, P. Lixon, M.P. Pileni, J. Phys. Chem. 97 (1993) 12974.
[6] J.P. Wilcoxon, R.L. Williamson, R. Baughman, J. Chem. Phys. 98
(1993) 9933.
[7] H. Ohde, F. Hunt, C.M. Wai, Chem. Mater. 13 (2001) 4130.
[8] Y.P. Sun, P. Atorngitjawat, M.J. Meziani, Langmuir 17 (2001) 5707.
[9] M.P. Pileni, Pure Appl. Chem. 72 (2000) 53.
[10] M.P. Pileni, A. Taleb, C. Petit, J. Dispersion Sci. Technol. 19 (1998)
185.
[11] A. Taleb, C. Petit, M.P. Pileni, Chem. Mater. 9 (1997) 950.
[12] A. Henglein, J. Phys. Chem. 97 (1993) 5457.
[13] A. Henglein, Langmuir 17 (2001) 2329.
[14] A. Henglein, Chem. Mater. 10 (1998) 444.
[15] V.V. Hardikar, D.V. Goia, E. Matijević, Colloids Surf. 159 (1999) 121.
[16] S.M. Heard, F. Grieser, C.G. Barraclough, J. Colloid Interface Sci. 93
(1983) 545.
[17] K. Yagi, K. Takayanagi, K. Kobayashi, H. Honjo, J. Cryst. Growth 28
(1975) 117.
[18] J.G. Allpress, J.V. Sanders, Surf. Sci. 7 (1967) 1.