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The Formation of Monodisperse Spherical Silver Particles: I.M. Yakutik, G.P. Shevchenko, S.K. Rakhmanov
The Formation of Monodisperse Spherical Silver Particles: I.M. Yakutik, G.P. Shevchenko, S.K. Rakhmanov
The Formation of Monodisperse Spherical Silver Particles: I.M. Yakutik, G.P. Shevchenko, S.K. Rakhmanov
Abstract
The process of formation of monodisperse spherical silver particles in gelatin-stabilized ammonia-tartrate electroless deposition solution
has been investigated. The production of monodisperse spherical silver particles, 150420 nm in size, was shown to be feasible, the particle
diameter depending on pH of the solution. The spherical silver particles, as evidenced by TEM, optical spectroscopy and X-ray diffraction
data, were comprised of 1015 nm sized particles, and hence, were formed by the colloidal aggregation mechanism. The optical spectra of the
sols largely composed of monodisperse silver particles over 300 nm in size demonstrate the absorption band in the region of silver plasmon
absorption (max = 420 nm), which is characteristic of colloidal particles.
2004 Elsevier B.V. All rights reserved.
Keywords: Monodisperse colloid; Colloidal aggregation; Silver
1. Introduction
Monodisperse colloids containing the particles uniform in
their size and shape comprise a field of investigations which
resulted in numerous applications being of technological interest for the production of ceramics, pigments and catalysts
[13]. The early work on synthesizing monodisperse colloids
was based on LaMer theory assuming spontaneous nucleation followed by diffusion growth of the nuclei [4,5]. However, the experimental evidence amassed by now showed
that the mechanism of formation of monodisperse nanoparticles of different shapes and sizes is far more complicated
than had been originally suspected. It includes several steps:
nuclei forming, nuclei growing via diffusion mechanism to
give primary particles and the latter aggregating [610]. The
mechanism of the colloidal aggregation is not yet entirely
elucidated. The reason for the particle size and shape selection remains obscure, that is, there is no way of telling
what makes the forming colloidal systems monodisperse,
and when the colloidal aggregation is directed so as to yield
spheres, platelets, rods or ellipsoids [913].
Colloidal particles of noble metals, among them silver,
are of great interest due to their unique optical, electrical
and other properties which make possible their use in micro
Corresponding author.
E-mail address: shevchenk@bsu.by (G.P. Shevchenko).
0927-7757/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2004.04.069
176
I.M. Yakutik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 242 (2004) 175179
2. Experimental
To investigate the process of formation of monodisperse silver nanoparticles, the following formulation of
the standard solution was used: CAgNO3 = 102 mol l1 ,
CAgNO3 :CKNaTart = 1:1, CAgNO3 :CNH3 = 1:2, wgelatin = 1%.
The process was carried out at 30 2 C, pH of the solution
was 8.5. K-Na-tartrate was chosen as the reductant because
it reduces silver ions readily in the solution bulk, that is, a
non-autocatalytic mechanism of the reaction prevails. Silver
is precipitated by its colloidal particles coagulating on a
substrate; hence, it can precipitate even on unactivated dielectric surfaces, i.e. without any catalytic particles thereon
[40]. To stabilize the ultrafine silver particles formed,
gelatin produced by the acidic technique was used, with the
isoelectric point in the pH range 8.59.2. To produce silver
nanoparticles, specified volumes of 0.1 M AgNO3 and of
13.8 M ammonia aqueous solutions were added to the solution of the stabilizer (gelatin) and then a specified volume
of 0.5 M K-Na-tartrate aqueous solution was added to the
mixture agitated vigorously by a magnetic stirrer. Silver
concentration in the reaction mixture was varied from 5
105 to 102 M, and pH was adjusted in the range between
1.0 and 10.0 by adding 1 M H2 SO4 or 1 M NaOH to AgNO3
and K-Na-tartrate containing solutions. The particle size
and shape were determined by TEM method with JEM-100
and EM-125 K instruments. The particle size distribution
was derived from the TEM data, using not less than 100
particles for the calculation. Specord M 40 spectrometer
was employed to register the absorption spectra of the sols
in 300800 nm wavelength region. X-ray diffraction analysis of the colloidal particles was carried out with DRON-2.0
X-ray diffractometer using Co K radiation.
sol has a deep red-brown colour. According to TEM evidence, silver particles are almost immediately formed in
the solution (Fig. 1): lots of fine silver particles, 1030 nm
in size, are produced in the first 4050 s of the reaction
(Fig. 1a). In 5 min, spherical silver particles of sizes 170
and 540 nm appear in the sol along with the fine ones, that
is, a bimodal size distribution of the spherical particles is
I.M. Yakutik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 242 (2004) 175179
177
178
I.M. Yakutik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 242 (2004) 175179
- Ag
100
90
80
70
60
50
40
30
Fig. 4. XRD data of silver particles in the sol produced by the colloidal aggregation method from the standard solution, t = 60 min.
to 7.0 have a substantial ultraviolet absorption, with a shoulder at 400450 nm, dropping to = 715 nm. Optical density
of the sols is also observed to change nonlinearly with pH.
There may be several reasons for the peculiarities of the optical spectra of the sols. First, the reduction in the pH range
from 1.0 to 7.0 being slow, the sols contain Ag+ ions absorbing in ultraviolet region [44]. Second, these ions adsorb on
silver particles causing the plasmon resonance band of the
latter to red-shift, with the optical density at max decreasing
and the absorption band broadening [14]. Third, the reaction
rate in this pH range can change non-monotonically with
pH because of the possible Ag+ complexation with gelatin
depending largely on pH of the solution [45].
Fig. 5. Electron micrographs of silver particles in the sol produced by the colloidal aggregation method from the standard solution, t = 60 min, pH: 1.0
(a), 3.0 (b), 5.0 (c) and 10.0 (d).
I.M. Yakutik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 242 (2004) 175179
Absorption
2,0
1,6
1,2
0,8
0,4
3
2
4
5
1
7
6
0,0
400
500
600
700
800
, nm
Fig. 6. UVvis absorption spectra of the sols produced by the colloidal
aggregation method from the standard solution, t = 60 min, pH: 1 (1), 2
(2), 3 (3), 5 (4), 7 (5), 8.5 (6), 10 (7); (6) and (7), diluted a hundred times.
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