Chiang Mai J. Sci. 2013; 40(6)
963
Chiang Mai J. Sci. 2013; 40(6) : 963-970
http://epg.science.cmu.ac.th/ejournal/
Contributed Paper
Effect of Silver Nanoparticle on Lead-based Art Glass
Fabricated from Thailand Quartz Sands
Pisutti Dararutana*[a], Krit Won-in [b] and Narin Sirikulrat [c]
[a] The Royal Thai Army Chemical Department, Phaholyothin Road, Chatuchak, Bangkok 10900, Thailand.
[b] Faculty of Science, Kasetsart University, Phaholyothin Road, Chatuchak, Bangkok 10900, Thailand.
[c] Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand.
*Author for correspondence; e-mail: [email protected]
Received: 11 April 2012
Accepted: 28 May 2012
ABSTRACT
In ancient time, yellow colored glass which used for luxury art glass was actually
silver nanotechnology at work by the addition of silver compound into the molten glass. In
this work, the lead-alkali silica glass which fabricated using local quartz sands as the silica raw
material was added with various concentrations of silver nitrate. Scanning electron microscope
coupled with energy dispersive X-ray spectroscopy (SEM-EDS) was used to characterize
their morphology. Physical and optical properties such as density, refractive index and optical
absorption were also measured. After the complete conventional melting process, the bubblefree yellowish glasses were yielded. SEM micrographs showed the presence of silver
nanoparticles in the glass matrix that confirmed by EDS. The refractive indices and densities
were increased as the increase of the silver contents. It was also showed that the more brilliance
on the surface of the glass products was obtained after fired.
Keywords: silver nanoparticle, art glass, lead-based glass, Thailand quartz sands
1. INTRODUCTION
It was reported in recent years that the
properties of commercial glass by
incorporation of noble metal particles of
nanometer size such as copper (Cu), silver
(Ag) and gold (Au), have been the subject of
intense investigations in advanced materials
research because of their unique electronic,
optical and thermal properties as well as
catalytic property for potential in different
fields of science and technology such as
physics, chemistry, biology, medicine and
materials science [1-4].
In fact, it was known that the
exploitations with nanotechnology in ceramics
and glass were not modern phenomena. Metal
colloids were the best example throughout
ancient, medieval and modern times. The
Lycurgus Cup (4th century A.D.) now with
the British Museum (London) is an example
of the colored Roman glass which the glass
matrix contains nanoparticles (approximately
70 nm) combines with gold and silver.
The opaque green cup looks translucent red
ruby when light shines through it [5, 6].
964
In the past years, oxide glasses containing
silver nanoparticles have been the promising
materials due to their non-linear optical
property and high potential figure of merit
for switching devices. They have attracted
quite some attention in possible applications
for optoelctronic purposes such as non-linear
optics [7], electrochemical devices [8], electrooptical devices [9] and dosimeters [10].
The silicate glasses provide an optically
transparent matrix in which atoms, molecules
and/or small particles can be physically
trapped. The method used to incorporate
the Ag inclusions into the silicate glasses
depended on the process used to prepare
them [11-14]. The glass that was prepared
from the conventional melting process; it was
found that the Ag was introduced in the form
of a metallic oxide, which was diluted in the
melted silica at high temperature [15-17].
This method produced dense glasses with low
degree of porosity. The optical spectrum of
silver-doped glasses showed different features
depending on the aggregation state of the
metal. It was also found that spherical silver
particles (~10 nm) produced an absorption
band around 410 nm, while spherical particles
split this absorption in two bands located
at shorter and longer wavelengths [18]. These
bands have been associated with the plasmon
absorption band in nanometric Ag colloidal
particles [19-21].
The production of colored lead crystal
glass is an important subject for the
manufacture of decorative pieces, especially
if the coloring consists in a superficial
layer. This is due to the future cut off of the
surface with ornamental designs that stick out
the intense coloring upon the transparency
and bright of the colorless lead crystal
glass. Yellow lead crystal glass has been
obtained due to the very low content of
thermoreducing agents such as by Ag+ ion-
Chiang Mai J. Sci. 2013; 40(6)
exchange in its composition. The color
obtained is amber or brown, produced by
small silver particles formed by reduction of
Ag+-ions with the Fe2+-ions from the glass
impurities [22].
In this work, the lead-based glass samples
were fabricated using Thailand quartz sand
and various concentrations of silver nitrate.
Their physical and optical properties were
determined and discussed.
MATERIALS AND METHODS
2.1 Sample Preparation
Glass samples were prepared in the
laboratory scale over the matrix of SiO2(Na2O, K2O)-CaO-PbO-Al2O3-MgO, labeled
as SG0. Local quartz sands from Trat site
(eastern province of Thailand) was used as
the source of silica raw material. It was the
surface-to-near surface glass sand deposit
which contained more than 98.0 wt% SiO2
and low iron content (0.05 wt%). It showed
in pink-gray color. Its grain was mostly angular
and fine. The values of grain size, grain
concentration and specific area were 250±100
μm, 0.166 %vol and 0.046 m2/g, respectively
[23-24]. Various concentrations of AgNO3
were added from 0.01 to 5.0 wt%, labeled as
SG1-1, SG2-1, SG3-1, SG4-1, SG5-1 and
SG6-1, respectively. The well-mixed and
dried powders mixture of 150 g each was
contained in a ceramic crucible for each
composition. They were melted using an
electric furnace at maximum temperature of
1050±50°C for 4 h and then cooled down to
room temperature.
2.
2.2 Refractive Index Measurement
Refractive index (nD) of these glass
samples was measured at room temperature
using a Rayner Duplex II refractometer with
a refractometer fluid nD ≤1.79 and 589-nm
sodium light. The uncertainty was ±0.005.
Chiang Mai J. Sci. 2013; 40(6)
2.3 Density Measurement
The density of the prepared glass samples
was measured by applying Archimedean
buoyancy method. All weight measurements
were done using an analytical balance Meltler
Toledo AG 104, with distilled water as the
immersion liquid at 25°C.
2.4 Optical Absorption Measurement
The optical absorption spectra were
recorded by Perkin Elmer Lambda 900 UVVIS-NIR spectrometer at room temperature
in a spectrum range of 300-800 nm with an
accuracy of ±0.8 nm in the visible range.
2.5 Microstructure Analysis
Sample SG6-1 which contained 5.0 wt%
AgNO 3 was fired using a gas torch at
temperatures around 600±100°C. Structures
and composition of the glass samples were
analyzed using a Jeol JSM 5410 LV scanning
965
electron microscope coupled with an Oxford
Instruments INCA Penta FETx3 analytical
system. The SEM system operated at 15 kV
with maximum magnification of x20000,
ellipse time of 60 s and detection area of
30 mm2. Prior to characterize, its surface was
coated with gold using Jeol JFC-1200 Fine
Coater.
RESULTS AND DISCUSSION
3.1 Color, Refractive Index and Density
The colors of all samples were shown in
Figure 1. It can be seen that the glass samples
were homogenous and free of bubbles.
The color of the based glass was colorless
while it changed to pale, bright and almost
opaque colors with increasing concentration
of AgNO3. SG4-1 was light brownish-yellow.
With maximum doping, SG6-1 became
opaque brownish-yellow and loosed visible
transmittance.
3.
Figure 1. Macroscopic appearance of the glass samples.
Results from the measurements, the
refractive indices and the densities of the glass
samples were 1.520 to 1.580 and 3.0026 to
3.1920 gcm-3, respectively, detailed in Table 1.
They were increased linearly as the increase
of AgNO3.
Table 1. The values of density and refractive index of the glass samples.
Sample no.
SG0
SG1-1
SG2-1
SG3-1
SG4-1
SG5-1
SG6-1
AgNO3 Conc., wt%
0
0.01
0.1
0.5
1.0
2.0
5.0
nD at 589 nm
1.520
1.520
1.525
1.530
1.535
1.545
1.580
ρ(gcm-3) at 25°C
3.0026
3.0030
3.0103
3.0408
3.0642
3.0814
3.1920
966
The appearance of brownish-yellow
color was a clear indication of the formation
of silver nanoparticles. This color exhibited
by metallic nanoparticles was due to the
coherent excitation of all the free electrons
within the conduction band, leading to an in
phase oscillation which was known as the
surface plasmon resonance (SPR) [25-27].
3.2 Optical Absorption
The UV-VIS absorption spectra of the
glass samples containing as-prepared silver
nanoparticles were shown in Figure 2.
The spectra exhibited a strong SPR
Chiang Mai J. Sci. 2013; 40(6)
absorption band of the glass samples
centered at 410 nm and certainly increased
in absorbance as a function of silver
contents without any shift in the peak
wavelength. The increase of absorbance
was observed when the rate of silver
nanoparticles formation has increased and
more amount of silver nanoparticles were
formed during the same time. It was
corresponded with the universally accepted
within the community that for the spherical
silver nanoparticles < 20 nm, the SPR band
centered around 410 nm depending on the
host matrix [15-17, 28-35].
Figure 2. UV-VIS spectra of the glass samples.
Absorption band which centered around
280 nm have been attributed to the presence
of Ag clusters of various sizes and charges,
which was known as the Ag 4d to 5sp
interband transition [1, 36-38].
3.3 Microstructure
SEM image has been shown individual
silver particles as well as numbers of
aggregates, as shown in Figure 3. The
morphology of the silver nanoparticles was
predominately spherical and aggregated
into larger irregular structure. EDS analysis
showed the presence of Ag on the surface at
this area of the sample. The presences of
the chromophore elements were O, Si and
Ag with different concentrations, illustrated
in Table 2.
It was shown that the more brilliance
on the surface of the glass product of
SG6-1 was obtained after firing using a
gas torch. Its color changed to shining
yellow, as shown in Figure 4 (a). Figure 4 (b)
showed micrograph of the brilliance
surface area with area-analysis EDS, Figure 4
(c). The analysis suggested that Ag was
metallic form and confirmed as Ag
nanoparticles.
Chiang Mai J. Sci. 2013; 40(6)
967
Figure 3. SEM micrograph of the glass surface (SG6-1).
Table 2. Composition of microstructure using EDS.
Position
#1
#2
#3
#4
#5
#6
#7
O
nd
nd
24.31
49.59
29.24
45.31
27.35
Figure 4. SG6-1 after firing with a gas torch.
Element, wt%
Si
48.73
73.34
38.32
47.26
35.50
48.79
39.10
Ag
51.27
26.66
37.37
3.15
35.26
5.90
33.55
968
It was proved that the glass which was
prepared from the melting process, the Ag
was introduced in the form of a metallic
oxide, which was diluted in the melted silica
at high temperature. [15-17]. In this case, the
reduction of the silver oxide rich regions to
metallic silver was achieved by post forming
heat treatment [28, 29].
CONCLUSIONS
The effects of silver on lead-based glass
which fabricated by local quartz sands has
been successfully investigated. Resulted
showed the changing not only in the color,
but also the refractive index and density.
The optical properties depended on the
concentration, size, shape and spatial
arrangement and configuration of the silver
nanoparticles in the glass matrix. The signatory
brownish-yellow color was obtained which
resulted due to the SPR vibrations of the silver
nanoparticles formed. The reaction could
easily be tracked by the change in color and
reconfirmed by UV-VIS spectroscopy.
The results reported in this work
increased the current knowledge of the silver
nanoparticle in the glass matrix with
conventional method as similar as the luster
production in ancient time. However, these
may be applied in the field of dosimeters.
4.
ACKNOWLEDGEMENTS
The research was partly funded by the
Faculty of Science at Kasetsart University.
The Glass and Glass Products Research and
Development Laboratory of the Science and
Technology Research Institute at Chiang Mai
University provided laboratory preparation
and team expertise. The measurements using
a refractometer, an analytical balance and an
UV-VIS-NIR spectrometer were performed
at the Faculty of Science at Kasetsart University
(Bangkok). The Institute of Product Quality
and Standardization at Maejo University
Chiang Mai J. Sci. 2013; 40(6)
(Chiang Mai) was also thanked for
providing SEM-EDS.
REFERENCES
[1] Kelly K.I., Coronado E., Zhao L.L.
and Schatz G.C., The optical
properties of metal nanoparticles: The
influence of size, shape and dielectric
environment, J. Phys. Chem. B, 2003;
107: 668-677.
[2] Podlipensky A., Grebenev V., Seifert
G. and Graener H., Ionization and
photomodification of Ag nanoparticles
in soda-lime glass by 150 fs laser
irradiation: a luminescence study, J. of
Luminescence, 2004; 109: 135-142.
[3] Mahnke H.-E., Schattat B., SchubertBischoff P. and Novakovic N., Ion beam
induced nanosised Ag metal clusters in
glass, NIMB, 2006; 245: 222-224.
[4] De G., Samar Kumar M., De S. and
Pal S., Metal nanoparticle doped
coloured coatings on glasses and
plastics through tuning of surface
plasmon band position, Bull.Mater.
Sci., 2008; 31: 479-485.
[5] Dararutana P., Dutchaneephet J.,
Chetanachan P., Wathanakul P. and
Sirikulrat N., Effect of gold nanoparticles on the fabrication of red
colored high refractive index lead glass,
Advanced Materials Research, 2008; 5557: 601-604.
[6] Deparis O. and Kazansky P.G., Novel
technique for engineering the structural
and optical properties of metal-doped
nanocomposite glasses, in Proceedings
Symposium IEEE/LEOS Benelux
Chapter, Ghent, 2004, 33-36.
[7] White C.W., Zhou D.S., Budai J.D.,
Zuhr R.A., Magruder III, R.H. and.
Osborne D.H., Colloidal Au nanoclusters formed in fused silica by MeV
ion implantation and annealing, Mater.
Res. Soc. Sym. Proc., 1994; 316: 499-505.
Chiang Mai J. Sci. 2013; 40(6)
[8] Minami T., Fast ion conducting glasses,
J. Non-Cryst. Solids, 1985; 73: 273-284.
[9] Lakshmikvm S.T. and Rastogi A.C.,
Selenization of Cu and In thin films for
the preparation of selenide photoabsorber layers in color cells using Se
vapour source, Solar Energy Mater., 1994;
32: 7-19.
[10] Belharouak L., Parent C., Tanguy B.,
Le Flem G. and Couzi M., Silver
aggregates in photoluminescent
phosphate glasses of the Ag2O-ZnOP2O5 system, J. Non-Cryst. Solids, 1999;
244: 238-249.
[11] Bamford C.R., Color Generation and
Control in Glasses, Elsevier Science
Publishing, New York, 1977.
[12] Borsella E., Cattaruzza E., De Marchi G.,
Gonella F., Mattei G., Mazzoldi P.,
Quaranta A., Battaglin G. and Polloni R.,
Synthesis of silver clusters in silica-based
glasses for optoelectronics applications,
J. Non-Cryst. Solids, 1999; 245: 122-128.
[13] Altarmirano-Juarez D.C., CarreraFigueiras C., Garnica-Romo M.G.,
Mendoza-L pez M.L., RiveraRodr guez C., Tototzintle-Huitle H.,
Valenzuela-J uregi J.J., VidalesHurtado M.A., Hern ndez-Landaverde
M.A. and Gonz lez-Hern ndez J.,
Effects of metals on the structure of
heat-treated sol-gel SiO 2 glasses,
J.Phys.Chem., 2001; 62: 1911-1917.
[14] Garnica-Romo M.G., Y nez Lim n
J.M., Gonz lez-Hern ndez J.,
Ram rez-Bon R., Tirado-Guerra S.,
Ram rez-Rosales D., Zamorano-Ulloa
R. and Tirado-Guerra S., Structure
and electron spin resonance of
annealed sol-gel glasses containing Ag,
J. Sol-Gel Sci. Technol., 2002; 24: 105112.
969
[15] Mel’nikov N.I., Peregood D.P. and
Zhitnikov R.A., Investigation of silver
centres in glassy B2O3, J. Non-Cryst.
Solids, 1974; 16: 195-205.
[16] Kreibig U., Small silver particles in
photosensitive glass: Their nucleation and
growth, Appl.Phys., 1976; 10: 255-264.
[17] Alenko Yu.N., Zhitnikov R.A.,
Krasikov V.K. and Peregud D.P.,
Electron spin resonance investigations
of silver centers in photochromic
glasses, Sov.Phys. Solid State, 1976; 18:
902-905.
[18] Villegas M.A., Vidrios dopados con
plata obtenidos por sol-gel, Bol. Soc.
Espa. Ceram. Vidrio, 1994; 33: 181192.
[19] Mie G., Beitrage zur optik truber
medien,
speziell
kollaidaler
metallosungen, Annalen der Physik,
1908; 25: 377-445.
[20] Nagami N., Sol-Gel Optics: Processing
and Applications, Kluwer Academic,
Hingham, M.A. 1994.
[21] Elena Zayas Ma., Arizpe-Ch vez H.,
Espinoza-Beltr n F.J., D az C., D azFlores L.L., Y ez-Lim n J.M. and
Gonz lez-Hern ndez J., Spectroscopic
studies on Na 2O-SiO 2 glasses with
differenct Ag Concentration using
silica obtained from wastes of a
geothermal plant, J. Non-Cryst. Solids,
2003; 324: 67-72.
[22] Gil C. and Villegas M.A., Ruby
coloured lead glasses by generation of
silver nanoparticles, Materials
Chemistry and Physics, 2004; 88: 155191.
[23] Dararutana P., Chetanachan P.,
Wathanakul P. and Sirikulrat N.,
Investigations on local quartz sands for
application in glass industry, Advances
in Geosciences, 2009; 13: 23-29.
970
[24] Dararutana P., Fabrication of lead-free
high refractive index glass using local
sand, Ph.D. Thesis, Chiang Mai
University, Thailand, 2008.
[25] Miotello A., Bonelli M., De Marchi
G., Mattei G., Mazzoldi P., Sada C.
and Gonella F., Formation of silver
nanoclusters by excimer-laser
interaction in silver- exchanged sodalime glass, Appl. Phys. Lett., 2001; 79:
2456-2458.
Chiang Mai J. Sci. 2013; 40(6)
[32] Pastoriza-Santos I. and Liz-Marzan
L.M, Synthesis of silver nanoprisms in
DMF, Nano Lett, 2002; 2: 903-905.
[33] Bahumov,V. Gueinzius K., Hermann
C., Schwarz M. and Kroke E.,
Polysilazane-derived antibacterial
silver-ceramic nanocomposites, Journal
of European Ceramic Society, 2007; 27:
3287-3292.
[26] Sun Y., Mayers B. and Xia Y.,
Transformation of silver nanospheres
into nanobelts and triangular nanoplates
through a thermal process, Nano Lett,
2003; 3: 675-679.
[34] Jimenez J.A., Lysenko S., Liu H.,
Fachini E., Resto O. and Cabrera
C.R., Silver aggregates and twofoldcoordinated tin centers in phosphate
glass: A photoluminescence study,
Journal of Luminescence, 2009; 129:
1546-1554.
[27] Udayasoorian C., Vinoth Kumar K. and
Jayabalakrishnan R.M., Extracellular
synthesis of silver nanoparticles using leaf
extract of cassia auriculata, Digest Journal
of Nanomaterials and Biostructures,
2011; 6: 279-283.
[35] Sileikaite A., Puiso J., Prosycevas I.
and Tamulevicius S., Investigation of
silver nanoparticles formation kinetics
during reduction of silver nitrate with
sodium citrate, Materials Science, 2009;
15: 21-27.
[28] Weyl W.A., Coloured Glasses, Society
of Glass Technology, Sheffield, 1976.
[36] Henglein A., Physicochemical
properties of small metal particles in
solution: “microelectrode” reactions,
chemisorption, composite metal particles,
and the atom-to-metal transition, J.
Phys. Chem., 1993; 97: 5457-5471.
[29] Ershov B., Janata E., Henglein A. and
Fojtik A., Silver atoms and clusters in
aqueous solution: absorption spectra and
the particle growth in the absence of
stabilizing Ag + ions, Journal of
Physical Chemistry, 1993; 97: 45894594.
[30] De Marchi G., Caccavale F., Gonella
F., Mattei G., Mazzoldi P., Battaglin
G. And Quaranta A., Silver nanoclusters formation in ion-exchanged
waveguiges by annealing in hydrogen
atmosphere, Appl. Phys. A., 1996; 63:
403-407.
[31] Garcia M.A., Paje S.E., Llopis J.,
Villegas M.A. and Fermandez
Navarro J.M., Optical spectroscopy
of arsenic-and silver-containing sol-gel
coating, J. Phys. D., 1999; 32: 975-980.
[37] Bositova T.B., Gorbunova V.V. and
Volkova E.I., Photochemical method of
controlling dispersity of nanostructures
of transition metals, Russ. J. Gen.
Chem., 2002; 72: 642-656.
[38] Evanoff D.D. and Chumanov G.,
Synthsis and optical properties of
silver nanoparticles and arrays,
Chem.Phys. Chem., 2005; 6: 1221-1231.