Trans Indian Inst Met

DOI 10.1007/s12666-014-0448-x

TECHNICAL PAPER

TP 2849

Stabilization of Nanocrystalline Silver by Sella and Mansoori

Rice Starch
Manish Kumar Singh Manjri Singh
Jaya Lakshmi Verma Nitish Kumar
R. K. Mandal

Received: 5 June 2014 / Accepted: 19 July 2014

The Indian Institute of Metals - IIM 2014

Abstract The silver nanoparticles (AgNPs) have been

synthesized by utilizing starch got from rice to serve as
stabilizer and reducing agent in presence of sodium
hydroxide. Two varieties of rice viz. Mansoori and Sella
grown in Uttar Pradesh (India) were utilized for getting
starch in this investigation. The starch hydrolysis yields
glucose for the reduction of silver nitrate precursor. UV
Vis spectra showed localized surface plasmon resonance
(LSPR) absorption peaks at 400 nm and 412 nm indicating
the formation of AgNPs in Mansoori and Sella rice-starch
respectively. Comparison of absorption plots based on Mie
scattering with those of experimental results showed that
diameter of AgNPs in sol statesare *11 and *16 nm for
the aforesaid rice-starches. Suspension of the AgNPs
formed by Sellaand Mansoori rice-starches was found to be
stable for more than 8 and 4 months respectively. The
particle sizes assessed by Transmission Electron Microscopy (TEM) are *11 and *12 nm for AgNPs stabilized
by Mansoori and Sella respectively. In contrast to these the
sizes measured from atomic force microscopy (AFM) for
the two are *110 and *73 nm respectively. They are
bigger than those observed under TEM. Such a change in
size can be understood by recalling that AFM is a surface
investigative tool that sees particles inclusive of starch
layer.

M. K. Singh
M. Singh
J. L. Verma
N. Kumar

R. K. Mandal (&)
Department of Metallurgical Engineering, IIT (BHU),
Varanasi 221 005, India
e-mail: rkmandal.met@itbhu.ac.in
M. K. Singh
M. Singh
J. L. Verma
N. Kumar

R. K. Mandal
DST Unit on Nanoscience and Technology, BHU,
Varanasi 221 005, India

Keywords Green synthesis
Stable silver sol

LSPR
Rice-starch

1 Introduction
The green synthesis of silver nanoparticles (AgNPs) has
attracted attention of researchers owing to their demands
for bio-medical applications [15]. One of the necessary
requirements for such applications pertains to their preparation, employing environmentally friendly and bio-medically benign chemicals to avoid possible toxic effects. In
addition to these, long term stability of AgNPs is a major
concern for the researchers [6]. The re-dispersible and
stable nanoparticles of novel metals like Ag and Cu are
expected to serve as interconnect for the next generation
devices in the area of microelectronics [7, 8]. Following
protocol of [9, 10], many researchers have studied the role
of stabilizers and accelerators [1115] on the synthesis of
metallic nanoparticles. It has been observed that addition of
NaOH in different molar concentration as an accelerator
[12], leads to change of pH of the resulting nanocrystalline
silver sol after completion of reaction. Such a change has
been attributed to hydrolysis of starch. Synthesis of nanocrystalline silver utilizing different sources of starch from
potato, corn, and maize [16, 17] have been reported in
literature.
In this investigation, hydrolysis of rice starch for getting
glucose in situ as reducing agent is utilized. The starch in
this investigation pertains to that obtained from rice gruel.
Two types of rice are used. They are grown in Uttar Pradesh (India) and are known as Sella and Mansoori. We
have studied effects of NaOH to get nanocrystalline silver
and optimized the dilution in the reactant solutions to have

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Fig. 1 UVVis evolution of MansoorinanoAg (a) and SellananoAg sols (b) along with insets showing Voigt fits of the UVVis spectra recorded
after a week time). c, d depict the variation of absorbance peaks versus time for the two sols. e, f show experimental and computer generated
absorbance of MansoorinanoAg and SellananoAg sols

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hydrolysis of rice-starch. Such an exploitation of in situ

generation of glucose from rice-starch to serve as reducing
agent for synthesis of AgNPs seems to be lacking in literature for rice. Thus, this route is environmentally friendly
and does not employ any toxic organic solvent. Attempts
have been made in literature [18] to correlate localized
surface plasmon resonance (LSPR) of silver sol with shape
and size distribution of AgNPs determined with the help of
small angle X-rays scattering (SAXS). In this communication, we have analyzed the nature of widths of absorption
peaks by finding out the Gaussian and Lorentzian contributions. The attempt has been made to correlate them with
the size and shape distribution of the nanoparticles. The
researches in the area of LSPR are being pursued from
various perspectives [1921]. They include discussion on
applications in the field of photonics, sensors, and biosensors [21]. It is expected that correlation of nature of
absorption peak with shape anisotropy may be helpful in
designing AgNPs with desired characteristics for some of
these applications.

2 Materials and Methods

Materials used for the synthesis of AgNPs included silver
nitrate (Qualigens, 99.8 %), Sella and Mansoori rice(acquired from local grocery shop), and NaOH (Qualigens,
97 %). De-ionized water was used throughout the experiments. The Toshniwal pH-meter was used for measuring
pH. The rice starch was obtained by boiling rice in water.
Two solutions namely, A and B were prepared. Former
contains 1.79 g of AgNO3 in 10 mL of water. Latter is
made with 0.65 g of NaOH in 60 mL of rice gruel. The pH
of the rice gruel obtained from Sella and Mansoori was
kept in the range of 4.55.5 and 6.06.5 respectively.
Solution B was magnetically stirred for 5 min by maintaining temperature *60 C. Solution A was then added
into solution B following protocol reported in earlier
investigations [6, 7]. The pH of the sols and various
solutions was measured. The light yellow color of solution
B changed to brown after addition of 23 drops of precursor solution indicating the start of reduction process.

Fig. 2 Selected area

diffraction patterns (a, c) and
BF-TEM images (b, d) of
MansoorinanoAg and
SellananoAg particles

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After total addition of precursor, the solution turned into a

dark brown color. The solution was left for 48 h. The sols,
thus obtained, were taken for recording UVVis spectra
with the help of PERKIN ELMER Lambda xls?. A drop of
sol was dispersed on carbon coated copper grid and air
dried. The sample on the grid, thus obtained, was observed
under FEI Tecnai20 G2 transmission electron microscope
operating at 200 kV. AFM imaging of the sol, dispersed on
a borosilicate glass substrate, was conducted with the help
of Multimode Scanning Probe Microscope (Veeco make).
To estimate the size of the nanoparticles in sol state, calculations were performed with software MiePlot v.3.4
[22]. Several calculations by changing the diameter of the
particles were made and wavelength of absorption with the

experimentally observed UVVis spectra was compared.

The initial choice of diameter of the nanoparticles as an
input in calculation was made based on TEM investigations. Further, poly-dispersed spheres in sol with standard
deviation of 30 % in these computations were assumed.

3 Results and Discussion

3.1 UVVis Spectrum of AgNPs Sols
AgNPs suspension exhibits a dark brown color owing to
LSPR, which results from collective excitation of the free
electrons in presence of visible radiations. SPR peaks can

Fig. 3 Particle size histogram of a MansoorinanoAg and b SellananoAg particles and their high magnification BF TEM showing growth twins
(arrows) in c, d respectively

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be used as a tool to estimate range of particle size and

stability of the NP suspensions. Fig. 1 shows the UVVis
spectra recorded from MansoorinanoAg and SellananoAg
sols. The nature of spectra with respect to time is depicted
to assert stability of the sol under ambient condition. The
absorption peaks range from 400407 nm and 412414 nm
for MansoorinanoAg and SellananoAg sols respectively.
UVVis results show stability of the sols up to 4 and
8 months for the AgNPs stabilized by Mansoori and Sella
starches respectively.
As mentioned above, the wavelength corresponding to
absorption peak kmax values changes from 400 nm (t = 0)
to 407 nm (4 months) indicating a red shift as a result of
slight amount of agglomeration (cf. Fig. 1c) in MansoorinanoAg sol. Absorbance reduced significantly and it
may be attributed to the decreased AgNPs concentration in
the sol with respect to time. The reduced concentration of
AgNPs in the sol could be the result of agglomeration that

was seen in the bottom of the test tube. This will be

explained further after presenting results of TEM. The
SellananoAg sol was found to be stable for 8 months. The
evolution of UVVis spectra is shown in the Fig. 1b. There
was slight change in kmax values (from 414 to 412 nm) for
the period of 8 months (cf. Fig. 1d). The decrease in
absorbance was marginal with respect to time (cf. Fig. 1b).
This AgNPs sol appears to be more stable than that of
MansoorinanoAg sol. Stability of the two sols can be
explained by invoking viscosity of the two rice-starches
utilized in the present study. The viscosity of starch is a
complex function of two basic units viz. amylose and
amylopectin [23]. It was observed that under similar conditions of starch extraction of the two rice (Sella and
Mansoori), the Sella based starch was more viscous than
that of Mansoori. The availability of amylose for hydrolysis is more abundant in case of Mansoori. This facilitates
reaction kinetics of nucleation of AgNPs during chemical

Fig. 4 AFM image of a MansoorinanoAg particles, b SellananoAg particles and their corresponding particle size distribution histograms in c,
d respectively

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reduction. This is reflected in the blue shift in UVVis

spectra vis-a`-vis that of Sella. AgNPs capped by thin layers
of starch owing to less viscous Mansoori rice-starch
compared to Sella one which is more viscous and hence
presents thicker layers of starch for the capping of AgNPs.
Thick layers of starch provided by Sella rice may enhance
the stability of SellananoAg sol.
From the Mie scattering calculations, we found that for
MansoorinanoAg sol, best fit between the experimental and
theoretical results was obtained for particle diameter of
11 nm. This is found in conformity with that measured
from TEM micrographs. Both absorbance curves (theoretical and experimental) for MansoorinanoAg sol are shown
in the Fig. 1e. The best fit of the absorption peak for SellananoAg sol was obtained for particle diameter of
16 5 nm. Figure 1f depicts the theoretical and experimental absorbance curves for SellananoAg sol.
3.2 TEM Analysis of AgNPs Sols
The polycrystalline diffraction pattern and a representative
bright field image from MansoorinanoAg sample are
shown in Fig. 2a and b respectively. The diffraction rings
could be indexed as (111), (200), (220), and (311) of FCC . We note presence
silver having lattice parameter *4.03 A
of sharp spots along with the rings. This may be due to the
presence of preferred orientations of some of the particles
with sharp faces (arrow marked in Fig. 2b). Figure 2c and
d display respectively the diffraction rings and a representative bright field image from the SellananoAg sample.
The rings belong to FCC silver with a lattice parameter of
. Unlike Fig. 3a, we do not see spots around the
*4.03A
polycrystalline rings in Fig. 3c. This indicates random
growth directions of nanocrystalline particles. Thus, uniform shape and size distribution in SellananoAg sample is
seen (cf. Fig. 2d). The average particle size of MansoorinanoAg and SellananoAg was found to be 11 3 nm and
12 3 nm respectively. The size distribution is depicted
by histogram in Fig. 3a and b respectively. TEM average
diameter was calculated by measuring 200 particles for
both the samples in random fields of TEM view. The high
magnification images given in Fig. 3c and d clearly bring
out the presence of twins in both of them (indicated by
arrow). This is consistent with earlier observations of
growth twins in nanocrystalline silver. The shape anisotropy in Fig. 3c is noted for MansoorinanoAg sample but
not in the Sella one (see Fig. 3d).
3.3 Morphologies of MansoorinanoAg
and SellananoAg Particles
The AFM surface morphologies of the AgNPs stabilized by
Mansoori and Sella are shown in the Fig. 4a and b

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respectively. The lateral size was measured using 50 nanoparticles from both MansoorinanoAg and SellananoAg
samples. The average particle size for MansoorinanoAg and
SellananoAg samples was found to be 110 23 nm and
73 23 nm which is larger in comparison to that observed
in TEM. This can be understood by recalling that AFM is a
tool to investigate the surface that will see, in this case starch
layers in the sample also. This is not the case for TEM.
For analyzing the nature of absorption peaks for the two
sols, we have fitted Lorentzian and Gaussian profiles. They
are shown as insets in Fig. 1ab. The width of the
absorption peak for MansoorinanoAg sol has both the
components whereas SellananoAg sol displays only
Gaussian component. The facetted particles in the former
sol may be giving rise to both types of contributions to
peak profiles. The predominant Gaussian component in the
SellananoAg sol may be attributed to random and isotropic
scattering of electromagnetic radiations from its surface.
Following above argument, we conclude that MansoorinanoAg sol has a mixture of random and isotropic as
well as anisotropic surface scattering by electromagnetic
radiations. This correlation is in agreement with our
assertion made in Sect. 3.2. The stability of NanoAgsol is
important for its potential uses in interconnect [7, 8] apart
from increasing its shelf-life for bio-medical applications.

4 Conclusions
We have synthesized AgNPs by utilizing rice-starch to
serve as stabilizer and reducing agent in presence of NaOH.
Glucose released during starch-hydrolysis acted as reducing agent. The MansoorinanoAg and SellananoAg sols
were found stable respectively for 4 and 8 months under
ambient condition.The particle size as measured by TEM
*11 and *12 nm for the MansoorinanoAg and SellananoAg samples respectively. The particle sizes measured
from AFM images are *110 and *73 nm for the two sols.
They are bigger than those observed under TEM. Such a
change in size can be understood by recalling that AFM is a
surface investigative tool that sees particles inclusive of
starch layer. Thus, we have successfully shown formation
of stable NanoAg sol by employing environmentally
friendly route of synthesis.
Acknowledgments Manjri Singh, SMIT of Sikkim Manipal University, Jaya Lakshmi Verma and Nitish Kumar from Central University of Jharkhand thank the Head of Department of Metallurgical
Engineering,IIT(BHU), Varanasi as well as Programme Co-ordinator
of Unit on Nanoscience and Technology, BHU for having permitted
to carry out this investigation on BHU campus. One of us (RKM) is
grateful to his IDD part IV students for carrying out experiments
suggested by him. He also thanks Department of Science and Technology, Government of India, New Delhi for support under NSTI
program.

Trans Indian Inst Met

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