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DEPARTMENT OF PHYSICS
ON
TAPAS MANDAL
PINTU MANDAL
PRASENJIT GHOSH
SUMANTA PAYIN
MANIK DAS
UJJAL JANA
UNDER THE GUIDANCE OF
Certificate
(To Whom It May Concern)
Date: Signature………………………
Place: Dr. AMIT KUMAR BHUNIA
Associate Professor
DEPARTMENT OF PHYSICS
BANKURA UNIVERSITY
BANKURA
INTRODUCTION
Silver is a chemical element with the symbol Ag (from the Latin
Argentinum , derived from the proto-indo-European h2erg “shiny or
white”) and atomic number 47 .A soft white ,iustrous transition
metal, it exhibits the highest electrical conductivity ,thermal
conductivity , and reflectivity of any metal. The metal is found in the
Earthis crust in the pure, free elemental form (“native silver”) , as an
alloy with gold and other metals, and minerals such as argentite and
chlorargyrite. Most silver is produced as a byproduct of copper, gold,
lead, and zinc refining.
SILVER IN PERIODIC TABLE:
Atomic number (Z) : 47
Group : group 11
Period : period 5
Block : d-block
Element category : transition metal
Electron configuration : [kr] 4d 5s
Electrons per shell 2,8,18,18,1
BASIC PROPERTIES OF SILVER
Phase at STP Solid
Melting point 1234.93K
Boiling point 2435K
Density(near r.t) 10.49 g/cm3
Electronegativity Pauling scale : 1.93
Atomic radius Empirical : 144 pm
Natural occurance Primordial
Crystal structure Face centered cubic(FCC)
Thermal conductivity 429W/m.K
Electrical resistivity 15.87 nano-ohm (at 20C)
Magnetic ordering Diamagnetic
Mohs hardness 2.5
Magnetic susceptibility -19.5*10(-6) cm3/mol (at 296 K)
Thermal diffusivity 174 mm2/s (at 300 K)
Poison ratio 0.37
NANOMATERIALS
Definition of nano-particle
A particle having one or more dimension of the order of 100 nm or
less is called nano-particles. A nanometer is one millionth of a
millimeter approximately 100000 times smaller than the diameter of
the human hair. Nano-materials are of interest because at this scale
unique optical , magnetic , electrical , and other properties emerge
from the properties of the bulk material. This makes the size of
particles or the scale of it’s features the most important attribute of
nano-particles .
NANO STRUCTURE AND THEIR ASSEMBLE
Nano structure size Material
Clusters, Nano Radius 1-10 nm Insulators ,
crystals , quantum semiconductors,
dots Metals, Magnetic
materials
Nano biomaterials Radius 5--10 nm Membrane protein
photosynthetic
reaction centre
Nano-wiress Diameter 1-100 nm Metals ,
Semiconductors,
Oxide, Sulphides,
Nitrides.
Nanotubers Diameter 1-100 nm Carbon, Layred
Chalcogenides, BN,
Gan
Nanobiorods Diameter 5 nm DNA
Two dimensional Area several square Metals ,
array of nano- nm semiconductors,
particles Magnetic materials
Surface and thin Thickness 1-10 nm Insulators ,
films Semiconductor
metals.
Three dimensional Several nm in three Semiconductors,
super lattice of the dimension Metals , Magnetic
nano-particles materials.
There is no strict dividing line Between nanoparticles and non nanoparticles. The
size at wich materials display different properties to the bulk material is
materialdependant and can certainly be claimed for many material much larger in
size than 100nm.
Definitions certainly become more difficult for materials that are a very long way
from being a sphere, such as carbon nanotubes for example. One of the aims for
these materials is to grow them into long tubes, certainly not ‘nano’ in length, but
as they have a diameter in the order of 3mm for a single walled tube,they have
properties that distinguish them form other allotropes of carbon, and hence cen
be described as ‘nanomaterials’.
This sort of nanomaterial has led to the extension of the idea of nanomaterials
being considered as such if any one of their structural fectures is on a scale of less
than 100mm, that cause their properties to be different from that of the bulk
material.
If the nanoparticles need to kept separate, than they must be prepared and stored
in a liquid medium designed to facilitate sufficient interparticle repulsion forces
to prevent aggregation.
Quantum confinement:
Quantum confinement is a change of electronic and optical
properties when the material sample is of sufficiently small size-typically 10
nanometers or less. The bandgap increases as the size of the nanostructure
decreases.Specifically, the phenomenon results from electrons and holes being
squeezed into a dimension that approaches a critical quantum measurement,
called the exciton Bohr radious.
NANOSILVER:
One of the substances used in nanoformulation is silver (nanosilver). Due to its antimicrobial
properties, silver has also been incorporated in filters to purify drinking water and clean swimming
pool water. To generate nanosilver, metallic silver has been engineered into ultrafine particles by
several methods; include spark discharging, electrochemical reduction, solution irradiation and
cryo- chemical synthesis [67]. Nano-silver particles are mostly smaller than 100 nm and consist of
about 20-15,000 silver atoms [67]. In addition, nanostructures can be produced as tubes, wires,
multifactes or films. At the nano-scale, the silver particles exhibit deviating physico-chemical
properties (like pH dependent partitioning to solid and dissolved particulate matters) and
biological activites compared with the regular metal [68].This is due to the higher surface area
per mass, allowing a larger amount of atoms to interact with their surroundings. Due to the
properties of silver at the nanoscale, nanosilver is nowadays used in an increasing number of
consumer and medical products. Because, silver is a soft white lustrous element, an important
use of silver nanoparticles is to give a products a silver finish. Still, the remarkably strong
antimicrobial activity is the major direction for development of nano-silver products. Examples
are food packaging materials and food supplements, odour-resistant textiles, electronics,
household appliances, cosmetics and medical advices, water disinfectants and room sprays.
Figure 4. (a) Real and (b) imaginary part of permittivities of the metal
candidates Ag, Au, Na K, and Al [36]. (c) Quality
factor of plasmon resonances of a metal nanostructure as a function of plasmon
frequency for two commonly used metals:
silver (dashed line) and gold (dotted line) [37].
Figure 5. (a) Localized surface plasmon resonance of Ag, Au, and Cu that covers most of the visible and near-infrared
wavelength range of sunlight [38]. (b) Comparative UV/Vis diffuse-reflectance spectra of (a) AgCl, (b) Ag@AgCl, and ( c )
N-TiO2
(soap, shampoo, textile, disinfecting medical devices and home appliances to water treatments)
with the highest degree of commercial value.
Recently, many techniques have been used for the synthesis of Ag-NPs by using chemical, physical,
photochemical, and biological methods. Each method has its pros and cons with common problems
of cost, scalability, uniform particle size, and the size distribution. Traditionally, metal
nanoparticles are produced by physical methods like ion sputtering or pulsed laser ablation and
chemical methods such as reduction, solvothermal synthesis, hydrothermal, sol-gel methods, and
so on. However, recently, the environmentally friendly synthesis methods (by using natural
products) have been developed under the branch of “green syntheses.” Depending upon the
selected path of synthesis and different experimental conditions, the silver NPs of different
morphology, sizes, and shapes can be obtained. Nevertheless, the most important criteria is the size
distribution that should be achieved as narrow as possible for the targetspecific applications [69].
Four important methods (chemical, physical, photochemical, and biological) for the synthesis of
nanoparticles are discussed as follows.
Chemical method
Among the existing methods, the chemical methods have been most common used for the
production of Ag-NPs. The chemical reduction of metal ions is the most universal and easy route
for the preparation of the metal nanoparticles.There are different types of chemical method-
Polyol process
Monodispersed solution of silver nanocubes were synthesized in large quantities by reducing silver
nitrate with ethylene glycol in the presence of the capping agent polyvinylpyrrolidone (PVP) [79],
which is an example of the so-called polyol process. In this case, ethylene glycol served as both
reducing agent and solvent. It shows that the presence of PVP and its molar ratio relative to silver
nitrate along with other additive formaldehyde, NaOH, played important roles in finalizing the
geometric shape and size of the product. It suggested that it is possible to tune the size of silver
nanocubes by controlling the experimental conditions.
Figure 11. (a) Polygonal (mainly triangular) silver nanoprisms were synthesized by boiling AgNO3 in N, N- dimethyl
formamide and PVP, [88] (b) TEM image of as-formed silver colloids and the corresponding particle size distribution
histogram and (c) UV-Vis spectrum of 150-fold diluted PQ-11 supported Ag NP solution of the dispersion synthesized at 100C
and 60min [89].
precursor solution into a hot solution is an effective mean to induce rapid nucleation in a short
period of time, ensuring the fabrication of Ag-NPs with a smaller size and a narrower size
distribution. Spherical Ag-NPs with a controllable size and high monodispersity were synthesized
under the polyol process with the help of the modified precursor injection technique. AgNPs of the
size 17 2 nm were obtained at an injection rate of 2.5 mLs1 along with the reaction temperature
100C. Nearly, monodisperse Ag-NPs have been prepared in a simple oleylamine-liquid paraffin
system [82] by using this technique.
Physical method
In the physical synthesis process of Ag-NPs, usually, the physical energies ( thermal, ac power, and
arc discharge) are utilized to produce Ag-NPs with a narrow size particle distribution. This
approach can permit us to produce large quantities of Ag-NPs samples in a single process. Under
the physical methods, the metallic NPs can be generally fabricated by evaporation-condensation
process that could be carried out in a tube furnace at atmospheric pressure. The large space of tube
furnace, consumption of large amount of energy, raising the environmental temperature around the
source material and a lot of time for achieving thermal stability, are the few drawbacks of the
method. Another physical method of synthesis of Ag-NPs is a thermal decomposition method that
used to synthesize the powdered Ag-NPs [90]. In particular case, Ag-NPs (particles with particle
size of 9.5 nm with a standard deviation of 0.7 nm) were formed by thermal decomposition of a
Ag1+– oleate complex, at high temperature of 290C. This indicates that the Ag-NPs were prepared
with a very narrow size distribution. Jung et al. [91] reported a small ceramic heater (with a local
heating area) for synthesizing the metal NPs and by evaporating the source materials under the
flow of carrier gas, i.e., air. It had been reported that the geometric mean diameter, the geometric
standard deviation, and the total concentration of spherical NPs without agglomeration increases
with the temperature of the surface of the heater. The testimony given by Tien et al. [92] reveal the
fabrication technique for the Ag-NPs by employing the electrical discharge machining (EDM)
without addition of any surfactants. Where, pure silver wires were submerged in deionized water
and treated as electrodes. The stability of suspension, concentration of particles, particle size,
solution properties, electric conductivity, and pH are the factors that may affect the synthesis of
NPs by enhancing the complex interactions to the nanofluid, in the form of van der Waals
combination force and electrostatic Coulomb repulsion force. Metallic Ag-NPs of the 10 nm size
and ionic silver of approximate concentrations 11–19 ppm were obtained by silver rod at the
consumption rate ~ 100mgmin1. More recently, Siegel et al. [93] reported an unconventional
approach for the physical synthesis of gold-NPs and Ag-NPs by the direct metal sputtering into the
liquid medium ( glycerol-to-water ).
Photochemical synthesis
Biological synthesis
This method of biosynthesis is very simple, requiring less time and energy in comparison to the
physical and chemical methods with predictable mechanisms. The other advantages of biological
methods are the availability of a vast array of biological resources, a decreased time requirement,
high density, stability, and the ready-to-soluble as-prepared nanoparticles in water [103].
Therefore, biogenic synthesis of metal NPs unwraps up enomorus opportunities for the use of
biodegradable or waste materials.
Figure 13. Biogenic synthesis of metal nanoparticle of various shape and size using microorganisms and plant tissues
extracts.
Dentistry
Additive in polymerizable dental materials
Patent
Silver-loaded SiO2 nanocomposite resin
filler (Dental resin composite)
Polyethylene tubes filled with fibrin
sponge embedded with Ag NPs dispersion
Food industry
Silver nanoparticles are already utilized for various applications in areas such as food
supplements, food packaging, and functional food ingredients. To protect the food from dust,
gases (O2, CO2), light, pathogens, moisture nanocomposite LDPE films containing Ag and ZnO
nanoparticles packaging, would be a safer, inert; cheaper to produce, easy to dispose and reuse-
way
Catalyst
In recent years, one of the most important applications of the AgNPs has been observed in
catalysis of chemical reactions. Nanosilver catalysts’ with their unique reactivity and selectivity,
stability, as well as recyclability in catalytic reactions with atom-economy and environmental
benign nature, increases the interest in nanosilver-mediated organic synthesis in the last few
years.
Drinking water purification
Studies supported that the silver nanoparticle (AgNP) can work as an excellent antiviral,
antimicrobial, and disinfectant agents. The results obtained showed that silver nanoparticles in
surface water, ground water, and brackish water are stable.
Bioaerosols are airborne biological origins such as viruses, bacteria, fungi, which are capable of
causing infectious, allergenic, or toxigenic diseases. Large quantities of these bioaerosols were
accumulated on the filters of heating, ventilating, and air-conditioning (HVAC) systems [138]. It
often resulted in the low quality of indoor air. The WHO estimated that 50% of the biological
contamination present in indoor air comes from filter-medium after air filtration, which can add on
microbial growth. These pathogens generate mycotoxins which are dangerous to human health. To
reduce the microbial growth in air filters, Ag-deposited-activated carbon filters (ACF) were
effectively used for the removal of bioaerosols. Antibacterial activity analysis of Ag-coated ACF
filters was checked for Bacillus subtilis and E. coli [138]. It was found that above two bacteria were
completely inhibited the physical properties of ACF filters such as pressure drop and filtration
efficiency with in 10 and 60 min, respectively.
Instrumentations
UV-VIS- SPECTROMETER
The optical absorption spectra of the nanocrystalites were measured using a UV spectrometer.
The diagrams of the components of a typical spectrometer is shown in the following figure.
Figure 1
The functioning of this instrument is relatively straightforward. A beam of light from a visible and UV
light source (coloured red) is separated into its component wavelengths by a prism or a diffraction
grating. Each monochromatic (single wavelength) beam in turn is split into two equal intensity beams
by a half mirrored device. One beam the sample beam (coloured magneta), passes through a small
transparent container (cuvette) the compound being studied in transparent solvent. The other beam, the
reference (coloured blue), passes through an identical cuvette containing only the solvent. The
intensities of these light beams are then measured by electronic detectors and compared. The intensity
of the reference beam, which should have suffered little or no light absorption is defined as 𝐼0 . The
intensity of the sample beam is defined as I. Over a short period of time, the spectrometer automatically
scans all the component wavelengths in the manner described.
The sample was dispersed for 15 min. Then to draw baseline alcohol was taken in glass tube. To
get the optical absorption spectra we take alcohol in one glass tube and sample in other glass tube.
The crystalline structure, size, and shape of the unit cell and the crystallite size of a material can be
determined using X-ray diffraction spectroscopy (XRD). Usually, X-ray diffraction peaks were
observed at 2θ = 38.00, 44.16, 64.40, and 77.33, which correspond to (111) , (200), (220), and
(311) Bragg’s reflections of the face-centered cubic (fcc) structure of metallic silver, respectively
(standard JCPDS card No. 04-0783 or 87-0597). The crystalline size of the particulate can be
estimated by using the Debye-Scherrer formula d = 0.89λβcosθ, where d is the particle size, λ is
the wavelength of Xray radiation (1.5406 Å), β is the full-width at halfmaxima (FWHM) of the
strongest peak (in radians) of the diffraction pattern and 2θ is the Bragg angle [104].
TRANSMISSION ELECTRON MICROSCOPE
Transmission electron microscope (TEM) are microscope that use a particle beam of electron
to visualize specimen and generate highly magnified image. TEMs can magnify object up to
two million times in order get a better idea of just how small that is ,think of how small a cell
is. It is no wonder TEMs have become so valuable within the biological and medical fields.
WORKING PRINCIPLE
TEMs employ a high voltage electron beam in order to create an image. An electron gun at
the top of a TEM emits electrons that travel through the microscope’s vacuum tube. Rather
than having a glass lens focusing the light (as in the case of light microscopes), the TEM
employs an electromagnetic lens which focuses the electrons into a very fine beam. This
beam then passes through the specimen with its assorted parts shown in different shades
according to its density appears on the screen. This image can be then studied directly within
the TEM or photographed. Figure 1 shows a diagram of a TEM and its basic parts.
Grown of Ag NPs
The silver nanoparticles are grown by simple chemical method. We used sodium borohydride
(NaBH4, 99.9%) as a reducing agent for reduction of Ag from AgNO3 solution. NaBH4 solution (30
mM, 10 ml)) was added drop wise into 20mL of AgNO3
Size Dependent Plasmonics of Chemically Grown Silver Nanoparticles solution (40 mM) that had
been chilled in an ice bath. The reaction mixture was stirred vigorously by a magnetic stirrer. The solution
turned light yellow after the addition of 1mL of NaBH4, and a yellow when all of the NaBH4 was added.
The entire addition took ~30min, after which the stirring was stopped. After 30 min reaction time the
solution color is yellow brownish. The colloidal silver was stable at room temperature and was stored in a
transparent vial. Similarly three different colloidal silver was prepared by changing the reaction time. The
reaction times are 40 min, 60 min and 90 min for other three Ag NPs colloidal solutions. The color of the
40 min reaction Ag NPs colloid is deep yellow brownish. The color of the 60 min and 90 min reaction
colloid solutions are yellow and faint yellow respectively.