Thermal and Rheological Measurement

Techniques for Nanomaterials

Characterization. A volume in Micro and
Nano Technologies 1st Edition Edition
Sabu Thomas
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 Thermal and Rheological
Measurement Techniques for
Nanomaterials Characterization
Volume 3
Edited by
Sabu Thomas
Raju Thomas
Ajesh K. Zachariah

Raghvendra Kumar Mishra

Elsevier
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List of Contributors
Jiji Abraham
Mahatma Gandhi University, Kottayam, India
Elaheh Allahyari
Mahatma Gandhi University, Kottayam, India; Islamic Azad University, Tehran, Iran
Gudimamilla Apparao
Acharya Nagarjuna University, Guntur, India
Jayesh Cherusseri
Mahatma Gandhi University, Kottayam, India
Cintil Jose Chirayil
Newman College, Thodupuzha, India
Soney C. George
Amal Jyothi College of Engineering, Kottayam, India
Gurram Giridhar
Acharya Nagarjuna University, Guntur, India
Jose James
St. Joseph’s College, Moolamattom, India
Karingamanna Jayanarayanan
Amrita Vishwa Vidyapeetham, Amrita University, Coimbatore, India
Nandakumar Kalarikkal
Mahatma Gandhi University, Kottayam, India
Obey Koshy
Mahatma Gandhi University, Kottayam, India
Sravanthi Loganathan
Mahatma Gandhi University, Kottayam, India
R.K.N.R. Manepalli
The Hindu College, Machilipatnam, India
Raghvendra Kumar Mishra
Mahatma Gandhi University, Kottayam, India; Indian Institute of Space Science and
Technology, Thiruvananthapuram, India
Oluwatobi S. Oluwafemi
University of Johannesburg, Johannesburg, South Africa
G. Pugazhenthi
Indian Institute of Technology Guwahati, Guwahati, India
Nanoth Rasana
Amrita Vishwa Vidyapeetham, Amrita University, Coimbatore, India

xi
xii List of Contributors

El Hadji Mamour Sakho

Mahatma Gandhi University, Kottayam, India
Ashin Shaji
Mahatma Gandhi University, Kottayam, India
Lakshmanan Subramanian
Amrita Vishwa Vidyapeetham, Amrita University, Kollam, India
Sabu Thomas
Mahatma Gandhi University, Kottayam, India
Ravi Babu Valapa
Centre for Biopolymer Science and Technology, A Unit of Central Institute of Plastics
Engineering and Technology (CIPET), Kochi, India
Ajesh K. Zachariah
Mar Thoma College, Tiruvalla, India
Editor Biographies
Professor (Dr.) Sabu Thomas is the Director of International and
Interuniversity Center for Nanoscience and Nanotechnology, Mahatma
Gandhi University, Kottayam, Kerala, India. He is also a full professor of
Polymer Science and Engineering and School of Chemical Science of the
same University. He is a fellow of many professional bodies. Professor
Thomas has co-authored many papers in international peer-reviewed
journals in the area of polymer processing. He has organized several
international conferences. Professor Thomas’s research group is in
specialized areas of polymers, which includes polymer blends, fiber-filled
polymer composites, particulate-filled polymer composites and their
morphological characterization, aging, and degradation, pervaporation
phenomena, sorption, and diffusion, interpenetrating polymer systems,
recyclability and reuse of waste plastics and rubbers, elastomeric cross-
linking, and dual porous nanocomposite scaffolds for tissue engineering.
Professor Thomas’s research group has extensive exchange programs with
different industries, research, and academic institutions all over the world
and is performing world-class collaborative research in various fields. The
Professor’s Center is equipped with various sophisticated instruments and
has established state-of-the-art experimental facilities which cater to the
needs of researchers within the country and abroad. He has more than 700
publications, 50 books, H Index-78 and 3 patents to his credit. He is a
reviewer to many international journals. Professor Thomas has attained
5th Position in the list of Most Productive Researchers in India in 2008e16.

Professor (Dr.) Raju Thomas is currently Vice Chancellor of Middle East

University FZE, Al Hamra, Ras Al Khaimah, United Arab Emirates.
Dr. Thomas started his Professorship from the Research and Postgraduate
Department of Chemistry, Mar Thoma College, Thiruvalla-3, Kerala,
India. Dr. Thomas procured his PhD under the supervision of Professor
(Dr.) Sabu Thomas, Director of International and Interuniversity Center
for Nanoscience and Nanotechnology, Mahatma Gandhi University,
Kottayam, Kerala, India. He has extensive research experience in
Nanoscience and Nanotechnology. He has 12 years of research experience
in the Organic Chemistry and Polymer Chemistry laboratories of the
School of Chemical Sciences, Mahatma Gandhi University, Kottayam,
Kerala, India. He has also worked in the laboratory of Applied Rheology
and Polymer processing of Katholieke University, Leuven, Belgium, and
in the laboratory at Leibniz Institute of Polymer Research, Dresden,

xiii
xiv Editor Biographies

Germany. He has widely studied the kinetics of curing, morphology

development, and structural characteristics of in situ-cured
nanocomposites based on epoxy resin and reactive rubbers. His research is
reflected in his six published research articles in international journals, and
additional articles which are currently under review. In addition, many
articles have been published in popular journals. He has co-authored many
chapters and is co-editor of a book entitled Micro and Nanostructured
Epoxy/Rubber Blends which was recently published by Wiley and Sons.
He has attended many national and international seminars/conferences and
presented many research papers. He is an approved research guide in
Chemistry at Mahatma Gandhi University, Kottayam, India and has
availed projects from University Grants Commission (UGC), Department
of Science and TechnologyeScience and Engineering Research Board
(DSTeSERB) and Kerala Science Council for Science, Technology, and
Environment (KSCSTE).

Dr. Ajesh K. Zachariah is working as Assistant Professor in the

Department of Chemistry, Mar Thoma College, Kerala, India. He has
many publications in the field of materials chemistry, and polymer
nanocomposites and has one national patent. He is an expert in
sophisticated techniques such as Atomic Force Microscopy (AFM), X-ray
diffraction Technique (XRD), Gas Permeability Tester, and Dynamic
Mechanical Analyzer (DMA). He has many years’ experience in the field
of nanoscience and nanotechnology.

Raghvendra Kumar Mishra is currently working as Senior Research

Fellow at the International and Interuniversity Center for Nanoscience and
Nanotechnology, Mahatma Gandhi University, India. He has received
India’s most prestigious Visvesvaraya Research Fellowship, and he is
currently serving as Visvesvaraya Fellow. He has widely studied the
processing of blends, in situ generation micro- and nanofibrillar
composites, electromagnetic shielding effect of nanocomposites,
decorating and alignment of carbon nanotubes, and thermal, dynamic
mechanical, and structural relationships in polymer blends and
nanocomposites. He has won several awards from different organizations
and technology events. He is serving as reviewer in many international
journals, for example, Environmental Chemistry Letters (Springer). He has
research experience in Mechanical Engineering, Materials Science and
Technology, and Nanoscience and Nanotechnology. His areas of research
are multidisciplinary, which include thermodynamics, heat transfer,
refrigeration and air-conditioning, fluid mechanics, machine design, solid
mechanics, machine theory, power plant engineering, metal and ceramic
 Editor Biographies xv

processing. In addition, he specializes in polymers, which include polymer

recycling, polymer blends, fiber-filled polymer composites, particulate-
filled polymer composites and their morphological characterization, aging
and degradation, nanomaterials e.g., metallic, metallic oxide, carbon
nanotubes, graphene, conducting polymer blends, composites and
nanocomposites, biodegradable polymer blends and composites. He has
expertise in sophisticated characterization techniques such as dynamic
mechanical analyzer, differential scanning calorimetry, thermogravimetric
analysis, spectroscopy, vector network analyzer, scanning electron
microcopy, and atomic force microscopy (AFM).
 Instrumental Techniques for the
Chapter
1
Characterization of Nanoparticles
Cintil Jose Chirayil1, Jiji Abraham2, Raghvendra Kumar Mishra2,
Soney C. George3 and Sabu Thomas2
1
Newman College, Thodupuzha, India; 2Mahatma Gandhi University, Kottayam, India; 3Amal Jyothi College
of Engineering, Kottayam, India

CHAPTER OUTLINE
1.1 Nanotechnology and Nanomaterials 2
1.2 Classification of Nanomaterials 3
1.3 Advantages and Disadvantages of Nanomaterials 4
1.4 Opportunities Presented by Nanomaterials 5
1.5 Characterization Techniques of Nanomaterials 5
1.5.1 Optical (Imaging) Characterization Techniques 6
1.5.1.1 Confocal Laser-Scanning Microscopy 6
1.5.1.2 Scanning Near-Field Optical Microscopy 8
1.5.1.3 Two-Photon Fluorescence Microscopy 10
1.5.1.4 Dynamic Light Scattering 10
1.5.1.5 Brewster Angle Microscopy 11
1.5.2 Electron Probe Characterization Techniques 13
1.5.2.1 Scanning Probe Electron Microscopy 13
1.5.2.2 Electron Probe Microanalysis 14
1.5.2.3 Transmission Electron Microscopy 15
1.5.2.4 Scanning Transmission Electron Microscopy 17
1.5.3 Photon Probe Characterization Techniques 18
1.5.3.1 Photoelectron Spectroscopy 18
1.5.3.2 UVeVisible Spectroscopy 19
1.5.3.3 Atomic Absorption Spectroscopy 20
1.5.3.4 Inductively Coupled Plasma Spectroscopy 20
1.5.3.5 Fluorescence Spectroscopy 20
1.5.3.6 Localized Surface Plasmon Resonance 21
1.5.4 Ion Particle Probe Characterization Techniques 22
1.5.4.1 Rutherford Backscattering 22
1.5.4.2 Small-Angle Scattering 22

Thermal and Rheological Measurement Techniques for Nanomaterials Characterization. http://dx.doi.org/10.1016/B978-0-323-46139-9.00001-3

Copyright © 2017 Elsevier Inc. All rights reserved. 1
2 CHAPTER 1 Instrumental Techniques for the Characterization of Nanoparticles

1.5.4.3 Nuclear Reaction Analysis 23

1.5.4.4 Raman Spectroscopy 24
1.5.4.5 X-Ray Diffraction 25
1.5.4.6 Cathodoluminescence 26
1.5.4.7 Nuclear Magnetic Resonance Spectroscopy 27
1.5.4.8 Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass
Spectrometry 28
1.5.5 Thermodynamic Characterization Techniques 29
1.5.5.1 Thermogravimetric Analysis 29
1.5.5.2 Differential Thermal Analysis 29
1.5.5.3 Evolved Gas Analysis 30
1.5.5.4 Differential Scanning Calorimetry 30
1.5.5.5 Nanocalorimetry 30
1.5.5.6 BrunauereEmmetteTeller Method 31
1.5.6 Other Important Techniques 31
1.5.6.1 Nanoparticle Tracking Analysis 31
1.5.6.2 Tilted Laser Microscopy 31
1.5.6.3 Turbidimetry 31
1.5.6.4 Field-Flow Fractionation 32
1.5.6.5 Size-Exclusion Chromatography 32
1.5.6.6 Hydrophobic Interaction Chromatography 32
1.5.6.7 z Potential Measurements 34
1.6 Conclusions 34
Acknowledgment 34
References 34

1.1 NANOTECHNOLOGY AND NANOMATERIALS

Nanotechnology is the art and science of handling matter at the nanoscale
(down to 1/10,000,000 the width of a human hair) to create new and unique
materials and products with properties that differ significantly from those on
a larger scale [1]. Early developments in nanotechnology were initiated by
Nobel Laureate Richard Feynman, who introduced the idea of molecular ma-
chines in 1959. The importance of nanotechnology comes from the
tunability of material properties by assembling such materials at the nano-
scale level. Norio Taniguchi’s 1974 paper is the first scientific publication
in which the term “nanotechnology” was used [2]. Now nanotechnology
can be identified as the driving force behind the industrial revolution. Owing
to its enormous potential to change society, both public and private sectors
are spending a lot of money on this new technology. At the same time, sci-
entists have anxieties about the adverse effects of the basic building blocks
of nanotechnologiesdparticles smaller than one-billionth of a meterdon
health and the environment. By using nanotechnology we can design,
 1.2 Classification of Nanomaterials 3

characterize, produce, and apply nanostructures, nanodevices, and nanosys-

tems by controlling shape and size at the nanometer scale. A nanometer is
one-billionth of a meter. The difference in the properties of materials at
nanoscale compared to bulk is due to two main reasons. First is the increased
chemical reactivity of nanomaterials due to their large surface area compared
to bulk. The second is the quantum confinement effect. A nanomaterial is an
object that has at least one dimension on the nanometer scale (approximately
1e100 nm). There are several ways to classify nanomaterials based on their
origin, dimensions, and structural configuration.

1.2 CLASSIFICATION OF NANOMATERIALS

According to their origin nanomaterials are classified as follows:
1. Natural nanomaterials
Natural nanomaterials belong to the natural nanoworld and originate
from animals or minerals without any human modification or
processing. Some important examples of natural nanomaterials
include inorganic natural nanomaterials (minerals, clays, etc.),
natural carbon nanoparticles (diamond and graphite), nanoparticles
from space, nanomaterials from the animal and plant kingdoms
(cotton, collagen, bacterial fibers, exoskeleton, and endoskeleton),
and nanomaterials in insects (chitin, sponge fibers) [3].
2. Artificial nanomaterials
These are fabricated by experimental and well-defined mechanical
and fabrication processes. Examples include carbon nanotubes,
graphene, metal oxides, quantum dots, etc.
According to their number of dimensions, which are not confined to the
nanoscale range (<100 nm), nanomaterials are classified as follows:
n Zero-dimensional
For this kind of material all the dimensions measured are within the
nanosize range. The most common demonstration of zero-
dimensional nanomaterials is nanoparticles. They are amorphous or
crystalline, single crystalline or polycrystalline; composed of single
or multiple chemical elements; exist individually or incorporated in a
matrix; exhibit various shapes and forms; and can be metallic,
ceramic, or polymeric.
n One-dimensional
For these materials one dimension is outside the nanoscale, which
leads to needle-like-shaped nanomaterials. One-dimensional
materials include nanotubes, nanorods, and nanowires.
4 CHAPTER 1 Instrumental Techniques for the Characterization of Nanoparticles

n Two-dimensional
Two of the dimensions are not confined to the nanoscale in two-
dimensional materials and they exhibit a plate-like geometry. Two-
dimensional nanomaterials include nanofilms, nanolayers, and
nanocoatings. Thickness is in the nanometer range.
n Three-dimensional
Bulk nanomaterials are materials that are not confined to the
nanoscale in any dimension. These materials are thus characterized
by having three arbitrary dimensions above 100 nm. Three-
dimensional nanomaterials can contain dispersions of
nanoparticles, bundles of nanowires, and nanotubes as well as
multiple nanolayers.
According to their structural configuration nanomaterials can be classified
into four types:
1. Carbon-Based Nanomaterials
Carbon-based materials have captured broad interest in the materials
science community for decades because of the versatility and
extremely low weight of carbon. Examples include carbon
nanotubes, graphene, fullerenes, etc. [4].
2. Metal-Based Materials
The main component of these materials is metal. Examples include
nanoplatinum, nanogold, nanosilver, metal oxides, quantum dots,
etc. [5].
3. Dendrimers
Dendrimers are nanosized, radially symmetric molecules with a well-
defined, homogeneous, and monodispersed structure that has a
typically symmetric core, an inner shell, and an outer shell [6].
4. Composites
Nanocomposites are multiphase solid materials in which at least one
phase is in the nano range. Composites are of three types, namely,
ceramic matrix nanocomposite, metal matrix nanocomposite, and
polymer matrix nanocomposite.

1.3 ADVANTAGES AND DISADVANTAGES OF

NANOMATERIALS
n Advantages
o small size
o high surface area
o easy to suspend in liquids
o deep access to cells
 1.5 Characterization Techniques of Nanomaterials 5

o tunable/tailorable physical, chemical, and mechanical properties

due to extremely small size (1e100 nm)
o high strength, toughness, and ductility
o reduced energy costs
o enhanced activity (extremely large specific surface area), surface-
dependent material properties
n Challenges
o The main challenges are to develop instruments to assess exposure
to engineered nanomaterials in the air and water.
o The second challenge is to develop and validate methods to eval-
uate the toxicity of engineered nanomaterials by 2020e2030.
o The last challenge is to develop tools to properly assess risks to
human health and to the environment.

1.4 OPPORTUNITIES PRESENTED BY

NANOMATERIALS
Now, nanotechnology is described as a revolutionary discipline because of
its possible impression on industrial applications. Through the use of
emerging nano techniques, nanotechnology can offer possible remedies to
many problems. Because nanotechnology is an interdisciplinary area there
are many research fields and several potential applications that involve
nanotechnology. Because nanomaterials possess unique, beneficial phys-
ical, chemical, and mechanical properties, they can be used for a wide va-
riety of applications. Fig. 1.1 shows some key applications of nanomaterials.

1.5 CHARACTERIZATION TECHNIQUES OF

NANOMATERIALS
Nanomaterials commonly consist of at least two of the following units:
metallic, semiconducting, and organic particles or molecules. Additionally,
nanomaterials are generally coated with polymers or biorecognition mole-
cules to improve biocompatibility and selective targeting of biologic mole-
cules. A common feature of all nanomaterials is their large ratio of surface
area to volume, which may be orders of magnitude greater than that of
macroscopic materials. Still, the final size and structure of nanomaterials
depend on the salt and surfactant additives, reactant concentrations, reaction
temperatures, and solvent conditions used during their synthesis. Thus, the
comprehension of these physicochemical properties as well as the funda-
mentals of the associated measuring methods is necessary before character-
izing nanomaterials and developing reproducible synthesis procedures to
optimize the medical application of nanomaterials.
6 CHAPTER 1 Instrumental Techniques for the Characterization of Nanoparticles

n FIGURE 1.1 Potential applications of nanomaterials.

Characterization refers to the study of a material’s features such as its

composition, structure, and various properties such as physical, chemical,
electrical, magnetic, etc. There are plenty of techniques available on the
market that were initially used for colloidal particles (e.g., microscopy,
spectroscopy, and magnetic resonance), but each of these techniques has
a certain degree of uncertainty. Particle size distribution (PSD) plays a
fundamental role in controlling the properties of different nanomaterials.
For example, the chemical reactivity of nanomaterials, which mostly differs
from that of macroscale or microscale materials, is usually affected by the
nanoparticle (NP) surface/volume ratio. Particle size also determines NP
diffusivity and the ability of NPs to permeate cell membranes. PSD analysis
thus allows monitoring of NP aggregation or release of NP-surface modi-
fiers. There are plenty of techniques available in the literature covering spe-
cific ranges of NP size distribution, as shown in Fig. 1.2 [7].

1.5.1 Optical (Imaging) Characterization Techniques

1.5.1.1 Confocal Laser-Scanning Microscopy
Confocal microscopy, most frequently confocal laser scanning microscopy
(CLSM), is a powerful technique to produce sharp images of a sample that
would otherwise appear blurred when viewed under a conventional micro-
scope. Reconstruction of three-dimensional structures from images obtained
by this technique is possible by taking a large number of images at different
depths (a process known as optical sectioning) within a thick object.
 1.5 Characterization Techniques of Nanomaterials 7

n FIGURE 1.2 Performance of various particle size measurement techniques (note: only a few techniques can measure particles in the nanoscale region) [7].
AFM, atomic force microscopy; NP, nanoparticle; SEM, scanning electron microscopy; TEM, transmission electron microscopy.

Scanning by one or more focused beams of light, usually from a laser or

arc-discharge source, across the specimen is used to obtain images by
confocal microscopy. An objective lens is used to focus the light beam
on the specimen and then the object is scanned using some form of scanning
device under computer control. The sequences of points of light from the
specimen are detected by a photomultiplier tube (PMT) and the output
from the PMT is built into an image and displayed by the computer [8].
n Advantages
o The ability to serially produce thin (0.5e1.5 mm) optical sections
through fluorescent specimens that have a thickness ranging up to
50 mm or more
o The ability to control depth of field
o The ability to isolate and collect a plane of focus from the sample,
thus eliminating the out-of-focus “haze” normally seen with a fluo-
rescent sample
8 CHAPTER 1 Instrumental Techniques for the Characterization of Nanoparticles

o Elimination or reduction of background information away from the

focal plane
o The ability to compensate for autofluorescence
o Minimum specimen preparation and instrument reconfiguration
n Disadvantage
o A disadvantage of CLSM is colocalization of fluorophores in the
confocal microscopedtwo or more fluorescence emission signals
can often overlap in digital images recorded by confocal
microscopy because of their close proximity within the specimen
n Applications
o This technique has gained popularity in the scientific and
industrial communities and typical applications are in life
sciences, semiconductor inspection, and materials science. It is
widely used in numerous biological science disciplines, from cell
biology and genetics to microbiology and developmental biology.
It is also used in quantum optics and nanocrystal imaging and
spectroscopy [9].

1.5.1.2 Scanning Near-Field Optical Microscopy

Scanning near-field optical microscopy (SNOM) gives simultaneous mea-
surements of topography and optical properties (fluorescence) and provides
a direct correlation between surface nano features and optical/electronic
properties. SNOM is based on scanning with an arbitrarily small aperture,
which is illuminated from the back side at a close but constant distance,
across a sample surface and recording optical information pixel by pixel,
collecting transmitted, reflected, or fluorescent light to form an image. In
SNOM, the excitation laser light is focused through an aperture with a
diameter smaller than the excitation wavelength, resulting in an evanescent
field (or near field) on the far side of the aperture. When the sample is
scanned at a small distance below the aperture, the optical resolution of
transmitted or reflected light is limited only by the diameter of the aperture.
The optical resolution attainable is in the range of 60e100 nm. The optical
image is generated by scanning the sample’s surface point by point and line
by line. A standard SNOM setup is shown in Fig. 1.3 [10].
n Advantages
o High resolution (up to 25 nm)
o Analysis of various properties made possible through contrast
o No special sample preparation needed
o Can be used for different kinds of samples (conductive, noncon-
ductive, and transparent)
 1.5 Characterization Techniques of Nanomaterials 9

n FIGURE 1.3 Standard scanning near-field optical microscopy setup consisting of (A) an illumination
unit, (B) a collection and redistribution unit, and (C) a detection module [10].

n Disadvantages
o Very low working distance and extremely shallow depth of field
o Limited to study of surfaces
o Not conducive to studying soft materials, especially under shear-
force mode
o Long scan times for large sample areas or high-resolution imaging
n Applications
This technique can be ideally suited to quickly and effortlessly
imaging the optical properties of a sample with resolution below
the diffraction limit. It can be used in various fields such as
nanotechnology research, nanophotonics and nanooptics, life
sciences, and materials researchdfor optical detection of the most
miniscule surface. Single-molecule detection is easily achievable
through this technique. Dynamic properties can also be studied at a
subwavelength scale.
10 CHAPTER 1 Instrumental Techniques for the Characterization of Nanoparticles

1.5.1.3 Two-Photon Fluorescence Microscopy

Two-photon laser scanning microscopy is established for studying biolog-
ical systems, enabling in vivo and in situ imaging. This technique was
invented by Denk, Webb, and coworkers in 1990 [11]. Two-photon fluores-
cence excitation of molecules is a nonlinear process that involves the absorp-
tion of two photons whose combined energy is greater than the energy gap
between the molecule’s ground and excited states and it is sufficient to make
a molecular transition to an excited electronic state. The probability of two-
photon absorption by a fluorescent molecule is a quadratic function of the
excitation radiance because this process depends on the simultaneous ab-
sorption of two infrared photons. Other than two-photo excitation, three-
photon and higher excitation is also possible [12].
n Advantages
o Compared with confocal microscopy, it offers the advantages of
deeper tissue penetration and less photodamage.
n Disadvantage
o Disadvantage of slightly lower resolution.
n Applications
o Two-photon microscopy has applications in the fields of physi-
ology, neurobiology, embryology, and tissue engineering, where
imaging of highly scattering tissue is required. Clinically, two-
photon microscopy may find an application in noninvasive optical
biopsy, for which high-speed imaging is required.

1.5.1.4 Dynamic Light Scattering

Dynamic light scattering (DLS) is a noninvasive technique for measuring
the size of particles and molecules in suspension [13]. It is also referred
to as photon correlation spectroscopy or quasielastic light scattering. The
technique measures the speed of particles undergoing Brownian motion
(due to random collisions with solvent molecules) and the speed is influ-
enced by particle size, sample viscosity, and temperature. This motion
causes the particles to diffuse through the medium. When a monochromatic
light beam such as a laser hits a solution containing spherical particles in
Brownian motion the wavelength of the incoming light is changed (Doppler
shift). This change in wavelength is related to the size of the particles. It is
possible to calculate the sphere size distribution by measuring the diffusion
coefficient of the particle and using the autocorrelation function. The diffu-
sion coefficient D is inversely proportional to the particle size according to
the StokeseEinstein equation. The velocity of the Brownian motion is
defined by the translational diffusion coefficient (D). The translational
 1.5 Characterization Techniques of Nanomaterials 11

diffusion coefficient can be converted into a particle size using the Stokese
Einstein equation:
kT
dH ¼
3phD

where dH is the hydrodynamic diameter, k is Boltzmann’s constant, T is the

absolute temperature, h is the viscosity, and D is the diffusion coefficient.
DLS measures variation in scattered intensity with time at a fixed scattering
angle (typically 90 degrees), while static light scattering measures scattered
intensity as a function of angle. When light is scattered by a molecule or par-
ticle some of the incident light is scattered. If the molecule were stationary,
then the amount of light scattered would be a constant. However, because all
molecules in solution diffuse with Brownian motion in relation to the detec-
tor there will be interference (constructive or destructive), which causes a
change in light intensity. By measuring the timescale of light intensity fluc-
tuations, DLS can provide information about the average size, size distribu-
tion, and polydispersity of molecules and particles in solution [14].
n Advantages
o Experiment duration is short.
o This method has modest development costs.
n Disadvantages
o Time-consuming, especially for slow dynamics
o Applicable only to transparent samples
o Sensitive to mechanical disturbances
o Lack of selectivity and relatively low signal strength
n Applications
o DLS measurement provides the size of various particles, including
proteins, polymers, micelles, carbohydrates, and NPs. If the system
is not dispersing in size, the mean effective diameter of the
particles can be determined. This measurement depends on the size
of the particle core, the size of the surface structures, the particle
concentration, and the types of ions in the medium.

1.5.1.5 Brewster Angle Microscopy

A Brewster angle microscope is a microscope for imaging thin films on
liquid surfaces. This microscopy technique was invented in 1991 and allows
the direct observation of ultrathin organic films on transparent dielectric
substrates. This technique is based on the principle that no light is reflected
from the airewater interface under Brewster’s angle incidence if p-polarized
light is used. With constant angle of incidence the formation of a monolayer
12 CHAPTER 1 Instrumental Techniques for the Characterization of Nanoparticles

n FIGURE 1.4 Principle of Brewster angle microscopy: making use of Brewster’s law for imaging
ultrathin films with high contrast [15].

on the water surface modifies the Brewster angle condition and light reflec-
tion is observed [15]. Fig. 1.4 illustrates the principle of obtaining the
contrast for a surface covered with a nanofilm by Brewster angle microscopy
(BAM). When a light beam passes the boundary between two media of
differing refractive index generally some of it is reflected. The Brewster
angle (qB) is a particular angle of incidence at which light with one particular
polarization state cannot be reflected. The state that cannot be reflected is
parallel to the plane of incidence. Light with this polarization is said to be
p-polarized.
n Advantages
o No fluorescent probe is added to the film.
o The film does not have to solubilize the probe.
o Any film with a refractive index different from that of water can
be observed.
o The technique allows more and easier study of optical anisotropy
of monolayers than polarized fluorescence microscopy.
n Applications
o BAM can be used for imaging either spread or adsorbed mono-
layers. BAM is used for studying phase transitions, characteriza-
tion of domain microstructure, studying phase separation in mixed
monolayers, following changes due to complex formation, and
observing collapse or multilayer formation. It has been applied to
monolayers of a range of macrocyclic compounds, especially
calixarene and cyclodextrin derivatives. BAM has been applied to
study chiral phase separation in monolayers of chiral amphiphiles.
It is possible to apply BAM in a quantitative manner to estimate
variations in monolayer thickness [16].
 1.5 Characterization Techniques of Nanomaterials 13

1.5.2 Electron Probe Characterization Techniques

1.5.2.1 Scanning Probe Electron Microscopy
Scanning probe microscopes are a family of tools used to make images of
nanoscale surfaces and structures, including atoms. Scanning probe micro-
scopy (SPM) uses light waves for imaging; the surface of the sample is
scanned by a very fine probe (“tip”), and the power of interactions between
the surface and the tip is monitored. It scans the surface with an atomically
sharp probe typically at a distance of a few angstroms or nanometers and the
interaction between the sharp probe and the surface provides a three-
dimensional topographic image of the surface at the atomic scale. Scanning
probe microscopes are a very powerful family of microscopes with resolu-
tion less than 1 nm. A schematic diagram for a general representation of
STEM is shown in Fig. 1.5. Generally scientists use two types of mode
for scanning depending upon the nature of information wanted from the
analysis, contact mode and noncontact mode. The force between the tip
and the surface is kept constant in contact mode, which allows the scientist
to quickly image a surface. In tapping mode, the cantilever oscillates, inter-
mittently touching the surface. Tapping mode is especially useful for imag-
ing a soft surface. There are several types of scanning probe microscope.
Atomic force microscopes measure the electrostatic forces between the
cantilever tip and the sample. Magnetic force microscopes measure magnetic
forces, and scanning tunneling microscopes measure the electrical current
flowing between the cantilever tip and the sample.

n FIGURE 1.5 (A) Formation of an image by a scanning transmission electron microscope. (B) A schematic diagram illustrating the common signals when a
high-energy beam of electrons interacts with a thin specimen [18]. ADF, annular dark field.
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A FEW GENERAL RULES AND DIRECTIONS FOR PRESERVING.

1. Let everything used for the purpose be delicately clean and dry;
bottles especially so.
2. Never place a preserving-pan flat upon the fire, as this will
render the preserve liable to burn to, as it is called; that is to say, to
adhere closely to the metal, and then to burn; it should rest always
on a trivet (that shown with the French furnace is very convenient
even for a common grate), or on the lowered bar of a kitchen range
when there is no regular preserving stove in a house.
3. After the sugar is added to them, stir the preserves gently at
first, and more quickly towards the end, without quitting them until
they are done: this precaution will always prevent the chance of their
being spoiled.
4. All preserves should be perfectly cleared from the scum as it
rises.
5. Fruit which is to be preserved in syrup must first be blanched or
boiled gently, until it is sufficiently softened to absorb the sugar; and
a thin syrup must be poured on it at first, or it will shrivel instead of
remaining plump, and becoming clear. Thus, if its weight of sugar is
to be allowed, and boiled to a syrup with a pint of water to the pound,
only half the weight must be taken at first, and this must not be
boiled with the water more than fifteen or twenty minutes at the
commencement of the process; a part of the remaining sugar must
be added every time the syrup is reboiled, unless it should be
otherwise directed in the receipt.
6. To preserve both the true flavour and the colour of fruit in jams
and jellies, boil them rapidly until they are well reduced, before the
sugar is added, and quickly afterwards, but do not allow them to
become so much thickened that the sugar will not dissolve in them
easily, and throw up its scum. In some seasons, the juice is so much
richer than in others, that this effect takes place almost before one is
aware of it; but the drop which adheres to the skimmer when it is
held up, will show the state it has reached.
7. Never use tin, iron, or pewter spoons, or skimmers, for
preserves, as they will convert the colour of red fruit into a dingy
purple, and impart, besides, a very unpleasant flavour.
8. When cheap jams or jellies are required, make them at once
with Lisbon sugar, but use that which is well refined always, for
preserves in general; it is a false economy, as we have elsewhere
observed, to purchase an inferior kind, as there is great waste from it
in the quantity of scum which it throws up. The best has been used
for all the receipts given here.
9. Let fruit for preserving be gathered always in perfectly dry
weather, and be free both from the morning and evening dew, and as
much so as possible from dust. When bottled, it must be steamed or
baked during the day on which it is gathered, or there will be a great
loss from the bursting of the bottles; and for jams and jellies it cannot
be too soon boiled down after it is taken from the trees.
 TO EXTRACT THE JUICE OF PLUMS FOR JELLY.

Take the stalks from the fruit, and throw aside all that is not
perfectly sound: put it into very clean, large stone jars, and give part
of the harder kinds, such as bullaces and damson, a gash with a
knife as they are thrown in; do this especially in filling the upper part
of the jars. Tie one or two folds of thick paper over them, and set
them for the night into an oven from which the bread has been drawn
four or five hours; or cover them with bladder, instead of paper, place
them in pans, or in a copper[166] with water which will reach to quite
two-thirds of their height, and boil them gently from two to three
hours, or until the fruit is quite soft, and has yielded all the juice it will
afford: this last is the safer and better mode for jellies of delicate
colour.
166. The fruit steams perfectly in this, if the cover be placed over.
 TO WEIGH THE JUICE OF FRUIT.

Put a basin into one scale, and its weight into the other; add to this
last the weight which is required of the juice, and pour into the basin
as much as will balance the scales. It is always better to weigh than
to measure the juice for preserving, as it can generally be done with
more exactness.
 RHUBARB JAM.

The stalks of the rhubarb (or spring-fruit, as it is called) should be

taken for this preserve, which is a very good and useful one, while
they are fresh and young. Wipe them very clean, pare them quickly,
weigh, and cut them into half-inch lengths; to every pound add an
equal weight of good sugar in fine powder; mix them well together,
let them remain for ten minutes or a quarter of an hour to draw out
the juice a little, then turn them into a preserving-pan, let them heat
rather slowly, but as soon as the stalks are tender boil the preserve
rapidly, stirring it well for about half an hour. It will be of excellent
flavour, and will serve admirably for tarts.
A somewhat cheaper mode of making the jam is to stew it until
tender in its own juices, and then to boil it rapidly until it is tolerably
dry, to add to it only half its weight of sugar, and to give it from twenty
to thirty minutes boiling.
Spring fruit (rhubarb), 4 lbs.; sugar, 4 lbs.: heated slowly, and
when tender, boiled quickly, 30 minutes.
 GREEN GOOSEBERRY JELLY.

Wash some freshly gathered gooseberries very clean; after having

taken off the tops and stalks, then to each pound pour three-quarters
of a pint of spring water, and simmer them until they are well broken;
turn the whole into a jelly-bag or cloth, and let all the juice drain
through; weigh and boil it rapidly for fifteen minutes. Draw it from the
fire, and stir in it until entirely dissolved, an equal weight of good
sugar reduced to powder; boil the jelly from fifteen to twenty minutes
longer, or until it jellies strongly on the spoon or skimmer; clear it
perfectly from scum, and pour it into small jars, moulds, or glasses. It
ought to be very pale and transparent. The sugar may be added to
the juice at first, and the preserve boiled from twenty-five to thirty-five
minutes, but the colour will not then be so good. When the fruit
abounds, the juice may be drawn from it with very little water, as
directed for apples, page 523, when it will require much less boiling.
Gooseberries, 6 lbs.; water, 4 pints: 20 to 30 minutes. Juice boiled
quickly, 15 minutes; to each pound, 1 pound sugar: 15 to 20 minutes.
 GREEN GOOSEBERRY JAM.

(Firm and of good colour.)

Cut the stalks and tops from the fruit, weigh and bruise it slightly,
boil it for six or seven minutes, keeping it well turned during the time,
then to every three pounds of gooseberries add two and a half of
sugar beaten to powder, and boil the preserve quickly for three-
quarters of an hour. It must be constantly stirred, and carefully
cleared from scum. This makes a fine, firm, and refreshing preserve
if the fruit be rubbed through a sieve before the sugar is added. If
well reduced afterwards, it may be converted into a gâteau, or
gooseberry-solid, with three pounds of sugar, or even a smaller
proportion. The preceding jam will often turn in perfect form from the
moulds or jars which contain it; and if freed from the seeds, would be
very excellent: it is extremely good even made as above. For all
preserves, the reduction, or boiling down to a certain consistence,
should take place principally before the sugar is mingled with them;
and this has the best effect when added to the fruit and dissolved in
it by degrees.
Green gooseberries, 6 lbs.: 6 to 7 minutes. Sugar, 5 lbs.; 3/4 hour.
 TO DRY GREEN GOOSEBERRIES.

Take the finest green gooseberries, fully grown, and freshly

gathered; cut off the buds, split them across the tops half way down,
and with the small end of a tea or of an egg spoon, scoop out the
seeds. Boil together for fifteen minutes a pound and a half of the
finest sugar, and a pint of water; skim this syrup thoroughly and
throw into it a pound of the seeded gooseberries; simmer them from
five to seven minutes, when they ought to be clear and tender; when
they are so, lift them out, and throw as many more into the syrup;
drain them a little when done, spread them singly on dishes, and dry
them very gradually in a quite cool stove or oven, or in a sunny
window. They will keep well in the syrup, and may be potted in it, and
dried when wanted for use.
Green gooseberries without seeds, 2 lbs.; water, 1 pint; sugar, 1-
1/2 lb.: boiled, 15 minutes. Gooseberries simmered, 5 to 7 minutes.
 GREEN GOOSEBERRIES FOR TARTS.

Fill very clean, dry, wide-necked bottles with gooseberries

gathered the same day, and before they have attained their full
growth. Cork them lightly, wrap a little hay round each of them, and
set them up to their necks in a copper of cold water which should be
brought very gradually to boil. Let the fruit be gently simmered until it
appears shrunken and perfectly scalded; then take out the bottles,
and with the contents of one or two fill up the remainder, and use
great care not to break the fruit in doing this. When all are ready pour
scalding water into the bottles and cover the gooseberries entirely
with it, or they will become mouldy at the top. Cork the bottles well
immediately, and cover the necks with melted resin; keep them in a
cool place; and when the gooseberries are used pour off the greater
part of the water, and add sugar as for the fresh fruit, of which they
will have the flavour and appearance; and they will be found more
wholesome prepared in this manner than if simply baked or steamed
in the bottles.
 RED GOOSEBERRY JAM.

The small rough red gooseberry, when fully ripe, is the best for this
preserve, which may, however, be made of the larger kinds. When
the tops and stalks have been taken carefully from the fruit, weigh,
and boil it quickly for three-quarters of an hour, keeping it well stirred;
then for six pounds of the gooseberries, add two and a half of good
roughly-powdered sugar; boil these together briskly, from twenty to
twenty-five minutes and stir the jam well from the bottom of the pan,
as it is liable to burn if this be neglected.
Small red gooseberries, 6 lbs.: 3/4 hour. Pounded sugar, 2-1/2
lbs.: 20 to 25 minutes.
 VERY FINE GOOSEBERRY JAM.

Seed the fruit, which for this jam may be of the larger kind of rough
red gooseberry: those which are smooth skinned are generally of far
inferior flavour. Add the pulp which has been scooped from the
prepared fruit to some whole gooseberries, and stir them over a
moderate fire for some minutes to extract the juice; strain and weigh
this; pour two pounds of it to four of the seeded gooseberries, boil
them rather gently for twenty-five minutes, add fourteen ounces of
good pounded sugar to each pound of fruit and juice, and when it is
dissolved boil the preserve from twelve to fifteen minutes longer, and
skim it well during the time.
Seeded gooseberries, 4 lbs.; juice of gooseberries, 2 lbs.: 25
minutes. Sugar, 5-1/4 lbs. (or 14 oz. to each pound of fruit and juice):
12 to 15 minutes.
 JELLY OF RIPE GOOSEBERRIES.

(Excellent.)
Take the tops and stalks from a gallon or more of any kind of well-
flavoured ripe red gooseberries, and keep them stirred gently over a
clear fire until they have yielded all their juice, which should then be
poured off without pressing the fruit, and passed first through a fine
sieve, and afterwards through a double muslin-strainer, or a jelly-
bag. Next weigh it, and to every three pounds add one of white
currant juice, which has previously been prepared in the same way;
boil these quickly for a quarter of an hour, then draw them from the
fire and stir to them half their weight of good sugar; when this is
dissolved, boil the jelly for six minutes longer, skim it thoroughly, and
pour it into jars or moulds. If a very large quantity be made, a few
minutes of additional boiling must be given to it before the sugar is
added.
Juice of red gooseberries, 3 lbs.; juice of white currants, 1 lb.: 15
minutes. Sugar, 2 lbs.: 6 minutes.
Obs.—The same proportion of red currant juice, mixed with that of
the gooseberries, makes an exceedingly nice jelly.
 UNMIXED GOOSEBERRY JELLY.

Boil rapidly for ten minutes four pounds of the juice of red
gooseberries, prepared as in the preceding receipt; take it from the
fire, and stir in it until dissolved three pounds of sugar beaten to
powder; boil it again for five minutes, keeping it constantly stirred
and thoroughly skimmed.
Juice of red gooseberries, 4 lbs.: 10 minutes. Sugar, 3 lbs.: 5
minutes.
 GOOSEBERRY PASTE.

Press through a sieve the gooseberries from which the juice has
been taken for jelly, without having been drained very closely from
them; weigh and then boil the pulp for upwards of an hour and a
quarter, or until it forms a dry paste in the pan; stir to it, off the fire,
six ounces of good pounded sugar for each pound of the fruit, and
when this is nearly dissolved boil the preserve from twenty to twenty-
five minutes, keeping it stirred without cessation, as it will be liable to
burn should this be neglected. Put it into moulds, or shallow pans,
and turn it out when wanted for table.
Pulp of gooseberries, 4 lbs.: 1-1/4 to 1-3/4 hour. Sugar, 1-1/2 lb.:
20 to 25 minutes.
 TO DRY RIPE GOOSEBERRIES WITH SUGAR.

Cut the tops, but not the stalks, from some ripe gooseberries of
the largest size, either red or green ones, and after having taken out
the seeds as directed for unripe gooseberries, boil the fruit until clear
and tender, in syrup made with a pound of sugar to the pint of water,
boiled until rather thick.
Seeded gooseberries, 2 lbs.; sugar, 1-1/2 lb.; water, 1 pint: boiled
to syrup. Gooseberries, simmered 8 to 12 minutes, or more.
Obs.—Large ripe gooseberries freed from the blossoms, and put
into cold syrup in which cherries or any other fruit has been boiled for
drying, then heated very gradually, and kept at the point of boiling for
a few minutes before they are set by for a couple of days, answer
extremely well as a dry preserve. On the third day the syrup should
be drained from them, simmered, skimmed, and poured on them the
instant it is taken from the fire; in forty-eight hours after, they may be
drained from it and laid singly upon plates or dishes, and placed in a
gentle stove.
 JAM OF KENTISH OR FLEMISH CHERRIES.

This is a very agreeable preserve when it is made as we shall

direct; but if long boiled with a large proportion of sugar, as it
frequently is, both the bright colour and the pleasant flavour of the
cherries will be destroyed.
Stone, and then weigh the fruit; heat it rather slowly that the juice
may be well drawn out before it begins to boil, and stew the cherries
until they are tolerably tender, then boil them quickly, keeping them
well turned and stirred from the bottom of the pan, for three-quarters
of an hour or somewhat longer should there still remain a large
quantity of juice. Draw the pan from the fire, and stir in gradually half
a pound of sugar for each pound of cherries. An ounce or two more
may occasionally be required when the fruit is more than usually
acid, and also when a quite sweet preserve is liked. When the sugar
is dissolved continue the boiling rapidly for about twenty minutes
longer; clear off all the scum as it appears, and keep the jam stirred
well and constantly, but not quickly, to prevent its adhering to the
bottom of the preserving-pan.
Stoned Kentish or Flemish cherries, 6 lbs.: without sugar, 1 hour or
rather more. Sugar roughly powdered, 3 lbs.: (or 3-1/2 lbs.) About 20
minutes quick boiling.
Obs.—Heat the fruit and boil it gently until it is quite tender, turning
it often, and pressing it down into the juice; then quicken the boiling
to evaporate the juice before the sugar is added. Cherries which are
bruised will not make good preserve: they always remain tough.
 TO DRY CHERRIES WITH SUGAR.

(A quick and easy method.)

Stone some fine, sound, Kentish or Flemish cherries; put them into
a preserving-pan, with six ounces of sugar reduced to powder, to
each pound of the fruit; set them over a moderate fire, and simmer
them gently for nearly or quite twenty minutes; let them remain in the
syrup until they are a little cooled, then turn them into a sieve, and
before they are cold lay them singly on dishes, and dry them very
gradually, as directed for other fruits. When the cherries are quite
ripe the stones may generally be drawn out with the stalks, by
pressing the fruit gently at the same time; but when this method fails,
they must be extracted with a new quill, cut round at the end: those
of the very short-stalked, turnip-shaped cherry, which abounds, and
is remarkably fine in many parts of Normandy, and which we have
occasionally met with here, though it is not, we believe, very
abundant in our markets, are easily removed with a large pin, on the
point of which the stone may be caught at the stalk end, just
opposite the seam of the fruit, and drawn out at the top, leaving the
cherry apparently entire.
 DRIED CHERRIES.

(Superior Receipt.)
To each pound of cherries weighed after they are stoned, add
eight ounces of good sugar, and boil them very softly for ten minutes:
pour them into a large bowl or pan, and leave them for two days in
the syrup; then simmer them again for ten minutes, and set them by
in it for two or three days; drain them slightly, and dry them very
slowly, as directed in the previous receipts. Keep them in jars or tin
canisters, when done. These cherries are generally preferred to such
as are dried with a larger proportion of sugar; but when the taste is in
favour of the latter, from twelve to sixteen ounces can be allowed to
the pound of fruit, which may then be potted in the syrup and dried at
any time; though we think the flavour of the cherries is better
preserved when this is done within a fortnight of their being boiled.
Cherries, stoned, 8 lbs.; sugar, 4 lbs.: 10 minutes. Left two or three
days. Boiled again, 10 minutes; left two days; drained and dried.
 CHERRIES DRIED WITHOUT SUGAR.

These are often more pleasant and refreshing to invalids and

travellers than a sweetened confection of the fruit, their flavour and
agreeable acidity being well preserved when they are simply spread
on dishes or hamper-lids, and slowly dried.[167] Throw aside the
bruised and decayed fruit, and arrange the remainder singly, and
with the stalks uppermost on the dishes. The Kentish cherries are
best for the purpose, but morellas also answer for it excellently. The
former are sometimes stoned, and simmered until quite tender in
their own juice, before they are dried; but this is scarcely an
improvement on the more usual method of leaving them entire.
167. The dishes on which they are laid should be changed daily.
 TO DRY MORELLA CHERRIES.

Take off the stalks but do not stone the fruit; weigh and add to it an
equal quantity of the best sugar reduced quite to powder, strew it
over the cherries and let them stand for half an hour; then turn them
gently into a preserving-pan, and simmer them softly from five to
seven minutes. Drain them from the syrup, and dry them like the
Kentish cherries. They make a very fine confection.