Professional Documents
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KUNAL PAL
Department of Biotechnology and Medical Engineering, National Institute of Technology, Rourkela, Odisha, India
ANGANA SARKAR
Department of Biotechnology and Medical Engineering, National Institute of Technology, Rourkela, Odisha, India
PREETAM SARKAR
Department of Food Process Engineering, National Institute of Technology Rourkela, Rourkela, India
NANDIKA BANDARA
Department of Food and Human Nutritional Sciences, Richardson Centre for Food Technology and Research,
University of Manitoba, Winnipeg, Manitoba, Canada
VEERIAH JEGATHEESAN
Water: Effective Technologies and Tools (WETT) Research Centre, School of Engineering, RMIT University,
Melbourne, Australia
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ISBN: 978-0-12-822858-6
v
vi Contents
1 Introduction 493
2 Biosensor 495
Contributors
ix
x Contributors
1
Fabrication of nanomaterials
Vaidhegi Kugarajaha,∗, Hushnaara Hademb,∗, Atul Kumar
Ojhab, Shivendu Ranjanc,d, Nandita Dasguptae, Bhartendu Nath
Mishrae, and Sangeetha Dharmalingama
a
Department of Mechanical Engineering, Anna University, Chennai, Tamil Nadu, India bCentre
for Nano Sciences and Technology, Pondicherry University, Chinna Kalapet, Kalapet,
Puducherry, India cFaculty of Engineering and the Built Environment, University of Johannesburg,
Johannesburg, South Africa dAnimal Cell and Tissue Culture Lab, Gujarat Biotechnology
Research Centre, Department of Science and Technology, Government of Gujarat, Gandhinagar,
Gujarat, India eDepartment of Biotechnology, Institute of Engineering and Technology, Dr. A.P.J.
Abdul Kalam Technical University, Lucknow, Uttar Pradesh, India
O U T L I N E
∗
Authors contributed equally.
Food, Medical, and Environmental Applications of Nanomaterials 1 Copyright # 2022 Elsevier Inc. All rights reserved.
https://doi.org/10.1016/B978-0-12-822858-6.00001-7
2 1. Fabrication of nanomaterials
1 Introduction
Nanotechnology deals with materials with 1–100 nm dimension in size. The concept of
nanotechnology was introduced by Richard P. Feynman (Nobel Laureate in Physics, 1965)
in “There’s Plenty of Room at the Bottom.” He introduced the concept of the possibility to
arrange the atoms in the nanoscale (Feynman, 1960). Nowadays, most electronics, optical
communications, and biological systems are based on nanotechnology (Enescu et al., 2019;
Mathew et al., 2019; Shang et al., 2019; Kumar et al., 2020). This is due to the unique physical,
chemical, and thermal properties and high surface area to volume ratio. It was found that
using nanotechnology, billions of transistors can be packed in computer chips (Srivastava
and Kotov, 2008). In biomedical, nanotechnology has been used to achieve targeted drug de-
livery (Oroojalian et al., 2020; Saxena et al., 2020), gene replacement (Pandey et al., 2019;
Cheng et al., 2020), tissue regeneration (Yang et al., 2019), etc. Optical lithography is another
best application of nanotechnology (Crucho and Barros, 2017; Karaballi et al., 2020), which
has been used for printing small objects (Albisetti et al., 2016; Bose et al., 2018). Also, nano-
technology has various applications such as in flat display devices (Lim, 2019), medical im-
aging (R€ othlisberger et al., 2017; Tibbals, 2017), paint (Lutz, 2019), additives, automobile
components (Werner et al., 2018), satellite components (Pourzahedi et al., 2017), high-energy
storage system, fuel cells (Elumalai and Sangeetha, 2018; Kugarajah and Dharmalingam,
2020), optical devices (Wang et al., 2019), electromagnetic interference shielding, food and
beverage packaging (Enescu et al., 2019), sensors (Farzin et al., 2020), aircraft components, etc.
Various methods are being used to fabricate nanomaterial-based products such as sol-gel
synthesis, plasma synthesis, chemical synthesis, hydrothermal synthesis, alloying, blending,
mechanical, and mechanochemical synthesis, etc. (Crucho and Barros, 2017; Dastan, 2017;
Jamkhande et al., 2019; Karaballi et al., 2020). In order to explain the fabrication, design,
and application of nanomaterials, nanoscience uses the basic concepts of properties and
mechanisms of nanomaterials used (Zhong, 2009). The historical aspect of nanotechnology
is mentioned in Table 1.
Crystallization process (nucleation and growth) has a great impact on the crystal structure
and shape during nanoparticle synthesis. The LaMer theory and Sugimoto model can be used
to study the kinetics of nucleation and growth mechanism of nanomaterials (Sugimoto, 2007;
Mehranpour et al., 2010). According to LaMer theory, when the solute concentration reaches
the critical concentration (which is the minimum concentration for nucleation), it starts nu-
cleating. Then, the solute concentration reaches its maximum, which decides the consump-
tion rate for the nucleation and the growth of the generated nuclei. However, a further
increase in the solute concentration for the growth of the generated nuclei results in the dec-
lination of the curve. It indicates the end of nucleation (as shown in Fig. 1) of the concentration
vs time curve. This theory was only proposed for monodisperse particle formation. The basic
assumptions of this theory were
(1) Mass balance between the supply rate of solute and its consumption rate for nucleation
and growth of the generated nuclei;
(2) The supply rate of solute is independent of the subsequent precipitation events;
(3) The nucleation rate is controlled only by the growth of the preformed nuclei at a fixed supply
rate of solute when precursor solute is transferred by slow irreversible generation in a closed
system or by a continuous feed from outside in an open system (LaMer and Dinegar, 1950).
1 Introduction 3
TABLE 1 Historical aspects of nanotechnology (Horikoshi and Serpone, 2013).
Year Remarks Country/people
1200–1300 Discovery of soluble gold Egypt and China
BC
290–325 Lycurgus cup Alexandria or Rome
AD
1618 The first book on colloidal gold F. Antonii
1676 Book published on drinkable gold that contains J. von L€
owenstern-Kunckel (Germany)
metallic gold in neutral media
1718 Publication of a complete treatise on colloidal Hans Heinrich Helcher
gold
1857 Synthesis of colloidal gold M. Faraday (The Royal Institution of Great
Britain)
1902 Surface plasmon resonance (SPR) R. W. Wood (Johns Hopkins University, United
States)
1908 Scattering and absorption of electromagnetic G. Mie (University of G€
ottingen, Germany)
fields by a nanosphere
1931 Transmission electron microscope (TEM) M. Knoll and E. Ruska (Technical University of
Berlin, Germany)
1937 Scanning electron microscope (SEM) M. von Ardenne (Forschungslaboratorium f€
ur
Elektronenphysik, Germany)
1959 Feynman’s Lecture on “There’s Plenty of Room R. P. Feynman (California Institute of Technology,
at the Bottom” Pasadena, CA, United States)
1960 Microelectromechanical systems (MEMS) I. Igarashi (Toyota Central R & D Labs, Japan)
1960 Successful oscillation of a laser T. H. Maiman (Hughes Research Laboratories,
United States)
1962 The Kubo effect R. Kubo (University of Tokyo, Japan)
1965 Moore’s Law G. Moore (Fairchild Semiconductor Inc., United
States)
1969 The Honda–Fujishima effect A. Fujishima and K. Honda (University of Tokyo,
Japan)
1972 Amorphous heterostructure photodiode created E. Maruyama (Hitachi Co. Ltd., Japan)
with bottom-up process
Continued
4 1. Fabrication of nanomaterials
Ccrit
C¥
l ll lll
Time
FIG. 1 LaMer diagram as a schematic explanation for the formation process of monodisperse particles, where C∞
and Ccrit are the equilibrium concentration of solute with the bulk solid and the critical concentration as the minimum
concentration for nucleation, respectively. The regions I, II, and III represent the prenucleation, nucleation, and growth
stages, respectively. Reproduced from Sugimoto, T., 2007. Underlying mechanisms in size control of uniform nanoparticles. J.
Colloid Interface Sci. 309, 106–118. https://doi.org/10.1016/j.jcis.2007.01.036.
2 Fabrication of nanomaterials 5
The size and the uniformity of the final nanoparticles can be controlled by reducing the
growth rate of nuclei, which is possible by detailed knowledge about factors such as tem-
perature, pH, adsorption of additives, and affinity of solvents (Sugimoto, 2007). Further,
fluorescent biosensor light-emitting diodes can be fabricated using these quantum dots
or nanoparticles (Lin et al., 2017; Mu et al., 2020). Sharp and symmetrical emission spectra,
high quantum yield, good photochemical stability, and size-dependent emission-
wavelength tenability are the main properties of quantum dots or nanoparticles, owing
to their quantum confinement effect (Raphaël et al., 2011). Therefore, semiconductor quan-
tum dots nanomaterials play a significant role in modern electronics light-emitting diode
(Cao et al., 2017; Dong et al., 2019), digital and analog integrated circuits, transistors, solar
cells (Ahmad et al., 2018), solar photovoltaic panels, wastewater treatment by adsorption of
pollutants (Mustapha et al., 2020), etc. Functionalization of nanomaterials offers to achieve
better performance and properties (Palit and Hussain, 2020). The functionalization of
nanomaterials is carried out based on the interaction between main nanostructured mate-
rials and neighboring material systems (Iordache et al., 2011). According to the Hall-Petch
equation, the nanomaterial-based composites system also shows better mechanical proper-
ties, according to which the strength of materials is inversely proportional to the root diam-
eter of grain. Nanomaterials offer excellent barrier properties due to the increased diffusion
length of the solvent gas. The main objective of this chapter is to explain the fabrication of
nanomaterials.
2 Fabrication of nanomaterials
nanomaterials depend on the fabrication techniques and precursors of the nanomaterials that
were used to fabricate them. The properties of nanomaterials decide the applications of
nanomaterials in various areas such as catalysis, food industry, medicine, and electronics.
Hydrothermal synthesis, combustion synthesis, gas-phase methods, microwave synthesis,
and sol-gel processing have been used to synthesize nano metal oxides (Cheng et al., 1995;
Gopal et al., 1997; Kim et al., 1999; Wang and Ying, 1999; Watson et al., 2004; Wolf, 2008).
Other technologies such as self-assembly, nontraditional lithography, template growth,
and biomimetics have also been used to produce nanomaterial-based products, quantum
dots, nanorods, nanotubes, etc. (Wolf, 2008). Nanomaterials have at least one dimension in
the nanometer range. The nanomaterials show different physical and chemical properties
from their bulk counterparts. Nanotechnology allows us to understand the size effect prop-
erties of nanostructured materials and their possible applications. Nowadays, nanotechnol-
ogy is being used as an interdisciplinary science and technology, which includes
nanochemistry, nanoelectronics, nanomaterials science, nanophysics, nanorobotics,
nanobiotechnology, nanometrology, etc.
In addition to the above, there are several methods, including coprecipitation, hydrother-
mal, microwave, microemulsion, ultrasound, template synthesis, biological synthesis, elec-
trochemical synthesis, etc. which are discussed in the following sections.
3 Top-down fabrication methods 7
ball-powder-ball collision in the case of shaker mills, frictional and impact forces in the case of
planetary ball mills (Prasad Yadav et al., 2012), and very high shear and impact forces in the
case of Attrition mills (Rajput, 2015). These mechanical and shear forces cause the powder par-
ticles to undergo deformation and/or fracture to achieve the desired microstructure of the
powder. The mechanical characteristics of powder component or powder mixture is a crucial
factor in mechanical ball milling; there are various types of powder mixture such as ductile-
ductile, brittle-brittle, ductile-brittle system (Benjamin and Volin, 1974; Davis et al., 1988;
Lee and Koch, 1988). However, the temperature and the nonuniformity of particle size during
milling profoundly affect the structural, microstructural changes (Su and Chang, 2018). The
speed of the ball, the material properties of the powder, and milling environment can influence
the temperature of powder during milling. Phase transfer can be induced by the ball milling,
which depends on the diffusivity and defect concentration in the powder, while, diffusivity
and defect concentration in the powder are influenced by the temperature of the powder
(Sun et al., 2002; Prasad Yadav et al., 2012). A scheme for the ball milling process is shown
in Fig. 4. The mechanical milling can be performed in various ways such as attrition ball mill,
planetary ball mill, vibrating ball mill, low-energy tumbling mill, and high-energy ball mill.
Nanoparticle-based powders can be easily produced by high-energy ball milling
( Jamkhande et al., 2019). In high-energy ball milling, powders and heavy steel or tungsten
carbide are loaded together in a container, and shaking or high-speed rotation is applied
to transfer the high energy on the loaded powder; the collision between balls generates the
energy. However, high-energy ball milling has certain drawbacks such as contamination
problems, low surface, highly polydisperse size distribution, and partially amorphous state
of the powder. To resolve this issue, inert atmosphere and/or high vacuum processes are ap-
plied. The milling duration, characteristics of materials, and size of ball are the main param-
eters (Prasad Yadav et al., 2012). Low-energy tumbling mill is employed to fabricate
nanoparticles-based alloy materials in a simple way and at low cost. Vibrating ball mills
are used to produce amorphous alloys. A vibrating ball supplies a high amount of energy
to the particles. The vibrating container is used to accelerate the milling process. The vibrating
frequency and amplitude of oscillation are found to be around 1500–3000 oscillation/min and
2–3 mm, respectively. The grinding ball is made of steel or carbide ball and is heavier than the
FIG. 5 SEM images of Mg-doped ZnO nanoparticle at different Mg contents (Suwanboon and Amornpitoksuk,
2012).
10 1. Fabrication of nanomaterials
Cu-ZrO2 nanocomposites up to 10% higher than that of pure copper, which enabled better
mechanical properties of the nanocomposites. Another study showed the influence of ball
milling in starch nanoparticle production for its application in drug and food formulations.
It was observed that the relative crystalline size decreased after ball milling with an average
nanoparticle size in the range of 9–12 nm (Ahmad et al., 2020).
FIG. 7 TEM micrographs of ZnO nanoparticles of heat treated at 300°C (Moballegh et al., 2007).
compared with those particles prepared by a common mixing device (Lin et al., 2010).
A recent report shows the preparation of InP/TiO2-C nanocomposites synthesized through
the mechanochemical process as an anode for its application in Li-ion batteries to improve
efficiency and stability (Hai Nguyen et al., 2020).
(A)
50 nm
(B) (C)
200 nm 200 nm
(D) (E)
200 nm 200 nm
FIG. 8 TEM images of nano-SiO2 (A) dispersed in D4(Octamethylcyclotetrasiloxane), hybrid particles prepared by
common method dispersed in PDMS (SiO2/TDI (B) and SiO2/TDI/(PDMS-OH) (C)), and hybrid particles prepared
by ball milling method dispersed in PDMS(SiO2/TDI (D) and SiO2/TDI/(PDMS-OH) (E)) (Lin et al., 2010).
positive resist, the negative resist is cheaper with low resolution and positive resist becomes
polymerized under light exposure. The system of photolithography can be contact printing
(photomask and photoresist show direct contact), proximity printing (proximate contact be-
tween mast and photoresist), and projection printing (projection printing by using a lens hav-
ing high resolution). The photolithography process scheme is shown in Fig. 9 (Mosher et al.,
2009; Khumpuang and Hara, 2015; Srivastava, 2016). In 2019, Liu et al. developed a new
method of photolithography based on electron beam (Liu et al., 2019). However, electron
3 Top-down fabrication methods 13
FIG. 9 Photolithography process.
beam lithography is a type of mask-less lithography employed for nanoscale patterns. Accel-
erated electron beams are exposed to the electron-sensitive materials. A conducting substrate
is used to overcome the charging. The result of this exposure can be a positive tone resist or
negative tone resist. The electron beam is scanned (layer-by-layer fashion) on the surface of
the resist with the diameter in the range of nanometers. Finally, the resulting pattern is
obtained by an etching process or vacuum evaporation, as shown in Fig. 10 (Pfeiffer, 2009,
2010). Similarly, extreme ultraviolet (EUV) lithography, another new technology (Torretti
et al., 2020), has been utilized to fabricate electronic circuits of sub-20 nm range using low-
energy electrons in tin-based nanomaterials (Bespalov et al., 2020). Also, soft lithography
has been used; microcontact printing is a kind of soft lithography. Micro- or nanostructured
surfaces are fabricated using microcontact printing (μCP); polymeric stamp with a relief pat-
tern is the main component of soft lithography. The substrate surface and stamp (inked) are
brought in contact to get the desired pattern; once the inked stamp is contacted with the sub-
strate, the pattern is transferred from the stamp to the substrate contact area. Elastomer and
conducting substrate
liftoff
metal deposition final structure
a b c
f e
FIG. 11 Key steps in microcontact printing (μCP): (a) a prepolymer is poured on a photolithographically structured
master, (b) the prepolymer is cured, and the elastomer stamp is peeled off the master, (c) the stamp is cut into smaller
pieces, (d) the stamp is inked by soaking it in an ink solution, (e) the ink is printed by contacting an inked stamp with a
suitable surface, and (f ) a patterned substrate is obtained. Alternatively, to (a) and (b), a stamp can also be obtained by
hot embossing. Alternatively, to (c), wafer-size stamps can also be used. Alternatively to (d), a stamp can be inked by
spreading a drop of ink on the stamp, or by using an ink pad (Kaufmann and Ravoo, 2010).
polymer ink are used as stamp in microcontact printing because they are flexible and mechan-
ically stable (Kaufmann and Ravoo, 2010). The key steps of microcontact printing are men-
tioned in Fig. 11.
Another approach, nanoimprint lithography, has been used to fabricate the nanostruc-
tured pattern ( Jiang et al., 2019). Nanoimprint and soft lithography are almost similar pro-
cesses. Nanoimprint lithography follows the two basic steps (Fig. 12):
(1) Imprint step produces a thickness variation pattern in the resist and
(2) Selective etching process of residual resist.
Totisesti onkin niin, että kyvykkäät ja ne, joiden päässä ei ole vain
kourallinen tietoa, eivät mielestänsä tiedä mitään, ennenkuin tietävät
kaikki. Mutta kun tämä on mahdotonta, jäävät he Sokrateen
kannalle, sanoen tietävänsä vain sen, etteivät mitään tiedä. Enpä
luule, että Homeros kiusasi mieltänsä tuumimalla kalamiesten
arvoitusta tai että Aristoteles, joka ymmärsi tiedon epävarmuuden ja
niin usein tunnusti ihmisen järjen liian heikoksi ymmärtämään
luonnon ilmiöitä, milloinkaan oli vähällä hukuttaa itsensä
koettaessaan selvittää Euripos-salmen virtauksia. Se, mitä tänään
opimme, saattaa jo huomenna paremman arvostelumme edessä olla
mitätöntä. Ja niinhän Aristoteles opettaa meille, mitä Plato oli hänelle
opettanut, nimittäin itsensä kumoamista. Olen tutkinut kaikkea, enkä
kuitenkaan voi tyytyä mihinkään, sillä jos ensimmäisten opintojemme
ja nuoruusvuosiemme harrastusten mukaan saattaisimmekin luulla
olevamme joko peripateetikkoja, stoalaisia tai akateemikkoja,
näyttävät minusta viisaimmat miehet ainakin lopuksi olevan
järjestään skeptikkoja, epäilijöitä, ja esiintyvät kaksinaamaisina kuin
Janus tiedon tantereella.
En ole vielä ollut avioliitossa ja yhdyn niihin, jotka eivät nai kahta
kertaa. Silti en tarkoita, etten hyväksyisi toista avioliittoa, niinkuin en
myöskään joka tapauksessa kieltäisi moniavioisuuttakaan, joka
joinakin aikoina ja ottaen huomioon eri sukupuolten epätasaisen
lukumäärän saattaisi olla välttämätönkin. Koko maailma luotiin
miestä varten, mutta kahdestoista osa miehestä naista varten; mies
on itsessään koko maailma ja Jumalan henkäys; nainen on miehen
kylkiluu ja koukero kappale. Olisin tyytyväinen, jos ihmissuku
lisääntyisi kuin metsä ilman yhtymystä, — jos maailma pysyisi
pystyssä ilman tuota alhaista ja joutavaa liityntää, sillä se on
hupsuinta, mitä viisas mies eläissään voi tehdä, eikä ole mitään
muuta, joka niin nolaisi hänen jälleen raitistunutta mielikuvitustaan,
kun hän muistelee, mihin eriskummaiseen ja arvottomaan
hullutukseen on tuossa teossa langennut.