Nanotechnology: Development and Challenges in Indonesia: Articles You May Be Interested in

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Nanotechnology: Development and

challenges in Indonesia
Cite as: AIP Conference Proceedings 1927, 020005 (2018); https://doi.org/10.1063/1.5021193
Published Online: 09 February 2018

I Made Joni, Vanitha Muthukannan, Wawan Hermawan, and Camellia Panatarani

ARTICLES YOU MAY BE INTERESTED IN

Detection of mercury ions using L-cysteine modified electrodes by anodic stripping


voltammetric method
AIP Conference Proceedings 1927, 030001 (2018); https://doi.org/10.1063/1.5021194

Preface: The 1st International Conference and Exhibition on Powder Technology Indonesia
(ICePTi 2017)
AIP Conference Proceedings 1927, 010001 (2018); https://doi.org/10.1063/1.5021187

Graphite tail powder and liquid biofertilizer as trace elements source for ground nut
AIP Conference Proceedings 1927, 030004 (2018); https://doi.org/10.1063/1.5021197

AIP Conference Proceedings 1927, 020005 (2018); https://doi.org/10.1063/1.5021193 1927, 020005

© 2018 Author(s).
Nanotechnology: Development and Challenges in Indonesia
I Made Joni1, 2, a), Vanitha Muthukannan2, b), Wawan Hermawan2, 3, c) and Camellia
Panatarani1, 2, d)
1
Department of Physics, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran,
2
Nanotechnology and Graphene Research Center, Universitas Padjadjaran,
3
Department of Biology, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran,
Jl. Raya Bandung-Sumedang KM 21, Jatinangor, Jawa Barat 45363, Indonesia
a)
Corresponding author: [email protected]
b)
[email protected], c)[email protected]

Abstract. Nanotechnology today is regarded as a revolutionary technology that can help to address the key needs related
to energy, environment, health and agriculture in developing countries. This paper is a short review on the development
and challenges of nanotechnology in Indonesia. Nanotechnology offers great potential benefits, there is emerging
concerns arising from its novel physicochemical properties. The main applications of nanotechnology in the different
sectors which is vital and its economic impact in Indonesia is also discussed. The achievment and development of
nanotechnology including synthesis and dispersion of nanoparticles (NPs) and its applications in various fields is briefly
addressed in Nanotehcnology and Graphene Research Center, Universitas Padjadjaran (Unpad). Despite
significant progress in developmental goals, many challenges in the development of nanotechnology proccesing need to
be resolved such as support infrastructure and evolution of new form of collaborative arrangements between various
sectors and policies which is emerged as an important factor enabling development.

INTRODUCTION
Nanotechnology can assist in controlling shape and size at the nanoscale (< 100 nm) level applied for the design,
characterization, production and application of structures, devices and systems which is incorporated in almost all
areas of science and engineering. Nanoscience and nanotechnology are transdisciplinary research that crosses many
disciplinary boundaries in scientific fields, such as chemistry, biology, physics, materials science and engineering.
Recently, the nanotechnology development attracted tremendous attention by making use of its advantages such as
novel and excellent properties at the nanoscale. Controlling shape and size at nanoscale i.e., tailoring matter at
atomic or molecular levels which is the fundamental units of materials where basic properties are initiated. This
means tailoring materials and system in terms of their fundamental characteristic and properties, i.e., developing
devices and systems with atom-by-atom engineering which involves understanding of the interaction between atoms
and molecules [1]. Therefore, to achieve this objective new knowledge, new tools and new approaches are necessary
[1-3]. Nanotechnology today is regarded as a revolutionary technology involving many important applications in the
field of energy, environment, health (medicine, cosmetics), electronics, food industry and agriculture.
Physiochemical characteristics of nanoparticles and engineered nanomaterials including size, shape, chemical
composition, physiochemical stability, crystal structure, surface area, surface energy and surface roughness
generally invoke different properties with desired purposes and also influence the toxic manifestations of these
nanomaterials. Atoms are governed by the laws of quantum mechanics and quantum mechanics is essential for the
understanding of atomic physics. The interactions between atoms are governed by quantum mechanics and so the
understanding of quantum mechanics is a prerequisite for understanding the nanoscience. The laws of quantum
mechanics predicts the way in which atoms form chemical bonds, even though chemical reactions are usually

The 1st International Conference and Exhibition on Powder Technology Indonesia (ICePTi) 2017
AIP Conf. Proc. 1927, 020005-1–020005-14; https://doi.org/10.1063/1.5021193
Published by AIP Publishing. 978-0-7354-1619-2/$30.00

020005-1
carried out in solutions where atoms of the solvent are constantly bombarding the atoms as they are undergoing
reactions.
Nanoparticles can also be used to prepare nanocomposites, which is integration of materials to form a new
material which has the properties of the combining materials and properties of its own. Nanocomposites have wide
range of applications which can be curtailed depending on the requirements. One such property of the
nanocomposite materials is its mechanical properties. Enhancement of mechanical properties also depends on other
microscopic filler-polymer interface factors. The use of fine-sized fillers does not follow this simple approach in all
cases, because due to size effects the following additional aspects have to be considered particle shape,
agglomeration and size distribution; particle specific surface area and related surface chemistry; particle-polymer
matrix interface and interaction; and compounding method and related shear forces. Therefore, understanding the
effects of the nanoparticle-sized fillers in the composite which enhances the mechanical, optical and
physicochemical properties is vital for the development of composite.
Despite many applications of nanotechnology, the debate still continues with varying opinions about exactly
what nanotechnology can achieve and do we have sufficient understanding or regulation of nanotechnology based
materials to minimize possible harm towards health and environment [4]. This paper is a short review on the
development and challenges of nanotechnology which offers great potential benefits due to the emerging concerns
arising from its novel physicochemical properties.

SYNTHESIS AND DISPERSION OF NANOPARTICLES (NPS)


Nanomaterials processing technologies that will support tailor-made products having functionality in critical
nanometer-scale dimensions and can be produced using novel technology systems with new phenomena of self-
assembly. The nanoscience focuses on the discovery of new materials, novel phenomena, new characterization tools
and introducing new functionality in nanomaterials system. Synthesis of nanomaterials is one of the most active
fields in nanotechnology. There are numerous methods for synthesizing nanomaterials of various characteristics. An
essential challenge in synthesis is controlling the structures with high yield for industrial applications. Techniques
are required for atomic and molecular control of material building blocks which is tailored for nano systems with
multi-functionality for many applications. Nanostructured materials may be defined as those materials whose
structural elements - clusters, crystallites or molecules - have dimensions in the range of 1 to 100 nm. Recent
advances in the synthesis and investigation of functional nanostructured materials, focuses on the novel size-
dependent physical and chemical properties.
Currently, polymers are widely used and play an important roles in various applications such as optoelectronic
industry, scratch resistance coating, UV resistance coating, conductive coating, heat resistance, etc. However,
several drawbacks prevent the application of polymers for advancing their expansion. For example, the refractive
index of a polymer can only be controlled within a very narrow range while keeping it transparent. In addition, the
refractive index is changed to large extent due to the temperature change. This is a serious problem for advanced
optical components and devices such as grating filters, lenses for high-resolution digital cameras and microlens
arrays for optical fiber communications. Also, the heat resistance of the polymer can only be controlled within a
very narrow range while keeping it mechanically strong and transparent. Various attempts have been made so far to
overcome such difficulties. In particular, nano-sized particles inclusion as composites for organic/inorganic
materials have been attracted for a while since, the properties of polymers such as optical, mechanical and thermal
stabilities can be modified by adding inorganic fillers [5-8]. However, the properties of the composite diminish due
to agglomeration of the inorganic particles as fillers during the preparation of composite. Thus, the state of well-
dispersed fillers suspension and stability of the dispersion is very crucial for enhancing the properties of composite.
In addition, nanoparticle reinforced composites are becoming an imperative topic of research in recent years.
Unlike in composite with micro- or larger sized reinforcements, effect of particles either submicron- or nano-sized
particles are found to be more unpredictable, sometimes enhancing the properties while other times diminishing it
[7-13]. Therefore, an appropriate design and selection of the nano-scaled building blocks and organic matrix are the
prerequisites for synthesizing nanocomposite. Moreover, the selection of the fabrication approaches and upgradation
of the compatibility between the inorganic and organic domains are essential in the preparation of nanocomposite.
There are three commonly developed fabrications routes to prepare inorganic-organic nanocomposite: Sol-gel route,
In situ formation of nanoparticle in polymer matrices and Ex situ synthesis method. The sol-gel process is based on
the hydrolysis and condensation of molecular precursors such as metal alkoxides to prepare three-dimensional
network-like inorganic or organic-inorganic hybrid materials. This route is actually a bottom-up method, which is

020005-2
versatile and can offer the potential of low-cost mass design and fabrication of organic-inorganic materials with
domain size approaching the molecular level under mild conditions.
One of the important route for the preparation of nanocomposite is integrating the pre-made nanoscale building
block such as inorganic nanoparticles into the polymer (blending route) or monomer which is subsequently
polymerized to form composite. This route is defined as the ex situ synthesis of nanocomposite. In this case, the
particles are prepared separately, isolated and purified or modified by surface capping agents before immobilization in
the polymer matrix. This method provides complete synthetic control over the particle size and size distribution as
well as the surface properties of nanoparticles. Therefore ex situ method is more suitable for large-scale industrial
applications than the above-mentioned method. Especially the in situ polymerizing route is a quite promising
approach for practical applications; however it is known that the nanoparticles tend to aggregate unless they are
modified at their surface to decrease the inter-particle attraction. The beads mill technology has been developed and
applied by Inkyo et al. [14] to obtain well-dispersed APTMS-capped TiO2 nanoparticles suspension in MMA and
subsequent in situ polymerization was used to prepare transparent TiO2-PMMA nanocomposite.

Synthesis of NPs by Sol-Gel Method


Sol-gel chemistry offers a flexible approach to obtain diverse range of nanostructured materials. Recent review
by G. J. Owens et al. [15] on various sol-gel methods with more detailed description of the biomedical areas, where
sol-gel materials have been explored and found to hold significant potential. The sol-gel process is based on the
hydrolysis and condensation of molecular precursors such as metal alkoxides to prepare three-dimensional network-
like inorganic or organic-inorganic hybrid materials. Usually, sol-gel method is applied for the preparation of glass
metal-oxides and ceramics by hydrolysing the precursor from liquid to gel phase simultaneously before evaporation
of the solution to form a glass metal-oxide or ceramic. Sol is a solid particulate colloid (undisolved) which is well-
dispersed in liquid media, while gel is a solid macromolecules inside the liquid media. Thus the sol-gel processes are
generally the formation process for oxide networks through polycondesation reaction of molecular precursor in the
liquid media. The sol-gel technology dramatically developed for engineering various structure and morphology of
materials such as gel-films, NPs coating, nanofiber, grain or spherical powder, porous gel and membrane. The sol-
gel is also potential method for preparing nanosystems such us delivery systems (i.e., drug delivery and pesticide
delivery, etc.) with three fundamental simultaneous process: monomer formation (partial hydrolysis), sol formation
(polycondensation) and networking or crosslink formation (gelation). Pirjo Kortesuo et al. [16] reported that sintered
silica xerogel prepared by sol-gel method did not show any tissue toxicity at the site of implantation, in the liver, or
in the kidneys.
The recent modification of sol-gel synthesis is adddition of polymer into the precursor after hydrolysis process.
In case of inorganic nanoparticles as target products, high temperature process is necessary to obtain high crystalline
materials. However, application of high temperature may initiate sintering form higher sized particles to aggregate.
Thus, Panatarani et al. [17] proposed addition of polymer such as PEG for preventing ZnO sintering and also
allowes lower temperature process since PEG initiates exothermic rection. Sol-gel with additional PEG can produce
finer particles size compared to the conventional PEG. In case of delivery systems prepared using sol-gel process the
products may be controlled at lower tempearture to form xerogel to purposely design amorphous inorganic nanoshell
such as core-shell structure [18].

Synthesis of NPs by Aerosol Method


The diversity of aerosol routes depends on the nature of the aerosol and the manner by which the aerosol
evaporation or decomposition energy is transferred to the system. There are two evident routes for all the well-
known routes: gas to particles and droplet to particles route [19]. For the gas to particles route, the particle formation
is derived from gaseous precursors. On the other hand, for the droplet to particles route, the particle formation is
derived from the discret aerosol droplets and control of the aerosol decomposition. The particle formation is affected
by solution properties and the applied thermal energy procedure to the precursors such as residence time and nature
of heat transfer. The advantages of an aerosol synthesis is that it offers a simple method for the production of oxide,
non-oxide, metal and composite powders with complex composition. On top of that, solution chemistry approaches
via aerosol processing, offers the design of materials at the molecular level, particles morphology, with narrow
particle size and a homogeneous composition can be achieved by properly adjusting the process parameters [20-23].

020005-3
Spray Drying
Spray-drying is a common technique used in pharmaceuticals to produce a dry powder from a liquid phase.
Newly invented spray dryer utilizes nebulizer to create tiny droplet such us two fluid nozzle equipped with
specially-designed nozzle, commercially available sprayer that utilizes a vibration mesh spray technology (by Büchi
Nano Spray Dryer B-90), or ultrasonic nebulizer. The particles size of the NPs obtained from spray drying depends
on the characteristics of the solutions, dispersions and emulsions. For pharmaceuticals application, spray-drying
process is applied to prepare and/or to dry polymeric nanoparticles formulations or intended for drug administration.
It also allows preparing innovative nanocoated-microparticles to control the drug release. Therefore, this method is
reasonably promising for synthesis of sophisticated nanoparticles and surface engineering for DDS (drug delivery
systems). Commonly such nanoparticles are made as clusters of primary nanoparticles by chemical reaction, aerosol
coagulation, sintering, surface growth and even fragmentation. This technique is employed as a microencapsulation
method because it can be adapted to the development of different systems, microspheres or microcapsules,
depending on the initial aqueous formulation, a solution, a suspension or an emulsion. Preparation of nanoparticles
by spray-drying and their use for efficient pulmonary drug delivery using nanoparticulate formulations dramatically
improves the efficiency of drug delivery to the lungs [24]. Mudit Dixit et al. [25], reported that spray drying of
Ketoprofen is a useful tool to improve wettability, solubility and hence the dissolution behavior of poorly water
soluble drugs.
Typical spray dryer equipment consists of an atomizer, for the atomization of a liquid source to generate droplets
from a spray solution and send them with sufficient initial velocity towards a controlled-temperature reactor and
droplets undergoes evaporation, precipitation and vaporization. Commercially available spray dryer usually use
nozzle for atomizer to receive higher rate of production, however higher size distribution of droplets is obtained .
Gas-phase (aerosol) technology is used widely in the manufacture of various nanostructured commodities with
high production rate. Spray-drying technique has been applied to prepare innovative nanoparticulate formulations
for drug administration and other types of nanosystems [26]. However, applications of polymeric nanoparticles tend
to agglomerate due to the reduced stability of formulations when conserved in aqueous medium for a long period.
Particle agglomeration and or aggregation, microbiological growth, polymer hydrolysis and physicochemical
instability as a consequence of particle aggregation may occur during the storage. Efforts to develop more stable
nanoparticle formulations have been carried out by controlling the type and the concentration of surfactants in the
formulations, but the results show good stability only in the short-term [27]. Other challenges are phase separation
that occurs after addition of various polymeric binders to aqueous suspensions of nanoparticles during the
incorporation of nanoparticles in solid dosage forms [28]. Therefore, efforts on the development of an effective
technique to improve the dispersion stability is very crucial. On the other hand, considering polymer-based nano
Drug Delivery System (nDDS), coating systems using organic solvents need to be avoided due to safety and
economic disadvantages. Thus researcher proposed useful methods to coat the microparticles and control the drug
release by using spray drying technique. This technique allows nanoparticle-coated drug-loaded organic-inorganic
microparticles. In addition, in one-step method the microparticles were prepared by the addition of the drug and
silicon dioxide directly into the nanoparticle suspension before the spray-drying. Other scenario is two-step process,
an organic-inorganic core is prepared by premixing the drug and silicon dioxide in acetone followed by solvent
evaporation under reduced pressure. This core is re-dispersed in the nanoparticle suspension before the drying
process.

Spray Pyrolysis
Pyrolysis is a phenomenon by which an organic material undergoes thermochemical decomposition at elevated
temperature in the absence of oxygen. It therefore involves simultaneous physical and chemical changes. An
offshoot to such a phenomenon is “spray pyrolysis”. It is a liquid-source chemical decomposition process that
involves spraying a metal salt solution onto a heated reactor. A typical spray pyrolysis equipment as shown in Fig. 1
consists of an atomizer, for the atomization of a liquid source to generate droplets from a spray solution and send
them with sufficient initial velocity towards a high temperature substrate, a precursor solution, which as it moves
through the heater ambient undergoes evaporation, precipitation and vaporization. The major requirements of a
precursor are it must be soluble in an alcoholic solvent or water (depending upon the spray pyrolysis technique
employed).

020005-4
Despite spray pyrolysis is a promising technique with various advantages like low-processing temperatures, high
homogeneity and purity of products among other advantages, the challenges include control over morphology and
composition of product particles. However, this can be resolved by atomization techniques that offer control over
droplet size & distribution such as ultrasonic nebulizer of two-fluid nozzles. Thus, spray pyrolysis (SP) is a
promising aerosol process to produce desired particles of precisely controlled size and designed morphology. The
capability of spray pyrolysis synthesis to produce controlled properties of particles provoked researchers on aerosol
process to believe that it may replace conventional processes such as solid state reaction process or liquid
precipitation method. However, productivity is the biggest obstacle in the development of a commercial scale
process because the aerosol process is essentially operated at low particle concentration compared to liquid phase
processes [29,30].
The early stage of spray pyrolysis (SP) development is called conventional spray pyrolysis (CSP) for producing
particulate materials that combines both liquid and gas phase aerosol processes. The SP system usually consists of
several main components such as a vessel for precursor solution, droplet generator, reactor and particles collector as
depicted in Fig. 1. In the CSP method of producing particles, a misted spray of precursor solution in the form of
droplets is dried, precipitated and decomposed in a tubular reactor. The precursor solution is atomized and misted by
means of an ultrasonic transducer. The mist is carried out by a gas flow into a hot wall tubular reactor then in-flight
heated for several seconds in the reactor. Finally, the resulted particles are collected using an electrostatic
precipitator.
During SP synthesis it is possible to use a heat source either from electric furnace, flame, microwave, or plasma.
The electric tubular furnace is the most commonly used type of reactor. The advantages of the electric furnace are
simplicity in construction and controllability of temperature which allowed a multi-zone reactor with separated
drying zone, it is very useful in designing nanostructured functional material via spray pyrolysis. A flame source
liquefied propane gas or hydrogen is also a well-known heat source because of productivity and can conveniently
attain high temperature compared with an electric furnace. However, control of flame temperature and flame zone
requires some experience.
The fundamental of the SP process are the formation of droplets by the atomizer, stream flow of droplets carried
by a gas into a reactor where droplets are evaporated and decomposed to form solid particles. The gas flow rate is
adjusted to several liters/minutes corresponding to the residence time of the particles inside the reactor; usually it is
around several seconds at atmospheric pressure. Therefore, to fulfill the end product specifications of particles, there
are three most important aspects that have to be considered prudently: the selection of precursors, method of droplet
generation and selection of heat source and reactor as discussed [30-32].
The characteristics of precursor depends on the physio-chemical properties of the solution. The physio-chemical
properties of the solution are surface tension, viscosity, density, concentration, pH and decomposition behavior.
These solution properties affect the droplets and morphology of particles formation. Disintegration of particles into
primary particles (nano-size) is one of the key mechanism to produce nanoparticles. However, inappropriate
selection of the solution properties leads to the formation of agglomerated nanoparticle that becomes the main
hindrance for the synthesis. Therefore, additional additives to solution are necessary to prevent agglomeration. In
addition, the additives also modify the physical properties of the solution such as viscosity or surface tension which
influences the droplet size or generation rate of the droplets generator.
Excluding the physical properties of the precursor, the droplets size distribution also depends on the atomization
technique. Mono-dispersed or poly-dispersed droplets may be obtained. Two-fluid nozzle and ultrasonic atomization
technique usually produce poly-dispersed droplets. The droplets are carried out by the flowing gas stream into a high
temperature tubular flow reactor. Therefore, the flow rate of the carrier gas signifies one of the most vital process
parameters enabling the control of supporting atmosphere as well as the aerosol flow rate and the droplet residence
time. Then, in the reactor, aerosol droplets undergo evaporation, drying and solute precipitation in a single-step
process caused by the mechanism of heat and mass transfer inside the droplets and between the droplets and
surrounding gas. Such a mechanism enables high surface reaction solution stoichiometric retention as well as
segregation suppression to the droplet scale. As a result, spherical solid, agglomerate-free, either nano scale or
submicron particles are achieved.
After the solvent evaporation/drying stage, consecutively solute precipitation and decomposition occurs at the
droplet level, the primary particles arise through the thermally induced process of nucleation formation, collision
and coalescence. Resulting particles then arise through the growth and aggregation of nanoscale primary particles
arranged in spherical structure called as the secondary particles. The secondary particles size and size distribution
are mainly influenced by the properties of aerosol generator and precursor solutions. The size of the primary
particles depends on the time-temperature history and material properties. For low temperature and short residence

020005-5
time, particle coalescence proceeds slowly compared to the collisions, producing weak agglomerate having a high
surface area [31,32]. On the contrary, at a higher temperature and for small particles, particle coalescence is the
dominant process resulting in primary particle growth, hard agglomerate and small specific surface area. Thus,
nanoparticles can be generated in accordance with this method by properly controlling the initial aerosol droplet
size, mechanism of the droplet collision and coalescence as well as by suppressing the excessive grain growth and
grain coarsening.
Many attempts have been made for the development of CSP method to synthesize nanoparticles that exhibit the
desirable properties of nanoparticles. There are many possible ways to develop CSP method that includes: (1) the
modification of the nano-sized droplet generator with high concentration and generation rate, (2) use of additives to
alter the interaction between primary particles within droplets, (3) Control the environment of the surrounding
process, i.e., low pressure condition and (4) the selection of heat source to modify the heat energy transfer behavior
of the droplets or aerosol.
The use of additional additives on the development of CSP method namely salt-assisted-SP (SASP) were
reported in by Xia et al. [33,34] and Panatarani et al. [17]. On the other hand, reduced droplet size can be achieved
either by using an electrospray which is capable of producing directly nanoscale monodispersed particles or by the
modification of atomizing techniques, like filter expansion aerosol generator (FEAG) assisted spray pyrolysis
(FEAG-SP) [35]. The low-pressure condition was applied in spray pyrolysis as an attempt to control the
environment of the surrounding processes as reported by Wang et al. [36], in the investigation of low pressure-SP
(LPSP). Furthermore, the development of SP method was based on the diversity of thermal energy behavior as a
heat source such as flame-SP (FSP) [37] and pulse combustion SP [38]. The early stage of pulse combustion SP
(PCSP) system, ultrasonic nebulizer was used as an atomizer. Finally, for improving production rate, two-fluid
nozzle was applied in PCSP systems [39].

Droplet

Pulse Combustion
Furnace Reactor

`
Precipitation Tpulse>Treaction
`

Particles bursting

washing

CSP SASP PCSP

FIGURE 1. Spray dryer and Spray FIGURE 2. Overview of spray pyrolysis process and its development
pyrolysis apparatus comparison of conventional SP, salt assisted SP and pulse combustion SP.

The overview of the particle formation mechanism of spray pyrolysis process is presented as a comparison for
CSP, SASP and PCSP as displayed in Fig. 2. The apparatus of the SASP method is similar with that of the CSP
method as shown in Fig. 1. Salt-assisted spray pyrolysis (SASP) is a modified method of CSP by introducing a salt
into the precursor solution before atomization [33,34]. The SASP method focuses on the strategy for preventing the
nanocrystallites from agglomeration [33]. In the SASP method, a salted-precursor solution is atomized, passed
through the reactor for several seconds and secondary particles which contain primary nanoparticles within a salt
matrix is obtained. The nanoparticles were obtained after washing the product with water. In contrast, the CSP
concept is derived from one droplet to one particle; therefore, the particle products are in the submicron size. On the
other hand, in the SASP concept, the particle size product is independent of the droplet size [17]. In contrast in
PCSP the integration of primary particles occurs due to acoustic oscillations of the droplet derived from combustion
and droplet pressure balances: laplace pressure (interfacial surface tension) and osmotic pressure (interaction
potential) [39].

020005-6
FIGURE 3. ZnO NPs prepared by Spray pyrolysis FIGURE 4. ZnO NPs prepared by Spray pyrolysis:
with LiNO3 as additive: (a) before washing, (b) after (a) zinc nitrate precursor, (b) zinc acetate precursor
washing
Figure 3 shows the SEM micrograph of primary ZnO NPs prepared by spray pyrolysis technique using LiNO3 as
additive. Before washing (Fig. 3a) the particles were aggregated into a larger particle, whereas after washing the
particle size decreased into their primary size and has near quasi-spherical shapes with good homogeneity. The SEM
micrograph of ZnO obtained using two different precursors such as zinc nitrate and zinc acetate is shown in Fig. 4 (a
& b). Different morphology was obtained using the different precursors, Fig. 4a shows some aggregation of smaller
spherical particles into some larger particles as highlighted. Fig. 4b shows that the ZnO NPs in the shape of
nanorods were obtained and are stacked together and appears like a sheet, the stacked nanorods have different
orientations. So if different nanostructure has to be formulated this technique can be used effectively but further
studies need to be done in tailoring the size to nanoscale levels.

Pulse Combustion Spray Pyrolysis (PCSP)


In the early stage of PCSP development, ultrasonic nebulizer was used as an atomizer. Droplet evaporation from
the pulse combustion (PC) engine occurs very rapidly because of acoustically high-fluctuating flow of the gas
pressure and temperature during self-ignition [38, 40]. Widyatstuti et al. [38], proposed a mechanism of particle
formation in ultrasonic assisted PCSP. Thus, in the case of ZnO nanoparticle preparation, the droplets may break-up
because of rapid draying rate at high temperature. The final particles could be fragmented into their multiple primary
sizes of nanoparticles. Thus, the formation of nanoparticles and break-up of the droplets, depends on the driving
force of the heat transfer and also physio-chemical properties of the precursor.
Despite the capability of PCSP in producing nano-sized particles, the production rate of the ultrasonic nebulizer
assisted pulse combustion-SP (PC-SP) is very low. Thus, a new technique has to be applied to improve the
production rate of the synthesis by using a two-fluid nozzle as an atomizer in the PCSP system. The effect of droplet
characteristics such as size distribution of droplets, concentration and their behavior in the reactor are the
determining factors for the particles formation. In addition, the position and direction of the two-fluid nozzle in the
system have impact on the droplets behavior [39].
Pulse combustor is a special oscillating process driven by combustion, coupled with a resonant oscillator of flow
in the tailpipe. Pulse combustion is recognized for high combustion, high heat transfer rates and lower pollutant
emission than steady combustion [40,41] There are three types of pulse combustors, such as Schmidt, Helmholtz and
Rijke tubes. The most commercially available pulse combustor is Helmholtz type. Typically, the important
components of a pulse combustor are the combustion chamber and tailpipe attached to the end of the combustion
chamber. The advantage of the pulse combustion (PC) is evaporation from the engine occurs very rapidly because of
acoustically high-fluctuating flow of the gas pressure and temperature during self-ignition [42].
The cycle of operation process of the self-excited pulse combustor is as follows. Initially, a heat source such as
pulse igniter is required to initiate the combustion when reactants initially flow into the combustion chamber. The
reaction between propane and air leads to a sudden pressure increase in combustion chamber, which subsequently
causes the flow to slow down into the combustion chamber. Flue gas from the reaction flows out of the combustion
chamber through the tailpipe, the combustion chamber pressure decreases. If the pressure level is lower than the
supply pressure of reactants, fresh reactants will flow into the combustion chamber again. At the same time, hot flue
gas in the tailpipe starts to slow down and eventually flows back toward the combustion chamber. This process
repeats itself over and over again. The pressure oscillation parameter (amplitude and frequency) depends on several
factors such as the geometry and the dimension of the pulse combustion, the operating power of the combustor, the
equivalence ratio of the reactant and so on [43].

020005-7
In addition, pulse combustion has been applied for spray drying in many industrial applications with high
production capacity. For those reasons, pulse combustion method is potentially applied as a heat source in spray
pyrolysis for nanoparticles synthesis. Widiyastuti et al. [38], for the first time, applied pulse combustion as a heat
source for conventional spray pyrolysis to synthesis ZnO nanoparticles. However, due to the limitation of the
ultrasonic nebulizer as the atomizer, the production rate was low because the ultrasonic nebulizer generates droplets
with low generation rate and low concentration. In contrast to other types of spray pyrolysis such as CSP, CASP and
FSP, the behavior of the droplets in the PCSP is fundamentally different due to the presence of an acoustic field
caused by fluctuating pressure and temperature. Thus, the behavior of the droplets in the presence of an acoustic
field is important. The high heat transfer rate with high temperature due to acoustic field leads to the unique particles
formation in PCSP in which the disintegration of droplet into their multiple primary nano-sized particles occurs.
The formation of ZnO particles using the PCSP synthesis depends on both the heat and pressure distribution and
the characteristics of the atomizer. The processing parameter characteristics are essential for the formation of
inorganic particles in PCSP. Schuller et al. [44] and Nguyen et al. [45], reported that heat stream from pulse
combustion was coming from the acoustically oscillating gas. On the other hand, it is well-known that the nature and
behavior of droplets depends on their atomization technique and physio-chemical properties of precursor. Moreover,
particle formation also depends on the nature of the droplets interaction and its distribution inside the furnace due to
acoustically oscillating gas flow [46,47].
During the pulse combustion spray pyrolysis, the secondary atomization may occur due to acoustically oscillated
pressure and lead to the increase in heat transfer due to their finer droplet size distribution [42]. Murray and Heister,
1999, studied the influence of acoustic frequency, intensity and gas/liquid density ratio up on the droplet behavior.
They confirmed droplet break up and showed three regimes of process: nipple, kidney and toroidal. For high weber
number (We) the droplet rapidly flattens in a plane perpendicular to the acoustic wave, break up time is inversely
related [42]. However, investigation of the literature showed that despite wide variety of pulse combustion
applications and the advantages of this process, knowledge of the pulse combustion spray pyrolysis mechanism is
limited. The process mechanism is sophisticated and this complex character is under the continuous investigation.

Dispersion of Nanoparticles by Beads mill


Utilization of nanoparticles, very often requires their dispersion in various liquids in order to enable homogenous
embedding of the final products. Currently, different grinding and dispersing processes are applied to produce
products of our daily life like filler for paper and plastics, pharmaceutical drugs, spices and pigments. Fine drug
particulates are especially desired in formulations designed for parenteral, respiratory and transdermal use. Most
drugs after crystallization have to be comminuted and this physical transformation is required to various extents,
often to enhance processability or solubility especially for drugs with limited aqueous solubility [48]. Qing Yao et
al. [49] reported redispersion of the shell-forming nanoparticles to improve oral bioavailability of core-shell
structured beads. Also, nanocrystalline solid dispersion of coenzyme Q10 prepared with cold wet-milling system to
enhance the dissolution and biopharmaceutical properties of CoQ10 [50]. The mechanisms by which milling
enhances drug dissolution and solubility altering in the size, specific surface area and shape of the drug particles as
well as milling induced amorphization and/or structural disordering of the drug crystal (mechano-chemical
activation) [48].
The development of recent milling technology [51-53] provide adjustable two rotors to control the speed and
designed degree of NPs crystallinity and enable the production of drugs of micro- and nano-particles size on a
commercial scale with relative ease. Chemical synthesis methods as bottom-up processes are commonly used to
produce fine, nano and submicron scaled particles. On the other hand, top-down process like comminuting or
mechanical grinding in stirred-media mills offers the possibility of sub-micron and nanoparticles production. The
beads mill process deals with two simultaneous processes of grinding and dispersing. Firstly, the bulk material is
grinded to get nano and/or submicron particles in liquid media. At the same time, the resulting smaller sized
particles of either submicron and/or nanoparticles scale are dispersed in liquid media. Alternatively, the beads
milling is applicable only for dispersion process in which the nanoparticles powder can be obtained commercially or
produced from bottom-up processes. The ultimate goal of the dispersion process is to separate the agglomerated
particles into their primary size and maintain the stability and or control the amorphous nature of the crystal to some
extent.
The success of the grinding process depends on the dispersion stability. Nevertheless, it is difficult to control the
stability of nanoparticles in liquids. Since most dispersion of nanoparticles are not thermodynamically stable and

020005-8
represent a metastable state as compared to the bulk material, agglomeration and coagulation of these materials tend
to occur spontaneously. The nature of nanoparticles shows distinctive surface structures and surface interactions
causing strong attractive forces and easily make re-agglomerated particles. Thus, it is important to develop
techniques to achieve the dispersion stability of nanoparticles suspension. Dispersion of nanoparticles in aqueous
media can be modelled with the theory by Deryagin, Landau, Verwey and Overbeek (DLVO). However, it is still a
challenging task to manage high-concentration nanoparticle suspensions in organic media. Surface modification of
nanoparticles is one of the most common methods to improve the dispersion stability of nanoparticles. It requires a
design of surface structure based on the type of nanoparticles and liquid media [54,55].
In general, dispersions of inorganic nanoparticles require the use of colloidal chemistry techniques. This
technique can be divided into three stages: wetting of the powder with liquid, breaking the agglomerates of the
primary nanoparticles by applying high shear forces and stabilizing by proper dispersing agents. Stabilization of
nanoparticles in dispersions is achieved by adding dispersing agents which lead to an increase in the energy barrier
for aggregation and leads to their kinetic stability.
The stability of nanoparticles is governed by the balance of various interactions, such as vanderwaals attraction,
electrical and steric repulsion. Thus, the optimal approach to obtain stable dispersions is by using stabilizers which
have affinity groups on the surface of the particles. These groups provide either only electro or electro-steric
stabilization. Making use of proper dispersing agent can lead to the formation of stable dispersions. To improve the
dispersion stability of nanoparticles, it is necessary to modify the particle surface with polymeric surfactants or other
agents in order to generate an effective repulsive force between the nanoparticles. Adsorption of a polymeric
dispersant on nanoparticles is one of the simplest surface modification techniques to improve the dispersion stability
of nanoparticles in liquid media. While dispersing hydrophilic nanoparticles in aqueous media or in organic solvents
with high polarities, anionic or cationic polymer dispersants are widely used to generate the steric repulsive force
originating from the polymer chains and to increase the surface charge. Although the DVLO theory is proved to be a
milestone in the area of colloid stability theory, the theory could not explain many experimental results. Sometimes,
the repulsive force between hydrophilic particles is very strong and arises at several nanometers of separation
distance between the approaching particles. All these surface forces, such a structural force, solvation force and
others have not been considered in DLVO theory that may cause deviation from the theoretical predictions.
Surface modification of the nanoparticles is necessary to employ them in targeted drug delivery applications
where beads milling process comes into picture. Nanoparticles i.e., TiO2 cannot be dispersed directly in organic
solvents which are less polar, beads milling process prevents agglomeration and paves way to endure dispersion
stability [51]. Conversion of materials to nanoparticles via beads milling occurs by mild dispersion and real
comminution routes. Two paths are influenced by density, speed of agitator and grinding media diameter. In mild
dispersion method the agglomerated particles are separated into discrete particles by removing the surface air and
wetting the particle surface. Control of beads size is also influenced by opting for smallest and densest media with
lowest tip speed. In real comminution the dispersion of particles in liquid phase leads to bead formation by high
shearing and impact forces. The dispersion of particles can be achieved after surface modification; specific
surfactant is essential for the formation of stable suspension [56]. Selection of appropriate additives is required to
stabilize and prevent the particles from re-agglomerating. For the preparation of colloidal particles stirred beads mill
with small beads are reported to be effective [57].

APPLICATIONS OF NANOTECHNOLOGY
Obviously many promising applications of nanotechnology in industries make a significant impact on the
society. Some of these applications utilize novel materials providing outstanding functionalities associated to
nanoscale. Materials at nanoscale include their form in a very thin films applied for catalysis and electronics, two-
dimensional nanotubes and nanowires for optical and magnetic systems and as nanoparticles applied for cosmetics,
pharmaceuticals, food, agriculture and coatings and as nano colloids such as fine bubbles (Micro-nanobubbles)
applied for aquaculture, water treatment and environmental remediation. Recently, most rapid development and
readily applied nanotechnology in industrial sectors are electronic and optoelectronic fields, food technology, energy
technology and medical products sector, pharmaceuticals and drug delivery systems, diagnostics and medical
technology. In addition, nanotechnology products may also offer novel challenges for the reduction of
environmental pollution, one such technology is nanobubble.

020005-9
Nanotechnology for Energy Applications
Recently, nanotechnology is considered to be the most recommended choices to solve the technological
challenges in renewable energies. Several comprehensive review on this issues were reported elsewhere [58], a brief
overview on the applications of nanotechnology is explained here. Furthermore, nanotechnology can be used to
improve renewable energy sources; for example, wind energy efficiency can be improved by using light, more
strengthened nano-materials for rotor blades. Nano-coatings can be used to prevent the corrosion in tidal energy
equipment’s, while nanocomposites are utilized to make drilling machines in geothermal energy with more fatigue-
resistance. The big challenge in solar harvesting technology is the weakness in the absorption properties of the
conventional fluids which reduces the efficiency of these devices, i.e., solar collector, the fuel cell, photocatalysis
and solar photovoltaic [59]. It was reported that by using nanomaterials the incident radiation can be increased by 9
times while the efficiency of the solar collector is 10% higher compared to that of a conventional flat plate solar
collector [60]. In the battery development, graphene is applied to have a higher specific energy, higher specific
capacity and lower cost than conventional batteries. If nano-graphene technology enhances battery power and
lengthens the life span, it will have attractive prospects in the field of electric vehicles [61].

Nanotechnology for Drug Delivery System


The detailed review on nanoparticle-based targeted drug delivery is reported by Rajesh Singh and James W.
Lillard, Jr. [62]. The following is a brief review on the drug delivery properties related to the nanostructured
materials. With decrease in the size of the particle at nanoscale, more number of atoms that constitute the
nanoparticles can be found on the surface making the materials highly reactive. One of the significant area in the
field of nanotechnology is drug delivery systems. The shortcoming experienced in traditional drugs can be overcome
by drug delivery system. Nanoparticles that are employed in drug delivery have the potentiality for improving the
drug activity. Nanoparticles act as a carrier and binds the drug on their surface and control them from being
degraded or denatured. Nanoparticle carriers also have the capability to co-deliver two or more drugs at the same
time. Surface modification makes the nanoparticle to adhere to specific ligands for targeted drug delivery [63]. The
important aspect in drug delivery using nanoparticle are particle size and size distribution which assists in
determining the in vivo distribution, toxicity, drug loading, drug release, stability of nanoparticles and targeting
ability of drugs. The use of nanoparticles in all these cases is preferred more than the microparticles owing to the
advantages such as higher uptake due to smaller size, larger surface area leading to rapid drug release, higher carrier
capacity of the former. Depending on the strategies for the preparation nanoparticles, nanocapsules, nanorods,
nanospheres can be obtained with different physical properties which can be tailored and tuned for the effective drug
delivery [64].
Particle size and size distribution are the most important characteristics of nanoparticles that affect the in vivo
distributon, absorption and biological fate, toxicity and targeting ability of the delivery systems. In addition, control
of particle size provides opportunity in fine-tuning drug release rates. Surface modification of nanoparticle can be
achieved by coating nanoparticles with hydrophilic polymers/surfactants or formulating nanoparticles with
biodegradable copolymers with hydrophilic characteristics such as polyethylene glycol (PEG), polyethylene oxide,
polyoxamer, poloxamine, or polysorbate 80 (Tween 80). A polymer of choice for some nanoparticle formulations is
PEG, which has little or no effect on drug-loading and interactions [65]. The surface modification of NPs is
designed for obtaining effective drug loading and controlling drug release. The surface characteristics of NPs also
determine the stability of the size and size distribution of the NPs suspension. In this case, zeta potensial was
employed to characterize the surface charge property of nanoparticles. When nanoparticles suspension with a zeta
potential above ± 30 mV it shows a stable suspension since the surface charge prevents aggregation of the particles.
In addition, zeta potential also can be used to determine whether a charged active material is encapsulated within the
center of the nanoparticle or on the surface. Other Qualitative and quantitative investigation of the adsorption can be
investigated by spectroscopic instruments such as TGTA and FTIR.
The drug-loading capacity of nanodelivery system should be as high as possible in order to reduce the quantity of
matrix materials for administration. There two routes on the drug loading: the drug is incorporated simultaneously
with the nanoparticles formation and inclusion of pre-made NPs with concentrated drug solution. The successful
drug-loading and entrapment depends on drug solubility in the matrix material. The drug solubility in the matrix
depends on the matrix composition, molecular weight, drug-polymer interactions and the presence of end functional

020005-10
groups (i.e., ester or carboxyl) in either the drug or matrix [66-68]. The electrostatic interaction of the encapsulated
NPs and drugs or protein drives the fusion process which determines the loading efficiency [69].
The charateristics of drug and biodegradable polymer determines the effectivity of the drug release. Rajesh Singh
and James W. Lillard Jr. [62] highlighted that in general, the drug release rate depends on: (1) drug solubility; (2)
desorption of the surface-bound or adsorbed drug; (3) drug diffusion through the nanoparticle matrix; (4)
nanoparticle matrix erosion or degradation; and (5) the combination of erosion and diffusion processes.

Nanotechnology for Food and Agriculture


Nanotechnology has proved to serve in the field of food science diligently. From increasing the shelf-life of food
product, better tracking and tracing of contaminants, upgraded storage of food, to the incorporation of health
supplements or antibacterial agents in food, it is indeed a great contribution by nanotechnology towards food science
[70]. Nanotechnology offers new opportunities for food and agricultural industries and several applications can be
found at different stages of the food production chain: agrochemicals delivery; nanomaterials for detection of animal
and plant pathogens; food and feed: food additives as color and flavor enhancers, food supplements (e.g. to increase
iron or other trace element bio-availability), novel food structure (e.g. nano-emulsion to reduce fat content),
nanoparticles for edible food and food packaging (nanoparticles with antimicrobial or antioxidant characteristics to
boost preservation of foodstuffs), food supplements: nanoparticle suspensions as antimicrobials, nano-encapsulation
for targeted delivery of nutraceuticals.

NANOTECHNOLGY CHALLENGES AND DEVELOPMENT OF


NANOTECHNOLOGY IN UNPAD
Despite significant progress in development of nanotechnology which can be used for the benefit of mankind,
many challenges on their development requires resolving support infrastructure and evolution of new forms of
collaborative arrangements between various sectors and policies which emerged as an important factor to enable
development. Challenges in nanotechnology developtment in Indonesia is based on available resources to enhance
potential economic impacts: Synthesis of inorganic nanoparicles with inexpensive raw materials and also high
production rate; Extraction of bioactive compound, nanoprocessing and functionalization; Dispersion of high
concentrate of suspension at particluar media for suspension (water or inorganic solvent); and Risk study on
nanotechnology.
Thus the Ministry of Research & Technology Republic of Indonesia (recently named Ministry of Research,
Technology and Higher Education) had proposed an initiative for national research agenda in White Book (2005-
2025) for new priority on advanced material and nanotechnology. The goals of this inniative is to make the resource
arrangements between various sectors to enable efficient development. In addition, in the year 2010, the Ministry of
Industry also provided nanotechnonolgy roadmaps for supporting national industry (Textile & Ceramic, Chemical
and Polymer Industry). In order to support the science and nanotechnology development, nanotechnology procesing
and product developtment in industry, the National Standard Body issued several standards which may be adopted
from several international standard as shown in Table 1 during the period of 2011-2012.
TABLE 1. National standard related to nanotechnology issued by National Standard Body Republic of Indonesia
Standard Number Regulation for
SNI ISO/TS 80004-1:2011 Nanotechnologies-Vocabulary-Part I: Core Term
SNI ISO/TS 27687:2011 Terminology and definitions fro nano-object-nanoparticles-nanofibre and nanoplate
SNI ISO/TS 80004-3:2011 Nanotechnologies-Vocabulary Part 3: carbon nano-objects
SNI ISO/TS 10867:2011 Nanotechnologies- Characterization of single-wall carbon nanotube uisng near infrared
photolumniscence spectroscopy
SNI ISO 29701:2011 Nanotechnologies- Endotoxin test on nanomaterial samples for in vitro systems-Limulus
amebocyte lysate (LAL) test
SNI ISO/TR 11360:2011 Nanotechnologies-Methodology for the classification and catagorization of nanomaterials
SNI ISO 10808:2012 Nanotechnologies-Characterization of nanoparicles in inhalation specifying nano-objects
SNI ISO/TS 12805:2012 Nanotechnologies: Materials specification-quidance on specifying nano-objects
SNI ISO/TS 80004-4:2012 Nanotechnologies-Vocabulary-Part 4: Nano structure materials
SNI ISO/TS 80004-5:2012 Nanotechnologies-Vocabulary-Part 5: Nano/bio interface
SNI ISO/TS 80004-7:2012 Nanotechnologies-Vocabulary-Part 7: Diagnostics and therapeutics for healtcare
Source-National Standard Body, Republic of Indonesia

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In addition, most importantly the newly propective processes and their products may expose humans and the
environment in general to a new health risks, possibly involving quite different mechanisms of interference with
humans and environmental species. Studies revealed that nanoparticles can enter the human body through the lungs,
intestinal tract and skin. Thus, researchers and workers who handle nanoparticles and nanomaterials can
theoretically and primarily be affected, whereas on the consumers this will have secondary effects. Therefore, we
should have sufficient understanding or regulation of nanotechnology based materials to minimize possible
hazardous to health and environment.
Nanotechnology is gaining attention in our society in Indonesia especailly at Universitas Padjadajaran and the
use of technology has remarkable development in the field of Science and Technology [53,71-73]. Initially the
development started from the nanotechnology proccesing including the synthesis and dispersion of NPs as a base
development for its applications in various fields in Nanotechnolgy and Graphene Research Center, Universitas
Padjadjaran. Since the remarkable gaining attention from our society, the development was clustered to enable
collaboration among various parties. The development for nanotechnology in Universitas Padjadjaran clustered into
five fields that includes: Nanotechnology for Life Science, Energy, Materials Processing, Computational
Nanomaterials and Instrumentations and Imaging Technologies at Nano Scale. In the clustered nanotechnology for
life science includes development of nanotechnology for agriculture, nanotechnology for biomedical applications
(Nano Dental Biomaterials and Nanotechnology for Pharmaceutical Materials) and nanotechnology for food
technology.

CONCLUSION
Despite significant progress on the developmental goals, many challenges on the development of
nanotechnology proccesing need to be resolved such as support infrastructure and evolution of new forms of
collaborative arrangements between various sectors and policies which emerged as an important factor enabling
development and also to enable identification of their potential risks towards human beings and environment.

ACKNOWLEDGMENT
The author acknowledged the financial support of the research under Academic Leadership Grant (ALG)
UNPAD for the contract no. 855/UN6.3.1/PL/2017 year of 2017.

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