Ceramic Nanoparticle Synthesis

Encyclopedia of
Nanoscience and
Nanotechnology
www.aspbs.com/enn
Ceramic Nanoparticle Synthesis

Xiangdong Feng
Ferro Corporation, Ohio, USA
Michael Z. Hu
Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA
CONTENTS bulk materials [6, 7]. This represents new opportunities in

science, such as the change of properties and laws as the
1. Introduction dimensions of the nanomaterials become comparable to,
2. Methods for Categorizing or smaller than, relevant length scales, such as the mean-
Nanoparticle Synthesis free path or the coherence length. New material properties
3. Descriptions of Major Synthesis result when the surface and the grain boundary atoms rep-
Methods by Media resent a large proportion of the total number of atoms, or
when processes become dominated by quantum effects, or—
4. Summary in general—by the transition from atomic and molecular
Glossary behavior to condensed matter behavior [8].
References The size range for nanoparticles may be more accurately
defined as the size range from 1 nm to the largest nano-
meter dimension, where the ratio of the number of atoms
1. INTRODUCTION on surfaces and at grain boundaries to those at the center is
such that new physical, chemical, and biological properties
Nanotechnology has been viewed as the “little big science”
occur, compared to bulk materials [9]. The upper limit of the
[1], which is considered the impetus for the next industrial
nanoparticle size may be different from 100 nm, depending
revolution. The ability to work at the molecular level, atom
upon the sizes of the atoms and molecules in question.
by atom, to create large structures with fundamentally new
Nanoparticles have large surface areas [7] and high reac-
properties and functions is the core of nanoscale science,
tivity due to the unsaturated bonds on their pristine surfaces.
engineering, and technology [2]. One of the building blocks
of nanotechnology is nanostructured materials such as nano- Nanoparticles tend to react among themselves to form neck-
particles [3]. ing, and hence agglomerate into large secondary particles.
Nanoparticles may be defined according to their physi- This imposes extreme challenges for industry to produce
cal dimensions as particles with a size range of 1 to 100 nm large quantities of nanoparticles with identical properties
[3, 4]. A typical nanoparticle most often consists of several inexpensively and reliably. Selecting the proper manufactur-
small “primary particles” [5]. The size of nanoparticles usu- ing methods for a specific application requires a thorough
ally refers to the “secondary” particle size. Primary parti- understanding of the fundamental aspects of nanoparticle
cles agglomerate into these “secondary” particles [5]. The formation.
primary particles have a very high surface-to-volume ratio. There are numerous reported synthetic methods for the
The proportion of atoms on the surface and at the grain production of nanoparticles [10]. The challenge is to con-
boundaries of a nanoparticle is significant. Nanoparticles trol the nanoparticle size, size distribution, morphology,
have about 98, 40, and 10% of their atoms on the surfaces crystallinity, shape, and properties, to assemble the nano-
or at the grain boundaries if their primary particles are 1, particles for a given purpose, and to make them from a
5, and 20 nm, respectively. The high proportion of surface variety of materials. The synthetic methods reported can be
and grain boundary atoms is responsible for the different classified according to synthesis strategies, the branches of
properties (electronic, optical, electrical, magnetic, chemi- science involved in the process, sources of energy input, and
cal, and mechanical) of nanoparticles with respect to the the media in which nanoparticles are formed.
ISBN: 1-58883-057-8/$35.00 Encyclopedia of Nanoscience and Nanotechnology

Copyright © 2004 by American Scientific Publishers Edited by H. S. Nalwa
All rights of reproduction in any form reserved. Volume 1: Pages (687–726)
688 Ceramic Nanoparticle Synthesis
2. METHODS FOR CATEGORIZING 2.2. By Nature of the Process

NANOPARTICLE SYNTHESIS Different nanoparticle-making techniques may involve dif-
ferent scientific processes, such as physical, chemical or bio-
2.1. By Synthesis Strategy
logical, or some combination of these processes.
Strategies are important for the synthesis of nanoparticles.
There are two basic strategies used in the syntheses of nano-
particles: bottom up and top down [9, 11]. 2.2.1. Physical Methods
A physical process involves only changes in physical state,
such as size, shape, and phase of the matter. Mechanical size
2.1.1. Bottom-Up Strategy reduction is a physical process. Condensing gaseous metal
This strategy is more in line with the basic strategy of nano- vapor into nanoparticles is another example. The forma-
science and technology. Here, nanoparticles are built up tion of nanoparticles in the gas phase is accomplished by a
atom by atom, or molecule by molecule, at the will of their rapid quenching of supersaturated metal vapors with room-
creators. Most nanoparticle syntheses belong to this cate- temperature or cold inert gas [20].
gory. A simple example of this approach is the flame syn-
thesis of TiO2 from gaseous TiCl4 and oxygen according to
2.2.2. Chemical Methods
TiCl4 + O2 → TiO2 + 2Cl2 Most nanoparticle syntheses involve chemical changes. For
instance, a sol–gel process converts metal alkoxides into
It has been shown that nucleation and surface growth deter- oxide particles [21]. A hydrothermal process converts tita-
mine the primary particle size of titania [12–14]. Other stud- nium isopropoxide and barium hydroxide into BaTiO3 [22].
ies [15, 16] show that coagulation of the primary particles of Other chemical methods will be described in more detail in
titania could also dominate particle growth during flame syn- following discussions.
thesis of TiO2 . The molecular TiO2 formed in the flame can
grow into particles through nucleation and surface oxidation 2.2.3. Biological Methods
of TiCl4 , aggregation, or the combination of both mecha-
nisms. Under certain processing conditions, either one of Nanostructured materials are synthesized in nature by a pro-
the mechanisms could dominate the overall particle growth. cess known as biomineralization (the in vivo formation of
inorganic crystals and/or amorphous particles in biological
systems [23, 24]). In nearly all cases, the growth of the inor-
2.1.2. Top-Down Strategy ganic phases is controlled by biologically produced mem-
This strategy is most applied in the traditional particle- branes or templates, which are usually composed of proteins
making process. Here, nanoparticles are synthesized by and/or polysaccharides [25]. In some cases, the phase of the
breaking down bulk materials gradually into smaller sizes inorganic element is dictated by the organic template, by
until they are nanosized. The end results could also be molecular complementarities, or by epitaxial matching of the
achieved by leaching out one type of molecule in a bulky organic and inorganic surfaces. In some cases, the biological
homogeneous molecular solid mixture. membrane may act to limit the size and morphology of the
Mechanical breakdown, such as high-energy ball milling, resulting crystal by providing a defined space and chemical
is a simple case of the top-down strategy. –Al2 O3 powders environment within which precipitation can occur. Fendler
have been ball milled into nanocrystalline alumina powders [26, 27] has shown that a mimetic approach in nanoparticle
with different surface areas of up to 100 m2 /g, depending synthesis addresses the essential requirement of biominer-
on the milling atmosphere of air or inert gases [17]. High- alization. It is to have compartments capable of providing
energy ball milling is useful for deriving nanocrystalline structural, spatial, and chemical controls for nanoparticle
materials of high-temperature phases without going to generation and stabilization. The mimetic approach using
extreme heat treatment, which would promote significant aqueous micelles, reverse micelles, microemulsions, vesicles,
grain growth and surface area loss. For example, nano- polymerized vesicles, monolayers, self-organized multilay-
crystalline –Al2 O3 with a high surface area was obtained ers, and bilayer lipid membranes has successfully generated
through ball milling [18]. nanocrystalline Ag2 O [28], and less than 10 nm monodis-
Another example of the top-down strategy is illustrated by persed Pt, Pd, Rh, and Ir particles [29, 30]. Pierre et al. have
the synthesis of nanosize yttrium-stabilized zirconia by leach- also demonstrated the synthesis of nanoscale (<10 nm) iron
ing bulky yttrium-doped BaZrO3 or bulky yttrium-doped oxide using protein cages and polysaccharide networks [31].
Na2 ZrO3 [19]. In this approach, yttrium-doped BaZrO3 or
yttrium-doped Na2 ZrO3 is first synthesized from BaCO3 ,
ZrO2 , and Y2 O3 , and from Na2 CO3 , ZrO2 , and Y2 O3 by 2.2.4. Combination Methods
a conventional solid-state reaction method. The synthesized Most of the synthetic methods for nanoparticles are a combi-
yttrium-doped BaZrO3 or yttrium-doped Na2 ZrO3 is then nation of both physical and chemical processes. The biolog-
boiled to leach away the unwanted species, BaO or Na2 O, ical method discussed above is more often a combination of
either in a diluted HNO3 solution for BaZrO3 or in water chemical and physical (structural and spatial) control. Many
for Na2 ZrO3 . The residues of the skeleton form fine, nano- of the synthetic methods to be discussed in detail below are
size yttrium-stabilized zirconia of 3–15 nm. combinations of chemical and physical processes.
Ceramic Nanoparticle Synthesis 689
2.3. By Energy Sources gas-phase methods are not as convenient for multiple com-
ponents as are solution methods. This is because of the dif-
Energy is always involved in the synthesis of nanoparticles.
ference in saturated gas vapor pressures and the difficulty of
Nanoparticle synthesis methods can then be classified based
controlling the reaction rates among different gases.
on the types of energy input used in the synthetic processes.
Gas-phase syntheses can be further divided into two broad
Laser synthesis, for example, refers to lasers being used as
types: vapor condensation and vapor reaction (the latter
the energy source in the production of nanoparticles. Lasers
includes vapor decomposition).
could be used for evaporating materials into gas phases,
promoting chemical reactions among gas molecules, and 3.1.1. Vapor Condensation Synthesis
decomposing molecules. The following are examples of syn-
thetic methods that are named after energy sources: This technique involves the physical conversion of gaseous
vapor into solid clusters and particles. Research on the vapor
• laser condensation method for nanoparticles started in the 1960s
• plasma [35–37]. Siegel [38] has summarized the early development
• joule heating of this type of synthesis, and Kimura has provided a review
• sputtering of its more recent development [20]. Two growth mecha-
• electron beam nisms have been proposed: the absorption growth process,
• microwave where particle nuclei grow with the absorption of metal
• hydrothermal atoms; and the coalescence growth process, where particles
• freeze drying grow by collision of particle nuclei and clusters. The advan-
• high-energy ball milling tages of these methods have been noted as having
• combustion
1. ultrafine sizes
• flame
2. particle surface cleanness
• supercritical
3. applicability to metals, alloys, intermetallic compounds,
ceramics, and semiconductors
2.4. By Media in which Nanoparticles 4. flexibility in controlling crystallinity.
are Formed Inert-gas condensation has been suggested as the best
method for making ultrafine metal particles [36]. Fuchs
Nanoparticles are always formed in a medium of either gas
and Sutugin [39] have pointed out the difficulties of such
phase, liquid phase, or solid phase. The classifications based
methods, which arise from the presence of the more highly
on the media where nanoparticles are formed are perhaps
volatile impurity oxides that become the first particles
the most important and most widely used classification [32,
formed, and also from impurities from the evaporation of
33]. By focusing on the media in which nanoparticles are
the chamber materials. Brock [40] has raised further con-
formed, many issues common to all of the techniques within
cern that the condensation method has not been shown to
each specific medium arise. By summarizing the very differ-
preserve stoichiometry. It is reasonable to suppose that the
ent techniques used for synthesis in any one medium, one
more volatile species will evaporate first, but condense last.
may perhaps learn and incorporate the best attributes of
Vapor condensation synthesis includes many different
the different techniques to develop a nanoparticle synthesis
methodologies:
method most suitable for one’s own applications. The media
for nanoparticle syntheses are usually classified as 1. inert gas evaporation technique [35], in which the tar-
get material is heated in a vacuum chamber with an
• gas phases atmosphere of several torr inert gas
• liquid phases 2. matrix isolation method, where a cold substance
• solid phases instead of a room-temperature wall is used to control
The detailed discussion in this chapter is arranged according particle agglomeration [38, 41, 42]
to this medium classification. 3. gas flow/cold trap method, where a vapor of organic
liquid is introduced into a particle carrier gas, and then
trapped on a liquid-nitrogen-cooled wall [20]
3. DESCRIPTIONS OF MAJOR 4. gas flow/solution trap method, where nanoparticles in a
carrying gas are bubbled through a precooled solvent,
SYNTHESIS METHODS BY MEDIA
such as ethanol, at −30 to 140 C, depending on the
3.1. Gas-Phase Synthesis organic solvent(s) [43].
Gas-phase syntheses described here are those methods Much of the vapor condensation work has used resistance
where particles are formed as a result of reactions among heating [38]. More and more work has been done with laser
gaseous molecules, gas molecule condensation and/or [44, 45], plasma discharging [46, 47], sputtering [48, 49], and
decomposition, nucleation, growth, and possibly agglomer- electron beam [50].
ation. In general, gas-phase syntheses using gases as reac-
tants involve low concentration because of the low density 3.1.2. Vapor Reaction Synthesis
of gases. This has an advantage for producing nanoparticles This is perhaps the most important technology in gas-phase
because nucleating particles in such low concentrations tend synthesis. It usually involves the reaction of two or more
to be less agglomerated [34]. It is also generally true that gaseous molecules to generate ceramic nanoparticles. Even
the simple decomposition of gaseous molecules, such as the Chemical Vapor Reactions Chemical vapor reactions for
chlorides and nitrates, usually involves the reaction of the gas-phase nanoparticle syntheses usually involve a mixture of
salt with oxygen molecules, as in the following example: gas reactants in a reaction chamber, and the chemical reac-
tions among the gas molecules are induced by an input of
SiCl4 + O2 → SiO2 + 2Cl2 energy such as resistant heating, laser, and plasma. Chlorides
are popular reactants for the formation of both nonoxides
This technique can be further divided into flame synthesis and oxides because of their generally low vaporization tem-
and chemical vapor reaction. perature and low cost. Some of the typical reactions include
Flame Synthesis Flame synthesis refers to a synthesis
in which gaseous reactants react in a flame to produce 6 TiCl4 (gas) +8 NH3 (gas) → 6 TiN (solid)+24 HCl (gas)
particles. The flame contains fuel molecules and oxidizing +N2 (gas) [59, 60]
molecules. Flames are exothermal systems, which provide
the energy for particle formation. Flame technology is an
established industrial process for the manufacture of car- SnCl4 (gas) + 2 H2 O (gas) → SnO2 (solid)
bon blacks and ceramic commodities, such as fumed silica,
pigment titania, zinc oxides, and alumina powders. The cur- + 4 HCl (gas) 61
rent production volume using this technology is on the order
of several million metric tons per year [51]. Pratsinis [52] M
–diketonate2 (gas)+H2 (gas) → M (solid metal)
provided a detailed review of this technology. Fumed sil-
ica is synthesized by feeding gaseous SiCl4 together with +2H
–diketonate) (gas) 62
air and hydrogen into the burner to form a silica aerosol
[53]. The silica is separated from the HCl-containing gases
by cyclone separators or filters. The specific surface area SiH4 (gas) → Si (solid) + 2H2 (gas) 63
of fumed silica is 50–380 m2 /g. The particles consist of
Di Lello et al. [64] synthesized 30 nm AlN nanoscale par-
aggregates of amorphous spherical primary particles up to
ticles from the vapor phase using ammonia and aluminum
a few nanometers [54]. Amorphous and –Al2 O3 powders
chloride vapor as reactants. van der Waals forces and the
of size 10–200 nm were obtained by reacting AlCl3 vapor
tendency for surface energy minimization cause the particles
in an oxygen–hydrogen diffusion flame [55]. Pratsinis [52]
to hold together, and what the SEM, in fact, revealed are
has pointed out that: (1) the role of gas or surface reaction
small particle aggregates. TEM observations, however, con-
on particle formation and growth in flame synthesis is very
firm the nanoscale nature of such particles, with an average
important since surface growth favors a much narrower size
particle size of 30 nm of single crystals.
distribution compared to pure coagulation; (2) the compe-
Jiang et al. [65] prepared Si-based nanopowders from
tition between collision and coalescence is responsible for
((CH3 3 Si)2 NH by chemical vapor decomposition (CVD).
aggregation, and aggregates collide much faster than equiv-
The powders synthesized at 1000–1500 C were all amor-
alent spheres; (3) reactant mixing is a critical variable in
phous. The particles synthesized were near spherical, with
controlling flame temperature and, subsequently, the chem-
sizes of 8–10 nm. After annealing at high temperatures, the
istry, size, and composition of aggregate and primary parti-
powders synthesized at low temperatures formed whiskers of
cles over a wide spectrum in diffusion flame reactors, which
mainly SiC with a small amount of Si3 N4 , while the powders
are widely used in industry; and (4) it appears that electric
synthesized at high temperatures formed 20–40 nm particles
fields across the flame provide one of the best means for
of mainly
–SiC, with a small amount of –SiC.
precise control of primary particle size and crystallinity—and
The energy input can be thermal plasma [66, 67], laser
even aggregate size [56].
[63, 68], or furnace heating [69]. Furnace-heated tubular
Janzen and Roth [57] prepared 4–20 nm single-crystal –
flow reactors have the advantages of simplicity, easy scale
Fe2 O3 nanoparticles via a gas-phase route using an H2 /O2 /Ar
up, and the ability to produce oxides, nonoxides, semi-
low-pressure flame. The burner-stabilized flame was doped
conductors, and metals. The disadvantages include hard
with different amounts of Fe–pentacarbonyl (Fe (CO)5 ,
agglomeration at high aerosol loading. The primary advan-
with concentrations in the range of 262–2096 ppm. The
tage of a laser-driven process is the production of high-purity
particles were analyzed in-situ according to their mass and
products, and its disadvantage is the requirement for com-
charge by a particle mass spectrometer.
plex and expensive systems. The plasma process is unique
The advantages of flame synthesis include: simple oxides
in its use of high melting point materials and rapid cooling,
easily produced in short residence time; scale up demon-
with the disadvantages of broad particle size distribution and
strated for SiO2 , TiO2 , Al2 O3 , and other oxides; and high
high-energy input.
purity. The disadvantages may include: formation of hard
agglomerates under most of the conditions; broad parti-
cle size distribution; nonuniform temperature and residence 3.1.3. Aerosol Synthesis
time profiles; and difficulties in producing other particles In general, gas-phase synthesis refers to those methods where
such as nitrides, borides, and so on. gaseous molecules and atoms are directly converted into
Kleinwechter et al. [58] have synthesized 4–8 nm ZnO nanoparticles through gas-phase reaction [14, 52], condensa-
in a low-pressure flame reactor and a microwave reactor tion, and/or decomposition, nucleation, growth, and possibly
in Zn(CH3 2 -doped H2 /O2 /Ar flames and Zn(CH3 2 -doped agglomeration. However, in an aerosol process, a homoge-
Ar/O2 plasmas, respectively. neous liquid starting material is converted into an aerosol
(i.e., small liquid droplets suspended in gas phase) [70–72]. When the droplets are carried into the furnace, the solvent
This aerosol is then converted into solid particles suspended begins to evaporate, and further hydrolysis occurs according
in a gas stream by heating. The aerosol syntheses discussed to
here are only pseudogas-phase syntheses. These pseudogas-
phase syntheses can be further classified into the follow- TiO2+ + x + 1 H2 O → 2H+ + TiO2 · xH2 O
ing two broad types: aerosol pyrolysis and flame–aerosol
pyrolysis. or
Aerosol Pyrolysis An aerosol pyrolysis process is also TiOCl2 + x + 1 H2 O → TiO2 · xH2 O + 2HCl.
called spray pyrolysis [73] or vapor pyrolysis. It consists of
three parts: aerosol generation, particle formation inside Upon further heating [77],
a furnace, and particle collection, as shown in Figure 1.
∼380 C
A homogeneous liquid solution (organic, aqueous, or a mix- TiO2 · xH2 O −−−−→ TiO2 (anatase) + x · H2 O
ture) containing the reactants is converted into an aerosol
using air, nitrogen gas, or a mixture of gases. The sizes of If BaCl2 is involved,
the droplets formed in the aerosol depend on the types of
aerosol generators used, the carrying gas volume, and the BaCl2 s + TiO2 (anatase) + H2 O g → BaTiO3 s
nature of the liquid [20, 74]. An ultrasonic generator usu- + 2HCl.
ally gives very fine droplets that may be suitable for making
nanoparticles [73]. The aerosol is then carried by the gas into If Ba(NO3 2 is used, the above reaction may also be involved
a preheated furnace, where the liquid droplets go through due to the formation of BaCl2 :
solvent evaporation, solute precipitation, solute decompo-
sition, and oxide sintering to final particles, as shown in Ba(NO3 )2 + 2HCl → BaCl2 + 2HNO3
Figure 1. Eventually, the particles are carried out by the
gases into a particle collection section, where the particles The following reaction has also been reported:
may be quenched with cold gases and collected by filters or
540–650 C
bags (Fig.1). Ba(NO3 )2 + TiO2 (anatase) −−−−−−→ BaTiO3 s
In order to generate uniform and small droplets of
1
aerosol, the first step of the process is to prepare a uniform + 2NO2 + O2
solution. In the case of making nano-BaTiO3 , the solution 2
contains barium and titanium. This solution can be made On the other hand, BaO is formed if organic barium sources
from simple inorganic salts such as TiCl4 and BaCl2 [75], or are used [78]:
TiCl4 and Ba(NO3 2 [76], in a mixture of water and ethanol.
The starting materials can also be a mixture of Ti alkoxides 600 C
Ba CH3 COO2 + 4O2 −−−→ BaO + 4CO2 + 3H2 O
and barium salts such as Ba(NO3 2 in a mixture of water and
alcohols [77, 78]. The sources of titanium and barium have
also been tried with both organometallic compounds such BaO + TiO2 = BaTiO3
as titanium alkoxides with barium acetate [78] and titanium
lactate and barium acetate [79]. Ogihara et al. [78] obtained dense spherical BaTiO3 of
The different starting materials affect the BaTiO3 for- 930 nm using Ti(iso-OC3 H7 4 and Ba(CH3 COO)2 , while hol-
mation mechanism and the characteristics of the BaTiO3 low spherical BaTiO3 was produced using Ti(iso-OC3 H7 4
formed. TiCl4 has a strong tendency to dissociate and and Ba(NO3 2 using aerosol pyrolysis at 900 C. They con-
hydrolyze according to the following solution reaction, in a tributed such a difference in the BaTiO3 due to the fact
bulky solution or in aerosol droplets [75]: that reaction (9) occurs much more easily than reactions (5)
and (7) at temperatures below 700 C.
TiCl4 + H2 O → TiO2+ + 2H+ + 4Cl− → TiOCl2 + 2HCl. Milosevic and co-workers [75] produced 530 nm BaTiO3
by aerosol pyrolysis of an ethanol/water solution of BaCl2
Furnace and TiCl4 using an ultrasonic atomizer. Cho et al. [76] pre-
pared BaTiO3 of size 300–900 nm by ultrasonic aerosol
pyrolysis of solutions containing Ba(NO3 2 and TiCl4 .
BaTiO3 particles were prepared in our laboratory using
Ti isopropoxide and barium acetate in an aerosol pyroly-
Solvent
Evaporation Precipitation Decomposition Sintering sis process, as shown in Figure 2 [80], where particles of
50–600 nm were obtained. These particles are tetragonal in
crystal structure, with a Ba/Ti ratio of 09999.
At issue in aerosol processes is the extent of agglomera-
tion (particle adhesion) and aggregation (particle sintering),
Aerosol Particle the latter referring to clusters of primary particles being
Generator Collector cemented together by interparticle necks. While it is virtu-
ally impossible to eliminate the agglomeration of pristine
nanopowders due to the strong van der Waals forces of
Figure 1. Schematic representation of an aerosol pyrolysis process. attraction that keep the particles together, aggregation can
Commercial H2O and CO2

titanium Oxygen emitted
precursor
Combustion
Quenc Collect
Alcohol Barium
Misting
hing ion
complex titanate
‘cocktail’ nanopowder
One-step
chemical
processing
Commercial
barium starting
material
Figure 3. Flowchart of a flame–aerosol pyrolysis process [83].
Figure 2. BaTiO3 made from an aerosol pyrolysis process [80]. through a heat-conducting wall. The burning of the fuels
in a flame process directly affects the product’s oxidation
states and purity, while the heating source in an aerosol
be restricted by controlled powder synthesis. Singhal et al. process does not introduce impurity into the final prod-
[81] developed a vapor-phase synthesis method, called com- ucts, except that contamination may come from the heat-
bustion flame/chemical vapor condensation. It involves the conducting walls.
pyrolysis of chemical precursors in a low-pressure flat flame, Brewster and Kodas [84] have demonstrated the for-
and is used to produce nanoparticles of TiO2 and Al2 O3 . mation of chemically pure, crystalline (primarily tetragonal
Nanoparticles of oxides that have an average secondary par- with hexagonal and cubic polymorphs), and unagglomerated
ticle size of approximately 100 nm, and an average primary dense BaTiO3 particles of about 1400 nm by flame–aerosol
particle size less than 25 nm, were produced by controlling of a 05 M solution of barium acetate titanium lactate and
the time–temperature history of the particles in the hot zone water at a flame temperature of >1500 C (adiabatic).
of the flame. These aerosol synthesis methods, aerosol pyrolysis and
In aerosol processes, it is important to analyze how the flame–aerosol pyrolysis, have produced BaTiO3 particles less
gas-phase molecules react, nucleate, agglomerate and sin- than 100 nm. The BaTiO3 particles in Figure 2 also show
ter, and how these steps control the size distribution and broad particle size distributions. In general, these aerosol
morphology of particles. Nakaso et al. [82] studied the ther- syntheses can produce spherical particles with clean sur-
mal decomposition of titanium tetraisopropoxide and oxida- faces, desired Ba/Ti ratio control, and good crystallinity
tion of TiCl4 by using a laminar-flow aerosol reactor. The via a continuous process. There are many reported studies
effect of reaction temperature on the size and morphol- in which nanoparticles of a few nanometers are produced
ogy of the generated particles was investigated under vari- [52, 74, 85–87]. In many cases, these are academic studies
ous conditions. The size distributions of agglomerates were involving the collection of a few particles on a TEM grid.
measured using a differential mobility analyzer/condensation These nanoparticles are extremely reactive, and agglomerate
nuclear counter system. The growths of both agglomerates quickly into large particles in an industrial collection system.
and primary particles were modeled simultaneously, using a The industrial process for producing large quantities of par-
two-dimensional discrete-sectional representation of the size ticles of nanosizes may require such a large dilution of the
distribution. particle stream with the carrying gas as to make this pro-
The advantages of aerosol pyrolysis for nanoparticle cess inefficient. The scale up to the production of tonnage
making include: (1) high purity, (2) spherical particles, quantity for the flame–aerosol process is much easier than
(3) an easy and quick one-step process, and (4) minimal for that of aerosol pyrolysis. In general, it is extremely chal-
agglomeration. The disadvantages are: (1) a large size dis- lenging to make unagglomerated particles with a narrow size
tribution, as shown in Figure 2, (2) the necessity of a large distribution.
amount of carrying gas dilution in order to reduce agglomer-
ation and aggregation, (3) low production rates, and (4) dif- 3.2. Liquid-Phase Synthesis
ficult scale up.
Liquid-phase syntheses are the most common and diverse
Flame–Aerosol Pyrolysis Flame–aerosol synthesis is a methods for nanoparticle synthesis. The critical particle for-
process in which an aerosol of starting materials is burned mation step occurs in the liquid phase; however, under
in a flame [73]. A flowchart of a flame–aerosol pyrolysis is supercritical conditions, the particle formation phase is at
shown in Figure 3 [83]. The chemistry in a flame–aerosol both the liquid and gas phase since there is no distinction
system is similar to that described for an aerosol pyroly- between gas and liquid under those conditions. The most
sis process. The differences include the source of heating: common solvent is water, but more and more organic sol-
flame–aerosol is heated by the burning of the fuel gases and vents are also used in an effort to reduce the agglomeration
organic solvents which are in direct contact with the precur- of nanoparticles. Common to all of the liquid-phase synthe-
sor materials. The heating in an aerosol process is usually ses is that they begin with solution preparation. A true solu-
external and indirect by resistance heating or gas heating tion means homogeneity at the atomic or molecular scale.
The central goal for the diverse solution synthetic methods colloid studies have indeed produced nanosized monodis-
is to preserve as much of this homogeneity as possible in the persed particles.
particle formation process. Major synthesis methods for ideal ceramic nanoparticle
Liquid-phase syntheses are generally wet-chemical solu- formation in the liquid phase depend on “controlled precip-
tion syntheses, sometimes called soft solution-processing itation” or “homogeneous precipitation” reactions involving
routes. There is an increasing role that solution synthesis sequential nucleation and growth processes. As a general
plays in the preparation of ceramic powders, particularly rule, a homogeneous solution system (consisting of ideally
nanometer-sized particles with controlled size and morphol- one phase where the monomer reservoir is normally built in
ogy [88]. Wet-chemical processes have been widely recog- the form of a solute) is necessary for generating uniform-size
nized as an efficient approach to prepare nanocrystalline nanoparticles. Reactions belonging to this category include
fine particles at low temperatures. In relation to other [94]: (1) the redox reaction, (2) precipitation by poor sol-
methods such as vapor-phase synthesis and physical meth- vents, (3) direct reaction of ions, (4) reaction of chelates,
ods (such as laser ablation and electron beam evapo- (5) decomposition of compounds, (6) hydrolysis in organic
ration), major advantages of the liquid-phase synthesis
media, and (7) hydrolysis in aqueous media. The particle
include: (1) the process can be scaled up easily due to
growth process can be either by molecular diffusion/addition
its bulk-processing nature; (2) the process is more con-
to the nuclei surface or by a particle aggregation mecha-
trollable because chemical reactor technologies developed
nism, both of which have been demonstrated to generate
for chemical synthesis may be adapted and applied to the
production of nanoparticles; (3) some processes require monodispersed particles [95–99]. To obtain uniform parti-
only mild conditions such as low temperature and atmo- cle size in a diffusional growth process, the nucleation stage
spheric pressure; (4) the chemical composition of nano- must be separated from the particle growth stage. Seeding is
particles can be tailored in a liquid phase; (5) in the liquid one approach to achieve the separation of nucleation from
phase, surface-controlling agents can be applied during and growth.
after nanoparticle formation to control the size and prevent In addition to the desirable goal of monodispersed par-
unnecessary agglomeration; and (6) monodispersed nano- ticles, anisotropic particles are also strongly needed for
particles can be made in the liquid phase via a homogeneous important applications, such as the fabrication of composite
nucleation, growth, and aggregation mechanism. Uniform materials and flat panel optical displays. Control of the size
particle size is extremely important to nanoparticle self- distribution, shape, and aspect ratio is a complex process
assembly-based systems. requiring a fundamental understanding of the interactions
Wet-chemical syntheses are particularly suited to the syn- among solid-state chemistry, interfacial reactions and kinet-
thesis of nanoparticles (solid, core–shell, or hollow) with ics, and solution chemistry [100].
tightly controlled parameters, such as: (1) the size and shape, Regardless of the methods used, achieving homogeneous
(2) the monodispersity, (3) the chemical composition and reaction or precipitation in homogeneous solutions is the
purity, (4) the bulk substructure, (5) the crystallinity (poly- key to producing uniform colloids or nanoparticles (either
crystalline, single crystalline, or amorphous), (6) the sur- isotropic or anisotropic). Precipitation of alkoxide solutions
face functional group (thus, the interfacial free energy and and forced hydrolysis of some metal salt solutions surely sat-
surface-charge density), (7) the shell-layer thickness in a isfy the “homogeneous” criteria. Enough attention has been
core–shell nanoparticle, or even (8) the size and shell thick- paid to the preparation of “ideal” sinterable ceramic nano-
ness of a hollow sphere particle. For ceramic processing, the powders with improved densification properties compared
above characteristics of nanoparticles will affect the process- with conventionally derived ceramic powders. In most lit-
ing behavior, as well as the properties of the final, casted, erature studies of nanoparticle synthesis, particle size may
sintered ceramic materials. not be monodispersed (due to the broad range of par-
The use of “nanoparticle(s)” as a popular technical term
ticle size distribution). The wet-chemical synthesis meth-
in the literature of wet-chemical synthesis of truly nanosized
ods that have been reported so far in the recent litera-
(i.e., <100 nm in particle size or crystallite size) ceramic par-
ture to produce ceramic (oxide or hydrous oxide) nano-
ticles did not appear until less than a decade ago. However,
particles or nanocrystalline powders can be mainly classified
research on ultrafine, monodispersed colloid particles has
been conducted as a major goal of colloidal science since the as chemical precipitation and coprecipitation, hydrother-
beginning of the 20th century. Some excellent review arti- mal synthesis, forced hydrolysis, sol–gel synthesis, synthe-
cles on monodispersed particles can be found [89, 90–94]. sis in microemulsion or reverse micelles, solvothermal syn-
Colloids are typically defined as particles with a particle size thesis and nonhydrolytic routes, microwave heating-assisted
ranging from 1 nm to 1 m, which is more or less defined synthesis, sonochemical synthesis, electrochemical synthesis,
by the importance of Brownian motion. Colloidal particles, and synthesis in supercritical fluids. Historically, the above-
(hydrous) oxides in particular, have long been utilized as mentioned methods have been developed or studied for
models or tools in scientific research; applied in fields such ultrafine ceramic particle synthesis. However, the majority of
as drug delivery, biodiagnostics, and combinatorial synthe- studies on these methods for the synthesis of truly nanosized
sis; and used as the major components of industrial prod- particles appeared well within the last decade. In the fol-
ucts such as paints, ink, foods, cosmetics, coatings, catalysts, lowing sections, each synthesis method will be reviewed and
pigments, papers, photographic films, recording materials, discussed, with a focus on its application in ceramic (oxide
films, and rheological fluids. Some of these monodispersed and hydrous oxide) nanoparticle or nanopowder production.
3.2.1. Chemical Precipitation and of uniform nuclei with a critical size which can be calculated
Coprecipitation from
Chemical, or reactive, precipitation can be generally
described by the solid phase formation from reactions of r ∗ = 2/kB T ln S
soluble reactive species (M1 , M2 , A) in a solution (aqueous
or nonaqueous) where = molecular volume of the precipitated embryo
(m3 , = surface energy (J/m2 , kB = Boltzmann’s constant
M1 aq + A aq → M1 A s (J/K), T = temperature (K), and S = supersaturation value.
A three-stage process was developed to produce
where M1 is a metal cation species and A (aq) represents ZnO nanoparticles [103], involving: (1) the formation of
an anion species from a precipitating agent such as NH4 OH, metastable zinc complexes through a slow addition of
NaOH, carbamate (NH2 CO2 NH4 , H3 PO4 , etc. When more ammonia; (2) the partial phase transformation of metastable
than one metal cation species is involved, for example, a zinc precursors to zinc oxide after washing the initial col-
second metal species, M2 (aq), could be coprecipitated loidal suspension with ethanol, Zn–OH (s) + C2 H5 OH(l) →
Zn–O–C2 H5 (s) + H2 O(l); and (3) the complete transforma-
tion to ZnO by thermal treatment. The main strategy used
M1 aq + M2 aq + A aq → M1 M2 A s
is the controlled release of cations from a homogeneous sus-
pension.
If A(aq) happens to be oxygen or a hydroxyl group, Water-soluble polymeric dispersants, such as poly (N–
M1 A (s) will be a single metal oxide or hydrous oxide, while vinylpyrrolidone) (PVP), polyvinyl alcohol (PVA), and
M1 M2 A (s) represents a mixed metal oxide. polyacrylic acid (PAA), have been utilized as stabiliz-
A chemical precipitation process consists of three main ers in chemical precipitation to prevent particle coagula-
steps: chemical reaction, nucleation, and crystal growth. tion/agglomeration and to control size. Zhang and Guo
Chemical precipitation is generally not a controlled process [104] prepared antimony oxide nanoparticles by a reflux-
in terms of reaction kinetics and the solid phase nucleation ing reaction between SbCl3 and NaOH in the presence of
and growth processes. Therefore, solids obtained by chem- PVA: Sb3 + OH− → Sb2 O3 + H2 O. Rasmussen et al. [105]
ical precipitation have a wide particle size distribution plus precipitated nanoscale aluminum hydroxide particles from
uncontrolled particle morphology, along with agglomeration. sodium aluminate solutions by dilution and neutralization
In the preparation process of particles via reactive precipita- with water and oxalic acid in the presence of the surface-
tion (A + B → P ), the chemical reaction is so fast that a high active polymers PVP and PVA. In the wet-chemical precipi-
degree of supersaturation of the product solute P will be tation of needle-shaped hydroxyapatite nanocrystals, Bouyer
achieved in local sites in the reactor. This causes the nucle- et al. [106] used the following reaction
ation to be dominated by homogeneous nucleation mecha-
nisms, where the value of the power order in the nucleation
rate expression equation can be in the range of 5–18 or so. 10Ca OH2 + 6H3 PO4 → Ca10 PO4 6 OH2 + 18H2 O
Any tiny variation of the supersaturation of product P will
lead to a significant change in the nucleation rate because In precipitating europium oxide nanoparticles with NaOH,
of this high value of powder order. However, because of its trioctyl phosphine oxide (TOPO) was used for the following
simplicity, rapid solid formation kinetics, and bulk process- three possible reasons [107]: (1) it prevents particle agglom-
ing capability, chemical reaction is still a viable option for eration (via steric passivation), (2) it achieves electrical pas-
nanoparticle production as long as strategies are considered sivation of surface dangling bonds (trap states); and (3) it
for controlling the kinetics (reactions between ions), reac- controls particle size at the nanometer level. Chen and Chen
tion uniformity, and agglomeration. To obtain nanoparticles [108] used PAA in the coprecipitation of strontium ferrite
with a narrow size distribution, one should do as much as nanoparticles (34–41 nm for calcined powders). Pardoe et al.
possible to meet the requirements of: (1) a high degree of [109] used dextran and PVA in the coprecipitation of nano-
supersaturation, (2) a uniform spatial concentration distri- scale iron oxide particles by ammonia.
bution inside a reactor, and (3) a uniform growth time for Some chemical precipitation of nanoparticles was con-
all particles or crystals [101]. ducted in nonaqueous background solutions. Carnes et al.
Recently, chemical precipitation and coprecipitation have [110] attempted an “alkoxide-based” synthesis involving the
been reported in the active literature for nanoparticle syn- NaOH precipitation of metal chloride in ethanol back-
thesis. Table 1 summarizes some of the major research work ground solutions. Chemical precipitation produces metal
on chemical precipitation of (hydrous) oxides, and Table 2 hydroxide solids which are converted to oxides by heating.
for chemical coprecipitation of mixed oxides. Most of the Wakefield et al. [107] precipitated europium oxide by NaOH
chemical precipitation processes are conducted in aqueous in a methanol background solution. Meulenkamp [111] pre-
solutions, but a few are in nonaqueous solutions. pared ZnO nanoparticles by the dropwise addition of LiOH
Zhou et al. [102] used NH4 OH to precipitate cerium (dissolved in ethanol) into an ethanolic zinc acetate solu-
nitrate at room temperature. They tried to obtain a high tion under vigorous stirring at 0 C. The presence of a
value for the supersaturation ratio (S), in order to estab- small, but strictly limited, quantity of water (from the acetate
lish an environmental condition that favors homogeneous salt) appeared necessary to warrant good particle growth.
nucleation, which typically results in the “burst” formation Manorama et al. [112] coprecipitated SnCl4 and copper
Table 1. Nanoparticle synthesis by chemical precipitation.
Nanoparticle Characteristics of
materials nanoparticle Brief process description Applications Ref.
CeO2 4–5 nm, round-shaped, Room-temperature Raman-allowed [102]

single crystals homogeneous modes shifting and
nucleation; cerium broadening; pressure-
nitrate solution was induced phase
added into aqueous transformation
NH4 OH precipitant
CuO, NiO 7–9 nm CuO and 3–5 Precipitated by NaOH CuO: in cataly- [155]
nm NiO crystallites, in ethanol background; sis, metallurgy,
aggregate to form larger “alkoxide-based” high-temperature
spherical particles synthesis involving superconductors;
metal chlorides, NiO: electronic/magnetic
ethanol, and water properties, catalysis,
p-type semiconductor
ZnO ∼1 m particle self- Acidified zinc acetate Pigments, rubber [103, 117, 111]
assembled with nano- aqueous solution additives, gas sensors,
crystals titrated with NH4 OH varistors, transducers;
Microspheres consisting of solution to pH 9 used in photocells, as
aggregates of nanoscale Ammonium carbamate as UV-absorbing material,
(10–15 nm) rod-shaped a precipitating agent; in sunscreen lotions, as
primary particles flow injection synthesis insulator, light-emitting
2–7 nm clean sol Addition of LiOH (in diodes, ceramics, ion-
ethanol) to an ethanolic insertion batteries,
zinc acetate solution electrochromic devices
Sb2 O3 10–80 to 200 nm sizes, Reaction between SbCl3 Flame retardants; optic [104]
polyhedral-shaped, and NaOH in the materials; high proton
polycrystalline cubic presence of polyvinyl conductivity; humidity-
phase alcohol in water sensing materials
solution
Fe2 O3 Spherical-shaped Ammonium acetate as Magnetic materials [95]
nanoparticles precipitating agent
Al(OH)3 80–300 nm in PVP; 200 Oxalic acid as Bayer process [105, 101]
nm–1.2 m in PVA precipitating agent Nanocomposites,
Nanofibrils (1–10 nm in High-gravity reactive pharmaceutics
diameter and 50–300 nm precipitation
in length)
Hydoxyapatite Needle-shaped, aspect Ca(OH)2 precipitated by Bioceramic for [106]
ratio (= length/width) = H3 PO4 , 25–85 C biomedical applications
2–10 such as bone substitute
Eu2 O3 2–40 nm, passivated with At room temperature; Luminescent phosphors [107]
trioctyl phosphine oxide precipitation of for flat-panel displays
(TOPO) EuCl3 by NaOH in a based on field-emitting
methanol background arrays
solution in the presence
of TOPO
In(OH)3 Multiple morphology Hydrolysis of indium Semiconductor and [114, 118]
precipitates which were chloride in EG/aqueous optical properties
peptized into 80–8000 nm NaOH solutions, plus
powders (round-shaped) peptization
Uniform colloidal rod-like Controlled double-jet
particles (aggregates of precipitation
nanosize subunits)
CaCO3 or SrCO3 CaCO3 (17–36 nm particle High-gravity reactive In many industries [101]
size) SrCO3 (∼40 nm precipitation such as electronics,
particle size) opticals, pulp and
paper, pharmaceutics,
etc.
696
Table 2. Nanoparticle synthesis by chemical coprecipitation.
Strontium 3.1 nm for mixed hydroxide Polyacrylic acid (PAA) sodium salt used Magnetic material with high coercivity [108]
ferrite precipitates; 34–41 nm for as protective agent; NaOH added to
(SrFe12 O19 calcined powder the mixed aqueous solution of PAA and
corresponding nitrates salts
Barium ferrite 4.5 nm for precipitate precursor; Same as above [282]
(BaFe12 O19 23–82 nm for calcined powder
LiMn2 O4 <100 nm crystal size, agglomerated Mn and Li acetate salts dissolved in citric Cathode material for lithium rechargeable [115]
for the calcined powder acid were precipitated by NH4 OH batteries
Ba2 Co2 Fe28 O46 10–25 nm grain size Nonaqueous coprecipitation by cooling the Magnetic material with unique phenomena [116]
mixed metal salt solution/sol (in stearic such as superparamagnetism and
acid background) from 80–100 C to quantum tunneling of magnetization
ambient temperature to gel
Fe3 O4 6–8 nm particle size and 1–6 nm Iron source (Fe3+ and Fe2+ was added Magnetic material, ferrofluids, biomedical [283]
crystal size, surfactant (Na oleate) dropwise into alkali source (NaOH) and diagnostic applications, MRI contrast
coated under vigorous mechanical stirring; agents
complete precipitation ∼pH 7.5–14
while maintaining Fe2+ /Fe3+ = 1/2 under
nonoxidizing environment
Cluster- and necklace-like chain Coprecipitation of Fe(III) and Fe(II) by [109]
aggregates (∼100–200 nm length) NH4 OH in the presence of polymer-
dispersant PVA or dextran
PVA coated (oxide core 5–10 nm, Coprecipitation of Fe(III) and Fe(II) by [284]
108–155 nm outside PVA shell) NH4 OH in the presence of polymer-
dispersant PVA
5 nm stable uncoated nanoparticle Precipitation of an aqueous solution of iron [285]
salts by tetramethylammonium hydroxide
(TMAOH)
1.5–12.5 nm particle size, free from Using NaOH, NH3 , or N(CH3 4 OH to [286]
polymer, surfactant, or ligands precipitate, adjusting pH and ionic
strength to control particle size
Sb-doped SnO2 4–9 nm particle size, spherical to SnCl4 dissolved in HCl, SbCl3 , and SbCl5 High n-type conductivity, high absorption [287]
ellipsoidal shaped, tend to form was added, dropped into cold water, and coefficient in the NIR and IR regions
string-like agglomerates precipitated by aqueous ammonia until (thus high reflective for IR radiation);
pH 3–4 was reached applications in photovoltaic and
optoelectronic devices, flat-panel displays
CuO-doped 3–5 nm crystallite size “Alkoxide-like” hydrolysis: copper acetate Catalyst for the oxidation of organics, [112]
SnO2 added into mixture of equal molar solid-state sensors for reducing gases,
solution of SnCl4 in water and ethanol, transparent conductive thin-film coatings

aged at 50 C to precipitate
Spinel ferrite A few nanometer to 20 nm grain Aqueous solutions of FeCl3 and Superparamagnetism; magnetic resonance [288]
MgFe2 O4 size MgCl2 ·6H2 O precipitated by NaOH contrast agents, high-density information
solution, digested in boiling water, storage, ferrofluids, magnetocaloric
washed until pH neutral refrigeration
In-doped Powder with nanocrystallites (NH4 2 C2 O4 ·H2 O as coprecipitating agent High-proton conduction in atmosphere [289]
CaZrO3 containing water at high temperature; as
electrolyte in solid-state electrochemical
devices
ZrO2 (3Y) Powder, 11–15 nm particle size, with Heating of ZrOCl2 and Y(NO3 3 solution High strength and toughness for structural [290]
weak agglomeration with an alcohol–water mixture, plus ceramics
NH4 OH as precipitating agent and PEG
as dispersant
acetate to obtain CuO-doped SnO2 via “alkoxide-forming” 1–2 min. The chemical reaction commences at the moment
reactions in the presence of ethanol: the solutions are mixed, and precipitation takes place and
is complete in a confined zone. In this way, agglomera-
SnCl4 + 4C2 H5 OH → Sn −OC2 H5 4 + 4HCl tion is greatly limited since the short residence time allows
Sn −OC2 H5 4 + 4H2 O → Sn OH4 + 4C2 H5 OH only primary nucleation. The mixing of solutions A and B
can be performed under reproducible conditions, and thus,
Sn OH4 → SnO2 + 2H2 O powders with identical properties can be obtained. Chen
et al. [101] have demonstrated a high-gravity reactive pre-
Sen et al. [113] prepared ferrite nanoparticles by a nonaque- cipitation (HGRP) technology to produce nanoparticles of
ous precipitation route: a homogeneous solution of stearic CaCO3 , Al(OH)3 , and SrCO3 with a very narrow size distri-
acid and iron (III) nitrate was treated with tetrahydrofuran bution and a controlled morphology. Per chemical engineer-
to obtain precipitates. ing analysis, micromixing (mixing on the molecular scale)
In some cases, chemical precipitation will generate large and macromixing (mixing on the macro scale) have a signif-
micrometer-size precipitates. Upon peptization, however, icant effect on particle size distribution (PSD) in a reactive
precipitates will be converted into nanosize particles. For precipitation process. Micromixing is a key factor determin-
example, Perez-Maqueda et al. [114] have prepared nano- ing the degree of the supersaturation concentration of the
size (as small as 80 nm) indium hydroxide by the peptization solute and its local spatial distribution. The reaction rate and
of colloidal precipitates. Precipitation was accomplished by subsequent nucleation in precipitation will be controlled by
the dropwise addition of an aqueous NaOH solution into the intrinsic kinetics without the influence of micromixing in
indium chloride dissolved in ethylene glycol (EG) at 175 C. the region of tm < , where tm is the micromixing time and
For the peptization, the colloidal precipitate was washed to is the induction time, defined as the time from the first cre-
eliminate the EG, and then dispersed in distilled water (or ation of the conditions for homogeneous nucleation to that
isopropanol) in an ultrasonic bath. Organic solvents such as of the establishment of a steady-state nucleation rate. The
ethanol or EG have a significant effect on the shape and region tm < should be chosen such that the rates of nucle-
other properties of particles obtained by precipitation. Thus, ation at different locations in a precipitator will be nearly
mixed solutions of ethanol and water or EG and water have the same, and so the PSD can be controlled at a uniform
been utilized as a strategy to produce colloidal oxides of level. On the other hand, micromixing has little effect on
different morphologies. EG offers two useful advantages: crystal growth. Therefore, a rule for selecting a precipita-
(1) a high dielectric constant, which enhances the solubility tion reactor is: a combination of a well-micromixed plug flow
of inorganic salts; and (2) a high boiling point (195 C at reactor (to separate the reaction and nucleation zones from
atmospheric pressure), which makes it possible to carry out the crystal growth zone) and a well-macromixed reactor (to
the preparation of inorganic compounds at relatively high locate crystal growth in a well-macromixed region). High-
temperatures using an open vessel. gravity technology in the form of a rotating packed bed of
For coprecipitation of multiple cations, the use of com- the earth is ideal to satisfy the above rule because it is effec-
plexing or chelating agents seems important for controlling tive in intensifying mass transfer, and is helpful in the gener-
the chemical stoichiometry of the precipitated solid. Hwang ation of higher supersaturated concentrations of the product
et al. [115] used citric acid in the coprecipitation of Mn and in the gas–liquid-phase reaction and precipitation process.
Li by NH4 OH. Xiong and Mai [116] used stearic acid to Another engineering process, controlled double-jet precipi-
dissolve mixed Ba, Co, and Fe salts at high temperature to tation (CDJP), has also been successfully utilized to produce
prepare a sol, which precipitated to form a gel upon cooling. uniform colloidal rod-like In(OH)3 particles (aggregates of
In addition to chemical strategies, such as using disper- nanosize subunits) from relatively concentrated solutions
sants and the controlled release of reactants, engineering [118]. Her and co-workers [119–123] have used CDJP to
approaches have been integrated into the chemical precipi- prepare colloidal spherical particles of SiO2 , Al(OH)3 , CuO,
tation process to achieve bulk processing and homogeneous and BaTiO3 of narrow size distributions. They [123]mixed
precipitation. Wang and Muhammed [117] used a flow injec- TiCl4 directly with 6 M NaOH/KOH to form BaTiO3 at
tion synthesis (FIS) technique to prepare ZnO nanoparticles 85 C within 3 min with the ability to control particle size
with rod-shaped morphology via precipitation by carbamate between 70 and 400 nm. The optimum condition identi-
fied was pH 14, 85 C, and with 0.1% cyclodextrin. The
5ZnCl2 +5NH2 CO2 NH4 +8H2 O → Zn5 OH6 CO3 2 s
BaTiO3 had a cubic structure with dielectric constants up to
+3CO2 g+10NH4 Cl 18,000. They also established a growth mechanism for the
uniform colloid formation under the CDJP condition [121]:
The solid precipitate decomposes upon calcination to ZnO: nanosized primary particles formed immediately after mix-
ing the reactants, followed by aggregation into larger uni-
Zn5 OH6 CO3 2 s → 5ZnO + 2CO2 + 3H2 O form particles.
FIS borrowed the concept from the flow injection analy-
sis (FIA) method in analytical chemistry. In an FIS pro- 3.2.2. Hydrothermal Synthesis
cess, a precise volume of reactant-containing solution is “Hydrothermal process” (also called thermal hydrolysis or
swept along by the carrier stream into the system. The main hydrothermal hydrolysis process) generally refers to process-
advantage of the FIS technique is that the precipitation ing aqueous solutions of metal salt(s) (metal and/or metal-
process is only allowed to continue for a limited period of lorganic) or autoclaving of precursor materials such as gels
at elevated temperatures (typically 100–300 C) and pres-

sures above 1 atm. In this method, ceramic sols are produced
by chemical reactions in an aqueous or organoaqueous solu-
tion under the simultaneous application of heat and pressure
in the presence of an alkali or acid that has a pseudocatalytic
effect upon the reaction [124]. The reaction equilibrium of a
metal salt aqueous solution changes with temperature, which
results in the formation of metal hydroxide or metal oxides.
Mineralization in nature, which has resulted in deposits and
rocks, could have occurred by a hydrothermal process. In the
laboratory, hydrothermal synthesis is typically used with a
batch-type autoclave, in which an aqueous solution is heated
up slowly to the target temperature, and then aged for sev-
eral hours or days.
Hydrothermal synthesis has been considered a cost-
effective and less complicated synthesis technique, suit-
able for large-scale production. There has been a trend
to develop “mild hydrothermal processes” (100 C ≤ T ≤
200 C, under autogenous pressure) for the synthesis of
advanced ceramic powders, extending from zeolites and
metal phosphates to binary and ternary transition metal
oxides [125]. The low-temperature technique is critical to the
formation of metastable phases not obtainable using tradi-
tional high-temperature methods. Process parameters, such
as the pH of the reaction medium, temperature, and the
cations in solution, determine what solid phases are formed.
Cations such as medium-size spherical organic cations (e.g., Figure 4. CeO2 nanoparticles made from hydrothermal process [126].
tetramethyl ammonium) and large surfactants may act as the
structure-directing species or template for the synthesis of
nanoporous or mesoporous (2–50 nm) materials. solution of FeCl3 , followed by aging and heating at 200 C
By changing the conditions of the solutions (pH, ionic and the completion of phase transformation at 300 C
strength, surfactant concentrations, cation concentrations,
anion concentrations, and solvents) and processing condi- FeCl3 + 3H2 O → Fe OH3 s + 3HCl hydrolysis
tions (temperature, duration, and stirring), one can effec-
tively control the nanoparticle size and shape, and the extent Fe OH3 →
–FeOOH → –Fe2 O3 (phase transformation)
of agglomeration. Nanoparticle CeO2 can be made in differ-
ent sizes and shapes by changing these reaction conditions In this process, ring-opening polymerization of EO may take
[126], as shown in Figure 4. place with FeCl3 as a catalyst or with iron alkoxide as an
Synthesis under hydrothermal conditions offers some sig- intermediate, which can be formed by the reaction of ethy-
nificant advantages over other chemical synthesis techniques lene glycol with FeCl3 or of EO with FeCl3 . Also, the pos-
[124]: (1) it is easy to control particle size and morphology by sible byproduct of ethylene glycol may effect the prevention
varying synthesis conditions; (2) many materials can be syn- of Fe(OH)3 nanoparticle agglomeration.
thesized directly in the desired crystalline phase at low tem- In contrast to “mild hydrothermal synthesis,” synthesis
perature (hydrothermal synthesis offers a low-temperature, under high temperature and pressure, as found in supercrit-
direct route to ultrafine oxide powders with a narrow size ical water conditions, also shows promise for the continuous
distribution, avoiding the calcination step required in sol–gel and rapid production of nanocrystals [129].
processing); and (3) the resulting sols can be used directly
in the production of green bodies via pressure filtration or 3.2.3. Forced Hydrolysis
extrusion. This method can be essentially considered a subcategory
There is an enormous amount of literature on the of the hydrothermal synthesis process at a relatively low-
hydrothermal processing of inorganic materials such as temperature range and using inorganic salt solutions, which
ceramic powders. Zeolite nanoparticles are a classic exam- are usually diluted (10−4 –10−2 M). In this method, aqueous
ple of hydrothermal synthesis [127]. Here, we only focus on metal salt solutions are aged (hydrolyzed) at elevated tem-
a review of the most recent work on the synthesis of true peratures (usually over the range 80–100 C per Matijevic
nanosize oxide particles (see Table 3). [92] and 50–150 C per Sugimoto [94]) for different periods
Hydrothermal synthesis can also be conducted in the pres- of time, depending on the hydrolysability of the cation in
ence of other nonaqueous additives or solvents. Dong and question. Forced hydrolysis takes advantage of the ability of
Zhu [128] prepared –Fe2 O3 nanoparticles by dropping a many metals ions (especially of polyvalent cations) to read-
mixture of ethylene oxide (EO) and ethanol into an aqueous ily hydrolyze in aqueous solutions at elevated temperatures.
Table 3. Nanoparticle synthesis by hydrothermal synthesis.
Mullite (3Al2 O3 · 2SiO2 55 nm–7.1 m particle size, irregular Mixture of TEOS and Al tri-sec- Monolithic or fiber-reinforced mullite [124]
shaped butoxide, 170 C 2 h components for high-temperature
applications
Boehmite (–AlOOH) Needle-like particles from low-pH acid Sols prepared from dispersion Al Precursor for preparing high-purity [124]
solution; platelet-shaped particles acetate, then autoclaved at 200– and high-strength monolithic
(40 nm diameter and 5 nm thickness) 300 C –alumina ceramics by sol–gel
from high-pH alkaline conditions technology, applications as substrate
for electronic circuits, abrasive
grains, high-temperature refractory
≤100 nm nearly monodispersed Prepared from amorphous hydrated materials, fibers and thin films; fillers [291]
microcrystals of boehmite with a alumina gels at 255 C for 24 h in plastics and polymers, adsorbents
parallelogram shape and catalysts
ZrO2 20–60 nm particle sizes, near spherical Zr acetate solution heated to 220 C to Structural and functional ceramics; [124]
shape produce a sol application as pump parts, engine
parts, pressing dies, refractories,
oxygen sensor in molten steel,
Yttria-doped zirconia ∼45 nm tetragonal 3mol% Y2 O3 -doped Sol from ammonia-precipitated gel for ceramic fiber coating, solid [292]
ZrO2 powder (uniform aggregates) (containing both Zr and Y) + urea, electrolyte
∼95 nm grain after sintering heated at 150 C, followed by a
washing–drying and calcination
TiO2 doped with ZrO2 9–13 nm crystallite size Direct precipitation by cohydrolysis of Catalyst for photodecomposition and [293]
acidic precursor solutions of TiOSO4 solar energy conversion, white
and Zr(SO4 2 at 200–240 C pigment materials, UV protection
TiO2 <20 nm anatase particle size Using amorphous titania as starting Photocatalysis, sensors [294]
(round shaped); rod-like rutile material and various acids (HF, HCl,
nanocrystallites (9–32 nm diameter, HNO3 , citric acids) as catalysts
26–73 nm length)
<50 nm round shaped Hydrothermally treating the titania [295]
sols after peptization with
tetraalkylammonium hydroxide at
240 C
continued
699
700
Table 3. Continued
Cerium oxide (CeO2 <5 nm particle size, well dispersed Citric acid as protective agent against Polishing agents, sunscreens, solid [296]
particle growth electrolytes in solid oxide fuel
cells, automotive exhaust catalysts
(supports), additives for glass,
∼6 nm cubic primary particle, <10 nm Thermal hydrolysis of cerium ammonium stabilizers for ZrO2 [297]
uniform size agglomerate of nitrate solutions at 150–240 C
indefinite shape or large spherical
agglomerate particle (∼150–180 nm) Sulfate ions cause spherical [298]
agglomeration of nanoparticles
10–25 nm, cubic or octahedral Heating solutions of cerium salts + urea
(120–180 C)
Mg(OH)2 and MgO Nanocrystallines with rod-, tube-, Using different magnesium precursors Use in catalysis, toxic waste remediation, [299]
needle-, or lamella-like morphologies, and solvents as the reactants or as additives in refractory, paint,
maintained during decomposition Decomposition: Mg(OH)2 → MgO and superconductor products
Maghemite (–Fe2 O3 Highly crystalline, monodispersed High-temperature (300 C) aging of Magnetic memory devices, ferrofluids, [300]
nanoparticles (4–16 nm) iron–oleic acid metal complex refrigeration systems, medical
that was prepared by the thermal imaging, drug targeting, catalysis
decomposition of iron pentacarbonyl
in the presence of oleic acid at
100 C, or direct oxidation of iron
pentacarbonyl in the presence of
oleic acid with trimethylamine oxide
as an oxidant
Hematite (–Fe2 O3 20–50 nm particle size Mixture (FeCl3 + EO + ethanol) heated [128]
at 200 and 300 C
ZnGa2 O4 Needle or rod-like particles plus 10– >180 C treatment of mixed metal Transparent and conductive materials, [297]

20 nm nanoparticles sulfate salt solutions +NH3 phosphors
BaTiO3 Nanocrystalline powders Amorphous Ti gel or anatase precursor Dielectric or ferroelectric materials [301]
in Ba(OH)2 solution
A commonly written equation for the hydroxylation of metal a solution, carbonate ions are produced, accompanied by
ions (M z+ ) is a simultaneous increase in the pH homogenously through-
out the whole solution, leading to the precipitation of metal
M z+ aq + zOH+ aq → M OHz basic carbonates.
It only represents the mass balance of a precipitation NH2 2 CO + 3H2 O → CO2 + 2NH+
4 + 2OH
−
process. In fact, metal complexes (also called solutes)

{[Mn (H2 O)np−m (OH)m ] nz−m+ } act as precursors to nucle- The gradual and uniform rise in pH can result in the nucle-
ation and affect particle growth. In other words, the ation and growth of uniformly nanosized particles. Calcina-
hydrolyzed species are intermediates to the precipitation of tion is usually required to transform the carbonates to metal
the corresponding hydroxides [130, 131] oxides. Rojas and Ocana [134] used HMTA to enhance the
forced hydrolysis of ceria (Pr doped). Song and Kang [135]
nM H2 Op z+ + mOH− → Mn H2 Onp−m OHm nz−m+ have taken advantage of the gradual urea decomposition in
+ mH2 O aqueous solutions of SnCl4 to prepare nanosized tin oxide
particles. Similarly, uniform colloids can be obtained by the
or controlled release of cations approach—the slow release of
cations from organometallic complexes, which then react
OH−
nM H2 Op z+ −−→ Mn H2 Onp−m OHm nz−m+ with hydroxide ions in solution [133].
Another entirely different approach is the thermal decom-
OH−
−−→ nM OHz position of complex solutes in solution. Metal chelates or
similar organometallic compounds can be decomposed in
During forced hydrolysis, the hydroxide ions are formed in- strongly alkaline solutions to yield uniform metal (hydrous)
situ by the deprotonation of water molecules coordinated by oxides. Complexing agents, such as triethanolamine (TEA),
the metal ions [131–133] according to nitrilotriacedic acid (NTA), and (ethylenedinitrilo) tetra-
acetic acid (EDTA), appear to prevent both nucleation and
nM H2 Op z+ → Mn H2 Onp−m OHm nz−m+ + mH+ coagulation during particle growth by shielding the metal
ions. Meanwhile, complexes may liberate metal ions by
At elevated temperatures, the above forced hydrolysis can degrees with the progress of precipitation. The decomposi-
occur in the absence of base. Raising the temperature and tion of metal chelates typically requires much higher tem-
adjusting the initial pH of the solution affects the hydroxyla- peratures (i.e., similar to hydrothermal conditions) due to
tion of metal ions and the generation of complexes responsi- the stability of metal complexes. Particles obtained by this
ble for particle nucleation and diffusional growth. Typically, method show a relatively large size and a different crystal
the pH decreases in the course of the reaction due to depro- shape, other than spheres.
tonation of the hydrated cations, eventually leading to the Some examples of using forced hydrolysis in (hydrous)
formation of solid hydrous oxides. The low pH used in these oxide nanoparticle synthesis are shown in Table 4.
systems is particularly important in order to keep a relatively Most of the forced hydrolysis processes use aqueous solu-
low supersaturation with hydroxide ions that are constantly tions of inorganic salts. However, hydrolysis and inorganic
furnished by dissociation of water as their reservoir. Coagu- polymerization can be carried out on salts dissolved in a
lation is prevented mainly by the repulsive force of the elec- nonaqueous medium such as a polyol medium. For exam-
tric double layer exerted from the positively charged surfaces ple, Ammar et al. [136] have used this polyol approach to
of each particle in the low pH range, which is effective at prepare monodispersed cobalt ferrite nanoparticles.
low ionic strength [94]. To consistently obtain particles with Instead of using a pure aqueous solution, the addition of
controlled characteristics, it is necessary to control the pH, alcohol to the solution could significantly affect the solid
the concentration of reactants, the temperature, the anions nucleation and growth kinetics, as well as the particle mor-
or counterions of a given metal salt solution, the method phology. Hu et al. [137] have demonstrated that the addition
of mixing, etc. Anions could be highly responsible for the of alcohol to an aqueous solution of metal salts can dramat-
particle morphology. Forced hydrolysis can yield particles of ically enhance the solid phase nucleation and growth rate,
different shapes (spherical, cubic, ellipsoidal, etc.), either of although the solid phase and morphology of the particles
the same or different chemical composition. may be different from those obtained from forced hydroly-
In summary, the forced hydrolysis method requires an sis of alcohol-free aqueous solutions. Li and Gao [138] pre-
acidic solution containing a metal salt at a given concen- pared nanocrystalline zirconia in a water–ethanol mixture
tration to be heated in order to produce hydroxide ligands solution.
in-situ by the deprotonation of bound water. A forced hydrolysis process has been coupled with
With less strongly hydrolysable cations, it is necessary to microwave heating (using a particularly fast heating rate) to
raise the pH somewhat by the addition of a weak base in enhance the process kinetics and uniformity of the nano-
order to promote or accelerate hydroxylation, and thus pre- particles. For example, Bellon et al. [139] prepared zirco-
cipitation. For example, the hydrolysis of cations can be nia sols (i.e., colloidally stable suspensions) and powders by
achieved by the controlled release of anions (hydroxide ions) the microwave heating of ZrCl4 solutions at 180 C. Zhu
into a metal salt solution [92] by gradual decomposition et al. [140] prepared tin oxide nanoparticles, and Liao et al.
of certain organic compounds such as urea, formamide, or [141] prepared amorphous hematite nanoparticles via this
hexamethylenetetramine (HMTA). When urea is heated in method.
702
Table 4. Nanoparticle synthesis by forced hydrolysis.
SnO2 ∼4 nm particle size Forced hydrolysis (160 C) of aqueous Gas sensors (H2 , CO, hydr4ocarbon, [302]
SnCl4 solutions for 2–24 h alcohol), catalysts, electrode materials
(transparent electrode, glass-melting
3–4 nm in diameter Homogeneous precipitation, aqueous electrode), applications in solar [135]
SnCl4 + urea, 90 C energy conversion (dye-based solar
∼3 nm particle size, 4–60 nm crystallite Microwave heating (refluxing) of cells), photocatalysis, electrochromic [140]
size in annealed powder (200–800 C) aqueous solution of SnCl4 and urea devices, and in optoelectronics
for 15 min
Pr-doped ceria ∼12 nm uniform, nonagglomerated Aging at 100 C for 2 h aqueous Three-way automotive catalysts, red [134]
nanoparticles solutions of cerium (III) nitrate, ceramic pigments, high-conducting
praseodymium (III) chloride, and solid electrolytes used in high-
hexamethylenetetramine (HMTA). temperature fuel cells and oxygen
HMTA is the precipitating agent sensors
CeO2 (20–100mol%)–ZrO2 2–3 nm particle size, cubic and/or Forced cohydrolysis of acidic Catalytic supports for automotive [303]
tetragonal fluorite-type structure aqueous solutions of ZrOCl2 and exhaust
(NH4 2 Ce(NO3 6 at 100 C
CoFe2 O4 5.5 nm particle size, monodispersed, In a polyol medium by forced hydrolysis Ferro fluids, magnetic drug delivery, [136]
almost equiaxial of ionic Co(II) and Fe(III) salts at magnetic high-density information
160 C storage
ZrO2 10–200 nm particle size, near Heating (95–120 C) of aqueous ZrOCl2 Nanophase ceramics for high [137]
monodispersed, monoclinic phase solution without and with addition of refractriness and corrosion resistance,
isopropanol mechanical strength and fracture
toughness, and ion conduction
randomly shaped 30 nm particle Flash synthesis by microwave-forced [139]
(aggregates of 3–4 nm tetragonal and hydrolysis of ZrCl4 and HCl for
monoclinic crystallites) 2–10 min
ZrO2 (3%Y2 O3 nanocrystalline, tetragonal phase, 300– Zr and Y salts dissolved in water– [138]

500 nm particle size ethanol mixture, PEG added
as dispersant, heated to high
temperature, followed by ammonia
precipitation
continued
Table 4. Continued
ZrO2 (3%, 12% Y2 O3 8–10 nm crystallite size Hydrolyzing ZrOCl2 aqueous solution, [304]
then the resulting acidic sol was
neutralized and coagulated with
ammonia solution
Mn3 O4 , –MnOOH, Mn2 O3 ∼20 nm colloid (equiaxial) Forced hydrolysis (80 C) of aqueous Catalysts in environmental reactions and [305]
Mn(II) acetate solutions in synthesis of organic compounds,
electrodes in alkaline batteries
or elongated (length <2 m and width In the presence of HCl, particle is
<0.4 m) elongated.
Mn3 O4 → Mn2 O3 (800 C)
–MnOOH → MnO2 (250–450 C) →
Mn2 O3 (800 C)
TiO2 40–400 nm monodispersed particles Forced hydrolysis of TiOCl2 (from Titania (rutile phase) as white pigments, [306]
(aggregates with primary particle size dilution of TiCl4 at 17–230 C coating materials for optical and
3–10 nm) electronic devices, photocatalysts
Nanosized (70–100 nm), near Forced hydrolysis of Ti(SO4 2 at boiling [307]
monodispersed spherical powder reflux for 5 h
Fe2 O3 3–5 nm primary particle size Microwave refluxing (10 min) of mixture Solar energy transformation, magnetic [308]
(amorphous), 12 nm crystallite in solution containing PEG, FeCl3 , and storage media, catalysts
sintered powder (400 C) urea
703
3.2.4. Sol–Gel Synthesis Sol–gel chemistry presents many advantages for the pow-
Metal alkoxides dissolved in homogeneous alcohol–water derless processing of ceramics, the molecular design of
solutions are typically used in a sol–gel process, which is so advanced materials, or the synthesis of hybrid organic–
named because it usually involves a stage of sol (solids sus- inorganic compounds. The sol–gel process has also been
pended in a continuous liquid phase) formation, and then reported for making nanophase ceramics (ceramic lay-
a stage of gellation (liquid particles/pockets suspended in a ers containing individual <10 nm nanoparticles) by using
continuous solid phase) process. Sol–gel also refers to pro- inverse micelle reaction media or acacH-modified alkoxides
cessing in a liquid medium to obtain solid matter (such as [144]. Pierre [142] has specifically discussed the principles
particles) which does not settle under the effects of gravity for achieving monodispersity during the sol–gel processing
[142]. Water and alkoxides are immiscible, and thus a mutual of ceramic powders.
solvent such as alcohol is utilized. Catalysts such as mineral Some recent efforts in the sol–gel synthesis of nanosized
acids (such as HCl) or bases (such as ammonia) are mostly oxide particles or nanocrystalline powders are summarized
used, as well as many others (acetic acid, KOH, amines, KF, in Tables 5 and 6. A classic example of sol–gel processes for
and HF). Acid-catalyzed processes tend to yield primarily making ultrafine particles is the one developed by Stöber
linear or randomly branched polymers for use as coatings, and Fink [146] for the production of monodispersed silica
while base-catalyzed processes yield highly branched clusters using an alkoxide (tetraethoxy silane, TEOS) and ammo-
for making particles. nia catalysis. The sizes of these so-called “Stöber spheres”
The sol–gel process typically involves alkoxide hydrolysis range from a few nanometers to a few micrometers, depend-
and a condensation reaction [143] ing on the conditions (concentrations of reactants such as
TEOS, ammonia, and water; reaction temperature and time;
M ORx + yH–OH → M ORx−y OHy + yROH method of mixing, etc.). Livage et al. [145] used acacH to
tailor the alkoxide condensation reaction kinetics, and thus
where R represents an alkyl group. The partially hydrolyzed the zirconia nanoparticle size. The mean diameter increases
species are then linked to form M–O–M bonds by conden- when the ratio of [H2 O]/[Zr] increases and the ratio of
sation via dehydration or dealcoholation [acac]/[Zr] decreases.
Some sol–gel processes do not have to use alkoxides
–M–OH + HO–M– → –M–O–M– + H2 O (dehydration) as starting precursors. Chen and He [147] used all inor-
ganic metal salts (with PAA as a complexing agent to cou-
–M–OH + RO–M– → –M–O–M– + ROH (dealcoholation)
ple the two metal species together) to achieve sol and gel
True metal alkoxides are highly sensitive to hydrolysis. formation, and thus produced nickel ferrite nanoparticles.
Condensation reactions can be controlled via the chemical In some other cases, transient alkoxide-like species were
modification of metal alkoxides with complexing/chelating formed from reactions of inorganic metal salts and alcohol.
ligands such as acetyl acetone (acacH) [144, 145] and Dong and Zhu [128] and Manorama et al. [112] prepared
others (polyols, organic acids,
–diketones, and allied nanoparticles with transient alkoxide formation processes.
derivatives). The M–acac bond, stabilized by chelation, Metallorganic compounds such as metal formates have also
and
–diketonates, is much more difficult to hydrolyze been used as precursors in the sol–gel synthesis of multi-
than alkoxy groups. This process, involving hydrolysis → component nanosize ceramic powders [148–151].
polymerization → nucleation → growth, condenses the For mixed metal oxide powder synthesis, the use of sin-
molecular units together into small clusters (the “sol”), gle molecular multimetallic alkoxide precursors has certain
eventually leading to the formation of an insoluble three- advantages, such as precise control of chemical stoichiom-
dimensional network (the “gel”), which can be further con- etry and composition homogeneity. Narayanan and Laine
densed into a solid. [152] developed the use of a trimetallic double alkoxide
Sol–gel processes, based on the hydrolysis and conden- precursor to prepare phase-pure potassium aluminosilicate.
sation of molecular precursors, have historically played a O’Brien et al. [153] used a bimetallic alkoxide to synthesize
significant role in glass and ceramic coating applications. monodispersed barium titanate nanoparticles in the 4–12 nm
Through these processes, homogeneous oxide materials particle size range.
with desirable properties like hardness, optical transparency, In addition to chemistry, other process strategies were
chemical durability, tailored porosity and thermal resistance taken into account to tailor the sol–gel synthesis of nano-
can be produced at room (or low) temperatures. This pro- particles. Kim and Kim [154] developed a “semibatch-batch
cess contrasts to the much higher melting temperatures two-stage reaction” to decrease the size of titania nano-
required in the production of conventional inorganic glasses. particles. The particle size was reduced to 132 nm in the first
Factors that affect the rate of hydrolysis and condensation stage, and decreased to 42 nm in the second stage. Better
reactions (and thus the microstructure of the solid sol–gel- uniformity was another benefit.
derived materials) include the pH, temperature, and time Sol–gel processes at low temperatures generate mostly
of reaction, reagent concentrations, catalyst nature and con- amorphous nanoparticles or gels, which require further high-
centration, water/metal molar ratio, aging temperature and temperature treatment such as calcination to obtain nano-
time, and drying. In addition, the chemical design of the crystalline powders. Some sol–gel processes are coupled with
molecular precursors provides an interesting tool to control hydrothermal processing (in an autoclave reactor) to pro-
condensation reactions and tailor the nanostructure of the duce some as-prepared particles with the desired crystalline
oxide materials [145]. phases [155–157].
Table 5. Synthesis of single metal–oxide nanoparticles by sol–gel processes.
materials nanoparticle Brief process description Ref.
SiO2 Amorphous monodispersed nanoapheres Ammonia-catalyzed hydrolysis and [146]

condensation of TEOS–ethanol–
water homogeneous solutions
13.7 nm monodispersed nanoparticles Semibatch method using TEOS, [309]
ammonia, ethanol, HPC, and water
ZrO2 Sol of amorphous, monodispersed Acetylacetone (CH3 –CO–CH2 –CO–CH3 [145]
nanoparticles (∼3 nm hydrodynamic added to the Zr(OPri 4 solution prior
dia.) <10 nm to hydrolysis to decrease reactivity:
Zr(OPri 4 + x acacH → Zr(OPri 3−x [144]
(acac)x + x Pri OH
Gel calcined into nanocrystalline phase Zr n–butoxide in terbutilic alcohol, with [310]
(10–32 nm crystallite size) hydrolysis catalyst HCl, C2 H4 O2 , or
NH4 OH, dried and annealed, then
sulfated with H2 SO4
SnO2 2–12 nm particle sizes, 2.4–5.5 nm Hydrolysis of Sn (IV)–isopropoxide [302]
crystallite sizes dissolved in ethanol
TiO2 Porous anatase nanoparticles, 9–15 nm Heating (348 K) of ethanol solution of [311]
particle size · crystallite size Ti tetra isopropoxide and H2 O2 →
Ti–peroxy compounds → Ti–peroxy
gel, which was treated at 348 K for
6–48 h
42 nm particle size Semibatch reaction (Ti(OC2 H5 4 /HPC/ [154]
ethanol feed into H2 O/ethanol,
stir for 60 min), followed by
batch reaction (add additional
Ti(OC2 H5 4 /HPC/ethanol and
H2 O/ethanol, stir 60 min), then
drying at 70 C for 12 h
10.7 nm particle size Semibatch method
1–5 nm core sizes (anatase), particle Hydrolysis at 60 C of Ti butoxide in the [309]
surface coated presence of acetylacetone and para-
toluenesulfonic acid; particle surface
protection through: (1) complexation
by acetylacetonato ligands, and (2)
adsorbed organic–inorganic layer
made with acetylacetone, para-
toluenesulfonic acid, and water.
5–12 nm crystallite sizes Hydrolysis of Ti(IV) isopropoxide; [312]
stabilized by hydroxylpropyl cellulose
(HPC)
[313]
ZnO 3–5 nm zincite crystallites, which Alkoxide-based synthesis involving [314]
aggregate into larger spherical diethylzinc, tert-butyl alcohol,
particles ethanol, and water:
Zn CH2 CH3 2 + 2 CH3 3 COH →
ZnOC CH3 3 2 + 2CH3 –CH3
ZnOC CH3 3 2 + 2H2 O (in ethanol) →
Zn OH2 + 2 CH3 3 COH
Zn OH2 → ZnO + H2 O (heating: RT →
90 C 15 min → 250 C 15 min)
∀–Fe2 O3 Nanosized Sol–gel process using ethylene oxide and [315]
FeCl3 as starting materials in ethanol
Sc2 O3 , ScOOH <80 nm, lozenge-shaped platelets (66 × Sc(acac)3 dissolved in 2–methoxyethanol, [316]
37 × 45 nm) in which water/methoxyethanol was
added, refluxed until yellow color
vanished, and a light bluish aspect
appeared.
Table 6. Synthesis of mixed metal-oxide nanoparticles by sol-gel processes.
Nanoparticle Characteristics
materials of nanoparticle Brief process description Ref.
NiFe2 O4 5–30 nm crystallite sizes Aqueous solution of Ni nitrate and Fe (III) nitrate, mixed with [147]
aqueous solution of PAA (as a chelating agent), then add nitric
acid → transparent green solution, evaporation at 50 C →
transparent sol, 50 C 10 h → viscous brown gel, calcined →
spinel nickel ferrite nanopowders
BaTiO3 Monodispersed nanoparticles Single bimetallic alkoxide molecular precursor method: barium [153]
(4–12 nm particle sizes) titanium ethyl hexano–isopropoxide is injected into a mixture of
diphenyl ether at 140 C under argon or nitrogen. The mixture is
cooled to 100 C and 30% H2 O2 is injected, stirred over 48 h to
promote further hydrolysis and crystallization of the product in an
inverse micelle condition.
Crystalline fine powders Dissolve Ba metal in 2–methoxyethanol → add Ti isopropoxide [317]
→ reflux under nitrogen at 135 C → hydrolyze with water
(water/alkoxide = 3/1) → amorphous gel powder → dry → calcine
→ powder
PbZrx Ti1−x O3 ∼17 nm nanocrystal size, free Sol–gel synthesis using lead acetate, Ti(IV) ethoxide and Zr(IV) [318]
(PZT) standing butoxide
Al2 O3 –TiO2 Nanocrystalline powder (1–150 Poly(ethylene glycol) (PEG) sol–gel method [319]
nm grain sizes), spherical or
cubic shaped
Binary and Calcined nanocrystalline powders Aqueous sol–gel method with formates and TEOS as precursors [148, 150, 151]
ternary oxide of BaO–SiO2 (60–150 nm),
nanopowders mullite (85–15 nm), eucryptitite
(140–205 nm), spodumene (150–
200 nm)
IrO2 –Ta2 O5 Ultrafine, irregular shaped IrCl3 dissolved in ethanol under nitrogen → Ir ethoxide → mixed [320]
with Ta(OC2 H5 5 → add ammonia → slow addition of H2 O2 (to
oxidize Ir precipitates) → dried, calcined
RuO2 –SnO2 Ultrafine, irregular shaped Hydrolysis and condensation of metal alkoxides in ethanol [321]
Al2 O3 and <2 nm crystallites in powders Sol–gel + autoclaving thermal conversion: modified aerogel [155]
Al2 O3 /MgO synthesis involving Al and Mg alkoxides, toluene, methanol,
ethanol, and water → gel → autoclave at 265 C
TiO2 Dispersed colloids of tightly Hydrothermal sol-gel [157]
aggregated secondary particles
(10 nm primary particle size,
100 nm secondary particle size)
<10 nm particle size Sol–gel synthesis → peptization → growth under hydrothermal [156]
treatment in a basic environment at 190–270 C
3.2.5. Solvothermal Synthesis and nucleation and growth of nanocrystals, and as a capping
Nonhydrolytic Route agent. Titanium alkoxide was modified by replacing one or
While water is used for the hydrothermal synthesis of more isopropoxide groups with donor functionalized alkox-
hydrated oxides, other nonaqueous solvents have also been ide ligands such as dimethylaminoethoxide (dmae) or diethyl
utilized for liquid-phase thermal processing. Nonaqueous aminoethoxide (deae), leading to the formation of more
solvothermal processes and some nonhydrolytic approaches fully saturated compounds that have reduced air/moisture
have been proven to play a significant role in the synthesis sensitivity compared to the parent alkoxides. In a typical syn-
of advanced nonoxide ceramic materials by using reactions thesis, TOPO was heated to 200 C, degassed (flushed with
in nonaqueous solutions [158–160]. argon), and heated to 325 C. Then the modified alkoxide
Parala et al. [161] have described a nonhydrolytic sol– precursor was injected rapidly into the reaction flask under
gel approach to the preparation of uniform, quantum- an argon atmosphere, and the reaction was maintained at
confined titania nanocrystals using an intramolecular 300 C for 15 min. The resulting nanocrystals (3–5 nm,
adduct-stabilized alkoxide precursor. The organic passivat- spherical shape) can be readily dispersed in polar solvents
ing ligand TOPO was used as the reaction medium for the like toluene or hexane. In contrast to aqueous sol–gel
processes, the nonhydrolytic sol–gel technique in hydrocar- of alcohol, oleic acid, and oleylamine [169]. By perform-
bon solvents at high temperatures allows access to very small ing the reaction in propylene glycol under reflux, Rajamathi
free-standing crystallites, and opens up new possibilities for et al. [170] were able to hydrolyze FeCl3 in the presence
control over size distribution, surface chemistry, and particle of n–octylamine to obtain soluble, monodispersed –Fe2 O3
agglomeration. (∼5 nm).
Nonaqueous solvothermal processes can be defined as
chemical reactions or transformations in an organic solvent 3.2.6. Microwave Heating Synthesis
under elevated temperature and pressure conditions, such as
Microwave-assisted synthesis for the production of inorganic
supercritical conditions or near such a pressure–temperature
compounds has been studied since 1986. As compared to
domain. The specific physicochemical properties of sol-
conventional oven heating (with a slow heating rate and
vents in supercritical conditions in particular can markedly heat transfer), microwave “volumetric” heating of liquids
improve the diffusion of chemical species [160]. The is an alternative heating approach with specific advantages.
chemical composition of the solvent must be adapted to Microwave heating of the hydrothermal reactor was found
the material to be prepared. Solvothermal processes have in some cases to cut the reaction time significantly, to gen-
been developed for: (1) the shaping of materials (crys- erate remarkable size uniformity, and to produce some new
tal growth or the preparation of fine microcrystallites), phases as well as known ones [171].
(2) the synthesis of new materials with interesting prop- Recently, there have been some reports on microwave
erties, and (3) the development of new processes for dielectric heating for the liquid-phase synthesis of nano-
preparing functional materials. In particular, the solvother- particles [172]. This literature is summarized in Table 7.
mal technique provides an alternative approach that allows
the economical synthesis of fundamentally important well-
defined nanometer-sized materials under mild conditions 3.2.7. Synthesis in Microemulsions or
[162]. On the other hand, the direct precipitation of Reverse Micelles
metal oxides from high-boiling-point organic solvents, as in Microemulsions are thermodynamically stable, fluid, and
“glycothermal synthesis,” presents an alternative to wholly optically clear dispersions (10–100 nm subphases) of two
aqueous hydrothermal material synthesis routes [160, 163, immiscible liquids such as water and oil. Microemulsions
164]. These processes have used nonaqueous solvothermal form when a surfactant, or more commonly a mixture of
processes to synthesize phyllosilicate-like oxides without the surfactants and cosurfactants, lowers the oil/water interfa-
OH groups and stabilized nitrides (such as Mo2N and/or cial tension to ultralow values, allowing thermal motions to
MoN fine particles and C3 N4 in nitriding solvents (NH3 or spontaneously disperse the two immiscible phases. Unlike
NH2 NH2 . Yin and Wang [165] prepared cobalt and cobalt conventional emulsions, however, microemulsion domains
oxide (CoO) nanocrystals by the chemical decomposition of fluctuate in size and shape, and undergo spontaneous coales-
Co2 (CO)8 in toluene (at 130 C), in the presence of sodium cence and break up [173]. Miniemulsions are systems where
bis(2–ethylhexyl) sulfosuccinate as a surface active agent. small droplets with high stability are created in a continuous
Adair et al. [163] synthesized alpha-alumina of controlled phase by using high shear [174]. Reverse micelles are molec-
particle size and shape in 1,4–butanediol solutions (with a ular self-assemblies from surfactants or block copolymers,
high boiling point). The glycothermal synthesis technique which have a spherical shape with a hydrophilic (water-
allows for the production of anisometrically shaped particles loving) core and a hydrophobic tail on the sphere surface.
with controlled morphology and size distribution [164]. Microemulsion synthesis is probably the most popularly
Hong et al. [162] developed a so-called “alcohol-thermal” reported method, in recent literature, for the synthesis of
route under mild conditions (110 C) to prepare CuO nano- nanosized inorganic particles (oxides, mixed oxides, semi-
particles (∼3–9 nm, depending on reaction temperature) conductor nanocrystals, metal nanocrystals or nanoclusters,
using copper acetate as the starting material. Hai et al. [166] coated nanoparticles, etc.). It is still an active research topic.
prepared SnS2 nanoparticles (∼150 nm average particle size, We, however, will mainly focus on the review of work on
laminar shape) by a solvent–thermal synthesis method using ceramic (oxide) nanoparticles. Self-assembly systems such
the precursor salts SnCl2 and CS2 dissolved in absolute alco- as water-in-oil microemulsions (or reverse micelles), or
hol autoclaved at 200 C for 16 h. Qiu et al. [167] synthe- other self-assembled structures of surfactants and block
sized nanosized Y–TZP powders (∼15 nm crystallite size) by copolymers, have been utilized as “nanoreactors” that con-
a coprecipitation, followed by the distillation of the result- fine a solid phase formation [175–177]. The application of
ing gel in n–butanol. In some cases, a small quantity of a microemulsion as a precipitation medium yields much
water may be involved. For example, Kominami et al. [168] smaller particles (with narrower size distribution) than can
synthesized nanocrystalline tantalum (V) oxide powders by be obtained from homogeneous solutions [178, 179]. In addi-
a solvothermal reaction of Ta pentabutoxide in toluene at tion, reverse micelles or water-in-oil (W/O) microemulsion
473–573 K in the presence of water. methods have been utilized for the growth of anisotropic
Organic solution-phase decomposition of iron precur- nanoparticles (such as plate-like oxides) and core–shell
sors at high temperatures has been widely used in iron nanoparticles (via arrested precipitation) [180].
oxide nanoparticle synthesis. Recent advances have demon- In a typical process for nanoparticle synthesis by a
strated the synthesis of high-quality, monodispersed – microemulsion technique, the organometallic and/or metal
Fe2 O3 and Fe3 O4 nanoparticles (<20 nm in diameter); one salt precursors are dissolved inside the water pools of the
such method uses the high-temperature (265 C) reaction reverse spherical micelles, and are allowed to react via
of Fe(III) acetylacetonate in phenyl ether in the presence droplet collision and rapid intermicellar exchange of their
Table 7. Microwave heating liquid-phase synthesis of nanoparticles and nanocrystalline powders.
ZrO2 Polymer stabilized ZrO2 nanopowders with Microwave heating in an aqueous solution [322]
average crystallite size of 2.0 nm containing Zr(NO3 4 , PVA, and NaOH
Randomly shaped particles of roughly 30 Flash synthesis by microwave-forced hydrolysis [139]
nm, which are aggregates of 3–4 nm
crystallites of tetragonal and monoclinic
phases
SnO2 ∼3 nm particle (or crystallite) size in as- Microwave irradiation heating-forced hydrolysis [140]
prepared powders; 4, 12, 18, and 60 nm of an aqueous solution in the presence of
avg. particle sizes for powders annealed at SnCl4 and urea
200, 400, 600, and 800 C
CeO2 Nanocrystalline powder (2.6 nm crystallite) Microwave-assisted heating routes [323]
from aqueous solutions containing
(NH4 2 Ce(NO3 6 , hexamethylenetetramine,
and poly(ethylene glycol)-19000 (PEG)
Monodispersed nanocrystalline powders Microwave irradiation of aqueous solution [308]
(2.0 nm crystallite size) containing (NH4 2 Ce(NO3 6 , PEG, and NaAc
∀–Fe2 O3 Monodispersed red hematite spherical Microwave hydrothermal treatment of solution [324]
particles (30–66 nm in diameters) containing FeCl3 and HCl at 100–160 C
2–8 h
Monodispersed hematite nanoparticles Microwave thermohydrolysis of nitrate iron [325]
(III) solutions
Uniform nanoparticles (coarse ∼70 nm Microwave refluxing of mixed solutions of [326]
particle size, tetragonal shape 80 nm Fe(NO3 3 and HNO3 , Fe(NO3 3 and NaOH,
diagonal length, or ellipsoidal 50–100 nm or Fe(NO3 3 and NaH2 PO4
particle sizes)
Amorphous Fe2 O3 ∼3–5 nm particle sizes in amorphous Microwave irradiation heating of an aqueous [308]
powder (agglomerate); sintered ∀–Fe2 O3 solution containing ferric chloride,
riziform particles (10 nm diameter × 30 polyethylele glycol-2000 and urea
nm length)
Binary oxides BaTiO3 , Particle sizes for as-prepared (heated) Microwave-assisted soft-chemical route: using [327]
Ba6 Ti17 O40 , BaZrO3 , powders (nm): 10 (20–30), 15 (40–50), precursor salts BaCl2 hydrate, Pb(Ac)2 ,
PbTiO3 ∼200 × 600 (same), and 5–7 (20–30), Ti(Opri 4 , and ZrOCl2
respectively. Crystallite sizes in as-
prepared (heated) powders (nm): 9 (19),
11 (26), 1.8 (24), and 1.2 (17), respectively
∀–Al2 O3 Crystalline powders (60–990 nm particle Microwave-assisted “combustion” of redox [328]
sizes) solution mixtures containing the desired
metal ions (from Al nitrate), urea as oxidizing
reactant and fuel
BaTiO3 Ultrafine tetragonal-phase powders Microwave heating of solutions containing [329]
BaCl2 , TiO2 , NaOH, and deionized water
water content [181]. The nanoparticle formation in the copolymer spherical micelles in tetrahydrofuran/hexanes as
microemulsion process is controlled mainly by diffusion, and templates for the preparation of inorganic nanoparticles
is also dependent on the nature of the surfactant. Two major (iron oxide, ∼4–16 nm particle sizes).
procedures have been reported: (1) the catalyst is already Tables 8 and 9 summarize some major microemulsion syn-
contained in the water phase, and the precursor (such as thesis work from recent years, with a focus on the nano-
an alkoxide), dissolved in the continuous medium, progres- particles of oxides and mixed oxides.
sively enters the water pools of the reverse microemul-
sion; and (2) the precursor and the catalyst are prepared 3.2.8. Sonochemical Synthesis
as two separate microemulsions, and are mixed together to Ultrasound has been applied to enhance chemical reactiv-
allow the reaction to proceed via micellar exchange of two ity, particularly in synthetic materials chemistry. The chemi-
microemulsions. cal effects of ultrasound are derived primarily from acoustic
Instead of water, an ethanol-in-oil microemulsion has cavitation. Bubble collapse in liquids results in an enormous
been prepared for the synthesis of zinc oxide nanoparticles concentration of energy from the conversion of the kinetic
[182]. Some nanoparticle synthesis work has also been energy of the liquid motion into heating of the contents of
done with oil-in-water microemulsions (or normal micelles) the bubble. The high local temperatures and pressures, com-
involving ionic surfactants, in which counter ions are bined with extraordinarily rapid cooling, provide a unique
replaced by ions participating in the chemical reactions means for driving chemical reactions under extreme condi-
[175, 181]. This technique demonstrated the use of triblock tions [183].
Table 8. Single-(hydrous)oxide nanoparticle synthesis in microemulsions (or reversed micelles).
Nanoparticle Characteristics of nanoparticle Brief process description Ref.
SiO2 30–70 nm diameters, Hydrolysis of TEOS in water-in-oil microemulsion [330]

monodispersed spheres consisting of polyoxyethylene (5) monylphenyl ether
(NP5)/cyclohexane/ammonium hydroxide
Monodispersed, 0.1–1.5 m avg. Mix W/O catalyst(NH3 )-containing microemulsion with [331]
sizes TEOS containing microemulsion
Particle sizes: 70–640 nm Microemulsion using block copolymers and nonionic [332]
surfactant
ZrO2 Amorphous as-prepared Reverse microemulsion: water–cyclohexane–hexanol– [333]
particles Triton X-100
Crystallized (tetragonal) at Two-emulsion precipitation technique: two solutions [334]
450 C∼4 nm 5–50 nm of reverse emulsion, one containing Zr4+ aqueous
particle size (by TEM) droplets, and the other aqueous ammonia (or
HMTA) droplets, with the same water/oil ratio are
prepared separately and mixed together to form a
slurry of ZrO2 precursors
5–8 nm spherical Ethanol-in-oil microemulsion: Zn-AOT/ethanol/isooct- [335, 182]
nonaggglomerated particles ane, Na–DEHSS (diethylhexyl) sulfosuccinate as
Zn oxalate precursor surfactant, Zn nitrate as salt precursor dissolved in
nanoparticles (5–13 nm) ethanol
Al oxide–hydroxide Amorphous, mean particle Hydrolysis of Al isopropoxide in the L- [336]
sizes of 1.0–2.4 nm 2 phase of amphiphilic (PDMS–POE)
polydimethylsiloxanepolyoxyethylene Silwet L-7607–
octanol/acetylacetone–water mixtures
TiO2 Nanoparticles (both anatase Hydrolysis of tetrabutyl titanate in water core [337]
and rutile phase) of a water-in-oil microemulsion, provided by a
functionalized surfactant Span-Tween 80 (mixture of
sorbitol monooleate and polysorbate 80)
20–50 nm particle sizes in Mix of microemulsions. Precipitation of Ti hydroxide [338]
agglomerated powders by NH4 OH in microemulsion (water/Triton
X-100/hexanol/cyclohexane).
Sb2 O4 Nanorods (50–175 nm Aqueous solution of SbCl3 and HCl → mixed with [339]
diameter and several toluene containing AOT → ultrasonication → add
micrometer length) NaOH slowly → take upper layer transparent
yellow-colored solution and reflux → organosol →
evaporation to get zerogel→ drying to get powder
Fe3 O4 <10 nm particle size, equiaxial O/w microemulsion using cyclohexane as the oil [340]
morphology phase, NP5 + NP9 as the surfactant phase, and a
Fe(II)/Fe(III) salt solution as the aqueous phase
∼4 to ∼16 nm sphere Use of triblock copolymer micelles with hydrophilic [175]
cores as templates
2–8 nm particle size range Use cyclohexylamine to precipitate Fe(II) and Fe(III) [341]
by mixing two microemulsions (inverse micelles), a
ternary system cyclohexane/Brij-97/water
–Fe2 O3 ∼10 nm spherical particle, Precipitation of FeCl3 by NaOH in microemulsion [342]
coated with DBS and CTAB water sodium dodecyle benzene sulphonate (DBS)/
(cetyltrimethyl ammonium toluene: Fe3+ + OH− → ∃–FeOOH → –FeOOH
bromide) → –Fe2 O3
TiO2 As small as 2 nm, amorphous Sol–gel reaction with Ti tetraisopropoxide in miw/o [343]
powder microemulsion containing water, cyclohexane, or
octane, and surfactant such as polyoxyethylene (10)
octylphenyl ether (TX-100), polyoxyethylene lauryl
ether, or bis (2-ethylhexyl) sodium sulfosuccinate
Er2 O3 5–30 nm in diameters Inverse microemulsion technique: cyclohexane as the [344]
oil phase, NP5 + NP9 as the surfactant phase, and a
Er(III) nitrate salt solution as the aqueous phase
continued
Table 8. Continued
Nanoparticle Characteristics of nanoparticle Brief process description Ref.
BiOCl Monodispersed 250 nm long Lyotropic liquid crystal nanoreactors: 3-D percolated [345]
arrowhead-shaped particles hexagonal liquid crystal and 2-D percolated lamellar
(from hexagonal phase) liquid crystal
or roughly spherical 5 nm
particles (from lamellar
phase)
SnO2 30–70 nm particle sizes Water-in-oil microemulsion: water, AOT (surfactant), [346, 347]
for precursor hydroxide and n–heptane (oil) SnCl4 containing microemulsion
particles, dried powder is was mixed with ammonia-containing microemulsion
agglomerated
GeO2 Polyhedron (43–342 nm Hydrolyzing Ge tetraethoxide in a 2,2,4– [348]
particle sizes), Spindle (445– trimethylpentane solution of sodium bis(2–
838 nm), Cube (612–947 nm) ethylhexyl) sulfosuccinate (AOT) as a function of
water content
CeO2 8–48 nm mean particle sizes Precipitation of Ce(NO3 )3 by ammonia in Titron N- [349]
101/ n–pentanol/n–octane/water microemulsion
The sonochemical decomposition of volatile organometal- chloride solutions with Sr2+ and Fe3+ salts, using commer-
lic precursors in low-volatility solvents has been a major cial Fe electrodes. This electrochemical procedure is based
technique in producing various nanostructured materials on the coprecipitation of oxides of Sr2+ , Fe3+ , and Fe2+
(such as metals/alloys, oxides, carbides, sulfides, nanosize (supplied from the Fe anode) in the solution and electrodes
colloids, etc.). Examples of decomposition include: (1) the under the action of the applied electrical field
decomposition of W(CO)6 and Fe(CO)5 , and (2) the decom-
position of urea to precipitate metal ions in solution. Fe → Fe2+ + 2e− (anode reaction)
Table 10 summarizes some of the most recent efforts 2H2 O + 2e− → H2 + 2OH− (cathode reaction)
in the sonochemical synthesis of inorganic nanoparticles
(mainly oxides) from liquid-phase reactions. Maghenite and magnetite are assumed to be produced in
the alkaline region near the cathode
3.2.9. Electrochemical Synthesis
2Fe3+ + 6OH− → –Fe2 O3 + 3H2 O
Electrochemical processes take advantage of not only solu-
tion chemistry, but also of electrical current-enhanced phe- Fe2+ + 2Fe3+ + 8OH− → Fe3 O4 + 4H2 O
nomena through electrode(s) and electrochemical reactions
at the electrode–solution interface. The resulting mixture of these oxides is further doped by
There are some recent reports on the synthesis of oxide Sr2+ , which partially substitutes the Fe2+ in the magnetite to
ceramic nanoparticles using electrochemical routes. Borgo- yield the final insoluble Sr–Fe oxide
hain et al. [184] prepared cuprous oxide (Cu2 O) quantum
particles as small as 2 nm by a novel electrochemical route. Sr2+ + –Fe2 O3 a Fe3 O4 b → –Fe2 O3 a Fe3 O4 b−1
A Cu anode and a Pt cathode were used in an electrolytic × SrFe2 O4 + Fe2+
bath consisting of a mixture of acetonitrile (CH3 CN) and
tetrahydrofuran (TMF) bubbled with nitrogen. The support- Similarly, Torres et al. [187] prepared Mn–Zn–Fe mixed
ing electrolyte, tetra–n–octyl ammonium bromide (TOAB), oxides (<50 nm nanoparticle size) as precipitates from chlo-
also served as a stabilizer. On application of an electric cur- ride and nitrate solutions of pH 1.5 with Mn2+ , Zn2+ , and
rent, the anode slowly dissolves, leading to the formation of Fe2+ or Fe3+ at temperatures between 40 and 80 C using
Cu ions, which get oxidized immediately after formation by electrodes of commercial iron.
the residual oxygen in the bath, and subsequently get passi- In addition to oxides, the electrochemical route also has
vated by the active TOAB species. The cluster size of Cu2 O been utilized for the synthesis of nonoxides. Griffiths et al.
was found to decrease with an increase in current density. [188] recently reported that the electrochemical oxidation
Pascal et al. [185] performed electrochemical synthesis in an of a titanium electrode in a solution of potassium amide in
organic medium for nanoparticles of maghemite –Fe2 O3 liquid ammonia resulted in the deposition of titanium nitride
(with narrow size distribution, average sizes varying from 3 as nanoparticles or as a thin film.
to 8 nm). Nyffenegger et al. [189] reported a hybrid “electrochem-
Electrochemical routes were also reported for the syn- ical/chemical (or E/C) method,” which is a relatively new
thesis of nanostructured mixed oxides. Amigo et al. [186] wet-chemical method, for the synthesis of zinc oxide (ZnO)
synthesized magnetic nanoparticles of Sr–Fe oxides (aver- nanoparticles (with mean diameters of nanocrystallites in
age sizes from 2 to ∼50 nm) in the shape of inverse cubic the range of 1.5–10 nm) and films (10–40 nm thickness,
spinels. The nanoparticles were precipitated from nitrate polycrystalline). The E/C procedure involves two steps: (1)
media in the pH range of 1–3, and from chloride media zinc metal is first electrochemically deposited at basal-plane-
within the pH range of 1–12, by electrolysis of nitrate and oriented graphite electrode surfaces from dilute aqueous
Table 9. Mixed-oxide nanoparticle synthesis in microemulsions (or reversed micelles).
Nanoparticle materials Characteristics of nanoparticle Brief process description Ref.
CoFe2 O4 Oval-shaped, avg. radius of 4.8 nm Templating synthesis: self-assembly of [350]

mixed-metal oxides in block copolymers
1–15 nm particle sizes AOT reverse micelles: adding aqueous [351]
solutions of Fe(II) and Co(II) salts to
AOT dissolved in isooctane
MFe2 O4 (M = Mn, 5.5 nm uniform size particle Two potions of solution of AOT in [352]
Fe, Co) isooctane were mixed with aqueous
solutions of the reactants, one containing
metal salts and another one containing
the precipitating agent NH4 OH
10–20 nm particle sizes, spherical shape Two potions of solution of AOT in [353]
isooctane were mixed with aqueous
solutions of the reactants, one containing
metal salts and another one containing
the precipitating agent NH4 OH
CoLn012 Fe188 O4 ∼20 nm particle size O/w micelles using sodium dodecyl sulfate [354]
(Ln = Ce, Sm, as the surfactant
Eu, Gd, or Er)
MnFe2 O4 uniform ∼10 nm particle size AOT (bis(2–ethylhexyl) sodium [355]
sulfosuccinate) in isooctane reverse
micelle solutions containing the reactants
FeSO4 , MnSO4 , NH4 OH (precipitant),
and H2 O2 (oxidant)
Eux Y2 O3 10–100 nm particle sizes, red-emitting Microemulsion containing petroleum [356]
nanophosphor ether (60–80 C), nonionic
surfactants NP5 /NP9 , aqueous yttrium
nitrate/europium nitrate and ammonium
hydroxide solution
Spherical shape, narrow size Precipitation of aqueous yttrium nitrate/ [357]
distribution, high crystallinity, strong europium nitrate solution using
photoluminescence ammonium hydroxide in the reverse
microemulsions based on polyoxyethylene
(5) nonylphenyl ether/polyoxyethylene
(9) nonylphenyl ether, cyclohexane, and
water
Ba-stabilized High thermal stability, high surface area, Microemulsion + hydrothermal techniques [358]
alumina uniform, long-shaped particles
(∼20 nm length and ∼8 nm width)
PbBi2 Ta2 O9 Precursor powders are soft agglomerates Colloid emulsion process [359]
with nanosized primary particles
(near spherical, 40 nm primary
particle size after calcinations)
Strontium ferrite 3.8 nm precursor parti- Coprecipitation of Sr2+ and Fe3+ in a water- [360]
cle sizes and in-oil microemulsion of water/CTAB/n–
50–100 nm calcined particle sizes butanol/isooctane → mixed hydroxide
precursor → calcinations at 700 C 5 h →
pure strontium ferrite
PbCrO4 3–100 nm uniform particles (spherical) W/o microemulsion: water/sodium bis(2– [361]
240 × 140 nm (rectangular shaped) ethylhexyl)sulfosuccinate (AOT)/n–
heptane Dropwise addition of Pb(NO3 )2
containing microemulsion (colorless)
into orange-colored K2 CrO4 -containing
microemulsion
Barium ∼10–30 nm (calcined at 500–1300 C) Sol–gel processing (controlled hydrolysis and [362, 363]
hexaaluminate condensation of B and Al alkoxides) in
reverse microemulsion media
3–10 nm precursor particle sizes [364]
continued
Table 9. Continued
Nanoparticle materials Characteristics of nanoparticle Brief process description Ref.
Barium ferrite Nanosized Mix two microemulsions: coprecipitation [365]

(BaFe12 O19 ) of ferri/barium salts by ammonium
carbonate in microemulsion containing
an aqueous phase, CTAB surfactant,
n–butanol cosurfactant, and octane (oil).
SiO2 -coated iron As small as 1–2 nm iron oxide uniform W/O microemulsion using nonionic [366]
oxide particle size, coating as thin as 1 nm surfactants (Triton X-100, Igepal CO-
520, and Brij-97), by coprecipitation
of Fe(II)/ Fe(III) salts by NaOH or
ammonia. Coating was with TEOS sol–
gel reaction in microemulsion
Titania-coated ∼60 nm monodispersed spheres Controlled hydrolysis of TEOS [367]
silica and Ti n–butoxide in Triton X-
45/cyclohexane/water reverse (w/o)
microemulsions
Silica–copper oxide 20–50 nm with uniform elemental Controlled hydrolysis/polymerization of [368]
composite distribution, narrow distribution of Na2 SiO3 and Cu(NO3 2 · 3H2 O via
mesopores (3–6 nm), 320–379 m2 /g partial-microemulsion and double-
microemulsion processes at 28 C,
consisting of sodium 1,4–bis(2–
ethylhexyl) sulfosuccinate and sodium
dodecyl sulfate, cyclohexane, and water.
Indium–tin oxide Monodispersed, 9–12 nm as-prepared Two emulsion mixing: ammonium hydroxide [369]
(ITO) particle size coprecipitation of aqueous solution of
indium nitrate and tin chloride in AOT-
based reverse microemulsions
25 nm crystalline agglomertates after
calcinations at 700 C
Cu2 L2 O5 Spherical calcined nanoparticle Mixing (NH4 2 CO3 -containing [370]
(L = Ho, Er) (15–25 nm in size) microemulsion with microemulsion
containing both Cu(NO3 )2 and L(NO3 )3
for coprecipitation. W/O microemulsion:
water/CTAB/n–octane/1–butanol
Precipitated Cu2 Ho2 (CO3 4 (OH)2
(25–30 nm) and Cu2 Er2 (CO3 4 (OH)2
(10–40 nm)
BaTiO3 Near-monodispersed, 6–17 nm sizes, Sol–gel reactions in W/O microemulsion [371]
nonagglomerated, cube-shaped without any sintering process
crystals (cyclohexane + 1–octanol + Tergitol™ +
water) + (Ti isopropoxide + Ba
isopropoxide)
Binary and ternary 8–19 nm crystallite sizes in Sol–gel chemistry plus W/O microemulsion [372]
metal oxides nanopowders Binary: TiO2 , ZrO2 technique
Ternary: BaTiO3 , BaZrO3 , SrTiO3 ,
SrZrO3
Perovskite-type ∼20 nm diameter metal oxalate particles, Oxalate precipitation in inverse micro- [373]
metal oxides calcined into single phase into emulsion
LaNiO3 , La2 CuO4 , and BaPbO3
solutions; and (2) this deposit is then permitted to spon- 2. electrochemical oxidation of these metal particles to
taneously oxidize and dehydrate at an open circuit in the MOn/2
pH = 1.0 plating solution. Most recently, Penner [190] uti- 3. displacement of the oxygen from MOn/2 using HX (for
lized the hybrid electrochemical/chemical (or E/C) method example) to yield nanoparticles of semiconductor MX.
for synthesizing oxide and semiconductor nanoparticles or
quantum dots on graphite surfaces. This E/C method for the The conversion from metal to metal oxide to metal salt
synthesis of quantum dots of the generic semiconducting salt occurs on a particle-by-particle basis. The quantum dots thus
MX typically involves three steps: prepared by the E/C method possess many of the attributes
of quantum dots synthesized using molecular beam epi-
1. electrochemical deposition of size-monodispersed taxy, including epitaxial orientation on a substrate surface,
nanoparticles of the metal M 0 from a solution of metal a narrow size distribution, and strong, particle size-tunable
ions M n+ photoluminescence.
Table 10. Liquid-phase sonochemical synthesis of metal–oxide nanoparticles.
Tungsten oxide Amorphous as-prepared particles Sonochemical decomposition: ultrasound [374]

(100–200 nm sizes), globular irradiation of a solution of tungsten
agglomerates composed of hexacarbonyl W(CO)6 in diphenylmethane
<5 nm dense primary particles) in the presence of an Ar(80%)–O2 (20%)
gaseous mixture at 90 C
Ceria Nanocrystalline powder (2.6 nm Sonochemical-assisted heating routes [323]
crystallite) from aqueous solutions containing
(NH4 2 Ce(NO3 6 , hexamethylenetetramine,
and poly(ethylene glycol)-19000 (PEG)
Monodispersed, mean particle Sonochemical synthesis using cerium nitrate [375]
size of ca. 3.3 nm and azodicarbonamide as starting materials,
and ethylenediamine or tetraalkylammonium
hydroxide as additives
Nickel aluminate Nanosized NiAl2 O4 particles with Sonicating an aqueous solution of nickel [376]
spinel a size of ∼13 nm (crystallite nitrate, aluminum nitrate, and urea yields and
size) precursor, which on heating at 950 C for 14
h yields nanosized particles
Yttria-stabilized Monodispersed, 4.7 nm Sonochemical treatment to induce [377]
zirconia (YSZ) nanocrystal size, on the surface crystallization of self-assembled hydrous YSZ
of SrCO3 nanoparticles on the surface of SrCO3 nanoparticles
∀–nickel hydroxide Scaly particles with a length of ca. Ultrasound radiation of an aqueous solution of [378]
120–200 nm and a width of ca. Ni nitrate and urea (purged with Ar, 80 C)
10–15 nm
CuO in PVA ∼5–10 nm particle sizes Ultrasonication of poly(vinyl alcohol) (PVA) [379]
and copper(II) acetate dissolved in water–
dimethylformamide (DMF) under Ar at room
temperature for 3 h
Amorphous iron Stable colloids of undecenoate, Sonochemical decomposition of volatile [380]
oxide Fe2 O3 dodecyl sulfonate, and octyl precursor Fe(CO)5 solution in decane, in the
phosphonate coated Fe2 O3 presence of different surfactants, under air
nanoparticles of 5–16 nm in atmosphere at 273 K for 3 h
diameters
Particle size of ∼25 nm Neat Fe(CO)5 or a solution in decalin was [381]
irradiated ultrasonically under air atmosphere
at 0 C for 3 h
Co3 O4 , ZnO 20–30 nm cobalt oxide particle Sonochemical irradiation of metal acetate [382]
sizes, 250–340 nm zinc oxide solutions in doubly distilled deoxygenated
particle sizes water or 10% water–DMF, under 1.5 atm of
argon at room temperature for 3 h
Fe3 O4 Pure nanocrystalline phase, Sonication of iron (II) acetate in water under [383]
particle size of ca. 10 nm, an argon atmosphere at 25 C for 3 h
minimal agglomeration
RuS17 Particle sizes of ca. 25 nm, Sonication of an aqueous solution of [384]
nanocrystalline powders with ruthenium chloride and thiourea → X-ray
certain aggregation amorphous product → heating at 650 C →
nanocrystalline ruthenium sulfide
3.2.10. Synthesis in Supercritical Fluids and temperature, and (3) the ability to provide homoge-
Supercritical fluid (SCF) processing has been considered for neous reducing or oxidizing atmospheres by introducing
particle design [191] and as a new route for materials syn- gases or additional components (O2 , H2 , H2 O2 .
thesis, such as for the formation of novel inorganic nano- When the fluid is water, the technique is called super-
particles, and for the preparation of different open-structure critical hydrothermal processing. The fluid could also be
oxy(hydroxy)fluorides [192]. There are certain advantageous another solvent, such as CO2 . Some solvothermal process-
features of using SCF processes for materials processing ing is, in fact, a subcategory of supercrical or subcritical
[129]: (1) the ability to form nanoparticles, (2) the ability fluid (solvent) processing. In particular, supercritical CO2
to control particle morphology to some extent with pressure and supercritical water (SCW) are chemically stable and
environmentally benign. SCF exhibits the combined charac- and (2) uses a reacting system in which one reactant is dis-
teristics of both gas and liquid solvents to provide a medium solved in the supercritical solution and one in the liquid
with densities characteristic of liquids, and with gas-like vis- receiving solution [204]. Supercritical ammonia, methanol,
cosities and diffusivities. Thus, mass-transfer rates approach and acetone solutions have also been used for RESS. Most
those of gases, while solvation properties resemble those of recently, a supercritical-assisted atomization (SAA) tech-
conventional liquid solvents. Furthermore, supercritical flu- nique was also proposed and demonstrated for producing
ids exhibit unique tunable solvation characteristics, as sub- nanoparticles of different kinds of compounds (supercon-
tle changes in pressure and temperature in SCFs alter the ductor and catalyst precursors, ceramics, and pharmaceuti-
solvent density. This property might be utilized to improve cal compounds) using different liquid solvents such as water,
many aspects of nanocrystal processing, such as size-selective methanol, and acetone [205]. The chemical transformation
separations, synthesis, and self-assembly [193]. of metallic precursors in a supercritical fluid (a mixture
Hydrothermal synthesis under supercritical conditions has of CO2 /C2 H5 OH or NH3 has been developed as a new
been studied for the synthesis of nanosize crystals of metal route for obtaining ultrafine homogeneous ceramic powders
oxides such as CeO2 and AlO(OH) [129]. In water, the (oxides [Cu2 O, Fe3 O4 , Ga2 O3 ] and nitrides [Cu3 N, Fe4 N]
dielectric constant dramatically decreases when heated and [206]). This process consists of the solubilization and subse-
pressurized above the critical point (Tc = 374 C, Pc = 221 quent thermal decomposition of acetylacetonates of metals
bar). The solubility of salts decreases, and the solubility of in SCF.
organics increases [193]. The lower dielectric constant at
supercritical conditions possibly results in enhancement of
3.3. Solid-Phase Synthesis
the hydrothermal reaction. There are two reasons why nano-
particles are formed at supercritical conditions: (1) larger Solid-phase syntheses are those methods in which nano-
particles are produced at subcritical conditions due to Ost- particles are formed directly from solids or semisolids
wald ripening, that could not be observed in supercritical (such as viscous liquids). Most of these types of synthe-
water because of the extremely low solubility; and (2) the ses belong to the top-down approach, which includes tradi-
nucleation rate is faster in supercritical water because of tional mechanical grinding and solid-state reactions. In the
the lower solubility and the extremely fast reaction rate effort to produce nanoparticles, some new innovations have
[129]. The use of stabilizing ligands to bind nanocrystal been added to these traditional methods, such as introduc-
surfaces, or using compartmentalized heterogeneous media ing reactive materials into the milling process, as shown
(such as micellar solutions) to control growth have recently in Figure 5, and combining milling with solid-state synthe-
been extended to SCFs with general success. When water is sis. Some new approaches include the extraction of solu-
heated and pressurized above the critical point, it becomes ble molecules from a uniform molecular solid mixture by
a suitable solvent to employ organic capping ligands (such acid/base leaching or evaporation to leave molecular skele-
as alkanediols) to control and stabilize the synthesis of ton residues that become nanoparticles.
nanocrystals. Ziegler et al. [193] have prepared monolayer-
stabilized copper nanocrystals (∼7 nm in diameter) in the 3.3.1. Mechanical Milling
presence of 1–hexanediol and Cu(NO3 2 . It is also reported Mechanical forces, such as those involved in high-energy
that metal oxides can be prepared in SCW using metal ball milling, are used to break bulk materials down. Plastic
nitrate salts, which decompose via a two-step mechanism of deformation and dislocation of cell structures are respon-
hydrolysis and dehydration [194]. The high temperature of sible for producing highly strained amorphous particulate
SCW promotes crystallization, which eliminates the need for materials. Crystalline nanoparticles can be produced when
postprocess annealing. Oxidizers/reducers can be added to the dislocation of cells disappears. High-energy ball milling
the reaction mixture to influence the product chemistry. is already commercialized for generating magnetic [207], cat-
Water-in-sc–CO2 microemulsions have been used as
alytic [208], and structural [209] nanoparticles.
“microreactors” to produce nanocrystals of cadmium sulfide
and silver [195, 196], while water-in-sc–ethane and water-in-
sc–propane microemulsions have been similarly used to pro-
Solid BaCO3 Solid TiO2
duce copper nanocrystals [197, 198]. Arrested precipitation
methods have also recently been utilized in SCFs to produce
sterically stabilized silicon nanocrystals (in sc–octanol and
Ball milled in NaCl to form BaTiO3
sc–hexane) [199] and silver, copper, palladium, platinum,
and iridium nanocrystals (in sc–CO2 [200].
Supercritical antisolvent precipitation (SAS), based on the
fast dissolution of a liquid solution in a supercritical fluid, Heat the mixture to completion
has been tested to produce nanoparticles of yttrium, samar-
ium, europium, gadolinium, and neodymium acetates to be
used as precursors for high-temperature superconductors Wash with H2O to remove NaCl
[201, 202] and as a zinc oxide precursor (zinc acetate) [203].
Rapid expansion of supercritical solution (RESS) is another
technique that has been tested for the preparation of nano- BaTiO3
scale PbS particles. In this technique, one: (1) expands the
supercritical solution into a liquid solution instead of a gas, Figure 5. Flowchart for a mechanochemical synthesis.
Bohwmik et al. [210] have obtained 16 nm nanoparticles two roles. The major role is to dilute or coat the BaTiO3 par-
of antiferromagnetic spinel CoRh2 O4 by the mechanical ticles formed so that the nanosized BaTiO3 will not agglom-
milling of bulk materials for up to 60 h. Magnetic measure- erate together. The second role may be to promote the
ments suggest that the antiferromagnetic ordering at TN at chemical reaction between BaCO3 and TiO2 . To complete
27 K exists in bulk as well as in nanoparticle samples. Nano- the reaction, the milled products were subjected to external
particle Co02 Zn08 Fe2 O4 spinel oxide was also synthesized heating for 30 min at 700 C. A final washing to remove
by room-temperature mechanical milling [211]. The system NaCl with large amounts of water is needed to recover
is stabilized mainly in the spinel oxide phase after 78 h of BaTiO3 . BaTiO3 of 50–100 nm was produced. However,
milling time, and no other phases have been observed. there are still issues regarding the ability to achieve phase-
The simplicity of mechanical milling has shown its poten- pure materials with the proper Ba/Ti ratio, the need to pre-
tial in nanoparticle synthesis without complex capital equip- vent contamination from milling media and NaCl, and the
ment. The development of new technologies such as bead desire to reduce the amount of waste water from extensive
mills with very small beads, and their use in combination water washing. Furthermore, it is difficult to keep the nano-
with classification/filtration, make this technology applicable sized BaTiO3 from agglomerating again during washing, fil-
to nanoparticle synthesis. A drawback in this technology is tering, and drying after the BaCl2 is dissolved away.
contamination from media. Mechanochemical processing has been demonstrated to
be very versatile in making a broad range of nanoparticles
(as shown in Table 11), including metals, oxides, carbonates,
3.3.2. Mechanochemical Processing and sulfides. The chemical reactions for particle synthesis
Mechanochemical processing is considered the natural could happen during milling, but it is not necessary that they
extension of mechanical processing. Here, the process not happen during this phase of the process. It is only neces-
only involves physical reduction in a material’s size, but sary for the crystal size to be refined to the nanometer level
it also uses the milling energy to initiate chemical reac- during milling, after which the chemical reactions can be
tions between the materials that are being milled. It usually induced with a low-temperature heat treatment. Particle size
involves two or more solid reactants. Sometimes, the start- control in this process is achieved via the milling conditions,
ing materials are milled together in the presence of a large and also by the addition of diluents, and this process has
amount of sacrificial salt, such as NaCl, which prevents the been shown to produce a range of sizes from 4 to 500 nm. It
agglomeration of the resulting nanoparticles, as shown in is cost effective in that it uses simple starting materials and
Figure 5 [212]. More and more mechanical milling processes simple milling equipment. The disadvantages of this process
are incorporating chemical reactions to make the process include contamination from milling vessels and media. The
more amenable to nanoparticle syntheses [213]. Table 11 washing of the byproducts after heat treatment also presents
shows examples of nanoparticles of ferrites, CaTiO3 , SnO2 , challenges because a large volume of water is consumed,
Ag, Fe2 O3 , CaCO3 , Cu, Al2 O3 , PbTiO3 , ZnO, CeO2 , Cr2 O3 , and because agglomeration of the particles may occur dur-
Gd2 O3 , ZrO2 , and Group II–VI semiconductors that were ing washing and drying.
made using mechanochemical methods.
Mechanochemical synthesis uses mechanical energy to 3.3.3. Cryochemical Processing
activate chemical reactions, and to cause surface and struc- Cryochemical processing is a low-temperature process in
tural change of the materials [214]. As a consequence, chem- which rapid cooling is applied to preserve the homogene-
ical reactions which otherwise require high temperatures can ity of atomic-level mixtures. The cooling is usually very fast
occur at low temperatures in a ball mill without external in order to prevent separate crystallization of solutions such
heating or with low external annealing. as soluble nitrates. This is usually achieved by spraying the
Abe and co-workers [215, 216] made submicron BaTiO3 solution into liquid nitrogen. Removal of frozen water is
by ball milling TiO2 with Ba(OH)2 ·8H2 O in acetone for 6 h usually accomplished by physical (freeze drying) or chemi-
without external heating. A boundary–reaction-controlled cal means. Many cryochemical techniques have been devel-
interface contracting kinetics, and contraction kinetics with oped for powder processing [219–222]. The process can be
a crystallinity gradient inside the TiO2 particles, have been described by the following diagram:
proposed for the formation of BaTiO3 .
van Hal et al. [217] showed the feasibility of making sub- Preparation of a clear solution
micron BaTiO3 by ball milling BaO2 with TiO2 for 256 h.
The products are BaTiO3 agglomerates consisting of 50%
particles with a crystallite size of 12 nm, 30% particles with Rapid freezing of the solution
a crystallite size of 2 nm, and 20% amorphous particles.
Heating of these agglomerates at 800 C did not significantly
improve the crystallinity. Freeze drying to remove water
McCormick and Tzuzuki [218] made truly nanosized
BaTiO3 by milling BaCO3 and solid TiO2 with a large
amount (three times the mass of BaCO3 plus TiO2 of sac- Thermal decomposition
rificial salts, such as NaCl, for a few hours. Such milling
induces reactions between BaCO3 and TiO2 , as well as mix-
Heat treatment
ing of BaCO3 and TiO2 . The diluent phase NaCl may have
Table 11. Nanoparticle synthesis by mechanochemical process.
Ferrites (Fe3 O4 /Fe2 O3 , 20–30 nm, spinel Mechanochemical reaction in Wide field of [385]
CoFe2 O4 , structure aqueous solution of various technological
Ni05 Zn05 Fe2 O4 corresponding chlorites and applications
NaOH in a horizontal mill
CaTiO3 20–30 nm crystallite Mixture of CaO and TiO2 was Dielectric [386]
milled in a planetary mill at materials
200–300 rotations/min for and other
2–10 h applications
SnO2 5–30 nm, tetragonal and Mechanochemical milling of Various [387]
orthorhombic SnO2 SnCl2 and Na2 CO3 followed applications
formed after heat by heat treatment in air
treatment
Ag 50–1000 nm metallic A solid-state displacement Electrode [388]
silver with minor reaction between AgCl material,
quantity of Ag2 Na and Na by ball milling in a pigment, etc.
planetary-type ball mill. The
byproduct NaCl was washed
out
Fe2 O3 Ammonium acetate as Magnetic [95]
precipitating agent materials
CaCO3 80–140 nm, crystalline Milling of a CaCl2 –Na2 CO3 Various [389]
powder mixture, followed applications
by heat treatment of the
as-milled powder at 350 C.
NaCl was washed away
Cu Cu crystallite size of Milling CuO–CuO · Al2 O3 mix- Electronic [390]
28 nm with 3vol% ture for 8 h materials,
CuO Al2 O3 pigments, etc.
Al2 O3 10–50 nm amorphous Milling ZnO and Al powder Coating, paints, [391]
alumina and various
applications
PbTiO3 10 nm grain size High-energy ball mill of Electric [392]
lead oxide and titanium applications
oxide for 20 h without any
posttreatment
ZnO, CeO2 , SnO2 28, 10, 40 nm crystalline Milling of chlorides and In many industries [393]
nanoparticles, carbonates, followed by
respectively water washing
Cr2 O3 10–80 nm crystalline Milling of NaCr2 O7 Various [394]
with S powder to form applications
amorphous Cr2 O3 ; crystalline
Cr2 O3 was formed after
annealing under vacuum at
520 C. Water washing to
remove Na2 SO4 formed
II–VI semiconductor <10 nm Milling of chloride salts and Various [395]
alkali or alkaline earth applications
chalcogenides, postheat
treatment, and washing
Gd2 O3 20 nm cubic structure Milling GsCl3 with NaOH Various [396]
in the presence of NaCl, applications
followed by calcinations at
500 C
ZrO2 15–18 nm crystallite size Milling (NH4)2Cr2 O7 with Coatings [397, 398]
stabilized zirconium in amorphous precipitation and other
c–ZrO2 polymorph with of Zr(=4) oxyhydroxide, applications
5 mol% Cr3+ and Cr4+ followed by heating at
500 C
Tretyakov and Shlyakhtin [222] have provided an excel- [227] and autoignition process [228], or is sometimes more
lent review of recent progress in the cryochemical syn- specifically called glycine–nitrate synthesis [229, 230], and
thesis of oxide materials. A broad range of materials has the organometallic polymer precursor method [231]. This
been synthesized using cryochemical methods. These mate- method utilizes rapid exothermic reactions to form solid fine
rials include ferrites, catalysts, resistive materials, high- particles directly. It involves a molecular mixture of oxidiz-
temperature superconductors, magnetic semiconductors, ers (e.g., metal nitrates, ammonia nitrates, or ammonia per-
superionics, and phosphors. One unique feature of this syn- chlorate) and reducers (e.g., carbonaceous materials such
thesis is that there is a large difference between the specific as urea, carbohydrazide, glycine, PVA, sucrose, and EDTA),
molar volumes of the frozen precursor salt and the oxide which can be ignited at relatively low temperatures. The
product formed after thermal decomposition of the precur- ratio of oxidizer to reducer is usually calculated according
sor salt. Thermal decomposition transforms the salt crys- to Jain and Adiga’s methods [232]. The combustion reaction
tallites into a porous oxide framework of almost the same can be initiated in a lab muffle furnace or even on a hot
size and shape as the initial salt crystallites. Subsequent heat plate at temperatures of lower than 500 C. The process can
treatment causes the rearrangement and sintering of frame- be illustrated by the following diagram:
work elements of 10–40 nm in size into larger aggregated In the above diagram, the route ending on the right side
particles of 50–300 nm. usually involves polymers such as polyvinyl alcohol (PVA),
McHale et al. [223] recently demonstrated the synthesis of carboxylated starch (PAA) or sucrose, or complexing agents
nanocrystalline BaTiO3 using cryochemical methods. They such as organic acids or organic amines and metal nitrates
first prepared a titanyl nitrate solution of pH 1.2 by dissolv- [227, 233, 234]. The route ending on the left side usu-
ing hydrolyzed titanium isopropoxide with a diluted nitric ally involves an unstable system such as metal nitrates and
acid. BaCO3 was added to this acidic solution to achieve glycine, which could initiate self-combustion at temperatures
a molecular mixture solution of Ba:Ti = 1:1. This nitrate as low as 200 C [235–237].
solution was then atomized using an ultrasonic spray nozzle, Pathak and Pramanik [227, 238] have synthesized over 50
and was rapidly frozen by allowing the aerosol to fall into different ceramic oxides using combustion methods. These
stirred liquid nitrogen. The fine white-to-pale-yellow parti- oxide systems include
cles (“snow”) were then dried in a freeze dryer at about • metal oxides: Fe2 O3 · NiO, Fe2 O3 ·CuO, Fe2 O3 ·TiO2
−30 C. The highly reactive precursor powder obtained from • metal phosphates: Co3 (PO4 2 , Ni3 (PO4 2 , Cu3 (PO4 2 ,
this freeze drying could be completely converted into 10– Ba3 (PO4 2 , AlPO3 , CrPO4 , FePO4
15 nm nanocrystalline BaTiO3 of cubic structure by heating • metal vanadates: Ca3 (VO4 2 , Co3 (VO4 2 , Ni3 (VO4 2 ,
at 600 C for 10 min. Prolonged heat treatment at 600 C for Cu3 (VO4 2 , CrVO4 , FeVO4 , MnVO4
up to 24 h resulted in little grain size growth. Higher temper- • metal molybdates: CaMoO4 , NiMoO4 , CoMoO4 ,
ature calcination and annealing, however, significantly grew MgMoO4 , Sm3 (MoO4 3 , Gd3 (MoO4 3
the grain size (500 nm at 1000 C), and resulted in the • metal tungstates: CaWO4 , MgWO4 , NiWO4 , CoWO4
appearance of the tetragonal form of BaTiO3 . • rare-earth aluminates: LaAlO3 , SmAlO3 , NdAlO3
Kirchnerova and Klvana [224] synthesized submicron • PZT and PLZT.
lanthanum–strontium transition metal-based perovskites
based on cryochemical methods. They used a reactive aque- Their methods involve the combustion of a polymer (PVA or
ous slurry of lanthanum (or another rare earth metal) sucrose) and/or complex-based (EDTA/TEA/DEA) nitrate
hydroxides and of metal nitrate solution as a starting solution(s). The polymer plays a dual role in the process:
material. This well-homogenized suspension was then spray it acts as a dispersing agent for the cations in the solution,
frozen, freeze dried, and calcined at as low as 627 C to and it also serves as a fuel that provides heat through com-
form the perovskite phase. bustion during calcination of the precursor powders. The
Thierauf et al. [225] produced superconducting YBCO principle of their methods is to atomistically disperse the
powders of less than 300 nm via a freeze-drying process metal ions in a matrix provided by a polymeric reagent
using the dissolved acetates as precursors. A crystalliza- or through complexation with various chelating agents that
tion temperature as low as 720 C in air was realized due possess good coordination properties with metal ions. Evap-
to the short diffusion lengths in the freeze-dried precursor oration of the precursor solutions results in a fluffy, volu-
materials. minous carbonaceous mass that constitutes the precursor
The cryochemical method has broad applications; how- materials. The resulting particles from combustion of the
ever, freeze drying itself cannot form the final prod- precursor powders are 10–90 nm in diameter, have a narrow
ucts directly. A final calcination and annealing are always size distribution of high purity, and are obtained at rela-
needed. This thermal treatment always aggregates, agglom- tively lower pyrolysis temperatures than those obtained from
erates the particles, and grows large crystals, which makes it direct calcinations.
difficult to synthesize monodispersed nanoparticles. Chick and co-workers [229, 230, 235, 236, 239–242] have
prepared nanosized metal powders such as Ni, Cu, and
Fe, or the two-metal system containing Ni and Cu, using
3.3.4. Self-Combustion Method a glycine–nitrate combustion method. Their method con-
The self-combustion method has been widely used in sists of two steps. First, metal nitrates and a low molecular
the synthesis of oxides/ceramic particles. It is known by weight amino acid are dissolved in water. Second, the solu-
different names, such as self-sustaining/propagating high- tion is boiled until it thickens and autoignites, undergoing
temperature synthesis (SHS) [226], the combustion method self-sustaining combustion. The ash from the combustion is
composed of the oxide products. The glycine molecule has

a carboxylic acid group at one end, with an amine group
at the other, and serves two purposes: it prevents selective
precipitation as water is evaporated, and it serves as fuel
for the combustion, being oxidized by nitrate ions. The fuel-
rich mixtures produce 10 nm spherical Ni (with 15% NiO),
30–40 nm Cu. The disadvantage of this method is that, in
general, the glycine–nitrate combustion tends to produce
agglomerated particles.
McKittrick et al. [243] prepared yttrium aluminum gar-
net (Y3 Al5 O12 , YAG) using a combustion process. They
dissolved the metal nitrates with carbohydrazide in water,
and placed the container in a muffle furnace preheated to
560 C. The reaction proceeds as the precursor solution first
boils, dehydrates, decomposes, and ruptures into a flame Figure 6. CeO2 nanoparticles prepared from a combustion method
after 5–10 min, with the flame being sustained for about [246].
15 s. The gaseous products that exist in greatest abundance
are N2 , CO2 , and H2 O if the ratio of fuel to oxidizer is stoi-
chiometric. The powders produced are single phase and well and electron diffraction studies have shown that the as-
crystallized. The combustion-synthesized powders have an prepared powder is phase-pure Ba2 HoZrO55 , and has a
unusual morphology, forming a porous, foamy network in complex cubic perovskite (A2 BB O6 structure with a lattice
the as-synthesized state, due to the rapid release of gaseous constant a = 8428 Å. The nanoparticles of Ba2 HoZrO55
products. The porous powders were easily reduced to a small could be sintered to 98% theoretical density at 1500 C.
particle size with light mixing. Combustion synthesis pro- Yu et al. [245] prepared nanosized PbTiO3 powders using
duces powders that are luminescent in the as-synthesized the self-combustion technique. Pb(CH3 CHOHCOO)2 was
state, an attribute unattainable by conventional methods. used as the Pb precursor, and was formed from the reaction
Another modification of combustion synthesis has been between PbO and CH3 CHOHCOOH, with viscous lactic
explored by Salze et al. [231] for synthesizing ZrO2 , acid as the solvent. The system lead lactate–lactic acid–
La2 NiO4 , and BaTiO3 . The initial organometallic solution ethanol–titanium butoxide was selected as the precursor for
is obtained by first making an organic solvent solution (dis- processing of PbTiO3 .
solution of 400 g citric acid in 500 mL of ethylene glycol). Feng [246] synthesized spherical CeO2 using a com-
The solution is mechanically stirred until it becomes clear. bustion method, as shown in Figure 6. He prepare an
To prepare tetragonal zirconia, zirconium n–propoxide and (NH4 2 Ce(NO3 4 aqueous solution, and added acetyl ace-
yttrium carbonate are dissolved in this organic solvent solu- tone and isopropanol as fuel and as complexing agents. This
tion. To prepare pure SrTiO3 or BaTiO3 , the corresponding clear solution was turned into a viscous liquid by evapora-
titanium isopropoxide and SrCO3 or BaCO3 (dissolved in tion, and further heating on a hot plate induced vigorous
formic acid) are dissolved in the above-mentioned organic self-combustion to form 15–80 nm crystalline CeO2 particles
solvent solution. To prepare doped SrTiO3 or BaTiO3 , nio- directly.
bium ethoide is also added to the solutions cited for prepa- Self-combustion synthesis has been widely demonstrated
ration of pure SrTiO3 or BaTiO3 . To prepare lanthanum as effective for synthesizing ceramic powders [228, 237,
nickelate, lanthanum and nickel hydroxides freshly precip- 240, 247–256]. The technique may need more development
itated from nitrate solutions are dissolved. After polymer- to prevent agglomeration and aggregation of the powders
ization at 110 C in an Al2 O3 crucible, a translucent resin during synthesis. Safe scale up to a commercial process
having a homogenous chemical composition is obtained. demands further optimization studies.
This resin is then combusted in air or pure oxygen to obtain
the desired powders. The mean diameters of individual par-
ticles observed by TEM are 10–60 nm for ZrO2 combusted 3.3.5. Solid-State Synthesis
in oxygen at 400–950 C, 10 nm for SrTiO3 in air at 600 C, This is the most traditional approach for making many
10 nm for BaTiO3 in air at 800 C, and 35 nm for La2 NiO4 ceramic powders such as BaTiO3 . It involves milling BaCO3
in air at 600 C. with TiO2 to achieve comminution and mixing. This mixture
Zhou et al. [228] have synthesized 10 nm ZrO2 containing is then calcined at 900–1200 C to generate BaTiO3 . The
up to 20mol% CeO2 using the autoignition method. Zirconyl reaction mechanism has been described in the literature to
nitrate, cerous nitrate, and urea powders with stoichiomet- have the following steps [257–259]:
ric composition are dissolved in water, and are then con-
verted to tetragonal ZrO2 by evaporation and combustion in 1. interface reaction by diffusion of Ba into TiO2 to form
a 600 C furnace. The result is a foamy yellow powder with a BaTiO3 shell (layer) around TiO2 ; the shell also lim-
the characteristic color of ZrO2 (CeO2 powders. its Ba diffusion into TiO2 :
Rajan et al. [244] recently synthesized 4–16 nm barium
holmium zirconate, a new complex perovskite ceramic oxide,
using a modified self-propagating combustion process. XRD BaCO3 + TiO2 → BaTiO3 + CO2
Instead of using solid TiO2 particles, Han and Koo [265]

Calcination precipitated titanium hydroxide/oxide particles directly onto
BaTiO3 the surface of BaCO3 . TiCl4 or Ti alkoxide solutions were
BaCO3 TiO2 added directly to an aqueous slurry containing fine particles
of BaCO3 and ammonia at pH 9.5–10.3. The nanoparticles
of titanium hydroxides/oxides were deposited or coated on
the surface of BaTiO3 , which effectively reduced the inter-
diffusion distance. The filtered slurry was then calcined at
Figure 7. Solid-state reaction through interdiffusion to form BaTiO3
during calcination.
950 C for 2 h to produce 180 nm BaTiO3 .
In a similar study, coprecipitation of a mixture of BaCl2
and TiCl4 with a solution of ammonium carbonate has
2. formation of the orthotitanate phase: also been studied [266]. It was found that crystallization
of amorphous barium tetratitanate was observed when the
BaCO3 + BaTiO3 → Ba2 TiO4 + CO2 precipitates were heated above 600 C. At the same time,
the following reaction is also suggested:
BaCO3 + TiO2 → Ba2 TiO4 + 2CO2 (less likely)
BaTi4 O9 + BaCO3 = 2BaTiO3 + 2TiO2 + CO2
3. final formation of BaTiO3 :
The newly formed TiO2 begins to react with BaCO3 directly
Ba2 TiO4+ TiO2 → 2BaTiO3 at 800 C:
The high calcination temperature is needed to promote the BaCO3 + TiO2 → BaTiO3 + CO2
interdiffusion of barium and titanium, which results in the
solid-state reaction to form barium titanate, as shown in The above reactions approached completion at 1100 C.
Figure 7. The distance of the interdiffusion depends on the Li et al. [267] used a solid-state reaction process to prepare
sizes of the raw materials BaCO3 and TiO2 used for syn- perovskite-type LaCoO3 nanocrystals with grain diameters of
thesis. After milling, these particles are usually in the range 15–40 nm. In the first step of the process, 5 nm composite
of 0.5 m, and the interdiffusion distance is usually larger hydroxide nanoparticles were prepared by the solid-state
than 1 m in the traditional solid-state synthesis. The reac- reaction of La(NO3 3·nH2 O and Co(NO3 2 6·H2 O with
tion rate is controlled by this diffusion [260]. The interdif- KOH at ambient temperature. A perovskite-type rhombohe-
fusion is usually incomplete during calcination due to the dral LaCoO3 phase appeared at 550 C after the hydroxide
large diffusion length, and therefore the final products usu- was calcined at various temperatures. The phase transfor-
ally contain titanium-rich and barium-rich intermediate par- mation process was complete at about 800 C, yielding a
ticles [257, 261]. single-phase binary oxide.
It has also been well known that BaTiO3 is formed Wang et al. [268] developed a one-step solid-state reaction
through a sequence of reactions and intermediate phases in the presence of a nonionic surfactant, PEG 400, to syn-
[258], and that prolonged calcinations at high temperature thesize CuO nanowhiskers with diameters of approximately
are usually needed to reduce the heterogeneities in the final 2–10 nm and lengths of more than 100 nm.
products. This usually results in large and agglomerated par- Zhuang et al. [269] prepared a precursor Co2 (OH)2 CO2
ticles which need extensive milling before BaTiO3 can be by the solid-state reaction of Co(NO3 2 6·H2 O with
used in the various forming processes. Milling introduces NH4 HCO3 at ambient temperature. Nanophase Co3 O4 with
high levels of impurities from the milling equipment and an average particle size of 13 nm was obtained by decom-
media, such as alumina, silica, zirconia, and phosphorus. position of the precursor at 250 C for 3 h.
These impurities are known to have a deleterious effect on Yu et al. [270] prepared CeO2 ultrafine particles by solid-
the electrical and mechanical properties of barium titanate- state reactions at room temperature. These particles were
based products [262]. found to have very fine particle sizes (∼3 nm) with a fluorite
Current efforts in solid-state methods for synthesizing structure (a = 542 Å). BET measurements showed that the
ultrafine particles of BaTiO3 have been aimed at reducing surface area of the particles was 96.2 m2 /g.
the interdiffusion distance by utilizing finer starting materi- All of these current efforts in solid-state synthesis focus
als or through intensive milling or utilization of precipitation on minimizing the interdiffusion distances of solid-state
to produce the solid starting materials in-situ. reactions through intensive milling, coating particles with
High-energy ball milling of BaCO3 and TiO2 (rutile) has nanoparticles, and coprecipitations. The reduced interdif-
reduced BaTiO3 formation temperatures down to 730 C, fusion effectively lowered the BaTiO3 formation temper-
and the resulting BaTiO3 has a crystallite size of 40 nm [263]. ature, but the completion of the formation reaction still
The detrimental phases, like Ba2 TiO4 (orthotitanate), have requires calcination temperatures from 750 to 1100 C. This
only been revealed as an intermediate minor phase that dis- high-temperature calcination will inevitably promote particle
appears by annealing at temperatures as low as 750 C. agglomeration and particle size growth. The improvement
It has also been shown that milling does change the reac- in the solid-state reaction technique may be able to produce
tion sequence between BaCO3 and TiO2 [264]. However, solid-state BaTiO3 down to 300 nm at industrial quantity,
milling reduces the formation temperature and accelerates but it is extremely difficult, if not impossible, to produce
the formation rate of BaTiO3 . BaTiO3 at about a 100 nm range via this method.
3.3.6. Colloidal Assembly Method and organized in 2-D superlattices. Changes in the hystere-
Colloidal assembly is a process by which nanometer-sized sis loop and in the blocking temperature are observed, and
colloids (nanoparticles) are organized into structures by mix- are attributed to a collective flip of the magnetization of
ing two or more particle types (differences in sizes and/or adjacent particles.
chemical nature [271]). Assembly is controlled by either Self-assembly of solid colloids into nanoparticles with the
specific or nonspecific interactions between particles. The assistance of organic molecules, surfactants, and polymer-
assembly process is usually performed such that smaller ized vesicles has also been inspired by Mother Nature’s orga-
particles assemble around larger ones. Examples include nizational ability [26, 27, 234, 271, 277–279]. This method
chemical bonding, biological interactions, electrostatic inter- could provide a unique way to synthesize stable and unag-
actions, capillary action, and physical adsorption. glomerated nanoparticles at low temperature and in an envi-
Pileni [272] has reviewed syntheses of nanosized parti- ronmentally friendly way [280, 281].
cles that used colloidal assemblies as templates. The chem-
ical mechanisms in nanoparticle production using colloidal 3.3.7. Selective Leaching of a Single-Phase
assemblies can differ from those usually observed in homo- Solid-Solution Method
geneous solutions. The colloidal systems mimic nature to
This is a top-down approach, but at a molecular scale. In
control the size and shape of nanomaterials. It is possible
this approach, a precursor powder of normal size (micro
to select the size and markedly reduce the particle size dis-
or macro) containing the desired elements is synthesized by
tribution by using a surface treatment of the nanoparticles.
any conventional method, such as a solid-state method. The
This favors the formation of mono- and multilayers made of
unwanted species are then chemically leached away in a suit-
nanoparticles. These particles form crystals organized in a
able liquid, which could be either water or an acid solution.
3-D face-centered cubic superlattice.
The concomitant change in volume and crystal evolution
An unusual phase diagram is presented by Pileni et al.
during leaching leads to the formation of molecular-level
[273]. It is composed of copper(II) bis(2–ethylhexyl) sulfos-
fragments, resulting in nanoparticles. Jiang et al. [19] have
uccinate Cu(AOT)2–isooctane–water. Syntheses performed
demonstrated the synthesis of nanosized yttrium-stabilized
in the various parts of the phase diagram show that the use
zirconium by using this method. They have demonstrated
of colloidal assemblies as templates favors control of the
this approach using two different precursors, Na2 ZrO3 and
shape of nanoparticles. Cylindrical metallic copper particles
BaZrO3 .
having the same size can be obtained in various parts of the
For the preparation of yttrium-stabilized BaZrO3 , the
phase diagram when the template is made of interconnected
starting materials BaCO3 , ZrO2 , and Y2 O3 were mixed in
cylinders. A small number of cylinders (13% of the amount
the requisite proportion, wet ball milled in alcohol for 24 h,
that could be formed) are formed when the synthesis is per-
and then dried. For the preparation of Y–Na2 ZrO3 , Na2 CO3
formed in cylindrical reverse micelles. When the colloidal
and commercial yttrium-stabilized zirconium (YSZ) pow-
self-assembly is a mixture of several phases, various types of
ders were mixed, wet milled, and then dried. The ball-milled
shapes can be obtained. In some cases, the polydispersity in
and dried powders were calcined at various temperatures,
size is so low that metallic particles are able to self-assemble
and the resulting powders were examined to ensure that
in a hexagonal network. Multilayers can be observed, and
completely converted single-phase precursor powders (i.e.,
are arranged in an FCC structure.
Y–BaZrO3 or Y–Na2 ZrO3 had been formed.
Monolayers of nanoparticles have been physically
Chemical leaching of BaO from Y–BaZrO3 was achieved
adsorbed onto highly oriented pyrolytic graphite, first by
in dilute aqueous HNO3 solution. The Y–BaZrO3 was boiled
self-assembly, and second by assembly as Langmuir films
in a dilute HNO3 solution, filtered, and washed repeatedly
and subsequent deposition. Nanoparticles have been self-
until the solution pH no longer changed. The washing pro-
assembled on gold, and immobilized by chemical absorption,
cess leached Ba2+ and left Y–ZrO2 behind:
using decanedithiol during assembly as a linking molecule.
Rolandi et al. [274] have obtained scanning tunneling micro-
scope images of the monolayers of gold nanocrystals, with Y–BaZrO3 + 2HNO3 → Ba NO3 2 + Y–ZrO2 + H2 O
mean diameter 2.8 nm, coated with an insulating chemically
stable self-assembled monolayer of dodecanethiol. For the Y–Na2 ZrO3 precursor, repeated boiling in water is
Kurth et al. [275] have demonstrated that self-assembly sufficient to remove sodium according to
of CdTe nanoparticles and alkylammonium surfactants gives
stable, hydrophobic surfactant-encapsulated CdTe clusters Y–Na2 ZrO3 + 2H2 O → 2NaOH + Y–ZrO2
that can be isolated as solid materials which dissolve in com-
mon organic solvents, spread at the air–water interface, and Chemical analysis of the boiled and washed powders showed
show enhanced photochemical stability. only ZrO2 and Y2 O3 .
Christophe and Pileni [276] have used colloidal assemblies XRD patterns of leached and washed powders from both
to synthesize FCC cobalt nanoparticles. The nanocrystals precursors were identical, even though they showed very dif-
are coated and extracted from micelles. These cobalt metal ferent XRD patterns before leaching. Both end products
particles are stable in air, and have a narrow size distribu- showed an XRD pattern similar to commercial Y–ZrO2 .
tion. After deposition on a graphite support, these nano- The particle size was a few nanometers, and increased to
crystals form a 2-D hexagonal network. The magnetic prop- tens of nanometers after thermal treatment at a temperature
erties are compared when they are dispersed in a solvent of 1000 C.
4. SUMMARY Sol–gel process Refers to processing in a liquid medium to

obtain solid matter at low temperature, and involves, first,
Here brief review of ceramic nanoparticle syntheses is pro-
the formation of sol, and then gel.
vided. Nanoparticles can be defined as particles with a size
range from 1 nm to a size whose ratio of the number of
atoms on the surfaces and at the grain boundaries to the
atoms at the center is such that new physical, chemical, and ACKNOWLEDGMENTS
biological properties occur when compared with their cor- Xiangdong Feng thanks the management (especially Brian
responding bulk materials. The challenges in manufacturing Foster, Steve Florio, Bob Her, Jack Prendergast, Steve Jolly,
nanoparticles are: controlling their size, morphology, crys- Ron Harris, Carl Lentz, and Robert Rieger) of Ferro Corpo-
tallinity, shape, and properties, and making them with a vari- ration for supporting this work, Vicky Bryg and Dave Gnizak
ety of materials at large volumes and at a reasonable cost. for the SEM and TEM work, Paul Seman, Anna Andrews,
The synthetic methods can be classified by the strategy of Bob Opalko, Tony Dean, and Mary Fedorcio for reviewing
the synthesis (top down or bottom up), by the nature of the manuscript, and Janice Ruf and Brook McGilvray for
the synthetic process (physical, chemical, or biological), by entering references. Michael Hu thanks the sponsorship by
energy sources (laser, plasma, sputtering, microwave, elec- the Materials Chemistry Program, Materials Sciences and
tron beam, heating, freeze drying, hydrothermal, mechan- Engineering Division, Office of Basic Energy Sciences, U.S.
ical milling, combustion, flame, supercritical, etc.), and by Department of Energy. Oak Ridge National Laboratory is
the media in which nanoparticles are formed (gas, liq- managed by UT-Battelle, LLC, for the U.S. Department of
uid, and solid). Gas-phase syntheses are actively coupled Energy under contract DE-AC05-00OR22725.
with liquid dispersion to achieve better deagglomeration.
There is an increasing trend of using nonaqueous solvents
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